TW200819872A - Liquid crystal alignment agent and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent to form a liquid crystal alignment film which is difficult to be scratched by rubbing. The liquid crystal alignment agent comprises an aromatic amine compound as shown in following formula (1), (Wherein, A is a aromatic group having three valence bonds, R1-R6 are aromatic groups and R1-R6 are the same or different each other.)

Description

200819872 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a liquid crystal alignment agent for forming a liquid crystal alignment film of a liquid crystal display element. More specifically, it relates to a liquid crystal alignment agent capable of forming a liquid crystal alignment film which is excellent in electrical properties and liquid crystal alignment and which is less likely to cause damage associated with the polishing treatment on the surface of the liquid crystal alignment film (hereinafter also referred to as "grinding damage"). [Prior Art] Conventionally, a TN type liquid crystal display element having a TN (Twisted Nematic) type liquid crystal cell is known which forms a positive dielectric between two substrates on which a liquid crystal alignment film is formed on a surface through a transparent conductive film. The anisotropic nematic liquid crystal layer constitutes a unit cell of a sandwich structure, and the long axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate to the other substrate. The alignment of the liquid crystal in the liquid crystal display such as the T N type liquid crystal display is usually realized by a liquid crystal alignment film which imparts an alignment energy to the liquid crystal molecules by the rubbing treatment. Here, as a material of the liquid crystal alignment film constituting the liquid crystal display element, resins such as polyimine, polyamide, and polyester are known. In particular, polyimine is used in many liquid crystal display elements because of its excellent heat resistance, affinity with liquid crystals, mechanical strength, and the like. Among the liquid crystal alignment film materials using a polyimide resin, Patent Document 1 exemplifies an improvement of the abrasion resistance. Patent Document 1 discloses a method of adding a nitrogen atom-containing epoxy compound to a polyimide and a polyphthalic acid resin. In contrast, the present inventors conducted intensive studies in order to make the liquid crystal alignment film material exhibit better abrasion resistance. In the inventors of the present invention, the structure of the compound containing two nitrogen atoms in the molecule disclosed in Patent Document 1 was examined and found to be The present invention can be further improved by using a specific aromatic amine compound together with a polyimine or a polyaminic acid to improve the abrasion resistance. The reason for improving the abrasion resistance is presumably because the presence of the specific aromatic amine compound f ' increases the film density and film hardness of the alignment film. In the first aspect, the present invention provides a liquid crystal alignment agent comprising an aromatic amine compound represented by the following formula (1) (hereinafter also referred to as "specific compound").

I Ά/3

I I R5 R4 ( 1 ) (wherein A represents a trivalent aromatic group, and R and R6 represent an aromatic group 'L to R6' may be different from each other or may be the same). Further, in the above formula (1), it is preferred that A is a benzene ring. Further, the aromatic amine compound is more preferably a compound represented by the following formula (2). 200819872

(wherein R? to Ru are each independently hydrogen, an amine group or a monovalent organic group). In the above formula (2), preferred are aromatic amine compounds in which L to R12 are each independently hydrogen or an amine group or aromatic amines in which R7 to R12 are each independently hydrogen or an epoxy group-containing tertiary amine group. Compound. Further, according to the '2nd' of the present invention, there is further provided a liquid crystal alignment agent characterized by comprising an aromatic amine compound which is an amine group of two of R7 to Ru in the above formula (2) and a tetracarboxylic acid dianhydride. Polylysine (hereinafter also referred to as "specific poly-proline"). Further, according to the third aspect of the present invention, there is provided a liquid crystal alignment agent comprising the above aromatic amine compound and/or polyglycolic acid polymer, and a repeat represented by the following formula (1-1) At least one polymer consisting of a polylysine composed of a unit and a repeating unit represented by (1-2).

(wherein P1 is a tetravalent organic group and Q1 is a divalent organic group), 200819872

(I-2) (wherein P2 is a tetravalent organic group and hydrazine is a divalent organic group). Further, the tetracarboxylic acid dianhydride used in the synthesis of the polyamidene composed of the repeating unit represented by the above formula (1-1) and the polyimine composed of the repeating unit represented by (1-2) It is preferred to include 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. According to the present invention, a liquid crystal alignment agent containing a specific aromatic amine compound capable of forming a liquid crystal alignment film which is less likely to cause abrasion damage can be provided. [Embodiment] Hereinafter, the present invention will be specifically described. The liquid crystal alignment agent of the present invention is constituted by dissolving a specific compound and/or a specific polyamic acid with at least one polymer selected from other polyamic acids and polyimine in an organic solvent. Further, the liquid crystal alignment agent of the present invention is dissolved in an organic solvent by reacting a compound represented by the formula (1) and/or a specific polyamic acid with at least one polymer selected from polyamic acid and polyimine. And constitute. [Specific compound and specific polyamine] In the above formula (1), A represents a trivalent aromatic group. Specifically, in particular, a benzenetriyl group, a biphenyltriyl group, a naphthalenetriyl group or the like can be given in 200819872. Among them, a benzenetriyl group and a biphenyltriyl group are preferred, and a benzenetriyl group is preferred. R1 to L represent an aromatic group, and R! to R6 may be different from each other or may be the same, and the structure thereof is not particularly limited, and is preferably a phenyl group. Further, in the above formula (2), R7 to R12 are each independently hydrogen or a monovalent organic group. Specifically, it may be a hydrogen atom, an amine group, a hospital group, a hospital oxygen group or a group represented by the following formula (3). (3)

N As the alkyl group and the alkoxy group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms is preferable. More specifically, examples of the alkyl group contained in these alkyl groups and alkoxy groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-methyl-propyl group, and 3 groups. -Methyl-propyl, n-pentyl, n-hexyl. Preferred examples of R7 to Rl2' include hydrogen, an amine group, a methyl group, an ethyl group, a methoxy group, an ethoxy group or a group represented by the formula (3). The following compounds are mentioned as a specific compound. 200819872

It is also possible to use a specific polylysine similarly to a specific compound. The specific polyamine is obtained by reacting a specific compound in which two of R? to Rn in the above formula (2) is an amine group with a tetracarboxylic acid dianhydride. In the case of synthesizing a specific polyamic acid polymer, the acid anhydride is not particularly limited, and preferably, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3 is exemplified. - dimethyl-hydrazine, 2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-six Hydrogen-5-(tetrahydro-2,5-dioxo-3-furylnaphthalene [l,2-c]-furan-1,3-dione, cis-3,7-dibutylcyclooctyl q,% two suspices-10-200819872 -1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2:3,5:6-dianhydride ,1,3,3&,4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c ]-furan-1,3-dione, 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-tris-2 - Residue norbornene - 2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1 ·02'6]undecane-3,5,8,10-tetraketone And pyromellitic dianhydride and the like. These acid anhydrides may be used singly or in combination of two or more kinds. Further, in addition to the 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) 3⁄4, 2, 2-di[4-(4-aminophenoxy)phenyl]hexa-propyl, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4' _ (p-extension) Phenyldiisopropyl)diphenylamine, 4,4'-(m-phenylene diisopropyl)diphenylamine, 1,4-cyclohexanediamine, 4,4 '-methyl Di(cyclohexylamine), 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-diamino Carbazole, N-ethyl-3,6-diaminocarbazole, fluorenylphenyl-3,6-diaminocarbazole, &^^'-bis(4-aminophenyl)-benzidine N, N '- bis (4-aminophenyl) -N, N' - dimethyl - benzidine. These other diamine compounds may be used singly or in combination of two or more kinds. -11- 200819872 The compounding ratio of these specific compounds is preferably 〇 with respect to 1 〇〇 by weight of at least the polymer selected from the specific polyamic acid 'other poly phthalic acid and polyimine. -1 parts by weight 'more preferably 〇·ι~30 parts by weight ° [other poly-proline] <tetracarboxylic dianhydride> Others constituted by the repeating unit represented by the above formula (1-1) The tetracarboxylic acid dianhydride used in the synthesis of polylysine may, for example, be butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl 1,2-,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dichloro -1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2 , 3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexane tetracarboxylic acid dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2:3,5:6-dianhydride, 2,3,4,5 - Tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3&am p;,4,5,91)-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2<]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan- 1,3-diketone, 1,3,38,4,5,913-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2 -c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3 -furyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-7-ethyl-5-(tetrahydrogen -2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-8-A 5-(4-hydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3·dione, 1,3,3&,4,5 , 91^hexahydro-8-ethyl-5-(tetra-12- 200819872 hydrogen-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3- Diketone, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l, 2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranmethyl)_3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, Double loop [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-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, An aliphatic or alicyclic tetracarboxylic dianhydride of 5,8,10-tetraketone, a compound represented by the following formulas (I) and (II),

(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 a plurality of R2 and R4 present may be the same or different). Pyromellitic acid dianhydride, 3,3 ',4,4 '-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylstilbene tetracarboxylic acid dianhydride, 1,4, 5, 8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3 ',4,4 '-diphenyl ether tetracarboxylic acid dianhydride, 3,3 ' , 4,4 '-dimethyldiphenylnonanetetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic acid Acid-13- 200819872 dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) Diphenyl sebacic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoro-exo-propyldiphenyl Formic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, di(phthalic acid) phenylphosphine oxide Diacid anhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4 , 4'-diphenyl ether II Anhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-di(hydrogen trimellitate), propylene glycol-di(hydrogen trimellitate), 1,4-butanediol-di(hydrogen trimellitate), 1,6-hexanediol-di(anhydrotrimellitic acid ester), 1,8-octanediol-di(dehydrated trimellitate) An aromatic tetracarboxylic acid dianhydride such as a compound represented by the following formulas (4) to (7), 2,2-bis(4-hydroxyphenyl)propane-di(hydrogen trimellitate) . These acid diacid anhydrides can be used singly or in combination of two or more kinds. -14- 200819872

^CH3 ~CH3

Ο

CH3 (6) o

o

/CH3 ^CH3 (7) The tetracarboxylic dianhydride is preferably a butane tetracarboxylic dianhydride or a 1,2,3,4· alkane from the viewpoint of exhibiting good liquid repellency. Carboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid crystals, cyclosuccinic acid -15 - 200819872 Anhydride, 1,2,3,4-tetramethyl -1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1 〇丄, 2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid Dry bismuth, 5-(2,5-dioxotetrahydrofuranmethyl)-3-methyl-3-cyclohexene® dianhydride, cis-3,7-dibutylcyclooctane-1 , 5-diene-1,2,5,6-tetradecanoic acid dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane·2:3,5:6-dioxalate, l ,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [furfuran-1,3-dione, 1,3, 3&,4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxy-3-furanyl)-naphthalene[l,2-c]furan-1 ,3-dione, 1,3,3&,4,5,913-hexachloro-4-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene n,2_c]furan-1,3-dione, 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-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxyl-norborn Alkane-2: 3,5:6-dianhydride, 4,9-dioxatricyclo[5·3·1·026]undecane-3,5,8,10-tetraketone, the above formula (I (a) represented by the following formula (1 1) in the alicyclic tetracarboxylic dianhydride of the compound represented by the following formula (8) to (10) and the compound represented by the above formula (11); The alicyclic tetrahydro acid dianhydride of a compound or the like is particularly preferable, and 1,2,3,4-cyclobutylene tetracarboxylic acid dianhydride, 1,3 -dimethyl-1,2,3 , 4-cyclobutane tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2, 5-dioxo-3-furanyl)-cai[l,2-c]pyran-1,3 -—·嗣, cis-3,7·一* butyl ring half_1,5_一^ Fine-1,2,5,6-tetradecanoic acid dianhydride, 3,5,6-dioleyl-2-indenyl norbornene-2:3,5:6-dianhydride, ^, ", bucket ^"Bihexahydro-^methyl: "tetrahydro-2,5-: oxo-3_furanyl"-naphthalene [l,2-c]isan-1,3-dione, 3-oxa Bicyclo[3.2.1] -16 - 200819872 Octane-2,4-dione-6-spiro-3,-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxo) Tetrahydro-3-furanyl-methyl Icyclohexyl-I,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5:6-dianhydride, 4,9-Dioxatricyclo[5.3.1·〇2,6]undecane-3,5,8,10-tetraketone and a compound represented by the following formula (8).

Preferred tetracarboxylic acid dianhydrides other than the alicyclic tetracarboxylic acid dianhydride include, for example, pyromellitic dianhydride and 3,3',4,4'-benzophenone. Tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyltricarboxylic acid dianhydride, 2,2 ',3,3,-biphenyltetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic acid dianhydride or 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 compound> The diamine compound used in the synthesis of polyproline acid-17-200819872 which is composed of the repeating unit represented by the above formula (1-1), for example, p-phenylenediamine, M-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4 '-Diaminodiphenylphosphonium, 2,2'-dimethyl-4,4,-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-ditrifluoromethyl-4,4' - Diaminobiphenyl, 3,3'-ditrifluoromethyl-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-aminophenoxyl) Phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoro Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3-di(4-amino) Phenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl M0-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, 1,4,4,-(p-phenylene isopropylidene)diphenylamine, 4,4'-(m- Phenyl isopropylidene)diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamine Benzyl-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 3,6 -diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminoguanidine Aromatic diamine such as oxazole; -18- 200819872 1, meta-xylylenediamine, 1,3-propanediamine, butanediamine, Diamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-diaminoheptanediamine, 1,4-diaminocyclohexyl, isophoronediamine, tetrahydrogen Dicyclopentadienyldiamine, hexahydromethylene quinone dimethylenediamine, tricyclo[6.2.1.02'7], undecene dimethyldiamine, 4,4 '-methyl bis ( Aliphatic and alicyclic di-2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, etc. ,6-diamino-2,3-dicyanobutyrazine, 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-di Amino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4· Triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamine • 6-phenylphenanthridine, 1,4-diaminopyridazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole , Ν-methyl- 3,6-diaminocarbazole, oxime-ethyl-3,6-diaminocarbazole, oxime-phenyl-3,6-diaminocarbazole, oxime, Ν' - bis(4-aminophenyl)-benzidine, anthracene, Ν'-bis(4-aminophenyl)_ν, Ν'-dimethyl-benzidine, etc. having two primary amine groups in the molecule And a diamine of a nitrogen atom other than the first-order amine group; a diamine-based organic oxime represented by the following formula (111). These diamine compounds may be used alone or in combination of two or more.

-19 - 200819872 (wherein R5 represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of existing r5 may be the same or different, P is an integer of 1 to 3, and q is an integer of 1 to 2 Å). Among them, p-phenylenediamine, 4,4 '-diaminobenzophenone, 4,4,-diaminodiphenyl sulfide, 2,2'-dimethyl-4,4' are preferred. -diaminobiphenyl, iota, 5-diaminonaphthalene, 2,7-diaminoguanidine, 9,9-dimethyl-2,7-diaminopurine, 4,4,-diamino Diphenyl 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-phenylene diisopropylidene) Diphenylamine, 4,4'-(m-phenylenediisopropylidene)diphenylamine, 1,4-cyclohexanediamine, 4,4'-methylbis(cyclohexylamine), 1, 4_bis(4-aminophenoxy)benzene, 4,4′-bis(4-aminophenoxy)biphenyl, 2,6-diamine fluorene ratio η, 3,4-diamine Pyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, oxime-methyl-3,6-diaminocarbazole, oxime -3,6-diaminocarbazole, fluorene-phenyl-3,6-diaminocarbazole, hydrazine, Ν'-bis(4-aminophenyl)-benzidine, anthracene, Ν' - Bis(4-aminophenyl)-indole, hydrazine , -Dimethyl-benzidine, and the like. V / _ Further The polyimine composed of the repeating unit represented by the above formula (1-2) can be produced by dehydrating and ring-closing the above polyamic acid. When the liquid crystal alignment agent of the present invention has a pretilt performance, it is preferred to use a part or all of Q1 and Q2 in the above formulas (1-1) and (1-2) as the following formula (Q-1). And a diamine compound (hereinafter also referred to as "specific diamine") of at least one group represented by the following formula (Q-2). That is, a diamine compound having a group represented by the following formula (Q-1) or the following formula (Q-2) is used. They may be used singly or in combination of two or more kinds. -20- 200819872 X—R6 Αϋ (Qi) (wherein X is a single bond, -〇-, -C〇-, -COO-, -〇C〇-C〇NH-, -S- or aryl group , r6 is a monovalent organic group having an alicyclic skeleton of 4 to 40 carbon atoms or a monovalent organic group having a fluorine atom of -20 at a carbon number of 10 〇 to 20 ° ° - £^-x-R7- xX^- (Q-2) (wherein X is a single bond, -〇-, -c〇-, _co〇-, -〇c〇-C〇NH_, -S- or an extended aryl group, and R7 is carbon The number of 4 to 40 framed divalent organic groups). In the above formula (Q-1), the carbon number represented by R6 is 1〇~, for example, n-decyl group, n-dodecyl group, n-pentadecyl group, or Temple. Further, the organic group having a carbon number of 4' alicyclic skeleton represented by R6 in . and R7 in the above formula (Q-2) may, for example, be a source of cyclopentane, cyclohexane or cyclodecane. The alicyclic skeleton of the isocycloalkane has a group of a steroid skeleton such as cholesterol or cholestyl alcohol; a group having a bridged ring skeleton such as adamantane or the like. Among them, the special group is a group. The organic group having the above alicyclic skeleton is preferably a fluorine atom or a fluoroalkyl group, preferably a substituted group. Further, the group having a carbon number represented by R6 in the above formula (Q-1), which is a fluorine atom, may, for example, be a n-hexyl group, an n-octyl group or a linear alkyl group having a carbon number of 6 or more; a cyclohexyl group or a cyclooctyl group; a group having a carbon number of 6 -, -NHC0-, an alkyl group having an alicyclic bone 20, and a hexadecane having the above formula (Q-1) to 4 0 a group having a cyclobutane; having a norbornene; having a steroidal body having a trifluoromethyl group of 6 to 20 or the like having a n-decyl group or the like having a carbon number of from 21 to 200819872 6 or more An alicyclic hydrocarbon group; an organic group such as a phenyl group or a biphenyl group having an aromatic hydrocarbon group having 6 or more carbon atoms; or a part or all of a hydrogen atom in the organic group substituted by a fluorine atom or a fluoroalkyl group such as a trifluoromethyl group; Group. Further, X in the above formula (Q-1) and the above formula (Q-2) is a single bond, -〇-, -C〇-, -C〇〇-, -〇C〇-, -NHC〇-, -C〇NH-, -S- or {Shenyl, as the aryl group, for example, a phenyl group, a tolyl group, a phenyl group, a naphthyl group or the like can be mentioned. Among them, a group which is particularly preferred is - 〇-, -C〇〇-, -〇c〇·. Specific examples of the diamine having a group represented by the above formula (Q-1) include dodecyloxy-2,4-diaminobenzene and pentadecyloxy-2. 4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, a compound represented by the following formulas (12) to (16) .

(14) (10)

(16) Further, as a specific example of the diamine compound-22-200819872 having a group represented by the above formula (Q-2), preferred are diamines represented by the following formulas (17) to (19). Compound.

Among them, particularly preferred are compounds represented by the above formulas )2), (14), (16), and (17). The ratio of use of the specific diamine to the total amount of the diamine varies depending on the magnitude of the pretilt angle to be expressed, but in the case of the TN type or STN type liquid crystal display element, it is preferably 0 to 5 moles. %, in the case of the vertical alignment type liquid crystal display element, it is preferably 5 to 100% by mole. <Synthesis of Polylysine> The use ratio of the tetracarboxylic dianhydride to the diamine compound to which the polyproline acid synthesis reaction is supplied is preferably an amine group based on 1 equivalent of the diamine compound, and the tetracarboxylic acid is used. The acid anhydride group of the acid anhydride is a ratio of 2 to 2 equivalents, more preferably a ratio of 0.3 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent at -2 (TC ～150 ° C, more preferably 0 to 10 0 (TC). Here, as an organic solvent, As long as it can dissolve the synthesized polyaminic acid, it is not particularly limited as long as it is -23-200819872, and examples thereof include h-methyl pirone, N,N-dimethylacetamide, N,N-dimethyl Methotrexate, % Butoxy_n & Dimethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, 3 hexyloxy?N,N_=methylpropionamidine Amidoxime solvent such as amine; aprotic polar solvent such as dimethyl sulfoxide, _butyrolactone, tetramethyl urea, hexamethylphosphonium triamine; m-methylphenol, xylenol, phenol, halogen Further, a phenol solvent such as phenol is used. Further, the amount (α) of the organic solvent is preferably such that the total amount (β) of the tetracarboxylic acid dianhydride and the diterpene & _ is relative to the total amount of the reaction solution (α+). β) is an amount of 〇3 to 3% by weight. Further, in the range in which the produced polyamine acid is not precipitated, a poor solvent of polylysine may be used in the above organic solvent (poor s〇lvent) Alcohols, ketones Examples thereof include esters, ethers, 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, 1,4-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 ethyl ether acetate, diglyme, Diethylene glycol diethylene, 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 - dichlorobutyl, trichloroethylene, chlorobenzene, o-dichlorobenzene, hexa, -24- 200819872 heptane, octane, benzene, toluene, xylene, diisobutyl Ketone, C Isoamyl ester, isoamyl isobutyrate, diisoamyl ether, etc. As described above, a reaction solution formed by dissolving polylysine is obtained. Then, the reaction solution is introduced into a large amount of poor solvent to obtain The precipitate can be obtained by drying the precipitate under reduced pressure or by distilling off the reaction solution with an evaporator under reduced pressure. Further, the polylysine is redissolved in an organic solvent, and then once or The polylysine can be purified by a process of precipitating with a poor solvent or a process of distilling off under reduced pressure with an evaporator. <Dehydration ring closure reaction> The polyimine constituting the liquid crystal alignment agent of the present invention can be passed A part or all of the above polyamic acid is dehydrated and closed to be synthesized. The dehydration ring closure of polylysine may be (i) by heating the poly-proline, or (ii) by dissolving the poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, as needed It is carried out by heating. i The reaction temperature in the method for heating poly-proline in the above (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C, the dehydration ring closure reaction cannot be completed. If the reaction temperature exceeds 200 ° C, the molecular weight of the obtained quinone imidized polymer may decrease. On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyamic acid solution of the above (ii), as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent is determined according to the desired imidization ratio, but it is preferably a repeating unit of 1·〇丨~2 〇mol relative to 1 mole of polyglycine-25-200819872. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 〇. 〇丨 丨〇 丨〇 相对 relative to the dehydrating agent used in 1 mol. The higher the amount of the above dehydrating agent and the dehydration ring-closing catalyst, the higher the yield of ruthenium. Further, as the organic solvent used in the dehydration ring-closure reaction, an organic solvent exemplified as a solvent used in the synthesis of polylysine may be mentioned. Further, the reaction temperature of the dehydration ring closure reaction is preferably 〇18 〇. (:, more preferably, it is from 10 to 150 ° C. Further, the obtained polyimine is purified by performing the same operation as in the polyamic acid purification method on the reaction solution thus obtained. The ratio of the repeating unit having a quinone ring in all repeating units (hereinafter also referred to as "deuterated imidization ratio") is 40 mol% or more, preferably 50 mol% or more. When a polymer having a ruthenium iodide ratio of 40 mol% or more is used, a liquid crystal alignment agent capable of forming a liquid crystal alignment film having a short image erasing time can be obtained. The brewing imidization ratio can be obtained by the following method. Method for determining the imidization ratio of imidized polymer] The ruthenium iodide polymer is dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl hydrazine, using tetramethyl decane as a reference substance. The W-NMR measurement was carried out at room temperature, and was obtained by the formula represented by the following formula (ii): oxime imidization ratio (%) = (1 - AVA2xa) xlOO------ (ii) A1: derived from The peak area of the NH-based proton (1 Oppm) A2: the peak area derived from other protons -26- 200819872 α : Polymer In the precursor (polyproline), the ratio of the number of other protons to one NH matrix is <end-modified polymer> The poly-proline and polyimine used in the present invention may also be The terminal-modified polymer having a molecular weight adjusted by using the terminal-modified polymer can improve the coating characteristics and the like of the liquid crystal alignment agent without impairing the effects of the present invention. In the synthesis of poly-proline, a monobasic acid anhydride, a monoamine compound, a monoisocyanate compound, or the like is added to the reaction system to synthesize it. Examples of the monobasic acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, and Mercapto succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, etc. Further, examples of the monoamine compound include aniline, cyclohexylamine, and n-butylamine. N-Pentylamine, n-Hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, positive fifteen Amine, Examples of the monoisocyanate compound include phenyl isocyanate, naphthyl isocyanate, and the like. Examples of the monoisocyanate compound include a hexadecanolamine, an n-octadecylamine, an n-octadecylamine, and a n-octadecylamine. Viscosity] The polymer used in the alignment agent of the present invention preferably has a viscosity of 20 to 800 mPa's, more preferably 30 to 500 mPa·s, in a solution of 1% by weight. The viscosity of the solution (mPa, s) was measured at 25 ° C using an E-type rotational viscometer -27-200819872 in a solution diluted to a predetermined solid concentration using a predetermined solvent. [Liquid alignment agent] The liquid crystal alignment agent of the present invention is preferably constituted by dispersing a specific pseudonylic acid with another polylysine and/or a polystyrene solvent. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 〇 ° C - more preferably 20 ° C to 60 ° C. The organic solvent constituting the liquid crystal alignment agent of the present invention may be a solvent exemplified as the solvent used in the synthesis reaction of the polyproline, and may be appropriately selected and used as a poor solvent which can be exemplified in the synthesis reaction of polyglycine. The solid content concentration in the liquid crystal alignment agent of the present invention is selected in consideration of viscosity and the like, and is preferably in the range of 1 to 10% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film as a liquid. When the solid content concentration is less than 1% by weight, the thickness is too small, so that it is difficult to obtain a good liquid crystal alignment film; when the concentration exceeds 10% by weight When % is used, the thickness of the coating film is too thick, and it is difficult to obtain a good liquid crystal alignment film, and the liquid crystal alignment agent is large, and the coating property is liable to be deteriorated. Further, the range of the particularly preferable solid content varies depending on the method used for the substrate alignment agent. For example, when it is spin-coated, it is preferably in the range of 1.5 to 4.5% by weight. When the printing method is used, the concentration of the body component is in the range of 3 to 9 % by weight, so that the t substance and/or the solution can be made to be -200 ° C, which is exemplified. In addition, when the volatility is said to be the same as the solid content of the coating film, the viscosity is increased by the liquid crystal method, and the specific solution viscosity is -28-200819872. The range of 50mPa.s. When the ink jet method is used, the specific component concentration is in the range of 1 to 5 wt%, so that the solution can be in the range of 3 to 15 mPa 's. As an organic solvent used in the liquid crystal alignment agent of the present invention, 1-methyl-2-indole is awakened, butyrolactone, T-butane dimethylformamide, hydrazine, hydrazine-dimethyl Acetamide, 4-hydroxy-4-indolone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methoxy ester, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ether N-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl hydride i diol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethanol diethyl ether, diethylene glycol monomethyl ether, two Glycol monoethyl ether, diethylene acetate, diethylene glycol monoethyl ether acetate, 3-butoxy-N,N-diamine, 3-methoxy·anthracene, hydrazine-dimethylpropanamide, 3-hexyloxy-N, propylamine, diisobutyl ketone (DIB oxime), isoamyl propionate, diisoamyl isobutyrate, etc. Among them, 3-butoxy-N,N-di Methyl acrylamide-N,N-dimethylpropanamide, 3-hexyloxy-oxime, fluorene-dimethylpropyl exhibits good printability and is particularly excellent. The liquid crystal alignment agent of the present invention does not damage The target physical property is improved from the viewpoint of the adhesion of the surface of the substrate, and may also contain decane. Examples of the compound containing a functional decane other than the specific compound, and examples of the compound containing a functional decane include 3-aminopropyl decane, 3-aminopropyltriethoxy decane, and 2-aminopropyl decane. 2-Aminopropyltriethoxydecane, Ν-(2-aminoethyl) is a solid viscosity falling agent, which can be amine, hydrazine, fluorenyl-mercapto-2-pentylpropionic acid, A Alcohol carrier), diethyl ether, diethylene glycol monomethyl ether methyl propyl hydrazine-dimethyl: isoamyl ester, 3-methoxy decylamine, due to the inclusion of functional groups. As this trimethoxytrimethoxy-3-aminopropyl-29-200819872 bistrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3 -ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxyanthracene-1 ,4,7-triazaindole, 10-triethoxy sand yard-1,4,7-triazaindole, 9-trimethoxy sand yard-3,6-diazepine Acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopurine/yltrimethoxydecane, N-benzyl-3 -Aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-di(oxyethylene) 3-aminopropyltrimethoxydecane, N-bis(oxyvinyl)-3-aminopropyltriethoxydecane, and the like. Examples of such an epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl Glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetrahydration Glyceryl-2,4-hexanediol, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-m-xylylenediamine, 1,3-bis(indole, hydrazine-diglycidylamino) Base) cyclohexane, hydrazine, hydrazine, Ν', Ν'-tetraglycidyl-4,4' diaminodiphenylmethane, 3-(Ν-allyl-Ν-glycidyl)amine Propyltrimethoxydecane, 3-(anthracene, fluorene-diglycidyl)aminopropyltrimethoxydecane, hydrazine, hydrazine-diglycidyl-benzylamine, hydrazine, hydrazine-diglycidyl-amine Methylcyclohexane and the like. The compounding ratio of the functional decane-containing compound or the epoxy group-containing compound is preferably 40 parts by weight or less, more preferably 30 parts by weight or less based on 100 parts by weight of the polymer. <Liquid crystal display element> The liquid crystal display element obtained by using the liquid crystal alignment agent of the present invention can be produced, for example, by the following method. (1) Applying the liquid crystal alignment agent of the present invention to one side of a substrate provided with a patterned transparent conductive film by a lithography method, a spin coating method or an inkjet printing method, followed by heating the coated surface A coating film is formed. Here, as the substrate, glass such as float glass or soda lime glass can be used; from polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, alicyclic A transparent substrate made of plastic such as polyolefin. As the transparent conductive film provided on one side of the substrate, a NESA film composed of tin oxide (Sn〇2) (registered trademark of PPG, USA) and indium oxide-tin oxide (1112〇3-311〇2) can be used. A ruthenium film or the like is formed, and the transparent conductive film pattern is formed by a photolithography method or a method in which a mask is used in advance. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a functional decane-containing compound, a functional titanium-containing compound, or the like may be applied to the surface of the substrate in advance. . After the application of the liquid crystal alignment agent, it is preferable to perform preliminary heating (pre-bake) for the purpose of preventing the applied alignment agent liquid from sagging or the like. The prebaking temperature is preferably from 30 to 300 ° C, more preferably from 40 to 200 ° C, and particularly preferably from 50 to 150 ° C. Then, the solvent is completely removed, and the calcination (post-baking (p Q s t - b a k e )) process is carried out for the purpose of hot amidation of polyglycine. The calcination (post-baking) temperature is preferably from 80 to 300 ° C, more preferably from 120 to 250 ° C, from -31 to 200819872. Thus, the liquid crystal alignment agent of the present invention contains a coating film for removing the organic solvent as an alignment film by coating, and further degassed to form a further yttrium-imided liquid crystal alignment film by further heating. The thickness of the liquid crystal to be formed is preferably 0.001 to 1 / m, more preferably 0.005 to 0.5 / / m (2) a roll of a cloth composed of fibers such as nylon or human cotton, which is formed on the surface of the formed coating film. Perform a treatment in a certain direction. Thereby, a liquid crystal molecule alignment alignment film is formed on the coating film. In addition, the film which is formed by the liquid crystal alignment agent of the present invention is irradiated with ultraviolet rays and the pretilt angle is changed as shown in JP-A-6-222366 or JP-A-6-A. In the publication, the protective film is partially formed on the surface of the liquid crystal alignment film to be applied, and the protective film is removed in a direction different from the first reason, so that the liquid crystal alignment of the film can be changed, thereby improving the liquid crystal. Visual field characteristics. (3) Two substrate substrates on which the liquid crystal alignment film formed as described above are formed are arranged to face each other through a gap (cell gap), and the polishing directions of the respective liquids are perpendicular or antiparallel to each other, and the two substrates are sealed with a sealing agent. The liquid crystal is injected into the crystal drawn from the surface of the substrate and the sealant, and the injection hole is closed to constitute a liquid crystal cell. Then, the outer surface of the cell, that is, the other side light plate of each substrate constituting the liquid crystal cell, has a polarizing direction and a polylysine formed on one side of the substrate, forming a closed loop of water, a synthetic fiber of the alignment film, and rubbing The liquid crystal liquid crystal of the grinding energy can be processed by the No. 281937, or the liquid crystal display element i plate is polished before the grinding treatment, and the two crystal alignment film parts are used in the cell gap, and the liquid crystal is aligned on the liquid crystal. -32-200819872 The rubbing direction is uniform or vertical, thereby producing a liquid crystal display element. As the sealant, for example, an alumina ball-containing epoxy resin as 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 azo-based liquid crystal, a biphenyl liquid crystal, or a phenyl ring can be used. Hexane liquid crystal, ester liquid crystal, diphenyl liquid crystal, biphenyl ring-based liquid crystal, chewing D-type liquid crystal, #一* and gossip liquid crystal, double-ring half-yard liquid crystal, AA square liquid crystal Wait. Further, cholesteric liquid crystals such as cholesteryl cholesteryl, cholesteryl phthalate, and cholesteryl carbonate may be added to these liquid crystals, and trade names "丨5" and "CB-15" (manufactured by Merck) It is used by selling chiral agents and the like. Further, it is possible to use a ferroelectric liquid crystal such as a fluorenyloxy-ykaryl-encapsulated-amino-2-methyl-butyl cinnamate. In addition, as a polarizing plate to be bonded to the outer surface of the liquid crystal, a polarizing film called a ruthenium film obtained by stretching and absorbing iodine with a polyvinyl alcohol, and a polarizing film sandwiched between a cellulose acetate protective film may be mentioned. Or 11 a polarizing plate made of the film itself. EXAMPLES Hereinafter, the present invention will be more specifically described by examples, but the present invention is not limited to the examples. [Abrasion Resistance of Liquid Crystal Alignment Film] A liquid crystal alignment film is formed on a quartz substrate. 'Rubb in gmach in e' using a roll equipped with a cloth made of rayon rayon is used in the length of the fluff - 33-200819872 0.8 mm, a light rotation speed of 400 rpm, a table moving speed of 3 cm / sec, and a grinding process of 2 times were performed, and the formed liquid crystal alignment film was washed with isopropyl alcohol, and visually confirmed whether or not the alignment film was used from the substrate. The upper part is detached or the abrasion damage is caused. 'No detachment and/or abrasion damage occurs as "〇", and what occurs is marked as "X". [Liquid alignment] The presence or absence of an abnormal region when the liquid crystal display element was turned on and off (applied-released) was observed by a polarizing microscope, and it was judged as "good" when there was no abnormal region. [Voltage retention ratio of liquid crystal display element] A voltage of 5 V was applied to the liquid crystal display element at 60 ° C at a time interval of 16.7 msec, and the voltage application time was 60 μsec, and the voltage holding ratio after the voltage was released to 16.7 msec was measured. . The measuring device used VHR-1 manufactured by Dongyang Technology Co., Ltd. [Measurement of ionization potential 値]

Ii The powdered compound was used as it was, and the ionization potential enthalpy was measured by an ultraviolet photoelectron analyzer AC-2 (manufactured by Detector). <Synthesis of Specific Compound> Synthesis Example 1 -34- 200819872

N〇2 catalyst

2.2 g (7 mm 〇l) of 1,3,5-tribromobenzene, 4.9 g (23 mmol) of 4-nitrodiphenylamine, 91.6 mg (0.1 mmol) of tris(dibenzylideneacetone) dipalladium, 2 - (di-tertiary butylphosphine)biphenyl 1 19 mg (0.4 mmol), grade 3 sodium butoxide 2.98 g (31 mmol) was placed in a three-necked flask equipped with a dimroth-type condenser. After evacuating with a vacuum pump, the system was purged with nitrogen. 20 ml of dehydrated toluene was added by a syringe. The mixture was heated and stirred at 80 ° C for 15 hours to complete the reaction. The reaction solution was cooled to room temperature, washed twice with a 1N-HC1 aqueous solution, and then washed once with saturated brine. The solvent was distilled off, and purified by a cerium oxide gel column to obtain 4 g of Compound 1. -35- 200819872 Synthesis Example 2

catalyst

2.6 g (3.68 mmol) of compound 1, 4.81 g (73.6 mmol) of zinc, hydrazine, 787 g (14.7 mmol) of ammonium chloride, 20 ml of ethanol, 2.5 ml of water in a three-necked flask equipped with a Dimrod condenser Mix. The reaction solution was stirred and heated at 100 ° C for 5 hours. The zinc in the reaction solution was filtered off, and the filtrate was dropped into 250 ml of water. The precipitated powder was filtered and dried to give 2.1 g of the objective compound 2 (specific compound A-1). Synthesis Example 3

Lg (1.66 mmol) of the compound 2, 1.85 g (20 mmol) of epichlorohydrin was mixed with heating in a mixed solution of 10 ml of THF and 1.5 ml of water at 80 ° C for 4 hours. After the reaction temperature was lowered to 60 ° C, lg 50% NaOH water-soluble -36-200819872 solution was added dropwise. After heating and stirring for 4 hours, unreacted epichlorohydrin was distilled off under reduced pressure. The residue was subjected to liquid separation washing with toluene/water, and the solvent was evaporated to give 1.0 g of the objective compound 3 (specific compound A-2). Polyimine synthesis example 1 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride 112 g (0.50 mol) and 1,3,3 &, 4,5,913-hexahydro- 8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)naphthalene [1,2-(:]furan-1,3-dione 1572 (0.50 mol), as two Amine compound p-phenylenediamine 9 4 g (0 · 8 6 5 mol), 3,3'-(tetramethyldioxane-1,3-diyl) di(propylamine) 25 g (0.10 Mo Ear) and 3,6-bis(4-aminobenzylideneoxy)cholesterane (formula 17) 13 g (0.02 mol), n-octadecylamine as a monoamine 8.1 g (0.03 mol) It is dissolved in 960 g of N-methyl-2-pyrrolidone and allowed to react at 60 ° C for 6 hours. The obtained polyamidamine solution is divided into small amounts, NMP is added, and the viscosity is measured by a solution having a solid concentration of 10%. It was 60 mPa, s. 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 1 1 ° C for 4 hours. After the amination reaction, the solvent in the system is solvent-substituted with a new r-butyrolactone (by this operation, the quinone imine) The pyridine and acetic anhydride used in the reaction were removed to the outside of the system, and the solution viscosity of the solid component concentration of I5 wt% and the solid component concentration of 6.0% (r-butyrolactone solution) was 16 mPai, and the sulfhydrylation rate was about 95% of a ruthenium iodide polymer (as a "polyimine (a-1)") solution. Polyimine synthesis example 2 2,3,5-tricarboxyl as a tetracarboxylic dianhydride Cyclopentyl acetic acid diacid-37- 200819872 Anhydride 2 2 4 g (1·0 mol), p-phenylenediamine 丨〇8 g (丄.〇旲) and 3,5-di as a diamine compound The cholesteryl aminobenzoate (formula 12) 782 (〇.〇15 mole) is dissolved in 3000 g of hydrazine-methyl-2-pyrrolidone and allowed to react at 60 ° C for 6 hours to obtain a solution. A polyaminic acid solution having a viscosity of about 4 〇〇 inpa.s, followed by 'addition of 34 〇〇g of N-methyl-2-pyrrolidone to the obtained poly-proline solution to add 3 96 g of pyridine and 3 〇6g acetic anhydride, dehydrated in n (rc) for 4 hours. After the hydrazine imidization reaction, the solvent in the system is replaced with a new r-butyrolactone (by this operation, the ruthenium iodide reaction in use The pyridine and acetic anhydride were removed to the outside of the system to obtain about 6800 g of a ruthenium iodide polymer having a solid concentration of 4 wt%, a solution viscosity of 40 mPa·s, and a ruthenium iodide ratio of about 89% (as a "polyimine" ( A_2)") solution. Polyamide synthesis example 1 196 g (l. mol) of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride as tetracarboxylic acid dianhydride as diamine compound 212 g (1.0 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl is dissolved in 370 g of N-methyl-2·pyrrolidone and 3 3 00 g of 7-butyrolactone. This was allowed to react at 40 ° C for 3 hours to obtain a solution of polylysine having a solution viscosity of 160 mPa·s (as a "polyglycine (b-1)") 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 (0.50 Mo (2), 2,7-diamino 芴i96g (l. oxime) as a diamine compound is dissolved in 230 g of N-methyl-2-pyrrolidone, 2 0 60 g of 7-butyrolactone, After reacting at 40 ° C for 3 hours, the temperature is -38-200819872. After 3 hours, the r-butyrolactone of 1 3 50g is chased to obtain a polylysine having a solution concentration of 125 mPa·s at a solid concentration of ι〇%. (It is about 3 600 g as a solution of "polyglycine (b-2)"). Examples 1 to 2 The ionization potentials of the respective compounds Α-1 and Α-2 were measured by AC-2. The results are shown in Table 1. Example 3 Polyimine (a-1) prepared in Polyimine Synthesis Example 1 and polylysine (b-oxime) prepared in Polyamine Synthesis Example 1 were polyimine. : Polyglycine = 20:80 (weight ratio) dissolved in a mixed solvent of N-methyl-2-pyrrolidone / butyl cellosolve (weight ratio 95/5), and 10 parts by weight of a specific compound A is added with respect to the polymer 100 -1, a solution having a solid concentration of 3.5% by weight was prepared. 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. A solution having a solid concentration of 3.5% by weight of the above liquid crystal alignment agent was applied to 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: 2500 rpm, coating time: 1 minute), by drying at 200 ° C for 1 hour, a film having a dry film thickness of 0.08 / / m was formed. The coating was ground by a sander equipped with a roller of a fabric made of rayon, at a roller speed of 400 μm: pm, a table moving speed of 3 cm/sec, and a fluffing length of 〇.4 mm. deal with. Next, after washing in ultrapure water for 1 minute with ultrasonic waves, dry in a clean oven at 1 °C for 1 〇 minutes. On the outer edges of the liquid crystal alignment film having the above-mentioned liquid crystal alignment film coating substrate of a pair of transparent electrode/transparent electrode-39-200819872 substrate, epoxy coated with alumina balls having a diameter of 5.5 μm was applied. After the resin adhesive, the liquid crystal alignment film surface is relatively heavily combined and pressed to cure the adhesive. Then, the liquid crystal injection element was filled with a nematic liquid crystal (MLC-6 22 1 manufactured by Merck & Co., Inc.) through a liquid crystal injection port, and the liquid crystal display element was sealed with an acrylic photocurable adhesive to form a liquid crystal display element. The voltage holding ratio evaluation and liquid crystal alignment evaluation of the obtained liquid crystal display element were carried out in accordance with the method described above. The liquid crystal alignment agent of the present invention prepared as described above was applied onto a quartz substrate having a thickness of 1.5 mm by a spin coater to form a coating film in the same manner as in the case of producing a liquid crystal display element, and the evaluation of the abrasion resistance was carried out according to the method described above. get on. The results are shown in Table 2. Examples 4 to 6 were carried out in the same manner as in Example 1 except that the polyamine imine, polylysine, and the specific compound were used as shown in Table 2. The results are shown in Table 2. Example 7 Polyimine (a-2) prepared in Polyimine Synthesis Example 2 was dissolved in a mixed solvent of N-methyl-2-pyrrolidone/butyl cellosolve (weight ratio 95/5), as opposed to 10 parts by weight of the specific compound A-1 was added to 100 parts by weight of the polymer to prepare a solution having a solid concentration of 3.5% 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. Using this alignment agent, a liquid crystal display element was produced in the same manner as in Example 1. -40-200819872 The voltage holding ratio evaluation and liquid crystal alignment evaluation of the obtained liquid crystal display element were carried out in accordance with the method described above. The liquid crystal alignment agent of the present invention prepared as described above was applied onto a quartz substrate having a thickness of 1.5 mm by a spin coater. A coating film was formed in the same manner as in the case of producing a liquid crystal display element, and the abrasion resistance was evaluated in accordance with the method described above. The results are shown in Table 2. Example 8 The same procedure as in Example 7 was carried out except that A-2 was used as the specific compound. The results are shown in Table 2. Comparative Examples 1 to 2 The same procedures as in Example 1 were carried out except that the poly-imine and polyamic acid were added to the specific compound using the substance '$ shown in Table 2, and the results are shown in Table 2. Comparative Example 3 was carried out in the same manner as in Example 7 except that no specific compound was added. The results are shown in Table 2. Comparative Examples 4 to 5 Polyimine and polylysine use the substance shown in Table 2 as a gastric compound, using N, N, N, N,-tetraglycidyl-m-xylylenediamine In the same procedure as in Example 1, except that (Compound X), N, N, N', N, tetraglycidyl-m-xylylenediamine was used as a product purchased from Mitsubishi Gas Chemical Co., Ltd. . The results are shown in Table 2 ° Comparative Example 6 Polyimine, polylysine using the substance shown in Table 2 as a special compound, using N, N, N', N' - tetraglycidyl The same procedure as in Example 7 was carried out except that the m-m-xylylenediamine (Compound X) was used. N, N, N', N'-tetraglycidyl-m-xylylenediamine was purchased from Mitsubishi Gas Chemical Co., Ltd. The results are shown in Table 2. Table 1

Specific compound ionization potential Example 1 A-1 5.1 eV Example 2 A-2 5.3 eV Table 2

Polyimine polyimine specific compound voltage retention rate alignment resistance to abrasion Example 3 a-1 b-1 A-1 > 99% Good 〇 Example 4 a-1 b-1 A-2 > 99% good 〇 Example 5 a-1 b-2 A-1 > 99% Good 〇 Example 6 a-1 b-2 A-2 > 99% Good 〇 Example 7 a-2 - A-1 >99% Good 〇 Example 8 a-2 - A-2 > 99% Good 〇 Comparative Example 1 a-1 b-1 M y \ n\ > 99% Good X Comparative Example 2 a-1 b- 2 彳πτ JiLC j \\\ >99% Good X Comparative Example 3 a-2 - MJ \ w > 99% Good X Comparative Example 4 a-1 b-1 Compound X 98% Partially defective X Comparative Example 5 a -1 b-2 Compound X 98% Partially defective X Comparative Example 6 a-2 - Compound X 98% Partially defective X [Simplified illustration] Μ 〇j\\\ -42-

Claims (1)

200819872 X. Patent application scope: 1. A liquid crystal alignment agent characterized by containing an aromatic amine compound represented by the following formula (1), The hole 5 is composed of 4 (1) (wherein, A represents a trivalent aromatic group, and 1^ to 116 represents an aromatic group, and R! to R6 may be different from each other or may be the same). 2. The liquid crystal alignment agent of claim 1, wherein in the above formula (1), A is a benzene ring. 3. The liquid crystal alignment agent of claim 1, wherein the aromatic amine compound is represented by the following formula (2), (wherein R7 to Rl2 are each independently hydrogen, an amine group or a monovalent organic group). 4. The liquid crystal alignment agent of claim 3, wherein in the formula (2), R7 to r12 are each independently hydrogen or an amine group. 5. The liquid crystal alignment agent of claim 3, wherein in the formula (2), r7 to R12 are each independently hydrogen or an epoxy group-containing tertiary amine g. A liquid crystal alignment agent comprising a polyglycolic acid polymer obtained by reacting a compound having two amine groups, R7 to R1, in the formula (2), from -43 to 200819872, with a tetracarboxylic acid dianhydride. A liquid crystal alignment agent characterized by containing an aromatic amine compound according to any one of claims 1 to 5 and/or a polyamic acid polymer according to item 6 of the patent application, and At least one polymer selected from the polyphthalamide formed by the repeating unit represented by the following formula (ι_ι) and the polyimine formed by the repeating unit represented by the following formula (1-2), HOOC, yCOOH (wherein P1 is a tetravalent organic group, and Q1 is a divalent organic group), Q Ο (wherein Pz is a tetravalent organic group, and Q2 is a '2-valent organic group). 8. The liquid crystal alignment agent of claim 7, wherein the polyamine contained in the repeating unit represented by the above formula (1-1) and the poly unit formed by the repeating unit represented by (1-2) The tetracarboxylic dianhydride used in the synthesis of the imine includes 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. A liquid crystal display element characterized by having a liquid crystal alignment film produced by using a liquid crystal alignment agent according to any one of claims 1 to 8 - 44 - 200819872 VII. Designation of representative drawings: (1) Designation of the case The representative picture is: None. (2) A brief description of the symbol of the representative figure: 〇 j\ w VIII. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: