TW200949389A - Liquid crystal aligning agent and method for forming liquid crystal alignment films - Google Patents

Abstract

A liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyamic acids, polyimides, and polyamic acid esters, said polymer having a group represented by general formula (1) or (2). In general formula (1), R1 and R2 are each independently hydrogen or a monovalent organic group, or R1 and R2 may be bonded to each other to form a ring; R3 is fluoro or cyano; a is an integer of 0 to 4; and * is a free valency, while in general formula (2), R4 is C1-40 alkyl or a C3-40 monovalent organic group containing an alicyclic group, with the proviso that the hydrogen atoms of the alkyl may be partially or completely replaced by fluorine atoms; R5 is fluoro or cyano; b is an integer of 0 to 4; and * is a free valency.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal alignment agent, a method for producing a liquid crystal alignment film, and a liquid crystal display element. [Prior Art] In the past, a nematic liquid crystal having positive dielectric anisotropy is in a substrate sandwich structure in which a transparent electrode having a liquid crystal alignment film is added, and if necessary, the long axis of the liquid crystal molecules is 0 to 0 between the substrates. 3, 60 degree continuous twisting is formed, and a liquid crystal display element having a liquid crystal cell such as a TN (torsional nematic) type, an STN (super twisted nematic) type, or an IPS (in-plane switching) type is known (refer to the special opening) 56-9 No. 277 and JP-A No. 1 - 1 20528). In these liquid crystal cells, in order to align liquid crystal molecules in a certain direction with respect to the substrate surface, it is necessary to provide a liquid crystal alignment film on the surface of the substrate. The liquid crystal alignment film is usually formed by a method (rubbing method) of reciprocating rubbing of the surface of the organic film formed on the surface of the substrate in a certain direction with a cloth such as a crucible. However, when the liquid crystal alignment film is formed by the rubbing treatment, dust or static electricity is easily generated in the process, so that dust adheres to the surface of the alignment film, which causes a display failure. In particular, in the case of a substrate having a TFT (Thin Film Transistor) device, the circuit of the TFT element is damaged by the generated static electricity, which is also a cause of a decrease in yield. Further, in the case of a liquid crystal display device which is gradually higher in definition, unevenness is generated on the surface of the substrate in accordance with the increase in density of the pixels, so that it is difficult to perform uniform rubbing treatment. -5-200949389 As another method for aligning a liquid crystal in a liquid crystal cell, a photosensitive film made of polyethylene laurate, polyamidiamine, azobenzene derivative or the like formed on the surface of a substrate is known. A polarized or non-polarized radiation is applied to thereby impart a light alignment method to the liquid crystal alignment energy. According to this method, static electricity or dust does not occur, and a uniform liquid crystal alignment can be achieved (refer to Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. 152475, JP-A-2000-144 No. 36, JP-A-2000-3 1 95 1 0, JP-A-2000- 2 8 1 724, JP-A-9-2973, No. 3, No. 2003, JP-A-2003 - Japanese Patent Laid-Open Publication No. 2004-250924, and JP-A-2002-250924. However, in a liquid crystal cell such as a TN (twisted nematic) type or an STN (super twisted nematic) type, it is necessary for the liquid crystal alignment film to have a pretilt characteristic which makes the liquid crystal molecules obliquely aligned at a predetermined angle with respect to the substrate surface. When the liquid crystal alignment film is formed by the photo-alignment method, the pretilt angle is usually imparted by inclining the irradiation radiation from the substrate normal to the incident direction of the substrate surface. Further, as an operation mode of the liquid crystal display element different from the above, a vertical (homeotropic) alignment mode in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned with the substrate is known. When the operation mode applies a voltage between the substrates to tilt the liquid crystal molecules in a direction parallel to the substrate, it is necessary to tilt the liquid crystal molecules from the substrate normal direction toward the substrate surface. As for the method for this, there are proposed, for example, a method of providing a protrusion on a surface of a substrate, a method of providing a stripe on a transparent electrode, and a liquid crystal alignment film from a normal direction of the substrate toward the surface of the substrate by using a rubbing alignment film -6 - 200949389 One way to tilt (pre-tilt), etc. It is also known that the above-described photoalignment method is also useful as a method of controlling the tilt direction of liquid crystal molecules in a liquid crystal cell of a vertical alignment mode. In other words, it is known that the tilting direction of the liquid crystal molecules when the voltage is applied can be uniformly controlled by using the vertical alignment film which imparts the alignment control energy and the pretilt angle exhibitability by the photo-alignment method (refer to Japanese Laid-Open Patent Publication No. 2003-307736, No. 2004). Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Thus, the liquid crystal alignment film produced by the above-described photoalignment method is effective for various liquid crystal display elements. However, in the past, it has been necessary to irradiate a large amount of radiation to obtain a large pretilt angle. For example, it has been reported that when a liquid alignment function is imparted to a liquid crystal by a photo-alignment method in a film containing an azobenzene derivative. In order to obtain a sufficient pretilt angle, it is necessary to irradiate a radiation line whose optical axis is inclined from the substrate normal at 10,00 0 J/m 2 or more (refer to JP-A-2002-250924, JP-A-2004-838-01, and J. of the SID 1 1/3, 2003, ρ·5 79 Bu, the liquid alignment film produced by the photo-alignment method is mainly composed of a photosensitive member on a side chain of a polymer, but a light-aligning material known in the past. It is a problem that the possibility of causing thermal decomposition of the photosensitive portion of the side chain during heating (especially post-baking) in the liquid crystal panel manufacturing step cannot be eliminated. As described above, it can be formed by a light alignment method with a small amount of radiation irradiation. A liquid crystal alignment agent which is excellent in liquid crystal alignment ability, excellent electrical characteristics, and high heat resistance, and which does not cause thermal decomposition during post-baking is unknown to date. -7- 200949389 [Summary of the Invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal alignment film which has good liquid crystal alignment energy and high heat resistance by irradiating a polarized or non-polarized radiation without performing rubbing treatment, and even if it is high in use. A liquid crystal display element which does not cause thermal decomposition in the case of the post-baking temperature, and a liquid crystal display element which is excellent in various properties such as a method for producing the liquid crystal alignment film and display properties and reliability. According to the above objects and advantages of the present invention, the first is achieved by a liquid crystal alignment agent containing at least one selected from the group consisting of polyglycolic acid, polyimine, and polyglycolate. a polymer, wherein the aforementioned polymer I 〇 has a group represented by the following formula (1) or (2):

One CH=CH—COO one * (1)

(R1 and R2 in the formula (1) are each independently a hydrogen atom or a monovalent organic group, or R1 and R2 may be bonded to each other to form a ring, R3 is a fluorine atom or a cyano group, and a is an integer of 0 to 4, "* </ RTI> means a bond, wherein R4 in the formula (2) is an alkyl group having 1 to 40 carbon atoms or a carbon number of 3 to 40% having an alicyclic group, wherein one of the hydrogen atoms of the aforementioned alkyl group -8 - 200949389 Part or all may also be replaced by a fluorine atom, R5 is a fluorine atom or a cyano group, b is an integer of 〇~4, "*" means a bonding bond), and the first system is aligned by the above liquid crystal The coating is applied to a substrate to form a coating film, which is achieved by a method of forming a liquid crystal alignment mold that irradiates the coating film with ray. [Embodiment] The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of polyamic acid, polyimine, and polyglycolate, wherein the polymer has the above formula (1) or (2) The basis of the representation. The one-valent organic group of R1 and R2 of the above formula (1) can be exemplified by, for example, a one-valent organic group represented by the following formula (R-1): R6-W-* (Ri) (in the formula (R-1) R6 is an alkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms having an alicyclic group, wherein part or all of the hydrogen atom of the alkyl group may be substituted by a fluorine atom, and W is a single A bond, an ether bond, an ester bond, a thioether bond, a thioester bond or a guanamine bond, "*" indicates a bond bond). Examples of the base of the carbon number of 1 to 40 of R6 can be exemplified by, for example, a methyl group or an ethyl group. , n-propyl, n-butyl, n-pentyl 'n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-lauryl, n-dodecane Base, n-tridecyl, n-fourteenth base, n-fifteenth base, n-hexadium base, positive-seventeen base, n-octadecyl, n-dodecyl , n-Eicosyl, 4,4,4-trifluorobutyl, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluoro Hexyl, 3,3,4,4,5,5,5-heptafluoropentyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoro 200949389 propyl, 2- (perfluorobutyl)ethyl, 2-(perfluorooctyl)ethyl' 2_(perfluorodecyl) Group. The one-valent organic group having 3 to 40 carbon atoms of the alicyclic group of R6 may, for example, be cholesteryl 'cholesteryl, adamantyl or the like. R1 in the above formula (1) is a group represented by the above formula (R-1) and R2 is a hydrogen atom, or R1 and R2 are bonded to each other to form a ring having a carbon number of 4 to 8 and preferably a ring thereof Any one of the carbon atoms (preferably other than the carbon atom constituting the pyrrolidine) is bonded to the group represented by the above formula (R-1).

R3 in the above formula (1) is preferably a fluorine atom, and a is preferably 〇, 1 or 4. The preferred R4 in the above formula (2) is the same as those described in r6 of the above formula (n). R5 in the above formula (2) is preferably a fluorine atom, and b is preferably ruthenium, 1 or 4 〇. The group represented by the above formula (1) or (2) is preferably located in polyamine or polyimine or On the side chain of the polyamidolate. The polyglycolic acid having a group represented by the above formula (1) or (2) is, for example, a compound represented by the following formula (3) by a tetracarboxylic dianhydride:

&quot;I \ /=\^NH〇CH=CH—COO-(CH2)c-X1-/ ^ (3) (In equation (3), R1, R2, R3 and a are respectively in the above formula (1) The same meaning 'c is an integer of 0~1〇' (; is 单 when χι is a single bond, ^ is an integer of uo when χΐ is a single bond, ether bond, ester bond, thioether bond, thioester bond or guanamine bond ), and a compound represented by the following formula (4): -10- 200949389

(In the formula (4), R4, R5 and b are the same as those in the above formula (2), and X2 is a single bond, an ether bond, an ester bond, a thioether bond, a thioester bond or a guanamine bond, and d is 0 to 10 An integer of at least one of the group consisting of X3 being a single bond when d is 0, and X3 is a single bond, an ether bond, an ester bond, a thioether bond, a thioester bond, or a guanamine bond when d is an integer of 1 to 10. The polydiimine having a group represented by the above formula (1) or (2) can be synthesized by a diamine reaction, for example, by subjecting the above polyamic acid to dehydration ring closure. &lt;tetracarboxylic dianhydride&gt; The tetracarboxylic dianhydride used for the synthesis of the polyamic acid or polyimine having the group represented by the above formula (1) or (2) can be exemplified by, for example, 2,3. , 5-tricarboxyfluorenylcyclopentyl acetic acid dianhydride, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2, 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,5,6-tricarboxy-norbornane-2-acetic acid dianhydride, 2.3. 4.5- Tetrahydrofuran tetracarboxylic dianhydride, 1,3,33,4,5,91)-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1, 2-£;]-furan-1,3-dione, 1,3,3&amp;,4,5,91?-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl )-8-methyl-naphtho[l,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene -1,2-dicarboxylic anhydride, bicyclo[2,2,2]-oct-7-ene-2.3.5.6-tetracarboxylic dianhydride, tetracarboxylic acid represented by the following formulas (1_1) to (7'_4) -11 - 200949389 Acid 9Η3 CHoI /C 3 CH (CH2)3 CH ch3 ο

Coo ο

Τ-1) ?H3 .ch3 ο

ο CH3 ch(ch2)2ch=c, coo

Ch3 (T-2, ch3 ο

COO ο C CH (CH2)3 CH'

(T-3) ch3 -12- 200949389

Pyromellitic dianhydride, 3,3',4,4'-biphenyl maple tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene Tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3, 3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxylic acid phenoxy Diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl succinic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy) Diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, double ( Phthalic acid) phenylphosphine oxide dianhydride, p-phenylene bis(triphenylphthalic acid) dianhydride, m-phenylene bis(triphenylphthalic acid) dianhydride, bis(triphenyl) Phthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, the following formula (T-5)~(T- 8) An aromatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride, etc.: ^ 广(Τ-5) Ο 0 13- 200949389 ο ο

These tetracarboxylic dianhydrides can be used individually or in combination of 2 or more types. The tetracarboxylic dianhydride for synthesizing the polyphosphonic acid or polyimine having the group represented by the above formula (1) or (2) preferably contains an i, 3, 3 a selected from the above, 4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-. ]-furan-1,3-dione, 1,3,3&amp;,4,5,913-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-8-methyl- Naphtho[l,2-c]-furan-1,3-dione, © 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, butane tetracarboxylic dianhydride, 1,3-dimethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4 '-Biphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4' - a diphenyl ether tetracarboxylic dianhydride and at least one of the group consisting of tetracarboxylic dianhydrides represented by the above formulas (T1), (T-2), (T-5) to (T-8) ( Hereinafter referred to as "specific tetracarboxylic dianhydride"). The tetracarboxylic dianhydride for polyaminic acid-14-200949389 or polyimine which has a group represented by the above formula (1) or (2), preferably with respect to all of the tetracarboxylic dianhydride Contains 20 moles. /. The above specific tetracarboxylic dianhydride as described above is preferably contained in an amount of 50 mol% or more, and preferably more than 8 mol%. The diamine for synthesizing polyphosphoric acid φ or polyimine having a group represented by the above formula (1) or (2) is selected from the group consisting of the compound represented by the above formula (3) and the above formula (4) And at least one of the groups represented by the compound. The compound represented by the above formula (3) is preferably exemplified by the compounds represented by the following formulas (3A) to (3C):

CH=CH—COO—(CH2) c CH=CH—COO—(CH2) C-X1 nh2 (3A)

NH2 (3B)

R6-W

CH=CH—COO—(CH2) C_X nh2 (3C) (In the formulas (3 A) to (3 C), R3 and a are the same as in the above formula (1), respectively, -15-200949389 meaning 'R6 and W respectively It is the same as in the above formula (R-1), and X1 and C have the same meanings as in the above formula (3), respectively. In the above formulas (3), (4) and (3A) to (3C), the diaminophenyl group on the right side is preferably a 2,4-diaminophenyl group, a 2,5-diaminophenyl group or 3 , 5-diaminophenyl. The diamine for synthesizing polyphosphoric acid or polyimine having a group represented by the above formula (1) or (2) may also be selected from only the compound represented by the above formula (3) and the above formula ( And 4) at least one of the group consisting of the compound represented by the compound represented by the formula (3) and at least one selected from the group consisting of the compound represented by the formula (3) and the compound represented by the formula (4) Other diamines. Other diamines which can be used herein can be exemplified by, for example, p-phenylenediamine, m-phenylenediamine, 4,4,-diaminodiphenylmethane, 4,4'-diaminodiphenyl. Ethylethane, 4,4,-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3,-dimethyl-4,4'-diaminobiphenyl , 4,4,-diaminobenzimidamide, 4,4,-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4, -diaminobiphenyl, 5-amino-1-(4,-aminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4,-aminobenzene Base)-: 1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 2,2-bis(4-aminophenoxy)propane, 2,2_ double [ 4-(4-Aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-amine Phenylphenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]milled, 1,4-bis(4-aminophenoxy)benzene, anthracene, 3 - bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2, 7-Diaminopurine, 9,9-bis(4-aminophenyl)-16-200949389 芴, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4 , 4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-(p-extension Phenyldiisopropylidene)diphenylamine, 4,4'-(m-phenylene isopropylidene)diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethyl) Phenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2) -trifluoromethyl)phenoxy]-octafluorobiphenyl, 6-(4-chalconyloxy)hexyloxy(2,4-diaminobenzene), 6-(4' -fluoro-4-chalconeoxy)hexyloxy (2,4-diaminobenzene), 8-(4-chalconeoxy)octyloxy (2,4-diaminobenzene) , 8_(4'-fluoro-4-chalconeoxy)octyloxy (2,4-diaminobenzene), 1-dodecyloxy-2,4-diaminobenzene, 1 -tetradecyloxy-2,4-diaminobenzene, 1-pentadeca alkoxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene 'cholesteryloxy-2,4-diaminobenzene, 1-cholesteryl Oxy-2,4-diaminobenzene, dodecyloxy (3,5-diaminobenzylidene), tetradecyloxy (3,5-diaminobenzimidyl), Pentadecyloxy (3,5-diaminobenzimidyl),hexadecanyloxy (3,5-diaminobenzimidyl), octadecyloxy (3,5-diamine) Benzobenzinyl), biliary alkenyloxy (3,5-diaminobenzimidyl), cholesteryloxy (3,5-diaminobenzimidyl), (2, 4-Diaminophenoxy)palmitate, (2,4-diaminophenoxy)stearate, (2,4-diaminophenoxy)-4-trifluoromethane benzoate An acid ester, an aromatic diamine such as a diamine compound represented by the following formulas (D-1) to (D-5): -17- 200949389

H2n 乂

0~f C2H4—ο

(D-4) -18- 200949389

(wherein y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5); an aromatic diamine having a hetero atom such as a diaminotetraphenylthiophene ; p-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine , 9-methylene diamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentanediene subdiamine, hexahydro-4,7-methyl bridge Aliphatic diamines and lipids such as dimethylenediamine, tricyclo[6.2.1.02'7]-exedecyldimethyldiamine, 4,4'-methylenebis(cyclohexylamine) a diamine-based organooxane such as a cyclic diamine; a diaminohexamethyldioxane; and the like. These other diamines may be used singly or in combination of two or more. The benzene ring of the above aromatic diamine may also be substituted by one or more of the substituents (preferably methyl) having 1 to 4 carbon atoms. The other diamine contained in the diamine for synthesizing the polyamine or the polyimine having the group represented by the above formula (1) or (2) is preferably selected from the above-mentioned p-phenylenediamine, 4 , 4'-diaminodiphenylmethane, anthracene, 5•diaminonaphthalene, 2,7-diaminopurine, 4,4'-diaminodiphenyl ether, 4,4,_(pair Phenyldiisopropylidene)diphenylamine, 2,2'·bis[4_(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexa Fluoropropane, 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4,-diamino-2,2,-bis (three Fluoromethyl) -19- 200949389 Biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, hexadecyloxy-2, 4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholestyloxy-2,4-diaminobenzene, 1-cholestyloxy _2,4-Diaminobenzene, hexadecyloxy (3,5-diaminobenzimidyl), octadecyloxy (3,5-diaminobenzylidene), cholesteric Alkenyloxy (3,5-diaminobenzimidyl), cholesteryloxy (3,5-diaminobenzimidyl) and Said compound of the formula (D-1) to (D-5) represents the group consisting of at least one (hereinafter referred to as "other specific diamine"). The diamine for synthesizing polyphosphoric acid or polyimine having a group represented by the above formula (1) or (2) is preferably selected from the group consisting of 10 mol% or more based on the entire diamine. At least one of the compound represented by the formula (3) and the compound represented by the above formula (4) is more preferably contained in an amount of 30 mol% or more, and more preferably 50 mol% or more. &lt;Synthesis of Polylysine&gt; The polyglycolic acid having a group represented by the above formula (1) or (2) can be synthesized by reacting a tetracarboxylic dianhydride as described above with a diamine. The ratio of the tetracarboxylic dianhydride to the diamine used in the synthesis reaction of polylysine is preferably the ratio of the anhydride group of the tetracarboxylic dianhydride to the amine group contained in one equivalent of the diamine. · 2 to 2 equivalents, more preferably 〇. 3 to 1.2 equivalents. The synthesis reaction of the above polylysine is preferably carried out in an organic solvent 'and preferably at -2 0 ° C to 150 ° C, more preferably at a temperature of 〇 1 to 10 ° C. 240 hours. The 'organic solvent is not particularly limited as long as it can be used to dissolve the synthesized polylysine which can be used in 200949389 , ,, for example, N-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethyl diol. Indoleamine, N,N-dimethylformamide, N,N-dimethylimidazolidinone, dimethyl hydrazine, γ-butyrolactone, tetramethyl urea, hexamethylphosphoric acid triamide Proton-based polar solvent; phenolic solvent such as m-cresol, xylenol, phenol, and dentated phenol. The amount (a) of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is from 0.1 to 50% by weight based on the total amount (a + b) of the reaction solution. More preferably in an amount of 5 to 30% by weight. A reaction solution for dissolving polylysine having a group represented by the above formula (1) or (2) is obtained as described above. The reaction solution can be used for preparing a liquid crystal alignment agent, and can also be used for preparing a liquid crystal alignment agent after being separated from the polylysine contained in the reaction solution, or can be purified by separately separating the polyamic acid. Modulation of liquid crystal alignment agent. When polypyridic acid is dehydrated and closed to polyimine, the reaction solution may be directly supplied to the dehydration ring closure reaction, or the polyamine acid contained in the reaction solution may be separately supplied to the dehydration ring closure reaction, or The isolated polylysine is purified for use in a dehydration ring closure reaction. The separation of the polyamic acid can be carried out by injecting the above reaction solution into a large amount of a weak solvent to obtain a precipitate, drying the precipitate under reduced pressure, or by distilling off the reaction solution by a rotary evaporator under reduced pressure. . Alternatively, the polylysine may be obtained by redissolving the polylysine in an organic solvent, followed by precipitation in a weak solvent, or by subjecting the step of distilling off under reduced pressure in a rotary evaporator one or several times. purification. -21 - 200949389 &lt;Synthesis of Polyimine&gt; The polyimine having the group represented by the above formula (1) or (2) can be obtained by using the polyamide obtained by the polyamine obtained as described above The acid structure is produced by dehydration ring closure. In this case, it may be a complete ruthenium imide formed by dehydration ring closure of the polydecanoic acid structure, or may be a deuterated acid structure and a quinone imine ring only by partially dehydrating and ringing the proline structure. Construct a coexisting part of the quinone imide. The dehydration ring closure of polylysine is carried out by (i) heating the poly-proline, or by dissolving the poly-proline in an organic solvent, adding a dehydrating agent and dehydrating ring-contact in the solution. The medium is carried out according to the method of heating. The reaction temperature in the method for heating polylysine in the above (i) is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. The reaction temperature is less than 5 (TC cannot sufficiently perform the dehydration ring-closure reaction, and the reaction temperature exceeds 200 ° C, which may lower the molecular weight of the obtained ruthenium iodide polymer. The reaction time in the method of heating polyglycine is higher. Preferably, it is 5 to 48 hours, more preferably 2 to 20 hours. On the other hand, in the above method (ii) in which a dehydrating agent and a dehydration ring-closing catalyst are added to the polyaminic acid solution, the dehydrating agent can be used, for example. An acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The amount of the dehydrating agent is preferably 0.01 to 20 moles per mol of the polyglycine structural unit. Further, the dehydration ring-closing catalyst may be, for example, pyridine. And a tertiary amine such as trimethylpyridine, lutidine or triethylamine. However, it is not limited thereto. The amount of the dehydration ring-closing catalyst used is preferably 0.01% with respect to the dehydrating agent used for 1 mole. 10 mol. The organic solvent used in the dehydration ring-closing reaction can be exemplified by the organic solvent exemplified in the polyglycolic acid synthesis-22-200949389. The reaction temperature of the dehydration ring-closure reaction is preferably 〇~180 ° C, more preferably It is 1〇~150°C. The reaction time is better. It is 0.5 to 20 hours, more preferably 1 to 8 hours. The polyimine obtained in the above method (i) can be directly supplied to the liquid crystal alignment agent, or the obtained polyimine can be purified and then supplied. The preparation of the liquid crystal alignment agent. On the other hand, in the above method (Π), a reaction solution containing polyimine can be obtained. The reaction solution can be directly supplied to the liquid crystal alignment agent, and the dehydrating agent can be removed from the reaction solution and dehydrated. The modulation of the liquid crystal alignment agent after the closed-loop catalyst can also be used to prepare the liquid crystal alignment agent after the separation of the polyimide, or to prepare the liquid crystal alignment agent after purification of the isolated polyimine. The dehydrating agent for removing the reaction solution and the dehydration ring-closure catalyst can be suitably used, for example, by solvent replacement, etc. The separation and purification of the polyimine can be carried out by performing the same operation as the above-described separation and purification of the polyamic acid. &lt;Synthesis of polyglycolate&gt;

The polyglycolate having a group represented by the above formula (1) or (2) can be obtained by reacting polylactoic acid with a compound represented by the following formula:

Ο CH=CH—COO—(CH2) e—Z1

(In the formula (5), R1, R2, R3 and a have the same meanings as in the above formula (1), respectively, Z is a transporting chlorine atom, a bromine atom or an iodine atom, and e is an integer of 1 to 1 Å), or Compound represented by formula (6): -23- 200949389

(In the formula (6), 'R4 and b respectively have the same meanings as in the above formula (2), Z2 is a hydroxyl group, a chlorine atom, a bromine atom or an iodine atom, and f is an integer of 〇~1〇', when X is 〇, X4 is Single-button '[X4 is a single bond, an ether bond, an ester bond, a thioether bond, a thioester bond or a guanamine bond when it is an integer of 丨~丨❹), preferably in an organic solvent' and optionally in a catalyst The reaction is synthesized by the next reaction. The above polylysine can be synthesized by reacting a tetracarboxylic dianhydride with a diamine. The tetracarboxylic dianhydride used herein may be exemplified by the same as the tetraresin dianhydride used in the synthesis of the polyglycolic acid having the group represented by the above formula (1) or (2). The diamine to be used can be exemplified by the same as those exemplified above for synthesizing a diamine having a polyglycolic acid having a group represented by the above formula (1) or (2). The diamine used herein is also preferably one which does not contain any of the compound represented by the above formula (3) and the compound represented by the above formula (4). Further, the diamine used therein is preferably one containing 20 mol% or more of the other specific diamines as exemplified above, more preferably 5 mol% or more, and more preferably It is good to contain more than 80% of the person. Z1 in the above formula (5) and z2 in the above formula (6) are each preferably a bromine atom or an iodine atom. The e in the above formula (5) and the f in the above formula (6) are preferably each an integer of from 1 to 6 -24 to 200949389. The compound represented by the above formula (5) can be exemplified by, for example, the compounds represented by the following formulas (5A) to (5C): r6~wv^ {A\ C〇〇-(CH2&gt; e__Zl Ο (5A) o

N CH=CH—COO—(CH2) e-Z1 (5B) CH=CH—COO—(CH2) e—Z1 (5C)

In the formulas (5A) to (5C), R3 and a are the same meanings as in the above formula (1), and R6 and W have the same meanings as in the above formula (R-1), respectively, and Z1 and e are respectively The same meaning in the formula (5)). The ratio of the compound represented by the above formula (5) or the compound represented by the above formula (6) used in the reaction of the polyamine acid with the compound represented by the above formula (5) or the compound represented by the above formula (6) The amount of the proline structure of the polyamic acid is preferably from 10 to 1,000 mol%, more preferably from 30 to 200 mol%, most preferably from 50 to 100 mol%. Preferred organic solvents to be used in the reaction can be exemplified by, for example, N-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylacetamide, hydrazine, hydrazine-dimethylformamide, N,N-- 25- 200949389 Dimethylimidazolidone 'dimethyl sulfoxide, γ-butyrolactone, tetramethyl urea, hexamethylphosphoric acid triamide, and the like. The preferred catalyst to be used in the reaction differs depending on the oxime 2 in the formula (5) or the oxime 2 in the formula (6). The catalyst for the case where Ζ1 or Ζ2 is a chlorine atom, a bromine atom or an iodine atom can be exemplified by, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, cesium carbonate, sodium methoxide, potassium methoxide, and B. An alkali catalyst such as sodium oxide, potassium ethoxylate, sodium propoxide, potassium propoxide, sodium butoxide, potassium butoxide, trimethylamine, triethylamine or pyridine. The catalyst when ruthenium 1 or ruthenium 2 is a hydroxyl group may, for example, be a dehydration catalyst such as dicyclohexylcarbodiimide or methyl chloroformate. These dehydrogenation catalysts may also be used in combination with the auxiliary catalyst of dimethylaminopyridine. The catalyst is used in a proportion of preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, per 100 parts by weight of the polyamic acid. A reaction solution containing a polyphthalamide having a group represented by the above formula (1) or (2) is obtained as described above. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or can be used for the preparation of the liquid crystal alignment agent after removing the catalyst from the reaction solution, or can be used for the liquid crystal alignment agent after the polyperurethane is separated. In the preparation, the isolated polyperurethane is purified and then supplied to the preparation of the liquid crystal alignment agent. The isolation and purification of the polyamidite can be carried out by performing the same operation as the separation and purification methods of the polyglycolic acid as described above. &lt;Other components&gt; The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of polyglycolic acid, polyamidene-26-200949389 and polyglycolic acid vinegar as an essential component. The polymer has a group represented by the above formula (1) or (2), but other components may be additionally contained as long as the effects and advantages of the present invention are not impaired. Examples of such other components include other polymers, compounds having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compounds"), functional sand compounds, and surfactants. The above other polymer can be further contained in the liquid crystal alignment agent of the present invention for the purpose of further improving the electrical properties of the liquid crystal alignment film to be formed. The other polymer may, for example, be a polyglycine (hereinafter referred to as "other polyamic acid") having no group represented by the above formula (1) or (2), and a polycondensation obtained by dehydrating the same. Imine (hereinafter referred to as "other polyimine") and the like. The ratio of the other polymer used to the total of 100 parts by weight of the polymer having the group represented by the above formula (1) or (2) (meaning having the group represented by the above formula (1) or (2) a combination of poly-proline, a polyimine having a group represented by the above formula (1) or (2), and a polyamine having a group represented by the above formula (1) or (2), the same It is preferably 1,000 parts by weight or less, more preferably 5,000 parts by weight or less. Further, in view of the adhesion of the liquid crystal alignment agent formed of the liquid crystal alignment agent of the present invention to the surface of the substrate, the above epoxy compound can be used, and for example, ethylene glycol diglycidyl ether or polyethylene is preferably exemplified. Glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, C3 Alcohol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl--27- 200949389 2,4-hexanediol, hydrazine, hydrazine, Ν', Ν'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, n,N,N,,N, _tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, and the like. Further, in order to efficiently cause the crosslinking reaction of the epoxy group, an alkali catalyst such as 1-benzyl-2-methylimidazole may be used together with the epoxide. The compounding ratio of the epoxy compound is a total of 100 parts by weight of all the polymers (meaning a polylysine having a group represented by the above formula (1) or (2), having the above formula (1) or 2) The total amount of the polyimine and the other polymer having the group represented by the above formula (1) or (2) and the other polymers are the same as the above, preferably 40 parts by weight or less. More preferably, it is 0.1 to 30 parts by weight. The use ratio of the base catalyst is preferably 0.01 to 1 part by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the total of the polymer having a group represented by the above formula (1) or (2). . The above functional decane compound can be used for the purpose of improving the adhesion between the obtained liquid crystal alignment film and the substrate. As the functional decyl group compound, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane '2-aminopropyltrimethoxydecane, 2-amine Propyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-three Ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl--28- 200949389 1,4,7-triazanonane, ι〇·triethoxydecyl-anthracene, 4,7-triazadecane, 9-trimethoxy Base alkyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyl Trimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltri Oxydecane, N-bis(oxiranyl)-3-aminopropyltrimethoxydecane, N-bis(oxiranethyl)-3-aminopropyltriethoxydecane, 3-shrinkage Further, glyceroloxypropyl φ yl trimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, etc. can be exemplified as described in JP-A-63-29 1 922. a reaction product of a tetracarboxylic dianhydride and a decane compound having an amine group. The content of the functional decane compound is preferably 50 parts by weight or less, more preferably 20 parts by weight or less based on the total of 100 parts by weight of the total polymer. The above surfactant may, for example, be a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric interface Q active agent, a cerium oxygen surfactant, a polyalkylene oxide surfactant, or a fluorine-containing interface. Active agent, etc. In the case where the liquid crystal alignment agent of the present invention contains a surfactant, the content thereof is preferably 1 part by weight or less, more preferably 1 part by weight or less based on 100 parts by weight of the total of the liquid crystal alignment agent. &lt;Liquid crystal alignment agent&gt; The liquid crystal alignment agent of the present invention is preferably composed of a polymer containing the above-mentioned polymer and any other component added thereto in an organic solvent. -29- 200949389 The organic solvent which can be used in the liquid crystal alignment agent of the present invention can be exemplified by a solvent exemplified by a user in the synthesis reaction of polylysine. Alternatively, the weak solvent exemplified may be used as appropriate for the synthesis reaction of poly-proline. The most preferred organic solvent to be used in the liquid crystal alignment agent of the present invention is N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactone, N,N-dimethylformamidine. Amine, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate Ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve) , ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like. These may be used singly or in combination of two or more. The optimum solvent composition is a composition obtained by combining the above solvents, and the polymer is not precipitated in the alignment agent, and the surface tension of the alignment agent is in the range of 25 to 40 mN/m. The solid component concentration in the liquid crystal alignment agent of the present invention, that is, the ratio of the weight of all components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent, is selected as a measure of viscosity, volatility, etc. It is preferably in the range of 1 to 10% by weight. The liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film as a liquid crystal alignment film. However, when the solid content concentration is less than 1% by weight, it is difficult to obtain a good liquid crystal distribution because the coating film thickness is too small. The condition of the membrane. On the other hand, when the solid content concentration exceeds ίο重量%, it is difficult to obtain a good liquid crystal alignment film because the coating film thickness is too large, and the viscosity of the liquid crystal alignment agent is increased to have insufficient coating properties. The optimum solid concentration range will vary depending on the method used to coat the liquid crystal alignment agent on the substrate. For example, a preferred range of the spin coating method is from 1.5 to 4.5% by weight. In the case of the printing method, the solid content concentration is in the range of 3 to 9 % by weight, whereby the solution viscosity is preferably in the range of 12 to 50 mPa*s. In the case of the ink jet method, the solid content concentration is in the range of 1 to 5% by weight, and accordingly, the solution viscosity is preferably in the range of 3 to HmPa.s. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 0. . 〜200T:, more preferably 2 (TC ～60 〇C ° &lt;Formation method of liquid crystal alignment film&gt; The liquid crystal alignment agent of the present invention can be preferably used for forming a liquid crystal alignment film by photo-alignment method. The liquid crystal alignment film may be, for example, a method in which a coating film of the liquid crystal alignment film of the present invention is formed on a substrate, and then a liquid crystal alignment energy is imparted to the coating film by a photo-alignment method. The liquid crystal alignment agent of the present invention is applied to the transparent conductive film side of the substrate of the conductive film by a suitable coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method. Preheating (prebaking) followed by firing (post baking), thereby forming a coating film. The prebaking conditions are, for example, a temperature of 40 to 120 ° C for 0.1 to 5 minutes, and a post baking condition of -31 to 200949389. Preferably, the temperature is from 120 to 300 ° C, more preferably from 150 to 250 ° C, preferably from 5 to 200 minutes, more preferably from 1 to 100 minutes. The thickness of the coating after post-baking is preferably from 0.001 to Ι μιη, more preferably. It is 0.005 to 0.5 μm. As the above substrate, for example, float glass, sodium can be used. a glass such as calcium glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate or polyether maple 'polycarbonate. The transparent conductive film can be used. A NESA film composed of Sn02, an ITO film made of In203-SnO2, etc. The patterning of the transparent conductive films may be by photolithography or a method of using a photomask when forming a transparent conductive film. When the alignment agent is applied, in order to improve the adhesion between the substrate or the transparent conductive film and the coating film, a functional decane compound, titanate or the like may be applied to the substrate and the transparent conductive film in advance. On the coating film, a linearly polarized or partially polarized radiation or a non-polarized radiation is irradiated, and in this case, heat treatment is further performed at a temperature of 15 0 to 25 ° C for preferably 1 to 120 minutes. For the radiation, for example, ultraviolet rays and visible rays containing light having a wavelength of from 150 nm to 800 nm can be used, but ultraviolet rays containing light having a wavelength of from 300 nm to 400 nm are preferably used. The radiation used is a straight line. In the case of polarized light or partial polarized light, the irradiation may be performed in a direction perpendicular to the surface of the substrate, or may be performed in an oblique direction for imparting a pretilt angle, or may be combined with the temple to enter fr. When irradiating the unpolarized light, the irradiation direction is It is necessary to be inclined. For the light source used, for example, a low-pressure mercury lamp, a high-pressure water-32-200949389 silver lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used. Ultraviolet light in the wavelength range can be obtained by simultaneously using the above-mentioned light source and such as a filter, a diffraction grating, etc. As for the radiation dose, it is preferably lj/m2 or more and less than 10,000 J/m2, more preferably. It is 10~3,000J/m2. Further, when the liquid crystal alignment energy is imparted to the coating film formed by the conventional liquid crystal alignment agent by the photo-alignment method, the amount of the ray irradiation is required to be 10,000 J/m2 or more. However, when the liquid crystal alignment agent of the present invention is used for 0, the irradiation amount of the radiation in the photo-alignment method is 3,000 J/m 2 or less, and even if it is 1 or less, 〇〇〇J/m 2 or less, it can be imparted with good. The liquid crystal alignment property can reduce the manufacturing cost of the liquid crystal display element. Further, the "pretilt angle" as used herein means an angle at which liquid crystal molecules are inclined from a direction in which a substrate surface is formed. &lt;Manufacturing Method of Liquid Crystal Display Element&gt; A liquid crystal display element formed using the liquid crystal alignment agent of the present invention can be produced, for example, as follows. Two sheets of the liquid crystal alignment film having the above-described liquid crystal alignment film were prepared, and liquid crystal cells were placed between the two substrates arranged in the opposite direction to manufacture a liquid crystal cell. The production of the liquid crystal cell is exemplified by, for example, the following two methods. The first method is a method known in the past. First, two substrates are placed such that the liquid crystal alignment films face each other and are interposed with a gap (cell gap). A liquid crystal is formed by bonding a peripheral portion of the substrate with a sealant to form a liquid crystal on the surface of the substrate and a sealant. After the inside of the cell gap is filled with the liquid crystal, the injection hole is sealed to thereby manufacture the liquid crystal cell. -33- 200949389 The second method is a special photo-curable sealant on one of the two substrates of the crystal alignment film called ODF (Dipper-filled), and the liquid crystal alignment film on the liquid crystal alignment film is opposite to the liquid crystal alignment film. The method and the other substrate are completely irradiated with ultraviolet light to harden the sealing agent, thereby heating or heating the liquid crystal to be in the same phase to room temperature by any method, thereby removing the liquid crystal injection. In the flow distribution, the surface is made into a liquid crystal display element by making the polarization direction of the polarizing plate and the alignment of the film easy to form a predetermined angle. In the liquid crystal distribution, a TN type or liquid crystal display element can be obtained by forming an angle of a polarizing plate formed by a polarization direction of linear polarized radiation on two substrates on which a liquid crystal alignment film is formed. On the other hand, in the case of liquid crystal alignment, the two substrates in which the liquid crystal alignment film is formed are formed so as to be parallel, and the liquid crystal display element of the vertical alignment type liquid crystal cell is formed in a direction in which the polarization direction is 45 degrees from the alignment. As the sealing agent, for example, an epoxy resin containing an aluminum ball and a curing agent can be used. As the liquid crystal, for example, a nematic type or the like can be used, but among them, a nematic liquid crystal is preferable. In the case of the S TN type liquid crystal cell, it is preferred to have a positive dielectric method. After the liquid crystal is applied by, for example, ultraviolet driing, the liquid crystal is applied to the liquid to form a liquid crystal, and then the liquid crystal is manufactured as a single liquid crystal, and then slowly cooled. The liquid crystal alignment polarizing plate of each substrate is bonded to the two-sentence film to be horizontally aligned, and the alignment is easy to be achieved by adjusting the irradiation degree and the vertical alignment of each of the substrates and the film of the STN type liquid crystal cell. When the polarizing plate is bonded, it can be an oxidized liquid crystal having a spacer, a smectic liquid crystal TN liquid crystal cell, or an anisotropic nematic type 200949389 liquid crystal. For example, a biphenyl liquid crystal or a phenylcyclohexane system can be used. A liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a chewing-system liquid crystal, a double-ring Xin-system liquid crystal, and a Cubane liquid crystal. Further, in the above liquid crystal, cholesteric liquid crystal such as cholesteric chlorine, cholesteryl phthalate or cholesteryl carbonate may be further added, and sold under the trade names C-15 and CB-15 (manufactured by Merck). Pair of palmitic agents; p-normetic oxygenator yoke-p-amino-2-methylbutyl laurate and other strong dielectric liquid crystal ©. On the other hand, in the case of a vertical alignment type liquid crystal cell, a smectic liquid crystal having a negative dielectric anisotropy is preferable, and for example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, or a Schiff base system can be used. Liquid crystal, azo oxide (az0Xy) liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, or the like. As for the polarizing plate to be used on the outer side of the liquid crystal cell, a polarizing film called a "H film" which is obtained by stretching and aligning polyvinyl alcohol while absorbing iodine may be exemplified by a polarizing plate held by a cellulose acetate protective film, or a ruthenium film. The polarizing plate itself is constructed. The liquid crystal display element of the present invention thus produced is excellent in performance such as display characteristics and reliability. EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by the examples. &lt;Synthesis of Compound represented by the above formula (3)&gt; -35-200949389 Example 1 (Synthesis of Compound (3A-1)) The synthesis of Compound (3 A-1) was carried out in accordance with Scheme 1 below:

C10H2i

CH=CH—COOH (3 A-1a) ch2ci K2C03 02N C10H21

ώΝ0

NO 2

2 N〇2 (3A-1b)

SnCI2.2H20 C10H21

o nh2 (3A-1) Reaction Scheme 1 (Synthesis of Compound (3 A-la)) 1 liter pear flask with reflux tube, nitrogen inlet tube and Dean-Stark -36- 200949389 tube 72 g of mercapto succinic anhydride, 49 cinnamic acid, 7 ml of triethylamine, 5 ml of toluene and 200 mmol of furan were fed in and the reaction was carried out under reflux for 36 hours. After the completion of the reaction, the reaction mixture was washed with dilute hydrochloric acid and water, and then the organic layer was concentrated with magnesium sulfate, and then re-supplemented with a solvent mixture of ethanol and tetrahydrofuran to obtain 72 g of compound (3A-la) as white crystals (purity: 99%) . φ (synthesis of compound (3A-lb)) 19 g of a compound (3A-la), 11 g of 3,5-dinitrobenzyl chlorocarbonate, and 5 g of a trihydrocarbon having a nitrogen gas introduction tube and a thermometer, 15 g of sodium iodide and 150 ml of N,N-dimethylformamidine were reacted at 90 ° C for 5 hours. After completion of the reaction, 300 mmol of ethyl ester was added to the reaction mixture, washed with water for 3 times, dried with a sulfur organic layer, and concentrated, and then recrystallized from methanol to obtain a compound (3A-lb). Yellow crystals. 〇 (Synthesis of Compound (3 A-1)) In a nitrogen inlet tube and a reflux tube, 500 ml of a three-necked portion was charged with 17 g of a compound (3A-lb), 68 g of tin chloride dihydrate and ethyl acetate. The reaction was carried out under reflux for 4 hours. After completion of the reaction, a potassium fluoride aqueous solution was added to the reaction mixture, and the precipitate was separated by filtration to remove the aqueous layer. Then, the aqueous layer was washed with a potassium fluoride aqueous solution and water, dried over magnesium sulfate, and concentrated, and then recrystallized from ethanol. The pale yellow crystal of the compound (3 A-1).克 4-amine liters of tetrahydrogen, dried sequentially, crystallized, obtained by feeding in a bottle, 21 g of amine, and magnesium acetate was added to feed a 9 gram bottle for 200 mM, then, through the machine layer, obtained -37 - 200949389 Example 2 (Synthesis of Compound (3A-2)) The synthesis of Compound (3A-2) was carried out according to the following Reaction Scheme 2: Ο f^N-^&gt;~CH=CH-COOH 〇(3A-1a) SOCI; 0

02N XX:

ϊ N—^ ^—CH=CH-COO O 02N ~^)~N〇2 (3A-2a)

SnCI2-2H20 NH,

Ci〇H21V^ /^X L^N-\&gt;-CH=CH-C00-y&gt; (3A-2)

Reaction Scheme 2 (Synthesis of Compound (3A-2a)) Into a 200 ml pear-shaped reaction flask equipped with a reflux tube, 19 g of a compound (3A-1 a), 0.1 g of hydrazine, hydrazine-dimethylformamide and 100 ml of sulfinium chloride was used and the reaction was carried out at 80 ° C for 1 hour. After the completion of the reaction, the thioxanthene chloride was distilled off from the reaction mixture under reduced pressure, and then 200 ml of dichloromethane was added to the residue. The organic layer was washed with water and dried over magnesium sulfate. Methyl chloride' and 200 ml of tetrahydrofuran (this is referred to as "reverse 1 J") On the other hand, in a 500 ml flask equipped with a dropping funnel and a thermometer, 9.2 g of 2,4-dinitro was fed under ice cooling. Phenol, potassium acid, 0.48 g of tetrabutylammonium and 1 ml of water were added thereto, and 1 part of the above reaction liquid was added thereto for 3 minutes, and the reaction was carried out under ice cooling. After the completion of the reaction, 300 ml of ethyl acetate was added. In the reaction, 'washed three times with water', dried with magnesium sulfate, and recrystallized by concentrated ethanol to obtain 23 g of a compound crystal of (3A-2a). (Synthesis of compound (3 A - 2 )) Nitrogen introduction tube and reflux tube of 500 ml three-necked into 17 g of compound (3A-2 a), 68 g of tin chloride dihydrate and ethyl acetate, and reacted under reflux for 4 hours.添加 Add potassium fluoride solution to the reaction mixture After the removal, the aqueous layer was separated by liquid separation, followed by a potassium fluoride aqueous solution and a water layer, and dried over magnesium sulfate. After concentration, 13 g of compound (3 A-2) pale yellow crystals were recrystallized from ethanol. Example 3 (Synthesis of Compound (3B-1)) The synthesis of Compound (3B-1) was carried out in accordance with the following Reaction Scheme 3. The liquid should be raised to three necks, 14 grams of carbon or more, and about 2 small mixtures, and then fed in a yellow bottle. After the bundle, the precipitate is washed and obtained -39- 200949389

C2f5c3h6-oh Ο

(3B-1a) CH=CH-COOH Q2F5C3H6—oco. ο CH=CH—COOH (3B-1b) K2C03

O ch2ci

O2n ^ N〇2 T Γ N—4 &gt;-CH=CH—COO—CH2 N〇2-0 N〇2 (3B-1c)

SnCI2.2H20 c2f5c3h6-oco nh2 nh2 (3B-1) Reaction Scheme 3 -40 200949389 (Synthesis of Compound (3B-la)) Feeding 丨98 g 1,2 in a 2 liter pear-shaped reaction flask equipped with a reflux tube 4-cyclohexanetricarboxylic anhydride, 500 ml of sulfinium chloride and 2 ml of N,N-dimethylformamide' were reacted at 80 ° C for 1 hour under reflux. After the completion of the reaction, the sulfite chloride was removed under reduced pressure, and dichloromethane was added to the residue. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, then dried over magnesium sulfate and concentrated and dried. After that, add 500 ml of tetrahydrofuran. On the other hand, 178 g of 4,4,5,5,5-pentafluoropentanol, 160 ml of pyridine and 1.25 liters of tetrahydrofuran were fed into a 3-liter three-necked flask equipped with a dropping funnel, a thermometer and a nitrogen introduction tube. And cooled in an ice bath. A tetrahydrofuran solution containing the above-mentioned reactant of I,2,4-cyclohexanetricarboxylic anhydride and sulfinium chloride was slowly added dropwise thereto, and the mixture was stirred at room temperature for further 4 hours. After the reaction was completed, it was extracted with ethyl acetate. The organic layer was washed with water and dried over magnesium sulfate. Then, the solvent was removed from the organic layer, and the residue was dissolved in a mixed solvent of hexane and ethyl acetate, and purified through a hydrazine column, followed by solvent removal and drying to obtain 268 g of compound (3B_1 a). (Synthesis of Compound 3 B -1 b)) 241 g of compound (3B-la), 109 g of 4-aminocinnamic acid, 190 ml of triethylamine were fed into a 200 ml pear-shaped flask equipped with a Dustast tube. 16 g of 4-dimethylaminopentylpyridine, 1 liter of toluene and 2 liters of tetrahydrofuran were reacted under reflux for 24 hours. After the reaction was completed, the reaction mixture was washed with dilute hydrochloric acid and water. The organic layer was dried over magnesium sulfate and then recrystallized from methanol to yield 78 g of cinnamic acid derivative (3B-lb). -41 - 200949389 (Synthesis of Compound (3B-lc)) In a 500 ml three-necked flask equipped with a nitrogen gas introduction tube and a thermometer, 25 g of a compound (3B-lb) and 11 g of 3,5-dinitrobenzyl chloride were added. 21 g of potassium carbonate, 15 g of sodium iodide, 150 ml of N,N-dimethylformamide, and reacted at 90 ° C for 5 hours. After the completion of the reaction, 300 ml of ethyl acetate was added, and the mixture was washed with water three times, dried over magnesium sulfate, and concentrated, and then recrystallized from ethanol to obtain 25 g of pale yellow crystals of compound (3B-lc). (Synthesis of Compound (3B-1)) In a 500-neck three-necked flask equipped with a nitrogen gas introduction tube and a reflux tube, 21 g of a compound (3B-lc), 68 g of tin chloride dihydrate, and 200 ml of ethyl acetate were fed. The ester was reacted under reflux for 4 hours. After the completion of the reaction, an aqueous potassium fluoride solution was added to the reaction mixture to remove the precipitate by filtration. After the aqueous layer was separated by liquid separation, the organic layer was washed with a potassium chloride aqueous solution and water, and dried over magnesium sulfate. Thereafter, it was recrystallized from ethanol to obtain 15 g of a pale yellow crystal of the compound (3B-1). Example 4 (Synthesis of Compound (3C-1)) The synthesis of Compound (3C-1) was carried out in accordance with the following Reaction Scheme 4: 200949389 H0OC;

COOH COOH H2N~0~

CH=CH—COOH

O CH=CH—COOH (3C-1a)

K2C03

CF3C3H6—I

HCI cf3c3h6- o CH=CH—COOH (3C-1b) K2C03

02N

CH2CI

NO,

Cf3c3h6. o CH=CH—COO—CH2

NO, A

SnCI2-2H2〇N02 (3C-1c) CF3C3H6- XX^nO~ch=ch-c〇0 - ch2h0 2 nh2 (3C-1) Reaction Scheme 4 -43- 200949389 (Synthesis of Compound (3C-la)) A 2-liter three-necked flask equipped with a reflux tube, a Dinstek tube, and a nitrogen introduction tube was fed with 90 g of 5-hydroxyphthalic acid and 500 ml of diethylbenzene, and refluxed for 1 hour. Next, 80 g of 4-aminocinnamic acid and 500 ml of tetrahydrofuran were added, and the reaction was carried out under reflux for 12 hours. After completion of the reaction, the reaction mixture was washed with dilute hydrochloric acid and water, and the organic layer was dried over magnesium sulfate, concentrated, and recrystallized from ethyl acetate and tetrahydrofuran to obtain 95 g of compound (3 C-1 a ). (Synthesis of Compound (3C-lb)) In a 500 ml pear-shaped flask, 75 g of the compound (3C-1 a), 70 g of potassium carbonate and 150 ml of N-methyl-2-pyrrolidone were fed into the chamber. After stirring at a temperature for 1 hour, 59 g of 4,4,4-trifluoro-1-iodobutane was added, and the reaction was stirred at room temperature for 24 hours. After the reaction was completed, 1 liter of water was added and the precipitate was recovered, dissolved in a mixed solvent of hexane and ethyl acetate, and purified by a silica gel column, and then the solvent was removed and dried to obtain 50 g of a compound (3c). -lb). (Synthesis of Compound (3 C -1 c)) In a 500 ml three-necked flask equipped with a nitrogen gas introduction tube and a thermometer, 21 g of a compound (3C-lb) and 11 g of 3,5-dinitrobenzyl chloride were fed. 21 g of potassium carbonate, 15 g of sodium iodide, 150 ml of hydrazine, hydrazine-dimethylformamide, and reacted at 9 (TC for 5 hours. After the reaction was over, add 300 ml of acetic acid B in the reaction mixture 200949389 After the ester was washed with water for 3 times, the organic layer was dried over magnesium sulfate, and concentrated, and then recrystallized from ethanol to give 20 g of compound (3C-lc) as pale yellow crystals. (Synthesis of compound (3C-1)) 18 g of the compound (3C-lc), 68 g of tin chloride dihydrate and 200 ml of ethyl acetate were fed into a 500-neck three-necked flask equipped with a nitrogen introduction tube and a reflux tube, and the reaction was carried out under reflux. After the reaction was completed, an aqueous potassium fluoride solution was added to the reaction mixture, and the precipitate was removed by filtration. The aqueous layer was separated by liquid separation, and then the organic layer was washed with a potassium fluoride aqueous solution and water, and dried over magnesium sulfate. After concentration, it was recrystallized from ethanol to obtain a pale yellow crystal of I2 g of compound (3C-1). Synthesis of Compound represented by the above formula (4) &gt; Example 5 (Synthesis of Compound (4-1)) Q The synthesis of Compound (4-1) was carried out in accordance with the following Reaction Scheme 5: -45 - 200949389

02N

CH=CH—COOH o2n

CH=CH—C00-C3H6CF3 (4-1 a)

SnCI2-2H2〇

H2N

CH=CH—COO-C3H6CF3 (4-1 b)

02N

CH=CH—COO-C3H6CF3 (4-1 d)

SnCI2-2H2〇

CH=CH - C00-C3H6CF3 (4-1) Reaction Scheme 5 -46- 200949389 (Synthesis of Compound (4-1 a)) 49 g in a 2-liter three-necked flask equipped with a thermometer and a nitrogen inlet tube Nitro cinnamic acid, 60 g of 4,4,4-tride-1-iododin, gram of potassium carbonate and 750 ml of 1-methyl-2-pyrrolidone, and stirred at 50 ° C for 1 hour . After the reaction was completed, ethyl acetate was added to the reaction mixture for extraction. The organic layer was washed with water, dried over magnesium sulfate, and concentrated to dryness to yield 70 g of compound (4-1 a). ❿ (Synthesis of Compound (4-lb)) In a 2-liter three-necked flask equipped with a thermometer and a nitrogen introduction tube, 70 g of a compound (4-1 a), 270 g of tin chloride dihydrate, and 750 ml of ethanol were fed. The reaction was stirred at 70 ° C for 1 hour. After completion of the reaction, the reaction mixture was poured into ice water, neutralized with a 2 NaOH aqueous solution, and ethyl acetate was added to remove the precipitate. Ethyl acetate was added to the filtrate to extract to obtain an organic layer. The organic layer was washed with water, dried over magnesium sulfate, and concentrated to dryness to yield 60 g of compound (4-1 b). (Synthesis of Compound (4-lc)) 60 g of a compound (4-lb) and 44 g of 1,2,4-cyclohexanetricarboxylate were fed into a 200 ml pear-shaped reaction flask equipped with a reflux tube and a nitrogen introduction tube. The acid anhydride and 500 ml of acetic acid were reacted under reflux for 1 hour. After completion of the reaction, the reaction mixture was extracted with ethyl acetate to give an organic layer. The organic layer was washed with water, dried over magnesium sulfate, concentrated, dried, and recrystallized from ethyl acetate and a mixture of hexanes to give a white powder of (5 - -47 - 200949389 lc) Crystallization (purity 98.3%). (Synthesis of Compound (4-ld)) In a 500 ml three-necked flask equipped with a nitrogen gas introduction tube and a thermometer, 23 g of a compound (4-lc), 11 g of 3,5-dinitrobenzyl chloride, and 21 g of carbonic acid were added. Potassium, 15 g of sodium iodide, 150 ml of N,N-dimethylformamide, and the reaction was carried out at 90 ° C for 5 hours. After completion of the reaction, 300 ml of ethyl acetate was added to the reaction mixture, and the mixture was washed three times with water, dried over magnesium sulfate, and concentrated, and then recrystallized from ethanol to obtain 21 g of compound (4-Id). crystallization. (Synthesis of Compound (4-1)) 19 g of a compound (4-ld), 68 g of tin chloride dihydrate and 200 ml of acetic acid B were fed into a 500-neck three-necked flask equipped with a nitrogen gas introduction tube and a reflux tube. The ester was reacted under reflux for 4 hours. After completion of the reaction, an aqueous potassium fluoride solution was added to the reaction mixture to remove the precipitate by filtration, and the aqueous layer was separated by liquid separation. The organic layer was washed with a potassium fluoride aqueous solution and water, and dried over magnesium sulfate. Thereafter, it was recrystallized from ethanol to obtain 13 g of pale yellow crystals of Compound (4-1). &lt;Synthesis of Compound represented by the above formula (5)&gt; Example 6 (Synthesis of Compound (5A-1)) The synthesis of Compound (5 A-1) was carried out in accordance with the following Reaction Scheme 6: 200949389 ο C10H21v-- ^ /^VL^n~\_/*ch==ch~c〇〇h (3A-1a) o soci, ▼ HO-C2H4—Br o

C10H21v^/( /^X 0Ν-Λ_/ CH=CH~C00*C2H4-Br (5A-1)

O Reaction Scheme 6 Feed a chelate (3 A-la), 0.1 g of N,N-dimethylformamide and 1 ml of chlorine in a 200 ml pear-shaped reaction flask equipped with a reflux tube and at 8 The reaction was carried out at 0 ° C for 1 hour. After the completion of the reaction, the mixed η was removed to remove the sulphuric acid, and then 2 〇〇 methane was added to the residue and washed with water. After drying over magnesium sulfate, dichloromethane was added under reduced pressure to add 200 ml of tetrahydrofuran. (will be used as the reaction liquid 2). On the other hand, 6.2 g of 2-bromoethane, 5.1 g and 50 ml of tetrahydrofuran were fed under ice cooling in a three-necked flask equipped with a dropping funnel and a warm 500 ml. Next, the reaction liquid 2 was slowly added dropwise to the body over 30 minutes, and the reaction was carried out. After the completion of the reaction, 2 ml of ethyl acetate was added to the reaction mixture layer and washed with water for 3 times, followed by magnesium sulfate. Drying, concentration, and recrystallization from the alcohol afforded 18 g of compound (5 Α-1) as pale yellow crystals. 9 grams of sulfite is pressed from the dioxane and the triethylamine reaction is again measured. In contrast, there is a synthesis of poly-proline which has a group represented by the above formula (1) or (2) in the range of B-49-200949389 &gt; Example 7 4.5 g (0.02 mol) as a tetracarboxylic acid 2,3,5-tricarboxycyclopentyl acetic acid dianhydride of dianhydride and gram (〇.〇2mol) as a diamine compound (3A-1) dissolved in 44 g of N-methyl.2-pyrrolidine A solution containing polyglycine (CPA-1) was obtained by performing a reaction at room temperature for 5 days in a ketone (reaction concentration: 25 wt%). A small amount of the obtained polyaminic acid solution was added, and a solution of N-methyl-2-pyrrolidone was added as a polyglycine solution having a concentration of 10% by weight to determine a viscosity of 27 mPa·s. [Examples 8 to 1 1] In the above Example 7, except that the diamine-substituted compound (3 A-1) shown in Table 1 was used, respectively, the reaction concentration was the same as in Example 7. The reaction was carried out in a manner of 25% by weight to obtain a solution containing polyglycine (CPA-2) to (CPA-5), respectively. The solution viscosity of the fluorene-methyl-2-pyrrolidone solution was determined for each solution by measuring the polyamine concentration of 1% by weight. Table 1 Diamine type solution viscosity OnPa. s) Polylysine name Example 7 3Α-1 29 CPA-1 Example 8 3Α-2 28 CPA-2 Example 9 3Β-1 25 CPA-3 Example 10 3C -1 26 CPA-4 Example 11 4-1 24 CPA-5 200949389 &lt;Synthesis of polyimine having a group represented by the above formula (1) or (2)&gt; Example 1 2 contained in 29 g 0.79 g of pyridine, 0.82 g of acetic anhydride and 116 g of N-methyl-2-pyrrolidone were added to the solution of the polylysine (CPA-1) obtained in Example 7, and dehydrated at 1 l ° C. Closed loop reaction for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced by a new N-methyl-2-pyrrolidone solvent (by this operation, the pyridine and Q acetic anhydride used in the dehydration ring closure reaction can be excluded from the system) About 72 g of a solution containing 10% by weight of a polyamidimide (CPI-1) having a ruthenium iodide ratio of about 50% was obtained. The solution was added in small portions, and N-methyl-2-pyrrolidone was added to adjust the concentration of the polyimide to 4.5% by weight to determine a solution viscosity of about 8 mPa·s. &lt;Synthesis Example of Other Polylysine&gt; Synthesis Example 1 109 g (0.50 mol) of pyromellitic dianhydride Φ as a tetracarboxylic dianhydride and 98 g (0.50 mol) 1, 2, 3 , 4-cyclobutane tetracarboxylic dianhydride and 200 g (1.0 mol) of 4,4-diaminodiphenyl ether as diamine are dissolved in 230 g of N-methyl-2-pyrrolidone and In a mixed solvent of 2,060 g of γ-butyrolactone, and after reacting at 40 ° C for 3 hours, about 3,800 g of 10% by weight of polyglycine was obtained by adding L3 50 g of γ-butyrolactone. (ΡΑ-1) solution. The solution has a solution viscosity of 200 mPa·s. Synthesis Example 2 98 g (0.5 Torr) of 12,3,4-cyclobutane-51 - 200949389 tetracarboxylic dianhydride and 109 g (0.50 mol) of pyromellitic acid as tetracarboxylic dianhydride Anhydride and 198 g (1.0 mol) of 4,4'-diaminodiphenylmethane as a diamine were dissolved in 230 g of N-methyl-2-pyrrolidone and 2,060 g of γ-butyrolactone. After reacting for 3 hours at 40 ° C in a mixed solvent, about 4,000 g of a solution containing 10% by weight of polyglycolic acid (ΡΑ-2) was obtained by adding 1,350 g of γ-butyrolactone. The solution viscosity of this solution is i25 mPa.s. Synthesis Example 3 196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 200 g (1.0 mol) of 4,4' as a diamine -Diaminodiphenyl ether was dissolved in a mixed solvent consisting of 225 g of N-methyl-2-pyrrolidone and 2,021 g of γ-butyrolactone, and reacted at 40 ° C for 4 hours. By adding 1,321 g of γ-butyrolactone, about 3,900 g of a solution containing 10% by weight of polyglycolic acid (ΡΑ-3) was obtained. The solution has a solution viscosity of 2 10 m P a · s 〇 Synthesis Example 4 196 g (io mole) of tetracarboxylic dianhydride, 2,3,4-cyclobutane tetracarboxylic dianhydride and As a diamine, 212 g (m·mole) of 2,2,-dimethyl-4,4'-diaminobiphenyl is dissolved in 370 g of N-methyl-2-pyrrolidone and 3, 300 g of γ-butyrolactone in a mixed solvent, and at 40. (: The reaction was carried out for 3 hours to obtain about 4,000 g of a solution containing 1% by weight of polyglycolic acid (ΡΑ_4). The solution viscosity of the solution was 16 〇mPa.s. -52- 200949389 Synthesis Example 5 224 g (1·〇mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride of carboxylic acid dianhydride and 108 g (1. Torrole) 4,4,-diamino group as diamine Diphenyl ether was dissolved in 29 88 g of N-methyl-2-pyrrolidone and reacted at 4 ° C for 4 hours to obtain about 3,300 g of 10% by weight polyglycine (PA-5). The solution has a solution viscosity of 200 mPa· ❹ &lt;Synthesis of a polyglycolate having a group represented by the above formula (1) or (2)&gt; Example 1 3 obtained in 100 g of Synthesis Example 5 18 g of compound (5A-1), 4.1 g of potassium carbonate, 0.50 g of potassium iodide and 560 g of N-methyl-2-pyrrolidone were added to the solution of poly-proline (PA-5) at 100 °C. The reaction was carried out for 7 hours. After the reaction was completed, the reaction mixture was poured into 3 liters of water and the resulting precipitate was recovered. The precipitate was dissolved in 150 ml of N-methyl-2-pyridolone, and the obtained Solution note In 1.5 liters of ethanol, the resulting precipitate was recovered and dried to obtain a polyphthalate (CPAE-1). &lt;Preparation of liquid crystal alignment agent&gt; Example 1 4 The polyamine obtained in the above Example 7 was obtained. The acid (CPA-1) is equivalent to 100 parts by weight (CPA-1) in terms of a solution having a polymer represented by the above formula (1) or (2), and is obtained in the same manner as in the above Synthesis Example 1. The solution of proline (PA-1) as a solution of other polymers is converted into (PA-1) equivalent to -53-200949389 400 parts by weight, and γ-butyrolactone and 丨-methyl_2- are added thereto. Pyrrolidone and butyl cellosolve, the solvent composition is γ_butyrolactone n-methyl-2-pyrrolidone/butyl cellulolytic = 20/3 0/50 (weight ratio), and the solution has a solid concentration of 3.0% by weight. The solution was filtered through a filter having a pore size of 1 μηι to prepare a liquid crystal alignment agent. Examples 15 to 2 7 The types and amounts of the polymer and other polymers having the group represented by the above formula (1) or (2) were respectively Other than those described in Table 2, the liquid crystal alignment agents a - 2 to A -1 4 were separately prepared in the same manner as in the above Example 14. A solution containing another polymer was not used in Examples 24 and 25. Example 2 8 The polyglycine (CPA-1) obtained in the above Example 7 was obtained as having the above formula (1) or (2) The solution of the polymer of the base is equivalent to 100 parts by weight of (CPA_1), and is equivalent to (PA_4) equivalent to the solution containing the polyamic acid (PA-1) obtained in the above Synthesis Example 4 as another polymer. The compound represented by the following formula (E-1) is added as a compound of the following formula (E-1) by adding 5 parts by weight (1 part by weight based on the total of all the polymers, equivalent to 1 part by weight of the total polymer). Epoxy compound, -54- 200949389

(E-1) Adding γ-butyrolactone, b-methyl-2-pyrrolidone and butyl-cellosolve' solvent composition to γ-butyrolactone/丨-methyl-2-pyrrolidone/butyl-cellulose = 20 /3 0/5 0 (weight ratio), a solvent solution having a solid concentration of 3.0% by weight. The solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent A-1 5 . [Example 2] In the above Example 28, except that a compound represented by the following formula (?-2) was used as the epoxy compound,

(Ε-2) The liquid crystal alignment agent Α-1 6 was prepared in the same manner as in the above Example 28. -55- 200949389 Table 2 Polymer type having a group represented by the above formula (1) or (2) Other polymer epoxy compound liquid crystal alignment agent name type (parts by weight) Type (parts by weight) Example 14 CPA-1 PA-1 400 — — A-1 Example 15 CPA-1 PA-1 300 I—A-2 Example 16 CPA-1 PA-2 400 One A-3 Example 17 CPA-1 PA-3 400 An A-4 Example 18 CPA-1 PA-4 400 - ~ A-5 Example 19 CPA-1 PA-5 400 — — A-6 Example 20 CPA-2 PA-4 400 — — A-7 Implementation Example 21 CPA-3 PA-4 400 One A-8 Example 22 CPA-4 PA-4 400 — — A-9 Example 23 CPA-5 PA-4 400 — — A-10 Example 24 CPI-1 — 一—A-11 Example 25 CPI-1 PA-4 400 — — A-12 Example 26 CPAE-1 — — — — A-13 Example 27 CPAE-1 PA-4 400 — — A-14 Example 28 CPA-1 PA-4 400 E-1 50 A-15 Example 29 CPA-1 PA-4 400 E-2 50 A-16

Example 3 &lt;Formation of Liquid Crystal Alignment Film and Manufacture of Vertical Alignment Type Liquid Crystal Display Element&gt; Coating on the transparent electrode surface of a glass substrate having a transparent electrode made of an ITO film by spin coating The liquid crystal alignment agent A-1 prepared in Example 1 was pre-baked on a hot plate of TC for 1 minute -56-200949389, and then heated in an oven which has been internally replaced with nitrogen at 200 ° C. After a few hours, it is baked to form a coating film having a film thickness of 0.1 μm. Then, a Hg-Xe lamp and a Glan-Taylor prism are used on the surface of the coating film, and 40 is formed from the normal to the substrate. 〇〇 (U/m2 contains a polarized ultraviolet ray of 313 nm ray to form a liquid crystal alignment film. This operation is repeated to form a pair (two pieces) of a substrate having a liquid crystal alignment film. The liquid crystal alignment film is formed on one of the substrates. The outer edge of the surface is coated with an epoxy resin adhesive having a diameter of 5.5 μηη alumina balls by H screen printing, and then one pair is made in such a manner that the directions of the ultraviolet light axes of the substrates toward the substrate surface are antiparallel. The liquid crystal alignment film of the substrate faces and is pressed, The adhesive was cured by heating at 150° C. for 1 hour, and then, after the liquid crystal injection port was filled with a negative liquid crystal (manufactured by Merck, MLC-66 08) in the gap between the substrates, an epoxy-based adhesive was used. The liquid crystal injection port is sealed. Further, in order to eliminate the flow alignment during liquid crystal injection, it is heated at 150 ° C and then slowly cooled to room temperature. Then, the polarizing plate is bonded to both sides of the substrate. The liquid crystal display elements were produced by the following methods, and the liquid crystal display elements were evaluated by the following methods. The liquid crystal display elements were evaluated by the following methods. The liquid crystal display elements were evaluated by the following methods. 3. <Evaluation method of liquid crystal display element> (1) Evaluation of liquid crystal alignment property The liquid crystal display element manufactured as described above was observed by a polarizing microscope when the voltage was turned on and off (applied/released) at -57-200949389 5V. Whether there is an abnormal block in the change of light and dark, and when there is no abnormal block, it is marked as "good." (2) Evaluation of the pretilt angle For the above-mentioned liquid crystal display element, according to TJ Scheffer et al. J. Appl. Phys. Vol. 19, p20 1 3 (1 980) The method of measuring the pretilt angle by the crystal rotation method using He-Ne laser light. (3) Evaluation of voltage holding ratio The liquid crystal manufactured above The display element was applied with a voltage of 60 V for an application time of 60 μs, and after a pulse of 167 ms was applied, the voltage holding ratio after 167 msec from the application release was measured. The measuring device used the VHR manufactured by Dongyang Technology Co., Ltd. -1. (4) Evaluation of heat resistance The above &lt;Formation of liquid crystal alignment film and manufacture of vertical alignment type liquid crystal display element&gt; In addition to the heating temperature of the oven formed by the film formation of 250 ° C The liquid crystal display element was produced in the same manner as described above. For the obtained liquid crystal display element, those who showed good alignment (black display with uniform display) were evaluated as "good", and those who saw light leakage were evaluated as "poor". Example 3 1 to 43 A liquid crystal alignment film was formed in the same manner as in Example 30 except that the type of the liquid crystal alignment agent used was as shown in Table 3, and a vertical alignment type liquid crystal display element was produced and evaluated. The results are shown in Table 3. -58-200949389 Example 4 4 &lt;Formation of Liquid Crystal Alignment Film and Manufacture of TN Alignment Type Liquid Crystal Display Element&gt; Using a spin coating on a transparent electrode surface of a glass substrate having a transparent electrode made of an ITO film The liquid crystal alignment agent A-8 prepared in the above Example 21 was coated by prebaking on a hot plate at 80 ° C for 1 minute, and then baked at 180 ° C for 1 hour in an oven. A coating film having a film thickness of 0.1 μm was formed. On the surface of the coating film, an Hg-Xe lamp and a Glan-Taylor prism were used, which was 40 from the substrate normal. A polarized ultraviolet ray of 313 nm glow line of 1,000 J/m 2 was irradiated in the direction of the tilt to impart a liquid crystal alignment energy to form a liquid crystal alignment film. The same operation as above was repeated to prepare a pair (two sheets) of a glass substrate having a liquid crystal alignment film on a transparent conductive film. On the outer edge of the surface of each of the pair of substrates on which the liquid crystal alignment film is formed, the epoxy resin paste containing the alumina sphere of 5.5 μm is coated by screen printing to make the polarized ultraviolet light direction orthogonal. The substrate was superposed and pressed, and heated at 150 ° C for 1 hour to harden the adhesive. Next, a negative nematic liquid crystal (manufactured by Merck, MLC-622 1, added with a palmitic agent) is filled in the gap between the substrates from the liquid crystal injection port, and the liquid crystal injection port is sealed with an epoxy-based adhesive. . Further, in order to eliminate the flow alignment at the time of liquid crystal injection, it was heated at 150 ° C for 10 minutes and then slowly cooled to room temperature. Then, a polarizing plate was bonded to both surfaces of the outer surface of the substrate so that the polarizing directions were orthogonal to each other and parallel to the polarizing direction of the liquid crystal alignment film, thereby producing a TN alignment type liquid crystal display element. -59-200949389 The liquid crystal alignment property and voltage holding ratio of this liquid crystal display device were evaluated in the same manner as in Example 3, and the liquid crystal alignment property was "good", and the voltage retention ratio was 98%. Further, in the above-mentioned "formation of a liquid crystal alignment film and production of a TN alignment type liquid crystal display device", the TN alignment type liquid crystal was produced in the same manner as described above except that the heating temperature of the oven was 250 ° C at the time of forming the mold. Display component. When the liquid crystal alignment property of the liquid crystal display element was evaluated as described above, it exhibited good TN alignment and sufficient heat resistance.实施 Example 4 5 A liquid crystal alignment film was formed as in Example 44 except that the liquid crystal alignment agent used was replaced with A-1 调制 prepared in the above Example 23, and a TN alignment type liquid crystal display device was produced and evaluated. The liquid crystal alignment property and the voltage holding ratio of the liquid crystal display device were evaluated in the same manner as in Example 30, and the liquid crystal alignment property was "good", and the voltage retention ratio was 98%. Further, in the above-mentioned "formation of the liquid crystal alignment film and the production of the TN alignment type liquid crystal display element", the TN alignment is produced as described above except that the heating temperature of the oven is 25 ° C when the coating film is formed. Type liquid crystal display element. When the liquid crystal alignment property of the liquid crystal display element was evaluated as described above, it exhibited good TN alignment and sufficient heat resistance. -60- 200949389 Table 3 Excipient Liquid Crystal Display Element Display Mode Liquid Crystal Alignment Pretilt Angle (.) Voltage Retention (%) Heat Resistance (Liquid Crystal Alignment) Example 30 A-1 VA Good 89 98 Good Example 31 A- 2 VA Good 89 98 Good Example 32 A-3 VA Good 89 98 Good Example 33 A-4 VA Good 89 98 Good Example 34 A-5 VA Good 89 98 Good Example 35 A-6 VA Good 89 98 Good Example 36 A-7 VA Good 89 98 Good Example 37 A-9 VA Good 89 98 Good Example 38 A-11 VA Good 89 98 Good Example 39 A-12 VA Good 89 98 Good Example 40 A-13 VA good 89 98 good example 41 A-14 VA good 89 98 good example 42 A-15 VA good 89 98 good example 43 A-16 VA good 89 98 good example 44 A-8 TN good - 98 good implementation Example 45 A-10 TN is good - 98 is good [Effect of the invention] The liquid crystal alignment agent of the present invention can be formed with less radiation exposure than the liquid crystal alignment agent which has been known to be suitable for the liquid alignment method as a liquid crystal alignment agent. Excellent liquid crystal alignment The electrical characteristics of the liquid crystal alignment film. Further, since the formed liquid crystal alignment film has high heat resistance, the liquid crystal panel can be produced without thermal decomposition. Therefore, when the liquid crystal alignment element is used for a liquid crystal display element, the liquid crystal display element can be manufactured more inexpensively than in the past, and the obtained liquid crystal display element is excellent in display characteristics and reliability. Therefore, the liquid crystal-61 - 200949389 display elements can be applied to various devices, and can be preferably used, for example, in a desktop computer, a watch, a desk clock, a counter display panel, a word processor 'personal computer, a liquid crystal television, or the like.

Ο -62-

Claims (1)

200949389 VII. Patent Application Range 1. A liquid crystal alignment agent characterized by containing at least one polymer selected from the group consisting of polyglycolic acid, polyamidiamine and polyamidolate, wherein the aforementioned polymer has the following The basis of the formula U) or (2): (R1 and R2 in the formula (1) are each independently a hydrogen atom or a monovalent organic group, or R1 and R2 may be bonded to each other to form a ring, R3 is a fluorine atom or a cyano group, and a is an integer of 〇~4, "* </ RTI> means a bond, wherein R4 in the formula (2) is an alkyl group having 1 to 40 carbon atoms or an alicyclic group having a carbon number of 3 to 40, wherein the hydrogen atom of the alkyl group is Some or all of them may be substituted by a fluorine atom, R5 is a town atom or a cyano group, b is an integer of 〇~4, and "*" means a bond bond). 2. The liquid crystal alignment agent of claim 1, wherein in the above formula (1), R1 is a group represented by the following formula (R-1), and R6-W-* (R-1) (formula (R) In the formula -1), R6 is an alkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms having an alicyclic group, wherein one part of the hydrogen atom of the alkyl group is -63 to 200949389 or all It may also be substituted by a fluorine atom, and W is a single bond, an ether bond, an ester bond, a thioether bond, a thioester bond or a guanamine bond, "*" represents a bond bond) and R2 is a hydrogen atom, or Ri and R2 are bonded to each other. The ring having a carbon number of 4 to 8 is formed, and any carbon atom of the ring (preferably other than the carbon atom constituting the pyrrolidine ring) is bonded to the group represented by the above formula (R-1). The liquid crystal alignment agent of claim 1, wherein the polymer is a polyamic acid selected from the group consisting of a tetracarboxylic dianhydride and a diamine containing a compound represented by the following formula (3), and At least one of a group consisting of polyamidimides obtained by imidating the polyphosphonium hydrazide, /=&gt;nh: CH=CH—COO—(CH2}c—X1~V. NH2 (3 (In the formula (3), R1, R2, R3 and a each have the same meaning as in the above formula (1), 〇 is an integer of 0 to 10, and when c is 〇, X1 is a single bond, and c is 1 to 10 In the case of an integer, X1 is a single bond, an ether bond, an ester bond, a thioether bond, a thioester bond or a guanamine bond). 4. The liquid crystal alignment agent of claim 1, wherein the polymer is a polyamic acid selected from the group consisting of a tetracarboxylic dianhydride and a diamine containing a compound represented by the following formula (4), and The polyimine formed by the imidization of the polyphosphonium amide constitutes R4—OCO—CH=CH X2-(CH2) ο -64 - 200949389 (In the formula (4), R4, R5 and b each have the same meaning as in the above formula (2) 'X2 is a single bond, an ether bond, an ester bond, a thioether bond, a thioester bond or a guanamine bond' d is an integer of 0 to 10, and when d is 0, X3 is a single bond, and (1 is an integer, X3 is a single bond, an ether bond, an ester bond, a thioether bond, a thioester bond or an acid amine bond). The liquid crystal alignment agent of claim 1, wherein the polymer is a polylysine obtained by reacting a tetracarboxylic dianhydride with a diamine, and a polycondensation obtained by reacting a compound represented by the following formula (5); Glutamine, (In the formula (5), R1, R2, 113 and a each have the same meanings as in the above formula (1), and Z1 is a hydroxyl group, a chlorine atom, a bromine atom or an iodine atom, and e is an integer of 〇1〇). 6. The liquid crystal alignment agent of claim 1, wherein the φ polymer is a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine, and is reacted with a compound represented by the following formula (6). Polyglycolic acid vinegar, (In the formula (6), R4, R5 and b are each the same meaning as in the above formula (2), Z2 is a hydroxyl group, a chlorine atom, a bromine atom or an iodine atom, and f is an integer of 〇~1〇, and when f When it is 0, X4 is a single bond 'When f is an integer of 1 to 1 时, X4 is a single bond, an ether bond, an ester bond, a thioether bond, a thioester bond or a guanamine bond). -65-200949389 7. A method for forming a liquid crystal alignment film, which comprises applying a liquid crystal alignment agent according to any one of claims 1 to 6 to a substrate to form a coating film, and irradiating the coating film with radiation. line. A poly-proline, a polyimine or a polyphthalate characterized by having a group represented by the above formula (1) or (2). _ 66 - 200949389 IV. Designated representative map: (1) The representative representative of the case is: None (2), the symbol of the representative figure is simple: no 200949389 V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: formula (1), formula (2) 〇 -4-