TW200912485A - Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display device - Google Patents

Abstract

The present invention discloses a liquid crystal orientation agent, which is composed of polyamide acid obtained from cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1,4-diaminocyclohexane, bicyclo[2.2,1]heptane-2,6-dimethanamine, 1,3-bis(aminomethylcyclohexane), isophorone or alkyl substitute of the diamine, and at least a part of tetracarboxylic dianhydride and diamine compound, its imidization polymer or a mixture of other imidization polymers, wherein the bonding unit of the amide acid has a rate of 5-80%. The present invention provides a liquid crystal orientation agent with high voltage maintainability and low cauterization feature.

Description

200912485 IX. Description of the Invention [Technical Field] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element. More specifically, the liquid crystal alignment agent obtained by the liquid crystal alignment agent and the liquid crystal display element having the film are excellent in the high voltage holding ratio regardless of the use temperature. [Prior Art] Conventionally, a TN type liquid crystal display element having a TN (T wisted N ematic ) type liquid crystal cell is known, and the element is formed between two substrates which form a liquid crystal alignment film on the surface through a transparent conductive film. The dielectric anisotropic nematic liquid crystal layer becomes a unit cell of 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, there is also a STN (Super Twisted Nematic) type liquid crystal display element in which the long axis of the liquid crystal molecules is continuously twisted by more than 180 degrees between the substrates by adding a palm powder, and the birefringence thus generated is utilized. effect. Furthermore, a guest-host reflective liquid crystal display device has recently been developed in which a nematic liquid crystal layer or a spiral axis having a vertical alignment state with negative dielectric anisotropy is formed in parallel with the substrate normal. A cholesteric liquid crystal layer in a state in which a pigment is added. The liquid crystal alignment in these liquid crystal display elements is usually expressed by a liquid crystal alignment film to which a rubbing treatment is applied. Here, as a material of a liquid crystal alignment film constituting a liquid crystal display element, polyamic acid imide, polyamine, and polyester are known. In particular, polyimine is used in most liquid crystal display elements because of its excellent heat resistance, affinity with liquid crystals, and mechanical strength -4 - 200912485. In order to improve the display quality and reduce the power consumption, which is represented by the high-precision of liquid crystal display elements, the high-performance display elements have been developed, and high voltage retention, high reliability, and low cauterization have been developed. A characteristic liquid crystal display element. However, in recent years, in addition to the conventional transmission type, the utilization range of liquid crystal display elements such as a reflective type and a semi-transmissive type has been expanded. Along with this, the performance requirements for the liquid crystal alignment film are also increasingly strict. In particular, liquid crystal display elements for the purpose of low-burning have become more stringent in terms of cauterization characteristics, and the performance of the conventional liquid crystal display elements is not sufficient. In the liquid crystal alignment film formed of a polyaminic acid precursor of a polyimine precursor or a quinone imine polymer having a structure obtained by dehydration ring closure, the liquid crystal alignment film is used. In the case of a liquid crystal display device, although the liquid crystal alignment ability is excellent and a sufficient voltage holding ratio and reliability are obtained, an alignment agent which lowers the cauterization characteristics due to the use temperature is often present. SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal alignment agent which is suitable as a liquid crystal alignment film, which is composed of a polyimide and a poly-imine of a precursor of polyimine, and which exhibits not only a high voltage. The retention rate and low burning characteristics regardless of the temperature of use. Another object of the present invention is to provide a liquid crystal alignment film which is obtained from the above liquid crystal alignment agent and which has excellent properties as described above. Still another object of the present invention is to provide a -5 - 200912485 liquid crystal display element comprising the liquid crystal alignment film of the present invention. Other objects and advantages of the present invention will be apparent from the following description. The above objects and advantages of the present invention are achieved by a liquid crystal alignment agent according to the present invention, which is characterized by having the following formula (I-1)

HOOC

HNOC

COOH CONH - Qx

(here, P 1 is a tetravalent organic group and contains a tetravalent organic group represented by the following formula (A),

Q1 is a divalent organic group and has the following formula (B), (C), (D) or (E) 200912485

A proline binding unit composed of a repeating unit represented by at least one of R1 to R11 independently of each other in the bonding unit represented by hydrogen or a carbon number of 1 to 4, and the following formula (1) -2 ) Ο 0

(here, the P2 is a tetravalent organic group and the Q2 is a divalent organic group), and the polymer of the quinone imine bond unit is formed, and for the proline bonding unit and the quinone imine bonding unit. In terms of the total number of bonding units, the ratio of the number of protonic acid bonding units is 5 to 80%. According to the present invention, the above objects and advantages of the present invention are achieved by the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention. According to the present invention, the above objects and advantages of the present invention are achieved by a liquid crystal display element comprising the liquid crystal alignment film of the present invention. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The liquid crystal alignment agent of the present invention contains a polymer having a repeating unit represented by the above formula (1_1) and a repeating unit represented by the above formula (I-2). The polymer may also be a mixture of a polylysine having a repeating unit represented by the above formula (1-1) and a polyimine having a repeating unit represented by the above formula (I-2), or may have the above A repeating unit represented by the formula (1-1) and a partially fluorinated polymer of the repeating unit represented by the above formula (1-2). Further, in addition to the polyamido acid/polyimine mixture and the partially sulfimine polymer, a polyamine which does not have the tetravalent organic group represented by the above formulas (B) to (E) may be added. acid. The polylysine may be obtained by subjecting a tetracarboxylic dianhydride to a diamine compound in a ring-opening polymerization. Polyimine is usually obtained by dehydration of polylysine. The partially ruthenium iodide polymer is usually obtained by a method of synthesizing a block copolymer by bonding a proline prepolymer to a quinone imine prepolymer. The ratio of the number of methionine bonding units must be 5 to 80% by mole, preferably 5 to 8 Moer%. If it is less than 5% ', the burning characteristic is lowered by 200912485, and if it exceeds 80% by mole, there is a possibility that the voltage holding ratio is lowered. <Polyuric acid and polyimine> [tetracarboxylic dianhydride] The tetravalent organic group represented by P1 in the repeating unit (proline unit) represented by the above formula (1-1) and the above formula (1) -2) The tetravalent organic group represented by P2 in the repeating unit (in the imine unit) is a group derived from a tetracarboxylic dianhydride. P1 in the above formula (1-1) has a tetravalent organic group represented by the following formula (A).

(A) The tetravalent organic group represented by the above formula (A) is derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride. Further, as the tetracarboxylic dianhydride constituting pl or P2, in addition to 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride may be mentioned. And 1,3,3&,4,5,91?-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2- At least one of C]-furan-1,3-dione is preferred. Other tetracarboxylic dianhydrides used for the synthesis of polylysine or polyimine, such as butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- ring Butane tetracarboxylic dianhydride, I,3·dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3 -dichloro-1,2,3,4-cyclobutane Alkane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl--9 - 200912485 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane Alkane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 3,5,6-three Carboxynorbornane-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)-naphtho[l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl- 5-(tetrahydro-2,5-dioxo-3-furyl)naphtho[l,2-c]-furan-l,3-dione, l,3,3a,4,5,9b-six Hydrogen-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3-dione, l, 3, 3a,4,5,9b-hexa-7-methyl-5-(tetraqi-2,5-oxo-3-furanyl)-cai[1,2,c]-furan-1, 3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(four -2,5-dioxo-3-furanyl)-naphtho[1,2-(;]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro- 8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3-dione, l,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1 , 3-dione, 5-(2,5-dioxotetrahydrofuranmethylidene)-3-methyl-3-cyclohexene-1,2-dicarboxylic 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), an aliphatic or alicyclic tetracarboxylic dianhydride of a compound represented by the following formulas (II) and (III); -10-200912485 ο ο

ο ο (wherein R1 and R3 represent a divalent organic group having an aromatic ring, R2 and R4 represent a hydrogen atom or an alkyl group, and each of R2 and R4 present may be the same or different); 3,3',4 , 4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylindole tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2 , 3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenyl Decane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis (3) , 4-dicarboxyphenoxy)diphenylthiophthalic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsebacic anhydride, 4,4'-bis (3, 4-Dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene di phthalic anhydride, 3,3',4,4'-biphenyl Tetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, meta-phenyl-bis(triphenylbenzene) Formic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride Bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(hydroper trimellitate), propylene glycol-bis (dehydrated trimellitic acid-11 - 200912485 ester ), 1,4-butanediol-bis(anhydrotrimellitic acid ester), 1, (dehydrated trimellitate), :1,8-octanediol-bis(deesterification), 2,2- Bis(4-hydroxyphenyl)propane-bis (dehydrated benzene) An dianhydride such as a compound represented by the following formulas (1) to (4). The tetracarboxylic dianhydride other than these may be used alone or in combination. 6-Hexanediol-di-trim trimellitic acid: triester), two or more groups of aromatic tetracarboxylic acid

^CH3, CH3 (2)

Ο

-12 - 200912485

/CH3 ~CH3 (4) Among the tetracarboxylic dianhydrides other than these, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 5- (2, 5-dioxotetrahydrofuran methylene)-3-methyl-3-cyclohexene-1,2-dicarboxylic 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), Among the compounds represented by the formula (II), the compounds represented by the following formulas (5) to (7) and the compounds represented by the following formula (8) among the compounds represented by the above formula (III) can be used. It is preferable from the viewpoint of making liquid crystal alignment excellent in performance. Ο 0

0 0

(6) -13- 200912485

The divalent organic group represented by Q1 in the repeating unit (the valeric acid unit) represented by the above formula (Il) and the divalent organic group in the repeating unit (the quinone imine unit) represented by the above formula (1-2) are A group derived from a diamine compound. Q1 in the above formula (1-1) has at least one of the divalent organic groups each represented by the following formulas (B) to (E).

-14- 200912485 (here, R 1 to R11 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms). Specific examples of the diamine compound to which the above-mentioned divalent organic groups (B) to (E) are given include 1,4-diaminocyclohexane and bicyclo[2.2.1]heptane-2,6-double. (Methylamino), 1,3-bis(aminomethyl)cyclohexane, a compound represented by the following formula (9), and the like are preferred.

Other diamine compounds used in the synthesis of polylysine or polyimine, such as p-phenylenediamine, m-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4'-diamine Diphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'diaminodiphenylanthracene, 3,3'-dimethyl-4,4'-diamine linkage Benzene, 4,4'-diaminobenzimidamide, 4,4'diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 5-amino-1-( 4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1-( 4'-aminophenyl )- 1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminodiphenyl Ketone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-amino) Phenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]indole, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy-15-200912485 base) Benzene, 9,9-bis (4-amino group) Phenyl)-10-hydroquinone, 2,7-diaminofuran, 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'-dimethoxy Biphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4'-(p-phenylene isopropylidene)diphenylamine, 4,4'-( Interphenylene isopropylidene)diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-di Amino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 4- An aromatic diamine such as (4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate; 1,1-m-xylylenediamine, 1, 3-propylenediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, tetrahydrodicyclopentadienediamine, hexahydro-4,7-methane Dimethylenediamine, tricyclo[6.2.1.0'7]-undecenedimethyldiamine, 1,4-dicyclohexanediamine, 4,4'-methylenebis(cyclohexyl) Aliphatic and alicyclic amines such as amines Diamine; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3 -dicyanopyrimidine, 5,6-diamino-2,4-diaminopyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triindole, 1 , 4-bis(3-aminopropyl) piperculating, 2,4-diamino-6-isopropoxy-1,3,5-three tillage, 2,4-diamino-6-methyl Oxy-1,3,5-three tillage, 2,4-diamino-6-phenyl-1,3,5-tri D and 2,4-diamino-6-methyl-s- Tri-D,2,4-diamino-1,3,5-tri-trap, 4,6-diamino-2-vinyl-s-trin, 2,4-diamino-5-benzene Thiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9 -diamino-2-ethoxyindole-16- 200912485 pyridine lactate, 3,8-diamino-6-phenylphenanthridine, I,4-diaminopiperidine, 3,6-di Aminopyridinium, bis(4-aminophenyl)phenylamine, and a compound represented by each of the following formulas (IV) to (V) have two primary amino groups in the molecule and other than the primary amine group. a diamine of a nitrogen atom;

(wherein R 5 represents a monovalent organic group having a ring structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, tri-nano, piperidine and piperazine, and X represents a divalent organic group).

(V) the valence organic group of pyrimidine, tri-till, piperidine and pipe trap, and R6 means divalent organic difference). (wherein, X represents a 2-group selected from pyridine and a cyclic structure having a nitrogen atom; and a plurality of X present may be the same or a monosubstituted 4- to amine represented by the following formula (VI); (VII) The diaminoorganomethoxy oxane shown; F?-R8 Μ H2N NH2 '17- (VI) 200912485 (wherein r7 is selected from the group consisting of -〇-, -COO-, -OCO-, - A divalent organic group of NHCO-'-CONH- and -CO-, and R8 represents a monovalent organic group selected from a steroid skeleton, a trifluoromethyl group and a fluorine group or an alkyl group having 6 to 30 carbon atoms.

(In the formula, R9 represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R9 groups present may be the same or different ' integers of 1 to 3 of P series, and q is an integer of 1 to 20). The compounds represented by the following formulas (10) to (14) and the like can be given. These other diamine compounds may be used alone or in combination of two or more.

-18- 200912485

(wherein y is an integer of 2 to 12, and z is an integer of 1 to 5). Among the diamine compounds other than these, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 1,3-bis(aminomethyl)cyclohexane, 4,4' are preferred. - Diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diaminostilbene, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4 -aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane , 2,2_bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylenediphenylene)diphenylamine, 4,4'-(meta-phenylene dipyridyl) Propyl) diphenylamine, 1,4-cyclohexanediamine, 4,4,-methylenebis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4 '-Bis(4-Aminophenoxy)biphenyl, 4-(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, the above formula ( 1 0 )~(1 4 ) each represented by a compound, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminopurine a compound represented by the following formula (15) and a compound represented by the above formula (V) among the compounds represented by the above formula (IV); Among the compounds represented by the following formula (16) and the compounds represented by the above formula (VI), the following formulas (17) to (23) and 4-(4trifluoromethoxybenzophenone) A compound represented by each of methoxy)cyclohexyl-3,5-diaminobenzoic acid ester and bisaminopropyltetramethyldioxane among the compounds represented by (VII).

H2N

COO-CH2CH

(15) (16) Η2Ν<^Ν[}(ί:Η2Κ^Ν 乂)- ΝΗ2

/CH3, -CH3 (20)

H2N

-20- (22) (23) (23) 200912485

[Synthesis Reaction of Polylysine] The ratio of use of the tetracarboxylic dianhydride to the diamine compound to be supplied to the polyaminic acid synthesis reaction is preferably one for the amine group contained in one equivalent of the diamine compound. The acid anhydride group of the tetracarboxylic dianhydride is made to have a ratio of 〇 2 to 2 equivalents, more preferably 比率 3 to 1.2 equivalents. The synthesis reaction of polylysine is carried out in an organic solvent, preferably at -2 0 to 150 ° C, more preferably at a temperature of 〇 1 to 1 ° C. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid, and examples thereof include N-methyl-2-pyrrolidone, hydrazine, and hydrazine-dimethyl B. An aprotic polar solvent such as decylamine, N,N-dimethylformamide, dimethyl hydrazine, γ-butyrolactone, tetramethylurea or hexamethylphosphonium triamine; m-cresol, A phenolic solvent such as cresol, phenol or halogenated phenol. Further, the amount (a) of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is from 0 to 1% by weight based on the total amount of the reaction solution (a + b ). The amount. [Weak solvent] In addition, in the range in which the produced polyamine does not precipitate, alcohols, ketones, esters, esters, esters, esters, esters, and esters of the weak solvent of polyglycine may be used in the above organic solvent. Classes, halogenated hydrocarbons, hydrocarbons, etc. Specific examples of such weak solvents include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, and ethylene glycol monomethyl. Ether, ethyl lactate 'butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, B Ethyl oxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl Ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate 'tetrahydrofuran, dichloromethane, 1,2-dichloro Ethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, and the like. As described above, a reaction solution in which polylysine was dissolved was obtained. The reaction solution may be used as it is for the preparation of a liquid crystal alignment agent, or may be used for preparing a liquid crystal alignment agent after separating the polyamic acid contained in the reaction solution, or purifying the separated polyamic acid. Thereafter, it is used for the modulation of the liquid crystal alignment agent. The separation of polylysine can be carried out by injecting the above reaction solution into a large amount of a weak solvent to obtain a precipitate, and the precipitate is dried under reduced pressure, or the reaction solution is distilled off under reduced pressure by an evaporator. Come on. Further, the polyamine can be purified by re-dissolving the polylysine in an organic solvent, followed by precipitation in a weak solvent, or a vacuum distillation step of one or several times with an evaporator. acid. -22- 200912485 [醯i-imidized polymer] The quinone imidized polymer constituting the liquid crystal alignment agent of the present invention is prepared by dehydrating and ring-closing a poly-proline as described above. The ruthenium iodide polymer of the present invention may also be a water-blocking ring having a sulfhydrylation ratio of less than i0%. The term "indenylation rate" as used herein means a fluorene represented by a percentage of a repeating single ratio having a quinone ring or an isoindole ring in a repeating unit of a polymer portion. Dehydration ring closure of polylysine, (i) by heating poly-proline, or (ii) by dissolving polyfluorene in an organic solvent, adding a dehydrating agent and a dehydrated medium to the solution, It is necessary to carry out heating. In the above method (i) for heating poly-proline, the reaction temperature is preferably from 50 to 200 ° C', more preferably from 60 to 170. (3. When the reaction temperature is lower than the 'dehydration ring closure reaction system, it is difficult to sufficiently carry out, and if the reaction temperature is 2 〇〇 ° C ', the molecular weight of the obtained ruthenium iodide polymer will decrease. On the other hand, in the above (ii) In the method of adding a water-reducing agent and a dehydration ring-closing catalyst to a polyaminic acid solution, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The use of the dehydrating agent is 1 mole of polyfluorene. The repeating unit of the amine acid is preferably 〇. 〇i Mo. In addition, as the dehydration ring-closing catalyst, for example, a cis-class amine such as pyridine, pyridyl, lutidine or triethylamine can be used. The amount of the dehydration ring-closing catalyst used is preferably 〇1 〇1 〜1 〇 耳 for the dehydrating agent of 1 mol. Further, as the organic solvent used in the decyclization reaction, It can be used as a polyphosphonic acid synthesis which can be used for the separation of all-position amine acid ring touches compared to 50 ° C over the amount of addition and removal, ~ 20 top three by the water used in this closed -23- 200912485 Organic solvent exemplified. Moreover, dehydration closed loop The reaction temperature should preferably be from 〜180 ° C, more preferably from 10 to 150 ° C. The ruthenium iodide polymer obtained by the above method (i) can be used as it is for the preparation of a liquid crystal alignment agent, or After the obtained ruthenium-imided polymer is purified, it can be used for preparation of a liquid crystal alignment agent. On the other hand, a reaction solution containing a ruthenium-imided polymer is obtained in the above method (ii). After removing the dehydrating agent and the dehydration ring-closing catalyst, it can be used for the preparation of the liquid crystal alignment agent as it is, or after the separation of the ruthenium-imiding polymer, for the preparation of the liquid crystal alignment agent, or the polymerization of the ruthenium iodide. After the material is purified, it is used for preparation of a liquid crystal alignment agent. In order to remove the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, for example, a method such as solvent replacement may be used. Separation and purification of the ruthenium-based polymer may be carried out by polymerization. The method for separating and purifying proline is carried out in the same manner as above. [End Modification] The polyamic acid and the ruthenium iodide polymer may also be a terminally modified type having a molecular weight adjusted by using the terminal modification. The polymer can improve the coating properties of the liquid crystal alignment agent, etc. without impairing the effects of the present invention. Such a terminal modification type can be obtained by synthesizing polyamic acid, an acid anhydride, a monoamine compound, A monoisocyanate compound or the like is added to the reaction system to synthesize it. Here, examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, and positive fourteen. Further, as the monoamine compound, aniline, cyclohexylamine, n-butylamine, n-pentyl-24-200912485 amine, n-hexylamine, n-heptylamine, and n-octyl group are mentioned. Amine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, N-dodecylamine and the like. Further, examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. [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 mPa's, in a solution of 1% by weight. Further, the solution viscosity (m Pa a · s ) of the polymer was measured by diluting to a predetermined solid content concentration using a predetermined solvent, and measuring at 25 t using an E-type rotational viscometer. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention comprises a composition in which the polyamic acid and the ruthenium iodide polymer are dissolved in an organic solvent. In the above polymer constituting the liquid crystal alignment agent of the present invention, based on the total number of bonding units of the poly-proline coupling unit and the quinone imine bonding unit, the number of the proline bonding unit is 20%. ~9 5 %, the number of sulfhydryl bond units accounted for 5 to 80%. The organic solvent constituting the liquid crystal alignment agent of the present invention is the same as the solvent exemplified as the polyamido acid synthesis reaction. These may be used singly or in combination of two or more. Further, it can be appropriately selected in combination with the same as the weak solvent exemplified as the polyamine acid synthesis reaction. A particularly preferable solvent composition is a composition obtained by combining the above-mentioned solvents, in the range of 25 to 40 mN/m, in which no polymer is precipitated in the alignment agent and the surface tension of the alignment agent is 25 to 40 mN/m. The solid content concentration of the liquid crystal alignment agent of the present invention is selected in consideration of viscosity, volatility, etc., and is preferably in the range of 1 to 1% by weight. That is, the liquid crystal alignment agent of the present invention is applied onto the surface of the substrate 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 becomes too small, and it is difficult to obtain a good film. Liquid crystal alignment film. When the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large, and it is difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases, and the coating property is liable to be deteriorated. Further, a particularly preferable solid content concentration range differs depending on the method used for coating the liquid crystal alignment agent on the substrate. For example, in the spin coating method, it is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9 % by weight, whereby the solution viscosity can be in the range of 12 to 50 mPa·s. In the case of the ink jet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, whereby the solution viscosity can be in the range of 3 to 15 m P a · s. Further, in the case of preparing the liquid crystal alignment agent of the present invention, the temperature is preferably from 〜200 ° C, more preferably from 20 to 60 ° C. From the viewpoint of improving the adhesion to the surface of the substrate, the liquid crystal alignment agent which forms the liquid crystal alignment of the present invention preferably contains a compound having at least one epoxy group in the molecule (hereinafter also referred to as "epoxy group-containing". Compound"). Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and new -26- 200912485 pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2·dibromo neopentyl glycol diglycidyl ether, N, N, N ',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-dihydroglycidylaminomethyl)cyclohexane, N,N,N',N'-four Glycidyl-4,4 '-diaminodiphenylmethane, and the like. The compounding ratio of the epoxy group-containing compound is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, per 100 parts by weight of the polymer. Further, the liquid crystal alignment agent of the present invention may further contain a compound containing a functional decane. Examples of the functional decane-containing compound include 3-amino-based vapor-based dimethoxy sand, 3-aminopropyltriethoxy sand, and 2-aminopropyltrimethoxydecane. 2_Aminopropyltriethoxydecane, N-(2-aminoethenyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)_3_amine propylpropyl Dimethoxyoxane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxy sand, N- Ethoxy-3-yl-aminopropyltriethoxylate, N_triethylenesulfonylpropyltriethyltriamine, N-trimethoxydecylpropyltriphenylethylamine , 10-trimethoxydecane, 1,4,7-triazadecane, 10_triethoxylated nonyl-1,4,7-triazadecane, 9-trimethoxydecyl- 3 , 6_ diazepine acetic acid vinegar, 9-triethoxy decyl-3,6-diazaindolyl hydrazine, hydrazine-benzyl hydrazine-aminopropyltrimethoxy decane, Ν-benzyl _3_Amino-based vapor-based diethoxy sand pot, Ν-phenyl_3-aminopropyltrimethoxy fluorene,, stupyl-3-aminopropyltriethoxydecane, N - bis (ethylene oxide) -3 _ 棊 棊 二甲 二甲 二甲 二甲 Ν Ν Ν Ν 二 二 二 二 二 。 。 。 。 。 。 。 。 。 。 。 。 。 -27- 200912485 The compounding ratio of such functional decane-containing compounds is preferably 40 parts by weight or less for 1 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 one side of a substrate by a method such as a roll coating method, a spin coating method, a printing method, an inkjet method, etc. 'The substrate is provided with a transparent conductive film forming a pattern, and then' The coating film is formed by heating the coated surface. Here, as the substrate 'for example, a glass such as float glass or soda lime glass, a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether maple or polycarbonate can be used. Transparent substrate. As the transparent conductive film provided on one side of the substrate, a NESA film (registered trademark of PPG, USA) and indium oxide-tin oxide (1 n 2 〇3 - S η 0) made of tin oxide (Sn〇2) can be used. 2) The resulting IT 0 film and the like. The patterning of these transparent conductive films is a lithography method or a method in which a photomask is used in advance. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a functional decane-containing compound or a functional titanium-containing compound may be applied to the surface of the substrate in advance. . The heating temperature after application of the liquid crystal alignment agent is, for example, 80 to 300 ° C, preferably 1 2 0 to 2 50 ° C. The liquid crystal alignment agent of the present invention containing polylysine may form a coating film as an alignment film by removing an organic solvent after coating, or may be subjected to dehydration ring closure by heating to form a coating film which is further imidized. . The film thickness of the formed coating film is preferably 0.001 to 1 μm, more preferably -28 to 200912485 0.005 to 0.5 μιη 〇(2) for the formed coating film surface, for example, wrapped with nylon, ray, cotton. The rolls of the cloth formed by the fibers are subjected to a rubbing treatment in a certain direction. This is a liquid crystal alignment film which imparts a liquid crystal molecule alignment ability to a coating film. In the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, a process of partially irradiating ultraviolet rays to change the pretilt angle as shown in Japanese Laid-Open Patent Publication No. Hei. 6-222366 or JP-A-6-281937 A resist film is partially formed on the surface of the liquid crystal alignment film subjected to the rubbing treatment as shown in Japanese Laid-Open Patent Publication No. Hei 5-105044, and the rubbing film is removed in a direction different from the previous rubbing treatment, and then the resist film is removed. The process of changing the liquid crystal alignment ability of the liquid crystal alignment film, whereby the visual field characteristics of the liquid crystal display element can be improved. (3) As described above, 'making two substrates in which the liquid crystal alignment film is formed', the two substrates are placed opposite each other with a gap (cell gap) in such a manner that the rubbing directions of the respective liquid crystal alignment films are perpendicular or antiparallel to each other. The peripheral portion of the two substrates is bonded with a sealant, and a liquid crystal is injected into the cell gap between the surface of the substrate and the sealant to seal the injection hole to form a liquid crystal cell. Then, a polarizer is disposed on the outer surface of the liquid crystal cell, that is, on the transparent substrate side constituting the liquid crystal cell, to obtain a liquid crystal display element. Here, as the sealant, for example, an alumina ball-containing epoxy resin or the like as a curing agent and a spacer can be used. Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, a -29-200912485 oxidized azo liquid crystal, or a biphenyl system can be used. Liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, ditriphenyl liquid crystal, biphenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cuba liquid crystal Wait. Further, a bile-type liquid crystal such as chlorinated cholesterol, cholesterol phthalate or cholesterol carbonate may be added to the liquid crystals, or sold under the trade names "c_15" and "CB-15" (manufactured by Merck). Used for palm and the like. Further, a ferroelectric liquid crystal such as p-methoxybenzylidene p-amino-2-methylbutyl myrcinate may also be used. In addition, as the polarizing plate which is bonded to the outer surface of the liquid crystal cell, a polarizing film called a ruthenium film which absorbs iodine while absorbing iodine is polarized by a cellulose acetate protective film. A plate or a polarizing plate composed of a diaphragm itself. EXAMPLES Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited by the examples. The oxime imidization ratio, voltage holding ratio, and coatability of the ruthenium iodide polymer in the examples and the comparative examples were evaluated by the following methods. [Method for Measuring the Amidation Rate of the Iridium Amineated Polymer] The solution of the ruthenium iodide polymer is put into pure water. The obtained precipitate is dried under reduced pressure at room temperature, and then dissolved in a heavy hydrogenated dimethyl group. In the dissolution of the hydrazine, tetramethyl decane was used as a reference material, and 1 Η - NMR was measured at room temperature, and the formula represented by the following formula (ii) was used to determine the -30-200912485 hydrazine imidization rate r/ OWl-AVA^cOxlOO (ii) A1: peak area from the proton of the NH group (l〇ppm) A2: peak area from other protons α: precursor of the polymer (polyproline) In the case of one proton of the N fluorenyl group, the ratio of the number of other protons [voltage holding ratio] applies a voltage of 5 V to the liquid crystal display element, and the voltage application time is 6 〇 microseconds, with a span of 167 ms ( After the application of span, the voltage holding ratio after the voltage was released to 167 ms was measured. The measuring device was a VHR-1 manufactured by Dongyang Technology. When the voltage holding ratio is 95% or more, the judgment is good, and the other cases are judged to be defective. [Burn test] A unit cell with an ITO electrode as shown in Fig. 1 was produced. At 4 (TC, 8 (TC), 20 volts DC voltage was applied to electrode A for 20 hours, and 0. 5 V DC voltage was applied to electrode B for 2 G hours. After stress was released, counter electrodes A and B were applied. A DC voltage of 0.1 to 3.0 V was applied with a gradient of 0.1 V. The burning characteristics were judged by the difference in luminance between the electrodes A and B at each voltage. When the luminance difference was large, the burning characteristics were judged to be poor. Synthesis Example 1 1 79.34 g (0.8 mol) of dianhydride 2,3,5-tri-31 - 200912485 carboxycyclopentyl acetic acid dianhydride and .86 g (G.2 mol) 1,3,3a,4,5 , 9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione, 82.46 g (0.7625 mol) of p-phenylenediamine, 24.85 g (〇_1 mol) bisaminopropyl tetramethyldioxane, 19.83 g (0.1 mol) 4,4'- Diaminodiphenylmethane and 13.15 g (0.03 mol) of 4-(4,-trifluoromethoxybenzylideneoxy)cyclohexyl 5-diaminobenzoate, 1.40 as a monoamine The gram (0.015 mol) aniline was dissolved in 1,550 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. A polyaminic acid solution having a solution viscosity of 60 m P a · s. Dissolving 1,920 g of N-methyl-2-pyrrolidone in the obtained polylysine, adding 2 3 7.4 g of pyridine and 3 0 6.4 g Acetic anhydride, dehydration ring closure at 1 1 ° C for 4 hours. After the imidization reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone solvent (in this operation, the ruthenium is imidized) The pyridine and acetic anhydride used in the reaction were removed to the outside of the system, and when the solid concentration was 15.0% by weight and the solid concentration was 1% by weight, the solution viscosity (N-methyl-2-pyrrolidone solution) was 45 mPa·s. When the solid content concentration is 6.0% by weight ((N-methyl-2-pyrrolidone solution), the solution viscosity is 12 mPa's, and the hydrazine imidization rate is 88% of 1,500 g of the ruthenium iodide polymer (A-1) solution. Synthesis Example 2 Will be regarded as tetracarboxylic dianhydride 2.09 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 157.15 g (0.50 mol) 1,3,3a,4,5, 9b-Hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furan-32- 200912485) naphtho[l,2-c]furan-1,3-dione 9〇 as a diamine compound 3 g (0.8325 mol) of p-phenylenediamine, 24.85 g (0.10 mol) of bisaminopropyltetramethyldioxane and 29.69 g (0.06 mol) of the diamine compound represented by the above formula (23) 140 g (〇.〇15 mol) of aniline as a monoamine was dissolved in 9 70 g of N-methyl-2-pyrrolidone, and reacted at 6 (TC for 6 hours to obtain a solution viscosity of 5 5 mPa·s. Proline. 2,800 g of N-methyl-2-pyrrolidone was dissolved in the obtained polylysine, and 158.2 g of pyridine and 2 〇 of 4.2 g of acetic anhydride were added, and the mixture was dehydrated at ll ° C for 4 hours. After the imidization 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 oxime imidization reaction are removed to the outside of the system) When the solid content concentration is 17.0% by weight and the solid content concentration is 10% by weight (N-methyl-2-pyrrolidone solution), the solution viscosity is 50 mPa's, and the solid content concentration is 6.0% by weight (N.methyl-2-pyrrolidone) The solution has a solution viscosity of 13 mPa·s, and a solution of 1,600 g of the ruthenium iodide polymer (A-2) having a ruthenium iodide ratio of 93%. Synthesis Example 3 Π0 g (0-5 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 160 g (〇.5 mol) of 1,3,3a,4 ,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-(;]furan-1,3-dione As a diamine compound, 96 g (0.865 mol) of p-phenylenediamine, 25 g (0.1 mol) of 1,3 -bis(3-aminopropyl)tetramethyldioxane, and 13 g (0.〇2mol) 3,6_bis(4-aminobenzylideneoxy)cholane, 8.1 g (〇·〇3 mol) N-octadecylamine dissolved as a monoamine -33- 200912485 In 960 g of N-methyl-2-pyrrolidone, reacted at 60 ° C for 6 hours to obtain a polyaminic acid solution having a solution viscosity of 60 m P a .s. 2,7 〇0 g of N-methyl-2-pyrrolidone was added to the proline solution, and 400 g of pyridine and 4 10 g of acetic anhydride were added to dehydrate the ring for 4 hours at 1 I 醯 °. After the reaction, the solvent in the system is subjected to solvent replacement with unused γ-butyrolactone (in this operation, the pyridine and acetic anhydride used in the oxime imidization reaction are removed to the outside of the system) 'When the solid content concentration is 15.0% by weight, the solid content concentration is 1% by weight% (y-butyrolactone solution), the solution viscosity is 70 mPa·s, and the solid content concentration is 6.0% by weight (y-butyrolactone solution) 1 6 · 0 m P a . s, 醯 胺 imidization rate of 9 5 % of a solution of 1,500 gram of imidized polymer (A-3). Synthesis Example 4 will be regarded as tetracarboxylic dianhydride 2 2 4 . 1 7 g (1·0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 106.5 g (0.985 mol) of p-phenylenediamine as a diamine compound, and 7.842 g (0.015 mol) of cholesteryl-3,5-diaminobenzoate was dissolved in 3,100 g of N-methyl-2-pyrrolidone and reacted at room temperature for 3 hours. A solution of polyacrylic acid having a solution viscosity of 2 10 m P a · s. Next, 3,400 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 400 g of pyridine and 300 g of acetic anhydride were added. 'Dehydration closed at 1 1 〇 ° C for 4 hours. After the hydrazine imidization reaction, the solvent in the system was solvent-substituted with unused γ-butyrolactone (in this operation, the yttrium imidization reaction was used. Pyridine The pyridine and acetic anhydride were removed to the outside of the system, and the solution viscosity of the solid concentration was 9.0% by weight, and the solid concentration was 3 · 1 -34 - 200912485 % by weight. 1 5.0 m P a · s, yttrium imidization rate 9 0% of 2,300 gram of imidized polymer (Α_4) solution. Synthesis Example 5 112.09 g (0.5 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride and 157.15 g (0.5 mol) 1,3,3a,4,5 , 9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione, 8 7 · 8 6 g (0.8125 mol) of p-phenylenediamine, 24.85 g (0.1 mol) of bisaminopropyl tetramethyldioxane, and 35·〇7 g of diamine compound (〇.〇) 8 mol) 4-(4,-Trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 1.40 g (0.015 mol) of aniline dissolved as a monoamine In ι, 250 g of Ν-methyl-2-pyrrolidone, the reaction was carried out at 60 ° C for 6 hours to obtain a polylysine having a solution viscosity of 5 5 mP a · s. 2,500 g of N-methyl-2-pyrrolidone was dissolved in the obtained polylysine, 3 297 · 2 g of pyridine and 4 1 0.1 g of acetic anhydride were added, and dehydrated at 1 1 ° C Closed loop for 4 hours. After the imidization reaction, the solvent in the system is replaced with an unused N-methyl-2-pyrrolidone (in this operation, the pyridine and acetic anhydride used in the oxime imidization reaction are removed to the outside of the system). When the solid content concentration is 7.0% by weight and the solid content concentration is 10% by weight (N-methyl-2-pyrrolidone solution), the solution viscosity is 50 mPa's, and the solid content concentration is 6.0% by weight (N-methyl-2-pyrrolidone) The solution has a solution viscosity of 1 3 · 0 m P a · s, a hydrazine imidization rate of 9.5 % of a 1,800 gram of imidized polymer (A - 5 ) solution. -35- 200912485 Synthesis Example 6 19 6 · 11 g (1 _0 旲 butane tetracarboxylic dianhydride, 142. ear as diamine compound) 1,3-bis (amine) Methyl)cyclohexane was dissolved in 2,200 pyrrolidone, and after 3 hours of reaction at 4,7, it was diluted at 2,25 Torr. A solution of polyamine (B -1 )) having a solution viscosity of 1 80 mPa S was obtained. Synthesis Example 7 1 6.1 1 g (1. 〇旲 butane tetracarboxylic dianhydride, 1 70 · ear as a diamine compound) which is tetracarboxylic dianhydride is shown as the above formula (9) The amine compound was dissolved in keto-2-pyrrolidone to react at 40 Torr for 3 hours. 150mPa.s of polyaminic acid (polyglycine (B-2)) Synthesis Example 8 will be taken as 200 grams of tetracarboxylic dianhydride (10 moles of tetracarboxylic dianhydride, as two 2 10 g of 2,2,-dimethyl- 4,4,-diaminobiphenyl of the amine compound is dissolved in 370 g of the alkanone, 3,300 g of γ-butyrolactone, and reacted at 4 ° C. Poly lysine with a viscosity of 160 mPa.s (polyammonic acid synthesis example 9 will be regarded as 98.05 g (〇.50 mol) of tetracarboxylic dianhydride 1,2,3,4-ring 25 g (1 .0 Mok N-methyl-2-D gram γ-butyrolactone acid (polyglycolic acid ear) 1,2,3,4-ring 30 g (1.0 mo 3230 g Ν-A to obtain a solution viscosity solution. ) 1,2,3,4-cyclobutane: (1.0 mol) N-methyl-2-indole ratio is slightly smaller, is dissolved; -3)) solution. Ear) 1, 2, 3, 4 · ring - 36- 200912485 Butane tetracarboxylic dianhydride, 109.06 g (0.50 mol) pyromellitic dianhydride, 200.24 g (丨·0 mol) 4,4'-diamino group as diamine compound Diphenyl ether was dissolved in 230 g of N-methylrhoalkanone and 2,100 g of γ-butyrolactone, and reacted at 25 ° C for 3 hours. Then, 1,400 g of γ-butyrolactone was added to obtain a solution of poly-aracine (polyamine acid (Β-4)) having a solution viscosity of 2 〇〇 mPa.s. Example 1 Polyimine (A-1) obtained in Synthesis Example 1, polylysine (B-1) obtained in Synthesis Example 6, and polylysine (B-3) obtained in Synthesis Example 8 were aggregated. Indoleamine (A-1): Polyproline (B-1): Poly (transamine) (B-3) = 1 0: 5 0: 40 (by weight) dissolved in butyrolactone / N-methyl-2 - pyrrolidone / butyl cellosolve mixed solvent (weight ratio 71 / 1 7 / 12) in 'relative to 1 part by weight of the polymer dissolved 10 parts by weight as an epoxy group-containing compound Ν, Ν, Ν ' , Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane, into a solid concentration of 3.5% by weight of the solution, after thorough stirring, the solution was filtered with a filter having a pore size of 1 μηη 'To prepare the liquid crystal alignment agent of the present invention. The liquid crystal alignment agent was applied to a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm by a spin coater (rotation speed: 2,500 rpm, coating time: 1 Minutes), at 20 (TC drying for 1 hour, a film having a dry film thickness of 〇·8 μm was formed. Using a friction machine having a roll of a twisted cloth, the roll speed was 400 rpm, and the stage moving speed was 3 cm/sec. The film was subjected to a rubbing treatment under the condition that the length of the pile was 0.4 mm, and the liquid crystal alignment film-coated substrate was subjected to ultrasonic cleaning in ultrapure water at -37 to 200912485 for 1 minute, and then cleaned at 100 ° C. The inside of the oven is dried for ί. After the oxy-resin adhesive, the liquid crystal alignment film surface is laminated and pressure-bonded to cause the adhesive to be cured. Then, after the liquid crystal injection port is filled between the substrates, the nematic liquid crystal (MLC-622 1 manufactured by Merck) is filled. Acrylic light curing The liquid crystal injection port is closed, and a polarizing plate is bonded to both surfaces of the substrate to prepare a liquid crystal display element. The voltage holding ratio of the obtained liquid crystal display element is evaluated. The voltage holding ratio of the liquid crystal alignment agent obtained by the present invention is displayed. The crucible was as high as 99% or more. In addition, the cauterization test showed that the stress temperature was good. Examples 2, 3 and Comparative Examples 1 to 5 The polyimine obtained in Synthesis Examples 1 to 5 ( A- 1 )~(A-5), polylysine (b-1) to (B-4) obtained in Synthesis Examples 6 to 9 and N, N, N, as an epoxy group-containing compound N'-tetraglycidyl-4,4,-diaminodiphenylcarbendide is dissolved in a mixed solvent containing γ-butyrolactone as a main component, and the solid content becomes 3 · 5 wt % The liquid crystal alignment agent of the present invention was prepared by dissolving the liquid crystal alignment agent of the present invention in a liquid crystal alignment agent of the present invention. The liquid crystal alignment agent prepared in the same manner as in Example 1 was used to form a film on the surface of the substrate. A liquid crystal display element is produced by using a substrate of the liquid crystal alignment film. Then, evaluation Pressure retention. In addition, a cauterization test was also performed, and each result is shown in Table 1. -38- 200912485 Table 1 Example polymer introduction weight ratio glutamate bonding unit rate epoxy group-containing compound introduction amount voltage retention rate cauterization Evaluation (good: 〇, difference: X) 1 Al/Bl/B-3=10/50/40 8.8% 10 >99 40°C〇, 80°C〇2 A-2/Bl=30/70 26.1 % 2 >99 40°C〇, 80°C〇3 A-5/Bl/B-3=10/50/40 9.5% 2 >99 40°C〇, 80°C〇4 Al/B- 2=20/80 17.6% 2 >99 40°C〇, 80°C〇Comparative Example 1 Al/B-3=20/80 17.6% 2 >99 40°Cx, 80°C〇2 A-3 /B-3=20/80 18.6% 2 >99 40°Cx, 80°C〇3 A-3/B-4=20/80 18.6% 10 <99 40°Cx, 80°Cx 4 A- 4=100 89.0% 2 >99 40°C〇, 80°Cx 5 B-3=100 0.0% 2 <99 40°Cx, 80°C〇6 B-4=100 0.0% 2 <99 40 ° Cx, 80 ° C 〇 7 A-3 = 100 93.0% 2 > 99 40 ° C 〇, 80 ° Cx * The amount of introduction (weight ratio) for 100 parts by weight of the polymer The effect of the invention is A liquid crystal alignment film formed by a liquid crystal alignment agent exhibits a high voltage in comparison with a conventional liquid crystal alignment film. Holdup, irrespective of why the use of low temperature burning of both, may be applied to TN type liquid crystal display element constituted, S TN type liquid crystal display device, a reflective liquid crystal display element and transflective LCD device such as various liquid crystal display element. The liquid crystal display element of the present invention can be effectively used in various devices, and can be suitably used as, for example, a display device for a desktop computer, a watch, a desk clock, a portable telephone, a counting display panel, a word processor, a personal computer, a liquid crystal television, or the like. . BRIEF DESCRIPTION OF THE DRAWINGS -39- 200912485 Fig. 1 is an explanatory view of a unit cell having an ITO electrode prepared for a cauterization test. -40-

Claims (1)

200912485 X. Patent application scope 1. A liquid crystal alignment agent characterized by having the following formula (I-1) HOOC HNOC X COOH CONH - Qx (here, P1 is a tetravalent organic group and contains a tetravalent organic group represented by the following formula (A), Q1 is a divalent organic group and has the following formula (B), (C), (D) or (E): RIO R11 -41 - 200912485 Each of the bonding units indicated by at least one of the bonding units, and R1 to R11 are independently hydrogen-based or a carbon number of 1 to 4, and the repeating unit is composed of a repeating unit. And the following formula (1-2) (1-2) (here, P2 is a tetravalent organic group, and Q2 is a divalent organic group), which is composed of a polymer of a quinone imine bond unit, and The ratio of the number of the protonic acid bonding units in the total number of bonding units of the amine bonding unit is 5 to 80%. 2. The liquid crystal alignment agent of claim 1 wherein P 1 or 2 contains from 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,3,33,4,5,91)- At least 1 selected for hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)·naphthoquinone, 2-c]-furan-1,3-dione A tetravalent organic group derived from tetracarboxylic dianhydride. 3. The liquid crystal alignment agent of claim 1, wherein the polymer further contains from 0. 1 to 30 parts by weight of a compound having at least one epoxy group in a part by weight of the polymer. A liquid crystal alignment film formed by the liquid crystal alignment agent of any one of claims 1 to 3. 42 - 200912485 5 . A liquid crystal display element characterized by having a liquid crystal alignment film of claim 4 of the patent application. -43-