TW201001029A - Liquid crystal aligning agent and liquid crystal aligning element - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent, even in the case of take ODF method to producing VA type liquid crystal display element, can provides a liquid crystal aligning film which generating no display unevenness and showing high vertical alignment controllability, besides, properties required for a liquid crystal aligning agent, particularly the printability, are good. The above liquid cryastal aligning agent comprising at least one polymer selected from the group consist of a polyamic acid and an imide polymer thereof, wherein the polyamic acid is obtained by reacting a tetracarboxylic dianhydride with a diamine which comprising a specific diamine represented by the formula (A-10) below.

Description

201001029 SUMMARY OF THE INVENTION Technical Field The present invention relates to a liquid crystal alignment agent and a liquid crystal display element. More specifically, it relates to a liquid crystal dropping method (ODF method) even in a liquid crystal charging step in which a liquid crystal display element is manufactured. In the case of 'liquid crystal alignment agent' which does not cause a liquid crystal alignment film of 0DF unevenness, and a liquid crystal display element which does not deteriorate even if the display quality is continuously driven for a long period of time. [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 on a surface of a substrate on which a transparent conductive film is provided. A liquid crystal aligning film formed of yttrium imine or the like is used as a substrate for a liquid crystal display element, and two of the substrates are opposed to each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a sandwich structure. The long axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate to the other. Furthermore, an STN (Super Twisted Nematic) liquid crystal display element and a IPS (in-plane switching) type liquid crystal display element with high contrast ratio and a VA (vertical alignment) capable of achieving high contrast compared to a TN type liquid crystal display element have been developed. The liquid crystal display element has an optical compensation curved (OCB) type liquid crystal display element which is excellent in viewing angle dependence and excellent in high-speed response of an image. As a material of the liquid crystal alignment film in these liquid crystal display elements, polyiminoimine, polyamide, polyester, and the like, particularly polyimine, have been previously known, because of their heat resistance, affinity with liquid crystal, and mechanical strength. It is excellent and is used in many liquid crystal display elements. 201001029 In recent years, the manufacturing steps of liquid crystal display elements have made great progress. In particular, technologies such as large-scale substrate transport technology and liquid crystal dropping method (ODF) used together with the enlargement of substrates have attracted attention. In the 〇DF method, a necessary amount of liquid crystal is dropped on a substrate on which a liquid crystal alignment film is formed, and after bonding to another substrate under vacuum, the liquid crystal sealing agent is UV-cured to fill the entire panel. The liquid crystal method is a technique capable of greatly shortening the engineering time of the liquid crystal charging step as compared with the conventional vacuum injection method. However, if the ODF method is employed in the production process of a VA type liquid crystal display element having a polyimine-based liquid crystal alignment film, there is a problem that display unevenness called "ODF unevenness" occurs. This phenomenon is considered to be caused by insufficient vertical alignment control force of the liquid crystal alignment film. In order to solve such a problem of the polyimine-based liquid crystal alignment film, a method of using a polyimine prepared by using a diamine containing a diamine having a hydrophobic functional group such as a long-chain alkyl group in a high content ratio is given, for example. (Refer to Patent Documents 1 and 2). This technique is considered to be an excellent technique for improving the effect of the vertical alignment control force, but a case where the printability of the liquid crystal alignment agent is impaired occurs. Therefore, there is a need for a liquid crystal alignment element which does not impair the various required properties required for a liquid crystal alignment agent, particularly a printability, a liquid crystal alignment film which can form a liquid crystal alignment film which does not cause the above ODF unevenness, and a liquid crystal display element which is excellent in display quality, particularly even A liquid crystal display element in which the picture quality does not deteriorate when continuously driven for a long time. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. When the ODF method is used in the manufacturing process of the display element, it is also possible to form a liquid crystal alignment film which does not cause display unevenness and exhibit high vertical alignment control force, and various properties required as a liquid crystal alignment agent, in particular, liquid crystal excellent in printability. An alignment agent and a liquid crystal display element excellent in display quality. Further 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, firstly, achieve a 'liquid crystal alignment agent comprising at least one polymer selected from the group consisting of polylysine and its ruthenium iodide polymer' Polylysine is obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (A).

(In the formula (A), R1 and R111 are each independently an ether bond, a thioether bond, an ester bond or a thioester bond, wherein the direction of the ester bond and the thioester bond is not limited, and R11 is a methylene group or a carbon number is 2 to 10 alkylene groups, RIV is a single bond, methylene or ethylene group, and X is a monovalent organic group having a steroid skeleton of 17 to 40 carbon atoms). 201001029 The above objects and advantages of the present invention are, in a second, achieved by a liquid crystal display element having a liquid crystal alignment film formed of the above liquid crystal alignment agent. [Embodiment] The liquid crystal alignment agent of the present invention comprises at least one polymer selected from the group consisting of polylysine and a quinone imidized polymer thereof, the polyphthalic acid is a tetracarboxylic dianhydride and contains the above The diamine reaction of the compound represented by the formula (A) is carried out. [Polyuric acid] The polyphthalic acid which may be included in the liquid crystal alignment agent of the present invention can be synthesized by reacting a tetracarboxylic dianhydride with a diamine containing the compound represented by the above formula (A). [Tetracarboxylic dianhydride] The tetracarboxylic dianhydride used in the synthesis of the polyamic acid which may be included in the liquid crystal alignment agent of the present invention may, for example, be butane tetracarboxylic dianhydride, 1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3 , 4-anthracene tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride 1, 1,2,4,5-nonane hexane tetracarboxylic dianhydride, 3,3' , 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2, 3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene 1,2-c]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3 -furyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-5-ethyl-5-(four 201001029 Hydrogen-2,5-dioxo-3-furanyl)-naphthalene furan '3_dione, 1,3,9,4,5,91>-hexahydrogen -7-Methyl.5_(tetrahydro-2,5-dioxo-3-indolyl)_naphthalene [l,2,cl·furan-U3-dione, ^^^'^hexahydro + B ^^tetrahydro-2,5-oxo-3-furanylnaphthalene tl,2_cbufuran·,3·dione, l,3,3a,4,5,9b-hexahydro-8-A _5_(tetrahydro-2,5-dioxo-3-furanylnaphthalene n,2-C]-furan-U3·dione, 1,3,33,4,5,9^hexahydro _8_Ethyl_5_(tetrahydro-2,5-oxo-3-furanyl)-naphthalene n,2_cbufuran-indanedione, ^^'^external-six-gas-^-dimethyl ^^4O^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ -3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2 2 bis]·oct-7-ene-2,3,5'6-tetracarboxylic dianhydride, 3_oxabicyclo[321 Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5,.dione), 5-(2,5-dioxotetraammonium)--3- Methyl-3-cyclohexene_1>2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-oxo-norbornane-2:3,5:6-dianhydride, 4,9-diox Heterotricyclo[5.3.1.〇26]dec-alkane-3,5,8,10-tetraketone, the following formula (T_I} and (such as T_nm compounds, aliphatic tetracarboxylic dianhydride and alicyclic) four Citrate dianhydride; Γ\

(Tl \ (Τ-ΙΙ) (In the above formula, 'R1 and R3 each represent a divalent organic group having an aromatic ring' R and R4 each represent a hydrogen atom or an alkyl group, and a plurality of R2 201001029 and R4 present may each be the same , or different); pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyl maple tetracarboxylic acid Anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid Anhydride, 3,3',4,4'-dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3 , 4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy Diphenyltriamine, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene Phthalic phthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) Phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) II Anhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4 diphenyl ether dianhydride, bis(triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis(hydrogen trimellitate), propylene glycol-bis(hydroper trimellitate), 1,4-butanediol-double (dehydration) Trimellitic acid ester), 1,6-hexanediol-bis(hydroper trimellitate), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2,2-dual (4 -Hydroxyphenyl)propane-bis(hydrogen trimellitate), an aromatic tetracarboxylic dianhydride such as a compound represented by the following formulas (T-1) to (T-4). They may be one or two The above combination is used. 201001029

Ch3 /CH3

The tetracarboxylic dianhydride used in the synthesis of polyphthalic acid which may be included in the liquid crystal alignment agent of the present invention is derived from the viewpoint of liquid crystal alignment which can be excellent in performance - 201001029, and preferably contains a selected butane. Tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1, 2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydrogen) -2,5-dioxo-3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8- Methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1,3-dione, 1,3,3a,4,5 ,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1,3-di Ketone, 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-carboxynorbornane-2:3,5:6-dianhydride 4,9-dioxatricyclo[5.3.1.02'6]-(-alkane-3,5,8,10-tetraketone, pyromellitic dianhydride, 3,3',4,4'- Benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyltricarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 1,4 , 5,8-naphthalenetetracarboxylic dianhydride, a compound represented by the following formula (T - 5) to (T - 7) in the compound represented by the above formula (T-I), and the above formula (T - II) At least one selected from the group consisting of the compounds represented by the following formula (T-8) in the compound to be represented (hereinafter referred to as "specific tetracarboxylic dianhydride (1)''). -11 - 201001029

(Τ-5)

(Τ-8) As the specific tetracarboxylic dianhydride (1), it is particularly preferably selected from the group consisting of 1,2,3,4·tetracarboxylic dianhydride and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. l,3,3a: hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(:]-furenedione, 1,3,3& 4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxoyl)-naphthalene [l,2-c]-furan-1,3-dione, 3 -oxabicyclo[3.2 -2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-tetrahydro-3-furanyl)- 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3 carboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxo[5.3.1.02 '6] At least one of the group consisting of undecane-3, 5,8,10-tetraketone, pyromellitic dianhydride, and a compound represented by (T-5). The liquid crystal alignment agent of the present invention may comprise a synthesis of polybutyric acid, cyclobutane, 4,5,9b-furo-1,3-substituted-3-furo.1]octane•dioxo,5,6- In the tetracarboxylic dianhydride used in the above formula, -12-201001029, the tetracarboxylic dianhydride used in the above formula preferably contains 20 mol% or more of the above specific tetracarboxylic dianhydride (1). More preferably, it contains more than 50% by mole, and particularly preferably contains more than 80% by mole. The diamine for synthesizing polyglycine which may be contained in the liquid crystal alignment agent of the present invention is a diamine containing the compound represented by the above formula (A). R1 and R111 in the above formula (A) are preferably each independently an ether. Key or ester bond. The direction of the ester bond is not limited. As R11, an alkylene group having 2 to 4 carbon atoms is preferred. As the RIV, a single bond or a methylene group is preferred. The steroid skeleton in X of the above formula (A) means a skeleton in which one or more of the cyclopentane-perhydrophenanthrene skeleton or the carbon-carbon bond contained therein is changed to a double bond. Examples of the X group having such a skeleton are, for example, groups represented by the following formulae (X-1) to (X-4).

-13- 201001029

(X-3) X1

(X4) (X1 in the above formula each represents a group represented by any one of the following formulae, *" represents a linkage bond),

("+" in the above formula is expressed as a connection key). Specific examples of the X group include a group represented by the following formula (X-1 - 1), (X-2 - 1), (X-3 - 1) or (X_4 - 1), -14 - 201001029

(Expressed in the above formula is a connection key). Specific examples of the compound represented by the above formula (A) include compounds represented by the following formulas (A-1) to (A to 29). -15- 201001029

N2 2 N c 2 2 o-house ^ο Η ο ο \I/ 99?c ^-wide

(A-2)

2 0 2 2 o— c 〇Η H〇 CJCICIC

(A-4) -16 - 201001029

2 2 2 2 Η Η Η H o-cl etc. CIO

(A-5)

(A-7)

(A-9)

201001029

Ch2 ch2 ch2 ch2 oco

(A-15)

-18- 201001029

-19- 201001029 2

, 02 2 2 〇 l ο Η Η Η o 9C-C-C 丨 c

(A-27)

-20- 201001029

CH, CH2 ch2 o - γ ΝΗ 2 ( A-29 ) NH2 These compounds can be synthesized by a conventional method of organic chemistry. For example, the compound represented by the above formula (A-1), (A-2) '(A-7) or (A-8) can be used by adding an acid anhydride to cholesterol or cholestyl alcohol, respectively. Dichlorohydrazine or the like is produced as a ruthenium chloride, and the ruthenium chloride is reacted with dinitrophenol in the presence of an equivalent amount or more of a base, and then reduced by a suitable reducing agent such as tin chloride to be synthesized. The compound represented by the above formula (A-3), (A-4), (A-9) or (A-10) may be respectively added to succinic anhydride on cholesterol or cholestyl alcohol in potassium carbonate. In the presence of the above, the adduct is subjected to an ester formation reaction with dinitrobenzidine chloride, and then synthesized by reduction with an appropriate reducing agent such as tin chloride. The compound represented by the above formula (A-5) or (A-1 1) can be obtained by toluene sulfonation of cholesterol or cholestyl alcohol with toluene sulfonium chloride or the like, respectively, and the resulting toluene sulfonated cholesteryl alcohol Or toluene sulfonated cholesteryl alcohol and dinitrobenzhydryl chloride and excess butane diol are reacted in the presence of a base to synthesize 'after obtaining dinitrobenzhydryl monobutylene glycol ester, with the previous toluene The sulfonated cholesteryl alcohol is heated in an appropriate organic solvent to form an ether bond, which is then synthesized by a method such as tin chloride or the like as a reducing agent. a compound represented by the above formula (A-6) or (A-12), after addition of succinic anhydride to cholesterol or cholesterol, is reduced to a methylene group by a carbonyl group of the above adduct, and then to a tribasic In the presence of the reduced product and 2,4-dinitrochlorobenzene, the reduction is carried out with a suitable reducing agent such as tin chloride: the toluenesulfonyl cholesteryl chethol prepared in the same manner as above, 1-(4-hydroxydinitrobenzene) obtained by the reaction with a base such as 2,4-dinitrochlorobenzene and an excess of potassium butoxide, heated in a suitable organic solvent to form ether tin The compound represented by the above formula (A-13) can be synthesized by a method such as reduction by a suitable reducing agent, and the toluenesulfonated cholesteryl alcohol which can be obtained by the sample, and the ethylene glycol derived from 2, 4-excess 1-(4-hydroxyethoxy)-2,4-dinitrobenzene in the presence of a base such as potassium butoxide or the like, and an appropriate reducing agent such as tin chloride after appropriate formation of an ether bond The above formula (A-14), (A-15) or (A-16) indicates that lanosterol, ergosterol or sterol can be used as the external, respectively. The compound represented by the above formula (A-6). The compound represented by the above formula (A-17) or (A-18) is an ethylene glycol in which the amount of methyl sulfonate is determined by using cholesteryl chloride or cholesteryl chloride. The monoether compound is synthesized by a displacement reaction, and the potassium butoxide or the like may be subjected to an ester formation reverse method by lithium aluminum hydride or the like, or the toluenesulfonated diol may be in the third-order G-butoxy group - 2, 4 _ bond. Then, using a ruthenium chloride, for example, a compound obtained by heating and reducing the above-mentioned homonitrobenzene benzene and an organic solvent obtained by the reaction is removed as a starting material by an object, and each of them can be pulverized. After the above reaction, the above monoether compound is reacted with 3,5-dinitrobenzimidyl chloride to synthesize the dinitrate, and the nitro group is reduced with a suitable reducing agent such as palladium carbon. And made. The compound represented by the above formula (A-19) or (A-20) can be formed into an ether bond by reacting cholesterol or cholesterol with potassium hydride or the like to form an ether bond with an excess of dibromopropane. The intermediate is prepared, and then the intermediate is reacted with 3,5-dinitrobenzoic acid in the presence of potassium carbonate to synthesize a dinitrate, and then the nitro group is reduced with a suitable reducing agent such as palladium carbon. . The compound represented by the above formula (A-21) or (A-22) can be respectively obtained by adding N,N-dicyclohexylcarbodiimide to succinic anhydride on cholesterol or cholesteryl alcohol. The reaction of 3,5-(N,N-diallyl)aminophenol is carried out by removing the allyl group with 1,3-dimethylbarbituric acid and hydrazine (triphenylphosphine)palladium. The compound represented by the above formula (A-23) or (A-24) can be obtained by reducing a carbonyl group by using a borane-oxy bridge complex after adding succinic anhydride to cholesterol or cholestyl alcohol, respectively. After the formation, the above intermediate is reacted with 3,5·dinitrobenzimidyl chloride in the presence of a base to synthesize a dinitro compound, and then the nitro group is reduced with a suitable reducing agent such as palladium carbon. The compound represented by the above formula (A-25) or (A-26) may be produced in the same manner as the compound represented by the above formula (A-4) or (A-1 0), except that glutaric anhydride is used instead of succinic anhydride. Got it.

The compound represented by the above formula (A-27), (A-28) or (A-29) may be used in addition to the use of the raw material lanosterol, ergosterol or sterol alcohol by hydrogenation with a suitable hydrogenation catalyst. The compounds represented by the above formula (A - 14), (A-23 - 201001029-15) or (A-16) are obtained in the same manner. The diamine for synthesizing polylysine which may be contained in the liquid crystal alignment agent of the present invention may be a compound represented by the above formula (A), or a compound represented by the above formula (A) may be used together with other diamines. Use together. Here, examples of the other diamine which can be used in combination with the compound represented by the above formula (A) include p-phenylenediamine, m-phenylenediamine, 4,4 '-diaminodiphenylmethane, and 4,4'. -diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4,-diaminodiphenylanthracene, 3,3'-dimethyl-4,4' -diaminobiphenyl, 4,4,-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, iota, 5-diaminonaphthalene, 2,2'-dimethyl- 4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4 '-Diaminobiphenyl, 5-aminoaminophenyl)-1,3,3-trimethylindan, 6-amino-i-(4'-aminophenyl)-1,3 , 3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3,-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4' -diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl] Hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4) -aminophenoxy)benzene, 1 3_bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2, 7-Diaminopurine, 9,9-dimethyl-2,7-diaminoguanidine, 9,9.bis(4-aminophenyl)anthracene, 4,4'-methylene-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, 4,4'-(p-phenylene isopropylidene)diphenylamine 4, 4'-(m-phenylene isopropylidene) diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoro-24- 201001029 Propane, 4,4,-diamino-2,2,-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy] - an aromatic diamine such as octafluorobiphenyl; 1,1-m-xylylenediamine, 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, hydrazine Diamine, 1,4 -diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7-methylene dimethylene diamine, tricyclic [6.2.1.02,7] undecene dimethyl diamine, 4, 4 - an aliphatic diamine such as methylene bis(cyclohexylamine) and an alicyclic diamine; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2 , 4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrrole, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino- 6-Dimethylamino-1,3,5-tri-trap, 1,4-bis(3-aminopropyl) pipe trap, 2,4-diamino-6-isopropoxy-1,3 , 5-trimole, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triad , 2,4-diamino-6-methyl-s-tripper, 2,4-diamino-1,3,5-tri-trap, 4,6-diamino-2-vinyl-s - three tillage, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-di Amino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4- Diaminopiperidine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diamine Gemazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, indole, Ν'-bis(4-aminophenyl)benzidine , the following A compound represented by - (I D)

H2N nh2 X1 a R5

(DI tri-trap, piperidine in (Formula (D-I), R5 represents a monovalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine-25-201001029 and piperene, and χ1 represents a divalent organic group Organic group), a compound represented by the following formula (D-II)

(D-Π) (In the formula (D-II), R6 represents a divalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triple trap, piperidine, and pipe trap, and X2 represents a divalent value, respectively. The organic group, the plurality of X2 present may be the same or different), and the diamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amine group; represented by the following formula (D-ΙΠ) Monosubstituted phenylenediamine (except for the compounds represented by the above formula (Α)), R7-R8

(D-III) (In the formula (D-III), 'R7 represents a group selected from the group consisting of 〇_, _c〇〇_, _〇c〇, -NHCO-, _C0NH_ and _c〇^ 2 organic groups, r8 And a monovalent organic group having a group selected from the group consisting of a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group, or an alkyl group having 6 to 3 Å of a carbon atom) A diamine-based organooxane such as a compound represented by the following formula (D-IV), R9 R9 Η2Η〇Η2々+-f. One + 士|CH today % R9 R9 (in the formula (D - IV), r (D-IV) base, the existence of multiple R9 each 1~3 integer, q is 1~

R9 each represents an integer of 1 to 20 in which the number of carbon atoms may be the same, and a compound represented by the following formula (D\-26-201001029)

H2N h2n- ch3 CH (CH2)3 CH. ^CHs ch3 coo

(D-2) ch3 rH I /CH3 pH (CH2)3 CH,

Hehe. -O h2n^=

o—(-c2h4-o^

(D-4) ch3 (D-3) ^νη2 -s- (D-5) (where y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is -27 - 201001029 Integer of 1 to 5) ° The above aromatic monoamine, diamine or monosubstituted phenylenediamine having two -amino groups in the molecule and a nitrogen atom other than the primary amine group (but the above formula (A) represents The benzene ring ' contained in the compound represented by the above formula (D-1) to (D~5) may be optionally substituted with an alkyl group (preferably a methyl group) having 1 to 4 carbon atoms. In the synthesis of the polyamic acid which may be contained in the liquid crystal alignment agent of the present invention, the other diamine used in combination with the compound represented by the above formula (A) preferably contains p-phenylenediamine selected from the above diamines. 4,4'-diaminodiphenylmethane, 4,4,-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diamine Biphenyl, 2,2,-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,7-diaminopurine, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-amino) Phenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene diisopropylidene)diphenylamine, 4,4 '-(m-phenylene diisopropylidene) bisdiphenylamine, 1,4-cyclohexanediamine, 4,4,-methylenebis(cyclohexylamine), 1,4-bis(4- Aminophenoxy)benzene, 4,4,-bis(4-aminophenoxy)biphenyl, a compound represented by the above formula (D-1) to (D-5), 2,6-diamine Pyridine '3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, oxime-phenyl-3,6-di A compound represented by the following formula (D-6) in the compound represented by the above formula (D-1), the above formula (D), an aminocarbazole, an anthracene, an anthracene, a bis(4-aminophenyl)benzidine, or a compound represented by the above formula (D - I) - Compound represented by the following formula (D-7) in the compound represented by II), -28- 201001029

(D-6)

H2n-^)-(^-c3h6-^n-^-nh2 (D and twelve-2,4-diaminobenzene, pentadecyloxy-2 in the compound represented by the above formula (D-III)) ,4-diaminobenzene, hexadecanol-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodeca-2,5-diaminobenzene, pentadecane Oxy-2,5-diaminobenzene, hexadecanol-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene and the following formula ~(D-1 6) h2n —0 NH2 (D-8) -7)) alkoxy alkoxyl alkoxy (D-8)

-29- 201001029

-30- 201001029

The diamines selected from the group consisting of the respective compounds are at least - "other specific diamines"). The diamine for polyglycolic acid which may be contained in the liquid crystal alignment agent of the present invention preferably contains 1 mol of a compound represented by the formula (Α), more preferably 2 to 20 mol / relative to the entire diamine. 5 to 1 0 Moh ° / 〇. The diamine for polyphthalic acid which may be contained in the liquid crystal alignment agent of the present invention preferably further contains % of the other specific diamine as described above with respect to all the diamines, more preferably 50% to 80%. ~99 moles %. - (hereinafter referred to as f% or more in the above-mentioned synthesis), particularly preferably in the synthesis of 20 to 99 moles of 9 9 mole %, -31 - 201001029 [Synthesis of poly-proline] Liquid crystal alignment of the present invention The polyglycine which may be contained in the agent can be obtained by reacting the tetracarboxylic dianhydride with a diamine as described above. The ratio of the tetracarboxylic dianhydride to the diamine used in the synthesis reaction of the polyproline is more Preferably, the ratio of the acid anhydride group of the tetracarboxylic dianhydride to the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents of the ratio of the synthesis reaction of the poly-proline, in organic The solvent is preferably carried out at a temperature of -20 ° C, more preferably 0 to 100 ° C, and the reaction time is 1 to 240 hours, more preferably 2 to 12 hours. The solvent capable of dissolving the synthesized polylysine is not limited thereto, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylguanamine, and N,N-dimethylformamide. Aprotic polar solvent such as dimethyl hydrazine, r-butyrolactone, ureido, hexamethylphosphonium triamine; m-methyl xylenol a phenolic solvent such as phenol or a halogenated phenol. Further, the organic amount (a) (wherein the organic solvent is used in combination with the following poor solvent) is preferably a tetracarboxylic dianhydride and two The amount of the total amount of the amine compound relative to the total amount of the reaction solution (a + b) is 0.1 to 30% by weight. In the above organic solvent, it is also possible to use a combination of the polyglycine which is not precipitated. Examples of the poor solvent of valine are alcohols, ketones, ester ethers, halogenated hydrocarbons, hydrocarbons, etc. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, and ethylene. Alcohol diol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexyl radical , which is "150 good agent, special base ethylene tetracresol, solvent refers to it S (b) range class, scorpion, propyl ester, ketone, -32- 201001029 methyl acetate, ethyl acetate, butyl acetate Methyl methoxypropionate, ethyl ethoxypropionate, 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 diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloro Ethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, propionic acid Amyl ester, isoamyl isobutyrate, isoamyl ether, etc. In the synthesis of polylysine, when the organic solvent is used in combination with a poor solvent, the ratio of use of the poor solvent to the total of the organic solvent and the poor solvent The amount is preferably 50% by weight or less, more preferably 10% by weight or less. As described above, a reaction solution in which polylysine was dissolved was obtained. The reaction solution may be directly supplied to the liquid crystal alignment agent, or the polylysine contained in the reaction pants may be separated and supplied to the liquid crystal alignment agent, or the separated polyamic acid may be purified. The preparation of the liquid crystal alignment agent is further supplied. The separation of the polyamic acid can be carried out by adding the above reaction solution to a large amount of a poor solvent to obtain a precipitate, and then drying the precipitate under reduced pressure or by subjecting the reaction solution to distillation under reduced pressure using an evaporator. Further, the poly-proline may be purified by a method of re-dissolving the polyamic acid in an organic solvent once or several times and then precipitating it with a poor solvent or by distilling off under reduced pressure with an evaporator. [醯i-imidized polymer] The ruthenium iodide polymer which may be contained in the liquid crystal alignment agent of the present invention may be obtained by dehydrating a polyamine acid as described above by hydrazine imidization by -33-201001029 . As the tetracarboxylic dianhydride used in the synthesis of the quinone imidized polymer, at least one selected from the group consisting of alicyclic tetracarboxylic dianhydrides (hereinafter referred to as "specific tetracarboxylic dianhydride (2)) is preferably used. ") tetracarboxylic dianhydride. As the specific tetracarboxylic dianhydride (2), it is particularly preferably selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3&, 4,5,91>-hexahydro-5-( Tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione, 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-oxa Bicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3 -furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride And at least one of the group consisting of 4,9-dioxatricyclo[5.3.1_02,6]undecane-3,5,8,10-tetraone. The tetracarboxylic dianhydride used in the synthesis of the quinone imidized polymer which may be contained in the liquid crystal alignment agent of the present invention preferably contains 20 mol% or more of the specific tetracarboxylic acid as described above with respect to all of the tetracarboxylic dianhydride. The acid dianhydride (2) preferably contains 50 mol% or more, and particularly preferably contains 80 mol% or more. The diamine used in the synthesis of the above ruthenium iodide polymer may be the same as the diamine used in the synthesis of the above polyamic acid. The above ruthenium iodide polymer may be a complete ruthenium imide of a lysine structure in which the proline acid structure of the raw material polyamic acid has a dehydration ring closure, or a partial hydrazine ring structure, a guanine structure and a guanidine structure. Part of the quinone imine compound coexisting with the imine ring structure. -34- 201001029 The ruthenium iodide polymer contained in the liquid crystal alignment agent of the present invention preferably has a ruthenium amination ratio of 20% or more, particularly preferably 40 to 80%. The above-mentioned ruthenium amination ratio means the total amount of the structure of the guanidine imide polymer and the number of the quinone imine ring structure, and the ratio of the number of the quinone imine ring structure is expressed by a percentage. At this time, a part of the quinone ring may also be an isoindole ring. The hydrazine imidization rate can be determined by dissolving the ruthenium iodide polymer in a suitable deuterated solvent (for example, deuterated dimethyl hydrazine), using tetramethyl decane as a reference substance, and measuring 1 H- at room temperature. NMR was determined from the measurement results according to the following formula (1). Ruthenium amination rate (%) = (1 - AVa2x a )xl 00 (1) (In equation (1), A1 is the peak area derived from the NH matrix near the chemical shift of 10 ppm, and A2 is derived from other The peak area of the proton, α is the number of protons relative to the one sulfhydryl group in the ruthenium polymer precursor (polyglycolic acid), and the number of other protons). In order to synthesize the dehydration ring closure of the polyamidic acid of the above ruthenium iodide polymer, (i) by heating the polyamic acid, or (ii) by dissolving the polylysine in an organic solvent, to the solution A dehydrating agent and a dehydration ring-closing catalyst are added and heated as needed. The reaction temperature in the method of 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 501:, the dehydration ring-closure reaction cannot be sufficiently carried out. When the reaction temperature exceeds 200 ° C, the molecular weight of the obtained ruthenium-imided polymer may be lowered. The reaction time is preferably from 1 to 2 hours, more preferably from 2 to 8 hours. In the above (Π) method of adding a dehydrating agent to a polyamic acid solution and dehydrating the -35-201001029 ring 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 preferably 0.01 to 20 moles per 1 mole of the repeating unit of the polyglycolic acid. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closure catalyst is preferably 〇. 〜 1 to 10 mols, relative to the dehydrating agent used in 1 mol. Further, as the organic solvent used in the dehydration ring-closure reaction, an organic solvent exemplified as a solvent used in the synthesis of polyglycolic acid can be mentioned. Further, the reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C, and the reaction time is preferably from 1 to 24 hours, more preferably from 2 to 8 hours. The quinone imidized polymer obtained in the above method (i) may be directly supplied to a liquid crystal alignment agent, or may be obtained by refining the obtained quinone imidized polymer and then supplying it to a liquid crystal alignment agent. Further, in the above method (Π), a reaction solution containing a ruthenium iodide polymer is obtained. The reaction solution can be directly supplied to the liquid crystal alignment agent, or can be prepared by removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and can also be supplied to the liquid crystal alignment agent. The formulation of the alignment agent or the separation of the separated ruthenium-imiding polymer may be supplied to the liquid crystal alignment agent. The dehydrating agent and the dehydration ring-closing catalyst are removed from the reaction solution, and a method such as solvent replacement can be employed. The separation and purification of the ruthenium iodide polymer can be carried out in the same manner as described above for the separation and purification method of polyglycine. - Terminal-modified polymer - 36-201001029 The poly-proline or the quinone imidized polymer which may be contained in the liquid crystal alignment agent of the present invention may be a terminal-modified polymer having a molecular weight adjusted. By using the terminal-modified polymer, the coating performance and the like of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention. Such a terminal-modified polymer can be carried out by adding a molecular weight modifier to a polymerization reaction system during the synthesis of poly-proline. The molecular weight modifier may, for example, be a monoanhydride, a monoamine compound or a monoisocyanate compound. As the above-mentioned monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl amber may be mentioned. Anhydride, etc. Examples of the above monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and positive ten. Dialkylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine, and the like. The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 5 parts by weight or less based on the total amount of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyglycolic acid. - Solution Viscosity - Polylysine or oxime imidized polymer prepared as above, preferably having a solution concentration of 10% by weight, having a solution viscosity of 20 to 800 mPa.s, more preferably 30~ Solution viscosity of 500 mPa's. The solution viscosity (mPa.s) of the above polymer is a concentration of 10% by weight of a good solvent (for example, r-butyrolactone, N-methyl-2-pyrrolidone, etc.) of -37-201001029 using the polymer. The polymer solution was measured by an E-type rotary viscometer at 25 ° C. <Other Additives> The liquid crystal alignment film of the present invention contains at least one polymer selected from the group consisting of polylysine as described above and a ruthenium-based polymer obtained by dehydration ring closure as an essential component And may also contain other ingredients as needed. Examples of such other components include a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound"), a functional decane compound, and the like. Preferred examples of the epoxy group-containing 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 hydrazine, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6- Tetraglycidyl- 2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(indole, fluorene-diglycidylamino Methyl)cyclohexane, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl- 4,4'-diaminodiphenylmethane, anthracene, hydrazine-diglycidyl-benzylamine, hydrazine, hydrazine - diglycidyl-aminomethylcyclohexane or the like. The mixing ratio of these epoxy group-containing compounds is a total amount of 100 parts by weight of the polymer (refers to the total amount of the polylysine and its ruthenium iodide polymer contained in the liquid crystal alignment agent. The same applies hereinafter). It is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight. The functional decane compound may, for example, be 3-aminopropyl-38-201001029-based trimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2- Aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, Ν(2-aminoethyl)-3-aminopropylmethyl Dimethoxyoxane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-B Oxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxy Cyclodecane-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diaza Heteroalkyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl- 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane N-bis(oxyvinyl)-3-aminopropyltrimethoxydecane, N-bis(oxyvinyl)-3-aminopropyltriethoxydecane, and the like. The mixing ratio of the functional decane-containing compound is preferably 40 parts by weight or less based on 100 parts by weight of the total amount of the polymer. The liquid crystal alignment agent of the present invention is preferably at least one polymer selected from the group consisting of polylysine as described above and its quinone imidized polymer, and other additives optionally blended as needed. It is composed of an organic solvent. The organic solvent which can be used in the liquid crystal alignment agent of the present invention may, for example, be a solvent exemplified as a solvent used in the polyamido acid synthesis reaction. Further, it is also possible to appropriately select a poor solvent which can be used in combination as a synthetic reaction of polylysine. Preferred examples of such an organic solvent are -39-201001029, which can be exemplified by, for example, N-methyl-2-diazolone, 7-butane vinegar, buteneamine, hydrazine, hydrazine-dimethylformamidine. Amine, ν, Ν-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, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, and the like. They may be used singly or in combination of two or more. In the liquid crystal alignment agent of the present invention, the solid content concentration (the ratio of the total weight of the liquid crystal alignment agent other than the organic solvent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., preferably 1 to 10 The range of % by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to remove the organic solvent to form a coating film as a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too small. In the case where it is difficult to obtain a good liquid crystal alignment film: on the other hand, when the solid content concentration exceeds 10% by weight, a case where the thickness of the coating film is too thick and it is difficult to obtain a good liquid crystal alignment film is also caused, and a liquid crystal alignment agent appears. The viscosity increases, resulting in poor coating performance. The particularly preferable solid content concentration range differs depending on the method used to apply the liquid crystal alignment agent to the substrate. For example, when the spin coating method is employed, it is particularly preferably in the range of 1.5 to 4.5% by weight. When the printing method is employed, it is particularly preferable to make the solid content concentration in the range of 3 to 9 wt%, so that the viscosity of the solution can be lowered from -40 to 201001029 in the range of 12 to 50 mPa.s. When the ink jet method is employed, it is preferable to set the solid content concentration to a range of 1 to 5 % by weight, so that the solution viscosity can be made to fall within the range of 3 to 15 mPa 's. <Liquid Crystal Display Element> The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention as described above. The liquid crystal display element of the present invention can be produced, for example, by the following method. (1) The liquid crystal alignment agent of the present invention is applied onto one surface of a substrate provided with a patterned transparent conductive film by, for example, a roll coating method, a spin coating method, a printing method, an inkjet method, or the like, followed by heat coating. The coated surface forms a coating film. Here, as the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether mill, polycarbonate, and alicyclic poly A transparent substrate made of plastic such as olefin. As the transparent conductive film provided on the surface of the substrate, an NESA film made of tin oxide (Sn02) (registered trademark of PPG, USA), an ITO film made of indium oxide-tin oxide (In2〇3 - Sn〇2), or the like can be used. The patterned transparent conductive film can be produced by, for example, forming a desired pattern by photolithography after forming a non-patterned transparent conductive film on a substrate. When a transparent conductive film is formed, light having a desired pattern is used. The cover 'a method of directly forming a pattern-shaped transparent conductive film. When the liquid crystal alignment agent is applied, in order to further improve the adhesion between the surface of the substrate and the resin film, for example, a functional decane compound, a functional titanium compound or the like may be applied in advance. After the application of the liquid crystal alignment agent, preheating (prebaking) is preferably carried out for the purpose of preventing the liquid of the applied alignment agent from sagging. The prebaking temperature is -41 - 201001029, preferably 30 to 200 ° C, more preferably 40 to 150. Hey, Tejia 40~100. (: The prebaking time is preferably from 0.1 to 10 minutes, more preferably from 0.5 to 3 minutes. Then, the firing (post-baking) step is carried out for the purpose of completely removing the solvent, etc. The post-baking temperature is preferably from 80 to 300. °C, more preferably 120 to 250 ° C. The post-coating time is preferably from 1 to 180 minutes, more preferably from 10 to 120 minutes. The liquid crystal alignment agent of the present invention is formed into an alignment film by removing an organic solvent after coating. Coating film, and when the polymer contained in the liquid crystal alignment agent of the present invention is poly-proline or a ruthenium-imided polymer having both a quinone ring structure and a proline structure, it is also possible to form a coating. The film is further subjected to a dehydration ring-closure reaction by further heating to form a further yttrium-imided coating film. The thickness of the coating film formed by the ruthenium is preferably 0.001 to Ιμηη, more preferably 0.005 to 0.5 μm. (2) Two substrates in which the liquid crystal alignment film is formed as described above are prefabricated, and liquid crystal cells are produced by arranging liquid crystal between the two substrates. The production of the liquid crystal cells includes, for example, the following two methods. The first method is a previously known method. First, pass The two substrates are disposed opposite to each other through the gap (cell gap), and the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together with a sealant, and are filled into the interstitial space surrounded by the surface of the substrate and the sealant. After the liquid crystal, the liquid crystal cell is obtained by closing the injection hole. The second method is a method called OneDF (One Dr〇p Fill) method, on one of the two substrates forming the liquid crystal alignment film. Applying, for example, an ultraviolet curable sealant material to the predetermined portion, and then dropping the liquid crystal on the liquid crystal alignment film surface, bonding the other substrate, and causing the liquid crystal alignment film to face the '42-201001029' and then irradiating the entire surface of the substrate with ultraviolet rays. The liquid crystal cell can be obtained by curing the sealant. The liquid crystal alignment agent of the present invention can form a liquid crystal alignment film excellent in vertical alignment, and thus can be manufactured even when a VA type liquid crystal display element is manufactured by the 〇Df method. There is no advantage of the liquid crystal display element having uneven 〇df. In any case, it is necessary to heat the liquid crystal cell to the liquid crystal used. After the temperature of the isotropic phase, the temperature is slowly cooled to room temperature to remove the flow alignment at the time of injection. Then, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. For the agent, for example, an epoxy resin containing an alumina ball as a curing agent and a separator can be used. Examples of the liquid crystal can be a nematic liquid crystal or a dish-shaped liquid crystal. Among them, a nematic liquid crystal can be used, for example, Schiff base liquid crystal, oxidized azo liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane a hexacyclic liquid crystal, a bicyclooctane liquid crystal, a cubic liquid crystal, etc. Further, cholesteric liquid crystal such as cholesteryl cholesteryl, cholesteryl phthalate or cholesteryl carbonate may be further added to these liquid crystals or may be commercially available. A chiral agent such as "C-15" or "CB-15" (manufactured by MERCK Co., Ltd.) is used. Further, a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutylcinnamate may also be used. Further, as a polarizing plate to be bonded to the outer surface of the liquid crystal, a polarizing film called a "H film" obtained by stretching and dispersing polyvinyl alcohol at the same time as an "H film" may be exemplified by a polarizing film sandwiched between a cellulose acetate protective film. A polarizing plate or a polarizing plate made of a ruthenium film itself. [Examples] Example 1 (Synthesis of a compound represented by the above formula (Α-10)) The compound represented by the above formula (Α-10) (hereinafter referred to as "compound (Α-10)") is synthesized according to the following Scheme 1 synthesis.

Synthesis of Route 1 (1) Synthesis of Compound (Α-10a) In a 5 L three-necked flask equipped with a stirrer, a nitrogen introduction tube and a thermometer, 389 g /3-cholestanol, 201 g of succinic anhydride, 15 g of N, N- -44- 201001029 Dimethylaminopyridine, 170 ml of triethylamine and 2 L of ethyl acetate were reacted at 90 ° C for 8 hours. After the completion of the reaction, the ethyl acetate was distilled off under reduced pressure, and 2 L of chloroform was added. The organic layer was washed three times with dilute hydrochloric acid and then four times with water and dried over magnesium sulfate. The organic layer was concentrated, and the resulting precipitate was filtered, and solvent was removed to yield 223 g of Compound (A-10a) as a white powder. Further, the synthesis of the compound (A-10a) can be repeated as needed to ensure the necessary amount of the following examples. (2) Synthesis of Compound (A-10b) In a 5 L three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 223 g of the above synthesized compound (A-10a), 108 g of 3,5-dinitrobenzene were added. Toluene chloride, 207 g of potassium carbonate, 150 g of sodium iodide and 1 500 ml of N,N-dimethylformamide were reacted at 60 ° C for 8 hours. After completion of the reaction, 3 L of chloroform was added, and the obtained organic layer was washed three times with water and then dried over magnesium sulfate. The organic layer was concentrated, and the precipitated solid was recovered, which was washed with ethanol to obtain 280 g of a pale yellow powder of compound (A - 10b). (3) Synthesis of Compound (A-10) To a 5 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 200 g of the above synthesized compound (A-10b), 680 g of tin chloride dihydrate, and 2 were added. L ethyl acetate was reacted under reflux for 4 hours. After the reaction was completed, the reaction mixture was washed successively with an aqueous potassium fluoride solution and water. The organic layer was dried over magnesium sulfate, and then concentrated, and then recrystallised from ethanol to give pale crystals of the compound (A-10). Example 2 (Synthesis of a compound represented by the above formula (A-18)) A compound represented by the above formula (A-18) (hereinafter referred to as "compound (A - 45-201001029)

H0-C2H4-0H

Synthesis of Compound (A-18a) on the Synthetic Route To a 1 L three-necked flask equipped with a dropping funnel, a thermometer and a nitrogen inlet tube, '117 g /3-cholesterol, 3.7 g of N,N-dimethyl The amino group was steep, 4 〇 0 ml of tetrahydrofuran and 55 ml of triethylamine were cooled with ice. Here, a solution of 3 ml of methanesulfonate chloride and 100 ml of tetrahydrofuran added to the dropping funnel was added dropwise over 1 hour, and the mixture was stirred at room temperature for 3 hours to carry out a reaction. -46 - 201001029 After the reaction was completed, 500 ml of ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed three times with water, and then dried over magnesium sulfate. Then, after concentrating the organic layer to about 300 ml, it was dispersed in 600 ml of ethanol, and the resulting white precipitate was collected by filtration and dried to obtain 117 g of a compound (A-1 8 a) 〇(2) compound (A- Synthesis of 1 8b) 46.7 g of the compound (A-18a) obtained above, 155 g of ethylene glycol and 200 ml of 1,4-dioxane were mixed, and the mixture was stirred under heating at 100 ° C for 20 hours to carry out a reaction. After the completion of the reaction, 500 ml of water and 500 ml of chloroform were added to the reaction mixture, and the mixture was stirred well, and the organic layer was separated, washed twice with 500 ml of aqueous sodium hydrogen carbonate, and twice with 500 ml of water. The organic layer was dried over magnesium sulfate, filtered and concentrated, and then, then, 500 ml of ethanol, and stirred at 〇 ° C, and allowed to stand overnight. After filtering off the white precipitate formed after standing, the filtrate was concentrated to remove the solvent to obtain 26.3 g of the crude product viscous liquid of the compound (A-18b). (3) Synthesis of compound (A-1 8c) A mixture of 26.3 g of the above compound (A-18b) and 14 g of 3,5-dinitrobenzimid chloride is mixed in 300 ml of tetrahydrofuran solvent, 〇° Stir for 10 minutes at C. After 8.4 ml of triethylamine was added dropwise thereto over 10 minutes, the reaction was carried out by stirring at room temperature for 3 hours. After completion of the reaction, the reaction solution was concentrated, and after adding 500 ml of chloroform, it was washed four times with 300 ml of water. The organic layer was dehydrated with magnesium sulfate, dried and concentrated to recover a viscous liquid. This viscous liquid was purified by column chromatography (purification solvent: chloroform) using a column to obtain 20 g of a pale yellow oily compound (A - 18c). -47- 201001029 (4) Synthesis of compound (A-18) Under a nitrogen atmosphere, 20 g of the above obtained (A-18c) and 78 g of tin(II) chloride dihydrate were mixed at 305 ml. The mixture was heated and stirred under reflux for 4 hours in an ethyl acetate solvent. Then, 400 ml of a 2 mol/L potassium fluoride aqueous solution was added and stirred, and the precipitated salt was filtered off. The organic layer was washed once with 400 ml of 2 mol/L potassium fluoride, washed three times with 400 ml of water, dehydrated with magnesium sulfate, filtered and concentrated to give a pale yellow powder. The obtained powder was purified by column chromatography (solvent: chloroform/ethanol = 95/5 (volume ratio)) to obtain 14 g of a white powder (A-18). Example 3 (Synthesis of Compound (A-24)) The compound represented by the above formula (A-24) (hereinafter referred to as "compound (A-24)") was synthesized according to the following Scheme 3. -48- 201001029

(A-lOa)

Coo ch2 ch2 COOH

BH3/THF

0 2 2 2 ο Η Η Η Η c\ cl cl cl o

02N o2n

COCI

0 2 2 2 ο Η Η H

(A-24b)

2 N (A24c) o2n

Synthesis of Route 3 (1) Synthesis of Compound (A - 2 4 b ) To a 500 ml three-necked flask equipped with a dropping funnel, a nitrogen inlet tube and a thermometer, 24 g of the compound (A-10a) and 150 ml of tetrahydrofuran were added. , cooled to _1 8 ° C. After 55 ml of a borane-tetrahydrofuran complex/tetrahydrofuran solution having a concentration of 0.9 mol/L was added dropwise thereto over 30 minutes, the mixture was reacted at room temperature for -16-201001029 for 16 hours. After the reaction was completed, the reaction mixture was cooled with ice, and 30 ml of water was slowly added thereto, and then ethyl acetate was added thereto, and the obtained organic layer was washed twice with a saturated aqueous solution of sodium hydrogencarbonate, and washed with water. After that, the organic layer was dried over magnesium sulfate, concentrated and dried to give a white powder of 17 g of compound (A-24b). (2) Synthesis of (A _ 24c) In a 500 ml three-necked flask equipped with a dropping funnel, a nitrogen introduction tube and a thermometer, 15 g of the compound (A-24b) obtained above, 4.5 ml of triethylamine and 1 00 were added. Ml tetrahydrofuran, cooled with ice. Here, 7.4 g of 3,5-dinitrobenzhydryl chloride dissolved in 50 ml of tetrahydrofuran was added dropwise with a dropping funnel over 1 hour, and the mixture was further reacted at room temperature for 2 hours. After the completion of the reaction, ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed twice with aqueous sodium hydrogen carbonate solution and then washed three times with water, and then the organic layer was dried over magnesium sulfate, then concentrated and dried Recrystallization in ethanol gave 10 g of the compound (A-24c). (3) Synthesis of compound (A _ 24) In a 1 L three-necked flask equipped with a reflux tube, a nitrogen introduction tube, and a thermometer, (A-24c), 95 mg, 5 wt%/〇 Carbon powder, 120 mmol of ethanol, 60 mmol of tetrahydrofuran, and 3·8 m of monohydrate monohydrate were stirred at room temperature for 1 hour, and then stirred at 70 ° C for 1 hour to carry out a reaction. After the completion of the reaction, the reaction mixture was filtered through Celite, and ethyl acetate (300 ml) was added to the obtained filtrate, and the obtained organic layer was washed three times with water, then concentrated and dried. The dried product was recrystallized from ethanol to obtain 7 g of a compound (A-24). -50-201001029 Example 4 The compound represented by the above formula (A-22) (hereinafter referred to as "compound (A-22)") was synthesized according to the following Synthesis Scheme 4.

Pd(PPh3)4

00H2H28 C-CICIC

H2n

(A-22) NH, Synthesis Scheme 4 (1) Synthesis of Compound (A-22b) 47 g of the compound (A-10a) and 28 g of 3,5-(N,N-diallyl)diaminophenol were mixed. Stir in 400 ml of tetrahydrofuran at 0 °C. After adding 25 g of N,N-dicyclohexylcarbodiimide and 2.4 g of N,N-dimethylaminopyridine to -51 - 201001029, the mixture was stirred at 25 ° C for 4 hours. Then, chloroform was added, and the organic layer was washed with water and then concentrated. The concentrate was purified by column chromatography (solvent: hexane: ethyl acetate = 8:1 (volume ratio)) to obtain a crude product of the compound (A - 22b > (2) Compound (A) - 22) Synthesis of 38g of the above (August 2213), 2381,3-dimethylbarbituric acid and l.lg tetrakis(triphenylphosphine) are mixed in 200 ml of dichlorocarbyl The reaction was carried out by stirring at 35 ° C for 7 hours. After the reaction was completed, the reaction mixture was washed successively with a saturated aqueous sodium hydrogen carbonate solution and water, and then the organic layer was concentrated to remove the solvent to give a brown viscous liquid. Column chromatography (purification solvent: chloroform: ethanol = 95:5 (volume ratio)) was purified, and then recrystallized from ethanol to obtain 13 g of a pale yellow powder of the compound (A-22). The compound represented by the above formula (A-26) (hereinafter referred to as "compound (A-2 6)") is synthesized according to the following Synthesis Scheme 5. -52 - 201001029

COO \ CH2

Ch2 I z ch2 f ^ COOH (A — 26a)

Synthesis of SnCI2 Synthetic Route 5 (1) Compound (A-26a) In a 10 L three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 778 g/3-cholalkanol, 458 g of glutaric anhydride, 30 g of N were added. , N-dimethylaminopyridine, 340 ml of triethylamine and 4 L of ethyl acetate, at -90-201001029 at 90 ° C should be 8 hours. After completion of the reaction, ethyl acetate was distilled off under reduced pressure, and 2 L of chloroform was added. The organic layer was washed three times with dilute hydrochloric acid and then four times with water and dried over magnesium sulfate. The organic layer was concentrated, and the resulting precipitate was filtered, and solvent was removed to give a white powder of 49 g of compound (A-26a). (2) Synthesis of Compound (A-26b) To a 5 L three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 254 g of the above synthesized compound (A-26a), 108 g of 3,5-dinitrobenzene were added. Toluene chloride, 207 g of potassium carbonate, 150 g of sodium iodide and 1500 ml of N,N-dimethylformamide were reacted at 60 ° C for 8 hours. After completion of the reaction, 3 L of chloroform was added, and the obtained organic layer was washed three times with water and then dried over magnesium sulfate. The organic layer was concentrated, and the precipitated solid was recovered, which was washed with ethanol to obtain 305 g of a pale yellow powder of compound (A-26b). (3) Synthesis of Compound (A-26) To a 5 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, '228 g of the above synthesized compound (A-26b), 680 g of tin chloride dihydrate, and 2 L were added. Ethyl acetate was reacted under reflux for 4 hours. After the reaction was completed, the reaction mixture was washed successively with an aqueous potassium fluoride solution and water. The organic layer was dried over magnesium sulfate, and then concentrated, and then recrystallised from ethanol to give 60 g of compound (A-26) as pale yellow crystals. Example 6 (Synthesis Example 1 of a ruthenium iodide polymer) 6 5 g (TCA) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride, and p-benzene as a diamine compound 31 g of diamine and 9.2 g of the compound (A-10) synthesized in the above Example 1 (relative to 1 molar equivalent of TCA, equivalent to 0.05 molar equivalent) were dissolved in 420 g of N-methyl-2-pyrrolidone, at - 54-201001029 Reaction at 6 ° C for 6 hours gave a solution containing 20% by weight of polyglycine. The solution viscosity of the polyaminic acid solution was 4,700 mPa_s. Then, 980 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 23 g of pyridine and 30 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone (in this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system. The same applies hereinafter). A solution containing 20% by weight of a ruthenium iodide polymer (PI-1) having a ruthenium iodide ratio of about 49% was obtained. A small amount of the solution was taken and diluted with N-methyl-2-pyrrolidone to a solution having a polymer concentration of 6.0% by weight, and the solution viscosity was determined to be 2 2 m P a s. Example 7 (Synthesis Example 2 of a ruthenium iodide polymer) 60 g (TCA) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride as a diamine compound 27 g of the amine and 17 g of the compound (A-10) synthesized in the above Example 1 (corresponding to 1 molar equivalent of TCA, equivalent to 0.1 molar equivalent) were dissolved in 420 g of N-methyl-2-pyrrolidone at 60 ° C. The reaction was carried out for 6 hours to obtain a solution containing 20% by weight of polyamic acid. The solution viscosity of the polyaminic acid solution was 3700 mPa_s. Then, 980 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 21 g of dioxin and 28 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain a ruthenium iodide polymer (PI-containing 20% by weight of ruthenium iodide ratio of about 50%). 2) solution. A small amount of this solution was taken and diluted with N-methyl-2-pyrrolidone to give a solution having a concentration of -55 to 201001029 to 6.0% by weight, and the solution viscosity was determined to be 20 mPa, s. Example 8 (Synthesis Example 3 of a ruthenium iodide polymer) 2,3 g (TCA) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride, and p-benzene as a diamine compound 9.0 g of diamine and 5.3 g of compound (A-18) synthesized in the above Example 2 (relative to 1 molar equivalent of TCA, equivalent to 0.1 molar equivalent) were dissolved in 140 g of N-methyl-2-pyrrolidone at 60 The reaction was carried out at ° C for 6 hours to obtain a solution containing 20% by weight of polyamic acid. The solution viscosity of the polyaminic acid solution is 3500 mPai» Then, 3 25 g of N-methyl-2-pyrrolidone is added to the obtained polyamic acid solution, and 15 g of pyridine and 19 g of acetic anhydride are further added at 110 ° C. A 4 hour dehydration ring closure reaction was carried out. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain a ruthenium iodide polymer (PI-) containing 20% by weight of a ruthenium iodide ratio of about 78%. 3) solution. A small amount of this solution was taken and diluted with N-methyl-2-pyrrolidone to a solution having a polymer concentration of 6.0% by weight, and the solution viscosity was measured to be 21 mPa's. Example 9 (Synthesis Example 4 of a ruthenium iodide polymer) 2,3,5-tricarboxycyclopentylacetic acid dianhydride 20 g (TCA) as a tetracarboxylic dianhydride and p-phenylene as a diamine compound 8.9 g of the amine and 5.6 g of the compound (A-24) synthesized in the above Example 3 (relative to 1 molar equivalent of TCA, equivalent to 0.1 molar equivalent) were dissolved in 140 g of N-methyl-2-pyrrolidone at 6 The reaction was carried out at 0 ° C for 6 hours to obtain a solution containing 20% by weight of polyamic acid. The solution viscosity of the polyaminic acid solution was 3600 mPa_s. Then, 3 2 5 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 14 g of pyridine and 19 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out at 4 °C to 201001029 hours at ll °C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain a ruthenium imidized polymer containing 20% by weight of a ruthenium iodide ratio of about 80%. (PI-4) solution. A small amount of this solution was taken and diluted with N-methyl-2-pyrrolidone to a solution having a polymer concentration of 6.0% by weight, and the solution viscosity was determined to be 22 mPa's. Example 10 (Synthesis Example 5 of a ruthenium iodide polymer) 2,3,5·tricarboxycyclopentylacetic acid dianhydride 20 g (TCA) as a tetracarboxylic dianhydride, and p-benzene as a diamine compound 8.9 g of diamine and 5.5 g of the compound (A-22) synthesized in the above Example 4 (corresponding to 1 molar equivalent of TCA' equivalent to 〇_1 molar equivalent) were dissolved in 140 g of N-methyl-2-pyrrolidone The reaction was carried out at 60 ° C for 6 hours to obtain a solution containing 20% by weight of polyamic acid. The solution of the polyaminic acid solution has a viscosity of 3 700 mPa·s. Then, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and then 14 g of pyridine and 19 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain a ruthenium iodide polymer (PI) containing 20% by weight of ruthenium iodide ratio of about 79%. - 5) solution. A small amount of this solution was taken and diluted with N-methyl-2-pyrrolidone to a solution having a polymer concentration of 6.0% by weight, and the solution viscosity was determined to be 22 mPa·s. Example 1 1 (Synthesis Example 6 of a ruthenium iodide polymer) 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 20 g (TCA) as a tetracarboxylic dianhydride, and p-benzene as a diamine compound 89 g of diamine and 5-8 g of the compound (A-26) synthesized in the above Example 5 (relative to 1 mol equivalent of TCA, equivalent to 0.1 mol equivalent) are dissolved in 14 g of N-methyl-2-pyrrolidone. -57-201001029 6 hours at 0 ° C to obtain a solution containing 20% by weight of poly-proline. The solution viscosity of the polyamic acid solution was 3 400 mP a·s. Then, 3 25 g of N-methyl-2-11 pyrrolidone was added to the obtained polyamic acid solution, and 14 g of pyridine and 19 g of acetic anhydride were further added, and dehydration ring closure reaction was carried out at 1 l ° C for 4 hours. . After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain a ruthenium iodide polymer (PI-containing 20% by weight of ruthenium iodide ratio of about 78%). 6) solution. A small amount of this solution was taken and diluted with N-methyl-2-pyrrolidone to a solution having a polymer concentration of 6.0% by weight, and the solution viscosity was measured to be 21 mPa's. Example 12 (Synthesis Example 7 of a ruthenium iodide polymer) 65 g (TCA) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride, and p-phenylene as a diamine compound Amine 31 g and 9.2 g of the compound (A-10) synthesized in the above Example 1 (relative to 1 molar equivalent of TCA, equivalent to 0.05 molar equivalent) were dissolved in 420 g of N-methyl-2-pyrrolidone at 60 ° The reaction was carried out for 6 hours at C to obtain a solution containing 20% by weight of polyamic acid. The solution viscosity of the polyaminic acid solution was 4700 mPa*s. Then, 980 g of N-methyl-2-3⁄4-rrolidone was added to the obtained polyamic acid solution, and 46 g of pyridine and 60 g of acetic anhydride were further added thereto at 1 1 Torr. <: A 4 hour dehydration ring closure reaction was carried out. After the dehydration ring closure reaction, the solvent in the system is subjected to solvent replacement with a new N-methyl-2-pyrrolidone to obtain a ruthenium iodide polymer containing 2% by weight of ruthenium iodide ratio of about 78% ( p ! — 7) solution. A small amount of this solution was diluted with N-methyl-2-pyrrolidone to a solution having a polymer concentration of 6.0% by weight, and the solution viscosity was determined to be 22 mpa.s. Example 13 (Synthesis Example 8 of ruthenium iodide polymer) -58- 201001029 2,3,5-tricarboxycyclopentylacetic acid dianhydride 60 g (TCA) as tetracarboxylic dianhydride and as a diamine compound 27 g of p-phenylenediamine and 7 g of the compound (A-1) synthesized in the above Example 1 (relative to 1 mol equivalent of TCA, equivalent to 0.1 mol equivalent) were dissolved in 42 g of N-methyl-2- The pyrrolidone was reacted at 60 ° C for 6 hours to obtain a solution containing 20% by weight of polyglycine. The solution viscosity of the polyaminic acid solution was 3700 mPa.s. Then, 980 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 42 g of pyridine and 56 g of acetic anhydride were further added thereto at 11 Torr. (: 4 hours of dehydration ring closure reaction. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain a 20% by weight hydrazine imidization rate of about 80 A solution of % ruthenium iodide polymer (PI-8). A small amount of this solution was diluted with N-methyl-2-pyrrolidone to a solution having a polymer concentration of 6.0% by weight, and the solution viscosity was determined to be 20 mPa. s. Comparative Synthesis Example 1 (Comparative Synthesis Example of Europium Amidated Polymer) 29 g (TCA) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride, as a diamine compound P-phenylenediamine 11g and the following formula (R-1)

The compound represented by 9.9 g (relative to 1 molar equivalent of TCA, equivalent to 0.2 mole equivalent) was dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours to obtain 20% by weight of poly A solution of proline. The solution of the polyaminic acid solution has a viscosity of 3 500 mPa_s. -59-201001029 Then, 500 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 1 g of pyridine and 13 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours at ll °C. After the dehydration ring closure reaction, 'solvent substitution of the solvent in the system with a new N-methyl-2-pyrrolidone' yielded a ruthenium-imided polymer containing 20% by weight of a ruthenium iodide ratio of about 49% (B- 1) solution. A small amount of this solution was taken and diluted with N-methyl-2-pyrrolidone to a solution having a polymer concentration of 6.0% by weight, and the solution viscosity was determined to be 19 mPai. Example 1 4 (Preparation and evaluation of liquid crystal alignment agent) <Preparation of liquid crystal alignment agent> (1) Preparation of liquid crystal alignment agent for evaluation of printability The ruthenium-containing imidized polymer obtained in the above Example 6 (PI - 1) solution was added with N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) to form a solvent composition of NMP: BC = 50: 50 (weight ratio), solid content concentration of 6.0 % by weight solution. This solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent for evaluation of printability. (2) Preparation of liquid crystal alignment agent for producing liquid crystal display element To the solution of the ruthenium imidized polymer (ΡΙ-1) obtained in the above Example 6, Ν-methyl-2-pyrrolidone was added. (ΝΜΡ) and butyl cellosolve (BC), a solvent having a composition of NMP: BC = 50:50 (weight ratio) and a solid content concentration of 4% by weight. This solution was filtered through a filter having a pore size of μηη to prepare a liquid crystal alignment agent for producing a liquid crystal display element. <Evaluation of Liquid Crystal Aligning Agent> Using any of these liquid crystal alignment agents, evaluation was carried out by the following method. The evaluation results are shown in Table 1. -60-201001029 (1) Evaluation of the printability The liquid crystal alignment agent for the printability evaluation prepared above was applied by a liquid crystal alignment film printer (manufactured by Nippon Photo Printing Co., Ltd.) under the following conditions. The transparent electrode surface of the glass substrate of the transparent electrode was heated at 80 ° C for 1 minute (prebaking) to remove the solvent, and then heated at 2 Torr (TC for 60 minutes (post-baking) to form a coating having a film thickness of 60 nm. The film was visually observed to investigate the presence or absence of wrinkles and uneven coating. When uneven printing and pinholes were not observed, the printability was evaluated as "good". (2) Evaluation of vertical alignment control force was used. The liquid crystal alignment agent for producing a liquid crystal display element prepared above was applied onto an IT 0 film transparent conductive film provided on one surface of a glass substrate having a thickness of 1 mm by a spin coater, and heated at 80 ° C for 1 minute (prebaking) After removing the solvent, it was further heated at 200 ° C for 60 minutes to form a coating film having a film thickness of 0.08 μm. Then, using a sander equipped with a roller wound with a rayon cloth, the table was moved at a roller rotation speed of 400 rpm. speed The coating film was sanded at a thickness of 0.4 mm for 3 cm/sec, and then ultrasonically washed in ultrapure water for 10 minutes, followed by drying in a clean oven at 100 °C. In a minute, a substrate having a liquid crystal alignment film subjected to a rubbing treatment was produced, and this operation was repeated to produce a pair of (two pieces) substrates having a liquid crystal alignment film subjected to a rubbing treatment. Then, the pair of substrates had liquid crystals. On each outer edge of the alignment film, an epoxy resin adhesive having an alumina ball of 5.5 μm in diameter is applied, and then the liquid crystal alignment film surface is repeatedly pressed and pressed in parallel, and the adhesive is cured. Then, The liquid crystal injection port is filled with a nematic liquid-61 - 201001029 crystal (MLC-660 8 manufactured by MERCK) between the pair of substrates, and the liquid crystal injection port is sealed with an acrylic photocurable adhesive to produce vertical alignment control force. The liquid crystal cell for evaluation. When the pretilt angle measured by the crystal rotation angle method is 86° or more, the vertical alignment control force is evaluated as “good”, and when it is less than 86°, vertical In addition, it is known that the polishing process performed as described above has a reduction effect on the vertical alignment control force of the liquid crystal alignment film. Therefore, even if the polishing process is performed, the pretilt angle of 8 6° or more is displayed, and the vertical direction is vertical. The alignment control force can be said to be extremely excellent, and the liquid crystal alignment agent capable of obtaining such a result can be known from the experience, even when it is used for manufacturing a VA type liquid crystal display element by the ODF method. (3) Voltage The evaluation of the retention ratio was carried out in the same manner as in the above (2) evaluation of the vertical alignment control force except that the polishing treatment was not performed. At 60 ° C, 5 V was applied to the liquid crystal cell in a time span of 16.7 msec. The voltage and voltage application time was 60 microseconds, and then the voltage holding ratio from the voltage release to 16.7 milliseconds was measured. (4) Evaluation of heat resistance (alternative evaluation of long-term continuous drive resistance) For the liquid crystal cell manufactured in the same manner as described above, first, a voltage of 5 V was applied for a time span of 167 msec, and the voltage application time was 60 μm. Seconds, then the voltage holding ratio from the voltage release to 167 milliseconds is measured. The number at this time is taken as the initial voltage holding ratio (VHRBF). After the VHRBF was measured, the liquid crystal display element was placed in an oven at 100 ° C, and -60 - 201001029 was applied for 1 hour of thermal stress. Then, after the liquid crystal display element was cooled to room temperature in the chamber, the voltage holding ratio (VHRaf) after the application of the thermal stress was measured under the measurement conditions of the initial voltage holding ratio. The voltage change rate (Δ VHR) before and after the application of the thermal stress is obtained by the following formula (2), and Δ VHR (%) = ((VHRbf - VHRaf) - VHRbf) x 1 00. The rate of change is less than 5%. The heat resistance was evaluated as "good 5% or more, and heat resistance was evaluated as "poor". The evaluation results are shown in Table 1. Example 1 5 to 2 3. Comparative Example 1 The composition of the liquid crystal alignment agent was as shown in Table 1, respectively. In the same manner as in Example 1 4 described above, two types of liquid crystal alignment agents were prepared in the same manner, and in Examples 15 and 1 7 to 23, after a predetermined solvent was dissolved in the polymer, the polymer was further added to 100 parts by weight of the polymer. 20 parts by weight of the epoxy compound represented by the following formula (E-1). The same holding ratio of the temperature (2) ” is added to the evaluation liquid.

The respective results are listed in Table 1. -63-201001029 Table 1 Liquid crystal alignment agent Liquid crystal cell polymer type Epoxy compound type Printability Vertical alignment control force Voltage retention ratio (%) Heat resistance Example 14 PI-1 - Good good 99 Good example 15 PI-1 E-1 Good and good 99 Good example 16 PI-2 - Good good 99 Good example 17 PI-2 E-1 Good good 99 Good example 18 PI-3 E-1 Good good 99 Good example 19 PI-4 E-1 Good and good 99 Good example 20 PI-5 E-1 Good good 99 Good example 21 PI-6 E-1 Good good 99 Good example 22 PI-7 E-1 Good good 99 Good example 23 PI —8 E-1 Good and good 99 Good comparative example 1 B-1 — Good bad 98 Bad [Simplified illustration] 〇j\w [Description of main component symbols] te . -64-

Claims (1)

201001029 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by comprising at least one polymer selected from the group consisting of polyamic acid and its ruthenium iodide polymer. The carboxylic acid di野 is prepared by reacting a monoamine containing a compound represented by the following formula (A), (A) (In the formula (A), R1 and R111 are each independently an ether bond, a thioether bond, a vinegar bond or a thioester bond, wherein the direction of the ester bond and the thioester bond is not limited, and R11 is a sub or a carbon number. The alkylene group is 2 to 10, and the RIV is a single bond, a methylene group or an ethylene group, and X is a monovalent organic group having a steroid skeleton having a carbon number of 17 to 40. 2. The liquid crystal alignment agent of the invention of claim 3, wherein the X group of the above formula (Α)Φ is a group represented by the following formula (X-1 - 1) or (Χ-2 - 1) - 65- 201001029 The connection key is represented by the above formula. A liquid crystal display element characterized by having a liquid crystal alignment film formed of the liquid crystal alignment agent of claim 1 or 2. A polyaminic acid or a quinone imidized polymer thereof, which is obtained by reacting four diamines containing a compound represented by the above formula (A) to obtain a compound of the formula (A). . Patent scope: carboxylic acid dianhydride -66 - 201001029 IV. Designation of representative drawings: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: te 〇 j\w 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: Nh2 (A)