TW201111416A - Liquid crystal alignment agent - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent which is capable of showing excellent property for coating. Polymer containing in the liquid crystal aligning agent does not precipitate even if continuous printing is proceeded for long period of time. A film property made form the liquid crystal aligning agent is uniform and excellent. Once liquid crystal alignment becomes liquid crystal alignment film, the liquid crystal alignment film is easy to peel. The liquid crystal aligning agent contains at least one polymer selected from the group consisting of polyamic acid and polyimide which is formed by dehydrating-cyclizing reaction; wherein polyamic acid is obtained by reacting tetracarboxylic acid dianhydride with diamine which is specific compound represented by and formula (A) (in formula (A), X is *-O- or *-COO-(wherein a bond with ''*'' is bonding with diaminophenyl); R is methylene, alkylene having 2-10 carbon atoms or arylene having 6-18 carbon atoms; RI is alkyl having 1-6 carbon atoms; n is an integer of 0 to 2.)

Description

201111416 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent. More specifically, the present invention relates to a liquid crystal alignment agent which is excellent in coatability and which is uniform in film quality and excellent in yield when producing a liquid crystal alignment film. [Prior Art] Currently known liquid crystal display elements can be classified into various types shown below depending on the electrode structure and the physical properties of the liquid crystal molecules used. First, a TN type liquid crystal display element having a so-called TN type (twisted nematic) liquid crystal cell is known, which is a liquid crystal alignment film formed on a surface of a substrate on which a transparent conductive film is provided, and is used as a substrate for a liquid crystal display element. The substrate is oppositely disposed, and a layer of nematic liquid crystal having positive dielectric anisotropy is formed in the gap thereof to form a cell of the sandwich structure, and the long axis of the liquid crystal molecule is continuously twisted from one substrate to the other substrate. ° (Patent Document 1)' and an STN (Super Twisted Nematic) liquid crystal display element having a high duty ratio (Patent Document 2) can be realized as compared with a TN type liquid crystal display element. Furthermore, it is also known to use the same counter electrode arrangement as the TN type liquid crystal display element, but injecting a layer of nematic liquid crystal having a negative dielectric anisotropy in the electrode gap, and making the liquid crystal substantially vertical with respect to the substrate. Aligned VA (Vertical Alignment) type display element (Patent Document 3) » This VA type display element can produce a display element of high contrast and large area. On the other hand, an IPS (In-Plane Switching) type liquid crystal in which the electrode pair is disposed in a comb-tooth shape in the plane of one substrate and only the liquid crystal driving direction when an electric field is applied is used as the in-plane direction of the base 201111416 Display element (Patent Document 4), and an FFS (Fringe Field Conversion) type liquid crystal display element (Patent Document 5) in which the IPS type electrode structure is changed and the aperture ratio of the display element portion is increased to improve the luminance, and their respective viewing angle characteristics are excellent. . In addition, an OCB (Optical Compensated Bend) type liquid crystal display element (Patent Document 6) having a small viewing angle dependency and excellent response speed of an image screen has been developed. As a material of the liquid crystal alignment film in these liquid crystal display elements, a resin material such as polyacrylic acid, polyimine, polyamide, or polyester, particularly a liquid crystal formed of polyacrylic acid or polyimine, is known. The alignment film is excellent in heat resistance, mechanical strength, affinity with liquid crystal, and the like, and is therefore used in many liquid crystal display elements (Patent Documents 1 to 4, 7 and 8). Such a liquid crystal alignment film is generally produced by a step of applying a liquid crystal alignment agent which forms a liquid crystal alignment film in a state of being dissolved in a solvent, and then removing the solvent. However, it has been pointed out that in the case of using a liquid crystal alignment agent known hitherto in the production of a liquid crystal alignment film, printing defects such as uneven printing or pores are generated on the formed coating film with a certain probability, and liquid crystal alignment is produced. The product yield at the time of the film is insufficient. For example, in the case of flexible printing, when the printing is continued for a long period of time, the polymer contained in the liquid crystal alignment agent is deposited on the anilox roll of the printing machine, resulting in poor printing. Such a printing failure is considered to be due to insufficient solubility of the polymer contained in the liquid crystal alignment agent. In other words, it is considered to have a liquid crystal alignment property, heat resistance, and the like which are various characteristics necessary for a liquid crystal alignment film. In any case, the molecules must have a straight constituent part in the molecule, so that it is relatively common organic solvent. The solubility is poor, whereby, during continuous printing for a long period of time, the organic solvent is slowly emitted from the roll, thereby causing the polymer molecules to agglomerate each other in the concentrated solution state of the resulting polymer, and thus the polymerization is observed. Material analysis. Further, when such a printing failure occurs, the liquid crystal alignment film which has been formed is peeled off by using a release agent, and the substrate is reused to obtain efficient use of resources, but is formed of the above-described polymer having low solubility. Since the liquid crystal alignment film is inferior in peelability, it is difficult to use it in this way. In the art, in order to achieve both the performance as a liquid crystal alignment film and the solubility in a solvent, the product has been continuously studied for many years. However, there is still a limit to the product yield when producing a liquid crystal alignment film. Therefore, it is expected that the probability of occurrence of a printing failure is extremely low, and even if a printing failure occurs, the liquid crystal alignment agent of the liquid crystal alignment film which has been formed can be easily peeled off. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide an excellent coating property, and even when continuous printing is performed for a long period of time, The polymer contained in the liquid crystal alignment agent is also not precipitated, and the formed film quality is uniform and good, and at the same time, the liquid crystal alignment film which has been formed is easily peeled off. Such a liquid crystal alignment agent is excellent in productivity in the production of a liquid crystal alignment film, and thus is expected in the art. Other objects and advantages of the invention will be apparent from the description which follows. According to the present invention, the above object of the present invention is achieved by a liquid crystal alignment agent comprising at least one selected from the group consisting of polylysine and polyamidene formed by dehydration of the polyglycolic acid. The polyamic acid is obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (A °).

In the formula (A), X is * - 〇 - or * - c 〇〇 -, the above-mentioned linkage bond is bonded to a diaminophenyl group, R is a methylene group, and the number of carbon atoms is 2 to 10 An alkylene group or an arylene group having 6 to 18 carbon atoms, R1 is an alkyl group having a carbon atom of 201111416 and a number of 1 to 6, and η is an integer of 〇~4, where z is a carbonyl group or a formula (Z-1) ) the indicated group, R11

RIII In the formula (Z-1), Rn and rUI are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. According to the present invention, it is provided that the coating property is excellent, and even when continuous printing is performed for a long period of time, the polymer contained in the liquid crystal alignment agent is not precipitated, and the formed film quality is uniform and good. Meanwhile, the already formed liquid crystal alignment film is easy. Peeled liquid crystal alignment agent. The liquid crystal alignment agent ' of the present invention can produce a film uniform and good liquid crystal alignment film with high product yield, and at the same time, contributes to the substrate yield of the liquid crystal display. Therefore, the liquid crystal display element having the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention can be displayed with high quality and is inexpensive, and thus can be applied to, for example, a timepiece, a game machine, a word processor, a notebook computer. Car navigation systems, camcorders, portable information terminals 'digital cameras, mobile phones' various displays, LCD TVs and other display devices. Further, the film formed of the polymer contained in the liquid crystal alignment agent can also be used as an insulating film for an electronic material. [Embodiment] Hereinafter, the present invention will be described in detail. The liquid crystal alignment agent of the present invention comprises at least one polymer selected from the group consisting of polylysine and polydecylamine formed by dehydration of the polyglycolic acid. The polylysine is by four The carboxylic acid dianhydride is obtained by reacting a diamine containing the compound represented by the above formula (A0). <Polyamic acid> [Tetracarboxylic dianhydride] As the tetracarboxylic dianhydride which can be used for the synthesis of the above polyamic acid, for example, butane tetracarboxylic dianhydride, 1, 2, 3, 4 - cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, i,3-dimethyl-i, 2,3,4 -cyclobutane tetracarboxylic dianhydride ' 1,3 -dichloro-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2, 3,4-cyclobutanetetracarboxylic dianhydride, hydrazine, 2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ,, 4,4,-dicyclohexyltetracarboxylic dianhydride 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3, 33,4,5,91>-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-5.methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(:]-furan _1,3-dione, 1,3,33,4,5,91?-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-purine-l,3-dione, i,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo -3-furan Naphthalene [He]·furan-i,3-dione, 1,3,33,4,5,91)-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo 3--3-furyl)-naphthalene [l,2-c]-furan-l,3-dione, i,3,3a,4,5,9b-hexahydro-8-methyl-5-(four Hydrogen-2,5-dioxo-3-furanyl)-naphthalene [丨,2<]-furan-1,3-dione, .201111416 l,3,3a,4,5,9b-hexahydro· 8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)·naphthalene [1,2-indolyl]-furanyl-1,3-dione, 1,3,33, 4,5,913-hexahydro-5,8-dimethyl-5-(tetramethylene-2,5-oxo-3-furanyl)-naphthalene[l,2-c]-furan-1,3- Diketone, bicyclo[2·2·2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3·oxabicyclo[3 2 1;] Xinyuan-2,4 — • Ketospiro- 3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-ring Hexene-i,2-dicarboxylic anhydride, 3,5,6-trimercapto-2-indolemethyl-Fanyuan-2: 3,5: 6-di-field, 4,9-dioxatricyclo [5·3_1·02,6]undecane-3,5,8,10-tetraketone, the following formula (τ—I) and (Τ—π)

(wherein R1 and R3 are each a divalent organic group having an aromatic ring, and R2 and R4 are each a hydrogen atom or an alkyl group, and a plurality of R2 and R4 present may be the same or different) each represented by a compound Aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride; pyromellitic dianhydride '3,3',4,4'-bisphenone tetracarboxylic dianhydride, 3,3',4 , 4'-diphenyltricarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4 , 4'·bisphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenyl Decane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4, bis(3,4-dicarboxyphenoxy)-10-201111416 diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3, 3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'- Biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, pair Propyl-bis(triphenylphthalic acid) dianhydride, meta-propyl-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4' -diphenylether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(hydrogen trimellitate), propylene glycol-double (dehydration partial Triglyceride), 1,4-butanediol-bis(anhydrotrimellitic acid ester), 1,6·hexanediol-bis(anhydrotrimellitic acid ester)' 1,8-octanediol- Bis(hydrogen trimellitate), 2,2-bis(4-hydroxyphenyl)propane-bis(anhydrotrimellitic acid ester), the following formula (T-1)~(T-4) -11- 201111416

-12- 201111416 CH /CH3

?h3

/CH3

(T-4)

An aromatic tetracarboxylic dianhydride such as a compound represented by each. The benzene ring of the above-mentioned tetracarboxylic dianhydride may be substituted by one or two or more alkyl groups (preferably methyl groups) having 1 to 4 carbon atoms. These tetracarboxylic dianhydrides may be used alone or in combination of two or more. The tetracarboxylic dianhydride which can be used for the synthesis of the poly-proline of the present invention contains butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic anhydride, 1,3- selected from the above. Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-ring aromatic atom combination, dipentane-caprate-13- 201111416 tetracarboxylic dianhydride, 2 ,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo -3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene- 2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'- Diketone), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxyl 2-carboxymethylnorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.02'6; H-alkane-3,5,8,10- Tetraketone, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyltricarboxylic dianhydride, 2,2',3,3'-linked Pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the following formula (T-5)~(T-7) in the compound represented by the above formula (T-I)

-14- 201111416 The compound represented by each and the compound represented by the above formula (T - n)m have the following formula (T-8)

At least one of the groups of the compounds (hereinafter referred to as "specific tetracarboxylic dianhydride")' is preferable from the viewpoint that the formed liquid crystal alignment film can exhibit good liquid crystal alignment. More preferably, it is selected from 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 13, 33, 4 as a specific tetracarboxylic dianhydride. ,5,913-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan·1,3-dione, 1,3,3&,4,5,91>-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1,3 -dione ' 3 -oxabicyclo[3.2.1]octane-2,4·dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5 -dioxotetrahydro-3-furanyl)3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane- 2·· 3,5: 6-dianhydride, 4,9-dioxatricyclo[5.3.1.02.6]undecane-3,5,8,10-tetraone, pyromellitic dianhydride and At least one of the groups consisting of the compounds represented by the above formula (τ-5) is particularly preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. The tetracarboxylic dianhydride which can be used for synthesizing the polyamic acid of the present invention preferably contains 50 mol% or more, more preferably 70 mol% or more, based on the total tetracarboxylic dianhydride, and is particularly preferably Containing 80 mol% or more of the specific tetracarboxylic dianhydride as described above. -15- f 201111416 As the four residues which can be used for the synthesis of the poly-proline of the present invention, only the specific tetracarboxylic dianhydride as described above is used. [Diamine] A compound represented by the name of the diamine of the polyglycolic acid of the present invention. The number of carbon atoms of R in the above formula (A) is 2 to 1 Torr, preferably a linear alkylene group having 2 to 6 carbon atoms. The arylene group wherein R is ό18 is preferably a carbon number of 6 to 10. Specific examples thereof include, for example, 1,4-propanyl group and 1,12-propanyl propyl biphenyl group. 4,4'-diyl, diphenylmethane 4,4' dimethylbiphenyl-4,4, diyl and the like. And each of them is preferably: wherein R in the above formula (Α°) is a linear alkyl group of carbon ～6; Ζ is a carbonyl group or a methylene group; and η is a diaminophenyl group in the above formula (Α°). The two amine groups 'better' are the 2,4-position or the 3,5-position. The compound represented by the above formula (Α°) has, for example, 1 - [ 2 - (3,5 · diamino.phenoxy)-ethyl]-11 ketone, 1-[3- (3,5-diamino-phenoxy)-propyl]-pyrrolidine 1·[4-(3,5-diamino-phenoxy)-butyl]•pyrrolidine-1-[ 5-(3,5-diamino-phenoxy)-pentyl]• 啦 slightly steep 1-[6-(3,5-diamino-phenoxy)hexyl]-pyrrolidine-2, 5-(2,5-dioxopyrrolidinium-bromoacetic acid, 3-(2,5-dioxopyrrolidinium)-pyridyl ester, 3 , 5-acid dianhydride, the alkylene group of the above formula (Α°), the arylene group having a carbon number, the 3-propyl group, the -diyl group, the 3,3 atomic number of 2 -2 Integral. For relative examples, it may be a pyridyl-2,5-di-2,5-dione, 2.5-diketone '2.5-diketone' ketone, 3,5-diamine 3,5-diamine -diamino-benzoyl-16- 201111416 4-(2,5-dioxo-pyrrolidin-1-yl)-butylate, 3,5-diamino-benzoic acid 5-(2, 5-dioxo-pyrrolidinyl-p-yl)-amyl ester, 3,5-diamino-benzoic acid 6-(2,5-dioxo-pyrrolidin-1-yl)-hexyl ester 1 -[2-(2,4-diamino-phenoxy) )-ethyl]-pyrrolidine-2,5-dione, 1-[3-(2,4-diamino-phenoxy)-propyl]-pyrrolidine-2,5-dione, 1-[4-(2,4-Diaminophenoxy)-butyl]-pyrrolidine·2,5-dione, Bu[5-(2,4-diamino-phenoxy) -pentyl]-pyrrolidine-2,5-dione, 1-[6-(2,4-diamino-phenoxy)-hexyl]-pyrrolidine-2,5-dione, 1-[ 2-(3,5-Diamino-phenoxy)-ethyl]-2-pyrrolidone, 1-[3-(3,5-diamino-phenoxy)-propyl]-2 - pyrrolidone, 1-[4-(3,5-diamino-phenoxy)-butyl]-2-pyrrolidone, [5-(3,5-diamino-phenoxy) )-pentyl]-2-pyrrolidone, 1-[6-(3,5-diamino-phenoxy)-hexyl]-2-pyrrolidone, 3,5-diamino-benzoic acid 2-(2-oxo-pyrrolidin-1-yl)-ethyl ester, 3,5-diamino-benzoic acid 3-(2-oxo-pyrrolidin-1-yl)-propyl ester, 3, 5-diamino-benzoic acid 4-(2-oxo-pyrrolidin-1-yl)-butyl ester, 3,5-diamino-benzoic acid 5-(2-oxo-pyrrolidin-1- -amyl ester, 3,5-diamino-benzoic acid 6-(2-oxo-pyrrolidin-1-yl)-hexyl ester, 1-[2-(2,4-diamino-benzene Oxy)-ethyl]-2-pyrrolidone, Bu [3-(2,4-diamino-phenoxy) )-propyl]-2-pyrrolidone, 1_[4-(2,4-diamino-phenoxy)-butyl]-2-pyrrolidone, Bu [5-(2,4-II) Amino-phenoxy)-pentyl]-2-pyrrolidone, 1-[6-(2,4-diamino-phenoxy)-hexyl]-2-pyrrolidone, and the like. The compound represented by the above formula (Α°) is preferably the following formula (Α) -17- 201111416

(A) (in the formula (A), a compound represented by the formula (A) wherein X's and Ri are respectively synonymous with the above formula (A.), and n is an integer of 〇2), more preferably the above formula (8) a compound of hydrazine, and particularly preferably selected from the group consisting of [2-(3,5-diamino-phenoxyethyl)-pyrrolidine-2,5-dione, diaminophenoxy)propyl] • pyrrolidine 2'5-ketone, 1-[4_(3,5-diamino-phenoxybutyl)pyrrolidine-2,5-dione, 1-[5-(3,5- Diamino-phenoxy)·pentyl]-pyrrolidine _25-dione, 1-[6·(3,5-amino-phenoxy)hexyl]-pyrrolidine_2,5·2 Ketone, 35·monoamino-benzoic acid 2-(2,5-dioxo-pyrrolidinyl)-ethyl ester, 3,5·diamino-benzoic acid 3-(2,5-di Oxo-pyrrolidinyl)·propyl ester, 3,5-diamino group_ Benzoic acid 4·(2,5-monooxo-pyrrolidinyl)-butyl ester, 3,5·diamine · 5-(2,5-dioxo-pyrrolidinyl-fluorenyl)-pentyl benzoate and 3,5-diamino-benzoic acid 6-(2,5-oxo-oxime ratio slightly steeper At least one of the groups consisting of -1-yl)-hexyl ester. The compound represented by the above formula (Α°) can be conventionally prepared by organic chemistry The method is suitably combined and synthesized. For example, in the above formula (Α), a compound wherein X is a fluorene-, η is fluorene, and a diaminophenyl group is a 3,5-diaminophenyl group, for example, can be synthesized according to the following synthesis scheme. a~c for synthesis" -18* 201111416

OH 2NH(CH2-CH=CH2)2

OH

/N(CH2-CH=CH2)2 n(ch2-ch=ch2)2 (A-1*13)

N_R-OH (A-1a) synthesis diagram a

Cl

Synthetic diagram b -19- 201111416

N(CHrCH=CH2)2 N(CHrCH=CH2)2

O N(CH2-CH=CH2)2 (A-1c)

ON-R-integration is not intended to be c (in the above synthetic scheme, R is synonymous with the above formula (A)) The reaction represented by the above synthesis scheme a can be obtained by making 1,3,5-trihydroxybenzene and The allylamine is preferably reacted in the presence of sodium hydrogen sulfite. The reaction can be carried out at a temperature of 5 to 40 ° C for a reaction time of 5 to 15 hours. By this reaction, a compound (A-1 - la) as an intermediate can be obtained. The reaction represented by the above synthesis scheme b can be preliminarily mixed in a suitable solvent by, for example, preliminarily mixing a compound (A la) having a desired group R and, for example, p-chlorobenzenesulfonyl chloride, in a suitable solvent. This is carried out by adding a suitable base such as monoethylamine. The addition of the base is preferably carried out at a low temperature such as a temperature of from $ -20 to 201111416 to 5 ° C. Then, the reaction system is heated to 1 right' to continue the reaction for about 2 to 4 hours, whereby the intermediate (A - 1 b) can be obtained.

The intermediate compound (a should be 'obtained by the above-mentioned compound (A-1_(A - lb)' preferably in the presence of potassium hydride and tetrabutylammonium bromide) Preferably, the reaction of the compound (A - lc) thus obtained is carried out at a temperature of 5 to 5 ° C for 8 to 15 hours, and the product may be obtained by removing the allyl group. The deallyl reaction can be carried out by In the presence of a compound (A- lc 1,3-dimethylbarbituric acid and hydrazine (triphenylphosphino)palladium, at a temperature of 20 to 40 ° C, preferably a reaction of 2 to 6 hours into C In the above formula (A), X is a compound of *-C00- (wherein a bond is bonded to a diaminophenyl group), and η is 0, and a diaminophenyl group is a phenyl group, for example, The synthesis diagram is as follows: 〇~3 0 C left interbody lc) reverse 1 a) and compound: lower, and more. The target is obtained, preferably in and preferably f ° "" , 5-diamine d is combined -21- 201111416 ο

Ν—R—OH +

(A-1a)

Synthetic Scheme d (in the above synthetic scheme, R is synonymous with the above formula (A)) which can be dissolved by dissolving a compound (a__^) having a desired group R and, for example, 3'5-dinitrophenylphosphonium chloride This is carried out by a method in which a suitable base (for example, triethylamine) is gradually added to a suitable organic solvent. The addition of the base is preferably carried out at a low temperature, for example, a temperature of -5 to 5. Then, the reaction system is heated to about 10 to 30 ° C, and the reaction is continued for about 2 to 4 hours to obtain an intermediate compound (A - 1 d). Next, an amine group is formed by reducing (hydrogenating) the nitro group of the compound (A - 1 d) by using a suitable reduction system such as zinc, ammonium chloride and water, whereby the intended product can be obtained. In the above formula (A), 'X is -〇-, and n is a compound in which the diaminophenyl group is a 2,4-diaminophenyl group', for example, according to the following synthesis scheme e into r c- Λ taj -22- 201111416

Line synthesis. 0 JI C^n~ -R-OH + N〇2 Ί) (A-1a) 02N

[^N-R—Ο ^}~N〇2 Ο 〇2N (A-1e)

(In the above synthetic scheme, 'R is synonymous with the above formula (A)) by dissolving a compound (A-la) having a desired group R and, for example, 2,4-dinitrofluorobenzene in a suitable organic solvent. In the middle, a suitable base (for example, triethylamine) is added thereto, and the reaction system is heated to about 30 to 501, and the reaction is carried out for about 8 to 15 hours to obtain an intermediate compound (a-leP, followed by using appropriate The reduction system, such as zinc, ammonium chloride and water, reduces (hydrogenates) the nitro group of the compound (A - Id) to form an amine group, whereby the desired product can be obtained. In the above formula (A°), X A compound wherein 0 - ' η is hydrazine, Z is a methylene group, and a diaminophenyl group is a 3,5 -diaminophenyl group can be synthesized, for example, according to the following Schemes 23 and 201111416.

N-R-OH (A-1f)

Synthetic diagram f

(A-1g)

N(CH2-CH=CH2)2 (A-1-1a)

(A-1h)

Synthetic Scheme g (in the above synthetic scheme, R is synonymous with the above formula (A °)) -24- 201111416 The reaction represented by the above synthesis scheme f can be carried out by the compound having the desired group R (A - If And a method in which, for example, p-chlorobenzenesulfonyl chloride is preferably pre-mixed in a solvent of an appropriate field and a suitable base (for example, diethylamine) is gradually added thereto. The addition of the base is preferably carried out at a low temperature of, for example, -5 to 5 °C. Then, the reaction system is heated to about 10 to 30 ° C to continue the reaction for about 2 to 4 hours, whereby an intermediate compound (A - I g) can be obtained. The reaction of obtaining the intermediate compound (A _ 1 h) in the above synthesis scheme g can be preferably carried out by using the compound (A _ 1 _ 1 a ) and the compound (A-If) obtained as described above in potassium hydride. It is preferably carried out in the presence of tetrabutylammonium bromide and preferably at a temperature of 5 to 5 ° C for 8 to 15 hours. Then, the thus obtained compound (A - 1 h) is removed from the allyl group to obtain the target product. The allyl group reaction can be carried out by using the compound (A-1h), preferably in the presence of 1,3-dimethylbarbituric acid and hydrazine (triphenylphosphino)palladium, and preferably at 20~ It is preferably carried out at a temperature of 40 ° C for 2 to 6 hours. In the above formula (A), X is a COO-, Z is a methylene group, n is a fluorene, and a diaminophenyl group is a compound of 3,5-diaminophenyl group, for example, according to the following synthesis scheme h is synthesized.

-25- 201111416

Nh2 Synthetic Scheme h (in the above synthetic scheme, R is synonymous with the above formula (A °)) which can be obtained by the compound (A - If) having a desired group R and, for example, 3,5-dinitrobenzene The ruthenium chloride is dissolved in a suitable organic solvent and is slowly added to a suitable base such as triethylamine. The addition of the base is preferably carried out at a low temperature such as a temperature of 5 to 5 °C. Then, the reaction system is heated to about 10 to 30 ° C, and the reaction is continued for about 2 to 4 hours to obtain an intermediate compound (A - li). Next, an amine group is formed by reducing (hydrogenating) the nitro group of the compound (A-1i) by using a suitable reduction system such as zinc, ammonium chloride and water, whereby the desired product can be obtained, and In the above formula (A°), a compound in which X is a fluorene-, z is a methylene group, and η is a fluorene-diaminophenyl group is a 2,4-diaminophenyl group, for example, may be -26-201111416 The synthesis scheme i described below was carried out for synthesis. 〇

02N — OH + f (A-1j)

°2n (A-1k)

N-R-0

NH2 h2n synthesis diagram i (in the above synthetic scheme, R is synonymous with the above formula (A.))

The compound (A ~ 1 j) and 2,4-dinitrofluorobenzene are dissolved in a suitable organic solvent, a suitable base (for example, triethylamine) is added thereto, and the reaction system is heated to 30 to 50 t : Left and right, the reaction is continued for about 8 to 15 hours to obtain an intermediate compound (a - lk). Next, the desired product can be obtained by reducing (hydrogenating) the nitro group of the compound (A - lk) by using a suitable reduction system such as zinc 'ammonium chloride and water to form an amine group. As the limb for synthesizing the poly-proline of the present invention, only the compound represented by the above formula (A) may be used, or the compound -27-201111416 and other diamines represented by the above formula (A) may be used. Used in combination. Examples of other diamines which can be used herein include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4,4,-diaminodiphenylethane. 4,4'-diaminodiphenyl sulfide, 4,4,-diaminodiphenyl-rolling 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4 , diamino benzanilide, 4,4'-diaminodiphenyl ether 1,5-diaminonaphthalene, 2,2,-dimethyl-4,4,-diaminobiphenyl, 5-aminol-1-(4'-aminophenyl !!, % trimethylindan, 6-amino-1-(4'-aminophenyl)-1,3,3-three Methyl indane, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone '3,4'-diaminobenzophenone, 4,4, diaminodiyl Benzophenone, 2,2-bis[4.(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2 , 2-bis(4-aminophenyl)hexafluoropropane, bis[4-(4-aminophenoxy)phenyl]anthracene, L4-bis(4-aminophenoxy)benzene, 4, 4'-bis(4-aminophenoxy)biphenyl, iota, 3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9, 9-bis(4-aminophenyl)- 1〇-hydroquinone, 2,7-diaminoguanidine, 9,9-dimethyl-2,7-diaminofuran, 9,9-bis(4-aminophenyl)anthracene, double (4 -amino-2-chlorophenyl)methane, 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro.4,4'- Amino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-(p-propyldiisopropylidene Bis(aniline), 4,4'-(dipropyldiisopropylidene)bis(aniline), 2,2'-bis[4-(4-amino-2-trifluoromethylbenzene) Oxy)phenyl]hexafluoropropane, 4,4'-diamino-3,3'-bis(trifluoromethyl)biphenyl, 4,4'-diamino-2,2'-bis ( Trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, the following formula (D-1) (D-5 ) -28- 201111416

(D-2)

(D-4)

(05) (In the formula (D-4), y is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5), and an aromatic diamine such as a compound represented by each; -m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, -29- 201111416 Nine methylene diamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7_extension Methylenediamine, tricyclo[6.2.1.02'7]-undecylalkyldimethyldiamine, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(amino group) Aliphatic diamines such as methyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane; and alicyclic diamines; 2,3-diaminopyridine and 2,6-diaminopyridine , 3,4-diaminopyridine, 2.4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrrole '5,6-diamino-2,4-dihydroxypyrimidine 2,4-Diamino-6-dimethylamino-1,3,5-tri-trap, 1,4-bis(3-aminopropyl) piperene, 2,4-diamino-6 -Isopropoxy-1,3,5-tri-trap, 2.4-diamino-6-methoxy-1,3,5-tri-trap, 2,4-diamino-6-phenyl- 1,3,5-three tillage, 2,4-diamino-6-methyl-s-tripper, 2,4-diamino-1,3,5-tri-trap, 4,6-diamine Base-2-vinyl-s-three-pill, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyl Uracil, 3,5-diamino-1,2,4-triazole, 3,8-diamino-6-phenylphenanthridine' 1,4-diaminopiperazine, 3,6-di Amino acridine, anthracene, Ν'-bis(4-aminophenyl)aniline, 3,6-diaminocarbazole, oxime-methyl-3,6-diaminopyrazole, oxime-ethyl -3,6-diaminocarbazole, hydrazine-phenyl-3,6-diaminocarbazole, ^1chuan '-bis(4-aminophenyl)-benzidine, 1 屮 bis (4- Aminophenyl)-indole, Ν'-dimethyl-benzidine and the following formulas (D-I) and (D-II) η2ν

(DI) Ονη2 Η2Νο-一(D-II) -30- 201111416 (In the formula (D - I), R5 is a nitrogen atom-containing cyclic structure having a group selected from the group consisting of pyridine, pyrimidine, tri, and pipe traps. 1 group, XI is a divalent organic group; in the formula (D-II), 'R6 is a 2 group of a nitrogen-containing atomic ring structure selected from the group consisting of pyridine, pyrimidine, tri, and pipe traps' Each of X2 is a divalent organic group, and a plurality of X2 groups present may be different from each other, and a diamine having a nitrogen atom other than the primary amino group in the molecule and the primary amine group; (D - III) Well, piperidine valence organic base, and pitched organic group have 2 phases

H2N

(D-III) (in the formula (D-III), R7 is selected from -〇-, _c〇〇_, -NHCO-, -CONH- or -CO-, and R8 is selected from the group consisting of a monosubstituted phenylenediamine such as a compound represented by a phenyl group, a trifluoromethoxyphenyl group or a fluorophenyl group; or a compound represented by a monovalent organic group or a 6-membered carbon group; D - IV) R9 R9 R9 R9 (D-IV) (In the formula (D-IV), each of R9 each having a carbon number of 12 is the same or different, and each of the mouth is an integer ( ^ is an integer represented by 1 to 20), such as a compound such as a di-O-O-, a steroid-forming group of ～30 alkane hydrocarbyl group, a self-organic 3-amino-organic-31-201111416 decane, etc. A benzene ring possessed by a diamine and a monosubstituted phenylenediamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amino group, and one or more carbon atoms may be used. Further, the alkyl group (preferably methyl group) of 丨~# is substituted. Further, the steroid skeleton in the above formula (D_ ΠΙ) means a skeleton formed by a cyclopentyl-perhydro phenanthrene nucleus or a carbon-carbon bond thereof. 1 in One or two or more skeletons of double bonds. These diamines ' may be used singly or in combination of two or more. As other diamines which can be used for the synthesis of the poly-proline of the present invention, it is preferred to use one selected from the above. P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl -4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,7-diaminofuran, 4,4'- Diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9·bis(4-aminophenyl)anthracene, 2,2-double [4-(4-Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-propyldiisopropylidene) Bis(aniline), 4,4'-(m-propyldiisopropylidene)bis(aniline), 1,4-bis(4-aminophenoxy)benzene, 4,4'-double (4-Aminophenoxy)biphenyl, 1,4-diaminocyclohexane, 4,4, methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane Alkane, a compound represented by the above formula (D-1) to (D-5), 2,6-diamine Pyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, oxime-methyl-3,6-di Amino carbazole, hydrazine-ethyl-3,6-diaminocarbazole, fluorenyl-phenyl-3,6-diaminocarbazole, hydrazine, Ν'-bis(4-aminophenyl)- The following formula (D-6) of a compound represented by the above formula (D-oxime) of benzidine, hydrazine, hydrazine bis(4-aminophenyl) hydrazine, fluorene tert- dimethylbenzidine •32- 201111416

Λ η2ν νη2 (D-6) The compound represented by the above formula (D-II), the following formula (D-7) H2N^0^NC^C3H6-HCN~^C)^NH2 ( D-7) a compound represented by the formula and the dodecyloxy-2,4-diaminobenzene or pentadecyloxy-2,4-diamino group in the compound represented by the above formula (D-III) Benzene, cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecane Oxy-2,5-diaminobenzene, hexadecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, the following formula (D-8) ~(D-15)

-33- 201111416

H2n

In the group consisting of the compound represented by each and the 1,3-bis(3-aminopropyl)-tetramethyldioxane in the compound represented by the above formula (D - IV)

At least one of -34- 201111416 (hereinafter referred to as "other specific diamine"). The diamine which can be used for the synthesis of the poly-proline of the present invention preferably contains 3 mol% or more, more preferably 5 to 90 mol%, and even more preferably 3 to 70, based on the entire diamine. Mole%, and particularly preferably contains 8 to 50 mol% of the compound represented by the above formula (A). The diamine which can be used for the synthesis of the poly-proline of the present invention preferably contains other specific diamines as described above in addition to the compound represented by the above formula (A). The ratio of use of the other specific diamines at this time is preferably 5 mol% or more, more preferably 1 to 97 mol%, still more preferably 30 to 95 mol%, and particularly preferably the total of the diamine. It is a 50-92 mol%» diamine which can be used for synthesizing the poly-proline of the present invention, and is preferably composed only of the compound represented by the above formula (A) and other specific diamines. [Synthesis of Poly-Proline] The poly-proline in the present invention can be obtained by reacting a tetracarboxylic dianhydride with a diamine containing the compound represented by the above formula (A). The ratio of use of the tetracarboxylic dianhydride to the diamine to be supplied to the polyaminic acid synthesis reaction is preferably 0.2 to 2 equivalents based on 1 equivalent of the amine group contained in the diamine. And further preferably a ratio of 0.3 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at -20 ° C to 150 ° C, more preferably at a temperature of 0 to 100 ° C, and preferably 0.1 to 24 Hours, preferably for 0.5 to 12 hours. As the organic solvent which can be used in the synthesis of polyamic acid, for example, an aprotic polar solvent, a phenol and a derivative thereof, an alcohol, a ketone, an ester 'ether, a halogenated hydrocarbon, a hydrocarbon, or the like can be listed. Examples of the aprotic polar solvent include N-methyl-2-zegitidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide. 'r_butyrolactone' tetramethylurea, hexamethylphosphonium triamide, etc., and examples of the phenol derivative include m-methylphenol and xylene hydrazine' halogenated phenol; and examples of the alcohol include methanol. , ethanol, isopropanol 'cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc.: Examples of the ketone include acetone and methyl ethyl Ketone, methyl isobutyl ketone, cyclohexanone; examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, and ethoxylate. Ethyl propyl propionate, diethyl oxalate, diethyl malonate, etc.; as the ether, for example, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol different Propyl ether 'ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol two Ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, etc.; as the halogenated hydrocarbon, for example, two Methyl chloride, 1,2-dichloroethane, 1,4-dichlorobutane 'trichloroethane, chlorobenzene, o-dichlorobenzene, etc.; as the above hydrocarbon, for example, hexane, heptane, octane Benzene, -36- 201111416 Toluene, xylene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like. Among these organic solvents, it is preferred to use one or more selected from the group consisting of an aprotic polar solvent and a phenol and a derivative thereof (the first group of organic solvents) or an organic group selected from the aforementioned first group. One or more of the solvents and a mixture of one or more selected from the group consisting of alcohols, ketones, ethers, halogenated hydrocarbons, and hydrocarbons (the second group of organic solvents). In the latter case, the ratio of the organic solvent used in the second group is preferably 50% by weight or less, more preferably 40% by weight based on the total of the organic solvent of the first group and the organic solvent of the second group. % or less, and further preferably 30% by weight or less. As described above, a reaction solution formed by dissolving polylysine can be obtained. The reaction solution may be directly supplied to the liquid crystal alignment agent, or may be prepared by separating the polyamic acid contained in the reaction solution and then supplying the liquid crystal alignment agent, or may further purify the separated polyamic acid. The preparation of the liquid crystal alignment agent is supplied. When polypyridic acid is dehydrated and closed to form a polyimine, the reaction solution may be directly supplied to a dehydration ring-closure reaction, or the poly-proline contained in the reaction solution may be separated and supplied to a dehydration ring-closure reaction, or The separated polyamic acid is refined and then supplied to a dehydration ring closure reaction. The separation of the polyamic acid can be carried out by adding the above reaction solution to a large amount of a poor solvent to obtain a precipitate, and then drying the precipitate under reduced pressure or by using an evaporator to reduce the organic solvent in the reaction solution. The method of pressure distillation is carried out. In addition, the polylysine may be re-dissolved in an organic solvent and then precipitated with a poor solvent, or -37- '201111416, one or several times using an evaporator for vacuum distillation. The method of the step of refining the poly-proline. <Polyimine> The polyimine in the present invention can be obtained by subjecting the polyamic acid as described above to dehydration and ring closure to carry out hydrazine imidization. The tetracarboxylic dianhydride which can be used for the synthesis of the above polyimine is exemplified by the same compound as the tetracarboxylic dianhydride which can be used for the synthesis of the above polyamic acid. The preferred type of tetracarboxylic dianhydride and its preferred use ratio are the same as those of polyglycine. As the diamine which can be used for the synthesis of the polyimine in the present invention, the same diamine which can be used for the synthesis of the above-mentioned polyamine can be mentioned. That is, a diamine which can be used for synthesizing the polyimine contained in the liquid crystal alignment agent of the present invention contains the compound represented by the above formula (A), and only the compound represented by the above formula (A) can be used. The compound represented by the above formula (A) and the above other diamine may also be used in combination. The preferred other diamine species and the preferred ratio of use of the various diamines are the same as in the case of polylysine. The polyimine in the present invention may be a fully ruthenium imide obtained by dehydrating and ring-closing a glycine structure of a polyamic acid as a raw material, or may be a structure only in a proline structure. A part of the hydrazine ring structure obtained by dehydration ring closure and the quinone imine structure coexisting with the quinone ring structure. The polyimine in the present invention preferably has a ruthenium amination ratio of 30% or more, more preferably 50% or more. The ruthenium imidization ratio is expressed as a percentage of the total number of quinone ring structures relative to the number of phthalic acid structures of the polyimine and the total number of yttrium ring structures -38-[s] 201111416. value. At this time, a part of the quinone ring may also be an isoindole ring. The dehydration ring closure of polylysine is preferably carried out by dissolving polyglycine in an organic solvent by means of a method of heating the poly (proline) or (π), adding a dehydrating agent and a dehydration ring-closing catalyst to the solution. And the reaction temperature in the above method (i) for heating the poly-proline is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. When the reaction temperature is less than 50 ° In the case of C, the dehydration ring-closure reaction cannot be sufficiently carried out, and if the reaction temperature exceeds 200 ° C, the molecular weight of the obtained polyimine decreases, and the reaction time is preferably 1.0 to 24 hours, more preferably 1.0 to 12 hours. On the other hand, in the above method (ii) in which a dehydrating agent and a dehydration ring-closing catalyst are added to a solution of poly-proline, as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The ratio is determined according to the desired ruthenium imidation ratio, but is preferably 0.01 to 20 moles relative to the protonic acid structure of 1 mole of poly-proline. As the dehydration ring-closing catalyst, for example, pyridine 'three-group can be used. Pyridine, dimethylpyridine And a tertiary amine such as triethylamine, but is not limited thereto. The use ratio of the dehydration ring-closure catalyst is preferably 〇. 〇1~1 〇mol. The above dehydrating agent and the dehydrating agent used for 1 mol. The more the amount of the dehydration ring-closure agent used, the higher the ruthenium amide ratio. The organic solvent which can be used for the dehydration ring-closure reaction is exemplified as the organic solvent used in the synthesis of polyglycine. The reaction temperature of the ring closure reaction is preferably 〇~i 8 〇 ° C, more preferably • 39-201111416 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours. The polyimine obtained in the above method (1) may be directly supplied to a liquid crystal alignment agent, or may be obtained by refining the obtained polyimine and then supplying the liquid crystal alignment agent. In the method (U), a reaction solution containing polyiminoimine can be obtained. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or can be supplied after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. The preparation of the liquid crystal alignment agent may also be carried out by separating the polyimine from the preparation of the liquid crystal alignment agent, or may further purifying the separated polyimine and then supplying the liquid crystal alignment agent. The dehydrating agent is removed from the reaction solution and The dehydration ring-closure catalyst can be, for example, a method such as solvent replacement. The separation and purification of the polyimine can be carried out in the same manner as described above for the separation and purification method of polyglycine. - Polylysine and Polyimine in the present invention, each of which may be a terminal-modified polymer having a molecular weight adjusted by using a terminal-modified polymer, without impairing the effects of the present invention Further, the coating property of the liquid crystal alignment agent, etc. can be further improved. Such a terminal modification type polymer can be carried out by adding a molecular weight modifier to a polymerization reaction system when synthesizing polyamic acid. The molecular weight modifier may, for example, be a monoanhydride, a monoamine compound or a monoisocyanate compound. Examples of the above-mentioned monoanhydrides include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, -40-201111416 n-tetradecyl succinic anhydride, and positive ten Hexa succinic anhydride or the like; examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, and Decylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n. An alkylamine or the like; and examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. The ratio of use of the molecular weight modifier to the total amount of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyglycolic acid is preferably 20 parts by weight or less, more preferably 10 parts by weight or less. - Solution Viscosity - Polylysine or polyimine obtained as above, preferably having a solution viscosity of 20 to 800 mPai, more preferably a solution having 30 to 500 mPa's when forming a solution having a concentration of 10% by weight. Viscosity. The solution viscosity (mPa_s) of the above polymer is a 10% by weight polymer solution prepared by using a good solvent (for example, r-butyrolactone, N-methyl-2-pyrrolidone, etc.) of the polymer. The enthalpy measured at 25 °C using an E-type rotational viscometer. <Other components> The liquid crystal alignment film of the present invention contains at least one selected from the group consisting of polylysine as described above and polyamidene formed by ruthenium iodide as an essential component, but Other polymers may also be included as needed. Examples of such other components include other polymers, for example, a compound having at least one epoxy group in the molecule -41 to 201111416 (hereinafter referred to as "epoxy compound"), a functional decane compound, etc. [other polymers] The above other polymers can be used to improve solution properties and electrical properties. The other polymer is a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine containing the compound represented by the above formula (A), and a polyimine formed by dehydration of the polyamic acid. The polymer other than the polycarboxylic acid (hereinafter referred to as "other polyamic acid") obtained by reacting a tetracarboxylic dianhydride with a diamine which does not contain the compound represented by the above formula (A), Polyimine (hereinafter referred to as "other polyimine"), polyphthalamide, polyester, polyamine, polyoxyalkylene, cellulose derivative formed by polypyridic acid dehydration ring closure Polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate, and the like. Among them, other polyamines or other polyimines are preferred, and other polylysines are more preferred. The ratio of use of the other polymer to the total amount of the polymer (refers to the polyamic acid obtained by reacting the above tetracarboxylic dianhydride with the diamine containing the compound represented by the above formula (A), and the polyfluorene is used. The total amount of the polyimine and the other polymer formed by the dehydration ring closure of the amino acid is preferably 90% by weight or less, more preferably 10 to 85% by weight, and still more preferably 30 to 80% by weight. . [Epoxy compound] The epoxy compound is preferably, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol di-42-201111416 glycidyl ether or tripropylene glycol. Diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2 ,2-dibromo neopentyl glycol diglycidyl ether ' N1,N,N ',N ·-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamine Methyl)cyclohexane, 叱叱心川'-tetraglycidyl-4,4'-diaminodiphenylmethane, 11 diglycidyl-benzylamine, N,N-diglycidyl- Aminomethylcyclohexane, hydrazine, hydrazine-diglycidyl-cyclohexylamine, etc. The blending ratio of these epoxy compounds is preferably 40 parts by weight based on the total amount of the polymer of 1 part by weight. Hereinafter, it is more preferably 0.1 to 30 parts by weight. [Functional decane compound] Examples of the functional decane compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 2-aminopropyltrimethoxydecane. 2-Aminopropyltriethoxydecane, Ν-(2-aminoethyl)-3-aminopropyltrimethoxydecane, Ν-(2-aminoethyl)-3-aminopropyl Methyl dimethoxy decane, 3-ureidopropyl trimethoxy decane, 3-ureidopropyl triethoxy decane, hydrazine-ethoxycarbonyl-3-aminopropyl trimethoxy decane, Ν-ethoxycarbonyl-3-aminopropyltriethoxydecane, Ν-triethoxydecylpropyltriethylidene triamine, Ν_trimethoxydecylpropyltriethylidene triamine , 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl- 3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazadecyl acetate, 9-43-201111416 trimethoxydecyl-3,6 -Methyl diazepine, methyl 9-triethoxydecyl-3,6-diazepine, N-benzyl-3-aminopropyltrimethoxyfluorene Alkane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxy Decane 'glycidyloxymethyltrimethoxydecane, glycidyloxymethyltriethoxydecane, 2-glycidyloxyethyltrimethoxydecane, 2-glycidyloxyethyl Triethoxy decane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and the like. The blending ratio of these functional decane compounds is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight, based on the total amount of the 100 parts by weight of the polymer. The liquid crystal alignment agent of the present invention is preferably at least one polymer selected from the group consisting of polylysine and polyimine as described above, and other additives optionally blended as needed, dissolved in It is composed of an organic solvent. As the organic solvent which can be used in the liquid crystal alignment agent of the present invention, for example, N-methyl-2·pyrrolidone, r-butyrolactone, r-butyrolactone, n,n-dimethylformamide , hydrazine, hydrazine-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, B Ethyl oxypropionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cyproterone), ethylene glycol dimethyl Ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether -44- t S1 201111416 acetic acid Ester, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate and the like. They may be used singly or in combination of two or more. The solid content concentration of the liquid crystal alignment agent of the present invention (the ratio of the total weight of the liquid crystal alignment agent other than the solvent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., and preferably 1 to 10 The range of % by weight. That is, the liquid crystal alignment agent of the present invention is coated on the surface of the substrate as described later, and preferably a coating film as a liquid crystal alignment film is formed by heating, but when the solid content concentration is less than 1% by weight, When the thickness of the coating film is too small to obtain a good liquid crystal alignment film, on the other hand, when the solid content concentration exceeds 10% by weight, the thickness of the coating film is too thick and it is difficult to obtain a good liquid crystal alignment film. In some cases, there may be cases where the viscosity of the liquid crystal alignment agent is increased to cause deterioration of coating properties. The range of the particularly preferable solid content concentration differs depending on the method used to apply the liquid crystal alignment agent to the substrate. For example, when a spin coating method is employed, it is particularly preferable that the solid content concentration is in the range of 1.5 to 4.5% by weight. When the printing method is employed, 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. When the ink jet method is employed, 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 mPa_s. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 1 Torr to 50 ° C, more preferably from 20 to 30 ° C. <Liquid Crystal Display Element> -45- [S1 201111416 The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention as described above. The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3). In step (1), the substrate used is different depending on the desired mode of operation. The various modes of operation of steps (2) and (3) are common. (1) First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then the coated surface is heated to form a coating film on the substrate. (1 - 1) When manufacturing a TN type, STN type or VA type liquid crystal display element, the two substrates on which the patterned transparent conductive film is provided are paired, and the liquid crystal alignment agent of the present invention is applied to each of the transparent layers. On the conductive film forming surface, each coated surface is heated to form a coating film. Examples of the coating method include an offset printing method, a flexographic printing method, an inkjet printing method, a roll coating method, and a spin coating method. However, when a flexible printing method is employed, the present invention can be maximized and the polymer orientation does not occur. The effect of precipitation on the anilox roll is therefore preferred. Here, as the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, or poly(lipid) can be used. A transparent substrate formed of plastic such as a cyclic olefin. As the transparent conductive film provided on one side of the substrate, a tin oxide film (NESA film formed of SnO〇 (registered trademark of PPG, USA), an ITO film formed of indium tin oxide (In2〇3—SnCh), or the like can be used. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by a transparent conductive film without a pattern, a method of forming a pattern by photolithography, or a method of forming a mask having a desired pattern when forming a transparent conductive film can be employed. In the case of coating a liquid crystal alignment agent, in order to make the adhesion between the surface of the substrate and the transparent conductive film and the coating film more excellent, it is possible to apply a functional decane compound to the surface on which the coating film is to be formed on the surface of the substrate. Pretreatment of a functional titanium compound, etc. After coating a liquid crystal alignment agent, preheating (prebaking) is preferably performed in order to prevent the applied alignment agent liquid from dropping down. The prebaking temperature is preferably 30 to 200 °. C, more preferably 40 to 150 ° C, and particularly preferably 40 to 10 CTC. Pre-baking time, preferably 〇 25 to 10 minutes, more preferably 0.5 to 5 minutes. Then 'for The firing (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermally imidating the proline unit during the polymerization. The firing (post-baking) temperature is preferably 80 to 300. More preferably, it is 120 to 250 ° C. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 0.005 to 0.5. Mo (1 - 2) On the other hand, when manufacturing an IPS type liquid crystal display element, the liquid crystal alignment agent of the present invention is applied to a conductive film formation surface of a substrate on which a patterned transparent conductive film is provided in a comb shape, And a coating film is formed by heating each coated surface on one surface of the counter substrate on which the conductive film is not provided. The coating method is the same as in the above (1 to 1). The substrate used at this time, the material of the transparent conductive film, and the transparent conductive film. The patterning method, the pretreatment of the substrate, the heating method after applying the liquid crystal alignment agent, and the film thickness of the formed coating film are preferably the same as those of the above (1_丨). (2) Liquid crystal produced by the method of the present invention. Display component is va type-47- In the case of the liquid crystal display element of 201111416, the coating film formed as described above can be directly used as the liquid crystal alignment film. However, it may be supplied and used after performing the polishing treatment as described below. On the other hand, other than the VA type is manufactured. In the case of a liquid crystal display element, the coating film formed as described above is subjected to a rubbing treatment to form a liquid crystal alignment film. The rubbing treatment can be carried out by using a roll of a cloth formed by winding a fiber such as nylon, rayon or cotton. The coating film surface formed as described above is rubbed in a predetermined direction, whereby the alignment property of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. Further, for the liquid crystal alignment film formed as described above, for example, A part of the liquid crystal alignment film is irradiated with ultraviolet rays as shown in the patent document 9 (Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. The treatment of the change in the inclination angle is as shown in the patent document 11 (Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. After forming a photoresist film on a part of the photoresist film, the polishing process is performed in a direction different from the previous sanding process, and then the process of removing the photoresist film is performed so that the liquid crystal alignment film has different liquid crystal alignment ability in each region', thereby being improved. The field of view characteristics of the obtained liquid crystal display element. (3) Two substrates of the liquid crystal alignment film formed as described above were prepared, and liquid crystal was placed between the two substrates arranged in the opposite direction to produce a liquid crystal cell. Here, when the coating film is subjected to the rubbing treatment, the two substrates are arranged to face each other such that the rubbing directions in the respective coatings are at a predetermined angle, for example, orthogonal or antiparallel. In order to arrange liquid crystal between two substrates, for example, the following two methods are exemplified. The first method 'is a previously known method. First, the rain block substrates are arranged to face each other with a gap (cell gap) therebetween, and the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together using a sealant, and are divided by the surface of the substrate and the sealant. After the liquid crystal is injected into the interstitial space, the injection hole is closed, whereby the liquid crystal cell can be manufactured. The second method' is a method called the One Drop Fill (ODF) method. Applying, for example, an ultraviolet curable sealing material to a predetermined portion of one of the two substrates forming the liquid crystal alignment film, and then dropping the liquid crystal on the liquid crystal alignment film surface, and then bonding the other substrate to make the liquid crystal alignment film face each other. Then, the entire surface of the substrate is irradiated with ultraviolet rays to cure the sealant, whereby the liquid crystal cell can be produced. In the case of using any of the above methods, it is desirable to further heat the liquid crystal cell as described above to a temperature at which the liquid crystal used is in an isotropic phase and then slowly cool to room temperature, thereby removing the flow when the liquid crystal is filled. Orientation. Then, by attaching a polarizer to the outer surface of the liquid crystal cell, the liquid crystal display element of the present invention can be obtained. Here, as the sealant, for example, an epoxy resin containing an alumina ball as a separator and a curing agent can be used. As the liquid crystal, for example, a nematic liquid crystal and a dish-shaped liquid -49-201111416 crystal or the like can be used, and among them, a nematic liquid crystal is preferable. In the case of VA type liquid crystal cells, it is preferred

A cyanobenzene liquid crystal, a sputum liquid crystal, a Schiff base liquid crystal, an oxy azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, or the like. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic liquid crystal having positive dielectric anisotropy is preferable, and for example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, or a triplet can be used. a benzene liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubic liquid crystal, or the like. A cholesteric liquid crystal such as cholesteryl choline or cholesteryl phthalate cholesteryl carbonate may be added to these liquid crystals; a chiral agent sold under the trade names of 015 and CB_15 (manufactured by Merck); A ferroelectric liquid crystal such as benzylidene-p-amino-2-methylbutyl cinnamate or the like is used. The polarizer to be bonded to the outer surface of the liquid crystal may be a polarizer formed by sandwiching a polarizing film called "H film" obtained by absorbing iodine while stretching the polyvinyl alcohol by a cellulose acetate protective film. A polarizer formed by the diaphragm itself. EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to the examples. The solution viscosity of each polymer in the following synthesis examples and the oxime imidization ratio of polyimine were measured by the following methods, respectively. [Solid viscosity of polymer] rc π I ^ i -50- • 201111416 The solution viscosity (mPa's) of the polymer is a polymer adjusted to the polymer concentration % specified in each synthesis example using the solvent described in each synthesis example. Solution, enthalpy measured at 25 ° C using an E-type rotational viscometer. [The yield of ruthenium imide of polyimine] A small amount of a solution containing the polyimine obtained in each synthesis example is added and put into pure water, and the obtained precipitate is sufficiently dried under reduced pressure at room temperature, and then dissolved in deuterated In the dimethyl hydrazine, tetramethyl decane was used as a reference material, and the 1 Η -NMR spectrum was measured at room temperature. From the measurement results, it was calculated by the following formula (1). Ruthenium amination rate (%) = (1 - AVA2X a )xl〇〇(1) (In equation (1), Α1 is the peak area from the ruthenium matrix near the chemical shift of 10 ppm, and Α2 is from other protons. The peak area, α, is the ratio of the number of protons to other protons relative to one sulfhydryl group in the polyimine precursor (polyglycolic acid). <Synthesis Example of Compound represented by the above formula (Α)> Synthesis Example A-1 According to the following synthesis scheme la~lc'

-51- 201111416

+ 2NH(CH2-CH=CH2)2

NaHS03

HO

, N(CH2*CH=CH2)2 N(CH2-CH=CH2)2 (A-1-1a) Synthesis Scheme 1 a 〇 II N-CH2CH2-OH + Cl——S 〇

Cl o

A -► NEt〇 II N—CH2CH2—〇—S Λ 〇o

Cl (A-1-1b) Synthetic Schematic lb -52- 201111416 ο ,N(CHrCH=CH2)2 /n-ch2ch2—ο—s

(A-1b) ΚΗ Bu4NBr ο N(CH2-CH=CH2)2 (A-1-1a) ο , N(CH2-CH=CH2)2 , Ν—CH2CH2—Ο Ο N(CH2-CH=CH2) 2 (A-1-1C) 1,3-Dimethylbarbituric acid: ^n-ch2ch2- Ο ΝΗ2 (Α-1-1) Synthetic diagram lc Synthesis [2-(3,5-diamino group) -phenoxy)-ethyl]-pyrrolidine-2,5-dione (compound (A-1 - 1)). [Synthesis of Compound (A-1 - la)] In a 20 L three-necked flask under nitrogen atmosphere, 126 l.ig (i〇>() Molar) 1,3,5-trihydroxybenzene, 4 85 8.0 g (50_0 mol) diallylamine and 1 24 8.7 g (12.0 mol) sodium hydrogen sulfite were stirred at room temperature for 8 hours to carry out a reaction. The resulting reaction mixture was concentrated using a rotary evaporator, except for the reacted diallylamine, then 10 L of toluene was added, and the resulting organic layer was washed with distilled water. The washed organic layer was subjected to desorption using magnesium sulfate, and then the solvent was removed using a rotary evaporator to obtain 270 1.8 g (9.5 mol, 帛-53-201111416 rate: 95.0%) of the intermediate compound (A - 1 - la) . [Synthesis of Compound (A-1 - lb)] In a 5 L three-necked flask, 214.7 g (1.5 mol) of ruthenium-(2. hydroxyethyl)succinimide, 422. .1 g (2.0 mol) p-chlorobenzenesulfonium chloride and 1 L of dichloromethane were stirred at 〇 °C. 312.0 mL (2.3 mol) of triethylamine was added dropwise thereto over 30 minutes, followed by stirring at room temperature for 3 hours to carry out a reaction. To the resulting reaction mixture was added 0.5 L of dichloromethane, and the obtained organic layer was washed with distilled water. The washed organic layer was dehydrated using magnesium sulfate' and then concentrated using a rotary evaporator. 3 L of ethanol was added to the obtained colorless viscous liquid, stirred well, and then the precipitated white solid was filtered and recovered to obtain 420.7 g (1.3 mol, yield: 88.3%) of the intermediate compound (A-1 - lb ). [Synthesis of Compound (A-1 - lc)] In a 5.0 L three-necked flask, 174.0 g (converted to 1.3 mol of pure potassium hydride) of potassium hydride (30 wt% of mineral oil suspension) was washed in a 5.0 L three-necked flask. Liquid) 'Removal of mineral oil, vacuum drying. 3.0 L of tetrahydrofuran' was added thereto and stirred at 0 °C. A solution of 341.3 g (1.2 mol) of the above-obtained compound (a-1-la) dissolved in 1.0 L of tetrahydrofuran was added dropwise thereto over 30 minutes, followed by stirring at 0 ° C for 15 minutes. Further, 317.8 g (1.0 mol) of the above-obtained compound (A-1 - 1 lb) and 32.2 g (0.1 mol) of tetrabutylammonium bromide were added thereto, and then stirred at room temperature for 1 hour to carry out a reaction. After completion of the reaction, an aqueous ammonium chloride solution was added to the reaction mixture to obtain an acidity, and then extracted with 4.0 L of ethyl acetate to obtain an organic layer of t-54-201111416. After the organic layer was washed with water, dehydration was carried out using magnesium sulfate, and the solvent was removed by a rotary evaporator to obtain a crude product. The obtained crude product was purified by column chromatography (tanning agent: phthalocyanine, developing solvent: hexane/ethyl acetate = 4/1 (weight ratio)), and the solvent was removed from the obtained fraction to obtain a brown viscous material. 262.1 g (0.6 mol, yield 58.6%) of the intermediate compound (A-1 - lc). [Synthesis of Compound (A-1 - 1)] Under a nitrogen atmosphere, 239.8 g (0.6 mol) of the compound (Al-lc) obtained above and 274.5 g (1.8 mol) were mixed in a 5.0 L three-necked flask. 3, dimethyl barbituric acid, 13.5 g (0. 〇12 mol) hydrazine (triphenylphosphino) palladium (0) and 2.5 L of dichloromethane' were stirred at 35 ° C for 4 hours to carry out a reaction. After the end of the reaction, the reaction mixture was washed with an aqueous solution of sodium carbonate to remove unreacted 1,3-dimethylbarbituric acid' and then washed with distilled water. The obtained organic layer was dried using magnesium sulfate, and then the solvent was removed using a rotary evaporator to give a crude product. The obtained crude product was purified by column chromatography (tanning agent: silica gel, developing solvent: chloroform/ethanol = 95/5 (weight ratio)), and the solvent was removed from the obtained fraction to obtain 33.9 g of a brown powder. (0_16 mol, yield 26.9%) Compound (A-1 - 1) (1·[2-(3,5-Diamino-phenoxy)-ethyl]-pyrrolidine-2,5- Diketone). The various operations of the above Synthesis Example A-1 were repeated at the above-mentioned scale as needed to ensure the compound (A-i-1) required for the synthesis of the polyimine which will be described later. Synthesis Example A — 2 -55- 201111416 According to the following synthesis scheme 0 Λ N_CH2CH2 - OH + F (A-2-1J) o2n nb3

THF p :N—CH2CH2—O—^ N〇2 02N (A-2-1k)

EtOH/H2〇

Zn, NH4CI

O:N—CH 2 〇H 2 —O—, /)—NH 2 H 2 n (A-2-1) Synthesis Scheme 2 Synthesis of [2-(2,4-diamino-phenoxy)-ethyl]-2 Pyrrolidone (compound (A - 2 - 1)). [Synthesis of Compound (A-2-lk)] In a nitrogen atmosphere, '29.2 g (l. oxime) 1-(2-hydroxyethyl)-2-pyrrolidone was mixed in a 2 L three-necked flask. 186.1 g (1.0 mol) of 2,4-dinitrofluorobenzene, 280 mL of triethylamine and 500 mL of tetrahydrofuran at 40. (The reaction was carried out by stirring for 10 hours. After the reaction was completed, 2 L of ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed with distilled water and then dried over magnesium sulfate, and then the solvent was removed by using a rotary evaporator to obtain a crude product. The obtained crude product was recrystallized from ethanol, and the crystals were recovered by filtration, and dried under vacuum at 6 ° C for 12 hours to obtain 206 g (0.70 - 56 · 201111416 mol, yield 70.0%) as a pale yellow powder. Intermediate compound (A-2 - lk) [Synthesis of compound (A-2 - 1)] 73.8 g (0.25 mol) of the above intermediate (A-2) was mixed in a 5 L three-necked flask under a nitrogen atmosphere. - lk), 327_0g (5 moles of zinc), 53.5g (l mole) ammonium chloride and 2.5L of ethanol - while stirring the mixture at 0 ° C, slowly adding 600 mL of water to it' then in the chamber The reaction was carried out by stirring at elevated temperature for 6 hours. After the reaction was completed, the catalyst was removed from the reaction mixture by filtration of calcium iron, and the solvent was removed from the filtrate using a rotary evaporator to obtain a crude product. :矽胶,Expand The obtained crude product was purified by solvent: tetrahydrofuran, and the solvent was evaporated from vacuo to yield to afford 52.3 g (0.22 mol, yield: 89%) of compound (A 2-1) as a brown liquid. Synthesis of Polyimine > Synthesis Example PI-1 1 10 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 160 g (0.50 mol) of tetracarboxylic dianhydride ,3,3&amp;,4,5,915-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[i,2-c]-furan-i , 3-dione, and 91 g (0'84 mol) of p-phenylenediamine as a diamine, 8 g (〇. 3 mol) of the compound (a-1 - 1) obtained in the above Synthesis Example A-1, 25 g (0.10 mol) 1,3_bis(3-aminopropyl)tetramethyldioxane and 9.6 g (〇.〇]5 mol) 3,6-bis(4-aminophenylhydrazine) Cholesterol, and 81 g (〇〇3〇莫耳) as a monoamine, dissolved in 960 g of N-methyl-2-pyrrolidone (NMp), and reacted at 60 C for 6 hours. 'A solution containing polylysine is obtained. A small amount of -57- r 201111416 is taken, and NMP is added to form a solution having a polyglycine concentration of 10% by weight. The measured solution viscosity was 60 mPa's. Next, 2,700 g of NMP was added to the obtained polyaminic acid solution, and 400 g of pyridine and 41 0 g of acetic anhydride were added, and dehydration ring closure was carried out at 110 ° C for 4 hours. After the dehydration ring-closing reaction, the solvent in the system is subjected to solvent replacement with a new r-butyrolactone (by the solvent replacement operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are discharged to the outside of the reaction system, The same), a solution containing about 15% by weight of a polyamidimide (pi-i) having a ruthenium iodide ratio of about 95% was obtained. A small amount of the obtained polyimine solution is added, and r-butyrolactone is added to form a solution having a polyamidene concentration of 10% by weight. The measured solution viscosity is 70 mPa·s °. The synthesis example PI-2 will serve as Ll〇g (〇.5〇莫) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride of tetracarboxylic dianhydride, and 3 8S (0.35 mol) p-phenylenediamine as diamine 13 g (0.05 mol) of the compound (A-1 -1) obtained in the above Synthesis Example A-1 and 52 g (0.1 Torr molar) 3 (3,5-diaminobenzoic acid oxy) cholelibox 'dissolved In 830 g of NMP, the reaction was carried out at 60 ° C for 6 hours to obtain a solution containing poly-proline. A small amount of the polyaminic acid solution was taken, and NMP' was added to form a solution having a polyglycine concentration of 1% by weight, and the measured solution viscosity was 60 mPa's. Next, i9〇〇g NMP ' was added to the obtained polyaminic acid solution, and 40 g of pyridine and 5 1 g of acetic anhydride were added to carry out a dehydration ring-closing reaction at 110 ° C for 4 hours. The solvent in the system was subjected to solvent exchange with a new NMP to obtain a solution of -58-! 201111416 polyimine (PI-2) containing about 15% by weight of ruthenium iodide. A small amount of the obtained polyimine solution was added, and NMP was added to form a solution having a polyimine concentration of 10% by weight, and the measured solution viscosity was 47 mPa·s. Synthesis Example PI-3 11 〇g (〇.50 mol) of 2,3,5·tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 32 g (0.30 mol) as diamine P-phenylenediamine, 20 g (0.1 mol) of 4,4'-diaminodiphenylmethane, 13 g (0.05 mol) of the compound (A-1 -1) and 26 g (0.05) obtained in the above Synthesis Example A-1 3 (3,5-diaminophenoxy)cholestane was dissolved in 800 g of NMP, and reacted at 60 ° C for 6 hours to obtain a solution containing polylysine. A small amount of the polyaminic acid solution was taken, and NMP was added to form a solution having a polyaminic acid concentration of 1% by weight, and the measured solution viscosity was 60 mPa*s. Next, 18,000 g of NMP was added to the obtained polyaminic acid solution, and 80 g of pyridine and 100 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 10 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is subjected to solvent replacement with a new r-butyrolactone to obtain a solution containing about 15% by weight of a polyamidimide (PI-3) having a ruthenium iodide ratio of about 80%. . A small amount of the obtained polyimine solution was added, and T-butyrolactone was added to form a solution having a polyamidene concentration of 10% by weight, and the measured solution viscosity was 87 mPaai. Synthesis Example PI - 4 10 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 49 g (0.45 mol) of p-phenylenediamine as diamine And 13 g (0.05 mol) of the compound (A-1) obtained in the above Synthesis Example A-1, -59-f 201111416 was dissolved in 1460 g of NMP, and reacted at 60 ° C for 6 hours to obtain 10% by weight of polydecylamine. Acid solution. The solution viscosity of the polyaminic acid solution was 65 mPa's. Next, 1 625 g of NMP was added to the obtained polyaminic acid solution, and 200 g of pyridine and 150 g of acetic anhydride were added, and a dehydration ring closure reaction was carried out at ll ° C for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with a new r-butyrolactone to obtain a solution containing about 15% by weight of polyimine (PI-4) having a ruthenium iodide ratio of about 90%. . A small amount of the obtained polyimine solution was added, and 7-butyrolactone was added to form a solution having a polyamidene concentration of 1% by weight, and the measured solution viscosity was 65 mPa_s. Synthesis Example PI-5 110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride, and 49 g (0.45 mol) of p-phenylenediamine as a diamine 12 g (0.05 mol) of the compound (A-2 2) obtained in the above Synthesis Example A-2 was dissolved in 1 540 g of NMP, and reacted at 60 ° C for 6 hours to obtain a polyglycine containing 10% by weight. Solution. The solution viscosity of the polyaminic acid solution was 7 3 m P a .s. Next, 171 gram of NMP was added to the obtained polyaminic acid solution, and 194 g of pyridine and 1,500 g of acetic anhydride were added, and a dehydration ring closure reaction was carried out at 11 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new butyrolactone to obtain a solution containing about 15% by weight of a polyamidimide (ΡΙ-5) having a ruthenium iodide ratio of about 88%. A small amount of the obtained polyimine solution was added, and r-butyrolactone was added to form a solution of -60-201111416 having a polypyridamine concentration of 1% by weight, and the measured solution viscosity was 60 mPa_s. &lt;Synthesis of Other Polymers&gt; [Synthesis of Other Polylysine] Synthesis Example PAR-1: 200 g (1.0 mol) of U 3 〆·cyclobutanine tetracarboxylic dianhydride as tetracarboxylic dianhydride With 210g (1.0 moles) of 22'-dimethyl-4,4'-diaminobiphenyl as a diamine, dissolved in a mixed solvent of 370g of NMP and 330〇gr • butyrolactone at 40 ° The reaction was carried out for 3 hours under C to obtain a solution containing 1% by weight of poly-proline (PAR-1). The solution viscosity of the polyaminic acid solution was 1 60 mPa·s. [Synthesis of Other Polyimine] Synthesis Example PIR-1 1 110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 38 g as a diamine (0.35 mol) p-phenylenediamine, 20 g (0.1 mol) of 4,4'-diaminodiphenylmethane and 26 g (0.05 mol) of 3(3,5-diaminophenhydryloxy Cholestane, dissolved in 800 g of NMP, was reacted at 60 ° C for 6 hours to give a solution containing poly-proline. A small amount of the obtained polyaminic acid solution was taken, and NMP was added to form a solution having a polyglycine concentration of 10% by weight. The measured solution viscosity was 60 mPa·s. Next, 1 800 g of NMP was added to the obtained polyaminic acid solution, 160 g of pyridine and 200 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out for 4 hours at 1 μ (TC). After the dehydration ring closure reaction, a new r-butan was used. The ester is subjected to solvent replacement of the solvent in the system to obtain a solution containing about 15% by weight of polyanisole (PIR-1) having a ruthenium iodide ratio of about 61-201111416 80%. The amine solution 'added r-butyrolactone' to form a solution having a polyamidene concentration of 1% by weight, and the measured solution viscosity was 87 mPa*s. Synthesis Example PIR-2 will be 110 g (0.50) of tetracarboxylic dianhydride. Molar) 2,3,5-trisole cyclopentyl acetic acid dianhydride' and 54 g (〇.5 mol) p-phenylenediamine as a diamine, dissolved in 1 476 g of NMP' at 60 ° C In an hourly reaction, a solution containing 1% by weight of polyglycolic acid was obtained. The solution viscosity of the polyaminic acid solution was 6 3 m P a. s 0 followed by 'adding i640 g of NMP to the obtained polyfluorenefee acid solution, and Add 200g of pyridin and 150g of acetic anhydride' for 4 hours dehydration ring closure reaction at 11〇乞. After dehydration ring closure reaction, use new γ-butane The solvent in the system is dissolved! I-replacement to obtain a solution containing about 15% by weight of polyimine (PIR-2) having a ruthenium iodide ratio of about 91%. A small amount of the obtained polyimine solution is obtained. 'Adding r-butyrolactone to form a solution having a concentration of 10% by weight of polystyrene, and the measured solution viscosity is 64 mPai. Synthetic example PIR-3 will be 110 g (0.50 mol) of tetracarboxylic dianhydride 2, 3,5-tricarboxycyclopentyl acetic acid dianhydride' with 6 g (0.01 mol) of 3,6-bis(4-aminophenoxy)cholesterane as a diamine, 17 g (0.04 mol) 4 -(4'-Trifluoromethoxyphenylhydroxy)cyclohexyl-3,5-diaminobenzoate and 482 (0.45 mol) p-phenylenediamine dissolved in 1 647 g of NMP 'at 60 The reaction was carried out for 6 hours at ° C to obtain a solution containing 10% by weight of polylysine. The solution viscosity of the polyaminic acid solution was -62 to 201111416 70 mPa·s. Next, the obtained polyglycine solution was added. 1830g NMP, and adding 200g of pyridine and 150g of acetic anhydride, 4 hours of dehydration ring-closing reaction at ll ° ° C. After dehydration ring closure reaction, solvent replacement of the solvent in the system with new r - butyrolactone A solution containing about 15% by weight of polyimine (PIR-3) having a ruthenium iodide ratio of about 89% is obtained. A small amount of the obtained polyimine solution is added, and r-butyrolactone is added to form a polyfluorene. A solution having an imine concentration of 10% by weight and a measured solution viscosity of 72 mPai. <Preparation and evaluation of liquid crystal alignment agent> Comparative Example 1 [Preparation of liquid crystal alignment agent] The content obtained in the above Synthesis Example PIR-1 Adding r-butyrolactone (BL), N-methyl-2-pyrrolidone (NMP) and butyl quercetin (BC) to a solution of polyimine (PIR-1), relative to 100 weight Polyimine (PIR-1), adding 10 parts by weight of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and stirring well to form a solvent composition BL : NMP ·· BC = 40 : 30 : 30 (weight ratio), a solution having a solid concentration of 6.0% by weight. The solution was filtered using a screening procedure having a pore size of 1 V m to prepare a liquid crystal alignment agent. [Evaluation of liquid crystal alignment agent] (1) Evaluation of printability The liquid crystal alignment agent prepared as described above was formed by using a liquid crystal alignment film printer (manufactured by 曰本写真印刷) and coated on an ITO film. The transparent electrode was placed on the transparent electrode surface of the glass substrate, and heated on a hot plate at -80 to 2011-11416 for 1 minute (prebaking) to remove the solvent, and then heated on a hot plate at 200 ° C for 10 minutes (post-baking) ), a coating film having an average film thickness of 600 A was formed. The film was observed using a microscope at 20 magnification to investigate the presence or absence of porosity and unevenness of printing and their extent. As a result, although no pores were observed, some uneven printing was observed. (2) Evaluation of film thickness uniformity of the coating film The film thickness of the center part of the substrate and the center portion of the outer side of the substrate were measured using a stylus type film thickness meter (manufactured by KLA TENCOR Co., Ltd.). Film thickness at 15 mm position. When the difference in film thickness between the two was 20 A or less, the film thickness uniformity was evaluated as "good", and the case where the film thickness difference exceeded 20 A was evaluated as "unqualified" film thickness uniformity. (3) Evaluation of the peeling property of the coating film The coating film formed as described above was immersed in a release agent "TS-204" manufactured by Sanyo Chemical Industries Co., Ltd. at 30 ° C for 5 minutes to carry out a peeling operation. After the peeling, the coating film residue was visually observed on the substrate. When the coating film residue was not confirmed on the substrate, the peeling property was evaluated as "good", and the coating film residue was confirmed as the peeling property "failed". In the comparative example, the coating remained on a part of the substrate. (4) In the case of continuous printing, 0.2 g of the above-prepared liquid crystal alignment agent was dropped onto an anilox roll of a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.) in one minute. , while rotating the anilox roller continuously. The polymer contained in -64-201111416 in the liquid crystal alignment agent was visually observed every hour to the anilox roll. In this comparative example, no precipitation of the polymer was observed 1 hour after the start of the experiment, but precipitation was observed after 2 hours, at which time the experiment was completed. Comparative Example 2 [Preparation of Liquid Crystal Aligning Agent] To a solution containing the polyimine (PIR-2) obtained in the above Synthesis Example PIR-2, r-butyrolactone (BL) and butyl celecoxib (BC) were added. And adding 10 parts by weight of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane with respect to 100 parts by weight of polyimine (PIR-2) The mixture was thoroughly stirred to form a solution having a solvent composition of BL: BC = 88:12 (weight ratio) and a solid concentration of 6.0% by weight. The solution was filtered using a screening procedure having a pore size of Ιμπι to adjust the liquid crystal alignment agent. [Evaluation of liquid crystal alignment agent] In the same manner as in Comparative Example 1, except that the liquid crystal alignment agent prepared above was used, the printability, the film thickness uniformity of the coating film, the peeling property, and the long-term continuous printing were evaluated. The evaluation results are shown in Tables 1 and 2. Comparative Example 3 [Preparation of Liquid Crystal Aligning Agent] To a solution containing polyethylenimine (PIR - 3 ) obtained in the above Synthesis Example PIR-3, r-butyrolactone (BL) and butyl quercetin (BC) were added. And adding 10 parts by weight of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane to 100 parts by weight of polyimine (PIR-3) Stir well to form a solution having a solvent composition of BL: BC = 88:12 (weight ratio) and a solid content concentration of 6.0-65-[S] 201111416%. The solution was filtered using a screening procedure having a pore size of l#m to adjust the liquid crystal alignment agent. [Evaluation of liquid crystal alignment agent] In the same manner as in Comparative Example 1, except that the liquid crystal alignment agent prepared above was used, the printability, the film thickness uniformity of the coating film, the peeling property, and the long-term continuous printing were evaluated. The evaluation results are shown in Table 1 and Table 2» Example 1 [Preparation of liquid crystal alignment agent] The solution containing the polyimine (PI-1) obtained in the above Synthesis Example PI-1 and the above synthesis example PAR-1 were mixed. The resulting solution containing other polyaminic acid (PAR-1) is made by adding polyamidiamine (PI-1): other polylysine (PAR-1) = 20:80 (weight ratio) and adding thereto R-butyrolactone (BL), N-methyl-2-pyrrolidone (NMP) and butyl cyanidin (BC), and added as an epoxy compound with respect to the total amount of 100 parts by weight of the polymer 10 parts by weight of 1^,1^1^',1^'-tetraglycidyl-4,4'-diaminodiphenylmethane and stirred well to form a solvent composition of BL: NMP: BC = 71: 17 : 12 (weight ratio), a solution having a solid concentration of 6.0% by weight. The solution was filtered using a screening procedure having a pore size of 丨v m to prepare a liquid crystal alignment agent. [Evaluation of liquid crystal alignment agent] (1) Evaluation of printability A coating film having an average film thickness of 600 A was formed in the same manner as in Comparative Example 1 except that the liquid crystal alignment agent prepared above was used. The coating film was observed using a microscope of 20 magnification to investigate the presence or absence of porosity and unevenness of printing and the extent of them. Here, -66-.201111416 For the uneven printing, it is investigated whether the occurrence of uneven printing is improved compared with the coating film of Comparative Example 1 above, and an improvement is observed (that is, compared with In the case where the degree of uneven printing was smaller than the coating film of Example 1, it was evaluated as "good". The evaluation results are shown in Table 1. (2) Evaluation of Film Thickness Uniformity of Coating Film, (3) Evaluation of Peelability of Coating Film, and (4) Evaluation of Continuous Printing The film thickness of the coating film was similar to that of Comparative Example 1 described above for the coating film formed as described above. Evaluation of uniformity, peelability evaluation of the coating film, and continuous printing evaluation. The evaluation results are shown in Tables 1 and 2. In addition, (4) continuous printing evaluation was observed for the fourth hour. Example 2 [Preparation of liquid crystal alignment agent] N-methyl-2-pyrrolidone (NMP) and butyl group were added to a solution containing polyimine (PI-2) obtained in the above Synthesis Example PI-2. Celluloid (BC), 10 parts by weight of oxime, oxime, Ν', Ν'-tetraglycidyl-4, 4 as an epoxy compound, relative to 100 parts by weight of polyimine (ΡΙ-2) '-Diaminodiphenylmethane was thoroughly stirred to form a solution having a solvent composition of NMP: BC = 50:50 (weight ratio) and a solid concentration of 6.0% by weight. The solution was filtered using a screening procedure having a pore size of 1 μm to modulate the liquid crystal alignment agent. [Evaluation of Liquid Crystal Aligning Agent], Evaluation was carried out in the same manner as in the above-mentioned Example 1-67-201111416 except that the liquid crystal alignment agent prepared above was used. The evaluation results are shown in Tables 1 and 2. Example 3 [Preparation of Liquid Crystal Aligning Agent] In addition to the above Comparative Example 1, a solution containing a polyimine (PI - 3 ) obtained in the above Synthesis Example PI _ 3 was used instead of the polyimine (PIR-1). The liquid crystal alignment agent was prepared in the same manner as in Comparative Example 1, except for the solution. [Evaluation of Liquid Crystal Aligning Agent] Evaluation was carried out in the same manner as in Example 1 except that the liquid crystal alignment agent prepared above was used. The evaluation results are shown in Tables 1 and 2. Example 4 [Preparation of liquid crystal alignment agent] The solution containing the polyimine (PI-4) obtained in the above Synthesis Example PI-4 and the other polylysine (PAR) obtained in the above Synthesis Example PAR-1 were mixed. - 1) solution, such that polyimine (PI-4): other poly-proline (PAR-1) = 20: 80 (weight ratio), and added r-butyrolactone (BL), N -methyl-2-pyrrolidone (NMP) and butyl quercetin (BC), and 10 parts by weight of N, N, N' as an epoxy compound, based on the total amount of 100 parts by weight of the polymer, N'-tetraglycidyl-4,4'-diaminodiphenylmethane and stirred well to form a solvent composition of BL: NMP : BC = 83 : 5 : 12 (weight ratio), solid content concentration of 6.0 weight %The solution. The solution was filtered using a screening procedure having a pore size of l/zm to prepare a liquid crystal alignment agent. -68-.201111416 [Evaluation of Liquid Crystal Aligning Agent] Evaluation was carried out in the same manner as in Example 1 except that the liquid crystal alignment agent prepared above was used. The evaluation results are shown in Tables 1 and 2. Example 5 [Preparation of Liquid Crystal Aligning Agent] In addition to the above Comparative Example 2, the solution containing the polyimine (PI-5) obtained in the above Synthesis Example PI-5 was used instead of the polyimine (PIR-2). The liquid crystal alignment agent was prepared in the same manner as in Comparative Example 2 except for the solution. [Evaluation of Liquid Crystal Aligning Agent] Evaluation was carried out in the same manner as in Example 1 except that the liquid crystal alignment agent prepared above was used. The evaluation results are shown in Tables 1 and 2. [Table 1] Table 1. Composition and printability of liquid crystal alignment agent and evaluation results of coating film - 69 - 201111416 Liquid crystal alignment agent coating film Polyimine other polyphthalic acid solvent composition (parts by weight) Printed film thickness uniform Peeling amount (parts by weight) Type (parts by weight) BL NMP BC Porous printing unevenness Comparative example 1 PIR-1 100 0 40 30 30 No good failures Comparative example 2 PIR-2 100 0 88 0 12 None Some good failures Comparative Example 3 PIR-3 100 0 88 0 12 φττ /«Vt Some good failures Example 1 PI-1 20 PAR-1 1 80 71 17 12 No good good Good example 2 PI — 2 100 0 0 50 50 No good good Good example 3 PI-3 100 0 40 30 30 No good good Good example 4 PI-4 20 PAR-1 80 83 5 12 No good good Good example 5 PI-5 100 0 88 0 12 It is not good and good. In addition, the abbreviation of the solvent in the solvent composition column of Table 1 shows the following. Bl : r - butyrolactone NMP: N -methyl-2-pyrrolidone BC : butyl cyproterone - 70 - .201111416 [Table 2] Table 2. Results of continuous printing evaluation Comparative Example 1 Comparison _ 2 Example 3 Example 1 Example 2 Example 3 Example 4 Example 5 1 hour without precipitation, no precipitation, no precipitation, no precipitation, no precipitation, no precipitation, no precipitation, 2 precipitation, precipitation, precipitation, no precipitation, no precipitation, no precipitation, no precipitation, no precipitation 3 hours without precipitation, no precipitation, no precipitation, no precipitation, no precipitation, 4 hours, no precipitation, no precipitation, no precipitation, no precipitation, no simple precipitation [simplified illustration] Μ . y\\\ [Main component symbol description] jw\ -71-

Claims (1)

201111416 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by containing at least one polymer selected from the group consisting of polylysine and polyamidene formed by dehydration of the polyamic acid. The polyamic acid is obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (A°). (R1).!—j~ /N—R—x In the formula (A°), X is *—〇—or *—COO—, in which the bond is attached to the diaminophenyl group, R a methylene group, an alkylene group having 2 to 10 carbon atoms or an arylene group having 6 to 18 carbon atoms, R1 is an alkyl group having 1 to 6 carbon atoms, and n is an integer of 〇4 to 4, Z is a carbonyl group or a group represented by the following formula (Ζ-1), R11 I —C—(Ζ-1) RIII In the formula (Ζ-1), Rn and Rni are each independently a hydrogen atom or a carbon atom. The liquid crystal alignment agent of the first aspect of the invention, wherein the compound represented by the above formula (A°) is a compound represented by the following formula (A), ' A R—X 〇 -72- 201111416 In the formula (A), X, R and N are synonymous with the above formula (A°), respectively! 1 is an integer of 〇 〜2. 3. The liquid crystal alignment agent according to claim 1 or 2, wherein the tetracarboxylic dianhydride comprises 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the polymer is a polyfluorene amine having a ruthenium iodide ratio of 30% or more. A liquid crystal alignment film formed by using the liquid crystal alignment agent according to any one of claims 1 to 4. A liquid crystal display element' characterized by having a liquid crystal alignment film according to item 5 of the patent application. 7. A polyglycolic acid which is obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the above formula (A.). 8. A polyimine which is formed by dehydration of a polyglycine which is obtained by reacting a tetrahydro acid dianhydride with a diamine containing a compound represented by the above formula (A). 9. A compound which is represented by the above formula (A). •73· 201111416 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: