TW200907513A - Liquid crystal alignment agent and liquid crystal display device - Google Patents

Abstract

TTo provide a liquid crystal alignment agent, which makes a polyimide-based liquid crystal alignment film to maintain the voltage holding ratio while reducing accumulated charges and further has outstanding printability, as well as a liquid crystal display element using the same. The aforementioned liquid crystal alignment agent is a polyimide-based liquid crystal alignment agent comprising a compound represented by the following formula (1). (In formula, two R1 are respectively and independently hydrogen, alkyl group, alkoxyl group or amino group; Y is any one of -S-, -NH-, -O-, -CH2- or single bonding; X1 and X2 are respectively and independently any one of the following structure. ) (In formula, Z1, Z2 and Z3 are respectively and independently hydrogen, alkyl group, alkoxyl group, amino group or diglycidylamino group. )

Description

200907513 IX. Description of the Invention: TECHNICAL FIELD The present invention relates to a liquid crystal display element and a liquid crystal alignment agent forming the same. More specifically, it relates to a liquid crystal alignment agent capable of forming a liquid crystal alignment film excellent in printing performance and a liquid crystal display element using the film. [Prior Art] At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called column type liquid crystal cell is known, which forms an alignment film such as polyacrylamide or polyimine on the surface of a substrate on which a film is provided. As a substrate for a liquid crystal display element, two sheets were provided, and a layer having positive dielectric anisotropy was formed in the gap to form a unit cell having a sandwich structure, and the long axis of the liquid crystal molecules was continuously twisted by 90 degrees from the other substrate. Further, a liquid crystal display element and a vertical alignment type liquid having a higher contrast ratio and a viewing angle-dependent S-hyper twisted nematic liquid crystal display element have been developed. In the S TN type liquid crystal display device, a liquid crystal of a chiral agent of an optically active substance in a nematic liquid crystal is used as a liquid crystal, and a birefringence is generated in which a long axis of the liquid crystal molecules is continuously twisted by 180 degrees between the substrates. effect. In contrast, as described in Patent Document 1, a vertical display element called an MVA type in which an alignment direction of liquid crystal is formed on ITO is proposed. VA VA type liquid crystal display, not only the viewing angle, the pair, but also in the process of forming the liquid crystal alignment film, the liquid crystal alignment film and the liquid crystal alignment TN are not required (the liquid crystal is twisted toward the transparent conductive substrate) One of the liquid crystal liquid crystal substrates is smothered with TN type liquid crystals (the crystal display element is blended as the use degree of the above-mentioned degree of use, and the patent document 1 is raised to control the apparent liquid crystal display ratio, etc.) 200907513 (rubbing) It is also excellent in the manufacturing process, etc. As a liquid crystal alignment film suitable for TN, STN, and MVA type, it is required to have a residual image erasing time of a liquid crystal display element, etc., and 'as an alignment for forming these liquid crystal alignment films. In addition, it is required to have excellent printability in the printing of the 版 set set 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 【 【 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 非 液晶 液晶 液晶 液晶 液晶,. 2,1 1 7 (1 9 9 9). SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a polyimine-based liquid crystal alignment A liquid crystal alignment agent which maintains a voltage holding ratio while reducing accumulated charges and having excellent printability, and a liquid crystal display element using the same. Other objects and advantages of the present invention can be seen from the following description. The above object and advantages of the present invention, first, achieved by a liquid crystal alignment agent, comprising: a polylysine composed of a repeating unit represented by the following formula (A) and having the following formula (B) a mixture of polyimine composed of a repeating unit represented by the above, or a polyimine composed of a repeating unit represented by the following formula (B); and a compound represented by the following formula (1) (hereinafter also referred to as " Specific compound").

(A) (P1 is a tetravalent organic group, and Q1 is a divalent organic group). 200907513

(wherein 2 R1 are each independently hydrogen, alkyl, alkoxy or amino group 'γ is _3_, -NH-, -Ο-, -CH2- or a single bond, X1 and X2 Each of them is independently one of the following structures)

The amine group or the diglycidylamino group) is preferably a specific compound in which two R1 in the above formula (1) are hydrogen, and any one of Z1, Z2 or Z3 is a diglycidylamino group or the above formula ( 1) A specific compound in which both R1 are hydrogen and any of Z1, Z2 or Z3 is hydrogen. Further, it is preferred that P1 in the above formula (A) and p2 in the above formula (B) are each derived from 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. According to the present invention, the above objects and advantages of the present invention, and secondly, are achieved by a liquid crystal alignment agent of 200907513, characterized by comprising: a polylysine composed of a repeating unit represented by the above formula (A) and having the above formula (B) a mixture of polyimine composed of a repeating unit represented by (B) or a polyimine composed of a repeating unit represented by the above formula (B); and 2 R1^ of the above formula (1) A poly-proline polymer obtained by reacting a compound in which hydrogen and Z1, Z2 or Z3 are both an amine group and di-hepatic acid. According to the present invention, the above objects and advantages of the present invention, and thirdly, are achieved by a liquid crystal display element characterized by having a liquid crystal alignment film produced by the above liquid crystal alignment agent of the present invention. [Embodiment] Hereinafter, the present invention will be described in detail. The liquid crystal aligning agent of the present invention is composed of a specific compound and polyimine, or a specific compound and polyamine and polyimine. [specific compound]

R1 R1

In the above formula (1), each of R1 is independently hydrogen, an alkyl group, an alkoxy group or an amine group. The alkyl group and the alkoxy group are specifically an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. Examples of the alkyl group in the alkyl group and the alkoxy group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 2-methyl-propyl group, and a 3-methyl-propyl group. N-pentyl, n-hexyl. Among them, R1 is preferably hydrogen or methyl. Y is any one of -S., -NH-, 200907513 -0-, -CH2- or a single bond, of which -S-, -NH- or a single bond is preferred. X 1 and X 2 are any of the following structures.

Among them, preferred is any of the following structures.

In the above formula, Z, Z2 and Z3 are each independently hydrogen, an alkyl group, an alkoxy group, an amine group or a diglycidylamino group. Among them, preferred are hydrogen, an amine group or a diglycidylamino group. As a specific compound, it can be mentioned

In the present invention, it is also possible to use a specific compound (hereinafter also referred to as "specific diamine") in which two R1 in the above formula (1) are all -10 200907513 hydrogen and Z1, Z2 or Z3 are both amine groups. The polyphthalic acid polymer (hereinafter also referred to as "specific poly-proline acid") obtained by the reaction of tetracarboxylic dianhydride replaces the above specific compound. In the synthesis of the specific polyamic acid, the acid anhydride is not particularly limited, and preferred examples thereof include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-diene. Methyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetrahydro-3- Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo -3-furylnaphthalene [1,2-c]furan-1,3-dione, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6 -tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2:3,5:6-dianhydride, 1,3,3a,4,5,9b-hexahydro-8 -Methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthoquinone, 2-^]furan-1,3-dione, 3-oxabicyclo[3.2.1] Octane 2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), pyromellitic dianhydride, etc. These acid anhydrides may be used in combination of two or more. In addition to the specific diamine, other diamine compounds may be used. Preferred other diamines may, for example, be p-phenylenediamine, 4,4,-diaminodiphenylmethane, 4,4'-di. Aminodiphenyl sulfide 2,2'-Dimethyl-4,4,-diaminobiphenyl, 1,5-diaminonaphthalene, 2,7-diaminopurine, 9,9-dimethyl-2,7- Diamino hydrazine, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propyl, 9,9-di(4-amino Phenyl) fluorene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4' -(p-phenylenediisopropylidene)diphenylamine, 4,4'-(m-phenylenediisopropylidene)diphenylamine, 1,4-cyclohexanediamine, 4,4'-Asia Methyl bis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diamine- 11- 200907513 Pyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3 ,6-Diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazol, N,N'-di(4-amino Phenyl)benzidine> 1-(3,5-Diaminophenyl)-3-indolyl succinimide, 1-(3,5-diaminophenyl)-3-octadecyl Amber succinimide, etc. These other diamines may be used alone or in combination of two or more. The mixing ratio of these specific compounds and/or specific polyaminic acid is preferably 0.1 in terms of the total amount of 100 parts by weight of polyglycolic acid (excluding specific polyamido acid) and polyamidiamine. It is preferably 40 parts by weight, more preferably 0.1 to 30 parts by weight. [Polyuric acid composed of a repeating unit represented by the above formula (A)] <tetracarboxylic dianhydride> as a polyvalent organic group capable of generating P\4 in the above formula (A) Examples of the tetracarboxylic dianhydride used in the synthesis of valine acid include alicyclic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Among them, an alicyclic tetracarboxylic dianhydride is preferred. Specific examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3,4-ring. Butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane Alkanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid Dihydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl ring Oct-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetrahydrogen) 3- 3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2 :3,5:6- Dihydride, 2,3/,5-tetrahydrofurantetracarboxylic acid Di-12- 200907513 Anhydride, 1,3,3&,4,5,913-hexahydro-5(tetrahydro-2,5-dioxo-3- Furyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5(tetrahydro-2,5 -dioxo-3-furanyl)-naphthalene[1,24]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-5-ethyl-5(tetrahydrogen) -2,5-dioxo-3-furan -Naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91?-hexahydro-7-methyl-5 (tetrahydro-2, 5-dioxo-3-furanyl)-naphthalene [1,2-(>]-furan-1,3-dione, 1,3,3&,4,5,915-hexahydro-7-ethyl -5 (tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, l,3,3a,4,5,9b - Hexahydro-8-methyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione, 1,3, 3&,4,5,91)-hexahydro-8-ethyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1, 3-diketone, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1 ,2-〇]-furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo

-13- 200907513 and R5 represent a hydrogen atom or an alkyl group, and a plurality of R3 and R5 present may be the same or different. Further, an aliphatic tetracarboxylic dianhydride such as butane tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3, 3',4,4'-biphenyltricarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3, 3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3',4,4' - tetraphenylnonane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl succinic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3 , 3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'- Biphenyltetracarboxylic dianhydride, di(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, meta-phenyl-bis(triphenylbenzene) Formic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenyl phthalic acid) )-4,4'-diphenylmethane dianhydride, ethylene glycol-di(hydrogen trimellitate), propylene glycol-di(hydroper trimellitate), 1,4-butanediol-di Dehydrated trimellitate), 1,6-hexanediol-di(anhydrotrimellitic acid ester), 1,8-octanediol-di(hydrogen trimellitate), 2,2-di ( 4-hydroxyphenyl)propane-di(hydrogen trimellitate), an aromatic tetracarboxylic dianhydride such as a compound represented by the following formulas (2) to (5). These tetracarboxylic dianhydrides may be used alone or in combination of two or more. 14- 200907513

ί

Among the above tetracarboxylic dianhydrides, preferred is 1,2,3,4-cyclobutane tetra-methyl-1,2,3,4-cyclobutane tetracarboxylic acid from the viewpoint of its performance. Acid dianhydride, 1,2,3,4 good liquid crystal alignment malic acid dianhydride, 1,3 -di-tetramethyl-1,2,3,4- -15- 200907513 cyclobutane tetracarboxylic dianhydride 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2 3 5 ·tricarboxycyclopentyl acetic acid: anhydride, 5·(2,5·: oxotetrahydrofuranyl) small methyl group- 3-cyclohexene-1,2-dicarboxylic anhydride, 5-(2,5-dioxo)-3-methyl-3-cyclohexene-oxime, carboxytetrahydrofuran, methylene hydrazide, cis- 3,7-Dibutylcyclooctane-1,5-diene-12,5,6-tetracarboxylic acid 3'5,6·Ηcarbonyl·2_carboxynorbornane-2:3,5:6- Dihydride, 1,3,3&,4,5,9-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]furan-oxime, 3_dione, 1,3,3&,4,5,9^hexahydro_8_methyl is^tetrahydro^-dioxy-^furanylnaphthalene^^-called furan-^-dione, l,3,3a,4,5,9b-/,hydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2_<: Furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic acid Anhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), a compound represented by the above formula (I) In the alicyclic tetracarboxylic dianhydride such as a compound represented by the following formulas (6) to (8), and the compound represented by the following formula (9) in the compound represented by the above formula (II), an alicyclic four or the like Residual acid di-hepatic 'as a special one' can be exemplified by 1,4 -cyclobutanine tetraresidic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetradecanoic acid dianhydride , 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)_3_methyl-3-cyclohexene-1,2-di Carboxylic anhydride, 1,3,3&,4,5,915-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]furan-1,3 -ketone, cis_3,7·-butylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-dicarbonyl_2-carboxyl Norbornane - 2:3,5:6-dianhydride, l,3,3a,4,5,9b_hexahydro_8-methyl-5-(tetrahydro-2,5-dioxo-3 -furanylnaphthalene [丨,2-.furan-1,3-one, 3-oxabicyclo[3.2.1]octane-2,4-dione_6_spiro_3'-(tetrahydrofuran-2 ',5'-dione) and represented by the following formula (6) Thereof ° -16 _ 200907513

Preferred among the tetracylene dianhydrides other than the alicyclic tetrahydro acid dianhydride are butane tetracarboxylic dianhydride, pyromellitic dianhydride, and 3,3', 4, 4'. -biphenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and the like. Among these tetracarboxylic dianhydrides, the alicyclic tetracarboxylic dianhydride is preferably 50 mol% or more based on the total tetracarboxylic dianhydride. <Diamine> As a polyamine derivative capable of producing Q (a divalent organic group) in the above formula (A), and/or a specific diamine used in the ruthenium iodide polymer thereof The diamine' may, for example, be p-phenylenediamine, m-phenylenediamine, 4,4,-diamino-phenyl-methyl' 4,4,-diaminodiphenylethane, 4, 4, ·Diaminodi-17- 200907513 Phenyl sulfide, 4,4'-diaminodiphenyl milling, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4 '_Diaminobenzimidanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl 5-aminoaminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydrazine Full, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone , 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2 - bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy) benzene 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone , 2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5, 5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3' -dimethoxy-4,4'-diaminobiphenyl, 1,4,4'-(p-phenylisopropylene)diphenylamine, 4,4'-(meta-phenylene isopropylidene Diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2' - bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, anthracene, Ν'-di(4- Aromatic diamines such as aminophenyl)benzidine; 1,1-m-xylylenediamine, 1,3-propylenediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octanediamine , hydrazine diamine, 4,4-diaminoheptyldiamine, 1,4 -diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, tricyclic [6.2.1 .〇2,7-undecene dimethyldiamine, 4,4'- Aliphatic and alicyclic diamines such as methyl bis(cyclohexylamine; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, -18-200907513 2, 4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6 -dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)pyridazine, 2,4-diamino-6-isopropoxy-1,3 ,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine , 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s - triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-di Amino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4- Diaminopyridazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 1-(3,5-diaminophenyl)-3-indenyl amber Amine, 1-(3,5-diaminophenyl)-3-octadecyl amber quinone and the following formula (I a diamine having two first-order amine groups and a nitrogen atom other than the first-order amine group in a molecule such as a compound represented by II) and (IV);

(wherein R6 represents a monovalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, acridine and pyridazine, and X3 represents a divalent organic group).

(wherein X4 represents a divalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, acridine and pyridazine, and R7 represents a divalent organic group, and a plurality of X4 present may be The same, can also be different). -19- 200907513 A monosubstituted phenylenediamine represented by the following formula (V); a diamine-based organodecane represented by the following formula (VI); /^===\^R8-R9 h2n^-^nh2 . (V) (wherein R8 represents a divalent organic group selected from the group consisting of _〇_, _C〇〇_, _〇C〇_, _NHcq, -CONH-, and -CO-, and R9 represents a solid selected from the group consisting of a monovalent organic group of a skeleton, a trifluoromethyl group, and a fluorine group or a hospital group having a carbon number of 6 to 30).

Ri〇 Rio

(In the formula, R1Q represents a hydrocarbon group having a carbon number of 1 to 12, and a plurality of Ri(R) existing may be the same 'may be different, p is an integer of 1 to 3, and q is an integer of 1 to 20). And a compound represented by each of the following formulas (10) to (14). These diamine compounds may be used singly or in combination of two or more. -20- 200907513

(wherein y is an integer of 2 to 12, and z is an integer of 1 to 5). Among them, preferred are p-phenylenediamine, 4,4'-diaminobenzophenone diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diaminopurine, 4, Diphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9-aminophenyl)anthracene, 2,2-di[4-(4-aminobenzene) Oxy)phenyl]hexafluoropropane, 4,4,-4,-diamine, 9-bis(4-alkane, 2,2--21-200907513 bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylenediisopropylidene)diphenylamine, 4,4'-(meta-phenyldiisopropylidene)diphenylamine, 1,4-cyclohexanediamine, 4, 4'-methylenebis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, the above formula ( 10) to (14) each represented by a compound, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, and the above formula Among the compounds represented by the following formula (15), the compound represented by the following formula (16) and the compound represented by the above formula (V) in the compound represented by the above formula (IV); Compounds represented by formulas (17) to (25) .

-22- (15)200907513

(17)

-23- 200907513 〆.

(twenty two)

<Synthesis of polyglycolic acid> -24- 200907513 The ratio of use of the tetracarboxylic dianhydride to the diamine supplied to the polyamido acid synthesis reaction is preferably a tetracarboxylic acid with respect to 1 equivalent of the amine group of the diamine The acid anhydride group of the acid dianhydride is in a ratio of ~. 5 to 2 equivalents, more preferably in a ratio of 0.74.2 equivalents. The synthesis reaction of polylysine is carried out in an organic solvent, preferably at a temperature of from -2 0 t to 150 ° C, more preferably at a temperature of from 〇1 to 1 °C. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyaminic acid, and examples thereof include 1-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylacetamide, and N, N. - dimethylformamide, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy-N, An aprotic solvent such as a guanamine solvent such as N-dimethylpropionamide; an aprotic polar solvent such as dimethyl hydrazine, γ-butyrolactone, tetramethyl urea or hexamethylphosphonium triamine; m-methylphenol; a phenolic solvent such as xylenol, phenol or halogenated phenol. Further, the amount of the organic solvent (〇0 is usually preferably such that the total amount (β) of the tetracarboxylic dianhydride and the diamine compound is from 0.1 to 30% by weight based on the total amount of the reaction solution (α + β). Further, in the above organic solvent, a poor solvent of polyglycolic acid (P0〇r solvent), an alcohol, a ketone, an ester, or an ether may be used in a range in which the produced polyaminic acid is not precipitated. Examples, halogenated hydrocarbons, hydrocarbons, etc. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, and 4-hydroxy-4-methyl-2-pentanone. Ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, lactated B' vinegar, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, Cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethoxypropyl propionate B-25-200907513 base, ester, chloro, methyl ether ether ethanediyl alcohol Ethyl mono 4-, octyl dipropyl ether methanol 1, Ethyl mono-monoethylene, hospital 'Alcohol Ethanol second-half-heptane glycol diol, U, base ethylene di-diester - «院乙' B, acid-'~~ Dihexyl ether, ether B 1,2, phenyl ether ether '1 phenyl ester propyl ethyl chlorodimethyl dimethyl diol di diol diol monochloro acid glycol glycerol one, two ethane diethylene glycol, styrene , B, dimethyl chloride, ether, ether, fur, ester ether ether ether hydroperyl ethyl ethyl methyl tetraethylene glycol butyl dichloride, di-n-alcohol monoester octane ethanol glycolic acid, 'two Diethylene glycol ester ether B, diether butyl, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, etc. The reaction solution in which polylysine is dissolved is obtained as above. Then, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried by a reduced pressure, or the reaction solution is distilled under reduced pressure with an evaporator to obtain a polyamic acid. Alternatively, the poly-proline may be purified by re-dissolving the poly-proline in an organic solvent, and then using a poor solvent to precipitate the solution, or by distilling the reaction solution under reduced pressure with an evaporator. > The stylimine constituting the liquid crystal alignment agent of the present invention can have the above formula ( The polyaminone group of the repeating unit represented by A) is partially or completely dehydrated and closed. The polyimine used in the present invention has a ratio of repeating units having a quinone ring in all repeating units (hereinafter, also referred to as The "yttrium imidation ratio" is preferably 40 mol% or more, more preferably 50 mol% or more. By using a polymer having a ruthenium iodide ratio of 40 mol% or more, it is possible to form a residue. A liquid crystal alignment agent such as a liquid crystal alignment film having a short elimination time. -26 - 200907513 The dehydration ring closure of polylysine can be (i) by heating poly-proline, or (Π) by dissolving poly-lysine in organic In the solvent, a dehydrating agent and a dehydration ring-closure catalyst are added to the solution and heated as needed. The reaction temperature of the above method (i) for heating the polyamic acid is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction cannot be sufficiently carried out. If the reaction temperature exceeds 20 (TC, the molecular weight of the obtained ruthenium-imided polymer may decrease. On the other hand, in the above (Π) In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a polyamic acid solution, as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent depends on the desired quinone imine. The amount of the repeating unit relative to 1 mole of polyamic acid is preferably from 1 to 20 moles. Further, as the dehydration ring-closing catalyst, for example, pyridine, trimethylpyridine or dimethyl group can be used. A tertiary amine such as pyridine or triethylamine. However, it is not limited thereto. The amount of the dehydration ring-closing catalyst is preferably 0.01 to 10 moles per mol of the dehydrating agent used. The more the amount of the catalyst used, the higher the yield of ruthenium. The organic solvent used in the dehydration ring closure reaction is exemplified as the solvent used in the synthesis of polylysine. Further, the reaction temperature of the dehydration ring-closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 15 (TC. Further, the same reaction as the polyamic acid purification method is carried out on the reaction solution thus obtained. The obtained polyimine can be purified. <End-modified polymer> The poly-proline and polyimine used in the present invention may also be a terminal-modified polymer having a molecular weight adjusted from -27 to 200907513. By using the polymer ', it is possible to impart coating characteristics to the agent without impairing the effects of the present invention. When the terminal-modified polymer is capable of synthesizing proline, a monobasic acid anhydride is added to the reaction system, The monoisocyanate compound or the like is synthesized, and examples thereof include maleic anhydride, phthalic anhydride, itaconic acid succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl n-hexadecyl succinic anhydride, and the like. Further, as a monoamine, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexyl, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-tridecylamine, N-tetradecylamine, Zhengshi The alkylamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine, etc. Further, the cyanate compound may, for example, be phenyl isocyanate or the like. [Solid viscosity of the polymer] When the polylysine and polyimine prepared above have a 10% solution, the viscosity has a viscosity of 30 to 800 mPa's of 30 to 500 mPa.s. In addition, the solution viscosity of the polymer (m P a · s) is a solution diluted to a solid component concentration of 10% by E-type rotation at 25 ° C. [Liquid crystal alignment agent] The liquid crystal alignment agent of the present invention is usually prepared by dissolving the above polyamine amine. It is composed of an organic solvent. The terminal modified type improves the liquid crystal by using a mono-anhydride in a poly-monoamine, an anhydride, an n-decyl succinic anhydride, and an amine, n-heptylamine dodecylamine, hexadecaneamine. , positive, as the monoisocyanato naphthyl ester is preferably formulated to have a constant solvent, the viscosity of the liquid crystal alignment agent is preferably adjusted in the acid and polyphthalocyanine-28-200907513, preferably ~ 2 〇 (rc, more preferably 20 ° C ~ 60 ° C. The organic solvent constituting the liquid crystal alignment agent of the present invention may, for example, be a solvent exemplified as a solvent used in the specific polyamine acid synthesis reaction. Further, it is also possible to appropriately select a poor solvent which is exemplified as a useful one in the synthesis reaction of a specific polyamine. The particularly preferable organic solvent to be used in the liquid crystal alignment agent of the present invention may, for example, be 1-methyl-2-pyridyl ketone, γ-butane vinegar, γ-butene amide, hydrazine, hydrazine-dimethyl methacrylate. Mercaptoamine, hydrazine, hydrazine-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methoxypropionic acid Methyl ester, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol 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, 3-butoxy-hydrazine, hydrazine-dimethylpropionamide, 3-methoxy-hydrazine, hydrazine - dimethylpropanamide, 3-hexyloxy-oxime, guanidine-dimethylpropionamine, diethyl carbitol, ethyl carbitol acetate, butyl carbitol, triethylene glycol Dimethyl ether, isoamyl isobutyrate, diisoamyl ether, and the like. Wherein 3-butoxy-indole, hydrazine-dimethylpropanamide, 3-methoxy-indole, hydrazine-dimethylpropanamide, 3-hexyloxy-oxime, hydrazine-dimethylpropionamidine The amine is particularly excellent in that it exhibits good printability. The solid content concentration in the liquid crystal alignment agent of the present invention is selected in consideration of viscosity, volatility, etc., and is preferably in the range of 1 to 10% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film as the liquid crystal alignment film -29-200907513. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too small, so that A good liquid crystal alignment film is obtained; when the solid content concentration exceeds 10% by weight, the thickness of the coating film is too thick, so that a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal alignment agent is increased, resulting in a change in coating characteristics. difference. In the liquid crystal alignment agent of the present invention, a functional decane-containing compound or an epoxy compound may be included from the viewpoint of improving the adhesion to the surface of the substrate within a range not impairing the physical properties of the object. As such a functional decane-containing compound, for example, 3-aminopropyl/yltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2 Aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyl Methyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N- Ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylethylamine, N-trimethoxydecylpropyltriethylamine, 10 -trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3 6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N -benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N -two Oxyethylene) - 3-amino propyl trimethoxy Silane, N- bis (oxyethylene) -3-aminopropyl triethoxy silane-like. The mixing ratio of these other functional decane-containing compounds is preferably 10 parts by weight or less, more preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the total amount of the polymer. Examples of such an epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and new Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four Glycidyl- 2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, :1,3-di(N,N-diglycidylamino) Methyl)cyclohexane, :N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl Aminopropyltrimethoxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, and the like. Further, as the epoxy group-containing compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl acid, tripropylene glycol diglycidyl ether, and polypropylene glycol dihydrate may be mentioned. Glyceric acid, neopentyl alcohol-glycidol, 1,6-hexanol diglycidyl acid, glycerol monoglycidyl ether, 2,2- bromopentyl glycol diglycidyl acid, hydrazine, 3, 5,6-tetraglycidyl-2,4-hexanediol, N,N,N,,N,_tetraglycidyl-m-xylylenediamine, anthracene, 3·2 (N,N-bi-diverted water) Glycerylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-monoamino-phenylmethane, N,N,N,,N,-four Glycidyl _4,4'·diamino-mono-gly- 1 4-di(N,N-diglycidylaminomethyl)cyclohexane, one base leg, '1 3. two (N N-diglycidylaminomethyl)benzene, anthracene, 4-bis(N,N-diglycidylaminomethyl)benzene, 3-(N-allyl-N-glycidyl)amine Propyl-indole, 3-(N,N-=glycidyl)aminopropyltrimethoxyfluorene A water supply methoxy sand caught glyceryl - benzylamine, Ν, Ν · _ diglycidyl amino alkyl, Ν, Ν-- cut day -31--200907513 methylcyclohexane. The mixing ratio of the glycidylamino group-containing epoxy group-containing compound is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, more preferably 〇·〇 with respect to 100 parts by weight of the polymer. 1 to 5 parts by weight. <Liquid crystal display element> The liquid crystal display element obtained by using the liquid crystal alignment agent of the present invention can be produced, for example, by the following method. (1) The liquid crystal alignment agent of the present invention is applied onto one surface of a substrate provided with a patterned transparent conductive film by a lithography method, a spin coating method or an inkjet printing method, followed by heating the coated surface A coating film is formed. Here, as the substrate, for example, glass such as float glass or soda lime glass can be used; and it is composed of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime or polycarbonate. Transparent substrate. As the transparent conductive film provided on one surface of the substrate, an NESA film made of tin oxide (Sn02) (registered trademark of PPG Corporation of the United States), an ITO film made of indium tin oxide (Mn 203-Sn02), or the like can be used. The pattern of formation of these transparent conductive films is a photolithography method or a method in which a mask is used in advance. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a functional decane-containing compound, a functional titanium-containing compound, or the like may be applied to the surface of the substrate in advance. . The heating temperature after application of the liquid crystal alignment agent is preferably from 80 to 300 ° C, more preferably from 120 to 25 ° C. The liquid crystal alignment agent of the present invention containing polylysine is subjected to coating to remove an organic solvent to form a coating film as an alignment film, which may be further subjected to dehydration ring closure by heating to form a further imidized coating film. The thickness of the formed coating film is, for example, 0.001 to Ιμηη, preferably 0.005 to 0.5 μm. -32- 200907513 (2) A rubbing treatment in which a coating film formed by a pair of rolls composed of fibers such as nylon, rayon, cotton or the like is rubbed in a certain direction is rubbed. Thus, the alignment energy of the liquid crystal molecules is generated on the coating film to form a liquid crystal alignment film. In addition, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is partially irradiated with ultraviolet rays as shown in Japanese Laid-Open Patent Publication No. Hei 6-222366, or the Japanese Patent Publication No. Hei. The treatment of the pretilt angle change, or the partial formation of the protective film on the surface of the liquid crystal alignment film subjected to the rubbing treatment as shown in Japanese Laid-Open Patent Publication No. Hei No. 5 - 1 0 7 4 4, in a direction different from the previous polishing process After the polishing treatment, the protective film is removed, and the liquid crystal alignment of the liquid crystal alignment film can be changed, and the visual field characteristics of the liquid crystal display element can be improved. (3) Two substrates on which the liquid crystal alignment film is formed are formed, and the two substrates are placed opposite each other through a gap (cell gap) so that the polishing directions of the respective liquid crystal alignment films are perpendicular or antiparallel to each other, and the peripheral portions of the two substrates are sealed. The agent is bonded, and a liquid crystal cell is formed by injecting a liquid crystal 'closed injection hole' into the cell gap which is divided by the surface of the substrate and the sealant. Then, on the outer surface of the liquid crystal cell, that is, the other side surface of each of the substrates constituting the liquid crystal cell, the polarizing plate is bonded so that the polarizing direction thereof coincides with or perpendicular to the rubbing direction of the liquid crystal alignment film formed on one side of the substrate. A liquid crystal display element is obtained. Here, as the sealant, for example, an alumina ball-containing epoxy resin as a curing agent and a spacer may be used. Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, or a phenyl ring can be used. Hexane liquid crystal and ester liquid-33-200907513 Crystal, terphenyl liquid crystal, biphenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal or the like. Further, in these liquid crystals, a bile-type liquid crystal such as chlorinated cholesterol, cholesterol phthalate or cholesterol carbonate, and a hand sold under the trade names "C-15" and "CB-15" (manufactured by Merck) may be added. It is used as a sex agent. Further, a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutylcinnamate may also be used. In addition, the polarizing plate to be bonded to the outer surface of the liquid crystal may be a polarizing plate obtained by stretching a polyvinyl alcohol and absorbing iodine while absorbing iodine, and a polarizing film called a ruthenium film is sandwiched between the cellulose acetate protective film or A polarizing plate composed of the enamel film itself. Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited to the examples. [Printability Evaluation] A 127 mm (D) x 27 mm (W) x l.lmm (H) glass substrate having a ruthenium film formed on one side of the entire surface was prepared in advance, and a liquid crystal alignment film coating printing machine was used (Japan Photo Printing Co., Ltd.) Manufactured, Angstromer S - 40L), the liquid crystal alignment agent prepared in the above experiment was filtered on a transparent electrode surface of the glass substrate after filtering with a micropore filter having a pore size of 0.2 μm. The film was dried by a hot plate preheater set at 80 ° C, and baked at 200 ° C for 10 minutes to form a liquid crystal alignment film on a glass substrate with an ITO film. The unevenness of the obtained alignment film was visually evaluated, and it was judged as "〇" without unevenness, and "X" was found to be uneven. [Voltage retention ratio] -34- 200907513 A voltage of 5 V was applied to the liquid crystal display element during the time interval of 67 ms. The voltage application time was 60 μsec, and then the voltage holding ratio from the voltage release to 167 ms was measured. In the measuring apparatus, VHR-1 〇 [Image Residual Test] manufactured by Toyo Technology Co., Ltd. was used to produce a unit cell having an ITO electrode as shown in Fig. 1. A DC voltage of 6.0 V was applied to the electrode A at room temperature for 24 hours, and a DC voltage of 0.5 V was applied to the electrode B for 24 hours. After the stress is released, 电极1 to 5.0 V DC voltage is applied to the electrodes A and B at an increment of 0·1 V, respectively, and the residual image characteristics are judged by the difference in luminance between the electrodes A and B at each voltage. When the luminance difference is large, the afterimage characteristic is judged to be poor. No residual image was found as ◦, a weak residual image was recorded as △, and a strong residual image was recorded as X. Synthesis Example 1 The following reaction was carried out in a nitrogen atmosphere according to the following scheme.

22g (0.2 mol) thiophenol, 31.2g (0.1 mol) 4,4, dibromobiphenyl, 69.lg (〇.5 mol) potassium carbonate, 500 ml DMF were installed in the Dimrod condenser Mix in a three-necked flask. Heat to 60 °C and stir for 8 hours. The reaction solution was cooled, and the reaction solution was added to 2 L of a 10% aqueous hydrochloric acid solution. Then add N Η 4 P F 6 (〇 · 2 m ο 1) and stir for 2 hours. The solid of -35-200907513 was filtered off, and the solid was washed successively with water and diethyl acid. Further purification by column chromatography gave 27.8 g of the title compound 1 (Compound A). Synthesis Example 2 The following reaction was carried out in a nitrogen atmosphere according to the following scheme.

31g (0.2 mol) of p-nitrothiophenol, 3128 (0.1 m〇l) 4,4'-dibromobiphenyl, 69.1 g (0.5 mol) of potassium carbonate, 500 ml of DMF were installed in Dimrot The three-necked flask of the condenser was mixed. Heat to 60 ° C and stir for 8 hours. The reaction solution was cooled, and the reaction solution was added to 2 L of a 10% aqueous hydrochloric acid solution. Further, 32.6 g (0.2 mol) of NH4PF6' was added and stirred for 2 hours. The precipitated solid was filtered, and the solid was washed with water and diethyl ether. Further purification by column chromatography gave 32.2 g of the title compound 2. Synthesis Example 3

30 g (0.065 mol) of the compound 2 was dissolved in 400 ml of ethanol, and 0.3 g of a 5% by weight carbon catalyst and 5. 〇g (〇.l mol) of hydrazine monohydrate were added, and the mixture was heated under reflux for 6 hours. The reaction solution was poured into a large excess of water and filtered through -36-200907513. The obtained solid was recrystallized from ethanol to obtain 169 g of the objective compound 3 (specific compound). Synthesis Example 4

Cl

ο 0,

ο 15 g (0.037 mol) of compound 3, 200 ml of DMSO, 41.4 g (0.3 m o 1) of potassium carbonate were mixed. After cooling the solution in an ice bath, 200 ml of a solution of 27.8 g (〇. 3 mol) of epichlorohydrin in DMS was added dropwise. After the completion of the dropwise addition, the temperature was raised to room temperature and stirring was continued for 4 hours. The reaction solution was filtered, and the filtrate was concentrated with a rotary evaporator. The excess added epichlorohydrin was removed by vacuum pump. The obtained crude product was diluted with 300 ml of toluene, and the solution was washed 4 times with 300 ml of distilled water. After adding sodium sulfate and allowing to stand overnight, sodium sulfate was decanted and the solvent was removed using a rotary evaporator. The obtained crude product was purified by ruthenium gel column chromatography to obtain 16.2 g of Compound 4 (Specific Compound B). Synthesis Example 5 (Synthesis of specific poly-proline A) 7.84 g (0.04 mol) was used as tetracarboxylic acid 1,2,3,4-cyclobutanetetracarboxylic dianhydride of acid dianhydride, 16 g (0.04 mol) of compound 3 as a diamine compound, dissolved in 180 g of N-methyl-2-pyrrolidone, It was allowed to react for 3 hours at 4 Torr. Next, the reaction solution was poured into a large excess of methanol to cause the reaction product -37-200907513 to sink. Then, washing with methanol was carried out by drying at 4 ° C for 15 hours under reduced pressure to obtain 12 g of polylysine (as "specific polyamido acid A"). Synthesis Example 6 As tetradecanoic acid dianhydride 2,3,5-dimercaptocyclopentyl acetic acid-hepatic 112.09 g (0.50 mol) and l,3,3a,4,5,9b-hexahydro-8-methyl_5_(tetrahydro-2, 5-dioxo-3-furanyl)-naphthalene H,2-c]furan-1,3-dione 157.15 g (0.50 mol), as a diamine compound, p-phenylenediamine 93.54 g (0.865 mol) , 3,3,-(tetramethyldioxanediyl)di(propylamine) 24.8 5 g (0.10 mol) and 3,6-bis(4-aminobenzylideneoxy)cholate 12.86 g (0.02 mol), 8.09 g (0.03 mol) of n-octadecylamine as a monoamine was dissolved in 4500 g of N-methyl-2-pyrrolidone, and allowed to react at 6 (TC for 6 hours). The reaction solution was poured into a large excess of methanol to precipitate a reaction product, and then washed with methanol and dried at 40 ° C for 15 hours under reduced pressure to obtain 3 80 g of polyamine having a logarithmic viscosity of 0.80 dl/g. 30 g of the obtained polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, and 23.4 g of pyridine and 1 were added. 8. lg acetic anhydride was dehydrated and closed at 11 ° C for 4 hours. Precipitation, washing and decompression were carried out in the same manner as above to obtain 18 polyimine (which was used as "polyimine" (a - 1) ”. Synthesis Example 7 2,3,5-tricarboxycyclopentylacetic acid dioxime as tetracarboxylic dianhydride 224.1 7 g (1.0 mol), p-phenylenediamine as a diamine compound 8.l4g (1.0 mol) and 3,5-diaminobenzoic acid cholesteryl pottery 7.482 g (0.015 mol) dissolved in 45 〇〇g N_methyl_2_pyrrolidone, making it at 60 ° The reaction was carried out for 6 hours at C. Next, the reaction solution was poured into a large excess of -38-200907513 methanol to precipitate the reaction product. Then, it was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain 40 0 g. Poly-proline with a logarithmic viscosity of 0.75 dl/g. 30 g of the obtained polylysine was dissolved in 570 g of N-methyl-2-D pyrrolidone, and 23.4 g of pyridine and 丨8·丨g acetic anhydride were added. The mixture was dehydrated and closed under u for 4 hours 'precipitation, washing, and reduced pressure in the same manner as above to obtain 19.2 g of polyimine (as "polyimine (a-2)"). will be used as 1,2,3,4-cyclobutanetetracarboxylic dianhydride of tetracarboxylic dianhydride 196_12 g (1.0 mol)' as a diamine compound 2,2'-dimethyl-4,4,diamine The phenyl benzene 212.3 g (1.0 mol) was dissolved in 4500 g of N-methyl-2-pyrrolidone and allowed to react at 40 ° C for 3 hours. Next, the reaction solution was poured into a large excess of methanol to precipitate the reaction product. Then, it was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain 390 g of polylysine (as "polyglycine (b-1)"). Example 1 Polyimine (a-1) obtained in Synthesis Example 6 and polylysine (b-1) obtained in Synthesis Example 8 were obtained by polyimine: polyglycine = 20:80 (weight ratio) dissolved in γ-butyrolactone / N-methyl-2-pyrrolidone / butyl cellosolve mixed solvent (weight ratio 71 / 1 7 / 12) 'add 2 parts by weight relative to 100 parts by weight of polymer Ν , Ν, Ν ', Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane, and 10 parts by weight of compound 4 is added relative to 1 part by weight of the polymer to give a solid concentration of 3.5% by weight solution and 6.0% by weight solution. After the respective solutions were thoroughly stirred, they were filtered through a filter having a pore size of 1 μηα to prepare a liquid crystal alignment agent of the present invention. -39- 200907513 A solution having a solid concentration of 3.5% by weight in the above liquid crystal alignment agent was applied onto a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm by a spin coater ( Rotation speed: 2500 rpm, coating time: 1 minute), and drying at 200 ° C for 1 hour to form a film having a dry film thickness of 0.08 μm. The coating was subjected to a sanding treatment using a roller equipped with a roll of rayon-made cloth at a roller rotation speed of 400 rpm, a table moving speed of 3 cm/sec, and a fluffing length of 〇.4 mm. The liquid crystal alignment film-coated substrate was immersed in isopropyl alcohol for 1 minute, and then dried on a hot plate at 100 ° C for 5 minutes. Then, on each of the outer edges of the liquid crystal alignment film of the liquid crystal alignment film coating substrate of the pair of transparent electrode/transparent electrode substrates, an epoxy resin adhesive having an alumina ball having a diameter of 5·5 μm is applied. Then, the liquid crystal alignment film surface is relatively heavily combined and pressed to harden the adhesive. Then, the liquid crystal injection port is used to fill the inter-substrate between the substrates (manufactured by Merck & Co., MLC-6221), and then the liquid crystal injection port is closed with a acrylic acid-based photohardening adhesive, and the polarized light is bonded to both sides of the substrate. The board is made into a liquid crystal display element. The voltage retention evaluation and the afterimage evaluation of the obtained liquid crystal display element were carried out in accordance with the method described above. The printability evaluation was carried out by the method described above using a solution having a solid concentration of 6.0% by weight. Example 2 The polyimine (a-2) obtained in Synthesis Example 7 was dissolved in a mixed solvent of Ν-methyl-2-pyrrolidone/butyl cellosolve (weight ratio 5 0 / 50). 2 parts by weight of >1', >^,-tetraglycidyl-4,4'-diaminodiphenylmethane, relative to 1 part by weight of polyimine (a-2), relative 00 parts by weight of polyamidiamine-40-200907513 (a-2), 10 parts by weight of compound 4 (specific compound b) is added to prepare a solution having a solid concentration of 3 · 5 % by weight and 6.0% by weight Solution. Each of the solutions was thoroughly stirred, and then filtered through a filter having a pore size of 1 m to prepare a liquid crystal alignment agent of the present invention. The method for producing a liquid crystal display, the method for evaluating a liquid crystal display element, and the method for evaluating the printability of an alignment agent were carried out in the same manner as in the first embodiment. Example 3 The polyimine (a-1) and the specific polyamic acid A prepared in Synthesis Example 6 were dissolved in γ_ by polyimine: specific polyaminic acid A = 20:80 (weight ratio). In a mixed solvent of butyrolactone/Ν-methyl-2-pyrrolidone/butyl cellosolve (weight ratio 7 1/17/1 2), relative to 1 part by weight of polyimine and specific polyphosphonium In total, 2 parts by weight of hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-4'4 diaminodiphenylmethane was added to prepare a solution having a solid concentration of 5.3 wt% and 6.0 wt%. The solution. After the respective solutions were thoroughly stirred, the liquid crystal alignment agent of the present invention was prepared by filtration using a filter having a pore size of 1 Μ "". Comparative Examples 1 to 4 - Polyimine, polylysine, and specific compounds were used in the same manner as in Example 1 except that the materials described in Table 1 were used. -41- 200907513

Table 1 Polyimine polyamine specific compound voltage retention rate afterimage printing Example 1 a-1 b-1 specific compound B > 99% 〇〇 Example 2 a-2 - specific compound B > 99 % 〇〇 Example 3 a-1 To be determined poly-proline A No > 99% 〇〇 Comparative Example 1 a-1 b-1 Μ > 99% X 〇 Comparative Example 2 al b-1 Compound A 98% △ X Comparative Example 3 a-2 _ none > 99% X 〇 Comparative Example 4 a-2 A compound A 98% Δ X In the table, 〇: excellent, △: good, χ: poor. Hereinafter, the present invention will use the direction of the arrow Y displayed as a transfer gas pattern in the semiconductor manufacturing apparatus as the front-rear direction. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view of a unit cell with an ITO electrode prepared for the image sticking test. [Main component symbol description]. -42-

Claims (1)

200907513 - Patent Application Range: A liquid crystal alignment agent comprising: a polylysine composed of a repeating unit represented by the following formula (A) and a repeating unit represented by the following formula (B) a mixture of polyimine or a polyimine composed of a repeating unit represented by the following formula (B); and a compound represented by the following formula (1), HOOC Vhnoc C00H CON Η—Q1 (A) P1 is a tetravalent organic group, and Q1 is a divalent organic group; X1—S P2 is a tetravalent organic group, and Q2 is a divalent organic group; R1 R1 =Bu Y-/)-S-X2 (1) wherein, two R1 are each independently hydrogen, alkyl, or alkane An oxy group or an amine group, Y is any one of -S-, -NH-, -0-, -CH2- or a single bond, and X1 and X2 are each independently one of the following structures; -43- 200907513 Base or diglycidylamino group. The liquid crystal alignment agent of claim 1, wherein in the above formula (丨), two R1 are hydrogen, and Z1, Z2 or Z3 are diglycidylamino groups. 3. The liquid crystal alignment agent of claim 1, wherein in the above formula ,), two R1 are hydrogen, and Z1, Z2 or Z3 are all hydrogen. 4. The liquid crystal alignment agent of claim 1, wherein P1 in the above formula (A) and P2 in the above formula (B) are both derived from 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. i. A liquid crystal alignment agent comprising: a polyamidene composed of a repeating unit represented by the above formula (A) and a polyimine composed of the repeating unit represented by the above formula (B) a mixture, or a polyimine composed of the repeating unit represented by the above formula (B); and a compound of the above formula (1) wherein both R1 are hydrogen and Z1, Z2 or Z3 are amine groups A polyaminic acid polymer obtained by reacting a carboxylic acid dianhydride or a polyimine obtained by dehydrating a closed polyamic acid polymer. A liquid crystal display element is characterized in that it has a liquid crystal alignment film produced by the liquid crystal alignment agent of any one of claims 1 to 5. -44-