TW201231505A - Liquid crystal alignment agent, liquid crystal alignment film and a liquid crystal display element, and compounds and polymers used in manufacture of those - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent, which is used in obtaining a liquid crystal display device having high voltage retention rate under high temperature environment and excellent low residual image property. The liquid crystal alignment agent contains at least one polymer which is selected from the group consisting of polyamic acid and imidization polymer thereof which are obtained by reacting of tetracarboxylic dianhydride and diamine. As the above-mentioned polymer, the polymer having a structure which is represented by following formula (1) is included.

Description

201231505 VI. Description of the Invention: [Technical Fields of the Invention]: Compounds and polymers such as an oriented agent, a 9-crystal alignment film, and a liquid crystal.

The present invention relates to a liquid crystal element, and a high temperature which is set in the summer when it is used in the manufacture of televisions, car navigation systems, and the like. Therefore, it is desired to develop a liquid crystal display which exhibits high-quality display properties and exhibits low residual afterimage characteristics, and requires liquid crystal display elements to be electrically connected to a direct current voltage even at a high temperature ring rate. % Valley easy to remove. For development, it is a special performance for voltage retention and residual DC. On the other hand, in the case of a low number of cases, the ions in the liquid crystal are excellent in low afterimage characteristics and high power. Today, liquid crystal displays are used in various types of machines such as mobile phones, and are used in various products. For example, the use of a car navigation environment and the long-term use of a liquid crystal display, in a high temperature environment while simultaneously displaying for a long time, the table. In addition, in order to obtain a liquid crystal display element having such a liquid crystal display element, it is possible to maintain a high voltage holding radiation accumulation (residual DC) and accumulate a liquid crystal alignment film afterimage which has a great influence on such a liquid crystal display element. The alignment film having good characteristics increases in density, and it is difficult to produce an alignment film which exhibits a pressure retention ratio. In order to solve such a problem, various proposals have been made for forming a liquid crystal alignment agent for a liquid crystal alignment film (for example, refer to Patent Document 1 or Patent Document 2). Patent Document 1 proposes a scheme of a liquid crystal alignment agent. The liquid crystal alignment agent comprises: a diamine having four primary amine groups in the molecule and a nitrogen atom other than the primary amine group, and a tetracarboxylic dianhydride. Reaction

S -4- .201231505 The ruthenium iodide contains a voltage in a concentration obtained by a 4,4′-di reaction. PRIOR ART DOCUMENT Patent Document Patent Document 1 Patent Document 2 [Invention] In recent years, components The present invention is superior to the material under high performance conditions. The present invention is useful for obtaining the low afterimage characteristics superior to the liquid crystal alignment and provides for use in order to solve the in-depth study. The present invention provides a component or a compound. Further, in Patent Document 2, a liquid crystal alignment agent such as a diamine represented by an amine-vinylamine and a tetrarubic acid is proposed to improve the retention and low afterimage characteristics. 。 特 开 1 1 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 405 Therefore, a liquid crystal alignment film material which is expressive is sought. Based on the above-mentioned deep questions, its main purpose is to exhibit a high voltage retention rate in a liquid crystal display element in a southern temperature environment; the composition of the agent 'useful new compound and the liquid crystal alignment film produced by Poly The liquid crystal shows the problems of the above-mentioned prior art, and the present invention has thus been found to complete the present invention by polymerizing a polylysine having a structure of a liquid crystal alignment agent and a brewing imidization thereof. Specifically, a liquid crystal alignment agent, a liquid crystal alignment film, a liquid, and a polymer. The use of polyacrylic anhydride dianhydride 13⁄4 warm cyclocrystals shows that the stricter ratio is to provide both the composition and the components. Human-containing compound, 'by crystal display

S -5-.201231505 According to the present invention, a nu-containing phthalic acid and a gf imidized polymer selected from the group consisting of tetracarboxylic dianhydride* The group h and the constitutive compound have a structure represented by the following formula (1), and the polymer 7

a *(1) oxy group or a film of each of them is used alone, and the pressure is maintained by the liquid crystal even when it is used in combination (two atoms, a carbon number of 丨~6), and the burning is 0~3 In the case of an integer, ... or 3, a plurality of R1 have the above definitions. "*" indicates a connection key. From the liquid crystal alignment agent of the present invention, a liquid crystal alignment liquid crystal alignment film system can be produced for obtaining high electric power in a high temperature environment. A liquid crystal display element having excellent rate and low afterimage characteristics. Further, by using the liquid crystal alignment film of the present invention, a liquid crystal display element can be manufactured, and the display element can maintain a high-quality display in a high-temperature environment, and can also be used for long-time display. In the present invention, as the diamine, an article represented by the following formula can be used. More specifically, as a in the following formula (2), it can be independently stretched or substituted. Phenyl compound,

(?1L In the formula (2), 'A each independently is a single bond, a methylene group, an alkylene group having 2 to 6 carbon atoms, a phenylene group, a naphthyl group, an n-pyridyl group, and a pyrimidinyl group. Or at least one of the hydrogen atoms possessed by the carbon atom may be substituted. B is each independently a single bond, _c〇-, -COO- or _c〇-NH-.

S -6- 201231505 is a tooth atom, a broken atom, 4 m is an integer of 0 to 3, and m is 2 or 3. In the case of an alkyl group, an alkoxy group or a gas fluorenyl group of J 6 , a plurality of Ri are each independently provided. Further, according to the present invention, a liquid crystal alignment film composed of the above-mentioned liquid crystal supported by the upper layer is provided, and The liquid crystal is provided with a 4-shaped member. These liquid crystal alignment films and liquid crystal display units are not suitable for use in liquid crystal display elements. In the IPs according to the present invention, the following formula 1 can be provided, and a compound which makes the compound and the tetradecanoic acid are not provided. Another poly-proline and its ruthenium imidized polymer), the polymer to which the anhydride is reacted ((3), (R2)r, where 'B is independently _C0_NH" R1 and self-independently Is a ^, -(3)-, _C〇〇- or an alkyl, alkoxy or fluoroalkyl group. The city is a 〇~^ slave atom number is 1~6, and a plurality of R1 each independently have the above-mentioned shark The number is an integer when the claw is 2 or 3, and when there are a plurality of R2, this is also defined by 0 to 4. The two opposites each independently have the above-mentioned [Embodiment] The reaction product of the tetraacid dianhydride and the diamine At least any of the polymerization agents will be described in detail. The liquid crystal alignment agent of the present invention comprises polyphosphoric acid and its quinone imidized polymer. The following 'liquid crystal alignment of the present invention <polyglycine> At least one part of the liquid crystal alignment agent of the present invention contains a structure represented by the following formula (1): (1) 201231505 (Rl)m In the formula (1), 'R 疋 halogen atom, carbon atom Number ^ A ^ . θ Λ an alkyl group having 1 to 6 alkyl groups, an alkyl group or a chaotic alkyl group, an integer of m疋〇~3, ^ 6 ^ ^ L « , a horse 2 or 3, a plurality of R1 independently In the above-mentioned formula (1), R1 in the above formula (1), as a halogen atom «@2, a fluorine atom, a ruthenium atom, a bromine atom, a ruthenium atom, etc. may be mentioned. The number of carbon atoms is 1~ The alkyl group of 6 may be θ ± A ± , b ^ ^ 疋 linear, or may be branched, specifically s ^ ^ , ethyl, n-propyl, isopropyl, n-butyl Base, isobutyl, di-A dibutyl, tert-butyl, n-pentyl, :, pentyl, neopentyl, n-hexyl, isohexyl, etc. As R1, the number of carbon atoms is 1 to 6诂# @ n β 扪 烷基 烷基 , @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 @ 至少 @ @ @ @ The alkoxy group having a ruthenium atom number of 1 to 6 is exemplified by a group in which the alkyl group having 1 to 6 atomic number of the carbon sulfonate is bonded to a milk atom, specifically ethoxylated. The base is exemplified by an integer such as methoxy, = 〇 〜3, preferably "an integer of 〜2, more preferably 〇. In addition, when 'm is 2 or 3', a plurality of R1 can be divided. Similarly, the binding position of the two NH*s in the pyridine ring of the above formula (1) is not particularly limited, and the ninth, the 6th, the 2, 5th position may be 2, 4-position, 3, 5-position, etc. Among them, the binding position of '2 NH groups is preferably 2, 6-position or 24-bit, more preferably 2, 6-position.

S "8 ~ 201231505 In order to obtain a polylysine having a structure represented by the above formula (1), for example, a tetracarboxylic dianhydride having a structure represented by the above formula (1) may be reacted with a diamine or a tetracarboxylic acid. The acid dianhydride is reacted with a diamine having the structure represented by the above formula (1). Among them, the latter is preferred. [Tetracarboxylic dianhydride] The tetracarboxylic dianhydride used for the synthesis of the polyamic acid in the present invention may, for example, be an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride or an aromatic tetra Acid dianhydride and the like. Specific examples of the aliphatic tetracarboxylic dianhydride include, for example, 1,2,3,4-butanetetracarboxylic dianhydride; and examples of the alicyclic tetracarboxylic dianhydride include 1, 2,3,4-cyclobutanetetradecanoic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3&, 4,5,91>-six rats-5-( Tetranitro-2,5-dioxo-3-°f. South base)-Qinda [l,2-c]n-fu-1,3-dione, 1,3,3a,4,5,9b -hexahydro-8-mercapto-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-(:]furan-1,3-dione, 3-oxo Miscellaneous mourning [3 · 2.1 ] 辛烧 - 2,4 -2 1 with -6-spiro - 3'-(tetrazole 2', 5'-dioxin), 5-(2,5- Dilactosyl-3-pyranyl)-3 -indolyl-3- lysine-1,2_diphthalic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane- 2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:3,5:6-dianhydride, 2,4,6,8- Tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0'6]undecane-3,5,8,10 - tetraketone, etc., 13,23,411,511-cyclohexanetetracarboxylic dianhydride, 111,28,43,511-cyclohexanetetradecanoic dianhydride, etc.; as aromatic tetracarboxylic dianhydride Examples thereof include pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-benzophenonetetracarboxylic dianhydride. In addition, -9 - 201231505 can be used in Japan -9 - 201231505. Tetracarboxylic acid dianhydride. In addition to the above, the above tetracarboxylic dianhydride may be used alone or in combination of two or more. One is for the above-mentioned polyamic acid, which is more than the lipid. The nuclear four-recorded brewing-fresh ^ ι± is a mono-anhydride. In this case, the ratio of the alicyclic tetracarboxy-sodium needle is used in comparison with the above-mentioned poly-proline acid synthesis - the total of the acid dianhydride The amount is preferably from 10 to 100 mol%, more than 〇5 〇lOOmol / 〇, and the step is preferably from 8 〇 to 1 〇〇 and then 1%. By repeating the range, the 诰 诰 曰 曰 曰 疋 疋 疋Immediately at the ancient (four) factory, the display element can maintain the door in a high temperature environment...1 retention rate' while making the low afterimage characteristics more. [Diamine] The diamine used to synthesize the polylysine in the present invention is preferably described. Compound represented by formula (2)^ (Hereinafter,% as the diamine (ΕΚ1)) diamine,

(2) Η2Ν - A—B—a β_α~Νη ^ (2), each independently being a single bond, a methylene group, a carbon atom or a two-extension group, a phenyl group, a naphthyl group, and a stretching group. ° ratio. At least one of the hydrogen atoms possessed by the carbon atom may be substituted by a base group, a (4) group, and a morphine group. B is each independently a single bond, _c〇...c〇〇· or _c〇nh_. 11 and m are the same as the definitions of R1 and m of the above formula (1), respectively. As the Ri in the above formula U), the description of the above formula (i) mRi can be directly applied. Further, the bonding position of the NH group in the pyridine ring can be directly applied to the description of the above formula (1).

S -10- 201231505 β 疋 single bond, -C〇_, -coo- or -C0_NH_, two B in formula (2) may be the same or different. B is preferably a single bond. In the above formula (2), A is as follows: as an alkylene group having 2 to 6 carbon atoms, it may be a straight-chain or a branched chain, for example, an ethyl group, an anthracene, a 3-propyl group. , hydrazine, 2 propyl, 1 'butyl butyl, etc.; soil ' as a stretching phenyl group, which may be exemplified by 1,3-extension, fluorene, phenyl, etc. And 1,4-naphthyl 'i, which is a pyridyl group, which may be exemplified by 2,4-extended pyridyl, 2 疋 疋, etc.; and as a pyrimidinyl group, 2, 5 The pyrimidinyl group and the like are exemplified; as the exotriene group, a 2,4-extension trisyl group or the like can be exemplified. Atom:: a substituent which these groups may have, and a group such as a group may be listed. Other than the halogen atom such as a halogen atom and a cyano group, the above formula R1 is preferably a substituted or unsubstituted phenyl group in A. The product (hereinafter, the fluorene diamine preferably contains a compound represented by the following formula (3). The present invention is referred to as a diamine (1) small 1)). The ruthenium containing diamine (m) as a crystal molecule can be easily induced in the formed liquid crystal alignment film, and has an interaction between the benzene rings to make the liquid crystal alignment property.

