TW201211111A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, polyamic acid, and polyimide - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent for obtaining a liquid crystal display element with excellent liquid crystal alignment and voltage maintain. The liquid crystal aligning agent comprises at least one of polyamic acid and imided polymer of the polyamic acid, wherein the polyamic acid is obtained from reacting tetracarboxylic acid dianhydride and diamine, and the aforementioned tetracarboxylic acid dianhydride contains at least one of aliphatic tetracarboxylic acid dianhydride and alicyclic tetracarboxylic acid dianhydride, and the aforementioned diamine contains following compound represented by the formula (D-1). In formula, for R1 to R10, one of R1 to R5 and one of R6 to R10 are a primary amino, others are each independently hydrogen atom, fluorine atom, or alkyl, alkoxy or fluoralkyl having 1 to 6 carbon atoms.

Description

201211111 VI. Description of the invention. [Technical field of the invention] The water distribution element is directed to the mold liquid pair, the 酉 方 .. 子 子 子 子 子 子 子 子 子 子 子 子 子 子a liquid crystal alignment film, a liquid crystal display element, a polyaminic acid, and a polyimine, and more particularly, a liquid crystal alignment agent and a liquid crystal alignment film which are suitable for use in a flat alignment type liquid crystal display element (horizontal alignment mode) and have the same A liquid crystal display of a liquid crystal alignment film. [Prior Art] At present, as a type of liquid crystal display element, there is known a horizontal alignment type such as a ugly column display mode (TN mode) and a lateral electric field display mode (Ips type) and a boundary electric field switching mode (FFS mode). Crystal_display element. In such a liquid crystal display device, liquid crystal molecules are sealed between a substrate disposed oppositely, and liquid crystal molecules are applied in a direction (horizontal alignment) in parallel with the substrate surface to cause a change in the direction of the liquid crystal molecules. Thereby, in the liquid crystal display element, the function of switching light is expressed by the liquid crystal. In the liquid crystal display, the alignment of the liquid crystal is controlled by the liquid crystal alignment film. In general, a liquid crystal alignment film is obtained by applying a liquid crystal alignment agent & containing a brewing Φ amine or poly phthalic acid to a substrate, and firing the surface of the film after rubbing with a cloth in a fixed direction. It is obtained by repeated processing. In order to improve the display performance of the liquid crystal display element, it is necessary to align the liquid crystal molecules in a specific direction when the power is not taken, and various liquid crystal alignment agents have been proposed in order to achieve this (for example, refer to the patent document). In 1, a liquid crystal alignment method using a polyimine obtained by polymerization of pyromellitic acid 201211111 (PMDA) and a diamine is disclosed. Aromatic polyimine manufactured by PMDA is uniaxially aligned by rubbing treatment. Further, it is high in liquid crystal molecular kinetics, and it is said that the liquid crystal alignment property is good, and it is said that it has the cyclo-cyclotetracarboxylic-acid (CB) etc. A liquid crystal.g hexane agent obtained by polymerization of an acid dianhydride of an alicyclic structure and a diamine, and the alicyclic polyimine of the alicyclic structure and the aromatic polyimine of the patent document 1 Compared with the absorption of the visible light region, the liquid crystal alignment film has a high light transmittance, and (2) the wear resistance is good. (3) The viscosity in the solution state is easily adjusted. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Unexamined Patent Application Publication No. JP-A No. No. No. No. No. No. No. No. No. No. [Problems to be Solved by the Invention] The liquid crystal alignment film formed of an alicyclic polyimine or the like has the above advantages (3) to (3), but is on the substrate. When liquid crystal molecules are injected between them, flow alignment in the direction of maneuvering when liquid crystal molecules are injected is likely to occur. Therefore, there is a concern that liquid crystal alignment ability due to flow alignment is lowered. Further, liquid crystals are formed by alicyclic polyimine or the like. In the case of the alignment film, a crosslinking agent such as a % oxygen compound is added for the purpose of improving mechanical strength, etc., but the addition of the crosslinking agent may lower the uniaxial ductility of the polymer. In this case, it is considered that flow alignment tends to occur. In the display element, in order to make the display quality better, the voltage holding ratio of 冋 is required. In the design of the liquid crystal alignment ,, it is necessary to study the voltage holding property of the liquid crystal display element. However, the present invention At the time of the study, it was confirmed that, as shown in the above-mentioned patent document, when pmda was used as the oxime anhydride, the liquid crystal alignment property was good, but the voltage retention rate of the liquid crystal became low. The present invention proposes % based on the above problems, and mainly It is an object of the present invention to provide a liquid crystal alignment agent which is used for obtaining a liquid crystal crystal display element which is excellent in both liquid crystal and the liquid crystal alignment film. [Means for Solving the Problem] The present inventors have found that Any one of the following liquid crystal alignment agents and liquid helium obtained by reacting at least any one of the polycrystals as a liquid crystal to complete the above problem, thereby completing at least one of the diamines of the present invention and the aliphatic tetrazoic acid. a tetrameric phthalic acid and a hydrazine imidized polymerization alignment agent thereof, wherein the acid dianhydride and the alicyclic tetracarboxylic acid didecylamine are formed by a chemical alignment agent represented by the following formula (D-1). Liquid crystal alignment film, crystal display element, liquid crystal alignment and voltage retention properties of the prior art problems, careful lysine and its ruthenium iodide polymerization Agent to the polymer component, can clear solution, the polyamide acid is a specific two junction Sf and alicyclic tetracarboxylic acid buffer needle. Specifically, a film and a liquid crystal display element are provided in accordance with the present invention. The liquid crystal tetracarboxylic dianhydride of at least one of the carboxylic dianhydride and the diamine is at least one of an aliphatic tetracarboxylic acid and the above dimer. 201211111

(wherein E E., E.g. is independently a hydrogen atom, a fluorine atom having a number of 1 to 6, alkoxy group or a burnt group). According to the liquid crystal alignment agent of the present invention, when an aliphatic tetracarboxylic acid- and an alicyclic tetracarboxylic acid dianhydride are contained as a mask and a tetracarboxylic dianhydride, a plurality of liquid crystal molecules can be formed. Inner button _ persuade the alignment of the liquid crystal alignment film. Further, when a liquid crystal film formed of the liquid crystal alignment agent of the present invention is used in the coronal display device, a high tensile pressure and an ancient liquid 曰χ & retention ratio are exhibited. Thus, according to the present invention, a liquid crystal display element having both a uniform orientation and a liquid crystal alignment property and a ruthenium retention property can be obtained from the daily alignment agent. Further, in the present invention, as the tetradecanoic dianhydride, at least any of the former M. melamine dianhydrides and the aromatic tetracarboxylic dianhydride may be used. 4 壬思独佶田ϋ Anhydride mixture. In this case, the Μ liquid crystal alignment is compared with the case of using the nearest one. Further, according to the present invention, a liquid guanamine of 40% is provided, and a liquid crystal alignment agent of the ruthenium is provided. In addition, there are liquid crystal display of 5 Xuan liquid crystal alignment film; in addition, at least 任 一 脂肪 脂肪 脂肪 脂肪 中 中 @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ (Dn斛_ from the diamine reaction of ^ 的 π b 社 社 社 社 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 [ [ [ [ [ [ [ [ [ [ [ Morphology] 201211111 The liquid crystal to which the liquid crystal of the present invention is aligned, and the oxime suboxide thereof, wherein the liquid crystal <polyglycolic acid> agent of the present invention contains a tetracarboxylic dianhydride and a diamine to react with an aminated polymer At least any one of them. § The agent has been described in detail. The polyamine contained in the agent can be obtained by reacting the diamine shown in 1). The tetracarboxylic dianhydride of the polyglycolic acid of the invention, which comprises the tetrabasic acid dianhydride of the present invention and the above formula (D [tetracarboxylic dianhydride]), comprises a fatty acid having an aliphatic structure. At least one of the four livers (hereinafter, referred to as an aliphatic four M ^ ^ ^ tetravalent dianhydride having a % structure of the following formula (hereinafter referred to as "four tetradecanoic acid").匕里脂族四录酿-g , 4 carboxy oxime octacarboxy- hydrazine anhydride 疋 疋 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接 连接The private four-shaped furnace n - 〃 is composed of a chain structure <, its - part may have a ring-shaped, a mouth-shaped or an aromatic ring knot "clothing connected to the aliphatic 戸μ月曰缞式四叛酸二肝" It refers to acid two needles. It: at least two enemy groups of nine are dehydrated in the molecule or a chain structure: the four-acid dianhydride m is composed of an alicyclic structure, specifically, a part of the rabbit may have a fang Ring structure: 1 2 3 4-T 乍 is an aliphatic tetracarboxylic dianhydride', for example, tetrahexanoic acid dianhydride. In addition, as a helmet π Lu-V- Π Π 1 Μ Anhydride, which can be listed as ## as a 曰%% tetracarboxylic acid ditricarboxycyclopentanyl, 2, anthracene tetracarboxylic dianhydride, 2,3,5-di- oxy lyic acid Liver, A33,4,5,915-hexahydro-5-(tetrahydro'5-yl)-naphtho[1,2_C]°folone, 5-hexahydro_8-fluorenyl_5_(tetrahydro- 2 5 _彳目il ft its 3 a base)_naphtho[1, fly 2,5_-sideoxy-3-furan,]furan],3-dione, 3_oxabicyclo[3.2.1] Xin-2,4- 201211111 Diketo-6-spiro-3 '-(tetrahydrofuran-2 ',5 '-dione), 5- (2,5-di-oxytetrahydro-3-furan) -3 - mercapto-3-cyclohexene-1,2-diphthalic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, 4,9-dioxatricyclo[5.3.1.02,6]undec-3,5 , 8,10-tetraketone, cyclohexanetetracarboxylic dianhydride, etc. Further, an aliphatic tetracarboxylic dianhydride other than the above described in JP-A-20 10-97 1888 and An alicyclic tetracarboxylic dianhydride. As an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride for synthesizing the polyamic acid in the present invention, among them, particularly preferred 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5- Tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[l,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro -8-Methyl-5-(tetrazol-2,5-di-oxy-3-°f-butyl)-n-[1,2-〇]°furan-1,3_dione, bicyclo [3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride and 1,2,3,4-butane tetracarboxylic dianhydride At least one of the selected groups. Further, from the viewpoint of further increasing the voltage holding ratio, it is more preferably 1,2,3,4-cyclobutanetetracarboxylic dianhydride, (1S, 2S, 4R, 5R)-cyclohexanetetracarboxylic acid. At least one selected from the group consisting of dianhydride, (111,23,43,511)-cyclohexanetetracarboxylic dianhydride and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride; The epoxy compound is more preferably 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3,3a, 4,5 from the viewpoint of exhibiting good liquid crystal alignment. 9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]furan-1,3-dione and 1,3,33, 4,5,91)-hexamethyl-8-mercapto-5-(tetrazol-2,5-di-oxo-3-'1f-fentyl)-naphtho[1,2-c]furan- At least one selected from the group consisting of 1,3-diketones. Among them, particularly preferred is 1,2,3,4-cyclobutanetetracarboxylic dianhydride. 201211111 In addition, the above-mentioned aliphatic tetrahexanoic acid liver and alicyclic ring may be used singly or in combination of two or more kinds: as the acid reading, at least one of the above fat and alicyclic tetracarboxylic dianhydride may be used. a tetrakisic acid dianhydride having an aromatic ring structure in an aromatic tetra(tetra) dianhydride and an alicyclic phthalic acid dianhydride (aromatic tetracarboxylic dianhydride) The above four carboxyl groups are dehydrated in the molecule as an aromatic tetrahydro acid, especially dianhydride (PMDA) or 3,3,,4,4, biphenyl tetrazoic acid, bismuth benzoic acid The aromatic tetrazoic acid PMDA described in the publication of the second liver, the sputum, the sulphate, the sulphate, the sulphate, the sulphate, the sulphate, the sulphate At least any one of tetracarboxylic dianhydride I mono anhydride and PMDA is preferred in terms of film-alignability. On the other hand, in the case of monotetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride, carboxy Compared with the mixed system of I-anhydride, the voltage can be increased. As the tetracarboxylic dianhydride, the aliphatic or fat is used. When the needle is used in combination with the aromatic tetracarboxylic dianhydride, the ratio of the aliphatic tetracarboxylic dianhydride is preferably 10 to 95 mol%, more preferably 3 to 9 mol%, based on the total amount of the tetracarboxylic acid. ～85 mol%, particularly preferably 60 to 80 mol%. The ratio of the aromatic tetracarboxylic dianhydride in this system can also be less than that of the tetracarboxylic dianhydride tetracarboxylic dianhydride. - Xuan) combination to receive the same or not acid dianhydride. Both of them are tetrabasic acid, 3,3,4,4,-di and Japanese special dianhydride. It is preferred to further improve the total amount of the tetra-acidic di- or alicyclic dianhydride of the formula in which the alicyclic tetracarboxylic acid alone and the alicyclic tetracarboxylic acid are used to improve the retention ratio of the aliphatic and the same aromatic. In this case, the cyclohexyl group of the tetracarboxylic dianhydride mixed with -10-'6 can be listed as | 201211111 total ϊ 'preferably 5 to 9 〇 mol%, more preferably ι 〇 ~ 70 mol%, into the good 15~50m〇l〇/o, especially good for 2〇~4〇Π1〇1%. When the liquid crystal alignment film is formed by the respective ranges, it is possible to achieve good balance between the electric dust retention rate and the excellent liquid crystal alignment property in the south, and the profitability is also good. [Diamine] at least one of the diamines used to synthesize the polyproline in the present invention

It is a compound represented by the above formula (D-1). In the above formula (D-1), one of R and one of R to R 是 is a primary amine group. That is, the compound which is not (D-1) is a diamine which is bonded to a different amine group on a different benzene ring. In R to R, the other group other than the -amino group may be a hydrogen atom or a group having a * atomic number of U6, an alkoxy group or a gas-burning edge, and α ^ @ ' may be different. The number of carbon atoms is 1 to 6 # σ, which is a straight bond, and may be branched, specifically, a mercapto group, an ethyl group, a n-propyl group, an isopropyl n-butyl group, a butyl group, : Τ grade ηρ | I, , and butyl, n-pentyl, isopentyl, neopentylisoyl and the like. Ή /3⁄43⁄4" is a group in which the number of carbon atoms is 俨~6, and the group of the case group is at least replaced by a fluorine atom for 4w generation. In addition, as the alkoxy group of the carbon atom, a group formed by attaching a group having the above-mentioned number of carbon atoms to the milk atom of the 7店 7 J may be mentioned, and for example, a hydrogen group is exemplified.弋T 虱 或 or ethoxy. In one step, select the upper display quality. The other part of 丨~R5 is a one-form of the above formula, and the fluorine is a group of a group, and the alkyl group having a hydrogen atom of 1 to 6 can be enumerated as the base, the dihexyl group, and the alkyl group having a hydrogen atom of 1 to 6 can be -11-201211111. The primary amine group is preferably attached to the position relative to _c〇〇_. Further, in R1 to R10, all of the groups other than the primary amino group are preferably a hydrogen atom, or the adjacent to the primary amine group is a non-hydrogen atom, and the other is a hydrogen atom. In the former case, I j enhances the planarity of the polylysine and its quinone imidized polymer, thereby promoting the liquid crystal alignment. In addition, in the latter case, in the latter case, the planarity of poly-proline or the like is lowered by the adjacent amine compound, whereby the aggregation can be improved, and the adjacent amines AMA w ± ', with moderate planarity, are Among them, a group having 1 to 3 carbon atoms, and τ is particularly preferably a methyl group or an ethyl group. The compound of the formula (D-ι)* is a group of 4,-aminophenyl benzoic acid, 3,3, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ,5,_Tetramethylphenyl I-aminophenyl ester, 3·methyl-4-I-amino female base-4,-aminobenzoic acid, especially 4-amino-based The benzoic acid ester, among them, is used as the = '4-aminobenzoic acid vinegar. The diamine of the poly-bristine in the above formula is used, and the compound and the compound shown by the mouth can also be used. The above formula can be exemplified as other diamines which can be used in the above-mentioned aliphatic diamines and disaccharides, and examples thereof include exemplified diamides and guanidines. 1 S — I monoamine oxime, 5-pentane-saddle, as alicyclic, hexamethylenediamine, etc.; calcination, hydrazine, methylene group can be exemplified by, for example, Μ-two...p ～(ring p vomit,... , makeup & % search, _ _ ' oxane, etc. As them, -amine, diamine-based organic oxime can be enumerated as m sub-' as an aliphatic diamine, m-xylenediamine, propylene propylene diamine, Μτ (cyclohexylamine), u-di(amino-12- 201211111 amine' To exemplify the example J#, a monoamine, m-phenyl 4,4'-diaminodiphenyl 2, 4 4'-dibenzoate, 1,5-diaminonaphthalene, 22, one by one. a fluorenyl-4,4,-diamine group as an aromatic amine, p-phenylenediamine benzene, 4,4,-diamino 2,2,-bis(trifluoromethyl)-linked; _β*Α - 甘, , 7 --amino hydrazine, one amino group, one base test, 2,2·two [4·(4, burnt, 9,9-di(4-aminophenyl)苟, 2,2 ^ yl) benzyl] propyl. ^ ^ a [4_(4-aminophenoxy)phenyl, fluoropropane, 2,2-di(4-aminophenyl) quinone $^ _ 丞),, fluoropropane, 4,4,-(p-phenyleneisopropylidene)bis(aniline), 4,4,_(^ λ Ί-isopropylidene)bis(aniline), 1, 4-bis(4-aminophenoxy)benzene, si4.., , 4,4 _(4-aminophenoxy), extra-, 2,6-diamino, 唆, 3, 4_Diamine, specific bite, 2,4-diamine mouth, 疋, 3,6-diamine, °, 3,6-diamino hydrazine. Sit, ^methyl _3,6 _Diaminocarbazole, hydrazine-ethyl-3,6-diamino hydrazine. Oxazole, hydrazine phenyl 3,6-diamino hydrazine, hydrazine, hydrazine, -di(4-aminophenyl) )_Linked amide, Ν Ν,-bis(4-aminophenyl)-ν,ν,_dimethylbenzidine, anthracene-bis(4•aminophenyl)-slightly oxime, 3,5-diaminobenzoic acid, twelve Alkoxy 2,4-diamino stupid, tetradecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2 , 4-diaminobenzene, octadecyloxy-2,4-diamino stupid, dodecyloxy-2,5-diaminobenzene, tetradecyloxy-2,5-diamine Benzobenzene, pentadecyloxy-2,5-diamino stupid, cetyloxy-2,5-diamino stupid, octadecyloxy 2,5-January female stupid, gallbladder Alkoxy_3,5-diaminobenzene 'cholestyloxy-3,5-monoaminobenzene, cholestyloxy-2,4-diaminobenzene, cholestyloxy·2 , 4-diaminobenzene, 3,5-diaminobenzoic acid cholesteryl ester, pentyl 5-diaminobenzoic acid cholalyl ester, 3,5-diaminobenzoic acid wool Alkyl ester, 3,6-bis(4-aminophenoxy)cholane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4,-trifluoromethane Oxybenzophenoxy)cyclohexyl·3,5_ -13- 201211111 monoaminobenzoate, 4-(4,-trifluoromethylbenzyloxy)cyclohexyl-3,5-di amine Benzoate, (aminophenyl)indenyl)phenyl)-4-butylcyclohexane, M-bis(4.((aminophenyl)indenyl)phenylheptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)4.heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl) )_4_(4_heptylcyclohexyl)cyclohexane, 2,4-diamino-N,N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 丨_( 2,4-diaminophenyl) piperidine carboxylic acid, 4-(morpholin-4-yl)benzene-1,3-diamine, bis(N-('aminophenyl)piperidinyl)propane, Α-amino-ω-aminophenyl olefin, and represented by the following formula (A1)

(where X1 and X11 are single bonds, *_〇·, *_c〇〇 or *-OCO- respectively (where the connection key with "*" is connected to the stupid ring), rI is a single bond, Aachen a group or an alkyl group having 2 or 3 carbon atoms, & is an integer of 0 to 2, c is an integer of 1 to 20, and η is 0 or 1. wherein a and b are not the same 〇). Examples of the diamine organooxosiloxane include 1,3-bis(3-aminopropyl)-tetradecyldioxane; and Japanese Patent Laid-Open Publication No. 2 0 10 9 7 1 8 8 The diamine other than the above in the diamine described. The divalent group represented by _xi_ri_xii_ in the above formula (A-1) is preferably a methylene group, an alkylene group having 2 or 3 carbon atoms, *_〇_, *_c〇〇_ or *-〇CH2CH2-〇- (where 'the linkage with '*' is attached to the diaminophenyl group). Specific examples of the group "-CcH2e+i" include, for example, anthracenyl group, ethyl 'n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n--14-201211111 heptyl-n-octyl group, and positive壬 暴 , , , , , , , , , , , , , , , , , , , — 十二 — — — — — — — — — — — — — — — — — — — — — — — — — — — Alkyl, .. 正. n-nonadecyl, n-icosyl and the like. Diamine The two amine groups of the basic group are in phase. For other groups, it is preferably 2,4-position or 3,5-

Specific examples of the compound represented by the formula: (Α·1) include, for example, the following formula: r λ 1 , J h2n H2N _ _ 丨 ) 〜 (A _ 3) Compounds, etc.

i/-C〇° h2n ~~~

〇5Ηή (Α-1-2) " threat. ~^〇- (- νη2 θ The ratio of the compound which is not represented by the formula (D 1) is preferably 10 to 100 m 〇 1% with respect to the total summer of the diamine. By selecting the above range, the use of the lipid: family or fat When the ring-shaped tetracarboxylic acid two needles are used as the tetracarboxylic acid bismuth, the liquid crystal alignment film which exhibits excellent liquid crystal alignment properties can be formed while forming a good liquid crystal voltage holding ratio. <Molecular oxime adjusting agent> When the polyamic acid is synthesized, a terminal modified type of the complex can be synthesized by using a suitable molecular weight modifier together with the tetracarboxylic acid diamine and the diamine as shown above. By forming the terminal modified type polymer, Further, the coating property (printability) of the liquid crystal alignment agent is further improved without impairing the effects of the present invention. -15 to 201211111 Examples of the molecular weight modifier include, for example, an acid monoanhydride, a monoamine compound, a monoisocyanate compound, and the like. For example, as an acid single needle, for example, maleic acid needle, ortho-phthalic anhydride, itaconic anhydride, n-decyl salicylic anhydride, n-dodecyl salicylic anhydride, n-tetradecyl group can be enumerated. Salicylic anhydride Hexaalkyl salicylic acid anhydride or the like; as a monoamine compound, <exemplified are, for example, aniline, cyclohexylamine n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc.; as a monoisocyanate compound' Examples thereof include, for example, a benzoic acid stearyl ester, an isocyanate isocyanate, etc. The use ratio of the molecular weight modifier is preferably 1 part by weight based on the total amount of the tetracarboxylic acid monohydride and the diamine used.夂1至里切切以下,更# is 1 〇 parts by weight or less. <Synthesis of polyglycine> As a ratio of use of polyamidoamine, an acid anhydride group is preferably a ratio. Sigh dianhydride and _ relative In an equivalent of 1 equivalent of diamine, the ratio of tetracarboxylic acid to liver is 0.2 to 2 equivalents, and more preferably - Wenjia is 〇·3~1.2 equivalent of heart-shaped 丨 丨 in the organic solvent. 隹~ The reaction temperature is preferably more enthalpy. In addition, the reaction time is preferably 0. Μ 4 hours, preferably 〇 ° C ~ l 〇〇 t. When more preferably 0.5 ~ 1 2 small here ' Examples of the organic solution sword include a solvent, phenol and a derivative thereof, and an alcohol 1 such as an aprotic polar hydrocarbon. Hydrocarbons, -16-201211111 Specific examples of these organic solvents include, as the aprotic polar solvent, for example, N-mercapto-2-pyrrolidone, anthracene, fluorenyl-dimercaptoacetamide. , hydrazine, hydrazine-dimethyl decylamine, dimercapto sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylenephosphonium triamide, etc.; as the phenol derivative, for example, hydrazine Phenol, dinonylphenol, liated phenol, etc.; examples of the alcohol include decyl alcohol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, and triethylene glycol. Ethylene glycol monodecyl ether or the like; examples of the ketone include acetone, methyl ethyl ketone, decyl isobutyl ketone, and cyclohexanone; and examples of the ester include ethyl lactate, butyl lactate, and acetic acid. Methyl ester, ethyl acetate, butyl acetate, decyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, etc.; as the ether, for example, diethyl Ether, ethylene glycol decyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl Ether, hexanediol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ether acetate, diethylene glycol didecyl ether, diethylene glycol diethyl ether, diethylene glycol monoterpene a base ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, etc.; as the halogenated hydrocarbon, for example, two gas Cyclohexane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-diphenylbenzene, etc.; examples of the hydrocarbon include hexane, heptane, and octane. Alkane, benzene, toluene, dinonylbenzene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like. -17- 201211111 Among these organic solvents, more than one selected from the group consisting of aprotic polarities and phenols and their derivatives (the first group of organic solvents) , or lessons & test, more than one of the above group of organic solvents and a group consisting of alcohols, ketones, oximes, ethers, commercial hydrocarbons and hydrocarbons: the second group of organic solvents) The selected ones are more than one mixture. In the latter case, the ratio of the use of the organic solvent in the second group is preferably 50% by weight or less based on the amount of the organic solvent of the first group and the organic solvent of the first group. More preferably, it is 40% by weight or less, and more preferably 30% by weight or less. The amount of the organic solvent (a) is preferably the total amount of the tetracarboxylic dianhydride and the diamine (b) relative to the total amount of the reaction solution (a + b) is the amount of 〇 〇 〇 0 如上 如上A reaction solution formed by dissolving polylysine. 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 separating the polyamic acid contained in the reaction solution. Alternatively, the isolated polyamic acid is refined to prepare a liquid crystal alignment agent. The separation and purification of the poly-aracine can be carried out by a known method. <醯i-Iminylated Polymer> The ruthenium iodide polymer (polyimine) in the present invention can be obtained by subjecting the above-mentioned synthesized polyglycine to a ring-opening oxime. In this case, the above reaction solution formed by dissolving polylysine may be directly used for the dehydration ring-closure reaction; or the poly-proline contained in the reaction solution may be separated and used for dehydration ring closure reaction or may be separated. After the polyamic acid is refined, it is used for the dehydration ring closure reaction. -18- 201211111 The polyimine in the present invention may be a fully ruthenium imide of a glycosidic acid structure in which the polyamic acid as a precursor thereof is dehydrated and closed; or may be only a part of the structure of the proline structure. The closed-loop 'halide acid structure and part of the ruthenium imine compound coexisting with the brewed imine ring structure. The ruthenium imidation ratio of the polyimine in the present invention is preferably 3% or more, more preferably 5 Å to 99 Å/〇, still more preferably 65 to 99%. The brewing imidization ratio is a ratio of the number of the quinone ring structure to the total amount of the guanidine structure of the polyimine and the total amount of the quinone ring structure. Here, a part of the quinone ring may be an isoindole ring. The dehydration ring closure of the polyamic acid is preferably carried out by heating the polyamic acid or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as needed. Wherein ' is preferably carried out in the latter method. In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyamic acid solution, as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic acid can be used. The amount of the dehydrating agent is preferably $ Gqi 2 to 2 mol with respect to the structure of the i-poly phthalic acid (tetra) aminic acid. The dehydration ring-closing catalyst may, for example, be a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine. The amount of the dehydration ring-closing catalyst used as the dehydrogenation agent is preferably 〇1 to 1 〇mole with respect to 1 mol of the dehydrating agent used. The organic solvent used in the dehydration ring-closure reaction may, for example, be an α-organic solvent exemplified as a solvent used for synthesizing polyglycine. The reaction temperature as the dehydration ring-closing reaction is preferably 〇~; [8 〇® is more preferably 10 to 1 50 eC. The reaction time is preferably from 1.0 to 1 20 hours, and f is preferably from 2.0 to 30 hours. -19- 201211111 Thus, a reaction solution containing polyimine can be obtained. 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 the reaction solution; and can also be used for preparing a liquid crystal alignment agent after separating the polyimine. Alternatively, the isolated polyimine may be purified to prepare a liquid crystal alignment agent. These purification operations can be carried out according to a known method. <Solution viscosity of polymer> The polylysine and the ruthenium iodide polymer (hereinafter referred to as a specific polymer) in the present invention obtained as above are in the form of forming a liquid having a concentration of 10% by weight. Preferably, it has a solution viscosity of 2 Torr to 8 Å mPa.s, more preferably a solution viscosity of 30 to 500 mPa·s. In addition, the solution viscosity (mpa.s) of the above polymer is prepared by using a good solvent of the polymer (for example, γ-butyrolactone, N_decyl-2-pyrrolidone, etc.) to a degree of 10% by weight. The polymer solution was measured at 25 ° C using an E-type rotational viscometer. <Other Additives>. The liquid crystal alignment agent of the present invention contains a specific polymer, and may have other components as needed. Examples of the other component include a compound having a ruthenium polymer and a ruthenium molecule having at least one epoxy group (hereinafter referred to as "epoxy compound"). a decane compound or the like. [Other Polymers] The Octal 5 can be used to improve solution properties and electrical properties. Examples of the other polymer, the polymer other than the specific polymer of the prefecture or the oxime, may be, for example, a polyamine obtained by reacting a diamine of the compound represented by the formula _ < -1) and a tetradecan-20-201211111 acid dianhydride. Polylysine obtained by reacting proline and aromatic tetracarboxylic dianhydride with diamine (hereinafter referred to as "other poly-proline"), and polyimine formed by dehydration of other polylysine (hereinafter, referred to as "other polyimine"), polyphthalate, polyester, polyamine, polyoxetane, cellulose derivative, polyacetal, polystyrene derivative, poly( Stupid ethylene-phenylmaleimide derivatives, poly(meth)acrylates, and the like. Among them, 'preferably other poly-proline or other polyimine, more preferably other poly-aracine. Further, as the tetracarboxylic dianhydride and the diamine for synthesizing other polyamines and other polyimines, a compound for synthesizing the above-mentioned special polymer may be mentioned. When other polymers are added to the liquid crystal alignment agent, the mixing ratio thereof is preferably 5% by weight based on the total amount of the polymer in the liquid crystal alignment agent.

More preferably, it is 0.1 to 40% by weight, and still more preferably 〇U0 weight 〇/〇. [Epoxy compound J is oxidized. The material can be used to increase the mechanical strength of the liquid crystal alignment film. Grind two, in the import? The display of the timing display device is not good. In addition, the use of epoxy. The earthworm 咼 liquid crystal alignment 臈 臈 臈 基板 基板 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = =喃, ', 7 i oil ether, polypropylene glycol diglycidyl ether, a glycidol, 〗 6 oil diglycidyl, -~, - hexanediol diglycidyl ether, Gan, di-methyl propane Triglycidyl ether, 2,2-di-21- 201211111 Mo Xinyi, a yeast, glycidol, shouting, heart, _ tetraglycidyl xylene diamine, 1'3-di (N, N diglycidylamine Guang Er Shao, N, N, N, N, -tetraglycidyl hydrazine, diamine bismuth, dihexyl N, N- diglycidyl aryl amine, N, N- diglycidyl Base: methylcyclohexane, N,N-diglycidyl, hexylamine and the like are preferred. When these epoxy compounds are added to the liquid crystal alignment agent, the mixing ratio thereof is 1 〇〇 by weight, preferably 40 parts by weight or less, more preferably 〇1 to 3 parts by weight, based on the total amount of the polymer contained in the liquid crystal alignment agent. . [Functional decane compound] Examples of the functional decane compound include 3-aminopropyldimethoxycarbazide, 3-aminopropyltriethoxysulfate, and 2-aminopropyltrimethyl Oxydecane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3 -Aminopropylmethyldimethoxydecane, 3-Validinopropyltrimethoxydecane,3·醯-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyl Trimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecane Propyl triethylamine, 10-trimethoxyoxyalkyl-1,4,7-triazadecane, 1〇-triethoxydecyl-1,4,7-three Azaindole, 9-trimethoxyoxyalkyl-3,6-diazaindolyl acetate, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9_trihexyloxymethane alkyl-3,6-diazaindolyl acetate, 9-trimethoxy sulfonium sulfonate-3,6-diazanonanoate, 9-three Ethoxy decyl _3,6-di-I-decanoic acid decyl ester, Ν-benzyl-3-aminopropyltrimethoxy oxime, Ν_节基_3_ -22- 201211111 Aminopropyl Triethoxy decane, N-phenyl-3-aminopropyltrimethoxy decane, N-phenyl-3-aminopropyltriethoxydecane, glycidyloxydecyltrimethoxy Decane, glycidoxymethyltriethoxydecane, 2-glycidoxyethyltrimethoxydecane, 2-glycidoxyethyltriethoxydecane, 3-glycidoxypropyl Trimethoxy decane, 3-glycidoxypropyl triethoxy decane, and the like. When these functional scouring compounds are added to the liquid crystal alignment agent, the mixing ratio thereof is 100 parts by weight or more, preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight based on the total amount of the polymer. [Organic solvent] The liquid crystal alignment agent of the present invention is preferably prepared by dissolving and containing a specific polymer and other additives optionally mixed as needed. Examples of the organic solvent which can be used in the liquid crystal alignment agent of the present invention include N-mercapto-2-indolyl ketone, γ-butyrolactone, γ-butylide, hydrazine, fluorenyl-difluorenyl. Indoleamine, hydrazine, hydrazine-dimercaptoacetamide, 4-hydroxy-4-mercapto-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methoxypropionic acid Ethyl ester, ethyl ethoxy propionate, ethylene glycol decyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve ), ethylene glycol didecyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monodecyl ether, diethyl Alcohol monoethyl ether, diethylene glycol monodecyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate , diisoamyl ether, ethylene carbonate, propylene carbonate and the like. They may be used singly or in combination of two or more. -23- 201211111 The solid in the liquid crystal alignment agent, from ΛΑ 、, \ / morning (the total weight of the components other than the solvent of the liquid crystal alignment agent 摅 ^ you 丨), Lao Lu 魟 from, liquid day The ratio of the total weight of the alignment agent is n ifi θ, and the content is preferably 1 to 10% by weight. The β A main and the daily alignment agent are applied to the surface of the substrate as described later. . . . , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The liquid is aligned to the membrane on a daily basis. On the other hand, when the concentration of the u component is more than 10% by weight on the solid 忐8, s, the film thickness of the coating film is too large, and it is difficult to obtain a good liquid crystal alignment film or a viscosity of the liquid 曰B alignment agent. Increased, coating properties may not be. A particularly good solid concentration of the catalyst J rail 111 is apparent by the method employed in coating the liquid crystal alignment agent on the substrate.丨丄, 丨丄 No, for example, when using the spin coating method, the solid content concentration is particularly preferably in the range of 1.5 to 4 4 . 5 Torr/〇. In the range of 3 to 9 wt% of the solid content of the printing company, the range of =:: degrees is 12 to 50 mPa.s. When using the ink jet method, it is particularly preferable that the solid point is eight: the range of the knife/length is 1 to 5 wt%, and thus the Loose/Night viscosity is in the range of 3 to 15 mPa·s. The temperature of the liquid crystal alignment agent invented by I ί is preferably 丨〇~5〇 C ' or more preferably 20~3 〇. Oh; &lt;Liquid crystal alignment film and liquid crystal display element&gt; The agent is formed. Another film. The STN type and the ffs of the present invention can also be used in the VA type, and the liquid crystal alignment film of the liquid crystal display element of the present invention can be used in the IPS type or the ΤΝ type. It is used in the horizontal alignment type operation mode of the type, and is used in the vertical g & type operation mode of the type, and the type "they" is particularly preferably used in the IPS type -24-201211111 or less, and the present invention A method of manufacturing a liquid crystal display element will be described. In the same description, a method for producing a liquid crystal alignment film of the present invention will be described. The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3). Step (1) differs depending on the desired mode of operation. Steps (2) and (3) are the same in various operating modes. [Step (1): Formation of Coating Film] First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then a coating film is formed on the substrate by heating the coated surface. When manufacturing a TN type, STN type, or VA type liquid crystal display element, UD forms a pair of two substrates on which a patterned transparent conductive film is formed, and preferably forms an offset printing surface on each of the transparent conductive film forming surfaces. Coating, spin coating, roll coating or ink jet printing, respectively, coating the liquid crystal alignment agent of the present invention, followed by heating each coated surface (preferably by preheating (prebaking) and firing (post baking) The two-stage heating) forms a coating film. In this case, as the substrate ', for example, glass such as float glass, sodium = glass, polyethylene terephthalate, polybutylene terephthalate-poly-stone, poly stone vinegar, poly ( A transparent substrate formed of plastic such as alicyclic olefin). As a transparent conductive film provided on the surface of the substrate, a NESA film formed of tin oxide (Sn〇2) (formed by Indium Oxide-Indium Oxide (In2〇3-Sn〇2) of ppG Corporation, USA) can be used. The IT0 film: 'In order to obtain a patterned transparent conductive film, it is possible to use a mask having a desired pattern by, for example, forming a transparent v-electrode film after forming a pattern by photo-etching, a transparent conductive film. The method is -2511, 201211111, etc. When the liquid crystal alignment agent is applied, in order to make the substrate surface film and the coating film "better, the surface of the substrate can be coated with the functional money". The compound and the functional compound 2 are pretreated. The coated surface after the liquid crystal alignment agent is applied is then prebaked. Then the firing (post-baking) is carried out to form a coating film. The prebaked strip is carried out at 40 to 120 ° C. After ou minutes, the conditions for the culture are better than the 3 sails, preferably 15〇~25〇. The mouth is preferably carried out 5~= in the bell, more preferably into the #10~100 minutes. The film formed by the film Thicker than knife 0.001 ~ Ιμπι, better for 〇〇〇 5 ~ 〇 5μι (1-2) On the other hand, in the case of manufacturing an lps type liquid crystal display element, the shape of the substrate on which the transparent conductive film forming the comb-tooth pattern is provided, the surface of the electric film, and the opposite direction in which the conductive film is not provided The liquid crystal alignment agent of the present invention is applied to the surface of the substrate, and then the coating film is formed by heating each of the coated surfaces. The material and the coating method of the substrate and the transparent conductive film used at this time, the heating conditions after coating, and the transparent conductive Pattern Formation Method of Film The pretreatment of the substrate and the preferred film thickness of the formed coating film are the same as those described above. 11 In the case of any of the above (1-1) and (1_2), the night crystal alignment agent is coated on the substrate. Thereafter, the organic solvent is removed to form a coating film which becomes an alignment film, and the polymer contained in the liquid crystal alignment agent of the present invention is a polyfluorene acid or a quinone imidization having a quinone ring structure and a proline structure. The polymer ruthenium may be subjected to a dehydration-removal reaction after heating to form a coating film by forming a coating film. -26- 201211111 [Step (2): Friction treatment] , STN type or ips type liquid crystal display element The coating film formed in the above step (1) is subjected to a rubbing treatment in a predetermined direction by, for example, a roll of a cloth formed of a fiber such as nylon yarn or cotton, whereby the alignment of the liquid crystal molecules can impart a liquid crystal alignment to the coating film. Then, the liquid crystal alignment 瞑 is processed to irradiate a part of the liquid crystal alignment film with ultraviolet rays to change a pretilt angle of a partial region of the liquid crystal; and after forming a resist film on a part of the liquid crystal matching surface, After the rubbing treatment with the previous rubbing treatment direction, the treatment for removing the resist film 'has a different liquid crystal alignment energy in each region of the film. At this time, the viewing angle property of the liquid crystal display element is good. Further, when a V A type liquid crystal display element is produced, the coating film formed in the step (1) can be directly used as a liquid crystal alignment film, and the coating film can also be subjected to a rubbing treatment. [Step (3): Configuration of Liquid Crystal Cell] The rubbing direction of the liquid crystal alignment film of the two substrates is orthogonal or oppositely disposed to the pair of substrates on which the liquid crystal alignment film is formed as described above, and the sealant is used to align the two The peripheral portion of the bulk substrate is filled with a crystal 'sealed injection hole' in a cell gap which is separated by a surface of the substrate and a sealant to constitute a liquid crystal cell. Then, the polarizing plate is bonded to the liquid crystal cell so that the polarizing direction thereof coincides with or is orthogonal to the rubbing direction of the alignment film formed on each of the substrates, whereby a liquid element can be obtained. When the piece is made, the artificial rubbing, the formation of the liquid crystal by the matching to the film to the different types of liquid crystal can be changed to the above-mentioned anti-parallel bonding between the cells, the liquid crystal display of the appearance of the filling liquid -27-201211111 铷 From: As the sealant, for example, an epoxy resin wax containing a hardener and a vaporized ball as a spacer can be used. The liquid crystal may be a nematic liquid crystal or a liquid crystal, preferably a nematic liquid crystal, and for example, a Schiff base crystal type, a nitrogen liquid, a biphenyl liquid crystal, or a phenylcyclohexene type may be used. Liquid cumin, a cation, liquid crystal, biphenyl cycline liquid crystal, liquid type 1: phthalocyanine liquid crystal, bicyclooctane. Liquid crystal, cubic alkane in these LCD orders, you can add and use vinegar, cholesterol! Cholesterol liquid crystal such as cholestyl chloride or cholesterol citrate "C bisphosphonate; a chiral reagent sold under the trade name "c_15", J (manufactured by Merck & Co., Ltd.); Methyl butyl cinnamic acid...dielectric liquid, crystal, etc. ^Acetate fiber ==The polarizing plate on the outer surface of the cell, which can be exemplified by the 濩 濩 濩 濩 濩 称作 称作 ^ ^ ^ ^ ^ ^ ^ ώ Η ^ 4. The eccentricity of the polarizing film formed by 犋 and the polarizing plate formed by Η臈 itself, the 归 醇 延 屉 阳 阳 阳 阳 阳 阳 阳 阳 阳 」 」 」 」 」 」 」 」 」 吸收 吸收 吸收 吸收 吸收 吸收 吸收 吸收 吸收 吸收 吸收 吸收 吸收 吸收 吸收 吸收The liquid crystal display element of the present invention can be set, for example, π ^ is effectively applied to various types of, for example, a clock, a portable type of computer, a navigation system, a video camera, a pen, a mobile phone, a variety of pro-thin It is used in display devices such as a ', PDA, digital camera, [Example], etc. Hereinafter, by way of example, the present invention is more specifically described in the present day, and the present invention is not limited by these examples. Further, the solution viscosity of the poly 8 yttrium type g 4 / 5 in the following synthesis examples is the value measured by the brewing::!. Further, the polyamidimide imidization ratio was measured as follows. H sing -28- 201211111 [The yield of ruthenium imide of polythenimine] The solution of polyimine is quenched in pure water and the resulting precipitate is dried under reduced pressure at room temperature. In dimethyl hydrazine, tetramethyl decane was used as a reference material' 1 1 h_nmr was measured at room temperature. From the obtained W-NMR spectrum, the brewing imidization ratio was determined by the formula shown in the following formula (1).醯 imidization ratio (%) = (1 · Α VA2xa) x 1 00 (i) (In the mathematical formula (1), A1 is the peak area of the proton from the NH group which appears near the chemical shift i0ppm, and A2 is from other The peak area of a proton 'a is the ratio of the number of other protons to the proton of the NH group in the precursor of a polymer (polyproline)). &lt;Synthesis of Polymer&gt; [Synthesis Examples 1 to 9 and Comparative Synthesis Examples 1 to 1 1] The amounts of diamine and tetradecanoic acid dianhydride shown in Table 1 below were added to the N-methyl group in this order. A solution having a monomer concentration of 15 wt%/〇 was formed in a ratio of -2 - ° to η η. Thereafter, the reaction was carried out for 6 hours at room temperature to obtain a solution containing polylysine (ΡΑ-1)~(ΡΑ-9) and (PAR-1)~(PAR-1 1), respectively. A small amount of each solution was taken, and N-methyl-2-pyrrolidone was added to form a solution having a polyglycine concentration of 10% by weight. The results of measuring the viscosity of the solution are shown in Table 1 below. Further, each of the half amounts in these polyaminic acid solutions was used in the following Examples 1 to 9 and Comparative Examples 1 to 11, respectively. In the above polylysine solution, the addition of N_mercaptopyrrolidone to the remaining half of (PA_2)~(PA_4) and (PAR-5)~(PAR-7) forms a polyglycine concentration of 6 % by weight solution. The valeric acid unit which is contained in the melamine of -29-201211111 1 m ο1, respectively, is heated to 110 ° C after adding pyridine and acetic anhydride to the molar ratio described in Table 1 below. 4 hours dehydration ring closure reaction. After the dehydration ring closure reaction, the solvent in the system is solvent-substituted with a new N-methyl-2-pyrrolidone (by this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system) Thus, a solution containing 15% by weight of polyimine (pM)~ and (PIR-1)~(PIR-3), respectively, was obtained. While measuring the brewing imidization ratio of each polyimine contained in these polyimine solutions, a small amount of each solution was taken, and Ν·甲Τ卷-2 -吼η respective ketone was added to determine the formation of polyfluorene. The imine concentration is 1 〇 by weight. / Six viscosity when the solution is ❶. The results of each measurement are shown in Table 1 below. Further, ^' occlusion liquid, and t. 醯 some of the polyimine solutions were used in the following Examples 10 to 12 and compared with |yJ i 2 to 1 4 , respectively. -30- 201211111 Polyimine name 1 乂CU CN cu cn 1 1 1 1 1 1 1 1 1 1 1 PIR-1 PIR-2 PIR-3 1 1 1 1 Effect garlic (mPa-s) 1 〇m &lt ;N 1 1 1 1 1 1 1 1 1 1 1 00 m 1 t 1 1 醯 imidization rate g 1 〇〇gg 1 1 1 1 1 1 1 1 1 1 1 00 00 CN 00 00 1 1 1 1 Dehydration Closed-loop reaction acetic anhydride (Morby) 1 &lt;N (N CN 1 1 1 1 1 1 1 1 1 1 1 CN (N CN 1 1 1 1 . than bite (Morbi) 1 ίΝ (N (N 1 1 1 1 1 1 1 1 1 1 1 (N CN (N 1 1 1 1 Polyamine name PA-1 PA-2 PA-3 PA-4 PA-5 PA-6 PA-7 PA-8 ! PA -9 PAR-1 PAR-2 PAR-3 PAR-4 PAR-5 PAR-6 PAR-7 PAR-8 PAR-9 PAR-10 PAR-11 /w' Λ Pl, dan g ο § »r&gt; g 00 o § On § 〇\ oso oo § CO § JO o Four oxo dianhydride _ (Morbi) ο U-) Ο m O ... Ο o O vn d inch ο omo CN d 〇^Ti 〇in o yr) 〇^Ti oo O v*&gt; dd 〇V) d 3 00 On &lt;Ν »—Η 卜 IT) »-H (N ( (\ 0\ oo &lt;N (N to 00 On oo 〇&gt 00 On 00 On (N CN (N ON ON g type II CS ΓΟ v〇Γγ OO 丄 OO -Λ Λ Λ (N -Λ CO Λ in rp OO ί! ♦1 (Morbi) ο ο d Dooad ir&gt; oo (N oo wo 〇tr&gt; 〇ui d vr&gt; d IT) do VO d vn 〇dd 3 inch y-^ inch inch*—H inch inch 1—H inch inch inch 00 Ό oor·^ On On s CN ooooo *~4 o inch type T3 Τί *—H XJ 1·Ή T) 4 ro CN TJ c〇-o «r&gt; (N 1 Ό CN TD (N TJ (N CN TD (N - ύ Synthesis Example 1 Synthesis Example) 2 Synthesis Example 3 Synthesis Example 4 j Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Comparative Synthesis Example 1 Comparative Synthesis Example 2 Comparative Synthesis Example 3 Comparative Synthesis Example 4 Comparative Synthesis Example 5 Comparative Synthesis Example 6 Comparative Synthesis Example 7 Comparative Synthesis Example 8 Comparative Synthesis Example 9 Comparative Synthesis Example 10 Comparative Synthesis Example 11 s 201211111 In Table 1, the abbreviations of diamine and tetracarboxylic dianhydride have the following meanings, respectively. &lt;Diamine&gt; d-1 · 4-aminophenyl-4'-amino benzoic acid vinegar d-2: 4,4'-diaminodiphenyl shry d-3 · 4,4'- * - Aminodiphenyl oxime d-4: 2,2-bis[4-(4-aminophenoxy)phenyl]propane d-5: p-phenylenediamine &lt;tetracarboxylic dianhydride &gt; t-1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CB) t-2: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride t-3 : l,3 ,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]furan-1 , 3 -dione t-4 : 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1, 2-c]furan-1,3-dione t-5: (13,23,411,511)-cyclohexanetetracarboxylic dianhydride t-6: (1R, 2S, 4S, 5R)-cyclohexane tetra Carboxylic acid dianhydride t-7 : 1,2,3,4-butane tetracarboxylic acid dianhydride t-8 : pyromellitic dianhydride (PMDA) (Example 1) &lt;Preparation of liquid crystal alignment agent &gt; In the solution containing the polylysine (PA-1) obtained in the above Synthesis Example 1, 'γ-butyrolactone (BL), N-mercapto-2-pyrrolidone (NMp) and butyl cellosolve (BC) were added. ), then add 1 part by weight as an epoxy compound of Ν, Ν, Ν ', Ν '-tetraglycidyl -4,4'-diaminodiphenyl decane as -32- 201211111 Crosslinking agent (tackifier) 'Forming solvent ratio is BL: Ν Μ P: BC = 4 0:4 0:2 0 (weight The ratio of the solid content was 4.0% by weight. /. The solution. After the solution was sufficiently stirred, it was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent. The alignment agent at this time is referred to as "a crosslinking agent", and no ruthenium, osmium, iridium, osmium, tetraglycidyl _4,4, diamino group is added to the preparation of the above liquid crystal alignment agent. The base burner has "no crosslinker". <Manufacture and Evaluation of Liquid Crystal Cell> Liquid crystal cells were produced using the liquid crystal alignment agent, and evaluated as follows. [Manufacturing of Liquid Crystal Cell] The above-prepared liquid crystal alignment agent was coated on a glass substrate having a thickness of 1 mm having a comb-shaped chrome electrode on one side of a spinner, and prebaked on a 80 C hot plate. After i minutes, it was post-baked on a hot plate of 2 3 Torr for 1 , to form a coating film having a film thickness of 8 〇〇A. Using a friction device having a roll of a nylon-made cloth on the formed coating film surface, a friction treatment was performed at a roll rotation number of 1,000 rpm, a platen moving speed of 25 mm/s, and a pile pressing length of 〇.4 mm. Give liquid crystal alignment energy. Next, the substrate was ultrasonically washed in ultrapure water for 1 minute, and dried in a clean flooding phase of 1 Torr for 10 minutes to produce a substrate having a liquid crystal alignment film on a surface having a comb-shaped chrome electrode. The substrate having the liquid crystal alignment film is referred to as "substrate A." Further, a coating film of a liquid crystal alignment agent is formed on the surface of a glass substrate having a thickness of 1 mm without the electrode, and is washed and dried in a rubbing place to be produced. A substrate having a liquid crystal alignment film on one surface. The substrate having the liquid crystal alignment film is referred to as "substrate B." -33- 201211111 Next, the outer edge of the surface of the substrate having the rubbed liquid crystal alignment film is coated with a diameter of 5.5. After the resin binder of the alumina ball of μηι, the two substrates A and Β are arranged oppositely through the gap so that the rubbing directions in the liquid crystal alignment films are anti-parallel, and the outer edges are contacted and crimped to make the adhesive. Hardening. Then 'from the liquid crystal injection port, filled with nematic liquid crystal (Merck, MLC 2〇42) between a pair of substrates, 'acrylic light-curing adhesive Sealing the liquid crystal injection port to produce an ips type liquid crystal cell. [Evaluation of liquid crystal display element] • Evaluation of liquid crystal alignment property The liquid crystal cell produced as described above was observed using a polarizing microscope. The evaluation of liquid crystal alignment was such that almost no light was observed. "Excellent", it is found that the material that is rarely transmitted through light is "good", and it is clear that the flow alignment and light transmission are "not good". In addition, the liquid crystal alignment is evaluated as "excellent". The order of goodness was evaluated as i, 2, and 3. The results are shown in the following Table 2. Evaluation of voltage holding property For the liquid crystal cell having "crosslinking agent" in the liquid crystal cell produced above, 30 was applied under C. The voltage sec of the second lv was measured at w and ,, and the voltage holding ratio after the application was released was measured by the frame ==. This measurement is shown in the measurement. In addition, in Table 2, the voltage holding ratio retention rate is two == price. - The table on the voltage 矣... is not ◎ '98% or more, less than 99% is not 〇, and less than 98% is expressed as X. -34 · 201211111 (Examples 2 to 12 and Comparative Example 1 14) Except in In the above Example 1, a liquid crystal alignment agent was prepared in the same manner as in Example 1 except that a solution containing the polymer shown in the above Table 1 was used as a polymer solution, and liquid crystal cells were produced to evaluate liquid crystal alignment properties and voltage holding properties. Table 2 is shown below. Table 2 Polymer type Liquid crystal alignment (with crosslinking agent) Liquid crystal alignment (no crosslinking agent) Voltage retention property (with crosslinking agent) Voltage retention [%] Evaluation Example 1 PA -1 Excellent (3) Excellent (3) 99.4 ◎ Example 2 PA-2 Good and good (3) 99.5 ◎ Example 3 PA-3 Excellent (3) Excellent (3) 98.7 〇 Example 4 PA-4 Excellent (3) Excellent (3) 98.8 〇 Example 5 PA- 5 Good and good (3) 99.5 ◎ Example 6 PA-6 Good and good (3) 99.6 ◎ Example 7 PA-7 Good and good (3) 99.1 ◎ Example 8 PA-8 Excellent (2) Excellent (3) 98.6 〇 Example 9 PA-9 Good and excellent (3) 98.4 〇 Example 10 PI-1 Excellent (3) Excellent (3) 99.6 ◎ Example 11 PI-2 Excellent (3) Excellent (3) 98.8 〇 Example 12 PI-3 Excellent (3) Excellent (3) 98.9 〇 Comparative Example 1 PAR- 1 Not good 99.5 ◎ Comparative example 2 PAR-2 is not good 99.3 ◎ Comparative Example 3 PAR-3 is not good 98.6 〇Comparative Example 4 PAR-4 is not good 99.5 ◎ Comparative Example 5 PAR-5 is not good 99.2 ◎ Comparative Example 6 PAR-6 is not good 98.7 〇Comparative Example 7 PAR-7 is not good 98.8 〇Comparative Example 8 PAR-8 is not good 99.6 ◎ Comparative Example 9 PAR-9 is not good 99.7 ◎ Comparative Example 10 PAR-10 Bad 98.5 〇Comparative Example 11 PAR -11 Excellent (1) Excellent (1) 97.5 X Comparative Example 12 PIR-1 Good and good 99.4 ◎ Comparative Example 13 PIR-2 Good and good 98.9 〇Comparative Example 14 PIR-3 Good and good 98.9 〇-35- 201211111 For liquid crystal alignment, no Example 1 when the agent was combined. Everything/discovers light. It is to be understood that among the examples 48 and 10 to 12, in the case where a crosslinking agent is present, almost no enthalpy permeates the flow alignment caused by the addition of the crosslinking agent. On the other hand, the voltage holding ratio in the case of having a crosslinking agent showed a particularly high value in Examples 2 and 1 . Among them, the voltage holding ratio of the solid 10 using CB alone as the tetracarboxylic dianhydride is 99.40/. As described above, it is particularly excellent in achieving both the alignment property and the electric retention property. Further, in the eighth embodiment of the mixing system of the spear MD A, in the embodiment, the crystal alignment was the best, and the voltage holding ratio was sufficiently higher than that of the examples 1 and 10. - In other respects, 'Comparative Examples 1 to 1 0, 1 2 to 1 4, although the voltage is maintained at the same level as that of the palladium examples 1 to 1 2, the liquid crystal alignment is worse than that of the embodiment 1 to 1 especially, respectively, containing poly-lysine par- 1 to PAR-10 Example 1 1 When adding a crosslinking agent, it is apparent that the flow alignment and light can be forbidden to be PAR-1 to PAR-10. Since the crosslinking agent is added, the alignment property is remarkably lowered. Further, those using an aromatic ring tetracarboxylic dianhydride (comparative example) have an excellent ratio of retention to spit, but the voltage holding ratio is less than 98%. [Simple description of the diagram] None. [Main component symbol description] None. -12 a few 1 ' 3 &gt; Bu Guangguang,, on 5, 6, 1 Example &gt; Liquid crystal I CB is liquid low, the ratio is compared with 1 2 !_ over. Liquid crystal LCD -36-

Claims (1)

201211111 VII. Patent application scope: 1. A liquid crystal alignment agent containing at least any one of a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine and a ruthenium imidized polymer thereof. The tetracarboxylic dianhydride contains at least one of an aliphatic tetrahydroxy dianhydride and an alicyclic tetracarboxylic dianhydride, and the diamine contains a compound represented by the following formula (D-1). In the formula, R1 to R10, one of R1 to R5 and one of R6 to R10 are a primary amino group, and the others are each independently a hydrogen atom, a fluorine atom or an alkyl group having 1 to 6 carbon atoms, an alkoxy group. Base or fluoroalkyl group. 2. The liquid crystal alignment agent of claim 1, wherein the aliphatic tetracarboxylic dianhydride is 1,2,3,4-butanetetracarboxylic dianhydride; and the alicyclic tetracarboxylic dianhydride is From 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-8- Mercapto- 5-(tetrazol-2,5-di-oxy-3-carboyl)-Chao Xi [1,2-(:]11-fu-1,3-dioxin, 1,3 ,3&amp;,4,5,91)-hexanitro-5-(tetradecene&gt;-2,5-di-oxo-3-'1f-furyl)-naphtho[1,2-c]furan At least one selected from the group consisting of: 1,3-diketone, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride One. 3. The liquid crystal alignment agent according to claim 1 or 2, wherein the tetracarboxylic dianhydride is at least any one of the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic acid-37-201211111 dianhydride. A mixture with an aromatic tetracarboxylic dianhydride. 4. The liquid crystal alignment agent of claim 1, wherein the alicyclic tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, (1S, 2S, 4R, 5R)-cyclohexanetetracarboxylic dianhydride, (1R, 2S, 4S, 5R)-cyclohexane tetracarboxylic dianhydride and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride At least one of the selected ones. A liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 4. A liquid crystal display element comprising a liquid crystal alignment film according to item 5 of the patent application. 7. A poly-proline acid which is at least any one of an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride and a diamine which is not represented by the following formula (D-1) The response is paid, Wherein R, one of R1 to R5 and one of R6 to R10 are a primary amine group, and the others are each independently a hydrogen atom, a fluorine atom or an alkyl group having 1 to 6 carbon atoms, an alkoxy group or Fluoroalkyl. 8. A polyimine which is obtained by imidization of a polyamidide as in item 7 of the patent application. -38- 201211111 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Benefits 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: