TW200831562A - Liquid crystal alignment agent and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent which maintains the voltage holding ratio while reducing accumulated charges and has outstanding printability. The liquid crystal alignment agent comprises a compound as shown in following general formula(1) or a polyamic acid which is obtained by the reaction of a compound as shown in following general formula(1') with tetracarboxylic acid dianhydride. (Wherein, R1 to R3 are individually hydrogen atom, alkyl group or alkoxyl group, R4 to R7 are individually hydrogen atom, aromatic group having one valence bond, aliphatic group having one valence bond, or aliphatic group having one valence bond comprising epoxy group, A1 and A2 are individually hydrogen atom, aliphatic group having one valence bond, or aliphatic group having one valence bond comprising epoxy group, n is an integer from 1 to 100.) (Wherein, R1 to R3, A1 and A2, as well as n are the same as those in aforementioned general formula (1).)

Description

[Technical Field] The present invention relates to a liquid crystal alignment agent and a liquid crystal display element for forming a liquid crystal alignment film of a liquid crystal display element, and more particularly to a film having good electrical properties and good printability. A liquid crystal alignment agent for a liquid crystal alignment film and a liquid crystal display element using the same. [Prior Art] At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN (Twisted Nematic) type liquid crystal cell is known, which is formed of polylysine, polyfluorene on the surface of a substrate provided with a transparent conductive film. A liquid crystal alignment film composed of an imine or the like is used as a substrate for a liquid crystal display element, and two substrates are opposed to each other, and a layer of nematic liquid crystal having positive dielectric anisotropy is formed in the gap to form a sandwich structure. The unit cell, the long axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate to the other substrate. Further, an STN (Super Twisted Nematic) type liquid crystal display element and a vertical alignment type liquid crystal display element having higher contrast and smaller viewing angle dependence than the TN type liquid crystal display element have been developed. The STN type liquid crystal display element uses a liquid crystal in which a chiral agent as an optically active substance is blended in a nematic liquid crystal as a liquid crystal by using a long axis of liquid crystal molecules to be continuously twisted by 180 degrees or more between substrates. The birefringence effect produced by the state. In contrast, as described in Non-Patent Document 1 and Patent Document 1, a vertical alignment type liquid crystal display element called a MV A (Multi_Domain Vertical Alignment) method in which protrusions are formed on a transparent conductive film to control a liquid crystal alignment direction is proposed. . The liquid crystal display element of the MVA type is excellent not only in the viewing angle, the contrast ratio of 200831562, but also in the process of forming the liquid crystal alignment film, and is also excellent in the manufacturing process. As a liquid crystal alignment film suitable for the TN, STN, and MVA systems, it is required that the residual image erasing time of the liquid crystal display element is short. Further, as an alignment agent for forming the liquid crystal alignment film, it is required to have excellent printing properties in lithography. [Non-Patent Document 1] "Liquid Crystal" Vol. 3 No. 2 1 1 7 (1 999) [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei 1 - 25 8 605 [Patent Document 2] Japanese Patent Laid-Open No. 6-2223 [Patent Document 3] Japanese Patent Laid-Open No. Hei. No. Hei. No. 5 - 1 07544 [Non-Patent Document 2] K. Hasegawa, Polymer Journal· Vol. [Patent Document 5] Japanese Laid-Open Patent Publication No. 2000-44683 (Patent Document 6) International Publication No. 2002/1 00949. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. The object of the invention is to provide a liquid crystal alignment agent which maintains a voltage holding ratio while reducing accumulated charges and which has excellent printability, and provides a liquid crystal display element using the same. Other objects and advantages of the invention will be apparent from the description which follows. According to the present invention, the above object of the present invention, first, is achieved by a liquid crystal alignment agent (hereinafter referred to as "first liquid crystal alignment agent") containing a compound represented by the following formula (1), 200831562

(wherein R1 to R3 are each independently a hydrogen atom, a substituent or a decyloxy group, and R4 to R7 each independently represent a hydrogen atom, a monovalent aromatic group, a monovalent aliphatic group or an epoxy group; The monovalent aliphatic group of the group, A1 and A2 are each independently a hydrogen atom, a monovalent aliphatic group or a monovalent aliphatic group containing an epoxy group, and η is an integer of from 1 to 100). The above object of the present invention, and secondly, is achieved by a liquid crystal alignment agent (hereinafter referred to as "second liquid crystal alignment agent"), which is characterized by containing a compound represented by the following general formula (1') and a tetracarboxylic acid dianhydride. The polylysine obtained by the reaction,

(wherein R1 to R^A1 and Α2 and η are the same as in the above formula (1)). The above object of the present invention is, in a third aspect, achieved by a liquid crystal display device comprising a liquid crystal alignment film formed of any one of the above liquid crystal alignment agents. [Embodiment] The first liquid crystal alignment agent of the present invention contains the compound represented by the above formula (1) in the above formula (1), and each of R1 to R3 is independently a hydrogen atom, an alkyl group or an alkoxy group 200831562 as the above alkyl group. Preferably, it is an alkyl group having a carbon number of 1 to 6, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 2-methyl-propyl group, and 3 -Methyl-propyl, n-pentyl 'n-hexyl, and the like. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a n-butoxy group. Base, 2-methyl-propoxy, 3-methyl-propoxy, n-pentyloxy, n-hexyloxy and the like. R4 to R7 in the above formula (1) are each independently a hydrogen atom-valent aromatic group, a monovalent aliphatic group or an epoxy group-containing monovalent aliphatic group. The monovalent aromatic group may, for example, be a phenyl group, a biphenyl group, a biphenyl group, a naphthyl group, a nonyl group, a fluorenyl group, a aryl group, an onion group or a fluorenyl group. Among them, a phenyl group is preferred. , biphenyl, terphenyl, naphthyl or anthracenyl. The monovalent aliphatic group is preferably a monovalent aliphatic group having 1 to 4 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. The monovalent aliphatic group having an epoxy group is preferably a group having a total carbon number of 2 to 4, and examples thereof include a glycidyl group and an i-methyl glycidyl group. A1 and A2 in the above formula (1) are each independently a hydrogen atom, a monovalent aliphatic group or a monovalent aliphatic group containing an epoxy group. Preferred as a preferred monovalent aliphatic group of A1 and A2 and a monovalent aliphatic group containing an epoxy group, and a preferred monovalent aliphatic group as R4 to R7 above and an epoxy group. The monovalent aliphatic groups are the same. 200831562 In the above formula (1), η is an integer of 1 to 100, preferably 1 to 50. In the above formula (1), R1 to R7 and Α1 and Α2 may be arbitrarily combined in such a preferred group. Among the compounds represented by the above formula (1), more preferably, the following compounds (Α) to (D) are mentioned. (Α) is that in the above formula (1), Ri to R3 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having a carbon number of i to 6, and R 4 to R 7 are a hydrogen atom, and A1 And A2 is a compound of a hydrogen atom. (B) In the above formula (1), Ri to R3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R4 to R7 have an epoxy group. The monovalent aliphatic groups 'A1 and A2 are each independently a hydrogen atom or a compound having a monovalent aliphatic group of an epoxy group. (C) In the above formula (1), R1 to R3 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R4 and R6 are a monovalent aromatic group. The group, R5 and R7 are a hydrogen atom or a monovalent aliphatic group, and each of A1 and A2 is a compound independently a hydrogen atom or a monovalent aliphatic group. (D) is a hospital group in which R1 to R3 are each independently a hydrogen atom, a carbon number of 1 to 6 or a carbon number of 1 to 6 in the above formula (1), and R4 and R6 are a monovalent aromatic group. The group of the group, R5 and R7 are a hydrogen atom or a monovalent aliphatic group having an epoxy group, and each of A1 and A2 is independently a hydrogen atom and a compound having an i-valent aliphatic group having an epoxy group. In this case, it is preferred to exclude a compound in which R5, R7, A1 and A2 are each a hydrogen atom. A preferred specific example of the compound represented by the above formula (1) is a compound represented by the following structural formula in 200831562.

-11- 200831562

(In the above structural formula group, η is from 1 to 100, and preferably, the second liquid crystal alignment agent of the present invention contains a polyamine which is obtained by reacting an upper compound with a tetracarboxylic acid dianhydride; an integer of from 1 to 50). The 表示 expressed by the equation (1 '). The compound represented by the above formula (1 ') -12-200831562 is preferably an alkyl group in which R1 to R3 are independently a hydrogen atom, a carbon number of 1 to 6 or a carbon number of 1 to 1 in the above formula (1). Alkoxy group of hydrazine, A1 and Α2 are chlorine atoms, and η is a compound of ι 〜5 。. A preferred specific example of the compound represented by #胃± ^式U') can be exemplified by a compound represented by the following structural formula. H2r^OfH-〇^u points NH2 Η2ΝΌ{!^^ points NH2 och3 money NHz

Nh2

Nh2

Nh2 200831562 (in the above structural formula group, n is an integer of 1 to 100, preferably 1 to 50). The tetracarboxylic acid dianhydride which can be used when the compound represented by the above formula (〖') is reacted with tetracarboxylic acid dianhydride to synthesize polyamic acid, and 1,2,3,4-cyclobutanetetracarboxylic acid is mentioned. Diacid anhydride, dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, l,3,3a,4,5,9b - hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]furan-1,3-dione, cis-3,7-dibutyl Cyclooctadiene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2:3,5:6-dianhydride, 1,3 , 3&,455,91>-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [He]furan-1,3·dione, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2,5,-dione), 5-(2,5-dioxo) Tetrahydro-3·furanyl)-3_methylcyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6- Anhydride, 4,9-dioxatricyclo[5·3·1·02,6]undecane-3,5,8,10-tetraone, pyromellitic dianhydride, and the like. These acid anhydrides may be used singly or in combination of two or more. When the polyamine acid is synthesized by reacting the compound represented by the above formula (1') with tetracarboxylic acid dianhydride, it is also possible to use other diamines simultaneously with the compound represented by the above formula (丨'). Preferred other diamines which can be used herein include, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 2, 2'-Dimethyl-4,4'-diaminobiphenyl, 1,5-diaminonaphthalene, 2,7-diaminopurine, 9,9-dimethyl-2,7-diamine Base, 4,4, diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9·bis(4-aminophenyl) Bismuth, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-di 200831562 (4-aminophenyl)hexafluoropropane, 4,4'-( p-Phenyldiisopropylidene)diphenylamine, 4,4'-(m-phenylenediisopropylidene)diphenylamine, 1,4-cyclohexanediamine, 4,4'_ Methyl bis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diamino Pyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminosostazole, N-methyl-3,6-di Aminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)- Benzidine, N, N'-II (4-Aminophenyl)-N,N'-dimethyl-benzidine or the like. These other diamines may be used alone or in combination of two or more. When the other diamine is used together with the compound represented by the above formula (1'), the amount of the other diamine used is the same as the total amount of the compound represented by the above formula (1 ') and other diamines. Preferably, it is 50% by weight or less. The polyamine acid can be synthesized from the compound represented by the above formula (1) and the tetracarboxylic acid dianhydride, and can be the same as the method described later for the synthesis method of polylysine which is one of the optional components of the liquid crystal alignment agent of the present invention. Conducted. The liquid crystal alignment agent of the present invention contains a compound represented by the above formula (1) or a polyglycine obtained by reacting a compound represented by the above formula (1 ') with a tetracarboxylic acid dianhydride as an essential component 'but other than this, It may be selected from the group consisting of polylysine having a repeating unit represented by the following formula (I-1) and a polyimine having a repeating unit represented by the following formula (I-2). At least one, tackifier, and the like.

Hood -HNOC

COOH CONH—Q1 (I -1 ) Λ -15- 200831562

(wherein P2 is a tetravalent organic group' and Q is a divalent organic group). The polyaminic acid having the repeating unit represented by the above formula (1) can be synthesized by the reaction of a tetracarboxylic dianhydride with a diamine. The polyimine having the repeating unit represented by the above formula (1-2) can be A polyglycine dehydration ring closure having a repeating unit of the above formula (I-1) wherein P1 is P2 and Q1 is Q2 is obtained by dehydration ring closure of the poly(p-amino acid) having the repeating unit represented by the above formula (1). The tetracarboxylic acid dianhydride may, for example, be an alicyclic tetracarboxylic dianhydride, an aliphatic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride or the like. The alicyclic tetracarboxylic dianhydride may, for example, be mentioned. 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2, 3,4-cyclobutylene tetraphthalic acid dianhydride, 1,3 -dichloro-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1 , 2,3,4-cyclobutanetetracarboxylic acid dianhydride, I2,3,4**cyclopentanetetracarboxylic acid dianhydride, I,2,4,5-cyclohexanetetracarboxylic dianhydride, 3 , 3', 4, 4, dicyclohexyltetracarboxylic dianhydride, cis, 3,7-dibutylcyclooctane-1, 5·Diene-1,2,5,6-tetracarboxylic dianhydride, 2 3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarbonyl-2-carboxyl-icing--16- 200831562 flane-2:3,5:6-dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, l,3,3a,4,5,9b-hexahydro-5-(tetrahydrogen -2,5-dioxo-3-furoyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91>-hexahydro- 5-methyl-5(tetrahydro-2,5-dioxo-3-furyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4 ,5,91>-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1,3-di Ketone, 1,3,31,4,5,913-hexahydro-7-methyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-indolyl]-furan- 1,3-diketone, 1,3,3&,4,5,91)-hexahydro-7-ethyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene l,2-c]-furan·1,3-dione, 1,3,3&,4,5,913-hexahydro-8-methyl-5(tetrahydro-2,5-dioxo-3 Furyl)-naphthalene [l,2-c]-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·dione, 1 3,3&,4,5,91>_hexahydro-5,8-dimethyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(: ]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranmethylidene)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, bicyclo[ 2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3·2·1]octane-2,4-dione-6·snail -3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2 -dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.02,6]Eleven Alkane-3,5,8,10-tetraketone, a compound represented by the following formula (I) or (II), 200831562

(wherein R8 and R1() represent a divalent organic group having an aromatic ring, R9 and R11 represent a hydrogen atom or a yard group, and a plurality of R9 and R11 present may be the same or different). The aliphatic tetracarboxylic acid dianhydride may, for example, be butane tetracarboxylic acid dianhydride or the like. Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'-di. Phenyl maple tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3',4,4'-di Phenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylnonane tetracarboxylic acid Anhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,45-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-di(3, 4-dicarboxyphenoxy)diphenylsebacic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,45-perfluoro Isopropylenedicarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, di(benzene) Dicarboxylic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) diacid 200831562 anhydride, two ( Triphenylphthalic acid)-4,4' -diphenylether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-di(hydrogen trimellitate), propylene glycol-di (dehydrated benzene) Triester), 1,4-butanediol-di(anhydrotrimellitic acid ester), 1,6-hexanediol-di(anhydrotrimellitic acid ester), 1,8-octanediol·two (dehydrated trimellitate), 2,2-bis(4-hydroxyphenyl)propane-di(hydrogen trimellitate), a compound represented by the following formulas (2) to (5), and the like.

-19- 200831562 These tetracarboxylic acid dianhydrides may be used alone or in combination of two or more. Among the above-mentioned tetracarboxylic dianhydrides, as the alicyclic tetracarboxylic dianhydride, a 1,2,3,4·cyclobutanetetracarboxylic acid is preferred from the viewpoint of imparting good liquid crystal alignment properties. Anhydride, dimethyl hm-cyclobutane tetraresic acid dianhydride, 1,2,3,4-tetramethylcyclobutane tetracarboxylic acid diacid field, 1,2,3,4-cyclopentan Tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid monoanhydride, 5·(2,5-dioxotetrahydrofuran methylene)_3_methyl-3_cyclohexyl-1,2 - monodecanoic acid dianhydride, cis_3,7-dibutylcyclooctane-indole-diene-1,2,5,6·tetradecanoic acid dianhydride, 3,5, "tricarbonyl-2-carboxyl Norbornane-2.3,5:6-monoanhydride, 1,3,3&,4,5,91>_hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)- Na[l,2-c]furan 4,^dione, hexahydro·8-methyl 5-(tetrahydro-2,5·monooxofuranyl bromide, ?.]furan-4,3 Diketone, anthracene, 353a, 4,5,9b.-hexahydro·5,8·dimethyl_5_(tetrahydro-2,5-dioxo_3_indolyl)-naphthalene [l,2- c] furanedione, bicyclo[2 2.2]-octyl-[ene'3'5,6-tetracarboxy@^-anhydride, 3_oxabicyclo[321]octane-2,4-dione i-spiro- 3 -(tetrahydrofuran-2,5,dione), fluorenyl-dioxotetrahydrofuran(furyl)-methylmethylcyclohexane bis-phthalic anhydride, 3,5,6·trisyl I fluorenyl Norbornane-2:3,5:6-dianhydride, 4, dioxatricyclo[5 31〇2'6] eleven'5,8'1〇tetramide in the compound represented by the above formula (1) Compounds represented by the formula (6) ~ (8), etc., • 20- 200831562

Or a compound represented by the above formula (II), (8) a compound represented by the following formula (9)

Particularly preferred are 1,2,3,4-cyclo1,3-1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid di-s-pentyl acetic acid dianhydride, 1,3. 3&,4,5,913-hexahydro-3-furanyl)·naphthalene [l,2-c]furan-1,3-dione, norbornane-2··3,5··6· dianhydride, 1,3,3a, -5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1 3-oxabicyclo[3.2.1]octane-2,4-dione- 6-spiro [butane tetracarboxylic acid dianhydride, I anhydride, 2,3,5-tricarboxycyclo-5-(tetrahydro-2,5-dioxo 3,5,6-dioleyl-2- Mercapto 4,5,9 b -hexa·8-methyl, 2-c]furan-1,3-dione, -3'-(tetrahydrofuran-2',5'--21-200831562 diketone) , 5 - (2,5-dioxotetrahydro-3-furanyl)-3-methyl-3::1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxyl Bornane·2:3 anhydride, 4,9-dioxatricyclo[5.3.1.02,6]undecane-3,5,8,10- and the compound represented by the above formula (6) is particularly preferably 2 Further, as the aliphatic tetracarboxylic dianhydride and the aromatic tetracarboxylic anhydride, preferred are butane tetracarboxylic dianhydride, pyromellitic anhydride, and 3 ,3,,4,4'-diphenyl Tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl® carboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, i,4,5,8- The acid dianhydride. When two or more kinds of tetracarboxylic acid dianhydride are used in combination, the preferred tetracarboxylic dianhydride is 50 Å based on the total tetracarboxylic acid dianhydride as the above formula (I-1). The diamine used in the polymerization of the repeating unit may, for example, be an aromatic diamine, an aliphatic cyclic diamine, or a diamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amine group. And a diaminoorganomethoxy alkane. The aromatic diamine may, for example, be p-phenylenediamine diamine, 4,4'-diaminodiphenylmethane or 4,4,-diaminodi Phenyl 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl milling, 2,yl-4,4'-diaminobiphenyl, 3,3'-di Methyl-4,4,-diaminobiphenyldiaminobenzamide, 4,4,diaminodiphenyl ether, 1,5-diamine 2,2, dimethyl-4,4, Diaminobiphenyl, 2,2'-ditrifluoromethyl-4, phenyl, 3,3'-ditrifluoromethyl-4,4,-diaminobiphenyl, 5-amino ring Burned , 5:6-ditetraone, pentyl acetic acid diacid phthalocyanine tetracarboxylate is an alicyclic ring; the ear% is contained in an amine acid or a fat, m-benzene: ethane, 2,-two A, 4, 4, naphthalene, 4,-diamine; small (4,--22- 200831562 aminophenyl)-l,3,3-trimethylindan, 6-amino-l- (4,-aminophenyl)-1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4 '-Diaminobenzophenone, 4,4,-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-di[4 -(4-Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4·(4-aminophenoxy) .) phenyl] hydrazine, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminobenzene) Oxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diaminopurine, 9,9-dimethyl-2,7-diaminopurine, ® 9,9-bis(4-aminophenyl)anthracene, 4,4,-methyl-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-phenylphenylidene)diphenylamine, 4,4,_(m-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 and the like. Examples of the aliphatic or alicyclic diamine include 1,1-isophenylene dimethylamine, 1,3-propanediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, and octane. Diamine, decanediamine, 4,4-diaminoheptyldiamine, l54-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7 - anthracene dimethylene diamine, tricyclo[6.2.1.〇2,7]-undecene dimethyldiamine, 4,4,-methyl bis(cyclohexylamine) and the like. Examples of the diamine having two first-order amine groups in the molecule and a nitrogen atom other than the one-group amine group include 2,3-diaminopyridine and 2,6-diaminopyridine. 4-diaminopyridine, 2,4-diaminopyridinium, 5,6-diamine-23- 200831562 base-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-di Amino-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-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridinyl lactate, 3,8-diamine -6-phenylphenanthridine, iota, 4-diaminopyridazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole , N-methyl_3,6-diaminocarbazole, N-ethyl-3,6-diaminosostazole, N-phenyl-3,6- Diaminocarbazole, N,N,-bis(4-aminophenyl)-benzidine, N,N,-bis(4-aminophenyl)-indole, indole, dimethyl-benzidine Wait. In addition, examples of the above-mentioned diamine organooxosiloxane include a compound represented by the following formula, and the like.

H2N-(-CH2^Si-

R

(10) (wherein R12 represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of Ri2 present may be the same or different, and P is an integer of 1 to 3, and q is an integer of 1 to 20). These diamines may be used alone or in combination of two or more. Among these diamines, p-phenylenediamine, 4,4, diaminodiphenylmethane, 4,4,-diaminodiphenyl sulfide, 2,2,-dimethyl-4,4 are preferred. , diaminobiphenyl, -24- 200831562 1,5-diaminonaphthalene, 2,7-diaminopurine, 9,9-dimethyl-2,7-diaminopurine, 4,4' -diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9·bis(4-aminophenyl)anthracene, 2,2-di [4-(4-Aminophenoxy)phenyl]hexafluoropropane, 2,2-di(4-aminophenyl)hexafluoropropane, 4,4'·(p-phenylene) Isopropylene)diphenylamine, 4,4'-(m-phenylenediisopropylidene)diphenylamine, 1,4-cyclohexanediamine, 4,4'-methyldi(cyclohexane) Amine), I,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4- Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminosostazole, N-methyl-3,6-diaminocarbazole, N -ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'_:(4-aminophenyl)-benzidine, N,N '-bis(4-aminophenyl)-N,N'-dimethyl-linked aniline. When the liquid crystal alignment agent of the present invention has a pretilt performance performance, it is preferred that a part or all of the diamine used in the polyamic acid synthesis having the repeating unit represented by the above formula (I-1) has the following formula. (Q-1) or a diamine of the structure represented by the following formula (Q-2) (hereinafter referred to as "specific diamine"),

(Q-1) (wherein X is a single bond, -0-, -CO-, -COO-, -OCO-, -Nhc〇, -CONH·, -S- or an aryl group, and R13 is a carbon number It is an alkyl group of 1 to 20 carbon atoms, a monovalent organic group having an alicyclic skeleton of 4 to 40 carbon atoms, or a fluorine atom-containing monovalent organic group having 6 to 20 carbon atoms. R14_x"O"" (q·2) -25 - 200831562 (where X is a single bond, -〇-, -c 〇-, - c Ο Ο -, - 〇C o. -CONH-, -S - or an aryl group, R14 is a divalent organic group of a skeleton having a carbon number of 4 to 4 Å). Thus, a part or all of the above formula (I group Q1 and base 圑Q2 can be a group of the above formula (Q-form), thereby contributing to the expression of the pretilt angle ί in the above formula (Q-1), as The carbon number represented by R13 is 1 group, and examples thereof include n-decyl group, n-dodecyl group, n-pentadecyl group, n-octadecyl group, n-icosyl group, etc. Further, (Q-1) R13 and the organic group having an alicyclic skeleton of carbon represented by R14 in the above formula (Q-2) may, for example, be a naphthenic acid such as butane, cyclopentane'cyclohexane or cyclodecane. a ring group; a group having a steroidal skeleton such as a cholesteric alcohol or a cholesteryl group; a group having a bridged alicyclic skeleton such as adamantane; and a group having a steroid skeleton. The skeleton may be a group substituted with a halogen atom, preferably a fluorine atom or a fluoroalkylfluoromethyl group. Further, as the fluorine atom-containing group of carbon represented by R13 of the above formula (Q-1), For example, an alicyclic hydrocarbon group having a carbon number of 6 or more, such as n-hexyl or n-octane, having a carbon number of 6 or more, a cyclohexyl group or a cyclooctyl group of 6 or more; a phenyl group or a biphenyl group; The carbon number is a group of a hydrogen atom of an organic group such as an aromatic hydrocarbon group or a fluoroalkyl group such as a trifluoromethyl group. Further, in the above formula (Q-丨) and the above formula (Q-2) -, -NHCO-, having the properties of the base 1) or (Q-2) in the alicyclic formula 1). The alkanoyl group of 0 to 20 and the group of 10 to 40 having the above formula are from the ring skeleton; and having an organic group in the ice, particularly preferably a number of 6 to 2; A group having a carbon number of 6 or more, such as a carboxy group or a fluorenyl group, is a fluorine atom or X is a single bond, -26 - 200831562 -Ο-, -CO-, -COO- ' -OCO-, -NHCO-, -CONH -, -S- or an aryl group, and examples of the aryl group include a stretching phenyl group, a stretching tolyl group, a stretching phenyl group, an anthranyl group, and the like. Specific examples of the diamine having the structure represented by the above formula (Q-1) include, for example, dodecyloxy-2,4-diaminobenzene and pentadecyloxy-2,4-diamine. Benzene, cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, a compound represented by the following formulas (11) to (15), and the like.

Specific examples of the diamine having a structure represented by the above formula (Q-2) include a compound represented by the following formulas (16) to (18). -27- 200831562

use. Among these specific diamines, preferred are the compounds represented by the above formula (1 1), (13), (15) or (16).

The use ratio of the specific diamine relative to the total amount of the diamine varies depending on the magnitude of the pretilt angle to be expressed, and in the case of the TN type or S TN type liquid crystal display device, it is preferably 〇5 to 5 mol%. In the case of the vertical alignment type liquid crystal display element, it is preferably 5 to 100% by mole. The acid anhydride group of the tetracarboxylic dianhydride is preferably a ratio of 2 to 2 equivalents per 1 equivalent of the amine group of the polyamine synthesized by the polyamine derivative having the repeating unit represented by the above formula (I-1). More preferably, it is a ratio of 〇·3 to ι·2 equivalent. The synthesis reaction of polylysine is preferably in the organic solvent at -20 ° C to 150 ° C, more preferably 0 to 10 Torr (at a temperature of TC, preferably 10 minutes to 5 minutes). 0 hours, more preferably 3 〇 minutes to 3 〇 hours. Here, 'as an organic solvent, as long as it can dissolve the synthesized polyaminic acid, -28-200831562 is not particularly limited, and examples thereof include 1-methyl group. -2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy- Amidoxime solvent such as N,N-dimethylpropionamide, 3-hexyloxy-N,N-dimethylpropionamide, dimethyl hydrazine, 7-butyrolactone, tetramethylurea An aprotic polar solvent such as hexamethylphosphonium triamine; a phenolic solvent such as m-methylphenol, xylenol, phenol or halogenated phenol. The amount of the organic solvent (α) is usually preferably a tetracarboxylic acid. The total amount (β) of the acid dianhydride and the diamine compound is from 0.1 to 30% by weight based on the total amount of the reaction solution ((χ + β). Within the range in which the produced polyaminic acid is not precipitated, Organic solvent as described above Some of them may be replaced by a poor solvent of polyphthalic acid (P〇〇r solvent), a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, etc. As a specific example of such a poor solvent, For example, methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol Methyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, Ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl Ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether Acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, Hexane, g Alkane, octane, benzene, toluene, xylene, isoamyl propionate, iso-29-200831562 isoamyl butyrate, diisoamyl ether, etc. The amount of poor solvent that can be used here, in all solvents It is preferably 50% by weight or less, more preferably 40% by weight or less. As described above, a reaction solution in which polyamic acid is dissolved is obtained. Then, the reaction solution is poured into a large amount of poor solvent to obtain a precipitate. The polylysine can be obtained by drying the precipitate under reduced pressure or by distilling off the reaction solution with a vaporizer. Further, the polylysine is redissolved in an organic solvent, and then precipitated with a poor solvent one or several times. The process can be purified by a process or a process of distilling off under reduced pressure with an evaporator. The polyimine having the repeating unit represented by the above formula (I-2) can be obtained by dehydrating and ring-closing polylysine having a repeating unit of the above formula (I-1) wherein P1 is P2 and Q1 is Q2. In the case of the dehydration ring closure, the proline structure may be dehydrated and closed to form a quinone ring, or only a part of the proline structure may be dehydrated to form a polymer in which the proline structure and the quinone ring structure coexist. The dehydration ring closure of polylysine is (i) a method of heating poly-proline, or (Π) by dissolving poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution. It is carried out according to the method of heating required. The reaction temperature in the method for heating poly-proline in the above (i) is preferably 50 to 200 ° C, more preferably 6 to 170 ° C. When the reaction temperature is less than 50 °C, the dehydration ring-closure reaction cannot be carried out completely. If the reaction temperature exceeds 200 °C, the molecular weight of the obtained quinone imidized polymer may be lowered. The reaction time is preferably from 10 minutes to 5 hours, more preferably from 30 minutes to 3 hours. -30- 200831562 On the other hand, in the case of the above-mentioned method of adding a dehydrating agent and a dehydration ring-closing catalyst to a polyamic acid solution, as the dehydrating agent, for example, acetic anhydride, propionic anhydride, trifluoroacetic acid can be used. Anhydride such as an anhydride. The amount of the dehydrating agent is determined depending on the desired imidization ratio, but is preferably from 0. 01 to 20 mol with respect to the repeating unit of 1 mol of polyamic acid. As the dehydration ring-closing catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst is preferably from 0.01 to 10 moles per mole of the dehydrating agent used. ^ The higher the amount of the above dehydrating agent and dehydration ring-closing catalyst, the higher the yield of ruthenium. Further, as the organic solvent used in the dehydration ring-closure reaction, an organic solvent exemplified as a solvent used in the synthesis of polylysine may be mentioned. Further, the reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. The reaction time is preferably from 30 minutes to 10 hours, more preferably from 1 hour to 7 hours. The obtained polyimine can be purified by performing the same operation as the method for purifying polylysine by the reaction solution thus obtained. 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 "deuterated imidization ratio") of 40 mol% or more, preferably 50 mol% or more. By using a polymer having a ruthenium iodide ratio of 40 mol% or more, a liquid crystal alignment agent capable of forming a liquid crystal alignment film having a short afterimage erasing time can be obtained. The method is as follows. [Method for measuring ruthenium iodide ratio of ruthenium iodide polymer] The ruthenium iodide polymer is dried under reduced pressure at room temperature, and then dissolved in deuterated-31-200831562 dimethyl hydrazine. Among them, tetramethyl decane was used as a reference material, and 1H-NMR measurement was carried out at room temperature, and it was obtained by the formula represented by the following (ii). The oxime imidization ratio (%) = (1 - aVa2x α ) χ 100 - - ( -) A1 : peak area of protons derived from NH groups (10 ppm) A2 : peak area derived from other protons α: in the precursor of the polymer (polyglycine), relative to one a ratio of the number of other protons of the NH proton having a repeating unit of the above formula (I-1) or a polyamine The polyimine having a repeating unit represented by the above formula (I-2) may also be a terminal-modified polymer having a molecular weight adjusted. By using the terminal-modified polylysine or polyimine, The coating property and the like of the liquid crystal alignment agent are improved without impairing the effects of the present invention. The terminal-modified poly-proline or polyimine can be added to the reaction system by adding a monoanhydride when synthesizing the polyamic acid. A monoamine compound, a monoisocyanate compound, or the like is synthesized, and examples of the monobasic acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, and Tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, etc. Further, examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine. , n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine N-octadecylamine, n-icosylamine In addition, examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. The polyfluorene-32-200831562-amino acid having the repeating unit represented by the above formula (I-1) obtained as above. Or the polyimine having the repeating unit represented by the above formula (I-2) preferably has a viscosity of 20 to 80 OmPai, more preferably 30 to 500 mPa of s in a 10% solution. Further, the solution viscosity (mPvs) of the polymer was measured in a solution diluted to a predetermined solid content concentration using a predetermined solvent, and the viscosity was measured at 25 ° C using an E-type rotational viscometer. When the agent is a polylysine containing a repeating unit represented by the above formula (I-1) or a polyimine having a repeating unit represented by the above formula (I-2), the ratio of use thereof for the first liquid crystal alignment agent With respect to 1 part by weight of the compound represented by the above formula (1), it is preferably 1 part by weight or less, more preferably 1 to 5,000 parts by weight. On the other hand, for the second liquid crystal alignment agent, the polyamic acid obtained by reacting the compound represented by the above formula (1 ') with the tetracarboxylic acid dianhydride is preferably 100 parts by weight or less, more preferably Preferably it is 5 to 80 parts by weight. The liquid crystal alignment agent of the present invention is usually constituted by dissolving the above specific polymer in an organic solvent. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 〇 ° C to 2 0 ° C, more preferably 20 ° C to 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 polyamido acid synthesis reaction. Further, it is also possible to appropriately select a poor solvent which can be exemplified as it can be used in the polyamic acid synthesis reaction. The solid content concentration in the liquid crystal alignment agent of the present invention is selected in consideration of viscosity, volatility and the like, and is preferably in the range of 1 to 1% 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 for the film. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too small, so that a good film cannot be obtained. When the concentration of the liquid crystal alignment component exceeds 10% by weight, the liquid crystal alignment film which is too thin in coating film thickness is obtained, and the liquid crystal alignment agent is large, and the coating property is deteriorated. Further, a particularly preferable solid content concentration range differs depending on the method used when the substrate is oriented. For example, when it is spin-coated, it is preferably in the range of 1.5 to 4.5% by weight. When the printing method is used, the body component concentration is in the range of 3 to 9 % by weight, so that it can fall within the range of 12 to 50 mPa*s. When the ink jet method is used, the specific component concentration is in the range of 1 to 5 wt%, so that the solution can be in the range of 3 to 15 mPa*s. As the organic solvent constituting the liquid crystal alignment agent of the present invention, such as 1-methyl-2-pyrrolidone, r-butyrolactone, r-butyrolactam methylformamide, N,N-dimethylacetamide , 4-hydroxy-4_methyl® ethylene glycol monomethyl ether, butyl lactate, butyl acetate, ethyl methoxypropyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ether, diethyl ether Ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve) dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monoester, diethylene glycol monoethyl ether acetate, 3-butoxy-N,N-dimethyl 3-methoxy-N,N-dimethylpropanamide, 3- Hexyloxy-N,N-diamine, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, etc. The liquid crystal will cause the film to be thickened and viscous. When applying the liquid crystal method, Tetejia is a solid solution viscosity, and the solid viscosity falls on, for example, N,N-di-2-pentanone, acid methyl ester, diol n-propene, ethylene glycol diglyme. Acetylacetamide, methyl propyl hydrazine, these can be -34- 200831562 Used alone or in combination of two or more. Among them, '3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropionamide, 3-hexyl Oxy-N,N-dimethylpropionamide is particularly excellent in exhibiting good printability. The liquid crystal alignment agent of the present invention is considered from the viewpoint of improving the adhesion to the surface of the substrate without impairing the physical properties of the object. The compound containing a functional sand compound or an epoxy compound may be contained (except for the compound represented by the above formula (1) or (丨').) As the functional decane-containing compound, for example, 3-amino group® may be mentioned. Propyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-Amino B >-3-Aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane , 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N- Triethoxy hydrazine Propyl triethylamine, N-trimethoxydecylpropyltriethyltriamine, 10-trimethoxydecyl-1,4,7-triazadecane, 10-three Ethoxy decyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9-triethoxydecyl-3 6-diazaindolyl acetate, Ν-benzyl-3-aminopropyltrimethoxydecane, Ν-benzyl-3-aminopropyltriethoxydecane, Ν-phenyl-3 -Aminopropyltrimethoxydecane, fluorenyl-phenyl-3-aminopropyltriethoxydecane, fluorene-bis(oxyvinyl)-3-aminopropyltrimethoxydecane, N-di ( Oxyvinyl)-3-aminopropyltriethoxydecane, and the like. Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tri-35-200831562 propylene glycol diglycidyl ether, and polypropylene glycol diglycidyl glycol. Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3, 5,6-tetraglycidyl 2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3 -di(N,N-di Glycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzyl Amine, N,N-diglycidyl-aminomethylcyclohexane, 3-(N-allyl-N-glycidyl)aminopropyldimethoxy sand, 3-(N , N-di-dihydrate, glyceryl, aminopropyltrimethoxydecane, and the like. The use ratio of the tackifier as described above is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight based on the compound represented by the above formula (1) with respect to 1 part by weight of the first liquid crystal alignment agent. Share. On the other hand, for the second liquid crystal alignment agent, the polyamic acid obtained by reacting the compound represented by the above formula (1 ') with tetracarboxylic acid dianhydride is preferably 3 parts by weight with respect to 100 parts by weight. Hereinafter, it is more preferably 〇. 1 to 2 5 parts by weight. The liquid crystal display element of the present invention can be produced, for example, by the following method. (1) Applying the liquid crystal alignment agent of the present invention to one side of a substrate provided with a patterned transparent conductive film by a lithography method, a spin coating method or an inkjet printing method, and then forming a coating layer by heating the coated surface membrane. Here, as the substrate, glass such as float glass or sodium alumina; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, alicyclic ring can be used. A transparent substrate made of a plastic such as polyolefin. As the transparent conductive film provided on one side of the substrate, a NESA film (registered trademark of PPG, USA) composed of tin oxide-36-200831562 (Sn02) and an indium oxide-tin oxide (Ιη203-Sn02) may be used. For the ITO film or the like, 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. . After the application of the liquid crystal alignment agent, in order to prevent the applied alignment agent liquid from sagging, it is preferred to perform preliminary heating (pre-bake). The prebaking temperature is preferably from 30 to 300 ° C, more preferably from 40 to 200 ° C, and particularly preferably from 50 to 150 ° C. Then, the solvent is completely removed, and a calcination (post-bake) process is carried out for the purpose of heat-imidization of the polyglycolic acid. The calcination (post-baking) temperature is preferably from 80 to 300 ° C, more preferably from 120 to 25 ° C. Thus, the liquid crystal alignment agent of the present invention containing polyglycolic acid is coated with an organic solvent to form a coating film as an alignment film, and further subjected to dehydration ring closure by further heating to form a further yttrium-imiding coating film. . The film thickness of the formed coating film is preferably 0.001 to Ιμηι, more preferably 0.005 to 0.5 μm. (2) The surface of the formed coating film is subjected to a rubbing treatment which is rubbed in a certain direction by a roll wrapped with a cloth composed of fibers such as nylon, rayon (registered trademark) or cotton. Thus, a liquid crystal alignment film in which liquid crystal molecules are aligned on the coating film is formed. In the liquid crystal alignment film which is formed by the liquid crystal alignment agent of the present invention, for example, it is partially shown in the patent document 2 (Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. The process of irradiating the ultraviolet ray to change the pretilt angle, or partially forming the protection on the surface of the liquid crystal alignment film after the sanding treatment is performed as shown in Patent Document 4 (Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei No. Hei No. Hei. After the film is subjected to a rubbing treatment in a direction different from the previous rubbing treatment, the protective film is removed, and a treatment for changing the liquid crystal alignment of the liquid crystal alignment film is performed, whereby the visual field characteristics of the liquid crystal display element can be improved. (3) Two substrates in which the liquid crystal alignment film is formed as described above are formed, and the two substrates are placed opposite to each other with 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 used. The sealant is bonded, and the liquid crystal is filled into the cell gap which is separated from the surface of the substrate and the sealant, and the injection hole is closed to form a liquid crystal cell. Then, on the outer surface of the liquid crystal cell, that is, on 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 is coincident or perpendicular to the rubbing direction of the liquid crystal alignment film formed on one surface of the liquid crystal cell. Thus, a liquid crystal display element was produced. Here, as the sealant, for example, an alumina ball-containing epoxy resin or the like as a curing agent and a spacer may be used. Examples of the liquid crystal include a nematic liquid crystal and a disk-shaped liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base 0 liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, or a phenyl group can be used. A cyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal, or the like. Further, cholesteric liquid crystals such as chlorinated decyl alcohol, cholesteryl phthalate, and cholesteryl carbonate may be added to these liquid crystals, and trade names "C-1 5" and "CB-15" (manufactured by Merck & Co., Ltd.) may be added. The chiral agent sold, etc. is used. Further, a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutylcinnamate may also be used. In addition, as a polarizing plate to be bonded to the outer surface of the liquid crystal, a polarizing film called a ruthenium film obtained by absorbing iodine while extending polyvinyl alcohol to one to 38-, 200831562 is sandwiched between cellulose acetate protection. A polarizing plate made of a film or a polarizing plate made of a ruthenium film itself. [Examples] Hereinafter, the present invention will be more specifically described by way of Examples, but the present invention is not limited to these Examples. In the following examples and comparative examples, evaluation of the liquid crystal alignment agent and the liquid crystal alignment film produced therefrom was carried out in the following manner. [Voltage Retention Rate] ® Apply a voltage of 5V to the liquid crystal display element at 60 °C for a period of 167 ms. The voltage application time is 60 microseconds, and then the voltage is released from the voltage release to 167 ms. Voltage retention rate. The measuring device used VHR-1 manufactured by Dongyang Science and Technology Co., Ltd. [After image experiment] A unit cell with an ITO electrode as shown in Fig. 1 was produced. At room temperature, a DC voltage of 6.0 V was applied to the electrode A for 24 hours, and a DC voltage of 0.5 V was applied to the electrode B for 24 hours. After the voltage was released, a voltage of 0.1 to 5.0 V DC was applied to the electrodes A and B in a gradient of 0.1 V ® , and the afterimage performance was evaluated. No residual image was found as "〇", and the residual image was marked as "△", and the residual image was marked as "X". [Printability Evaluation] A 127 mm (D) x 27 mm (W) x 1.1 mm (H) glass substrate having a ruthenium film formed on one side of the entire surface was prepared, and the liquid crystal alignments obtained in the respective Examples or Comparative Examples were aligned. The solution was filtered through a micropore filter having a pore size of 〇·2 μιη, and then coated with a liquid crystal alignment film coating printing machine (Japanese Photo Printing Co., Ltd. -39-200831562, and human 1183^〇11^18-401〇). On the transparent electrode surface of the glass substrate, the solvent was removed by a hot plate-type preliminary pre-drying machine set at 80 ° C, and baked at 200 ° C for 60 minutes to form a liquid crystal alignment film on the glass substrate with the ITO film. The unevenness of the obtained alignment film was visually evaluated, and no unevenness was found as "〇", and unevenness was found as "X". Synthesis Example 1 Synthesis Example 1 according to Non-Patent Document 2 (κ· Hasegawa, Polymer Journal Vol. 31, No. 2, 206 (1 999)) 6.4 g (20 mmo1) of 4,4'-dibromobiphenyl and 2.16 g of p-phenylenediamine (2 0 mm) under nitrogen atmosphere. 1) Add to a three-necked flask of 300 ml, add 80 ml of toluene to dissolve it, and add 5.8 g of 3-stage butoxy sodium at room temperature ( 60 mmol), bis(monodecylacetone)-pin (Pd2(dba)3) 0.46 g (0.5 mmol), 2,2'-bis(diphenylphosphine binaphthyl (BINAP>0.93 g (1.5 mm〇l) The reaction solution was stirred at 1 ° C for 1 hour to react. Then the reaction solution was returned to room temperature, using a separatory funnel, using 2 liters of 25% by weight aqueous ammonia and methanol. The mixed solution (ammonia/methanol = 1 / 4 (volume ratio)) was washed into a strip. The organic solvent layer was dehydrated with sodium sulfate and concentrated by a rotary evaporator. The obtained crude product was subjected to silica gel column chromatography. Purification 'to obtain 2 · 1 g of the compound A-1 as shown by the following formula (A-1)

(where m is the number of repetitions) By repeating the same operation, a sufficient amount of the compound A-1 was used in the following experimental example -40-200831562. Synthesis Example 2 10 g of the compound A-1 synthesized in the above Synthesis Example 1 was dissolved in 50 mL of dimethyl hydrazine (DMSO) in a three-necked flask. An excess potassium carbonate aqueous solution was mixed in the solution. After the mixture was cooled in an ice bath, a solution of oxybromophenone in DMSO (concentration: 1 mol/L) was added dropwise to an excess. After the dropwise addition, the mixture was returned to room temperature, followed by stirring for 48 hours. The reaction mixture was filtered, and the filtrate was washed with chloroform / brine. Then, the solvent was distilled off, and reprecipitation was carried out with methanol to obtain a mixture A-2 of the compound represented by the following formula.

(wherein m' and m5' are the number of repetitions, respectively). Polyimine synthesis example 1 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride 112 g (0.50 mol) and 1,3,3 &4,5,91>- Hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-called furan-1,3-dione 1578 (0.50 mol), As a diamine compound, p-phenylenediamine 96g (〇.89 mole), 3,3'-(tetramethyl-sodium oxalate-1,3-diyl) bis(propylamine) 25g (0.10 mole) And -41 - 200831562 3,6-bis(4-aminobenzylideneoxy)cholestane 13g (0.020 mol), n-octadecylamine as a monoamine 8.1 g (0.03 0 mol) dissolved It was allowed to react at 60 ° C for 6 hours in 9 60 g of N-methyl-2-pyrrolidone. The obtained polyaminic acid solution was fractionated, NMP was added, and the viscosity was measured at a solid concentration of 1% by weight in a solution of 60 mPaai. Next, 270 g of N-methyl-2-pyrrole ketone was added to the obtained polyamic acid solution, and 396 g of pyridine and 409 g of acetic anhydride were added thereto, and the mixture was dehydrated and closed at 110 ° C for 4 hours. After the imidization reaction, the solvent in the system is replaced with a new r-butyrolactone (by this operation, the pyridine and acetic anhydride used in the oxime imidization reaction are removed to the outside of the system) to obtain about 2000 g. When the solid content concentration is 15 wt%, the solid content concentration is 6.0 wt% (r - butyrolactone solution), the solution viscosity is 16 m P a · s, and the oxime imidization polymer having a ruthenium iodide ratio of about 95% ( It acts as a "polyimine (a-1)") solution. Polyimine synthesis example 2 224 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, p-phenylenediamine l 8 g as a diamine compound ( l. 〇Moel) and 3.8 g (0.015 mol) of 3,5-diaminobenzoic acid cholesteryl ester dissolved in 3 03 9 g of N-methyl-2-pyrrolidone at 60 ° C The reaction was carried out for 6 hours to obtain a polyaminic acid solution having a solution viscosity of about 260 mPa_s. Next, 2700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 39.6 g of pyridine and 3,6 g of acetic anhydride were added, and the mixture was dehydrated and closed at 1 1 ° C for 4 hours. After the imidization reaction, the solvent in the system is replaced with a new r-butyrolactone (by this operation, the pyridine and acetic anhydride used in the oxime imidization reaction are removed to the outside of the system) to obtain about 3 When the solid concentration of 000g is about 9.0wt%, and the concentration of solid component is 5.0% by weight, the solubility of (r-butyrolactone solution) is -42-200831562. The viscosity of the solution is 7 2 m P a · s, and the yield of hydrazine is about 5 % of a ruthenium iodide polymer (which acts as a "quinone imidized polymer (a-2)") solution. Polylysine Synthesis Example 1 196 g (1.0 mol) of 1,2,3,4-cyclobutane tetraresic acid dianhydride as tetrakis acid anhydride as 2,2,-dimethyl diamine compound The base-4,4,diaminobiphenyl 212g (l. oxime) was dissolved in 370 g of N-methyl-pyrrolidone and 33 〇〇gr-butyrolactone to react at 401: for 3 hours. A solution of polypyridic acid having a solution viscosity of 160 mPai (which is referred to as "polyglycine π-")") solution was about 10 3700 g. Polylysine Synthesis Example 2 1,2,3,4-cyclobutanine tetraresic acid dianhydride as tetracure acid dianhydride 95 g (0.50 mol), pyromellitic dianhydride i 〇 9 g (〇. 5〇莫耳), as a diamine compound, 2,7-diaminopurine 196g (l. oxime) is dissolved in 230g of N-methyl-2-pyrrolidone, 2 0 60 gr - butyrolactone, so that It's at 4 〇. (: 3 hours under the reaction of 3 hours to add 1 3 5 0 gr - butyrolactone to obtain a polyamic acid having a solution concentration of 125 mPa > s at a solid concentration of 1 〇% by weight (as poly phthalic acid (b • - 2)") A solution of about 3 600 g. Example 1 Polyimine (a-1) obtained by synthesizing polyimine in Synthesis Example 1 and polylysine obtained by synthesizing Synthesis Example 1. (b-1), in the form of polyimine: poly-proline = 20:80 (by weight), but soluble in γ-butyrolactone/N-methyl-2-pyrrolidone/butyl cellosolve In the solvent (weight ratio 71/17/12), 2 parts by weight of hydrazine, hydrazine, Ν', Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane is added with respect to 100 parts by weight of the polymer. And the compound A-1 obtained in the above Synthesis Example 1 as a compound represented by the above formula (1) is added in an amount of 3 · 5 with respect to 100 parts by weight of the polymer plus -43 - 200831562 as a compound represented by the above formula (1). A solution of the weight % and a solution of 6.0% by weight. After thoroughly stirring the solutions, the mixture was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent of the present invention. Speed: 205 rpm, coating time: 1 minute) A solution having a solid content concentration of 3.5% by weight in the liquid crystal alignment agent applied to one surface of a glass substrate having a thickness of 1 mm is composed of an ITO film. On a transparent conductive film, it is dried at 200 ° C for 1 hour to form a film of dry ® film thickness of 〇 8 μιη. Using a sander with a roller wound with rayon cloth, the roller speed is The film was polished at 400 rpm, the table moving speed was 3 cm/sec, and the fluffing length was 〇.4 mm. The liquid crystal alignment film coated substrate was ultrasonically washed in ultrapure water. After a minute, it was dried in a clean oven at 1 ° C for 10 minutes, and then coated on each outer edge 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 binder of alumina balls having a diameter of 5.3 μm is added and a liquid crystal injection port is left, and then the liquid crystal alignment film faces are relatively recombined and pressed to cure the adhesive. Then, through the liquid crystal injection Inlet to substrate A liquid crystal display element was formed by charging a nematic liquid crystal (manufactured by Merck, MLC-622 1 ) and then sealing the liquid crystal injection port with an acrylic photocurable adhesive. The liquid crystal display element was obtained by the method described above. Evaluation of voltage holding ratio and image sticking evaluation. Further, 'the printing property was evaluated by the method described above using a solution having a solid content concentration of 6.0% by weight. Examples 2 to 4 - 44- 200831562 In addition to the above formula (1) The compound was used in the same manner as in Example 1 except that the compound shown in Table 1 was used as the polyimine and polylysine. Example 5 Polyethylenimine (a-2) prepared in Polyimine Synthesis Example 2 was dissolved in a mixed solvent of N-methyl-2-pyrrolidone/butyl cellosolve (weight ratio 5 0/5 0) ' Add 2 parts by weight of N,N,N,,N,-tetraglycidyl-4,4'-diaminodiphenylmethane to 100 parts by weight of the polymer, and add 1 to 10 parts by weight of the polymer. 0 parts by weight of the compound A-1 obtained in the above Synthesis Example 1 as the compound represented by the above formula (1) was prepared as a solution having a solid concentration of 3.5% by weight and a solution of 6.0% by weight. After the respective solutions were thoroughly stirred, they were filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent of the present invention. The method for producing a liquid crystal display device, the method for evaluating a liquid crystal display device, and the method for evaluating the printability of an alignment agent were carried out in the same manner as in Example 1. (Example 6) The same procedure as in Example 5 was carried out except that the substance shown in Table 1 was used as the compound represented by the above formula (1). Comparative Examples 1 to 2 The same procedures as in Example 1 were carried out except that the materials shown in Table 1 were used, and the compound represented by the above formula (1) was not used, except that the polyimine and the polyamic acid were used. Comparative Example 3 The same procedure as in Example 5 was carried out except that the compound represented by the above formula (1) was not added. -45- 200831562 Comparative Examples 4 to 5 In Example 1, except for the polyimine and polylysine, the compounds shown in Table 1 were used, and the compound represented by the following structure (hereinafter referred to as "Compound X" was used. In the same manner as in Example 1, except that the compound represented by the above formula (1) was used. Further, the compound X is synthesized in accordance with the method described in Patent Document 5 (Japanese Patent Application Laid-Open No. Hei.

Comparative Example 6 The same procedure as in Example 5 was carried out except that the compound X was used instead of the compound represented by the above formula (1). Comparative Examples 7 to 8 In Example 1, the materials shown in Table 1 were used except for the polyimine and polylysine, and a polymer having a repeating unit represented by the following structure (hereinafter referred to as "polymer" was used. Y") was carried out in the same manner as in Example 1 except that the compound represented by the above formula (1) was used. The polymer Y was synthesized in accordance with the method described in Patent Document 6 (International Publication No. 2002/1 00949). Its number average molecular weight Μη is 15000, and the weight average molecular weight Mw Μ 30000 〇 -46- .200831562

Comparative Example 9 In Example 5, the same procedure as in Example 5 was carried out except that the polymer Y was used instead of the compound of the above formula (1). All of the above results are listed in Table 1. In addition, in Table 1, "~," indicates that the component in the column is not used. In addition, in the column of the electric κ retention rate

">99%" means that the measured enthalpy exceeds 99%. Table 1

Compound of formula (1) Polyimine polyimine other compound voltage retention rate afterimage printing Example 1 A-1 a-1 b-1 </ br> gt-2 a 〇〇 Example 2 Α-2 a — 1 b-1 — &gt; 99% 〇〇 Example 3 Α-1 a-1 b-2 — &gt; 99% 〇〇 Example 4 Α-2 a-1 b-2 —— &gt;99% 〇 〇Example 5 Α-1 a-2 — — &gt; 99% 〇〇 Example 6 Α-2 a-2 — One &gt; 99% 〇〇 Comparative Example 1 — a— 1 b— 1 — &gt; 99% Δ 〇 Comparative Example 2 - a-1 b-2 - &gt; 99% △ 〇 Comparative Example 3 - a-2 - - &gt; 99% Δ 〇 Comparative Example 4 - a-1 b - 1 Compound X 98% Δ 〇 Comparative Example 5 - a-1 b-2 Compound X 98% Δ 〇 Comparative Example 6 - a-2 - Compound X 98% Δ 〇 Comparative Example 7 - a-1 b-1 Polymer Y 98% 〇X Comparative Example 8 A a-1 b-2 Polymer Y 98% 〇X Comparative Example 9 - a-2 - Polymer Y 98% 〇X -47- 200831562 [Simplified illustration] Fig. 1 shows the residual of the examples and comparative examples A pattern diagram of a unit cell produced by a shadow experiment.

-48-

Claims (1)

Temple Temple 200831562 X. Patent application scope: 1. A liquid crystal alignment agent characterized by containing a compound represented by the following formula (1). (wherein R1 to R3 are each independently a hydrogen atom, an alkyl group or an alkoxy group, and R4 to R7 each independently represent a hydrogen atom, a monovalent aromatic group, a monovalent aliphatic group or an epoxy group; The monovalent aliphatic group of the group, A1 and A2 are each independently a hydrogen atom, a monovalent aliphatic group or a monovalent aliphatic group containing an epoxy group, and η is an integer of from 1 to 100). 2. The liquid crystal alignment agent according to claim 1, wherein in the formula (1), Ri to R3 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms. The oxy group, A 1 and A 2 are a hydrogen atom. 3. The liquid crystal alignment agent of claim 1, wherein in the formula (1), R1 to R3 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms; The oxy group, R4 to R7 are a monovalent aliphatic group containing an epoxy group, and each of A1 and A2 is independently a hydrogen atom or a monovalent aliphatic group containing an epoxy group. 4. The liquid crystal alignment agent of claim 1, wherein in the formula (1), R1 to R3 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms; The oxy group, R4 and R6 are monovalent aromatic groups. R5 and R7 are a hydrogen atom or a monovalent aliphatic group, and each of A1 and A2 is independently a hydrogen atom or a monovalent aliphatic group. The liquid crystal alignment agent of the first aspect of the invention, wherein, in the formula (1), R1 to R3 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a carbon number of 1 Alkoxy groups of 1-6, R4 and R6 are monovalent aromatic groups, R5 and R7 are a hydrogen atom or a monovalent aliphatic group containing an epoxy group, and A1 and A2 are each independently a hydrogen atom or contain a ring. A monovalent aliphatic group of an oxy group. 6. A liquid crystal alignment agent comprising a polylysine obtained by reacting a compound represented by the following formula (I5) with a tetracarboxylic acid dianhydride, (wherein R1 to R3, A1 and A2 and η are the same as in the above formula (1)). The liquid crystal alignment agent of any one of Claims 1 to 6, which further contains a polyamic acid comprising a repeating unit represented by the following formula (I-1) and contains the following formula (I - 2) at least one selected from the group consisting of polyimines of the repeating unit, / HOOCx /COOH -Vhnoc^ ΌΟΝΗ—Q1 (wherein P1 is a tetravalent organic group and Q1 is a divalent organic group), -50- 200831562 (In the formula, P2 is a tetravalent organic group, and Q2 is a divalent organic group). 8. The liquid crystal alignment agent of claim 7, which comprises a polylysine comprising a repeating unit represented by the above formula (I-1) and a polyfluorene comprising a repeating unit represented by the above formula (I-2) Amines, and these polyamic acids and polyimines are synthesized from tetracarboxylic dianhydrides and diamines including 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. A liquid crystal display element comprising a liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 8.