TW201241047A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The present invention aims to provide a liquid crystal alignment film agent which can form a liquid crystal alignment film. The liquid crystal alignment film can maintain good electrical characteristics even if it is driven continuously in a severe environment of photostress, heat, moisture and the like. The liquid crystal alignment agent of the present invention contains [A] polyamic acid and a polymer selected from a group consisting of polyimide obtained by dehydration and ring-closure of polyamic acid, and [B] antioxidants. The present invention is characterized in that [A] the polymer is a polymer obtained by reacting tetracarboxylic acid dianhydride with diamine, wherein tetracarboxylic dianhydride comprises 1, 3, 3a, 4, 5, 9b-hexahydro-8-methyl-5-(tetrahydro-2, 5-dioxo -3-furanyl)-naphtho[1, 2-c]furan-1, 3-dione and the like, or diamine at least comprises at least one selected from a group consisting of 1-(4-aminophenyl)-2, 3-dihydro-1, 3, 3-trimethyl-1H-indene-5-amine and 1-(4-aminophenyl)-2, 3-dihydro-1, 3, 3-trimethyl-1H-indene-6-amine.

Description

201241047 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment agent and a liquid crystal display device. Seed liquid θ day alignment film and a [previous technique] 'STN (^^^ optical compensation bending) type display mode electric field switching type, 0CB (any one of the modes: f crystal display element. These display discs In the alignment state of the liquid crystal, the liquid crystal alignment agent of the liquid crystal alignment center and the liquid crystal alignment agent 1 of the liquid crystal alignment agent 1 exhibits a material of the liquid crystal alignment film. I. Some characteristics affect the characteristics of the liquid crystal display element as the liquid crystal alignment. The material of the agent is known as a resin material such as polyglycolic acid, polystyrene, polyamide, polyester, etc., especially a liquid crystal alignment agent of phthalic acid or polyimine, which is composed of a polyamine, a mechanical The strength and the heat resistance of the liquid 曰S曰 alignment film are excellent in affinity and are used in most liquid m display elements (see the patent document μ. In recent years, it is entering the thousand |VV* n , _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The cathode ray tube TV has a liquid crystal alignment When a liquid crystal display element of a film (formed by a liquid crystal alignment agent containing poly-tylinic acid or a quinone imine) is continuously driven for a long time under a severe environment such as light stress, heat, 201241047, moisture, or the like, liquid crystal The alignment film is deteriorated and the electrical characteristics of the liquid crystal cell are deteriorated, which causes the display port to be significantly deteriorated." Based on such a situation, it is desired to develop a liquid crystal alignment agent which can be formed continuously even after a long period of time. In the case of the liquid crystal alignment film of the electrical property of the present invention, the liquid crystal alignment film is good. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 4_ΐ53622 [Patent Document 2] Japanese Patent Laid-Open No. 6〇1〇7〇 [Patent Document 3] Japanese Patent Laid-Open No. 5 6 -9 丨 2 7 7 [Patent Document 4] US Pat. No. 5,929,333 [Patent Document 5] Japanese Patent Laid-Open No. 62-165628 [Patent Document 6] Japanese Patent Laid-Open 1 1 2586〇5 [Summary of the Invention] [Problems to be Solved by the Invention] The present invention is based on the above circumstances. A liquid which can form a liquid crystal alignment ^ can be maintained even when driven by light stress, heat, moisture, or the like. Electrical characteristics Section] The purpose of the present invention is to provide a crystal-aligning film-forming agent. The liquid crystal alignment film is continuously subjected to a long-term continuous operation in a severe environment. In order to solve the above problems, the following invention is proposed: A liquid crystal alignment agent, kansin λ, which contains [Α] At least one polymer selected from the group consisting of polylysine and dehydrating the polylysine and closed from the group of polyamidimines (hereinafter referred to as "^[A] polymer") and [ B] Antioxidant. 201241047 It is characterized in that [A] polymer is, and the polymer is reacted as tetracarboxylic acid, carboxy hydrazine anhydride and diamine for a long time. Sf " ί人人+ hexahydro _8 -Methyl- 5-(tetrahydro', 3 contains l,3,3a,4,5,9b--di-side furan-1,3-di-, id, milk-3·furazanyl) -naphtho[l,2-c] _3_furanyl)-naphtho[1,2,c]furan a虱'5' (tetrahydro-2,5-di-oxobicyclo[3.3.0]octane _2,4,6,8, -^'^2, and 2,4,6,8-tetracarboxy, or at least one selected from the group consisting of at least 1 of the diamine, -1,3,3-三曱基-11^-节_$(Aminophenyl)-2,3-dihydro'amine and 1 - (4 - belly: -1,3,3 -dimethyl-1H -茚_6__ Makeup Phenyl phenyl)-2,3 -dihydro sturdy group ^ φ, vertical The liquid crystal alignment agent is at least one kind by human. Even in light stress, 埶, ,, 8 households. The product and [B] antioxidant, / cooked 'gas, etc., can also maintain good performance when driven by a strict gik ring. Brother, under the long-term continuous Ding electrical characteristics.

[B] The antioxidant is preferably a group A. It is a group represented by the following formula (1) or formula (7): R1 X1 R3 — X3 R4 X5--R5 (1) (In the formula (1), R1 is a hydrogen atom, an alkyl group having a carbon number of 20, and a carbon number of 6 to 2. An aryl group of fluorene, an aralkyl group having 7 to 13 carbon atoms, a 1,3-di-terminated butyl group or a 1,4-di-terminated oxybutyl group. Further, the group represented by the formula (1) may also be derived from R1. The alkyl group, the aryl group, the aralkyl group, the 1,3-di-terminated oxybutyl group and the i,4-di-terminated oxybutyl group are removed to form a divalent group to form a divalent group to form a part of the molecular chain. 201241047 R2 to R5 are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 13 carbon atoms. X1 is a single bond, a carbonyl group, *-(CH2)n-0 -, *-0-, or *-CONH-. Among them, the connection key indicated by * is the part indicating the connection with the brigade. Further, η is an integer of 1 to 4. X2 to X5 are each independently a single bond. , carbonyl, **-CH2-CO- or **-CH2-CH(OH)-, wherein the bond represented by ** is the moiety which is bonded to the piperidine ring.

(In the formula (2), R6 is a hydrocarbon group having 4 to 16 carbon atoms. The hydrocarbon group may have an oxygen atom or a sulfur atom in the carbon skeleton chain. a is an integer of 0 to 3. R7 is a hydrogen atom or a carbon number. a hydrocarbon group of 1 to 16. When R7 is plural, a plurality of R7 may be the same or different.) [B] An antioxidant can further enhance the south and the temperature by the group having the specific structure described above. Southern wetness. A liquid crystal alignment film formed of the liquid crystal alignment agent and a liquid crystal display element having the liquid crystal alignment film are all suitable for the present invention. The liquid crystal display element can be suitably used in various devices, such as: clocks, handheld game consoles, word processors, notebook computers, car navigation systems, cameras, portable information terminals, digital cameras, mobile phones, various displays, LCD TVs, etc. Display device. 201241047 [Effects of the Invention] According to the liquid crystal alignment yoke of the present invention, even in the case of severe stress such as light stress gas, e.g., e. It can form good liquid electrical properties and is used as a liquid daily alignment film. Therefore, the liquid aa display element of the present invention having the liquid crystal film is known to be effectively applied to various types of display devices having a low display quality, and can be suitably used for, for example, a timepiece, a hand-held machine, and a word processor. , notebook computer, car navigation system: machine, portable information terminal, digital camera, mobile phone, various display:, LCD TV and other display devices. [Embodiment] [Formation of the Invention] <Liquid Crystal Aligning Agent> The liquid crystal alignment agent of this month contains ".哕]3 has [A] polymer and [B] antioxidant so that #康* has [] polys and [B] antioxidants, even in the first stress, heat, moisture ^ ^ ^ The long-term continuous driving in the environment also maintains good electrical characteristics.

Further, the liquid crystal alignment agent may contain other optional components in IP: "Bei: within the scope of the effect of the present invention < [A] polymer> Hereinafter, each component is described in detail" [A] The polymer contains polyfluorene The polyaminic acid which is a [Α] polymer in the group of polyethylenimine which is obtained by dehydration and dehydration of the polyamidamine is a polymer of at least one type. Get it. Next, the detailed description of four:: the two-needle and diamine reaction [tetracarboxylic dianhydride] V oxime anhydride and diamine. Examples of the tetra-acid dianhydride include aliphatic tetracarboxylic acid dianhydride 201241047, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. These tetracarboxylic acid dianhydrides can be used singly or in combination of two or more. The aliphatic tetracarboxylic dianhydride may, for example, be butane tetracarboxylic dianhydride or the like. Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, and 1,3. 3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1 ,3,3冱,4,5,913-hexahydro-8-mercapto-5-(tetrazine-2,5-di-flavor-3-mercapto)-n-[1,2-(;]1 *Fr. 13 South-1,3-dioxin, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione , 5-(2,5-di-oxotetrahydro-3-furanyl)-3-indolyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2 -Carboxydenyl norbornane-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-tetraone, etc. As the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride Other tetracarboxylic dianhydrides include tetracarboxylic dianhydrides described in Japanese Patent Application No. 2010-97 1 88. The tetracarboxylic dianhydride preferably contains an alicyclic tetracarboxylic dianhydride. Further, more preferably, it contains 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. 1,3,3a,4,5,9b-hexa-8-methyl-5-(tetrazo-2,5-di-oxo-3-0-f-butyl)-naphtho[1,2-c Furan-1,3-dione, l,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphtho[1, 2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2,4,6,8-dianhydride, 1,2,3,4 - cyclobutane tetracarboxylic dianhydride. Further, particularly preferably contains 1,3,3 a, 4,5,9b-six 201241047 nitrogen_5_(tetrahydro-2'5_di-side oxygen~3 ten south ))·naphthoquinone, 2 kefuran-u-one ketone, l,3,3a,4,5,9b-hexahydro-8-royage $>»土土故,姑" LT base_ 5-(tetrahydro-2,5-di-oxo-3-funyl)-naphthoquinone [l,2_c]furan_13_di r. . niJ, ^ ^ m 2,4,6, 讧tetracarboxyl Bicyclo [3.3.0] octane 2,4,6,8-dianhydride. As an enemy - hydrazine is a tetracarboxylic dianhydride, the above-mentioned special compound can be used to improve light resistance and high temperature and high temperature. With the above-mentioned special best, ... the outer six gas _5_ (four gas_2, 5_ two sides ^ "fumanyl" _ naphthacene π, 2 foreign fumon], 3 • two 〆, gas - 8_ Methyl-5-(four osmosis - 2 5 -phase 丨,. 虱, 5- side oxy-3-furanyl) _naphthoquinone, 2_c] -, - ketone, 2, 4, 6, 8-4 renecrole double ring [3 3 g]^_2,4,68_: in terms of proportion, relative to all of the four acid dianhydrides, preferably, above the ear/〇, more preferably 2 〇 mole %~9〇mole%. The [diamine] and / are diamines, and examples thereof include an aliphatic diamine, an alicyclic diamine, a sulphur diamine, a diamine organic _% alone or in combination of two or more. - the amine T is as early as the aliphatic diamine", for example, m-xylylenediamine: 1,3-propanediamine, tetradecanediamine, pentadecanediamine, hexamethylenediamine, as Examples of the aliphatic diamines include M-diaminocyclohexane methylene bis(cyclohexylamine) and 1,3 -bis(aminomethyl)cyclohexane. The aromatic diamine may, for example, be a p-diamine, a 4,4,-di-di-n-ylmethyl, a 4,4, a diaminodiphenylthio, an iota, a 5-diamine group - Dimercapto-4,4,diaminobiphenyl, 4,4,-diamino-2,2,-bis(fluoro@methyl)biphenyl, 2,7-diamino, 4, 4,-Diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)-10 · 201241047 1,2,2_bis[4_(4-aminophenyloxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene) Diisopropylidene)benzidine, 4,4'-(meta-phenyldiisopropylidene)benzidine, anthracene, 4_bis(4-aminophenoxy)benzene, 4,4'- Bis(4-aminophenoxy)biphenyl, 2,6-diaminoacridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine , 3,6-diaminocarbazole, ^-methyl-3,6-diaminocarbazole'; ^_ethyl_3,6-diamine taste ° sit, heart phenyl-3,6 - Diamine based taste. Sit,]^,1^,_bis(4_aminophenyl)-bibenamine, N,N-bis(4-aminophenyl)_n,n,-dimethylbenzidine, 1,4 - bis(4-aminophenyl)-piperidin, anthraquinone phenyl) 2,3 dihydro-1,3,3-trimethyl-1H-indole-5-amine, 1-(4 -aminophenyl)_2,3_dihydro-1,3,3-dimethyl-1H-indol-6-amine, 3,5-diaminobenzoic acid, cholesteryloxy-3, 5-diaminobenzene, choline alkenyloxy-3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene 'cholestyloxy 2,4_ Diamine basic, 3,5-monoaminobenzoic acid bile retention vinegar, 3,5-diamino benzoic acid cholesteryl ester, 3,5-diamino benzoic acid wool residual ester, 3,6_ Bis(4-aminophenyl) choline, 3,6-bis(4-aminophenoxy)cholane, 4-(4'-trifluoromethoxyphenyloxy) Cyclohexyl-3,5-diaminobenzoic acid vinegar, 4-(4'-trifluoromethylbenzylideneoxy)cyclohexyl__3,5-diaminobenzoic acid vinegar, 1,1-double (4-((Aminophenyl)methyl)phenyl)-4-4-butylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4h-heptyl ring Hexane, oxime, ^ (4-((Amino-p-oxy)methyl)phenyl)_4-heptylcyclohexane, hydrazine, 1-bis(4-((aminophenyl)methyl)phenyl)_4·(4 _heptylcyclohexyl)cyclohexane, 2,4-diamino-indole, fluorenyl-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine and represented by the following formula (3) Compounds, etc. 201241047

In the above formula (3), R8 is an alkyl group having 1 to 3 carbon atoms, *-0-, *-COO- or *-OCO-. Wherein * is a site bonded to a diaminophenyl group. b is 0 or 1. c is an integer of 0 to 2. d is an integer of 1 to 20. The two amine groups in the diaminophenyl group are preferably bonded at positions 2, 4 or 3, 5. In addition, a and b are preferably both non-zero. The compound represented by the above formula (3) may, for example, be a compound represented by the following formula.

Examples of the diamine organooxosiloxane include 1,3-bis(3-aminopropyl)-tetramethyldioxane. Examples of the other diamines include diamines described in Japanese Patent Application No. 20 10-97 1 8 8. As the diamine, those containing an aromatic diamine are preferred. Further, it is more preferred to contain 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indole-5-amine and 1-(4-amino group). At least one selected from the group consisting of phenyl)-2,3-dihydro-1,3,3-tridecyl-1H-indol-6-amine. As a diamine, by using the specific compound described above, -12-201241047, the method further improves the light resistance and high resistance, "Ancient, Stomach@ as the above-mentioned specific servant 仏] 円 / inter-dish wetness. '丄1^1) 疋1 1-(4-Amino-based, 33--1,3,3-trimethyl fluorenyl)-2,3-一风1,.. 5-amine And ^(an anionyl stupid)-2 3 - i -1,3,3_trimethyl 11^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ As the above preferred diamine, the use ratio of h(tetra)-amine is preferably 80%. More than or equal to the ear' is better than 5 〇. /〇 Above, special 1 Gui is 8 0 Mo〇 / 〇 or more. . Phenylphenyl)-2,3·-aza-external' as at least ^ containing the above-mentioned more preferred amine phenyl)_23__Γ,, 3_trimethyl-1H- isomer-5-amine and oxime. 1,3,3·^ f base_1HH amine group selected ratio, relative to all two ears 0 / 〇 or more, f estimated & 敉佳马10莫更佳佳 2〇莫耳%~9 〇莫耳〇/〇. The diamine used in the synthesis of polyamic acid in the VA type alignment oxime has a pretilt angle of A, and preferably contains 5 mol% of hexadecyloxy-2,4-diamine relative to all diamines. Dodecyloxy-2,5-diamine pentadecyloxy-2,5-diamine octadecyloxy-2,5-diaminophenylphenylphenylbenzene, undecyloxyl of j Benzyl-2,4-diaminobenzene, tetradecyloxy-2,4 diamine, pentadecanoate, oxy-2,4-diamine, octadecyloxy-2,4-diamine Pyronyltetradecyloxy-2,5-diaminophenylhexadecyloxy-2,5-diaminophenylcholestyloxy-3,5-diaminobenzene, choline Oxy-3,5-aminobenzene, cholalyloxy-2,4-diaminobenzene, cholestyloxy•2,4-diaminobenzene, 3,5-diamino Benzoic acid cholestyramine, 3,5-diamino benzoic acid lanosterol ester, 3,6-bis(4-aminophenylhydrazineoxy) cholesteryl, 3'6-bis(4-amine Bisyloxy)cholane, 4-(4,-trifluorodecyloxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 4-(4,-three-fail基-13- 201241047 Benzene oxy)cyclohexyl-3,5-diaminophenyl phthalate, 丨'丨-double^ — Ben-yl group Yue-yl) phenyl) -4-butylcyclohexyl hospital, 1,1_ bis (4_ (Ben-ylmethyl amino) phenyl) -4-heptyl cyclohexane, ^ - bis. (aminophenoxyindenyl)phenyl)-4-heptylcyclohexane' 1,1_bis(4-(aminophenylmethyl)phenylheptylcyclohexyl)cyclohexane, the above formula The compound represented by (3), etc., more preferably contains 1% by mole. [Synthesis method of poly-proline] and poly-proline in the liquid crystal alignment agent are obtained by the above-mentioned tetracarboxylic dianhydride reaction. The acid anhydride group of the tetracarboxylic dianhydride is preferably from 0.3 equivalents to 1.2 equivalents based on the ratio of the use of the tetrabasic acid dianhydride in the synthesis reaction for supplying the polyamic acid. The amount of amine 〇.2 equivalents to 2 equivalents contained in one equivalent of the diamine is more preferably the synthesis of the poly-branched acid. The attack is carried out in an organic solvent. In terms of degree, it is preferably _2〇〇U. ,,,G Chengshi ^ 15〇C, more preferably 〇°c~1〇0〇C.

In terms of reaction time, it is preferably from 1 hour to 24 hours, more preferably from 5 hours to 12 hours. As a solvent, benzene and its derivatives, etc. The ketone, the self-acting, the ether, the halogenated hydrocarbon, and the hydrocarbon are mentioned as the above-mentioned aprotic 2-pyrrolidone, n, n_: N, for example, N-mercaptodimercapto sulfoxide, butyl f-methyl hydrazine Amine, N,N-dimercaptocarbamide, amine, and the like. Examples of the alcohol and the derivative include, for example, methanol, m-nonylphenol, diterpene ethanol, and the like. Propanol, -14- 201241047 Cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monodecyl ether, and the like. The ketone may, for example, be acetone, methyl ethyl ketone, decyl isobutyl ketone or cyclohexanone. Examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, and diethyl oxalate. Ester, diethyl malonate, and the like. Examples of the ether include diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol. Mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monodecyl ether , diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran and the like. Examples of the halogenated hydrocarbon include hydrazine such as dioxane, 1,2-diethane, 1,4-dichlorobutane, tri-ethane, gas benzene, and o-diphenylbenzene. For example, hexane, heptyl, octyl, benzene, toluene, xylene, isoamylpropionate, isoamyl isobutyrate, diisoamyl ether, etc. are mentioned. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent, phenol and a derivative thereof (the first group of organic solvents) or one or more selected from the first group of organic solvents are preferably used. A mixture of one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (second group of organic solvents). The total amount of D' relative to the first group and the second group of organic solvents is preferably 50% by mass or less, more preferably 4% by mass or less, based on the ratio of the second group of organic solvents to -15-30 201241047. Below mass%. The amount of use of the organic solvent is preferably from 0.1% by mass to 50% by mass based on the total amount of the tetracarboxylic dianhydride and the two. The reaction solution obtained by dissolving polyamic acid was obtained as described above. The reaction solution may be supplied to the preparation of the liquid crystal alignment agent as it is, or may be separated into the preparation of the liquid crystal alignment after the polyamic acid contained in the reaction solution is separated or the separated polyamic acid is purified and supplied to the liquid crystal formulation. In the preparation. When polypyridyl acid is dehydrated and closed to prepare polyimine, the reaction solution is supplied to the dehydration ring-closure reaction as it is, or the polylysine contained in the reaction solution may be separated and then supplied to the dehydration reaction. Or the separated polyamic acid is refined and supplied to the dehydration ring closure. The separation and purification of polylysine can be carried out according to a well-known method. [Synthesis method of polyimine] The polyimine which can be contained in the liquid crystal alignment agent is obtained by dehydrating ring-opening of lysine and ruthenium. Examples of the tetracarboxylic dianhydride and the diester used in the synthesis of the polyimine include a tetracarboxylic dianhydride used in the synthesis of polyamic acid and two identical compounds. The type and ratio of the preferred tetradecanoic dianhydride and diamine are also the same as in the synthesis of polyamic acid. The polyimine may be a fully dehydrated ring-closed fully sulfimine of the acid structure of the starting material poly-glycolic acid, or may be a partially dehydrated ring of a proline structure and a proline structure and a ruthenium structure. The amipenem is a part of the quinone imide that can coexist with the amine-only ring-16-201241047 structure. The ruthenium imidation ratio of the polyiminoimide in the liquid crystal alignment agent is preferably 3% by weight or more, more preferably 5% by weight to 99% by weight: particularly preferably from 65% to 99% by weight. The degree of nitrification is expressed as a percentage of the number of sub-structures relative to the total number of structures of the proline and the number of the quinone ring structures of the polyimine. At this time, the sputum of the quinone ring can be diazepam. The ruthenium amination rate can be known by the H-NMR of polyimine. ^ In addition, the ruthenium amide ratio in the present specification is that after the polyimine is sufficiently dried under reduced pressure in the chamber, it is dissolved in deuterated dimethyl sulfoxide, and tetramethyl decane is used as a reference material. The lH NMR measured at room temperature was determined according to the following formula (3). Brewing imidization rate (%) = 丨〇〇 (3) In the above formula (3), the peak area of the proton from the / group appears near the chemical shift of A 疋 A, and A2 is the peak area from other protons. The ratio of the number of other protons of protons relative to one νη group in the precursor of polyimine (polyproline). The dehydration ring closure of the polyamic acid for synthesizing the above polyimine is a method of heating poly-proline, or by dissolving poly-proline in an organic agent, adding a dehydrating agent to the solution The closed-loop catalyst is dehydrated and heated as needed. The latter method is preferred. Examples of the dehydrating agent include acid needles such as acetic anhydride, propionic anhydride, and trifluorocuric acid. The amount of the dehydrating agent to be used is preferably from 0.01 mol to 20 mol with respect to the structural unit of the molybdenum polyamine. The dehydration ring-closure catalyst may, for example, be a tertiary amine such as pyridine, trimethylpyridine, monomethylpyridine or triethylamine. As a dehydration closed-loop catalysis -17- 201241047 dosage of the use of the ear ~ ίο Moer. Take the closed loop reaction as a polyhydrazine. . ~150. . More preferably, it is 2.0 times. The reaction solution can be carried out from the reaction, to the liquid crystal, to the liquid crystal alignment, to the liquid crystal water-containing closed-loop catalysis separation, and to the liquid crystal-adjusted molecular polymer, and the coating is coated with the lysine. As a compound, a military as a monoanhydride, itaconic acid, n-tetradecane as an upper, n-butylamine, and a dehydrating agent for use with respect to 1 mol, it is preferred to use 〇〇i Mo as an organic solvent used in a dehydration ring closure reaction. An organic solvent exemplified by the k-acid synthesis. As the reaction temperature for the desorption, hydrazine is preferred. (:~1801, more preferably. The reaction time is preferably 1. 〇 hours~1 2 〇 hours, 〜30 hours. The liquid is supplied as it is to the preparation of the liquid crystal alignment agent, and the solution is also dehydrated. In the preparation of the agent and the dehydration ring-closing catalyst, the preparation of the donor may be carried out after the separation of the polyimine, or the preparation of the separated agent by refining the separated polyimine. Dehydration is removed from the reaction solution. As the agent and the release agent, for example, a method such as solvent replacement can be applied, and the polyimine can be produced by a known method. The polyamine or polyimine which the alignment agent can contain can be an amount of the terminal-modified polymer. By using the terminal trimming, the effect of the present invention can be impaired, and the liquid crystal properties and the like can be improved. Such a terminal-modified polymer is obtained by adding a molecular weight modifier to the polymerization reactor by the polymerization reaction, the music, and the death. The molecular weight modifier may be listed, for example, a mono-anhydride, a monoamine isocyanate compound or the like.

.-~叫-那+ — T BSL anhydride, n-decyl succinate, long-term n-dodecyl succinic anhydride butyl Ding "sour sour liver, 正六拉裳"Τ ^ 八沉基Succinic anhydride and the like. The monoamine compound may, for example, be anthranilamine, cyclohexylamine n-pentylamine, iL hexylamine, n-heptylamine, n-octylamine, n-decylamine-18-201241047 n-decylamine, n-undecylamine, ortho- 12 Amine, n-tridecylamine, n-tetradecylamine-p-pentadecylamine, n-hexadecylamine 'n-heptadecaneamine, n-octadecylamine, n-dodecylamine, and the like. The monoisocyanate compound may, for example, be isocyanate phenylacetic acid or naphthyl isocyanate. The use ratio of the molecular weight modifier is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the total of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyamic acid. The polyplycosic acid or polyimine obtained as above is produced at a concentration of 10%. / 谷液时' is preferably 201111 > 3% ~ 800 melon? The solution viscosity of &.8 is more preferably a solution viscosity of 3 〇 mPa.s to 500 mPa.s. - In addition, the present specification allows the solution viscosity (mPa.s) of the polymer to be a polymer solution having a concentration of 丨〇% by mass using a ruthenium/mixture, and a value measured at 25 using an E-type rotational viscometer. <[B]Antioxidant> The factory is called an antioxidant, and is a compound that can capture and decompose peroxidation free hydrogen peroxide generated by ultraviolet light or heat, thereby suppressing substances and oxidative degradation. If the activity of the free radicals in the [A] polymer is carried out by ultraviolet male ^ ^ , . ^ a, external line or enthalpy, a new radical secondary pervaporation is generated by the free radical, Λ-丞 基 基. (Peroxide--steps generate new radicals as described above), combined with the effect of causing the functional properties of the ruthenium molecular material, β (three) has a number of 丨 to make this & self- ά, [] antioxidant is As a result of the invalidation of the radical generated by the π-k-like sample, the function of the oxidized earth-foot agent of the polymer material can be prevented, and the pores can be prevented from being deteriorated. As the [B] antioxidant, a group which is preferably represented is preferred. [B] The antioxidant has a group having a specific structure represented by the above formula (1) or (2), and can further improve light resistance and high temperature and high humidity resistance by -19-.201241047. In the above formula (1), R1 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or a 1,3-di-butyloxybutyl group or 1,4-one oxobutyl. Further, the group represented by the formula (1) may also be one hydrogen removed from the leukoyl group, the aryl group, the aralkyl group, the 1,3-di-butyloxybutyl group and the 1,4-di-butyloxybutyl group represented by R1. The atom becomes a divalent group and forms part of the molecular chain. R to R are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having an inverse number of 7 to 13. X1 is a single bond, a carbonyl group, *-(CH2)n-0-, *-0-, or *-CONH-. Here, the linkage indicated by * is a moiety indicating a bond with a piperidine ring. Further, η is an integer of 1 to 4. X2 to X5 are independently a single bond, a few bases, and **_Ch2_ch(oh)-. Here, the connection key indicated by ** is a portion indicating a bond with the pipetting ring. In the above formula (2), R is a hydrocarbon group having 4 to 16 carbon atoms. The above hydrocarbon group may have an oxygen atom or a sulfur atom in the carbon skeleton chain. & is an integer of 〇~3. R7 is a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms. When R7 is plural, a plurality of R7s may be the same or different. Examples of the alkyl group having 1 to 2 carbon atoms represented by R include a mercapto group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, and an eleventh group. Alkyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadelonyl and the like. Examples of the aryl group having 6 to 2 carbon atoms represented by the above Ri include, for example, a strepyl group, a 3-fluorophenyl group, a 3-acetophenyl group, a 4-phenylene group, a 4-isopropylphenyl group, and 4 _ n-Butylphenyl, 3-nitro-4-methylphenyl, 4-bromodinyl, 2-phenyl-4-quinolinyl, 2-(4,-3-tributylphenyl)_4_quina Orolinyl, 2-(2,-phenylthio)-4-quinolinyl and the like. The alkyl-20-201241047 group having the carbon number i to 6 represented by the above R2 to R5 may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. The aryl group which has a carbon number of 7 to 13 represented by the above R1 to R5 may, for example, be a benzyl group or a phenethyl group. Examples of the aryl group having 6 to 12 carbon atoms represented by the above r2 to r5 include a phenyl group and the like. The hydrocarbon group having 4 to 16 carbon atoms which may have an oxygen atom or a sulfur atom in the carbon skeleton chain as the above-mentioned r6 may, for example, be a tertiary butyl group, a 1 -fluorenyl pentyl group, or an octylmethylthio group. Dodecylmethylthio and the like. The hydrocarbon group having 1 to 16 carbon atoms represented by R7 may, for example, be a methyl group, a tertiary butyl group, a 1-methylpentadecyl group or an octylmethylthio group. As the [B] antioxidant, a commercially available product can be used, and examples thereof include a phenol-based antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and a mixed compound thereof. They may be used alone or in combination of two or more.

As a commercial product of a phenolic antioxidant, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-80, ADK STAB AO-330 (above made by ADEKA), IRGANOX 1010, IRGANOX1 035, IRGAOX1076, IRGANOX1 098, IRGANOX1 135, IRGANOX1 330, IRGANOX1726, IRGANOX1425, IRGANOX1520, IRGANOX245, IRGANOX259, IRGANOX3114, IRGANOX3790, IRGANOX5057, IRGANOX565, IRGAMOD295 (above) Manufactured for BASF )) and so on. Examples of commercially available products of the amine-based antioxidant include ADK STAB LA-52, LA-57, LA-63, LA-68, LA-72, LA-77-21-.201241047, LA-8 1, LA-82, LA-87, LA-402, LA-5 02 (above manufactured by ADΕΚΑ), CHIMASSORB1 19, CHIMASSORB 2020, CHIMASSORB944, TINUVIN622, TINUVIN123, TINUVIN144, TINUVIN765, TINUVIN770, TINUVIN111, TINUVIN783, TINUVIN791 (above BASF)曰本制造), etc. As a commercially available product of a phosphorus-based antioxidant, for example, apk STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-36 'HP-10, 2112 (above, manufactured by ADEKA), IRGAFOS168, GSY-P101 (above), IRGAFOS168, IRGAFOS12, IRGAFOS126, IRGAFOS38, IRGAFOS P-EPQ (above, manufactured by BASF). The commercially available product of the sulfur-based antioxidant may, for example, be ADK STAB AO-412, ADK STAB AO-503 (above, manufactured by ADEKA), IRGANOX PS 800 or IRGANOX PS 802 (above, BASF manufactured by BASF). Commercially available products of the mixed antioxidant include, for example, ADK STAB A-611, ADK STAB A-612, ADK STAB A-613, ADK STAB AO-37, ADK STAB AO-15, ADK STAB AO-18, 328 (above is manufactured by ADEKA), TINUVIN111, TINUVIN783, TINUVIN791 (above, manufactured by BASF). Among these commercially available products, preferred are phenol-based antioxidants and amine-based antioxidants. The content of the [B] antioxidant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, particularly preferably 0.1 part by mass to 3 parts by mass or less per 100 parts by mass of the [A] polymer. -22-201241047 <Optional Ingredients> For the liquid crystal alignment agent, in addition to "A1 poly", you may contain [A], and may contain [A in the range which does not impair the effect of the present invention. Any other component such as a polymer other than the polymer or a functional decane compound. Each of the optional components may be used singly or in combination of two or more. Hereinafter, each component will be described in detail. [Other polymers] Other polymerizations The material can be used to improve solution characteristics and electrical properties. As other polymers, for example, polyphthalate, polyester, polyamine, polyoxo, cellulose derivative, polyacetal, polystyrene can be cited. Ethylene derivative, poly(styrene-phenylmaleimide) derivative, poly(methyl) acrylate vinegar, etc. In addition, the content of other polymers can be appropriately determined according to the purpose [s energy smashing The compound may contain a functional decane compound from the viewpoint of further improving the printability of the liquid crystal alignment agent. Examples of the functional decane compound include 3-aminopropyltrimethoxy decane and 3-aminopropyl acrylate. Base three Basear, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxysulfate, N-(2-aminoethyl)-3-aminopropyltrimethoxycarbazide, Ν-(2·Aminoethyl)_3_aminopropylmercaptodimethoxydecane, 3-ureidopropyltrimethoxy decane, 3-ureidopropyltriethoxy decane, hydrazine- Ethoxycarbonyl-3-aminopropyltrimethoxydecane, Ν-ethoxycarbonyl-3-aminopropyltriethoxydecane, Ν-triethoxydecylpropyltriisoethylenetriamine , Ν-trimethoxydecylpropyltriamine, tris-tridecyloxy-1,4,7-triazadecane, 10-triethoxydecyl-1,4, 7-三-23- 201241047 Azadecane, 9-trimethoxydecyl _3 6 匕 oxadiazepine 7 ώ 9 -diethoxy sulphide-3,6-dioxanthracene 7 夂 夂 vinegar, 丞 acetate, Ν-propyl trimethoxy decane, Ν-benzyl w, decyl-3-amine ''mercaptopropyl three, N-phenyl-3-amino Propyltrimethoxy 石 χ τ _~ 一 — /, Ν, Ν-phenyl _ ethoxy decane, Ν-bis (epioxyethyl) hexyloxydecane 3 'aminopropyl jj alkane, Ν-double Oxygen oxyethyl)_3_aminopropyldioxadimethoxy sulfonium & oxetene, yoshizhe, leuco pentane compound, the ratio of use 疋4. as a compound, preferably 2 mass The liquid crystal alignment agent is preferably the above-mentioned agent. Preferably, it is 0.1 parts by mass or more by mass. Preferably, it is 0.1 part by mass to 1 part by mass. <Preparation method of liquid crystal alignment agent> And an optional component added as needed: a composition called an antioxidant to form a solution. "In an organic solvent, the preparation is as an organic solvent, for example, Ν-methyl-2-pyrrolidone, γ-butylene S曰, γ_butylide, Ν di-methylformamide, ν,ν-dimethylacetamide, 4-hydroxy-4-indolyl-2-pyrene, pentylene, butyl citrate , butyl acetate methoxy propylene vinegar, ethyl ethoxy propionic acid brewing, ethylene glycol monomethyl ether, ethylene glycol monoethyl isopropyl hydrazine, ethyl propyl propyl sulfonate, ethylene glycol % early n-butyl ether (butyl race), ethylene glycol dimethyl test, ethyl alcohol ethyl ether acetate, diethylene glycol didecyl ether, di-fermented diethyl shunt, two Glycol monomethyl...ethylene glycol Ethyl vinegar, "methyl ether ethyl vinegar, diethylene glycol monoethyl ether acetate I: isobutyl _, isoamyl propionate, isoamyl isobutyrate, di: diether, carbonic acid extension Ethyl ester, propyl carbonate, and the like. They can be used alone or in combination of 'and s'. '24- 201241047 The solid content concentration of the liquid crystal alignment agent (the ratio of the total mass of the components of the liquid crystal alignment agent excluding the organic solvent to the total mass of the liquid crystal alignment agent) is preferably selected in consideration of viscosity, volatility, etc., preferably i mass%~1 〇 quality 罝%. When the liquid crystal alignment agent is applied to the surface of the substrate and the coating film constituting the liquid crystal alignment film is formed by removing the organic core agent, when the solid content concentration is less than 1% by mass, the film thickness of the coating film is too thin, and it is difficult to obtain a good liquid crystal alignment. On the other hand, when the solid content concentration exceeds ίο% by mass, the film thickness of the positive coating film is too thick, and it is difficult to obtain a favorable liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent may increase to deteriorate the coating characteristics. The more preferable solid content concentration range differs depending on the method used when the night crystal alignment agent is applied to the substrate. For example, it is preferably in the range of from h5 mass% to 4.5 mass% by spin coating. By the printing method, it is more than 3 mass. /. The range of ~9 mass%' solution viscosity is in the range of 12 milk·s~5〇mPa_s. By 1 - * 0 / , ^ θ U body composition concentration is preferably in the range of Berry / 〇 ~ 5 Bay $ %, the range of solution viscosity · S. Further, it is preferably 3 mPa.s to 15 mPa as the liquid crystal alignment agent, more preferably (10) to 3 (rce degree, preferably (10) to (4) < formation method of liquid crystal alignment film by 兮ta, Method for producing a member> "Liquid alignment film formed by a liquid helium alignment agent and having the same

. The liquid crystal display elements of the film are suitably packaged with Bgs--^ in any of the present invention. The liquid crystal .4 is suitable for use in various devices, such as machine, word processing, m m. clock, palm game, note information terminal, number navigation system, camera LCD TV and other display devices. ° Various .4 Unhelpful, -25- 201241047 The liquid crystal alignment film of %% is coated on the substrate by the liquid crystal alignment agent', and then formed on the substrate by heating the coated surface. Further, the liquid crystal display element of the present invention comprises the liquid crystal alignment film. The method of forming the liquid crystal alignment film and the method of producing the liquid crystal display element will be described below in detail. (1-1) When manufacturing a TN type, STN type or VA type liquid crystal display element, it is preferable to form a pair of substrates on which the patterned transparent conductive film is provided as a pair, and to form a surface of each of the transparent conductive films. The liquid crystal alignment agent of the present invention is applied by a plate printing method, a spin coating method or an inkjet printing method, and then a coating film is formed by heating each coated surface. As the substrate, for example, glass such as floating glass or soda glass; plastic containing polyethylene terephthalate, butylene dibutyl phthalate, polyether sulfone, polycarbonate, alicyclic olefin, or the like can be used. Transparent substrate. As the transparent conductive film 'provided on one surface of the substrate, a NESA film made of tin oxide (Sn〇2) (registered trademark of PPG, USA), an ITO film made of indium oxide-tin oxide (IhOrSnO2), or the like can be used. . As a method of obtaining the patterned transparent conductive film, for example, a method of forming a pattern by forming a transparent conductive film without a pattern, a method of forming a pattern with a desired pattern when forming a transparent conductive film, or the like can be exemplified. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the plate and the transparent conductive film and the coating film, the pre-coated functional stone compound compound can be applied to the surface on which the surface of the film is formed on the surface of the film. , -& 前 Pre-treatment of b-titanium compounds, etc. After the liquid crystal alignment agent is applied, in order to prevent dripping, the -26-201241047 is preheated (pre-twisted, 咏, .., top L-peel). As the prebaking temperature, it is preferably 30 C to 200 ° C, and more. wide,.吏佳 is 40C~150C, especially good 40. (:~100. (:.

As a pre-baked time, it is preferable to use 2. 2 5 for the clock ~ 1 〇 minutes, more preferably 〇 5 minutes ~ 5 minutes. In order to completely remove the solvent, according to the requirement I, the conjugated yoke (post-baking) of the hot yttrium-polymerized polyamic acid is used as the post-baking temperature, preferably 80 ° C~3 〇〇. ", φ技术* n Λ. More preferably 1 2 0 C~2 5 0 ° C. The time for post-cultivation is preferably 5 minutes to 2 minutes, more preferably 1 minute to 1 minute. The film thickness of the coating film to be formed is preferably (4), more preferably 0.005 μηι 〇.5μηι ° (1-2) When the i^ips type liquid crystal display element is manufactured, the ^Hi 丨卞吋 is set at 6 On the side of the vine-rained conductive film forming surface of the substrate of the transparent conductive film patterned by the comb-tooth and the opposite substrate on which the conductive film is not provided, it is also recommended that the stencil printing method The liquid crystal alignment agent of the present invention and the known liquid crystal alignment agent are respectively applied by a spin coating method or an inkjet printing method, and then a coating film is formed by heating each coated surface. The material of the substrate for the enamel and the transparent conductive film, and the pattern of the transparent conductive film are slaughtered. The method of pre-treating the substrate, the pretreatment of the substrate, and the heating method after applying the liquid crystal alignment agent are the same as the above-mentioned u-υ. The preferred film thickness of the formed coating film is the same as that of the above (丨_丨). (2) When the liquid-day display element of the sk manufactured by the method of the present invention is a VA-type liquid crystal display element, it may be such as μ Λ / 2, such as The coating film formed by the coating is used as the liquid crystal alignment film as it is, but it can be used after the rubbing treatment which is desired to be returned in the future. On the other hand, when the liquid crystal display element other than the eight types is manufactured, 'The liquid crystal alignment film is produced by the coating film formed as described above. The -27-201241047 is rubbed with nylon, for example, with respect to the coating film surface formed as described above. The roll of the cloth made of fibers such as crepe or cotton is rubbed in a predetermined direction. Thereby, the alignment of the liquid crystal molecules can be applied to the coating film to form a liquid crystal alignment film. Further, for the liquid crystal alignment film formed as described above, for example, A process of changing a pretilt angle of a portion of the liquid crystal alignment film by irradiating ultraviolet rays to a portion of the liquid crystal alignment film shown in Japanese Patent Application Laid-Open No. Hei 6-222366, No. Hei. - After forming a resist film on a portion of the surface of the liquid crystal alignment film shown in 1 0 7 5 4 4, after performing rubbing treatment in a direction different from the previous rubbing treatment, 'removing the protective film By making the liquid crystal alignment film have different liquid crystal alignment energy in different regions, the field of view characteristics of the obtained liquid crystal display device can be improved. (3) Preparing two substrates on which the liquid crystal alignment film has been formed, by two substrates disposed in opposite directions The liquid crystal cell is disposed between the liquid crystal cells. Here, when the coating film is subjected to the rubbing treatment, the two substrates are disposed at a predetermined angle to each other in the rubbing direction of each of the coating films, for example, vertically or anti-parallel. The liquid crystal cell system can be exemplified by the following two methods. As a first method, a well-known method is known. First, each liquid crystal alignment film is opposed to each other with a gap (cell gap) therebetween. The peripheral portion of the bulk substrate is bonded with a sealant, and after filling the liquid crystal into the liquid crystal cell partition defined by the surface of the substrate and the sealant, the liquid crystal cell is produced by closing the injection hole. As a second method, a method called a DropDF (One Drop Fill) method applies a UV curable sealing material to a predetermined position on a substrate of two substrates 10 on which a liquid crystal alignment film is formed, and further Liquid -28- 201241047 BB Pressurized Heat Chamber Crystal Ball 〇 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶 晶The substrate is simultaneously exposed to the entire surface of the substrate. Then, the entire surface of the substrate is irradiated with ultraviolet light, and the sealing agent is hardened to produce a liquid crystal cell. In either method, it is desirable to add the liquid crystal cell produced above to the temperature at which the liquid crystal used is at the temperature of the isotropic phase, and then slowly cool to a temperature to remove the flow alignment at the time of liquid crystal injection. Thus, the liquid crystal display element is obtained by bonding a polarizing plate to the outer surface of the liquid cell. The sealant' may, for example, be an epoxy resin containing alumina and a curing agent used as a spacer. As the liquid crystal, for example, a liquid crystal, a liquid crystal, or the like can be cited. Among them, a nematic liquid crystal VA type liquid crystal cell is preferable, and a nematic liquid crystal having a negative dielectric anisotropy is preferable. Examples of such a liquid crystal include, for example, a dicyanobenzene-based liquid, a harpyridin liquid crystal, a Schiff base liquid crystal, an oxyazo liquid crystal, a biphenyl liquid t, and a phenylcyclohexane liquid crystal. In the case of a 液晶-type liquid crystal cell or a liquid-type cell, it is preferable that the positive dielectric anisotropy is such a liquid crystal, and examples thereof include a liquid crystal and a phenylcyclohexene-1 liquid crystal. , a triphenyl liquid crystal, a joint stupid gas burning liquid to the liquid. In addition, the cyclooctane liquid crystal can be further added, for example, as a chaotic cholesterol, cholesterol acid alcoholic liquid crystal (manufactured by Merck, c 5 9 S sterol carbonate, etc.; A commercially available hand-dielectric liquid crystal or the like such as oxybenzylidene or 215) is used. Mercaptobutyl cinnamate, etc. As a polarizing plate bonded to the outer surface of the liquid crystal cell, vinegar -29-.201241047

The acid cellulose protective film is sandwiched between a value called "H < _,." J J. Nine film, or a polarizing plate composed of a ruthenium film itself, which is obtained by absorbing iodine while being alcohol. The invention is described in detail below based on the examples, but the description based on the examples is not intended to limit the explanation of the invention. , μ <[Α] Polymer Synthesis> [Synthesis Example 1] 2,3,5-tris-m-cyclopentylacetic acid di-hepatic (TCA) as Siqian Erxuan 17.9 g (0.08^^) ^l5353a5 4 5 5 5 9b^^.5. (Eg4.2; 5. Bilateral oxy-3-indolyl)_naphthoquinone, 2_c]. Furan], 3_dione (τ 6 (0.02 mol), and p-phenylenediamine (pDA) 2 & ((4) 2 mol), 3,5-diaminobenzoic acid cholesta Alkyl ester (HCDA) l〇.4g (〇.〇2mol) and 3,5-diaminobenzoic acid (DAB) 9 lg (〇% molar) dissolved in i82g of N-methyl-2-pyrrole In a ketone (NMp), a solution having a solution containing 10% by mass of polyaminic acid obtained by reacting for 6 hours under 6 〇χ: solution has a solution viscosity of 99 mPa·s. Then, the obtained poly is obtained. 423 g of NMP 'Addition of pyridine 7.9 g and acetic anhydride i〇.2 g were added to the proline solution, and the dehydration ring-closure reaction was carried out for 4 hours at u〇°c. After the dehydration ring closure reaction, the solvent in the system was used. The NMP is subjected to solvent replacement to obtain a solution containing i 5 mass% of polyimine (A_i) having a ruthenium iodide ratio of about 51%. A small amount of the obtained polyimine solution is added and NMP is added to obtain a solution. The solution having a polyimine concentration of 10% by mass was measured to have a solution viscosity of 55 rnpa·s. [Synthesis Example 2] 18.0 g (0.08 mol) and 1,3,3a, - as TCA of tetracarboxylic dianhydride. 30- 201241047 4,5,9b-hexahydro-8-methyl _5_(tetrahydro-2,5_di-sideoxy-3_furanyl)_cai[1,2<]furan-1,3-dione (]^丁〇8)6.3§(0.02 mol), And PDA 2.2g (0.02 mol), HCDA 10,5 g (〇.02 mol) and DAB 9.2 g (0,06 mol) as diamine were dissolved in 185 g of NMP and reacted at 60 ° C. In the hour, a solution containing 10% by mass of poly-proline was obtained. The solution viscosity of the obtained polyaminic acid solution was 92 mPa·s. Next, 429 g of NMP was added to the obtained poly-proline solution, and pyridine 8.0 g was added. And dehydration ring closure reaction of acetic acid g^1〇3g at 4 ° C for 4 hours. After the dehydration ring closure reaction, 'the solvent in the system was replaced with a new NMP solvent to obtain 15% by mass. A solution of polyimine (A_2) having an imidization rate of about 48%. A small amount of the obtained polyimine solution was added and NMp was added to prepare a solution having a polyamidene concentration of 1% by mass. The solution viscosity was 50 mPa·s. [Synthesis Example 3] 18.0 g (0. 〇8 mol) and 2,4,6, 8-tetracarboxybicyclo[3.3.0]octane of TCA as tetracarboxylic dianhydride. -2,4,6,8-dianhydride (B〇DA) 5.0g (0.02 mol), and as Amine PDA 2.2 g (0.02 mol), HCDA l〇.5 g (0. 〇 2 mol) and DAB 9.2 g (0.06 mol) were dissolved in I79 g of NMP 'reaction at 60 ° C for 6 hours to obtain A solution containing 1% by mass of polyglycine. The solution viscosity of the obtained polyaminic acid solution was 8 μmPa·s. Next, 4 16 g of NMP was added to the obtained polyaminic acid solution, and 7.9 g of pyridine and 1.0 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out for 1 hour at 1 1 (TC). By dissolving the solvent in the system with a new NMP, a solution containing 15% by mass of a polyamidimide (A-3) having a ruthenium iodide ratio of about 50% was obtained. Polythene-31-.201241047 The imine solution was added with NMP ', and the solution having a polypyramine concentration of 丨〇% by mass was determined to have a solution viscosity of 42 mPa·s. [Synthesis Example 4] Anhydride TCA 22.5 g (0.1 mol), and 1-(4-aminophenyl)-2,3-dihydro-l,3,3-trimethyl-1H-indole-5- as a diamine a mixture of an amine and 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indole-6-amine (TMDA) 10.7 g (0.04 mol) and HCDA 10.5 g (〇.〇2 mol) and DAB 6.1 g (0.04 mol) were dissolved in i99 g of NMP, and a solution containing 1 〇 mass% polyaminic acid was obtained at 60 ° (6 hours). The solution viscosity of the obtained polyaminic acid solution was 8 OmPa·s. Then, the obtained polyfluorene 4 6 2 g of Ν Μ P was added to the amine acid solution, and 7.9 g of bite and 10.2 g of acetic acid were added for 4 hours of dehydration ring closure reaction at 1 l ° ° C. After dehydration ring closure reaction 'by The solvent was replaced with a new solvent 'P to obtain a solution containing 15% by mass of a polyamidimide (Α-4) having a ruthenium iodide ratio of about 44%. The solution was added with ΑΝΜρ to prepare a solution having a concentration of 1 〇 mass%, and the measured solution viscosity was 66 mPa·s. [Synthesis Example 5]

TCA 18.0 g (0.08 mol) and TDA 6.0 g (0.02 mol) as tetracarboxylic dianhydride, and TMDA 5.3 g (〇.〇2 mol) as a diamine and HCDA 10.5 g (〇.〇) 2 Mohr) and DAB 9_2g (0.06 mol) were dissolved in 19 6 g of NMP at 60. The mixture was reacted for 6 hours to obtain a solution containing 1% by mass of poly-proline. The solution viscosity of the obtained polyaminic acid solution was 84 mPa*s. Then, 455 g of NMp ' was added to the obtained polyamic acid solution. The pyridine was 7.9 g and acetic anhydride 1 g 2 g, and the -32-201241047 dehydration ring-closing reaction was carried out at 110 ° C for 4 hours. After the dehydration ring-closure reaction, a solvent containing 5% by mass of a polyamidiamine (A-5) having a ruthenium amination ratio of about 49% was obtained by solvent-replacement of a solvent in the system with a new NMP. A small amount of the obtained polyimine solution was added and NMP was added to prepare a solution having a polypyridamine concentration of 1 〇% by mass, and the measured solution viscosity was 52 mPa·s. [Synthesis Example 6] TCA, which is tetracarboxylic dianhydride, 17.9 g (0.08 mol) and MTDA 6.3 § (0. 〇 2 mol), and as a diamine, butyl glutinous glutinous glutinous rice Ears, HCDA 10.4g (0.02 moles) and DAB 9.1g (0.06 moles) were dissolved in 196 g of NMP at 60. The reaction was carried out for 6 hours under the arm, and a solution containing 10% by mass of poly-proline was obtained. The solution viscosity of the obtained polyaminic acid solution was 75 mPa*s. Next, 455 § of NMP was added to the obtained polyamic acid solution, 7.9 g of pyridine and 酎i〇 2 g of acetic acid were added, and a dehydration ring-closure reaction was carried out for 4 hours at 1 μC. After the dehydration ring-closure reaction, a solvent containing 5% by mass of ruthenium iodide (a-6) having a ruthenium iodide ratio of about 5% by mass was obtained by replacing the solvent in the system with a new NMP. A small amount of the obtained polyimine solution was added and NMP was added to prepare a solution having a polyamidene concentration of 1% by mass, and the measured solution viscosity was 49 mPa·s. [Synthesis Example 7] TCA 17 8 g (〇〇8 mol) and B〇da 5-_0 g (0.02 mol) as tetracarboxylic dianhydride, and tmdA 5.3 g as diamine (〇_〇2 Mo) Ears, HCDA 10.4g (0.02 moles) and DAB 9.1g (0.06 moles) were dissolved in 190 g of NMP at 60. (: The next reaction was carried out for 6 hours to obtain a solution containing 1% by mass of poly-proline. The solution viscosity of the obtained polyaminic acid solution was 85 mPa*s *, and then added to the obtained poly-proline solution - 33- .201241047 NMP, adding pyridine 7.9g and acetic anhydride l〇.2g, 4 hours of dehydration ring closure reaction at 1 lCTC. After dehydration ring closure reaction 'by solvent replacement of the solvent in the system with new NMP, A solution of a polyimine (A-7) having an imidization ratio of about 15% by mass of about 15% was obtained. A small amount of the obtained polyimine solution was added and NMP was added to obtain a polyfluorene. A solution having an imine concentration of 1 〇 mass%, and a solution viscosity of 5 〇mP a · s was measured. [Synthesis Example 8] TCA 20.1 g (0.09 mol) and TdA 3.0 g (0.01) were used as the tetracarboxylic dianhydride. Mohr), and Pda 2.2g (〇.〇2 Moer), HCDA l〇.4g (〇_〇2 Moer) and DAB 9_lg (0_06 Moer) as diamines are dissolved in NMP 17 9g, The reaction was carried out at 60 ° C for 6 hours to obtain a solution containing 1% by mass of poly-proline. The solution viscosity of the obtained polyaminic acid solution was 1 12 mPa*s. NMP in the proline solution was added with 7.9 g of pyridine and 10.2 g of acetic anhydride, and the dehydration ring-closure reaction was carried out for 4 hours under 1 l〇t: After the dehydration ring closure reaction, the solvent in the system was used. The new NMP was subjected to solvent replacement, and a solution containing 15% by mass of a polyamidimide (A-8) having a ruthenium iodide ratio of about 52% was obtained. A small amount of the obtained polyimine solution was added and NMP was added. A solution having a polyamidene concentration of 10% by mass was obtained, and the measured solution viscosity was 69 mPa·s. [Synthesis Example 9] TCA 20.2 g (0.09 mol) and MTda 3.1 将 (tetracarboxylic dianhydride) were used. 0.01 mol), and as a diamine, 2.28 2.2§(〇.〇2mol), HCDA 10.5g (0.02 mol) and DAB 9.1g (0.06 mol) are dissolved in 18 lg of NMP, The reaction was carried out at 60 ° C for 6 hours to obtain a solution containing 1% by mass of poly-proline. The solution viscosity of the obtained polyaminic acid solution was -34 - 201241047 120 mPa · s. Next, the obtained polyamine solution was obtained. 419 g of NMP was added, and 10.2 g of pyridine 8. 〇g and acetic anhydride was added, and a dehydration ring-closure reaction was carried out at 10 ° C for 4 hours. Thereafter, a solution containing 15% by mass of a polyamidimide (A-9) having a ruthenium iodide ratio of about 49% was obtained by subjecting the solvent in the system to a solvent replacement with a new NMP. The solution of the polyimine solution was added to NMP to prepare a solution having a polyamidene concentration of 1% by mass, and the measured solution viscosity was 75 mPa.s. [Synthesis Example 10] 20.2 g (〇.09 mol) of TC A as a tetracarboxylic dianhydride, and BOD A 2.5 § (0.01 mol), and as a diamine. 〇8 2.2§ (0.02 mol), HCDA 10.5g (0.02 mol) and DAB 9_lg (〇.〇6 Moer) are dissolved in 17 8g of NMP at 60. The mixture was reacted for 6 hours to obtain a solution containing 1% by mass of poly-proline. The solution viscosity of the obtained polyaminic acid solution was 119 mPa·s. Next, deuterated NMP was added to the obtained polyamic acid solution, and 7.9 g of pyridine and 2 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out for 4 hours at ll °C. After the dehydration ring closure reaction, a solvent containing 5% by mass of ruthenium iodide (a-1 〇) having a ruthenium iodide ratio of about 5% by mass was obtained by replacing the solvent in the system with a new NMP. A small amount of the obtained polyimine solution was added and NMP was added to prepare a solution having a polyamidene concentration of 1% by mass, and the measured solution viscosity was 68 mPa·s. [Synthesis Example 1 1] 22.4 g (0.1 mol) of TCA as a tetracarboxylic dianhydride, and 2.7 g (0. 〇l mol) as a diamine, and HCDA 10.5 g (0. 〇2 mol) as a diamine. And DAB 10.7 g (0.07 mol) was dissolved in i85 g of NMP, and reacted at 6 ° C for 6 hours to obtain a solution containing 1 〇 mass % polyaminic acid. The obtained poly-35- 201241047 proline solution has a solution viscosity of 10 1 mPa · s. Next, 429 g of NMP was added to the obtained polyamic acid solution, and 7.9 g of pyridine and 10.2 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out for 4 hours at 1 l °C. After the dehydration ring closure reaction, a solvent containing 15% by mass of a polyamidimide (A-1) having a ruthenium iodide ratio of about 53% was obtained by subjecting the solvent in the system to a solvent replacement with a new NMP. A small amount of the obtained polyimine solution was added and NMP was added to prepare a solution having a polyamidene concentration of 1% by mass, and the measured solution viscosity was 59 mPa*s. [Synthesis Example 12] 22.4 g (0.1 mol) of TCA as tetracarboxylic dianhydride, and as two

Amine PDA 2.6 g (0.02 mol), HCDA 10.4 g (0.02 mol) and DAB 9.1 g (0.06 mol) were dissolved in 18 g of NMP at 60. The reaction at C was carried out for 6 hours to obtain a solution containing 10% by mass of poly-proline. The solution viscosity of the obtained polyaminic acid solution was 102 mPa·s. Next, 410 g of NMP was added to the obtained polyaminic acid solution, and pyridine 7_9 g and acetic anhydride 1 〇 2 § ' were added to carry out a dehydration ring-closure reaction at 1 10 C for 4 hours. After the dehydration ring closure reaction, a solvent containing 15% by mass of a polyamidimide (A-12) having a ruthenium iodide ratio of about 47% was obtained by subjecting the solvent in the system to a solvent replacement with a new NMp. A small amount of the obtained polyimine solution was added and NMp was added to prepare a solution having a polyamidene concentration of 1% by mass, and the measured solution viscosity was 56 mPa·s. [Synthesis Example 1 3] TCA 22 3 g (molar) as a tetracarboxylic dianhydride, and 4,4'-diaminodiphenyl decane as a diamine 39 g (〇〇2 mol) , 5.2g (0_01 mol), cholalyloxy·2 4 diaminobenzene * -36· .201241047 Mo) and DAB 9_lg (0.06 mol) dissolved in i82g of NMP at 60 ° The reaction was carried out for 6 hours under C' to obtain a solution containing 1% by mass of poly-proline. The solution viscosity of the obtained polyaminic acid solution was 1 1 7 mP a · s. Next, 423 g of NMP was added to the obtained polyamic acid solution, and a dehydration ring-closure reaction was carried out at 10 ° C for 4 hours by adding 〇 咬 〇 2 2 2 2 2 。 。 。 。 。 。 。 。 。. After the dehydration ring closure reaction, the solvent was replaced by a solvent of the system using a new Ν μ P to obtain a 15% by mass of a styrene (A-1 3 ) having a ruthenium iodide ratio of about 67%. )The solution. A small amount of the obtained polyimine solution was added and hydrazine was added to prepare a solution having a polythenimine concentration of 1% by mass, and the measured solution viscosity was 70 mPa*s. <Preparation of Liquid Crystal Aligning Agent> The [B] antioxidant used in the preparation of each liquid crystal alignment agent is as follows. <[B]Antioxidant> B-1 : IRGANOX 1010FF (phenolic antioxidant) B-2 : ADK STAB LA-72 (amine antioxidant) B-3 : TINUVIN622LD (amine antioxidant) B · 4 : IR GAFOS 1 2 (filling antioxidants) B-5 : IRGANOX PS 800FL (sulfur-based anti-gasification agent) B-6 : ADK STAB AO-40 (phenol-based antioxidants) [Example 1] Containing 100 masses As a solution of [A] poly eight private & l J non-σ polyimine (Α-1), hydrazine and ethylene glycol-mono-n-butyl butyl butyl ether were added, and 3 parts by mass were added as [ B] The above-mentioned (B-1) of the antioxidant and the stirring of the 兄八兄 knife, and the solvent composition is NMP: ethylene glycol-mono-n-butyl 鲢 = 6 ου · 4 〇 (mass ratio), solid-37- 201241047 A solution having a body composition concentration of 3 · 〇 mass %. This solution was filtered using a filter of pore size ημηι to prepare a liquid crystal alignment agent. [Examples 2 to 2 3 and Comparative Examples 1 to 9] The liquid crystal alignment agents were prepared in the same manner as in Example 1 except that the types and contents of the components to be formulated were the same as those described in Table 1. In addition, "-" in Table 1 indicates that the component is not used. <Formation of Liquid Crystal Alignment Film> Each liquid crystal alignment agent was applied by a spin coater on a transparent electrode surface of a glass substrate having a transparent electrode including a ruthenium film having a thickness of 1 mm, on a hot plate at 80° Prebaking was carried out for 1 minute at C, followed by post-grinding at 30 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of about 80 nm. <Production of Liquid Crystal Display Element> The liquid crystal alignment film is formed to obtain a pair of (two pieces) substrates having a liquid crystal alignment film. Then, after applying an epoxy resin adhesive having a diameter of 5 · 5 μm oxidized to Lu ball on the outer edge of a certain block of the liquid crystal alignment film having the pair of substrates, the liquid crystal alignment film surface is pressed against the film. , harden the binder. Next, a nematic liquid crystal (manufactured by Merck, MLC-6608) was filled between the pair of substrates by a liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell. In addition, the operation is repeated to fabricate another pair of liquid crystal cells. <Evaluation> The liquid crystal alignment film formed above and the produced liquid crystal display element were evaluated as follows. The results are shown together in Table 1. [Lightfastness] -38- 201241047 The above-mentioned „ oblique a team + time and 167° °. . After applying a voltage of 5 V at an interval of 60 μsec applied ,, use τ〇γ〇

The VHR measured by the Corporation has a measured voltage holding ratio of 1 (except for the initial 167 ms connection (4) and the initial voltage holding ratio (VH1) (%). Receiver, the initial voltage holding rate of the light source is measured. Box Zhao _ _ main ^ use carbon arc as ... invites ... hours of light. After the light is irradiated, the liquid cell is again measured in the same way as the previous method. The voltage is the voltage after the light is irradiated (4) (VH2) (%) ^^ Measuring ring (10)) is obtained by the following formula as light resistance. AVHR(%) = vHl-vH2 △ When the anger is less than 2.5%, it is judged that the light resistance is excellent, and when it is 2.5% or more and less than 5.0%, it is judged to be light resistant. Good, it is judged that the light resistance is not good at 5.〇%. [耐尚温南湿性] The other pair of liquid crystal cells of the above system are at 7 〇. The application time of 6 〇 microseconds is After a voltage of 5 V was applied to the interval of 167 msec, the voltage holding ratio after 167 msec from the release of the application was measured by VHR] manufactured by τογο Corporation. This value is used as the initial electric power retention ratio (vH3) (%). The liquid crystal cell after the voltage holding rate is stored in an oven set to 6 (rc, humidity 90% for 5 hours) The voltage holding ratio was measured again by the same method as described above. This value was taken as the voltage holding ratio (VH4) (%) after high temperature and high humidity resistance. The amount of decrease in voltage holding ratio ΔVHR,") was obtained by the following formula. High temperature and high humidity. △ VHR'(〇/〇) = VH3-Vh4 △ When VHR is less than 3.0%, it is judged that it is excellent in high temperature and high humidity resistance. When it is -39 to 201241047 3.0% or more and less than 5.0%, it is judged that high temperature and high humidity resistance are good. When it is 5.0% or more, it is judged that the high temperature and high humidity resistance are unacceptable. [Table 1] Evaluation of composition of liquid crystal alignment agent [Α] Polymer [Β] radical supplement VH, (%) Light resistance (%) Resistance to moisture (%) Type content (parts by mass) Type content ( Parts by mass) Example 1 Α-1 100 Β-1 3 99.1 3.8 2.6 Example 2 Α-2 100 Β-1 3 99.2 3.4 2.5 Example 3 Α-3 100 Β-1 3 99.1 4.4 2.7 Example 4 Α- 4 100 Β-1 3 99.1 4.2 2.9 Example 5 Α-5 100 Β-1 3 99.4 2.2 2.1 Example 6 Α-6 100 Β-1 3 99.6 2.4 1.5 Example 7 Α-7 100 Β-1 0.1 99.2 2.5 1.8 Example 8 Α-8 100 Β-1 10 98.9 4.4 4.6 Example 9 Α-9 100 Β-1 5 98.8 4.2 4.8 Example 10 Α-10 100 Β-1 3 98.9 3.8 4.1 Example 11 Α-11 100 Β-1 3 98.9 3.9 4.1 Example 12 Α-4 100 Β-2 3 99.5 4.2 2.6 Example 13 Α-4 100 Β-3 3 99.5 4.0 2.6 Example 14 Α-4 100 Β-4 3 99.1 4.7 2.8 Implementation Example 15 Α-4 100 Β-5 3 99.1 4.9 2.8 Example 16 Α-4 100 Β-6 1 99.4 4.1 2.5 Example 17 Α-4 100 Β-1 0.1 98.9 4.9 3.9 Example 18 Α-4 100 Β- 1 10 99.8 3.1 4.8 Example 19 Α-5 100 Β-2 3 99.5 1.9 2.2 Example 20 Α-5 100 -3 3 99.2 2.0 2.5 Example 21 Α-11 100 Β-4 3 98.7 4.5 4.7 Example 22 Α-11 100 Β-5 3 99.0 4.2 4.7 Example 23 Α-11 100 Β-6 3 98.9 3.9 4.8 Comparative Example 1 Α-12 100 - - 97.2 10.5 9.9 Comparative Example 2 Α-12 100 Β-1 3 99.2 3.8 8.8 Comparative Example 3 Α-12 100 Β-2 3 99.5 3.5 6.9 Comparative Example 4 Α-12 100 Β-3 3 99.4 3.8 7.7 Comparative Example 5 Α-13 100 - - 97.6 9.1 10.3 Comparative Example 6 Α-13 100 Β-1 3 99.5 3.1 6.2 Comparative Example 7 Α-13 100 Β-1 10 99.5 3.0 10.7 Comparative Example 8 Α-1 100 - - 97.2 10.2 6.9 Comparative Example 9 Α-1 100 - - 97.3 8.8 5.3 -40- .201241047 The results from Table i can be clearly seen in the case of light stress, heat and m. In addition, the liquid crystal alignment agent according to the present invention can form a good electric power for a long period of time under a severe environment of ', ', and humidity f. Characteristic liquid crystal alignment 胄. Therefore, the display quality of the liquid crystal display element of the present invention is suitable for use in various devices, such as: watches, processors, notebook computers, car navigation systems, digital cameras, digital cameras, mobile phones, various displays, etc. Device. [Simple description of the diagram] None. [Main component symbol description] None. The liquid crystal alignment agent continuously performs the crystal alignment film in time. Even when the light stress is applied and driven, the liquid crystal alignment can be reduced less, and there can be a handheld game machine, a text camera, a video camera, a portable display, and a liquid crystal.

Claims (1)

• 201241047 VII. Patent application scope: 1 · 'A liquid crystal alignment agent, and Λ Λ -JL·. Γ A -1 ^ * /, system 3 has [A] containing poly-proline and dehydrating the poly-aracine At least one polymer selected from the group consisting of closed-loop polyacrylonitriles and [B] an antioxidant characterized in that [A] a polymer is a polymer obtained by reacting a tetracarboxylic dianhydride with a diamine The four (four) two liver system contains ^ hawthorn, 5, 9b", hydrogen-8-methyl_5_ (tetrahydro-2,5 di-oxo-Nanbub and [l,2-c] fur. South- 1,3_dione, hexahydro_5 (tetrahydro-2,5_sideoxy 3 vonanyl)_cai[ihc]pyrandione and 2,4,6,8_tetracarboxyl and 1⁄4[3.3. 0] at least one selected from the group consisting of octazone 2,4,6,8-dianhydride, or as a diamine containing at least 丨-(4-aminophenyl) 2.3-hydrogen-1,3,3 At least one selected from the group consisting of trimethyl-1H•茚·5 amine and 1 (4-aminophenyl) 2.3 monohydrogen 1,3,3-dimethyl-1H-indole-6-amine. 2. The liquid crystal alignment agent according to item J of the patent application scope, wherein the antioxidant is a group represented by the following formula (1) or formula (2): In the formula (1), 'R1 is a hydrogen atom, an alkyl group having a carbon number of 20, an aryl group having a carbon number of 6 to 2 Å, an aralkyl group having a carbon number of 7 to 13, an i, 3 di-oxybutyl group or an anthracene. , 4_ di-side oxybutyl 'in addition, the group represented by the formula (1) can also be represented by R1 -42 - 201241047 alkyl, aryl, aralkyl, 1,3-di- oxybutyl and 1 On the 4-dioxybutyl group, one hydrogen atom is removed to become a divalent group to form a part of a molecular chain; and R2 to R5 are each independently an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms; Or an aralkyl group having a carbon number of 7 to 13; X1 is a single bond, a carbonyl group, *-(CH2)n-0-, *-0-, or *-CONH-, wherein the linkage represented by * is represented by a site in which a pyridine ring is bonded; η is an integer of 1 to 4; and X2 to X5 are each independently a single bond, a carbonyl group, **-CH2-CO- or **-CH2-CH(OH)-, wherein The linkage indicated by ** is the moiety indicating a bond to the pipe D; In the formula (2), R6 is a hydrocarbon group having 4 to 16 carbon atoms, wherein the above hydrocarbon group may have an oxygen atom or a sulfur atom in the carbon skeleton chain; a is an integer of 0 to 3; and R7 is a hydrogen atom or a carbon number of 1 to When a hydrocarbon group of 16 has a plurality of R7, a plurality of R7 groups may be the same or different. A liquid crystal alignment film formed of a liquid crystal alignment agent as disclosed in claim 1 or 2. A liquid crystal display element comprising a liquid crystal alignment film according to item 3 of the patent application. -43- 201241047 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: