TW200821372A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent comprising an amino group substituent of 4,4'-diaminophenyl or an amino group substituent of 2,7-diaminofluorene. A liquid crystal alignment film made from the liquid crystal alignment agent has good properties of electricity and printing.

Description

200821372 IX. Description of invention:

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, 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 characteristics and excellent printability, the liquid crystal alignment film, and a liquid crystal display element having the same. [Prior Art] At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN type (Twisted Nematic) 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 imine or the like is used as a substrate for a liquid crystal display element, and two substrates are arranged to face each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a unit cell having a sandwich structure. The long axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate to the other substrate. Further, STN (Supei: 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 device 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 more than 180 degrees 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 MV A method in which protrusions are formed on ITO to control the alignment direction of liquid crystals has been proposed. The liquid crystal display element of the MVA type is excellent not only in viewing angle and contrast, but also in the process of forming a liquid crystal alignment film, and it is not necessary to perform the rubbing treatment in 200821372, and is therefore excellent in the process. As a liquid crystal alignment film suitable for the TN, 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. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 11-258605 (Non-Patent Document 1) "Liquid Crystal" V ο 1 · 3 N 〇. 2 1 1 7 (19 9 9) [Invention] The present invention is in view of the above. The object of the present invention is to provide a liquid crystal alignment film capable of forming a liquid crystal alignment film which maintains a voltage holding ratio while reducing accumulated charges, and which has excellent printability, and provides the liquid crystal alignment film and liquid crystal using the same Display component. Still other objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above objects and advantages of the present invention are achieved by a liquid crystal alignment agent characterized by containing a group consisting of a compound represented by the following formula (A): @% and the following formula (B). One less g of a compound (hereinafter, also referred to as a specific compound), /

200821372

(wherein R13 and Rm are each independently a hydrogen atom, a decyl group, an alkoxy group or a aryl group] R15 and Rl7 are a scented group, and Ri6 and Ri8 are each independently a hydrogen atom. Or a glycidyl group, and X represents a divalent organic group, -〇- or -NH-). Further, the liquid crystal alignment agent of the present invention preferably further contains at least one polymerization selected from the group consisting of polylysine represented by the following formula (I-1) and polyimine represented by (I-2). Things. (1 - 1)

HOOC, /COOH HNOC CONH-Q1 (wherein P1 is a tetravalent organic group, and Q1 is a divalent organic group), 200821372 ο ο

(wherein Ρ2 is a tetravalent organic group, and Q2 is a divalent organic group). According to the liquid crystal alignment agent of the present invention, it is possible to provide a liquid crystal alignment film capable of forming a liquid crystal alignment film while maintaining a voltage holding ratio while reducing accumulated charge, and having excellent printability, a liquid crystal alignment film thereof, and a liquid crystal display having the same element. [Embodiment] Hereinafter, the present invention will be described in more detail. The liquid crystal alignment agent of the present invention is constituted by dissolving a specific compound and at least one polymer (hereinafter, also referred to as a specific polymer) selected from polyphthalic acid and polyimine in an organic solvent. [Specific Compound 1] A compound represented by the formula (Α) is referred to as a specific compound 1. In the formula (Α), R8 is each independently a hydrogen atom, an alkyl group, an alkoxy group or an aromatic group. Specific examples of the alkyl group and the alkoxy group are an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. Examples of the alkyl group in the alkyl group and the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-methyl-propyl group, 3-methyl-propyl group, and a positive group. Amyl, n-hexyl. Further, examples of the aromatic group of Ri to R8 include a phenyl group. R9 and R10 200821372 are aromatic groups, and specific examples thereof include a phenyl group and a naphthyl group. R1G and R12 each independently represent a hydrogen atom, an alkyl group or a glycidyl group. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group. In the formula (A), preferably R2, R4, R5 and R7 are ammonia, and Ri, R3, R6 and R8 are each independently hydrogen, methyl or ethyl, R9 and Rm are each a phenyl group, R 1 0, R 1 2 is a glycidyl group. Specific examples of the specific compound 1 include the following

Further, in the above compounds, Me is a methyl group and Et represents an ethyl group. [Specific Compound 2] The compound represented by the formula (B) is referred to as the specific compound 2. In the formula (B), Rls and r14 are each independently a hydrogen atom, an alkyl group, an alkoxy group or an aromatic group. Specific examples of the alkyl group and the alkoxy group are preferably an alkyl group having 1 to 6 carbon atoms and an alkoxy group having a carbon number of 丨6. Examples of the alkyl group in the alkyl group and the 200821372 alkoxy group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 2-methyl-propyl group, and a 3-methyl-propyl group. N-pentyl, n-hexyl. Further, examples of the aromatic group of R13 and R14 include a phenyl group. R15 and R17 are an aromatic group, and specific examples thereof include a phenyl group and a naphthyl group. R16 and r18 each independently represent a hydrogen atom, an alkyl group or a glycidyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group. X is a divalent organic group, -〇- or -NH-. As a preferable divalent organic group, for example, -CH2- or -CH2CH2. In the formula (B), it is preferred that r13 and r14 are hydrogen, r15 and r17 are all phenyl groups, Rl6 and Ri8 are glycidyl groups, and X is -NH-, -CH2- or -CH2CH2-. Specific compounds of the specific compound 2 include the following compounds.

[Polyuric acid] <tetracarboxylic dianhydride> As the tetracarboxylic acid dianhydride used in the synthesis of the above polylysine, alicyclic tetracarboxylic dianhydride or aliphatic tetracarboxylic acid can be used as -10-200821372 Acid dianhydride or aromatic tetracarboxylic acid dianhydride. Among them, an alicyclic tetracarboxylic acid dianhydride is preferred. Specific examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 1,2-dimethyl-1,2,3,4. - cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4- Cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane IV Carboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis_3,7-dibutyl Cyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxy-2 -carboxynorbornane-2: 3,5:6-dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-( Tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-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)-naphthalene [l,2-c]- Furan-1,3-diketone, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91)_hexahydro-7-ethyl-5-(tetrahydro-2,5-di Oxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91>-hexahydro-8-methyl-5 -(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-indolyl]-furan-1,3-dione, 1,3,3&,4,5,913_hexahydrogen _8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3& ,4,5,91^-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanylnaphthalene [l,2-c]-furan-1, 3-di-ketone, 5-(2,5-dioxotetrahydrofuranmethylene)-3-methyl-3-cyclohexene-1,2- 200821372 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-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2- Dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5:6-dianhydride, 4,9-dioxo a heterotricyclo[5.3.1.02,6]undecane-3,5,8,10-tetraone, a compound represented by the following formula (I) and (Π),

(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 1^4 present may be the same or different). Further, an aliphatic tetracarboxylic acid dianhydride such as butane tetracarboxylic acid dianhydride; pyromellitic dianhydride; 3,3',4,4'-benzophenonetetracarboxylic dianhydride; 3',4,45-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',4,45-dimethyldiphenylnonane tetracarboxylic acid dianhydride, 3,3',4,4'- Tetraphenylnonane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid II 200821372 anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsebacic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3 , 3',4,4'-perfluoroisopropylidene di phthalic anhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'- Biphenyltetracarboxylic acid dianhydride, di(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenyl) Phthalic acid) dianhydride, di(triphenylene) Phthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-di® (dehydrated trimellitic acid) Ester), propylene glycol-di (dehydrated trimellitate), 1,4-butanediol-di(anhydrotrimellitic acid ester), 〗 〖, 6-hexanediol-di(dehydrated trimellitic acid ester) 1,8-octanediol-di(anhydrotrimellitic acid ester), 2,2-bis(4-hydroxyphenyl.)propane-di(anhydrotrimellitic acid ester), the following formula (1) An aromatic tetracarboxylic acid dianhydride such as a compound represented by (4). They may be used alone or in combination of two or more.

-13- 200821372

ο

ο

^CH3 \ CH3 (2)

Η3

/CH3 ^CH3 (3)

Among the above tetradecanoic acid 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-14-200821372-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetraphthalic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetraammonium methylene) 3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, cis_3 7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid Acid dianhydride, 3,5,6-trimethyl-2-carboxynorbornane·2: 3,5:6-dianhydride, 1,3,3a,455,9b_A ammonia-5-(tetrahydro-2 ,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-u-dione, 1,3,3&,4,5,91>-hexahydro-8-methyl -5-(tetrahydro-2,5-dioxo-3-pyranyl)-naphthalene [1,2·χ]_furan-1,3-dione, 1,3,33,4,5, 91^Hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-indolyl]-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-indole, 2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5:6-dianhydride, 4,9-dioxa a tricyclic [5.3.1.02,6]undecane-3,5,8,10-tetraketone, a compound represented by the following formula (5) to (7) in the compound represented by the above formula (1); An alicyclic tetracarboxylic dianhydride such as a compound represented by the following formula (8) in the compound represented by the above formula (II), and the like, and 1, 2, 3, 4. Cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride , hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthoquinone, 2-c]-furan-13-dione, cis-3,7-dibutyl ring Oct-1,5-diene•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-diketone, 3-oxa Ring 200821372,,5,-dione), L-ene-1,2-dicarboxyl;:6-dianhydride, 3-ketone, and the following [3.2.1]octane-2,4-dione-6- Spiro-3'-(tetrahydrofuran-2 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3_cyclo[acid anhydride, 3,5,6-tricarboxy-2 -carboxynorbornane_2 : 3,: 4,9-dioxatricyclo[5.3.1.02,6]undecane-3,5,8,10-1; a compound represented by the formula (5).

As the other four preferred tetracarboxylic dianhydrides other than the alicyclic tetracarboxylic dianhydride, for example, butane tetracarboxylic pyrogate dianhydride and 3,3',4,4'-benzophenone tetracarboxylate are mentioned. Diphenyl maple tetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetra-1,4,5,8-naphthalenetetracarboxylic acid dianhydride, and the like. In the carboxylic acid dianhydride, the acid dianhydride, the retic anhydride, the 3,3,4,4,-decanoic acid dianhydride, -16-200821372, among these tetradecanoic acid diacids, the alicyclic tetradecanoic acid II is preferred. The acid anhydride is 50 mol% or more based on the entire tetracarboxylic acid dianhydride. <Diamine> Examples of the diamine used in the synthesis of polylysine include p-phenylenediamine, m-phenylenediamine, 4,4, diaminodiphenylmethane, and 4,4. , diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4,-diaminodiphenyl milling, 2,2'·monomethyl-4,4' -diaminobiphenyl, 3,3,-dimethyl-4,4,-diaminobiphenyl, 4,4'-diaminobenzimidamide, 4,4,-diaminodiphenyl Ether, diaminonaphthalene, 2,2'-ditrifluoromethyl_4,4,-diaminobiphenyl, 3,3,-ditrifluoromethyl-4,4'-monoaminobiphenyl ,5.Aminoaminophenyl)-i,3,3-trimethylindan, 6-amino-1-(45-aminophenyl)-l,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- Bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]leaf, 1,4-mono(4-aminophenoxy)benzene 1,3-bis(4-aminophenoxy) , ι,3-di(3 _aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diaminopurine, 9,9-di Methyl-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'-(meta-phenylene) Propylene)diphenylamine, 2,2,-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2, An aromatic diamine such as 2,-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl 200821372; , 1-m-xylylenediamine, 1,3-propanediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-diaminoglycol Diamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienyldiamine, hexahydro-4,7-methylene quinone dimethylenediamine, tricyclic [6·2 ·1.02'7]-undecene Aliphatic and alicyclic diamines such as diamine, 4,4'-methylbis(cyclohexylamine); 2,3·diaminopyridine, 2,6-diaminopyridine, 3,4- Diaminopyridine, 2,4 · diaminopyrimidine, 5,6-diamino-2 5 3 -dicyanopyridine, 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-isopropyl Oxy-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-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthrene Pyridine, 1,4-diaminopyridazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole, oxime-methyl- Molecules such as 3,6-diaminocarbazole, oxime-ethyl-3,6-diaminocarbazole, oxime-phenyl-3,6-diaminocarbazole 1 having two stages and the amine nitrogen atom of the stage 1 group other than a diamine; siloxane diamine and the like silicones represented by the following formula (V). These diamines may be used alone or in combination of two or more.

(V) 200821372 (wherein R5 represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R5 groups may be the same or different, P is an integer of 1 to 3, and 9 is an integer of 〜2 )). Among them, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4,-diaminodiphenyl sulfide, 2,2'-dimethyl-4,4' are preferred. _Diaminobiphenyl, U-diaminonaphthalene, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 257-diamino hydrazine, 9,9-dimethyl -2,7-diaminopurine, 4,4'-diaminodiphenyl ether, 2, octa[4-(4-aminophenoxy)phenyl]propane, 9,9-di (4 -aminophenyl)anthracene, 2,2-® bis[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,-Extension methyl bis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2 ,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopickylate, 3,6-diaminoacridine, 3,6-diaminocarbazole, guanidine-A Alkyl-3,6-diaminocarbazole, oxime-ethyl-3,6-diaminocarbazole, fluorenyl-phenyl-3,6-diaminocarbazole, and the like. • When the liquid crystal alignment agent of the present invention has a pretilt performance performance, it is preferred that some or all of Qi and Q2 in the above formulas (I-1) and (Ι-2) are represented by the following formula (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.

x—R6 (Q-1) 19- 200821372 (wherein X1 is a single bond, -0-, -CO-, -COO-, -OCO-, -NHCO·, -CONH-, -S- or 延芳And R6 is an alkyl group having a carbon number of from 10 to 20, a monovalent organic group having an alicyclic skeleton having a carbon number of 4 to 40, or a monovalent organic group having a fluorine atom having a carbon number of 6 to 20. ). X2- R7- (Q·2) (wherein X2 is a single bond, -0-, -CO-, -COO-, -OCO·, -NHCO-, -CONH-, -S- or an aryl group, R7 is a divalent organic group having an alicyclic skeleton having a carbon number of 4 to 40). 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, a group φ 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, adamantane, or the like a group of a bridge-ring skeleton, and the like. 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. In addition, 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 or n-octyl-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 hydrogen atom portion of an organic group such as a hydrocarbon group having a carbon number of 6 or more such as a phenyl group or a biphenyl group; All groups substituted by a fluorine atom or a fluoroalkyl group such as a trifluoromethyl group. Further, X1 of the above formula (Q-1) and X2 of the above formula (Q-2) are a single bond, -0-, -CO-, -COO-, -OCO-, _NHCO_, -CON Η- '-S - Or stretch the base. Examples of the aryl group include a phenyl group, a tolyl group, a biphenyl group, a naphthyl group and the like. Among them, particularly preferred are groups represented by -〇-, -COO-, and -OCO-. 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 (9) to (13).

(11)

(13) Further, as a diamine having a group represented by the above formula (2), 200821372

As a typical example, 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). 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, and in the case of the TN type or STN type liquid crystal display element, it is preferably 0 to 5 mol%. 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 supplied to the polyaminic acid synthesis reaction is preferably a tetracarboxylic dianhydride relative to the amine group of 1 equivalent of the diamine The acid anhydride group is a ratio of 〜 2 to 2 equivalents, more preferably a ratio of 〜 3 to 12 equivalents. The synthesis reaction of the polyfluorene Fee acid is preferably carried out in an organic solvent at a temperature of from _ 2 〇 ° c to 15 ° C, more preferably from 0 to 100 ° C. m is 'as an organic solvent' as long as it can dissolve the synthesized polyaminic acid, and -22-200821372 is not particularly limited, and examples thereof include methyl 2-pyrrolidone and N, N•dimethyl B. Indoleamine, N,N-dimethylformamide, 3-butoxy-N,N-methylpropane, 3 -methoxy-N,N-methylpropanamide, 3_ An aprotic solvent such as decylamine such as hexyloxy-N,N-dimethylpropionamide; dimethyl hydrazine, r-butyrolactone, tetramethylurea or hexamethylphosphonium triamine; Phenolic solvents such as m-cresol, xylenol, phenol, and halogenated phenol. Further, the amount (ct) of the organic solvent is usually preferably an amount such that the total amount (β) of the tetracarboxylic acid dianhydride and the diamine compound is % by weight relative to the total amount (α + β) of the reaction solution. Further, in the above-mentioned organic solvent, alcohols, ketones, esters, ethers, halogenated groups of a poor solvent of polyglycine may be used in the range in which the produced polyamine acid is not precipitated. Hydrocarbons, hydrocarbons, etc. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, and 1,4-butane. Alcohol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, propanone, 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 Alcohol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichloro Butane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, propane-23-200821372 isovalerate, isobutyl Isoamyl acid, diisoamyl Ether, etc. The reaction solution formed by dissolving polylysine was obtained as described above. Then, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate. The precipitate is dried by a reduced pressure or the reaction solution is distilled off under reduced pressure with an evaporator to obtain a polyamine. Further, the polylysine is re-dissolved in an organic solvent, and then the polypergic acid can be purified by performing a process of precipitating with a poor solvent once or several times or by vacuum distillation using an evaporator. ® <Dehydration ring closure reaction> The polyimine in 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. The dehydration ring closure of the poly-proline may be carried out by heating the poly-proline, or (π) by dissolving the poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution and heating as needed. The reaction temperature in the method for heating poly-proline in the above (1) 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 completely. If the reaction temperature exceeds 200 ° C, the molecular weight of the obtained ruthenium-imided polymer may decrease. On the other hand, the dehydration is added to the poly-proline solution in the above (ii). In the method of the agent and the dehydration ring-closing catalyst, 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 hydrazine imidization ratio, preferably relative to The repeating unit of 1 mole polyproline is 0.01 to 2.0 moles. In addition, as a dehydration ring-closing catalyst, -24-200821372 can be used, for example, pyridine, trimethylpyridine, lutidine, triethylamine, etc. amine However, it is not limited to these. The amount of the dehydration ring-closing catalyst is preferably 0.01 to 10 moles per mol of the dehydrating agent used. The more the dehydrating agent and the dehydration ring-closing catalyst are used, the more In addition, the organic solvent used for the dehydration ring-closure reaction is exemplified as the organic solvent used for the synthesis of the poly-proline, and the reaction temperature of the dehydration ring-closure reaction is preferably 0. ～180°c, more preferably 1〇1 to 150°C. Further, the specific polymer obtained can be purified by performing the same operation as the method for producing the polyamide amine acid by the reaction solution thus obtained. The ratio of the repeating unit having a quinone ring in all the repeating units used in the invention (hereinafter, also referred to as "deuterated imidization ratio") is 40 mol% or more, preferably 50 mol. By using a polymer having a ruthenium iodide ratio of 40% by mole or more, a liquid crystal alignment agent capable of forming a liquid crystal alignment film having a short afterimage erasing time can be obtained. The yield of ruthenium can be obtained by the following method. _ [Method for Measuring the Amidation Rate of the Iridium Amineated Polymer] After drying the ruthenium iodide polymer under reduced pressure at room temperature, it is dissolved in deuterated dimethyl hydrazine, and tetramethyl decane is added. The 1H-NMR measurement at room temperature as a reference substance can be obtained by the following formula (ii). The oxime imidization ratio α)xl00..........--(ii) A1: from NH The peak area of the protons (1〇ppm) A2: the area of the peaks derived from other protons α: the ratio of the number of other protons in the precursor of the polymer (polyproline) relative to one NH proton . -25-200821372 <Terminal-modified polymer> The specific polymer used in the present invention may also be a terminal-modified polymer having a molecular weight adjustment. By using the terminal-modified polymer, the coating property and the like of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. Such a terminally modified polymer can be synthesized by adding a monobasic acid anhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system in the synthesis of polyamic acid. Among them, as the monobasic acid anhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl group Succinic anhydride and the like. Further, examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and the like. N-dodecylamine, n-tridecylamine, n-tetradecylamine, n-five-family amine, hexadecanolamine, n-xylamine, n-octa-amine, and hexaamine. Further, as the monoisocyanate compound, for example, phenyl isocyanate, naphthyl isocyanate or the like can be exemplified. [Solid 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 m P a · s when it is a 10% solution. Viscosity. Further, using a specified solvent, the solution viscosity (mPa «s) of the polymer was measured under an E-type rotational viscometer for a solution diluted to a specified solid concentration. [Liquid Crystal Aligning Agent] The liquid crystal alignment agent of the present invention is usually constituted by dissolving the above specific compound -26 - 200821372 in an organic solvent. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 0 ° C to 200 ° C, more preferably from 20 ° C to 60 ° C. The organic solvent constituting the liquid crystal alignment agent of the present invention may, for example, be a solvent exemplified as a synthesis reaction for polyglycine. Further, it is also possible to appropriately select a poor solvent exemplified as a poor solvent which can be used in the synthesis reaction of polyproline. The solid content concentration in the liquid crystal alignment agent of the present invention is selected in consideration of viscosity, volatilization, etc., 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 which is a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small to be obtained. A good liquid crystal alignment film, when the solid content concentration exceeds 10% by weight, causes the film thickness of the coating film to be too thick, so that a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal alignment agent is increased, and the coating property is deteriorated. . In addition, the range of the particularly preferable solid content concentration differs depending on the method used for the substrate coating of the liquid crystal alignment agent. For example, in the case of using a spin coating method, it is particularly preferably in the range of 1.5 to 4.5% by weight. When the printing method is used, the solid content concentration is in the range of 3 to 9 % by weight, and particularly preferably, the solution viscosity is in the range of 12 to 5 Å HiPa s. When the inkjet printing method is used, the solid content concentration is in the range of 1 to 5 wt%, and particularly preferably in the range of 3 to 15 mPa «s of the solution viscosity. Examples of the organic solvent constituting the liquid crystal alignment agent of the present invention include 1-methyl-2-pyrrolidone, r-butyrolactone, r-butylide, n, n--27-200821372 dimethyl group. Indoleamine, N,N-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-N,N-dimethylpropanamide, 3-methoxyindole, hydrazine-dimethylpropanamide, 3-hexyloxy-N,N- Dimethylpropionamide, diisobutyl ketone (DIB K), isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like. They can be used alone or in combination of two or more. Among them, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy-N,N-dimethylpropyl The guanamine is particularly excellent in exhibiting good printability. The liquid crystal alignment agent of the present invention may further contain a functional decane-containing compound or an epoxy compound from the viewpoint of improving the adhesion to the surface of the substrate within a range not impairing the physical properties of the object. As such a functional decane-containing compound, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2- Aminopropyltriethoxydecane, N-(2-aminoethyl)-3.aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxyoxane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-B Oxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylethylamine, N-trimethoxydecylpropyltriethylamine, 10- Trimethoxydecane-1,4,7_-28- 200821372 Triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3 , 6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxysulfonium , N- bis (ethyl extend oxygen) _3- aminopropyl trimethoxy Silane, N- bis (oxo extending ethyl) 3-amine propyl triethoxy silane-yl 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, and polypropylene glycol diglycidyl ether. , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -tetraglycidyl-2,4-hexanediol, hydrazine, hydrazine, Ν'Ν'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamino) Methyl) cyclohexane, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl) Aminopropyltrimethoxy sand, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, N,N-disubstituted® glyceryl-benzylamine, hydrazine, hydrazine Glycidyl-aminomethylcyclohexanthes and the like. The compounding ratio of the functional decane-containing compound and the epoxy group-containing compound is preferably 40 parts by weight or less, more preferably 1 to 30 parts by weight, per part 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 a surface 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 forms a coating film. Here, 'as a substrate, glass such as float glass or soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, alicyclic poly A transparent substrate made of plastic such as olefin. As the transparent conductive film provided on one surface of the substrate, a NES A film (registered trademark of PPG, USA) formed of tin oxide (SnO 2 ), an ITO film formed of indium tin oxide (ln203 — SnO 2 ), or the like can be used. These transparent conductive film patterns are formed by photolithography or a method of using a mask 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 preferred to carry out preliminary heating (pre-baking) for the purpose of preventing the liquid of the applied alignment agent from flowing down. The pre-bake temperature is preferably from 30 to 300 ° C, more preferably from 40 to 2001: and particularly preferably from 50 to 150 ° C. Thereafter, the solvent was completely removed to carry out a calcination process (post-bake) for the purpose of heat-imidating the polyglycolic acid. The calcination (post-baking) temperature is preferably from 80 to 300 ° C, more preferably from 120 to 250 ° C. Thus, the liquid crystal alignment agent of the present invention containing polyglycolic acid is subjected to coating to remove the organic solvent to form a liquid crystal alignment film as a liquid crystal alignment film. It is also possible to carry out dehydration ring closure by further heating to form a further yttrium-imided liquid crystal alignment film. The film thickness of the liquid crystal alignment film to be formed is preferably 〇 〇 〇 1 to 1 μπι, more preferably 〇 . 〇 〇 5 〇 . 5 μπι. (2) Grinding the formed coating film surface with a roller wrapped with a cloth made of fibers such as nylon, rayon, cotton, etc., rubbing in a certain direction -3 0 - 200821372. Thereby, the alignment of the liquid crystal molecules can be imparted to the coating film to form an alignment film. Further, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is partially irradiated with ultraviolet rays as shown in, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. The process of changing the pretilt angle, or performing the process of partially forming a resist film on the surface of the liquid crystal alignment film which has been subjected to the rubbing treatment, as shown in Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei No. Hei. After the treatment, the resist film is removed, and the liquid crystal alignment of the liquid crystal alignment film can be changed, whereby the visual field characteristics of the liquid crystal display element can be improved. (3) Two substrates in which the liquid crystal alignment film was formed as described above were produced, and the two substrates were arranged to face each other through the gap (cell gap) so that the polishing directions of the respective liquid crystal alignment films were perpendicular or antiparallel to each other, and the two substrates were The peripheral portion is bonded with a sealant, and a liquid crystal is filled into the cell gap which is separated from the surface of the substrate and the sealant, and the injection hole is closed to constitute a liquid crystal cell. Then, the polarizing plate is bonded to the outer surface of the v liquid crystal cell, that is, the other side surface of each of the substrates constituting the liquid crystal cell, so that the polarizing direction thereof coincides with the rubbing direction of the liquid crystal alignment film formed on one side of the substrate or Vertically, a liquid crystal display element is produced. Here, as the sealant, for example, an alumina ball-containing epoxy resin as a curing agent and a spacer may 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 azo liquid crystal, a biphenyl liquid crystal, or a phenyl ring can be used. A hexane 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, or a cuba liquid crystal. Further, cholesteric liquid crystals such as chlorinated-31-200821372 cholesterol, cholesteryl phthalate, cholesteryl carbonate, and the like, and trade names "C-15" and "CB-15" may be added to these liquid crystals. The chiral agent sold by Merck & Co., Ltd. is used. Further, a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutylcinnamate may also be used. In addition, as a polarizing plate to be bonded to the outer surface of the liquid crystal, a polarizing plate or a crucible formed by sandwiching a polyvinyl alcohol and absorbing iodine, which is a bismuth film, is sandwiched between a protective film of cellulose acetate. A polarizing plate made of the film itself. Here, as the sealant, for example, an alumina ball-containing epoxy resin or the like as a curing agent and a gap 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 azo liquid crystal, a biphenyl liquid crystal, or a phenyl ring can be used. A hexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenyl cyclohexane 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-15" 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 may also be used. In addition, as a polarizing plate to be bonded to the outer surface of the liquid crystal, a polarizing plate or a crucible formed by sandwiching a polyvinyl alcohol and absorbing iodine, which is a bismuth film, is sandwiched between a protective film of cellulose acetate. A polarizing plate made of the film itself. [Embodiment] -32-200821372 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 1 27 mm (W) x 1.1 mm (Η) glass substrate having an ITO film formed on the entire surface of one surface was prepared, and the liquid crystal alignment agent obtained in the above experiment was made to have a pore diameter of The filter was applied to a transparent electrode surface of the glass substrate by a liquid crystal alignment film coating printer (Angstromer S-40L, manufactured by Nippon Photo Printing Co., Ltd.). The film was dried by a hot plate-type preliminary pre-drying machine set at 280 ° 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 resulting alignment film was visually evaluated. [Voltage Retention Rate] In a temperature of 60 ° C, a voltage of 5 V was applied to the liquid crystal display element at a time interval of 167 msec, the voltage application time was 60 μsec, and then the voltage was released from the time of the voltage release to 167 ms. Voltage retention rate. The measuring device uses VHR-1 manufactured by Dongyang Technology Co., Ltd. ^ [Image Residual Experiment] A unit cell having an ITO electrode as shown in Fig. 1 was produced. At room temperature, a DC voltage of 6.0 V was applied to the electrode A for 24 hours, and a DC voltage of 0.5 V was applied to the electrode B for 24 hours. After the stress was released, a voltage of 〇·1 to 5.0 V DC was applied to the electrodes A and B in a gradient of 〇.IV. The image sticking characteristics were judged by the difference in luminance between the electrodes A and 各 at each voltage. When the luminance difference is large, the afterimage characteristic is judged to be poor. <Synthesis of Specific Compound> -33- 200821372 Synthesis Example

catalyst_

(A - 1) Toluene 20 ml of toluene in a 500 ml four-necked flask under nitrogen atmosphere, acetic acid pin (11) 0 · 4 2 g (0 · 0 0 1 8 m 0 1), butyl phosphine 1 · 5 g (0.0 0 7 5 m ο 1), after stirring for a few minutes, the 4,4 '-dibromobiphenyl 2 9.3 g ( 0.0 9 4 m ο 1) toluene solution 1 〇〇m 1 , further stir for 1 〇 minutes. Next, force D was added to a solution of 18.3 g (0.196 mol) of aniline in 200 ml of toluene, and then 15.86 g (0.165 mol) of sodium 3-butoxide was added thereto, and the mixture was heated under reflux for 4 hours to cause a reaction. After the reaction was completed, water was added to the vessel and extracted with diethyl ether. After dehydration with sodium sulfate, sodium sulfate was filtered off and the solvent was removed by rotary evaporator. The crude product was purified by hydrazine column chromatography to give a specific compound (A-1). Synthesis Example 2

(B-1) -34- , 200821372 Toluene 2〇1111, catalyst palladium acetate (n) 0.42g (0.0018m〇l), 3-stage butyl was added to a 5〇〇ml four-necked flask under nitrogen atmosphere. 1.5 g (0.0075 mol) of phosphine, after stirring for a few minutes, a solution of 2,7-dibromofluorene 3 0.4 g (0.094 mol) in toluene at 100 m was further stirred for 10 minutes. Then, after adding 200 ml of a toluene solution of aniline 18.3 g (0.196 mol), 15.86 g (0.165 mol) of sodium butoxide sodium salt was further added, and the mixture was heated under reflux for 4 hours to cause a reaction. After the reaction was completed, water was added to the vessel and extracted with diethyl ether. After dehydration with sodium sulfate, sodium sulfate was filtered off and the solvent was removed by rotary evaporator. ^ The crude product was purified by hydrazine column chromatography to give the specific compound (B-1). Synthesis Example 3

(A - 2) The synthesis was carried out in the same manner as in Synthesis Example 1 except that the aniline used in Synthesis Example 1 was replaced with 4-n-propylaniline to give a compound (A-2) 〇 -35- 200821372

The compound (B-2) was synthesized by the same procedure as in Synthesis Example 2 except that the aniline used in Synthesis Example 2 was replaced with 4-n-propylaniline. Synthesis Example 5

(A-3) Mixing a specific compound (A-1) with 3.36 g (0.01 mol), THF 1 0 0 m 1 , sodium azide 1 · 5 6 g (0.0 4 m ο 1) in a 500 ml three-necked flask . The solution was heated to reflux for 2 hours. The reaction solution was cooled, and 3.42 ml (0.04 mol) of epibromohydrin was added dropwise. After the completion of the dropwise addition, the mixture was heated to 80 ° C and stirred for 6 hours. After removing the THF by a rotary evaporator, chloroform was added. The solution was washed with a solution of -36-200821372 1 〇% hydrochloric acid aqueous solution and saturated brine. The organic layer was dried over anhydrous magnesium sulfate and filtered and evaporated. The solvent was distilled off from the organic layer. Further, it was purified by ruthenium oxide column chromatography to obtain a specific compound (Α - 3). The specific compound (A-3) contains two kinds of products as shown in the above formula. Synthesis Example 6

Compound (B-1), 17.4 g (0.05 mol), DMSO 120 ml, and potassium carbonate 16.59 g (0.12 mol) were mixed in a 500 ml three-necked flask. After the solution was cooled in an ice bath, 160 ml of a solution of 16.44 g (0.12 mol) of oxidized bromopropane in DMSO was added dropwise. After the addition was completed, return to room temperature and continue stirring for 48 hours. The reaction solution was filtered, and the filtrate was concentrated by a rotary evaporator, and the excess of the epibromo-bromopropane was removed by a vacuum pump. To the obtained crude product, 200 ml of toluene was added for dilution, and the solution was washed 4 times with 100 ml of distilled water. After adding sodium sulfate and allowing to stand for 1 night, sodium sulfate was filtered off, and the solvent was removed by a rotary evaporator. The obtained crude product was purified by yttrium oxide column chromatography to give a specific compound (B-3). B-3 contains two products as shown in the above formula. -37- 200821372 Synthesis Example 7

(A-4) A specific compound (A-4) was obtained by the same procedure as in the synthesis example 5 except that the specific compound (a-1) used in the synthesis example 5 was replaced by (A-2). A-4 contains two products as shown above. Synthesis Example 8

The specific compound (Β-4) was obtained by the same procedure as in Synthesis Example 6 except that the specific compound (Β_1} used in Synthesis Example 6 was replaced by (Β-2). Β-4 contained the above formula. Two products shown. Polyimine synthesis Example 1 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetraterpene dianhydride 112 g (0.50 mol) and 1,3,3a,4 ,5,9b-hexahydro-8-methyl-5-(tetrahydro-38-.200821372-2,5-dioxo-3-furanyl)-na[1,2-indole]-pyran-1 , 3-Beli 157 (0.50 mol), p-phenylenediamine as diamine compound 96g (0.89 mol), 3,3'-(tetramethyldioxane·1,3-diyl Bis (propylamine) 25 g (0.10 mol) and 3,6-bis(4-aminobenzylideneoxy)cholalane 13 g (〇.020 mol), n-octadecylamine as a monoamine 8· lg (0·03 0 mole) is dissolved in 960 g of N-methyl-2-pyrrolidone and allowed to react at 6 ° C for 6 hours. The obtained polyamidamine solution is taken out in small portions. NMP was added, and the viscosity was measured by a solution having a solid concentration of 1% by weight, which was 60 mPa, s. Then, the obtained polylysine was dissolved. • Add 2700 g of N-methyl-2-indole ketone to the solution, add 396 g of D-steep and 409 g of acetic anhydride to dehydrate the mixture for 4 hours at 110 ° C. After the imidization reaction, the system The solvent in the solvent is replaced by a new r-butyrolactone (in this operation, the pyridine and acetic anhydride used in the oxime imidization reaction are removed to the outside of the system) to obtain a solid concentration of about 2,000 g. 5 wt%, a solid concentration of 6.0% (r-butyrolactone solution), a solution viscosity of 16 mPa.s, and a ruthenium iodide ratio of about 95% of the ruthenium iodide (which acts as a "polyimine ( a — 〇”) solution. Polyimine synthesis example 2 2,4,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 2 2 4 g (1·0 mol) as two The amine compound p-phenylenediamine 1 〇8 g 〇. 〇mol) and 3,5-diaminobenzoic acid cholesteryl ester 7.8 g (0.015 mol) dissolved in 3 0 3 9 g N-A In the thiopyrrolidone, it is subjected to a reaction at 60 ° for 6 hours to obtain a polyaminic acid solution having a solution viscosity of about 260 mPa·s. Next, a further addition of 2 7 to the obtained poly-proline solution is obtained. 0 0 g N-methyl-2-pyrrolidone, adding 396 g of pyridine and 306 g of acetic anhydride, dehydrating at ll ° ° C -39-200821372 closed-loop for 4 hours. After the hydrazine imidization reaction, the solvent in the system was The new 7-butyrolactone is subjected to solvent replacement (in this operation, the pyridine and acetic anhydride used in the oxime imidization reaction are removed to the outside of the system) to obtain a solid concentration of about 3,000 wt%, a solid concentration of 5.0. % (r-butyrolactone solution, liquid) solution viscosity 72mPa, s, yttrium imidization rate of about 89% yttrium imidized polymer (as a "noniminated polymer (a - 2) ”) solution. Polylysine Synthesis Example 1 196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride as tetracarboxylic acid dianhydride as 2,25·dimethyl group of diamine compound -4,4'-diaminobiphenyl 212 g (1.0 mol) was dissolved in 3 70 g of N-methyl-2-pyrrolidone and 3 3 00 g of r-butyrolactone, and allowed to react at 40 ° C for 3 hours. A solution of about 3700 g of a solution having a viscosity of 160 mPa, s poly-proline (as a "poly-proline (b-1)") solution was obtained. Polylysine Synthesis Example 2 1,5,3,3,4-cyclobutanetetracarboxylic acid dianhydride as tetracarboxylic acid dianhydride, 95 g (0.50 mol), pyromellitic dianhydride l 9 g (0.50) Mohr), 2,7-diaminopurine as a diamine compound, 196 g (l. mol) dissolved in 230 g of N-methyl-2-pyrrolidone and 2060 g of r-butyrolactone at 40 ° C After reacting for 3 hours, 1 3 5 0 g r -butyrolactone was added to obtain about 3600 g of a polyamic acid having a solid concentration of 10% and a solution viscosity of 125 mPa.s (as "polyglycine (b-2)"). Solution. Example 1 Polyimine (a-1) prepared in Polyimine Synthesis Example 1 and Polylysine (b-1) prepared in Polyamine Synthesis Example 1 as Polyimine :聚醯-40- 200821372 Amino acid = 20: 80 (weight ratio) dissolved in γ-butyrolactone / N-methyl-2-pyrrolidone / butyl cellosolve mixed solvent (weight ratio 71/1 7/12) Adding 2 parts by weight of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane to 100 parts by weight of the polymer, relative to 1 part by weight of the polymer 1 part by weight of a specific compound (A-1), 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 Ιμπι to prepare a liquid crystal alignment agent of the present invention. A solution having a solid concentration of 3.5 parts by weight / 〇 in the above liquid crystal alignment agent was applied to a transparent conductive film formed of an ITO film provided on one side of a glass substrate having a thickness of 1 mm using a spin coater (rotation speed: 2500 rpm, coating time: 1 minute), and dried at 200 ° C for 1 hour to form a film having a dry film thickness of 0.08 μm. Using a sander equipped with a roller of a woven fabric made of rayon, the film was ground at a roller speed of 400 rpm, a table moving speed of 3 cm/sec, and a fluffing length of 〇.4 mm. deal with. Ultrasonic washing was performed in ultrapure water for 1 minute and dried in a 100 °C clean oven for 1 minute. 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 coated with alumina balls having a diameter of 5 · 5 μm is applied. Subsequently, the liquid crystal alignment film surface is relatively recombined and pressed to cure the adhesive. Then, a nematic liquid crystal (MLC-622 1 manufactured by Merck & Co., Ltd.) was filled between the substrates through a liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to form a liquid crystal display element of the present invention. The evaluation of the voltage holding ratio and the afterimage of the obtained liquid crystal display element was carried out in accordance with the method described above. The printability evaluation was carried out by the method of -41 200821372 using the solution having a solid content concentration of 6.0% by weight. Examples 2 to 8 were carried out in the same manner as in Example 1 except that the materials shown in Table 1 were used for the polyimine, the polyamic acid, and the specific compound. Example 9 Polyethylenimine (a-2) prepared in Polyimine Synthesis Example 2 was dissolved in a mixed solvent of N_methyl-2-miraxolone/butyl cellosolve (weight ratio 5 0 / 5 0 In the case of adding 2 parts by weight of N,N,N',N'-tetraglycidyl oil-based-4,4'-diaminodiphenylmethane relative to 1 part by weight of the polymer, relative to 1 〇 0 parts by weight of the polymer was added to 10 parts by weight of the specific compound (A-1) to prepare a solution having a solid concentration of 3.5% by weight and a solution of 6.0% by weight. After each solution was thoroughly stirred, it was filtered with a filter having a pore size of 1 μm 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 1 0 to 1 2 The same procedure as in Example 9 was carried out except that the specific compound was used as shown in Table 1. Comparative Examples 1 to 2 The same flow g 31 as in Example 1 was carried out except that the material shown in Table 1 was used for the polyimine and the polyamic acid, and the specific compound was not added. Comparative Example 3 was carried out in the same manner as in Example 9 except that no specific compound was added. -42- 200821372 Comparative Examples 4 to 5 In addition to polyimine and polylysine, the materials shown in Table 1 were used, and N,N'-diphenyl-N,N'-di(m-tolyl) was used. The same procedure as in Example 1 was carried out except that benzidine (Compound Z) was used instead of the specific compound. Comparative Example 6 The same procedure as in Example 9 was carried out except that N,N'-diphenylanthracene, yttrium-di(m-tolyl)benzidine (compound) was used instead of the specific compound.

Polyimine polyamine specific compound voltage retention rate image-printing Example 1 a-1 b- 1 Specific compound A_1 > 99% 〇〇 Example 2 a-1 b-1 Specific compound B-1 &gt 99% 〇〇Example 3 a-1 b-1 Specific compound A-4 > 99% 〇〇 Example 4 a-1 b-1 Specific compound B-4 > 99% 〇〇 Example 5 a- 1 b-2 specific compound A-3 > 99% 〇〇 Example 6 a-1 b-2 Specific compound B-3 > 99% 〇〇 Example 7 a-1 b-2 Specific compound A-4 &gt 99% 〇〇Example 8 a-1 b-2 Specific compound B-4 > 99% 〇〇 Example 9 a-2 - Specific compound A-1 > 99% 〇〇 Example 10 a-2 Specific Compound B-1 > 99% 〇〇 Example 11 a-2 - Specific Compound A-4 > 99% 〇〇 Example 12 a-2 - Specific Compound B-4 > 99% 〇〇 Comparative Example 1 A- 1 b- 1 Μ /\\\ >99% Δ 〇Comparative Example 2 a-1 b-2 4Ε /\\\ >99% Δ 〇Comparative Example 3 a— 2 — 4rrr. >99% Δ 〇Comparative Example 4 a— ib — 1 Compound Ζ 98% 〇X Comparative Example 5 a-1 b-2 ζ 98% 〇X Comparative Example 6 a-2 — Compound ζ 98% 〇X In the table, 〇·· excellent, △: good, X: poor-43- 200821372 [Simple illustration] ^ Figure 1 is the residual An explanatory diagram of a unit cell produced by a shadow experiment. -44-

Claims (1)

200821372 X. Patent application scope: 1. A liquid crystal alignment agent characterized by containing at least one compound selected from the group consisting of a compound represented by the following formula (A) and a compound represented by the following formula (B). (wherein, Ri to R8 are each independently a hydrogen atom, an alkyl group, an alkoxy group or an aromatic group, R9 and Rn are an aromatic group, and R1() and R12 are each independently a hydrogen atom or an alkyl group; Or glycidyl), Ruler 16〆 R 18 (B) (wherein R 1 3 and R 1 4 are each independently a hydrogen atom, a substituent, an aristocratic group or an aromatic group, R!5 and Ru are aromatic groups, and R16 and R18 are each Independently a hydrogen atom, an alkyl group or a glycidyl group, and X represents a divalent organic group, -〇- or -NH-). 2. The liquid crystal alignment agent of claim 1, wherein the aliphatic group of R1〇 and R12 in the formula (A) is an epoxy group-containing aliphatic group. 3. The liquid crystal alignment agent of claim 1, wherein the aliphatic group of R16 and R! 8 in the formula (B) is an epoxy group-containing aliphatic group. The liquid crystal alignment agent according to any one of claims 1 to 3, further comprising a polyaminic acid represented by the following formula (I-1) and the following formula (I-2) At least one polymer selected from the group consisting of polyimine, HOOC, .COOH (I-1) X HNOC CONH-Q1 In the formula, P2 is a tetravalent organic group, and Q2 is a divalent organic group. 5. The liquid crystal alignment agent of claim 4, wherein the polyamic acid represented by the above formula (I-1) and the tetracarboxylic acid used in the synthesis of the polyimine represented by the above formula (I-2) The acid anhydride comprises 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. A liquid crystal alignment film produced by using a liquid crystal alignment agent according to any one of claims 1 to 5. A liquid crystal display element characterized by having a liquid crystal alignment film according to item 6 of the patent application. -46-