S -11- 201231505 In the formula (3), 'B is independently a bond, -CO-NH-. R2 is each independently a halogen atom, a carbon group having a carbon number of 丨^, an alkoxy group or a fluoroalkyl group. r is each an integer of 〇~4, and when R2 is plural, these R2 each independently have the above definition. The sub-forms are the same as the definitions of f and m of the above formula (1), respectively. m is the same as the above-exemplified R2 of the above formula (3). The enthalpy of the description of U) is preferably 〇 〜 2, more preferably 〇. · In the benzene ring bonded to B, the binding site of the primary amine group is defined, but preferably it is 3_position or 4/0 for 0, and there is a special ruler of the parent class 1 /1 as a diamine (D·1) Specifically, it is preferably 26, 雔 ', , _ bits. Amino) ° bite, 2,4, bis(4-aminoanilino) ton. 2, 2 (4_Aminoanilino)pyridine, 2,4·bis(3-aminoanilino)pyridine, 'this oxime (3-aminobenzene is preferably 2,6-double (4_) Aminoanilino)pyridine. By at least one of the special 'in particular, in the main chain of poly-proline, σ _ _ ” ” έ έ έ έ , , , , , , , , , , , Therefore, it is considered that when the liquid crystal liquid crystal display element formed is used, the voltage retention property and the low afterimage characteristic in the case of the 亓 Λ & && As a poly-proline which is used in the synthesis of the present invention, it is possible to use only the diamine (D-丨) shown in the above formula (2), or (D-υ). And other diamines. The diamine is used as the other diamine which can be used herein, and the following - ΑΛ tu TU exemplifies, for example, the aliphatic diamine, the alicyclic diamine, and the aromatic diamine group. As a specific example of these, Bayi's A month's sickle can be cited as Feng Yue's fat diamine, such as hydrazine, m-xylenediamine-butyl-, propylenediamine, J one , pentamethylenediamine, hexamethylenediamine, etc.; 201231505 as an alicyclic diamine such as 1,4-diaminocyclohexane, 4,4'-arylene di(cyclohexylamine), 1,3-double (amino fluorenyl) cyclohexane or the like; as an aromatic diamine, such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl decane, 4, 4 '-Diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimercapto-4,4'-diaminobiphenyl, 4,4'-diamino-2 , 2'-bis(trifluoromethyl)biphenyl, 2,7-diaminostilbene, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminobenzene) Oxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2 - bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenyldiisopropylidene)bis(aniline), 4,4'-(m-phenyldiisopropylidene) double (aniline), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4 -diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminol 11 丫π定, 3,6-diaminol °K, N-methyl-3,6-di Amino σ card. Sit, Ν-ethyl-3,6-diaminocarbazole, oxime-phenyl-3,6-diaminocarbazole, oxime, Ν'-bis(4-aminophenyl) )-benzidine, anthracene, Ν'-bis(4-aminophenyl)-indole, Ν'-dimethylbenzidine, 1,4-bis(4-aminophenyl) piperene, 3,5 -diaminobenzoic acid, dodecamidyl-2,4-diamino stupid, tetradecyl lactyl-2,4-diaminobenzene, pentadecyloxy-2,4-diamine Benzobenzene, cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, fourteen Alkoxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, cetyloxy-2,5-diaminobenzene, octadecyloxy-2 , 5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-2,4-diamine Benzobenzene, cholestyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid, wool retentate, 3,6-bis (4-

S -13- 201231505 Aminobenzoquinone-based oxy)choline, 3,6-bis(4-aminophenoxy)cholesteridine, 4-(4'-trifluoromethoxybenzonitrile Cyclohexyl·3,5•diaminobenzoic acid vinegar, 4-(4,-tris-mercaptophenyloxy)cyclohexyl_3,5-diaminobenzoate, 1,1 - bis(4-((aminophenyl)indenyl)phenyl)-4-butylcyclohexane 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-heptyl Cyclohexane, 1, bis(4-((aminophenoxy)indolyl)phenyl)-4-heptylcyclohexane, fluorene-bis(4-((aminophenyl)indenyl) Phenyl)_4_(4-heptylcyclohexyl)cyclohexane, 2,4-diamino-N,N-diallylaniline, 4-aminobenzylamine '3-aminobenzylamine, 1 -(2,4-diaminophenyl) brigade _4_capric acid, 4_(味琳_4-yl) benzene-1,3-diamine, anthracene, 3·bis (N_(4·amino group) Phenyl)piperidinyl)propane, α-amine

'2c+1 benzyl-ω-aminophenylalkylene and a compound represented by the following formula (A-1); H2N>/=\ (A-1) Η2Ν·丨 and -xl,i (Al Wherein 'X and Xn are each a single bond, _〇_ or {(10)_, rI is an alkylene group having 1 to 3 carbon atoms, a is 〇 or 1, b is an integer of 〇~2, and c is 1~ The integer 'n' of 20 is 〇 or 1. However, when 3 and 5 are not the same, 〇β is used as the diamine organooxane, and examples thereof include hydrazine, 3_bis(3-aminopropyl)-tetradecyldioxane, and the like; Any of the above-described diamines described in Japanese Laid-Open Patent Publication No. 2010-97188. The divalent group represented by the above formula (a-ι)-χΜκΛχ11) is preferably an alkylene group having 1 to 3 carbon atoms, 〇_, ICOO- or i〇-CH2CH2-0- (wherein 'The bond with "*" is bonded to the diaminophenyl group). Specific examples of the radical CCH2C + 1- include, for example, anthracenyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl , Zheng 10201231505 n-tetradecyl, n-pentadecyl, n-hexadecyl, jadecyl, n-octadecyl, n-nonadecyl, n-icosyl and the like. The two-stage amine groups in the diaminophenyl group are preferably 2, the heart position or the 3,5-position relative to the other groups. Specific examples of the compound represented by the above formula (A-1) include compounds represented by the following formulas (A-1-1) to (A-i-3), and the like.

(A-1-1)

(A-1-2) (A-1-3) The ratio of the above diamine (EK1) to the total amount of the diamine maintains a high voltage holding ratio in a high temperature environment and further improves low afterimage characteristics. From the viewpoint, it is preferably from 10 to 100 m〇1%, more preferably from 50 to 100 m〇i%, and further preferably from 80 to 100 mol%. <Molecular weight modifier> In the synthesis of polyamic acid, a terminal modified polymer can also be synthesized by using a suitable molecular weight modifier together with the above-described tetracarboxylic acid diamine and diamine. By forming the terminal-modified polymer, the coating property of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention (printability, and 0 is a molecular weight modifier, and examples thereof include acid monoanhydride, monoamine compound, and single Isocyanate compound, etc. As a specific example of these,

S -15- 201231505 respectively, as an acid monoanhydride, such as maleic anhydride, liver phthalate, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic acid needle Succinic anhydride, hexamethylene phenolic anhydride, etc.; as a monoamine compound, such as aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine 'n-heptylamine, n-octylamine, etc.; as a monoisocyanate compound' For example, phenyl isocyanate, naphthyl isocyanate, etc. The ratio of use of the molecular weight modifier is preferably 20 parts by weight with respect to the total of 1 part by weight of the four acid dianhydrides and diamines used. Hereinafter, it is more preferably 10 parts by weight or less. <Synthesis of Diamine (D-1-1)> The novel compound diamine (D-1-1) represented by the above formula (3) can be suitably produced by a conventional method of organic chemistry. Specifically, in the above formula (3), when B is a compound of a single bond, for example, 'the compound (M-1) represented by the following formula and the compound (M-2) are first reacted to obtain an intermediate ( ··3) (Refer to the following reaction formula (I)), (R1)m ο2ν (R2);

B—NH2 + Y (M-1) ♦ (R^m

O2n (R2V

(M-2)

b<T (l) (3), iodine is preferably wherein Y is a halogen atom. The definitions of R, R2, m and r of R1 and R2 are the same. Examples of the halogen atom of Y include a bromine atom, a chlorine atom, and a fluorine atom. In these terms, from the viewpoint of reactivity, the side atoms.

S-16-201231505 The reaction of the reaction formula (i) is preferably carried out by using a catalyst such as a palladium catalyst in the presence of a base. In this case, it is preferred to further use a phosphine compound as the catalyst used in the above reaction, and it is exemplified. For example, ginseng (dipyridyl) acetone dipalladium, Pd(PPh3)4, PdCl2(PPh3)2, Pd(OAc)2, ginseng(dibenzylideneacetone) dipalladium apo composition, and the like. Examples of the phosphine compound include 2-(di-tertiary butylphosphino)biphenyl, stilbene (tri-butyl)phosphine, tricyclohexylphosphine, 1, fluorene, bis (di-tertiary) Ferrocenyl)ferrocene, 2,2'-bis(di-tertiary butylphosphino)_l5l, _binaphthyl, 2-di-tertiary butylphosphino-2',4,6,- Triisopropylbiphenyl, 2-(dicyclohexylphosphino)biphenyl, and the like. The base may, for example, be a reaction of the reaction formula (I) such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium ethoxide, sodium t-butoxide or sodium acetate. The temperature can be appropriately set according to the reaction method, and is preferably -15 to 15 (rc, more preferably 80 to 15 (rc.) The organic solvent used for the reaction may, for example, be toluene or the like.

(3) The compound diamine (D-b is carried out under the original conditions,

rO~B'K_0~NH'B-Q > Go. Thus, the above formula can be obtained by referring to the following reaction formula (π)), wherein R1, R m and r have the same definitions. The reaction of the formula and the reaction formula (II) with Ri, Rz, and 201231505 in the above formula (3) is carried out by using a catalyst such as nickel, ruthenium-iridium, Pt〇2, or Pd(OH)2, preferably at - Push down at 20~150°c, - Γ 仃 ' is more preferably carried out at 〇~120 °C. As a solvent used in the reaction,

T is exemplified by, for example, tetrahydrofuran, methyl, N,N-dimethylformamide, N^^0N,N-dimethylacetamide, 1-methyl-2-pyrrolidone or the like. <Synthesis of Polylysine> The polyglycine in the present invention, for example, ± j is preferably contained in the compound of the above formula (2). a compound diamine which is obtained by reacting the above-mentioned tetracarboxylic dianhydride with < 0 Φ # m Zn ^ ^ as a tetracarboxylic dianhydride used in the combined reaction of polyaminic acid and The amine group of two equivalents of diamine, the ":: two" of Ming Erxuan, more preferably 0.3 to 1-2, and more preferably becomes 〇.2~2 polylysine, relative to the ratio of 1 equivalent. The synthesis reaction is preferably in the presence of ::::. The reaction temperature at the time is preferably carried out in an organic catalyzer. This. In addition, it is better to change from 0 to 24 hours. . ~ at hours. More preferably, it is 0.5 to 12. Here, as an organic solvent, a solvent, phenol, and a derivative thereof are, for example, an aprotic electrode or the like. ® 曰 ether, dentate hydrocarbon, specific aprotic polarity, and Rongli, which are these organic solvents, are listed as

Lingling agent', for example, Ν-甲其0 L dimethyl acetamide 7丞_2-pyrrolidine S, N,N- '-methylcarbamamine, -Tallon lactone, tetramethyl urea, ' Speaking well, a f-based mill, γ_butyl', octamethylphosphoric acid triterpene 作为 · as the above-mentioned benzene-producing organisms, such as phenol, etc.; hydrazine, xylenol, halogen 201231505 as the above alcohol, for example Sterol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc.; as the above ketone, such as acetone, methyl ethyl ketone, A Isobutyl ketone, cyclohexanone, etc.; as the above ester, such as ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethoxypropyl propionate Ester, diethyl oxalate, diethyl malonate, etc.; as the above ether, such as diethyl ether, ethylene glycol decyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol Propyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol didecyl ether, diethylene glycol diethyl ether, diethyl Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, etc.; as the above-mentioned _hydrocarbon, for example, two Chloroform, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-diphenyl, etc.; as the above hydrocarbons, such as hexane, heptane, octane, Benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and phenol and a derivative thereof (the organic solvent of the first group), or an organic selected from the first group is preferably used. One or more solvents selected from the group consisting of alcohols, ketones, S, ethers, halogenated hydrocarbons, and hydrocarbons (the organic solvent of the second group). In the latter case, the ratio of the organic solvent used in the second group is preferably 50% by weight or less, more preferably 50% by weight or less based on the total of the organic solvent of the first group and the organic solvent of the second group. 40% by weight or less.

S -19- 201231505 The amount of the organic solvent (a), preferably the total of the tetracarboxylic dianhydride and the diamine (b), is 〇1 to 50% by weight based on the total amount of the reaction solution (a + b) The amount of ruthenium is as above, and a reaction solution formed by dissolving polylysine can be obtained. The reaction solution can be used as it is for the preparation of a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after the polyamic acid contained in the reaction solution is isolated. Alternatively, after the isolated polyamic acid is refined, it is used to prepare a liquid crystal alignment agent. The isolation and purification of polylysine can be carried out by a conventional method. <醯iimylated polymer> The ruthenium iodide polymer (polyimine) in the present invention can be obtained by subjecting the above-mentioned synthesized polyglycine to dehydration ring-opening oxime. In this case, the above reaction solution formed by dissolving polylysine may be directly used for the dehydration-closure reaction; or may be used after the poly-proline acid contained in the reaction solution is used for dehydration ring closure reaction. Alternatively, the isolated polyamic acid is refined and used for a dehydration ring closure reaction. The polyimine in the present invention may be a complete ruthenium imide of a proline structure in which the proline of the precursor has a glycosidic acid structure; or a part of the proline structure may be dehydrated and closed, and the guanamine A partial quinone imide that has an acid structure and a quinone ring structure. The ruthenium imidization ratio of the polyimine in the present invention is preferably 30% or more, more preferably 5 Å to 99%, still more preferably 65 to 99%. The ruthenium imidization ratio is expressed as a percentage, and the ratio of the amount of the ruthenium ring structure to the total amount of the ruthenium acid structure of the polyaniline and the number of the quinone ring structure. Here, a part of the brewing amine ring may be an isoindole ring. «··»

P -20- 201231505 Method A, " Dehydration ring closure of bupropion, preferably by heating poly-proline, dissolving polylysine in an organic solvent, in which the agent and dehydration ring-closing catalyst , according to the need to heat the square = ', preferably by the latter method. An acid needle such as acetic anhydride, propionic acid or trifluoroacetic acid anhydride can be used as the dehydrating agent by adding a dehydrating agent and a dehydration ring-closure catalyst to the polyamic acid solution. The amount of the dehydrating agent is preferably 0.01 to 20 m〇l relative to the structure of the chiral acid of the ruthenium (tetra) poly-:-acid. As the dehydration, a secondary amine such as pyridine, trimethylpyridine or dipyridylethylamine is exemplified. The amount of the dehydration ring-closing catalyst is preferably 〇1 to 1〇m〇l relative to the dehydrating agent of 丨m〇1. The organic solvent used in the dehydration ring-closure reaction is exemplified as an organic solvent which is not exemplified for the synthesis of polyglycolic acid. The reaction temperature of the dehydration ring-closure reaction is preferably 〇I80 c, more preferably 10 to 15 (rc. The reaction time is preferably 丨〇~ι2〇h), more preferably 2.0 to 30 hours. a reaction solution of ruthenium imine. The reaction solution can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after removing a dehydrating agent and a dehydration ring-closing catalyst from a reaction solution; For preparing a liquid crystal alignment agent; or after refining the isolated polyimine, for preparing a liquid crystal alignment agent. These purification operations can be carried out according to a conventional method. <Solid solution viscosity of the polymer> The polyaminic acid or quinone imidized polymer of the present invention (hereinafter also referred to as a specific polymer) is preferably a solution having a temperature of 20 to 800 rnpa.s when it is made into a solution having a concentration of 丨〇% by weight. Viscosity, more preferably -21 - 201231505 is a solution viscosity of 30 to 500 mPa.s. In addition, the solution viscosity (m Pa a · s ) of the above poly-Q Q is a good solvent for using the polymer (for example, v, j-lactone, N-mercapto- 2-pyrrolidone or the like) A polymer mash having a concentration of 1% by weight is prepared and measured at 25 ° C using an E-type rotational viscometer. <Other Additives> The liquid crystal alignment agent of the present invention contains The specific polymer as described above may contain other components as needed. As the other component, for example, a polymer other than the specific polymer or a compound having one less epoxy group in the molecule may be mentioned (hereinafter referred to as "epoxy compound,", = decane compound, etc. g [other polymers] Other polymers can be used to improve solution properties and electrical properties. The other polymers are polymers other than specific polymers' as TJ For example, a poly-proline which is obtained by reacting a diamine which does not contain the compound represented by the formula (2) and tetraterpenoids (hereinafter referred to as '(4) "other polyamine amine dianhydride other polyimine" Polyacetamide, polyester, polyamine, polyimine (hereinafter referred to as >) formed by dehydration of other polylysine, polyfluorene oxide, cellulose derivative, polycondensation Acid, poly"

^ The present ethylene derivative, B styrene-phenylmaleimide derivative, poly", poly(I)methyl propylene oxime, etc., preferably other polyaminic acid or other polyphthalamide Amines are specialized in lysine. In addition, as a tetrahydro acid dianhydride for the formation of other polyamines = 匕 醯 imine, and a second-time grazing, it is possible to formulate a compound of a specific polymer. + is used to add other polymerization enthalpy in the liquid crystal alignment agent, and the yield can be 'the ratio of the mixing ratio relative to the total amount of the polymer in the liquid a aligning agent, and the gestational parent is 5 〇% by weight.

S •22- 201231505 下 'More preferably 〇 】 】 舌 。. / . .40 heavy /. Further preferably, it is 01 to 30 weight 0/.

[Epoxy compound J as the upper oxime epoxy compound may, for example, be diglycidic acid, blister 7 f styrene 1 ethyl alcohol diglycidyl ether, propylene glycol diglycidyl hydride 2: diol diglycidil light , polypropylene glycol diglycidyl transfer, alcohol diglycidyl hydrazine, hexanediol diglycidyl ether, glycerol-glycidyl ether, trimethylolpropane triglycidyl ether, 2 2 neopentyl glycol diglycidyl ether, n , n, n,, n, _ tetra-toluene toluenediamine, s-glycidylaminomethyl): hexene N, N, N, N'-tetraglycidyl _4 · _ one, one Amino-monomethane, glycidyl-nodal amine, n,n-diglycidylaminomethyl hexane, N,N-diglycidyl-cyclohexylamine, etc. are preferred. By. When the epoxy compound is added to the liquid crystal alignment agent, the mixing ratio of the polymer is preferably 40 parts by weight or less, more preferably the weight of the polymer, based on the total amount of the polymer contained in the liquid crystal alignment agent. Share. </ RTI> [Functional decane compound] Examples of the functional decane compound include, for example, a 3-propyl propyl sulfoxide, a 3-amino group, a triethoxy aryl group, a bis-decyloxy decane. , 2·Aminopropyltriethoxydecane, &amp;Aminoethylaminopropyltrimethoxydecane,Ν-(2-Aminemethine) Aminopropylmethyldimethoxyxanthine , glycosylpropyl three: oxy-V: 3 · ureidopropyl triethoxy decane, hydrazine, ethoxycarbonyl carbonyl amine ^ trimethoxy shi Xiyuan, Ν ethoxy group _3_ amine Propyl triethoxy hydrazine _ diethyl hydrazino propyl propyl triethyl ethamine, \ _ trimethoate

S -23- 201231505 Carboxyalkyl propyl triethylidene triamine, 1 〇 _ tridecyloxycarbazinyl-1,4,7-diazadecane, 10-triethoxycarbamyl _ 1,4,7-triazaindene, 9-trimethoxycarbamimidyl-3,6-diazaindolyl acetate, 9-monoformylmethylcarbazide _3,6-nitrogen Heterohydrazide acetate, 9-triethoxycarbamimidyl-3,6-diazaindolyl acetate, 9-trisethoxydecylalkyl-3,6-diazepine ruthenium Ester, 9·triethoxycarbamidomethyl-3,6-diazepine methyl ester 'N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-I-aminopropyl Triethoxy decane, N_phenyl_3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, glycidyloxymethyltrimethoxy Decane, glycidyloxymethyltriethoxydecane, 2-glycidyloxyethyltrimethoxydecane, 2-glycidyloxyethyltriethoxydecane, 3-glycidyloxyl Propyl trimethoxy zebra, 3-glycidyloxypropyl triethoxy zebra and the like. When such a functional decane compound is added to the liquid crystal alignment agent, the mixing ratio thereof is preferably 2 parts by weight or less, more preferably 2 to 0.2 parts by weight, based on the total mass of the polymer. [Organic solvent] The liquid crystal alignment agent of the present invention is preferably an organic solvent which is used as a liquid crystal alignment agent of the present invention by dissolving a specific polymer and other additives which are required to be mixed as needed, and is preferably contained in an organic solvent. For example, N-decyl·2·pyrrolidone, γ-butyrolactone, γ-butylide, hydrazine, fluorenyl-dimercaptoamine, ν, Ν-dimercaptoacetamide, 4-经4-methyl-2-pentanone, ethylene glycol monodecyl ether, butyl lactate, butyl acetate, decyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol sulfhydryl Ether, ethylene

S -24- 201231505 Ethyl ethyl n-butyl ether acetate glycol ether acetate isoamyl ester, carbon-based liquid or other than the range of considerations to the substrate or the percentage of liquid crystal that is not full: film, this Hey. Special cloth LCD. In the case. The scope of the scope of use. Ether 'Ethyl alcohol n-propyl ether' Ethylene glycol isopropyl ether, ethylene glycol bond (butyl cellulolytic), ethylene glycol dimercaptopurine, ethylene glycol ethyl: , diethylene glycol dimethyl (tetra), diethylene glycol diethyl ether, bis-methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ethyl alcohol monoethyl ether acetate , diisobutyl ketone, propyl, isoamyl isobutyrate, diisoamyl ether, propylene glycol diacetate, and the like. &quot; can be used alone or in combination. = (4) component concentration of the alignment (the ratio of the total weight of the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) :: volatility or the like is appropriately selected 'preferably 1% by weight. That is, the liquid daily alignment agent of the present invention is coated as follows. The coating = coating is a coating film for forming a coating film of a liquid crystal alignment film by heating, but at this time, the film is aligned at a concentration. On the other hand, when it is difficult to obtain a good coating film, the film factory "W" has a solid concentration of more than 10%, and it is difficult to obtain a good liquid crystal alignment. The viscosity of the alignment agent increases. The method of deteriorating the characteristics, preferably the solid concentration of the solid component, is a method used for the alignment agent, for example, in the case where the coating-component concentration on the substrate is particularly preferably iy β::, the solid component is made heavy by ink The viscosity of the liquid is (10) one / Ά, and the solid cerium concentration is "5 201231505% by weight". Therefore, it is particularly preferable to set the solution viscosity to a range of 3 to 15 mPa_s. The temperature at which the liquid crystal alignment agent of the present invention is prepared. Preferably, it is 1 〇 5 5 ° C, more preferably 20 to 30 ° C. &lt;Liquid crystal alignment film and liquid crystal display element&gt; The liquid crystal alignment film of the present invention is formed by the above liquid crystal alignment agent. Further, the liquid crystal display device of the present invention has a liquid crystal alignment film formed by the above liquid crystal alignment agent. The operation mode of the liquid crystal display element can be applied to an IPS type or a TN type 'STN type horizontal alignment type' It is suitable for the vertical alignment type of the VA type, and is preferably a horizontal alignment type. Among them, it is particularly preferably applied to the IP S type. Hereinafter, a method for manufacturing the liquid crystal display element of the present invention will be described, and at the same time, The method for producing a liquid crystal alignment film of the present invention will be described. The liquid crystal display device of the present invention can be produced, for example, by the following steps (1) to (3). Step (1) According to the desired operation mode, the substrate used is the same Steps (2) and (3) are common to various modes of operation. L Step (1): Formation of Coating Film First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then, by heating the coated surface, on the substrate A coating film is formed on the machine. (1-1) When manufacturing a 1^ type, a coffee type, or a ¥8 type liquid crystal display element, the two substrates having the patterned transparent conductive film are used as a pair of conductive conductive On the film formation surface, the liquid helium alignment agent of the present invention is preferably applied by a lithography method, a coating method or a mouth ink printing method, respectively, followed by twisting each coated surface... 4^^人w α ... Hewen Qiufu (preferably including preheating (grilling) And a two-stage heating of the firing (post-bake) to form a coating film. -26-

S 201231505 λ as the substrate, for example, glass containing float glass, sodium break, etc.; polyethylene terephthalate, polybutylene dimerate, polymylon, polycarbonate, poly (aliphatic ring) A transparent solar substrate such as a compound hydrocarbon. As the transparent conductive film provided on one side of the substrate, NESA film containing tin oxide (Sn〇2) (registered trademark of PPG, USA) and IT containing indium oxide and tin oxide (In2〇3_Sn〇2) can be used. 〇 film and so on. In addition, in order to a to the patterned transparent conductive film, a method of forming a pattern by photo-etching may be formed by, for example, no-image transparency: after the formation of the electric film;

In the case of an electric film, a method of using a mask having a desired pattern or the like is used. V coating liquid crystal alignment material, in order to make the substrate surface and the transparency and the adhesion of the coating film more 'can be applied to the surface of the substrate, and the surface of the coating film is applied in advance. Compounds and the like are treated before. After coating the liquid crystal alignment agent, the coated surface is preheated (and then fired (post-baked) to form a coating film. The prebaking conditions are, for example, 4 〇 to 1 2 0 C for 0 _ 1 to 5 minutes, The batches of the glutinous rice are best served in the roasting conditions at 12〇~3〇〇〇c, more preferably 150~250 °C, 轫杵&amp; $eight right 5 for 5~200 minutes, more Preferably, the film thickness of the formed film is preferably 0.001 to Ιμιη, more preferably 0.005 to 0.6 μη^ (1 - 2) in the manufacture of IP S. The type, the state a 93⁄4 — - * π / night when the day is not the case, will be set

The transparent lead-shaped pattern of the comb-shaped pattern is coated with the conductive film forming surface of the substrate of the Ik-iA film, and the side of the facing plate on which the conductive film is not provided, respectively, is coated with the present invention

The liquid crystal alignment agent is then heated to form a coating film by adding each of the coated surfaces. The substrate used at this time and the transparent guide amine are used to separate the material, coating method, and coating.

S -27- 201231505 The heating conditions of the front and back of the method and the substrate, and the pattern formation of the transparent conductive film

Coating film. At this time, the film thickness of the formed coating film is the same as that of the above (1-1). The polymer is a polymer of the group 1) and (1-2). In the case where the coating liquid on the substrate is removed by removing the organic solvent, the polymer contained in the liquid crystal alignment agent of the present invention as an alignment film is decylamine. When the acid is a ruthenium-imided polymer having a quinone ring structure and a valine structure, the film may be further subjected to a dehydration ring-closure reaction by heating to form a further yttrium-immobilized coating film. . [Step (2): Rubbing Treatment] When manufacturing a TN type, STN type or IPS type liquid crystal display element, the coating film formed as described above is wound with a cloth formed of a cloth made of fibers such as nylon, rayon or cotton, for example. The rubbing treatment is performed by rubbing in a certain direction to thereby impart the alignment energy of the liquid crystal molecules of the coating film to form a liquid crystal alignment film. Further, in the liquid crystal alignment film, a portion of the liquid crystal alignment film is irradiated with ultraviolet rays to change a pretilt angle of a partial region of the liquid crystal alignment film; or a resist film is formed on a portion of the surface of the liquid crystal alignment film, before and after The rubbing treatment is performed on different kinds of radix, and after the rubbing treatment, the treatment of removing the resist film can improve the viewing angle characteristics of the obtained liquid crystal display element by making the liquid crystal alignment film have different liquid crystal alignment energy in each region. . Further, when the V A type liquid crystal display element is produced, the coating film formed as described above can be used as the liquid crystal alignment film as it is, and the above-described rubbing treatment can be performed. -28-201231505 [Step (3). Configuration of Liquid Crystal Cell] For the substrate on which the liquid crystal alignment film is formed as described above, the rubbing directions of the liquid crystal alignment films of the two substrates are arranged orthogonally or antiparallel to each other to form a liquid crystal cell. . For example, the following two methods can be used to constitute a liquid crystal cell. In the first method, first, the two substrates are arranged opposite to each other, so that each liquid crystal alignment film phase is opposed to each other, and two substrates are sealed using a sealant. The surrounding parts fit together. After receiving the Bodhisattva and Zuoyi+, the filling is filled in the interstitial space divided by the surface of the substrate and the sealant, and the +~^ has a brother's day and the day, and then, through the sealed injection hole, constitutes a liquid crystal cell. - The second method is a method called "〇 邛 邛 邛 邛 ( ( ( ( ( ( ( ( ( 在 在 在 在 在 在 在 在 在 在 在 在 n n n n n n n n n n n n n n n n n n n n n n n For example, an ultraviolet curable sealant is applied, and then a liquid crystal is dropped on the liquid crystal alignment film surface, and then the liquid crystal alignment film is bonded to the other substrate in the opposite direction. Then, the entire surface of the substrate is irradiated with ultraviolet light to cause a sealant. As the post-sealing agent, for example, an epoxy resin containing a curing agent and an alumina ball as a separator may be used. Examples of the liquid crystal may include nematic liquid crystal and smectic liquid crystal; For the nematic liquid crystal, for example, a Schiff type liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenyl cyclohexane can be used. Liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal 'cubic alkyl liquid crystal, etc. Further, in such liquid crystals, for example, cholestyl chloride and cholesterol can be further added and used. Cholesteric liquid crystals such as phthalate esters, cholesterol carbonates, etc.; under the trade name "c_15,,," CB_15,, (Merck

A chiral reagent sold by S-29-201231505, manufactured by the company; a ferroelectric liquid crystal such as a non-oxybenzylidene group or a methylbutylcinnamic acid. &lt;,,; after the liquid crystal cell on the outer surface of the composition, the person is attached to the direction of the polarized light and the liquid formed on each of the substrates, the direction - or ... thereby, the liquid crystal display can be obtained; The polarizing plate which is bonded to the surface of the liquid crystal material may be a polarizing plate or a ruthenium film formed by sandwiching a polarizing film which absorbs a hard polyvinyl alcohol 7 side, which is called a "H film". It is itself: a polarizing plate. The liquid crystal display element of the present invention can be effectively applied to various devices such as a clock, a portable game machine, a word processing system, a notebook computer, a car navigation system, a video camera, a pDA, a digital camera, and an action. In the display device such as a telephone, various monitors, and a liquid crystal television, the present invention will be described more specifically by way of examples, but the present invention is not limited by the embodiments.

&lt;Synthesis of diamine [Synthesis Example 1J] Compound (d-1) was synthesized according to the following synthesis route 1. Further, if necessary, it is necessary to repeat the following scale to ensure the following synthesis examples of the polyamic acid. O2n N〇2 -^ N〇2 201231505 Synthetic route 1 In a 1 L three-necked flask equipped with a condenser and a thermometer, 33 g of 4-nitroaniline, 23.7 § 2,6-dibromopyridine, 3 &amp; Palladium (dibenzylidene)acetone, 2.4 g of 2_(di-tertiary butylphosphino)biphenyl, 28.8 g of sodium tris-butoxide, 500 mL of stupid mixture 'under n〇r The mixture was heated and stirred for 12 hours to carry out a reaction. After cooling, the precipitate was recovered by filtration. After washing with steamed water and ethanol, it was sufficiently dried to obtain 28.8 g of an intermediate (yield 82%). Next, 28.8 g of an intermediate, 5.0 g of Pd/C, 400 ml of tetrahydroanion, and 100 ml of ethanol were mixed and stirred in a 1 L three-necked flask equipped with a condenser and a thermometer under a nitrogen atmosphere. 41 ml of hydrazine monohydrate was added dropwise, and the mixture was stirred at 25 ° C for 1 hour and then at 70. (: The reaction was carried out by heating and stirring for 6 hours. After adding 1 〇〇ml of N,N-dimethylguanamine in the reaction solution, the Pd/C was removed by filtration through diatomaceous earth. The filtrate and 300 ml were removed. The mixture was mixed with distilled water, and the precipitate was recovered by filtration. After washing with distilled water and ethanol, the mixture was sufficiently washed and dried to obtain 18.4 g of a diamine compound (d-oxime) (yield: 77%). &lt;Synthesis of polyglycine&gt; [Synthesis Example 2] In 2800 g of N-methyl-2-pyrrolidone, a compound (dl) 291 g (l. 〇mol) as a diamine was dissolved, and ι, 2, 3 as a four-rebel acid liver 4_ 环丁院tetracarboxylic dianhydride 1 96g (1.0mol) 'At 40. (: 4 hours of reaction. This gives a solution containing 15% by weight of poly-proline (PA-1). The solution was diluted to 10% by weight. 'The viscosity was measured and the result was 5 8 mPa·s. -3 1-

S. 201231505 [Synthesis Examples 3 to 8 and Comparative Synthesis Examples 1 to 6] The same as in Synthesis Example 1, except that the types of tetracarboxylic dianhydride and diamine and the number of moles used were as shown in the following Table 1. A solution containing 15% by weight of polyglycine (PA-2)~(PA-7), (PAR-1)~(PAR-6). [Table 1] tetrazoic acid di/mol diamine/mol polymer T-1 T-2 T-3 d-1 d-2 d-3 d-4 d-5 d-6 name solution viscosity / mPa- s Synthesis Example 2 - - 1 1 - - - - - PA-1 58 Synthesis Example 3 - - 1 0.5 0.5 - - - - PA-2 73 Synthesis Example 4 - 0.5 0.5 1 - - - - - PA-3 89 Synthesis Example 5 - 0.2 0.8 0.5 0.5 - - - - PA-4 82 Synthesis Example 6 - - 1 0.5 - 0.5 - - - PA-5 52 Synthesis Example 7 - - 1 0.5 - - 0.5 - - PA-6 47 Synthesis Example 8 0.8 0.2 - 0.5 0.5 - - - - PA-7 80 Comparative Synthesis Example 1 - - 1 - - - - 1 - PAR-1 77 Comparative Synthesis Example 2 - - 1 - - - - - 1 PAR-2 65 Comparative Synthesis Example 3 - - 1 - 0.5 - - 0.5 - PAR-3 74 Comparative Synthesis Example 4 - 0.5 0.5 - - - - 1 - PAR-4 91 Comparative Synthesis Example 5 - 0.2 0.8 - 0.5 - - 0.5 - PAR-5 81 Comparative Synthesis Example 6 - - 1 - - 0.5 - 0.5 - PAR-6 60 In Table 1, the abbreviations of tetracarboxylic dianhydride and diamine are as follows. [tetracarboxylic dianhydride] T-1 : 2,3,5-tricarboxycyclopentyl acetic acid dianhydride T-2 : pyromellitic dianhydride T-3: 1,2,3,4-cyclobutane Tetraphthalic acid dianhydride [diamine] d - 2 : p-phenylenediamine d-3 : 1,3-bis(4-aminophenoxy)benzene d-4 · 4-aminophenyl-4'- Aminobenzoic acid @为d-5 _ 4,4'-diaminodiphenylamine d-6 . 2,4'-diaminodiphenylamine

S-32-.201231505 &lt;Preparation of liquid crystal alignment agent> [Example 1] γ-butyrolactone (BL) was added to a solution containing the poly-proline (ρΑ^) obtained in the above Synthesis Example 2, N-methyl-2-pyrrolidone (NMp) and butyl cellosolve (BC), and then added 20 parts by weight of n, n, n, as an epoxy compound, relative to the total weight of the polymer. n, tetraglycidyl-4,4, diaminodiphenylmethane, fully stirred, the solvent composition of the solution is BL: NMP: BC = 40:40:20 (weight ratio), solid concentration is 4 〇 % by weight » The solution was filtered using a filter of pore size ημηι to obtain a liquid crystal alignment agent. [Examples 2 to 7, Comparative Examples 1 to 6] The same as Example 1 except that the type of polyamic acid was changed to any of (ΡΑ_2) to (PAR-1) to (PAR-6). A liquid crystal alignment agent is prepared. &lt;Production of Liquid Crystal Cell&gt; The prepared examples were coated on a transparent electrode surface of a glass substrate having a transparent rabbit pole formed of an IT0 film using a spin coater 丨~~/, Comparative Examples 1 to 6 A variety of liquid crystal alignment agents, on a hot plate of 8 (rc, heat for 1 minute (pre-bake) 'after removing the solvent, on the 2:. (: hot plate, add cooked 1 () eight clocks ( After baking, a coating film having an average film thickness of 6 〇〇 is formed. For the coating, a friction machine having a roller wound with rayon cloth is used, and the number of rolls is 1 〇〇 (^pm, platen movement The speed is 25mm/s, the length of the fluff is 0.4mm, and the soil is rubbed to give the liquid crystal alignment energy. After that, the ultrasonic cleaning is performed in ultrapure water, followed by drying in a clean oven at 1 °C. After a minute, a substrate having a liquid crystal alignment film was obtained by drinking. This operation was repeated to obtain a substrate having a liquid crystal alignment film (two pieces). 201231505 Next, on the outside of any one of the pair of substrates having a liquid crystal alignment film The edge is coated with an epoxy tree with a diameter of 5 5 μηη alumina balls. Thereafter, the liquid crystal alignment film surface is opposed to each other, and the rubbing direction of each alignment film or the orthogonal direction is superposed and pressure-bonded to cure the adhesive. Next, a nematic liquid crystal is filled between the pair of substrates from the liquid crystal injection port (Merck Co., Ltd.) After the production of MLC-2042, an acrylic photocurable adhesive was used to seal the liquid crystal injection port to produce a liquid crystal cell. <Evaluation of liquid crystal cells> (1) Measurement of voltage holding ratio For the liquid crystal cell produced above, 9 (At a temperature of TC, a voltage of 5 V was applied at intervals of 60 μm, and 167 ms, and the voltage holding ratio (VHR) after the release of the application to 167 ms was measured. The measuring device used TOYO. Vhr] manufactured by Corporation. When the voltage holding ratio is 90% or more, it is "good", and when it is less than 90%, it is "poor". (2) Measurement of residual DC is performed at the temperature of 6 〇 for the liquid crystal cell manufactured above. Next, a rectangular wave of 30 Hz/±3 V with a 3 V compensation voltage was applied for 1 2 〇 minutes, and the residual DC voltage (V) remaining on the liquid crystal cell after the 3 v compensation voltage was cut by the flash elimination method was evaluated. The voltage is "good" below IV, large The result of the above (1) and (2) is shown in the following Table 2. β -34- 201231505 [Table 2] Polymer voltage retention low afterimage characteristics VHR/% Evaluation of residual DC voltage /V Evaluation Example 1 PA-1 95.6 Good 0.2 Good Example 2 PA-2 91.5 Good 0.3 Good Example 3 PA-3 92.1 Good 0.6 Good Example 4 PA-4 90.3 Good 0.4 Good Example 5 PA-5 91.5 Good 0.1 Good Example 6 PA-6 94.2 Good 0.1 Good Example 7 PA-7 90.4 Good 0.2 Good Comparative Example 1 PAR-1 89.7 Bad 1.4 Poor Comparative Example 2 PAR-2 85.1 Poor 2 Poor Comparative Example 3 PAR-3 80.2 Poor 1.5 Poor Comparative Example 4 PAR-4 84.0 Poor 2.4 Poor Comparative Example 5 PAR-5 77.8 Poor 1.8 Poor Comparative Example 6 PAR-6 79.6 Poor 1.2 Poor As shown in Table 2, the liquid crystal cells of Examples 1 to 6 were in a high temperature environment. The voltage retention underneath is good, and the residual DC properties are also good. In particular, the voltage holding ratio of the liquid crystal cells of Examples 1 and 6 at 90 ° C is a high value of 94% or more, and the residual DC voltage measured is 0.2 V or less, and the voltage retention in a high temperature environment. Both the low afterimage characteristics are particularly excellent. On the other hand, the voltage holding ratios of the liquid crystal cells of Comparative Examples 1 to 6 were all below the lower value of 90%, and the residual DC voltage showed a larger value of 1 · 2 V or more. [Simple description of the diagram] None. [Main component symbol description] No 0

S -35-

Claims (1)

201231505 VII. Patent application scope: 1 · A liquid crystal alignment agent' characterized in that it comprises at least one selected from the group consisting of polylysine obtained by reacting a tetracarboxylic acid bis-amine and a ruthenium iodide polymer thereof A polymer having a structure represented by the following formula (1): (R1)m JN-* (1) In the formula (1), R1 is a halogen atom and an alkyl group having 1 to 6 carbon atoms Or alkoxy or fluoroalkyl; m is an integer of 〇~3, and when m is 2 or 3, a plurality of R1 each independently have the above definition; "*" represents a linkage. 2. The liquid crystal alignment agent of claim 1, wherein the diamine is a compound represented by the following formula (2), H2N-A-B- +-N-B-A-NH2 (2) In the formula (2), A is each independently a single bond, a methylene group, a stretching group having a carbon number of 2 to 6, and a sleeve-poor, _ y. 1 methyl group, anthranyl group, pyridine At least one of the wind atoms possessed by the carbon atom, or at least one of the wind atoms, may be substituted; B is independent of θ β 立 立 立 疋 、 、, -CO-, -COO- Or -CO-NH-; Ri is a halogen atom, an alkyl group having a carbon number of 1 to 6, an alkoxy group or an H group; m is a plate of 〇~3 w. 0 ^ ^ • number, m When it is 2 or 3, a plurality of rulers | each independently have the above definition. ^. As claimed in the second paragraph of the patent application, the day-to-day alignment agent, wherein the A independently extends the base or the substituted benzene is 201231505. 4. A liquid crystal alignment film, as claimed in claims 1 to 3 A liquid crystal alignment agent according to any one of the items. 5. A liquid crystal display element The liquid crystal display element has a liquid crystal alignment film according to item 4 of the patent application. 6. a compound represented by the following formula (3), In the formula (3), B is each independently a single bond, -CO-, -COO- or -CO-NH-; and R1 and R2 are each independently an _ atom, an alkyl group having 1 to 6 carbon atoms, and an alkane An oxy or fluoroalkyl group; m is an integer of 0 to 3, and when m is 2 or 3, a plurality of R1 each independently have the above definition; r is each independently an integer of 〇~4, and when a plurality of R2 are present, R2 and the like each independently have the above definition. A polymer which is obtained by reacting a compound of the sixth aspect of the patent application with a tetracarboxylic dianhydride. S -37- 201231505 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: