TW200846788A - Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display device - Google Patents

Abstract

To provide a liquid crystal aligning agent which develops high voltage holding capacity and shows excellent sticking characteristics at any use temperature. The liquid crystal aligning agent contains a polymer having an amic acid bond unit and an imide bond unit, the rate of the number of imide bond units to the total number of amic acid bond units and imide bond units being 10 to 80%; and an imidazole compound expressed by formula (A).

Description

200846788 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, it relates to a liquid crystal alignment agent which exhibits a high voltage retention ratio and exhibits good scorch characteristics at any use temperature, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element including the film. [Prior Art] In the past, a transparent conductive film was used to form a layer having a positive dielectric anisotropic nematic liquid crystal as a cell of a sandwich structure between two substrates on which a liquid crystal alignment film was formed. A TN type liquid crystal display element having a TN (Twisted Nematic) type liquid crystal cell whose major axis of the liquid crystal molecule is twisted by 90 degrees from one substrate to the other substrate. Further, there is also a STN (Super Twisted Nematic) in which the long axis of the liquid crystal molecules is continuously twisted between the substrates via 180 degrees or more by the addition of the palm reagent, and the complex refractive effect produced thereby is utilized. Type liquid crystal display element. Recently, a nematic liquid crystal layer or a spiral axis having a homeotropically aligned state of a negative dielectric anisotropic between the opposite substrates forms a cholesteric liquid crystal layer parallel to the substrate normal, and is added to the liquid crystal layers. A guest-host reflective liquid crystal display element of a pigment has also been developed. The alignment of the liquid crystals in these liquid crystal display elements is generally exhibited by a liquid crystal alignment film which is subjected to rubbing treatment. Among them, polyimine, polyamide, polyester, and the like have been known as materials for the liquid crystal alignment film constituting the liquid crystal display element. In particular, it is widely used in liquid crystal display elements because it is excellent in heat resistance, affinity with liquid crystals, mechanical strength, and the like. In the past, we have developed a high-voltage display rate, high reliability, and low performance for the purpose of highly developing high-performance display elements, such as high-definition display quality improvement and low-power consumption of liquid crystal display devices. A liquid crystal display element having a scorch characteristic. However, in recent years, in addition to the past transmission type, the utilization range Φ of the reflective type or semi-transmissive liquid crystal display element has also expanded. As a result, the required performance of the liquid crystal alignment film is also increasingly strict. In particular, in the liquid crystal display element for the purpose of low scorch marks, the demand for the scorch property is severe, and it is difficult to say that the performance of the liquid crystal display element has been sufficient in the past. In the liquid crystal alignment film formed of a polyimidazolium precursor of a polyimine precursor or an imine polymer having a structure obtained by dehydration ring closure, a liquid crystal display element is formed using the liquid crystal alignment film. In the case of having excellent liquid crystal alignment ability and sufficient voltage holding ratio and signalability, there is often an alignment agent which deteriorates the scorch property due to the use temperature. SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer having a phosphoric acid bond unit and an imine bond unit which is a polyimide precursor useful for a liquid crystal alignment film, which can exhibit high voltage retention. A liquid crystal alignment agent which exhibits low scorch characteristics at a rate and at any use temperature. Another object of the present invention is to provide a liquid crystal alignment film which has the above-mentioned excellent properties as obtained by the above liquid crystal alignment agent. Still another object of the present invention is to provide a liquid crystal display element comprising the liquid-5-200846788 crystal alignment film of the present invention. Still other objects and advantages of the present invention will be apparent from the following description. According to the first invention of the present invention, the imine linkage unit represented by the following formula (1-1) and the imine bond unit represented by the following formula (1-2) can be used. And a polymer having a ratio of the number of units of the imine bond to the total number of units of the imine bond unit and the number of the above-mentioned imine bond units is from 1 to 80%, and containing the following formula (A) The imidazole compound shown is a special liquid crystal alignment agent.

HOOC, /CQOH

I X - HNOC CONH - Q1 wherein P1 is a tetravalent organic group and Qi is a divalent organic group. Ο 0

〇 0 wherein P2 is a tetravalent organic group, and Q2 is a divalent organic group (A) wherein R1, R2 and R3 are mutually independent hydrogen atoms or alkyl groups, and η is an integer of 〇~3. The above objects and advantages of the present invention can be attained by the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention -6-200846788 by the second invention. The above objects and advantages of the present invention can be attained by the liquid crystal display device comprising the liquid crystal alignment film of the present invention. 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 bond unit (or repeating unit) represented by the above formula (I-1) and a bond unit (or repeating unit) represented by the above formula (1-2) and the above formula The imidazole compound shown in (A). The polymer may be a mixture of a polyimidic acid having a repeating unit represented by the above formula (I-1) and a polyimine having a repeating unit represented by the above formula (1-2), and may have the above-mentioned A partially imidized polymer having a repeating unit represented by the formula (1-1) and a repeating unit represented by the above formula (1_2). The above poly-proline can be obtained by subjecting a tetracarboxylic dianhydride to a diamine compound by ring-opening addition polymerization, and the polyimine is generally obtained by dehydration ring closure of polyamic acid. Part of the imine polymer is generally obtained by combining a prolinic acid prepolymer with an imine prepolymer to synthesize a block copolymer. <Polyaramine and Polyimine> [Tetracarboxylic Acid dianhydride] The tetravalent organic compound represented by P1 in the repeating unit (imine linkage unit) represented by the above formula (I-1) The tetravalent organic group represented by the repeating unit (imine bond unit) P2 represented by the above formula (1-2) is a group derived from a tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a54,5,9b-hexahydro·8-methyl group containing at least one of 200846788. -5-(tetrahydro-2,5-dioxo-3-furan)-naphtho[l,2-c]-furan-1,3-dione, 1,2,3,4-cyclobutane Tetracarboxylic dianhydride is preferred. Examples of the other tetracarboxylic dianhydride used for the synthesis of polyimidic acid include butane tetracarboxylic dianhydride and 1,2-dimethyl-1,2,3,4-cyclobutane IV. Carboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane tetracarboxylate Acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic 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- Furan)-naphtho[l,2-c]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-5-methyl-5-(tetrahydro-2,5 -dioxo-3-furan)-naphtho[1,2-(indole-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5 -(tetrahydro-2,5-dioxo-3.furan)-naphtho[l,2-c]-furan-1,3-dione, 1,3,3&, 4,5,91> -hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furan)-naphtho[l,2-c]-furan-1,3-dione, l 5 3 5 3 a, 4, 5, 9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furan)-naphtho[1,2-(:]-furan-1,3-dione, 1 ,3,3&,4,5,91^hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furan)-naphtho[l,2-c]-furan -1,3-diketone, 1,3,3,4,5,91)-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furan )-naphtho[l,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran)-3-methyl-3-cyclohexane-1,2-di Carboxylic dianhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3·oxabicyclo[3.2.1]octane-2,4--8 - 200846788

Diketo-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furan)-3-methyl-3-cyclohexane Alkane-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5:6-dianhydride, 4,9-dioxatriazole [5.3.10] 6] undecyl-3,5,8,10-tetraketone, an aliphatic or alicyclic tetracarboxylic dianhydride such as a compound represented by the following formulas (1) and (11);

(II) (wherein R4 and R6 represent a divalent organic group having an aromatic ring, R5 and R7 represent a hydrogen atom or an alkyl group, and R5 and R7 each may exist in the same or different degrees) 3,3',4 , 4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4, biphenyl milled 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′-dimethyldiphenyldecane tetracarboxylic acid Acid dianhydride, 3,3',4,4'-tetraphenylnonane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis (3,4- Dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-di Carboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene dipeptide dianhydride, 3,3',4,45-biphenyltetracarboxyl 200846788

Acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, bis(peptide acid) phenylphosphine oxide dianhydride, P-phenylene-bis(triphenylpeptide) Anhydride, m-phenylene-bis(triphenylpeptide) dianhydride, bis(triphenylpeptide)-4,4'-diphenyl ether dianhydride, bis(triphenylpeptide)-4 ,4,-diphenylmethane dianhydride, ethylene glycol-bis(trimellitic acid ester), propylene glycol-bis(trimellitic acid ester), 1,4·butanediol·bis(trimellitic acid) Ester), 1,6-hexanediol-bis(trimellitic acid ester), 1,8-octanediol-bis(trimellitic acid ester), 2,2-bis(4-hydroxyphenyl) An aromatic tetracarboxylic dianhydride such as a propane-bis(p-benzoic acid ester) or a compound represented by each of the following formulas (1) to (4). These other tetracarboxylic dianhydrides may be used alone or in combination of two or more.

/CH3 ~CH3 (2) -10- (3) 200846788

(4) Among them, butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentene tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuran)-3-methyl- 3-cyclohexyl-1,2-dicarboxylic dianhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxobicyclo[3.2. 1] Octane-2,4-dione-6-spiro-3,-(tetrahydrofuran-2',5,-dione), the compound of the above formula (I), the following formula (5)~ Among the compounds shown in each of (7) and the compound represented by the following formula (8) in the compound represented by the above formula (11), it is preferred from the viewpoint of exhibiting good liquid crystal alignment. -11- 200846788

ο ο

Examples of the diamine compound used for the synthesis of polyimidic acid or polyimine include phenyldiamine, m-phenylenediamine, and 4,4'-diaminediphenylmethane. 4,4'-diamine diphenylethane, 4,4'-diamine diphenyl sulfide, 4,4'-diamine diphenyl®, 3,3'-dimethyl-4,4 '-Diamine biphenyl, 4,4'-diamine benzanilide, 4,4'-diamine diphenyl ether, 1,5-diamine naphthalene, 2,2'-dimethyl-4, 4'-diamine biphenyl, 5-amine-1-(4,aminophenyl)-1,3,3-trimethylindan, 6-amine-1-(4'-amine phenyl)-1 , 3,3-trimethylindan, -12- 200846788 3,4'-diamine diphenyl ether, 3,3'-diamine benzophenone, 3,4'-dimethylketone, 4, 4.5-diamine benzophenone, 2,2-bis[4-(4-aminophenoxy)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro 2, 2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenylphenyl) maple, 1,4-bis(4-aminophenoxy)benzene, 1,3 - bis(4-amine)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminephenylhydroquinone, 2,7-diamine oxime, 9,9- Dimethyl-2,7-diamine oxime, 9,9-bis φ phenyl芴, 4,4'-methyl-bis(2-chloroaniline), 2,2',5,5' 4,4'-diamine biphenyl, 2,2'-dichloro-4,4, Diamine-5,5,dimethoxy 3,3'-dimethoxy-4,4'-diamine biphenyl, 1,4,4'-(|>-phenylene)diphenylamine , 4,4'-(m-phenylphenylidene)diphenylamine, [4-(4-amine-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, amine-2,2 '-Bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-yl)phenoxy]-octafluorobiphenyl, 4-(4'-trifluoromethoxybenzene A) an aromatic diamine such as cyclohexyl-3,5-diamine benzoate; • 1,1-m-xylylenediamine, I,3-propanediamine, tetra-methyl, and penta-methyl Amine, hexamethylenediamine, heptamethyldiamine, bisamine, hexamethylenediamine, 4,4.diamine heptamethylamine, amine cyclohexane, isophorone II Amine, tetrahydrobicyclopentadienyl dihydro-4,7-methanol decane dimethylene diamine, tricyclo[6.2.1. 02 carbene dimethyl diamine, 4,4 M methyl An aliphatic cyclic diamine such as bis(cyclohexylamine), 1 aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane; 2,3-di Aminopyridine, 2,6-diamine pyridine, 3,4-diamine pyridine, amine diphenyl) phenylpropane, oxy) phenoxy)-10-(4-amine tetrachloro-biphenyl, isopropylidene 2,2,-bis 4,4,-ditrifluoromethyl decyloxydiamine octatropin 1,4-diamine, hexa-, 7---, 10-bis (family and lipid 2,4-di -13-

200846788 Amine pyrimidine, 5,6-diamine-2,3-cyanopyrazine, 5,6-diamine-2,4-dihydroxypyridine, 2,4-diamine-6-dimethylamine-1, 3,5-triazine, 1,4-bis(3-amineproperazine, 2,4-diamine-6-isopropoxy-1,3,5-triazine, 2,4-diamine- 6_yl-1,3,5·triazine, 2,4-diamine-6-phenyl·1,3,5-triazine, 2,4-dimethyl-3-triazine, 2,4- Diamine-1,3,5-triazine, 4,6-diamine-2-vinylazine, 2,4-diamine-5-phenylthiazole, 2,6-diamine oxime, 5,6-di Amine dimethyl uracil, 3,5-diamine-1,2,4-triazole, 6,9.diamine-2-acetidine propanolate, 3,8-diamine-6-benzene Ketidillin, 1,4-diamine piperidinar 3,6-diamine acridine, bis(4-aminophenyl)aniline, 3,6-diamine, oxazolidine-3,6-diamine oxazole, Ν-ethyl-3,6-diamine oxazole, hydrazine-phenyldiamine oxazole, hydrazine, Ν'-bis(4-aminophenyl)-benzidine and each of the following formulas (~(VI) a diamine having two primary and other nitrogen atoms other than the amine group in the molecule; a pyrimido) methoxyamine-6-s-tris-1,3-oxazine, ^ Ν--3,6 -III) Amino group

Wherein R8 represents a monovalent organic group having a ring structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine and piperidine, and X represents a divalent piperazine group.

(wherein, X represents a divalent organic group having at least one ring structure of a nitrogen atom-containing ring selected from the group consisting of pyridine, pyrimidine, triazine and piperazine, and R9 represents an organic group, and X in the plural may be the same or different. -14 - , piperazine 2 200846788 a monosubstituted phenylenediamine represented by the following formula (V); a diamine organooxane represented by the following formula (VI);

(wherein R10 represents a divalent organic group selected from the group consisting of -0, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, and R11 represents a steroid skeleton, a trifluoromethyl group, and a monovalent organic group of a fluorine group or an alkyl group having a carbon number of 6 to 30.) Η

PR12

Ch2卜nh2 (VI)

P (wherein R12 represents a hydrocarbon group having 1 to 12 carbon atoms, and R12 of each of plural numbers may be the same or different, P is an integer of 1 to 3, and q is an integer of 1 to 20). Each of the compounds shown in 9) to (13). These diamine compounds may be used singly or in combination of two or more. -15- 200846788

^CH3 ~CH3 (10)

/CH3, ch3 (11)

(12)

NH2

(13) (wherein y is an integer of 2 to 12, and z is an integer of 1 to 5.) Among them, P-phenylenediamine, 4,4'-diaminediphenylmethane, 4, 4'-Diamine diphenyl sulfide, 1,5-diamine naphthalene, 2,7-diamine oxime, 4,4, diamine diphenyl ether, 2,2-bis[4-(4-amine Phenoxy)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-phenylenediisopropylidene)diphenylamine, 4,4'-(m-phenylphenyldiisopropylidene) double Aniline-16- 200846788, 1,4-cyclohexanediamine, 4,4'·methyl bis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4' - bis(4-aminophenoxy)biphenyl, 4-(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diamine benzoate, the above formula (9)~ (13) each of the compounds shown, 2,6-diamine pyridine, 3,4-diamine pyridine, 2,4-diaminopyrimidine, 3,6-diamine acridine, 3,6-diamine oxime Oxazole, N-methyl-3,6-diamine carbazole, N-ethyl-3,6-diamine carbazole, N-phenyl-3,6-diamine carbazole, N,N'-di (4-aminophenyl)-benzidine Among the compounds represented by the above formula (III), the compound represented by the following formula (14), the compound represented by the following formula (1) in the compound represented by the above formula (IV), and the above formula (V) Among the compounds shown, dodecyloxy-2,4-diamine benzene, pentadecyloxy-2,4-diamine benzene, hexadecyloxy-2,4-diamine benzene, eighteen Alkoxy-2,4-diamine benzene, dodecyloxy-2,5-diamine benzene, pentadecyloxy-2,5-diamine benzene, hexadecyloxy-2,5- Diamine benzene, octadecyloxy-2,5-diamine benzene, a compound represented by each of the following formulas (16) to (22), and 1, 3 of the compound represented by the above formula (VI) - bis (3-aminopropyl tetramethyl bismuth oxide is preferred. -17- (14) 200846788 COO - CH2CH2~^^ H2N-1〇LnH2 (15)

/CH3 CH3 (19) (21) -18- 200846788

CHS

[Synthesis reaction of poly-proline] The ratio of the use of the tetracarboxylic dianhydride to the diamine compound in the synthesis reaction of poly-proline, and the tetracarboxylic acid for 1 equivalent of the amine group contained in the diamine compound The acid anhydride group of the acid dianhydride is preferably a ratio of 0.5 to 2 equivalents, more preferably 0.7 to 1.2 equivalents. The synthesis reaction of poly-proline is carried out in an organic solvent, preferably at -20 to 150 ° C, more preferably at a temperature of 〇 1 to 1 ° C. In addition, as the organic solvent, only the synthesized polyimidic acid can be dissolved, and it is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N. , aprotic polar solvent such as N-dimethylformamide, dimethyl hydrazine, 7-butyrolactone, tetramethyl urea, hexamethylphosphonium; m-cresol, xylenol, phenol A phenolic solvent such as a halogenated phenol. Further, the amount (a) of the organic solvent used is such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is from 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution. good. [Weak solvent] In the above organic solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, or the like of a weak solvent of polyphosphoric acid is used in combination in a range in which the produced polyamic acid is not precipitated. Specific examples of the related weak solvent include, for example, A-19-200846788 alcohol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanol, diethyl alcohol, and B. Glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propyl Acid ester, ethyl ethoxy propionate, monoethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl acid, ethyl ether, ethyl alcohol-propyl, ethylene Alcohol-i-propyl ether, ethylene glycol·η-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloro Methane, 〗, plant dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, hydrazine-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, iso Pentylpropionate, isoamyliso Butyrate, diisoamyl ether, and the like. As the above, a reaction solution obtained by dissolving polyphosphamic acid can be obtained. On the other hand, the reaction solution is poured into a large amount of a weak solvent to obtain a precipitate, and the precipitate is dried under reduced pressure, or the reaction solution can be distilled off under reduced pressure in a distiller to obtain polyphosphonic acid. Further, the polypyridic acid can be purified by dissolving the polyimidic acid in an organic solvent, followed by a step of precipitating with a weak solvent or a step of distilling off under a reduced pressure in a retort. [Iminized polymer] The imidized polymer constituting the liquid crystal alignment agent of the present invention can be prepared by subjecting the polyamic acid as described above to a ring closure by dehydration. The polyimine used in the present invention may be a partially dehydrated ring-closing -20-200846788 having an imidization ratio of less than 100%. Here, the "imidization ratio" is a ratio of a ratio of repeating units having an imine ring or an imine ring in a total repeating unit of the polymer expressed as a percentage. An alignment agent containing an imidized polymer having an imidization ratio of 10 to 80% is particularly useful for evaluation of a high voltage holding ratio when used in a TFT type element. The dehydration ring closure of poly-proline can be carried out by (i) heating the poly-proline, or by dissolving the poly-proline in an organic solvent, adding a dehydrating agent and dehydrating ring-contact The medium is carried out as necessary by heating. The reaction temperature in the above (i) method of heating the polyimidic acid is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. When the reaction temperature is less than 50, the dehydration ring-closure reaction is difficult to proceed sufficiently, and if the reaction temperature exceeds 200 ° C, the molecular weight of the imidized polymer obtained is lowered. On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the solution of the poly-proline in the above (ii), as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent to be used is preferably 0.01 to 20 moles per 1 mole of the repeating unit of polyamic acid. Further, as the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to this. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 moles per 1 mole of the dehydrating agent used. Further, examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified for the synthesis of polyimidic acid. The reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, preferably from 10 to 15 ° C. Further, with respect to the reaction solution thus obtained, the imine-21 - 200846788 polymer can be purified by the same operation as the purification method of poly-proline. The imidization ratio can be determined by the following method. Method for determining the imidization ratio of imidized polymer The imidized polymer is dried under reduced pressure at room temperature, and then dissolved in a hydrogenated monomethyl yam, which uses tetramethyl sand as a reference substance. 1H-NMR was measured at a temperature, and it was obtained by the formula represented by the following formula (ii). _ imidization rate (%) II (l-AVA^a) xi00 ______( ϋ) A1·Crest area of protons from NH group (10 ppm) A2: Peak area from other protons (2: Polymer drive The ratio of the number of other protons of one NH matrix in the body (poly-anisic acid) [end modification] ^ The above poly-proline and imidized polymers may also be molecularly modified end-modified By using the terminal-modified polymer, the coating property of the liquid crystal alignment agent can be improved without impairing the effects of the present invention, etc. Such an end-modified type can be obtained by using an acid when synthesizing poly-proline A monoanhydride, a monoamine compound, a monoisocyanate compound, or the like is added to the reaction system to synthesize it. Examples of the acid monoanhydride include maleic anhydride, peptide anhydride, itaconic anhydride, η-fluorenyl anhydride, and η- The lauryl group is an acid anhydride, η-tetradecyl succinic anhydride, η-hexadecyl succinic anhydride, etc. Further, examples of the monoamine compound include aniline, cyclohexylamine, η-butylamine, and η-pentyl. Amine, η-hex-22-200846788 amine, η-pentylamine, η-octylamine, η-壬, η-decylamine, η-undecylamine, n-laurylamine, η-tridecylamine, η-tetradecylamine, η-pentadecaneamine, n-hexadecylamine, n-ten Further, as the monoisocyanate compound, for example, phenyl isocyanate or naphthyl isocyanate may be mentioned. Solution viscosity is used for polymerization of the alignment agent of the present invention. When the amount is 1% by weight of the solution, it is preferably a viscosity of 20 to 800 mPa·s, and a viscosity of 30 to 500 mPa·s is preferable. Further, the solution viscosity of the polymer (mPa · s) In order to use the predetermined solvent, the solution diluted to the solid content concentration was measured at 25 ° C using an E-type rotary viscometer. <Imidazole compound> The liquid crystal alignment agent of the present invention contains the above formula (A). The imidazole compound may be used singly or in combination of two or more kinds. In the above formula (A), R1, R2 and R3 each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a carbon number of 1 to 4. Alkyl. Further, :^ is an integer of 0 to 3, preferably 〇 or 1. As an imidazole compound, for example Preferred examples of the respective compounds represented by the following formulas (23) to (27) are mentioned. The addition ratio of these oxime compounds is preferably from 0 to 1 to 40 parts by weight based on 100 parts by weight of the polymer. -23- 200846788

H3c (27) <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is composed of the above polyimine acid, the imine compound, the above-mentioned imidazole compound, and any other added organic solvent. The concentration of the liquid crystal alignment agent constituting the present invention is 10 to 80% in terms of the total number of bond units of the imine linkage unit and the imine bond unit. The organic solvent constituting the liquid crystal alignment agent of the present invention can be suitably selected as the same weak solvent which can be catalyzed by the synthesis reaction of polyimidic acid in the same tank as exemplified for the synthesis reaction of polyimidic acid. Use it later. Examples of the particularly preferred organic solvent used in the tank of the present invention include N-methyl-2-pyrrolidone, γ-butyrolactam, N,N-dimethylformamide, and N. N- = ubiquinone or polyfluorene is dissolved in the compound, and the number can be exemplified. Also, used together: crystal alignment agent ketone, T-butyl. methyl ethyl hydrazine-24-200846788 amine, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate , butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-η-propyl ether, ethylene glycol -i-propyl ether, ethylene glycol-η-butyl ether (butyl glycol 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 An acid ester, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether or the like. These can be used singly or in combination of two or more. A particularly preferable solvent composition is a composition obtained by combining the above solvents, a polymer is not precipitated in the alignment agent, and the surface tension of the alignment agent is in the range of 25 to 40 mN/m. The solid content concentration in the liquid crystal alignment agent of the present invention can be selected in consideration of viscosity, volatility, and the like. It is preferably in the range of 1 to 10% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film as a liquid crystal alignment film. However, when the solid concentration is less than 1% by weight, the film thickness of the coating film is too small, and it is difficult to obtain a good liquid crystal alignment. membrane. When the solid content concentration exceeds 10% by weight, the film thickness of the coating film is too large, and it is difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent is increased to easily deteriorate the coating properties. Further, the particularly preferable range of the solid content concentration differs depending on the method used for applying the liquid crystal alignment agent to the substrate. For example, it is particularly preferably in the range of 1.5 to 4.5% by weight by the spin coating method. When the printing method is carried out, the solid content concentration is in the range of 3 to 9 % by weight, whereby the viscosity of the solution is particularly preferably in the range of 12 to 50 mPa · s. When the ink jet method is carried out, the solid content concentration is in the range of 1 to 5 % by weight, whereby the solution viscosity -25 - 200846788 is particularly preferably in the range of 3 to 15 mPa · s. Further, the temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 0 to 200 ° C, more preferably 20 to 60 ° C. In the liquid crystal alignment agent which forms the liquid crystal alignment film of the present invention, a compound having at least one epoxy group in the molecule (hereinafter also referred to as "epoxy group-containing compound" is contained from the viewpoint of improving adhesion to the surface of the substrate. ") is better. Examples of the epoxy group-containing compound include ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, and tripropylene glycol diepoxypropyl ether. Polypropylene glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, glycerol diepoxypropyl ether, 2,2-di Bromo neopentyl glycol diepoxypropyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N'-tetraepoxy Propyl-m-xylenediamine, 1,3-bis(N,N-diglycidylmethyl)cyclohexyl, N,N,N',N'-tetraepoxypropyl-4,4 Preferred examples of '-monoamine-phenyl ketone, N,N,-diepoxypropyl-benzylamine, N,N-diepoxypropyl-amine methylcyclohexane, and the like. The addition ratio of the epoxy group-containing compound is preferably 40 parts by weight or less, more preferably ο1 to 30 parts by weight, based on the parts by weight of the polymer loo. Further, the liquid crystal alignment agent of the present invention also contains a compound containing a functional government. Examples of the compound containing a functional sand chamber include 3-aminopropyltrimethoxysulfonium, 3-aminopropyltriethoxylate, 2-aminopropyltrimethoxycyanate, and 2- Aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, Ν(2-aminoethyl)-3-aminopropylmethyldimethoxy sand , 3-Uropropylpropyltrimethoxycurement, ureidodiethoxydecane, oxime-ethoxycarbonyl-3-aminopropyltrimethoxy oxime, oxime-ethoxy-26-200846788 carbonyl 3-aminopropyltriethoxydecane, N-triethoxycarbamidopropyltriethylenetriamine, N-trimethoxymethylmercaptopropyltriethyltriamine, oxime-trimethoxy Methyl decyl-1,4,7-triazadecane, 10-triethoxymethyl sulfonyl 1,4,7-triazadecane, 9-trimethoxyformamidin-3, 6-diazaindolyl acetate, 9-triethoxycarbamido-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-Benzyl-3-aminopropyldiethoxy oxime, N-phenyl-3-aminopropyldimethoxy sulfoxide, N-phenyl-3-aminopropyltriethoxy Base decane N - bis (oxyethylene) -3 - aminopropyl trimethoxy Silane, N- bis (oxyethylene) -3-aminopropyl triethoxy silane-like. The addition ratio of the compound containing a functional decane is preferably 40 parts by weight or less based on 100 parts by weight of the polymer. <Liquid crystal display element> The liquid crystal display element obtained by using the liquid crystal alignment agent of the present invention can be produced, for example, by the following method. (1) The liquid crystal alignment agent of the present invention is applied to a substrate surface on which a patterned transparent conductive film is provided, for example, by a roll coating method, a spin coating method, a printing method, an inkjet method, or the like. Next, a coating film is formed by heating the coated surface. Wherein 'for the substrate, for example, glass such as floating glass or soda lime glass can be used; and polyethylene terephthalate, polybutylene terephthalate, polyether maple, polycarbonate, and fat can be used. A transparent substrate made of plastic such as a cyclic polyolefin. As the transparent conductive/electric film provided on the surface of the substrate, an ITO film made of tin oxide (Sn02), a ITO film made of indium oxide-tin oxide (In2〇3_Sn02), or the like can be used. -27- 200846788. The pattern of the transparent conductive films forms a method which can be used by photolithography or a pre-mask. When the liquid crystal alignment agent is applied, the surface of the substrate and the adhesion between the transparent conductive film and the coating film are further improved, and a compound containing a functional decane or a compound containing a functional titanium may be applied to the surface of the substrate in advance. Wait. The heating temperature after application of the liquid crystal alignment agent is, for example, 80 to 3 〇〇 ° C, more preferably 120 to 250 ° C. The liquid crystal alignment agent of the present invention containing polyimidic acid can form a coating film as an alignment film by removing an organic solvent after coating. The film thickness of the liquid crystal alignment film formed is preferably 0.001 to Ιμηι, more preferably 0.005 to 0.5 μm. (2) On the surface of the formed coating film, for example, a cloth made of fibers such as nylon, rayon, or cotton is taken up in a tubular shape and then subjected to rubbing treatment in a predetermined direction. Thereby, the alignment of the liquid crystal molecules can be imparted to the liquid crystal alignment film of the coating film. Further, in the liquid crystal alignment film formed by the liquid crystal of the present invention, the pretilt angle is generated by partial irradiation with ultraviolet rays as disclosed in Japanese Laid-Open Patent Publication No. Hei. 6-222366 or JP-A-6-28193A. The treatment is carried out under the change, or a photoresist film is partially formed on the rubbed liquid crystal alignment film, and the rubbing treatment is performed in a direction different from the preceding rubbing treatment, and the foregoing is removed. The photoresist film can be processed under the aligning energy of the liquid crystal alignment film to improve the visual field characteristics of the liquid crystal display element. (3) Two substrates formed by the liquid crystal alignment film are formed, and the rubbing directions of the liquid crystal alignment films are orthogonal or antiparallel, and the two substrates are arranged opposite to each other with a cell gap. The peripheral portion of the substrate is bonded by a sealing agent, and liquid crystal is injected into the gap defined by the surface of the substrate and the sealing agent -28-200846788, and the injection hole is sealed to constitute a liquid crystal cell. On the outer surface of the liquid crystal cell, that is, on the outer side of each of the substrates constituting the liquid crystal cell, a liquid crystal display element is obtained by disposing a polarizing plate. Here, as the sealing agent, for example, a curing agent and an epoxy resin containing an alumina ball as a spacer can be used. Examples of the liquid crystal include nematic liquid crystal and smectic type liquid crystal. Further, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a triphenyl liquid crystal, or a combination can be used. A benzocyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal, or the like. Further, a cholesteric liquid crystal such as chlorinated gallbladder, cholestyl phthalate or cholestyl carbonate may be added to the liquid crystal, or the product name "C-1 5" or "CB-15" (Merck) ) Used after the sale of palmar reagents. Further, a ferroelectric liquid crystal such as P-methoxybenzylidene-P-amine-2-methylbutylcinnamate may be used. In addition, as a polarizing plate which is bonded to the outer surface of the liquid crystal cell, a polarizing plate in which a polyvinyl alcohol is stretched downward and a polarizing film which absorbs iodine and is called an H film is held by a cellulose acetate protective film, or the H film itself is exemplified. The resulting polarizer. As described above, the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention exhibits a high voltage holding ratio as compared with the conventional alignment film, and exhibits a low scorch mark at an arbitrary use temperature, which is suitable for forming a TN type liquid crystal display. Various types of liquid crystal display elements such as an element, an STN type liquid crystal display element, a reflective liquid crystal display element, and a transflective liquid crystal display element. The liquid crystal display element of the present invention can be effectively used on various devices. Example -29- 200846788 Applicable to desktop computers, wristwatches, clocks, mobile phones, counting display boards, word processors, personal computers, LCD TVs, etc. [Embodiment] EXAMPLES Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited by the examples. The imidization ratio, voltage holding ratio, and coatability of the imidized polymer in the examples and the comparative examples can be evaluated by the following methods. [Method for measuring imidization ratio of imidized polymer] The imidized polymer is dried under reduced pressure at room temperature, and then dissolved in dimethyl hydrazine, and tetramethyl decane is used as a reference material. 1 H-NMR was determined by the temperature in the middle, and was obtained by the formula represented by the following formula (ii). Amination rate (%) = ( l-AVA2x a ) xlOO ......( ϋ ) A1: peak area of protons from NH groups (10 ppm) A2: peak area from other protons α: before polymer In the body (poly-proline), the ratio of the number of other protons of one ruthenium matrix [voltage retention rate] -30- 200846788 is performed on the liquid crystal display device at a voltage of 5 V for 60 microseconds plus time, to 1 After the addition of the 67 msec time, the voltage holding ratio after 167 ms after the external release was measured. The measuring device used (share) VHR-1 manufactured by Dongyang Techniea. When the voltage holding ratio was 95% or more, it was judged to be good, and otherwise, it was judged to be defective. [Coke Trace Test] As shown in Fig. 1, a unit cell having an ITO electrode was produced. A DC voltage of 6.0 V was applied to the electrode A, and a DC voltage of 0.5 V was applied to the electrode B, and the temperature was applied at room temperature and 80 ° C for 20 hours. After the pressure is released, the DC voltages 〇 1 to 3.0 V are applied to the electrodes A and B at a scale of 0 · 1 V. The scorch property was judged by the difference in luminance between the electrodes A and B of the respective voltages. When the difference in luminance is large, it is judged that the scorch characteristic is poor. Synthesis Example 1 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride 11 〇g (〇.5 摩尔) and 1,3,3&, 4,5,91>- Hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furan)naphtho[i,2-c]furan-1,3-dione 160g (0.55 mol) , as a diamine compound, p_phenylenediamine 96g (0.87 mole), 1,3-bis(3-aminopropyl)tetramethyldioxane 25g (〇.l mole), and 3,6-bis(4-aminobenzoic acid) cholestane 13 g (〇.〇2 mol), N-octadecylamine as a monoamine 8.1 g (0.03 mol) dissolved in N-methyl- 2-Pyrrolidone 9 60 g, 6 hours reaction at 60 ° C to obtain a poly-prolinic acid solution with a solution viscosity of 60 mPa · s (this is called poly-proline-31 - 200846788 (B - 1 )) . Next, 2,700 g of N-methyl-2-pyrrolidone was added to the obtained poly-proline solution. After 400 g of pyridine and 41 〇g of acetic anhydride were added, the mixture was dehydrated and closed at 1 〇 ° C for 4 hours. After the imidization reaction, the solvent in the system is solvent-substituted with unused r-butyrolactone (the pyridine and acetic anhydride used in the imidization reaction of the present operation are removed from the system) to obtain a solid concentration of 15.0. The solution viscosity at a weight % and a solid concentration of 6.0% by weight is 16. 〇111?&.5, and the imidization polymer "A-1" solution having an imidization ratio of 95% is 1,500 g. Synthesis Example 2 190 g (0.85 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 1,3,3&,4,5,91?-hexahydro-8 -Methyl-5-(tetrahydro-2,5-dioxo-3-furan)naphtho[1,2-(:]furan-1,3-dione 478 (0.15 mol), as a diamine Compound p-phenylenediamine 92g (0.86 mole), 1,3 bis(3-aminopropyl)tetramethyldioxane 25§ (0.1 mole), and 3,6-double ( 4-aminobenzoic acid) cholestane l9g (〇.〇3mol), aniline as a monoamine 2.8g (0.03 mol) dissolved in N-methyl-2-pyrrolidone l, l〇〇g, After 6 hours of reaction at 60 ° C, a poly-prolinic acid solution having a solution viscosity of 60 mPa · s was obtained. Next, 3,900 g of r · butyrolactone was added to the obtained poly-proline solution, and 400 g of pyridine and 410 g of acetic anhydride were added. , dehydration ring closure at 1 10 ° C for 4 hours. After the imidization reaction, the solvent in the system is solvent-substituted with unused N-methyl-2-pyrrolidone (the operation is used in the imidization reaction). Pyridine and acetic anhydride were removed from the system to obtain a solid content concentration of 15.0% by weight, solid content Degree -32- 200846788 The viscosity of the solution at 6.0% by weight is 16.0 mPa · s, and the imidization rate of 95% of the imidized polymer (A-2) solution is 1,600 g. Synthesis Example 3 will be used as the tetracarboxylic dianhydride. 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 220 g (1.0 mol), p-phenylenediamine ii〇g (〇·99 mol) as a diamine compound, and cholestane Base 3.8,5-diamine benzoate 7.8 g (0.015 mol) was dissolved in N-methyl-2-pyrrolidone 3,100 g, and the reaction was carried out for 3 hours at room temperature to obtain a solution viscosity of 21 OmPa · s. a poly-proline solution (this is called poly-proline (B-2)). Secondly, a trace of N-methyl-2-pyrrolidone in the obtained poly-proline solution is 3,400 g. Add 400g of pyridine and 300g of acetic anhydride, and carry out dehydration ring closure at 10 ° C for 4 hours. After the imidization reaction, the solvent in the system is replaced with the solvent of unused r - butyrolactone (this operation) The pyridine and the acetic anhydride used in the imidization reaction are removed from the system to obtain a solution viscosity of 15.0% by weight of the solid component concentration and 3.1% by weight of the solid component concentration of 0.1 OmPa · s, and an imidization ratio of 90%. 2,300 g of a solution of the polymer (A-3). Synthesis Example 4 200 g (1.0 mol) of 1,2,3,4·cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride as a diamine compound 2,2'-Dimethyl-4,4'-diamine biphenyl 210g (1.0 mole) dissolved in N-methyl-2-pyrrolidone 3 70g, 7-butyrolactone 3,300g, 40 ° C The reaction was carried out for 3 hours to obtain a solution of poly-proline (this is called poly-proline (B_3 - 33 - 200846788)) having a solution viscosity of 160 mPa·s. Synthesis Example 5 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride 110 g (0.5 mol) and 1,3,3a,4,5,9b-hexahydro-8-A -5-(tetrahydro-2,5-dioxo-3-furan)naphtho[1,2-indolylfuran-1,3-dione 160§ (〇·5 mol), as a diamine Compound P-phenylenediamine 82g (0.76 mole), bisaminopropyltetramethyldioxane 25g (0.1 mole), 4-(4'-trifluoromethoxybenzylideneoxy Cyclohexyl-3,5-diamine benzoate 35 g (0.0 8 mol), and 4,4'-diamine diphenylmethane 9.9 g (〇.〇5 mol), aniline as a monoamine 1.4 g (0.015 mol) was dissolved in N-methyl-2-pyrrolidone 1,3 〇〇g, and reacted at 60 ° C for 6 hours to obtain a polyimidic acid having a solution viscosity of 55 mPa·s. The obtained polyimidic acid was dissolved in 2,500 g of N-methyl-2-pyrrolidone, 400 g of pyridine and 410 g of acetic anhydride were added, and dehydration ring closure was carried out at 110 ° C for 4 hours. After the imidization reaction, the solvent in the system is substituted with an unused N-methyl-2-pyrrolidone (the pyridine and acetic anhydride used in the imidization reaction of the present operation are removed from the system) to obtain a solid component. The solution having a concentration of 17.0% by weight and a solid content concentration of 6.0% by weight was 1,300 g of a solution of imidized polymer (A-4) having a solution viscosity of 1 3 · 0 mPa·s and an imidization ratio of 95%. Example 1 The polyimine (A-1) obtained in Synthesis Example 1 and the poly-proline (B-3) obtained in Synthesis Example 4 were polyiminimide: polyimidic acid = 20:8〇 -34- 200846788 (by weight) dissolved in 7-butyrolactone / N-methyl-2 - benzophenone / butyl glycol ether mixed solvent (weight ratio 7 1 /1 7 / 1 2 ) For 100 parts by weight of the polymer, 2 parts by weight of N,N,N',N'_tetraepoxypropyl-4,4'-diamine diphenylmethane is dissolved, and for 1 part by weight of the polymer, 2.5 parts by weight of a compound represented by the above formula (2 3 ) as an imidazole compound, and a solution having a solid concentration of 6 wt%, which was sufficiently stirred, was filtered using a filter having a pore size of 1 μm to prepare a solution. The liquid crystal alignment agent of the invention. The imidization ratio is applied to a transparent conductive film formed by providing an ITO film on one surface of a glass substrate having a thickness of 1 mm, using a liquid crystal alignment film printer (manufactured by Nippon Photocopier Co., Ltd.). After drying on a hot plate at 80 ° C for 1 minute, it was dried on a hot plate at 200 ° C for 10 minutes to form a film having an average film thickness of 600 Å. On the film, a rubbing machine having a drum wound with a rayon cloth was used to perform a rubbing treatment at a drum rotation number of 400 rpm, a table moving speed of 3 cm/sec, and a bristle length of 0.4 mm. The liquid crystal alignment film-coated substrate was subjected to ultrasonic cleaning in ultrapure water for 1 minute, and then dried in a clean oven at ° C for 10 minutes. Next, a liquid crystal alignment film having a diameter of 5.5 μm is applied to a liquid crystal alignment film having a pair of transparent electrode/transparent electrode substrates on the liquid crystal alignment film, and then a liquid crystal alignment film is applied. The surface is superposed and pressed against the lower side to harden the adhesive. Next, after the liquid crystal injection port is interposed between the substrates, the nematic liquid crystal (manufactured by Merck Co., Ltd., MLC-622 1) is filled, and the liquid crystal injection □ is sealed with an acrylic photocurable adhesive, and the polarizing plates are bonded to both sides of the substrate. A liquid crystal display element is produced. The voltage holding ratio of the obtained liquid crystal display element was evaluated. The liquid crystal alignment -35-200846788 obtained by the present invention shows a higher voltage of 99% or more in voltage holding ratio. Further, after the scorch test, the results were unsatisfactory at any pressure and temperature. Examples 2, 3 and Comparative Examples 1 to 1 0 Polyimine (A-1) to (A-4) and polyphosphite (B-1) to (8-) obtained in Synthesis Examples 1 to 5 3) and >1,>^'3'-tetraepoxypropyl-4,4'-diaminediphenylmethane is dissolved in a mixed solvent containing r-butyrolactone as a main component, and is further implemented In the examples 2 and 3 and the comparative examples 1, 3, 5, 7, and 9, the imidazole compound represented by the above formula (24) was dissolved to obtain a solution having a solid concentration of 6 wt%, and the solution was filtered through a filter having a pore size of Ιμπι. The liquid crystal alignment agent of the present invention is used. Using the liquid crystal alignment agent thus prepared, a film was formed on the surface of the substrate in the same manner as in Example 1, and a liquid crystal display element was produced using the substrate on which the liquid crystal alignment film was formed. The voltage retention rate is evaluated. Also, a scorch test was also performed. The results are shown in Table 1.

-36- 200846788

I漱Scratch evaluation (good: 〇, poor: X) Room temperature 〇, 80 ° C 〇 room temperature 80, 80 ° C 〇 room temperature 80, 80 ° C 〇 1 room temperature 〇, 80 ° C x room temperature 〇, 80 ° C x room temperature X, 80 ° c 〇 room temperature x, 80 ° C 〇 room temperature x, 80 ° C 〇 room temperature 80, 80 ° C 〇 room temperature 80, 80 ° C x room temperature x, 80 ° C 〇 Room temperature x, 80 ° c 〇 room temperature X, 80 ° C 〇 voltage retention rate (%) >99 >99 >99 1______>99^I >99 <99 <99 <99 > 99 >99 >99 <99 <99 §§__ 翠 W £_ m tr> (N ^Τϊ (N 〇(NO <n r4 ο <Ν ο ΙΤϊ (N o imidate bond) Unit (%) 18.6 19.1 19.0 93.0 93.0 〇o ο 18.6 89.0 19.0 Ο o Polyimine: Polyimine weight ratio 20/80 20/80 20/80 100/0 100/0 0/100 0/100 1 0/100 20/80 100/0 20/80 0/100 0/100 Polymer PQ m < A-2, B-3 A-4, B-3 H << ώ ώ rn ώ ώ f Η—Η < Α-3 A-4, B-3 B-2 (N 实施 Example (N mi comparison example, etc. < (N m inch 〇〇 〇〇 〇〇 ON o φ>__*Νφ>¥« 00Ι 仞 迄 ** -37- 200846788 Schematic description of Figure 1 shows the use of the burn test Creating an explanatory view of a crystalline ITO electrodes of the cell.

-38-

Claims (1)

200846788 X. Patent application scope 1. A liquid crystal alignment agent characterized by having an imine bond unit of the following formula (I) and an imide bond polymer represented by the following formula (1-2), wherein The ratio of the number of imine bond units per unit of the phosphoric acid bond unit to the imine bond unit bond is 10 to 80%, and the total amount of the unit containing the formula (A); Have the following HO〇C\ COOH HNOC〆 \〇ΝΗ —Q1- i-i) (where p1 is a tetravalent organic group and (^ is a divalent organic group) ο ο (wherein Ρ2 is a tetravalent organic group and Q2 is a divalent organic group) R3 (Α) η is 0. The acid dianhydride 3-furan (wherein R1, R2, and R3 are each independently a hydrogen atom or an alkyl group, an integer of 〜3). 2. The liquid crystal alignment agent of claim 1, wherein Ρ1 or Ρ2 is selected from the group consisting of 2,3,5-tricarboxycyclopentylethyl, 1,3,3&, 4,5,91)- Hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-39-200846788 )-naphtho[l,2-c]-furan-1,3-one-one and mi-cyclobutane The tetracarboxylic dianhydride in which the tetracarboxylic dianhydride is grouped removes the residue of the two acid anhydride groups. 3. The liquid crystal aligning agent according to claim 1 or 2, wherein the polymer further contains 〇. 1 to 30 parts by weight of at least one epoxy in the molecule. Base compound. A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of claims 1 to 3. A liquid crystal display element characterized by having a liquid crystal alignment film according to item 4 of the patent application. -40-