TW201221554A - The liquid crystal orientation agent, the liquid crystal orientation membrane, the liquid crystal display device, compounds and polymers - Google Patents

Abstract

The present invention is concerned with a liquid crystal orientation agent, a liquid crystal orientation membrane, a liquid crystal display device, compounds and polymers. The present invention provides the liquid crystal orientation agent to obtain the liquid crystal display device with excellent after-image characteristics. The liquid crystal orientation agent comprises at least one polymer selected from a group consisting of a polyimide polymer and a polyamic acid obtained by reacting diamine and tetracarboxylic acid dianhydride. The above-mentioned polymer contains the polymer having a structure represented by the following formula (1) in the backbone.

Description

201221554 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystal alignment display element, and to the manufacture of: 曰 alignment film and liquid crystal, particularly θ s and polymers. In particular, it is about the kind of supply.羊细欣曰曰',,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, And using the [prior art] 彳 "displayed components. Straight, as the long axis of the liquid crystal display crystal molecules by - a beautiful board ^ known for example, the formation of liquid called TN (twisted nematic 2, · The so-called STN (super jade and sundial) on the s of the type of the twisted 9 (the long axis of the liquid crystal molecule in the liquid day display element or the twisted tow direction between the long axes of the W) The display of the elemental crystal molecules is matched with & g & 5 liquid crystal display in the first part of the liquid." The liquid crystal alignment film is subjected to the rubbing treatment, the strength of the film, the night = crystal matching film material, from heat resistance, machine Polyurethane or polypyrene = affinity, etc., generally used in order to make the liquid crystal display Yuanlin - crystal alignment is suitable for people who do not perform well, it is necessary to permeate the liquid species in order to produce -: alignment of liquid crystal molecules Control, it has been many months b enough to achieve this effect It is proposed (for example, 液晶 直 丨曰曰 丨曰曰 丨曰曰 的 的 的 的 的 液晶 液晶 液晶 液晶 液晶 含有 含有 含有 含有 含有 含有 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 液晶 液晶 。 液晶 液晶 液晶 液晶 液晶 液晶A liquid hydrazine such as a polydecanoic acid, and a polyalkylamine of a 4-cyclohexene alkyl group, the daily aligning agent 0, which has a total of 1 2 orders, by using the above structure in the liquid crystal -4- 201221554 alignment agent. Stabilization of the pretilt angle on the liquid crystal alignment film formed by the poly-proline or polyimine, and specifically the stabilization of the temperature change by the pretilt angle. PRIOR ART DOCUMENT Patent Document Patent Document 1 Patent Document 2 When the voltage is not applied to the liquid crystal display element, the voltage is released after the voltage is applied to the liquid crystal display element.胄衧The liquid crystal molecules cannot be restored to the alignment state before the voltage is applied. In the case of the liquid crystal molecules, the transmission/shading of the light cannot be properly performed. Therefore, after the voltage is applied, the display image may be afterimage. However, in the above Patent Document #卜2, although the pretilt angle changes with respect to temperature

The stability of the study was carried out, and the stability of the pretilt angle after the application of the voltage was removed. 饬B Hs - - & In view of the above-mentioned problems, the liquid crystal alignment agent of the liquid crystal display element of the liquid crystal display element of the liquid crystal display element is used as the liquid helium. The novel compounds in which the quinone agent component is effective and the polymerization are liquid crystal alignment films and liquid crystal display elements produced by them. Make a research! The inventors have carried out nine problems in order to solve the above-mentioned problems of the prior art, and as a result, it has been found that the above problem can be solved by the poly(decylene)-cycloalkylene group, thereby & Specifically, the following liquid crystal distributions are provided according to the present invention: 201221554 Crystal alignment film, liquid crystal display element, compound and polymer. According to the present invention, there is provided a liquid crystal alignment agent characterized in that it has at least one polymer composed of polyacrylic acid and a quinone imidized polymer thereof, and the polyamic acid is a tetracarboxylic acid - another It is obtained by a reaction of a diamine, and the polymer has a structure represented by the following formula (1) in the main chain. Nope

(In the formula (1), R1 is a hospital group having a carbon number of 6, a courtoxy group or a fluoroalkoxy group, m is an integer of 〇4, and when 111 is an integer of 2 to 4, R1 is independently The above definition is defined. 11 is an integer of i to 3, and when η is 2 or 3, R1 and m each independently have the above definition. It represents a bond.) μ The liquid crystal alignment agent according to the present invention can be formed before and after voltage application 'The liquid crystal alignment film which makes the pretilt angle stable and maintains a fixed angle. As a result, a liquid crystal alignment film having excellent afterimage characteristics can be obtained. In the present invention, the helmet _ 乍 is the above-mentioned one amine, preferably a compound represented by the following formula (2), and more hydrophobic ,, specifically, as in the following formula (2) A, it is preferred to use a compound which is independently depleted and has a phenyl group or a substituted phenyl group.

(In the formula (2), the oxime is independently a single bond, a fluorenylene group, a carbon atom number (2) is a stretching group of 2 to 6, a stretching cage thereof, a fluorene group, a thiophene group, a pyridyl group, a pyrimidine group At least one hydrogen atom of the base or the three-pronged carbon atom can be substituted by 201221554. B is an independent single bond, -〇, · C 〇〇_ or _ 〇C Ο _. R 1 is a carbon atom The number is 1 to 6 of a pyridyl group, an alkoxy group or a fluoroalkyl group. The claws are integers of 4 to 4, and when m is an integer of 2 to 4, R1 each independently has the above definition. n is an integer of 1 to 3. When η is 2 or 3, R1 and m each independently have the above definition.) Further, according to the present invention, there is provided a liquid crystal alignment film formed of the above liquid crystal alignment agent, and a liquid crystal display having the liquid crystal alignment film element. The liquid crystal alignment film and the liquid crystal display element are particularly applicable to a TN type liquid crystal display element. According to the present invention, a compound represented by the following formula is provided. Further, a polymer obtained by reacting the compound with tetrazoic acid dianhydride (polyglycine and its oxime imidized polymer) is also provided.

(In the formula (3), 'b is an independent single bond, _〇_, ·(:〇〇_ or -OCO·.R) and R2 are each independently an alkyl group having 1 to 6 carbon atoms, and are burned. a milk base or a fluoroalkyl group. m is an integer of 0 to 4, and when 111 is an integer of 2 to 4, R1 each independently has the above definition. r is each independently an integer of 〇~5, when there are a plurality of R2 In the meantime, R2 each independently has the above definition. η is an integer of 1 to 3, and when η is 2 or 3, 1 and 111 each independently have the above definition.) [Embodiment] The liquid crystal alignment agent of the present invention contains At least one of the polyamic acid and the quinone imidized polymer obtained by reacting the tetrabasic acid dianhydride with a diamine 201221554 polymer (hereinafter also referred to as a specific polymer). Hereinafter, the liquid crystal alignment of the present invention The agent is described in detail. <Polyuric acid> At least a part of the polyamic acid contained in the liquid crystal alignment agent of the present invention has a structure represented by the above formula (1) in the main chain. The proline acid, for example, a tetracarboxylic dianhydride and a diamine having a structure represented by the above formula (1) in the main chain The tetracarboxylic dianhydride is reacted with a diamine having a structure represented by the above formula (1) in the main chain, and the latter is preferred. [Tetracarboxylic dianhydride] As a synthesis for use in the present invention Examples of the tetracarboxylic dianhydride of the polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. Specifically, as an aliphatic tetracarboxylic acid An acid dianhydride such as 1,2,3,4-butanetetracarboxylic dianhydride or the like; as an alicyclic tetracarboxylic dianhydride, for example, 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-oxo-3-furanyl)- Naphthalene [l,2-c]furan-1,3-dioxin, 1,3,3a,4,5,9b-hexanitro-8-mercapto-5-(four-rat-2,5-two-side Oxy-3-ol-nomanate)-naphthalene [1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-diI--6- Spiro-3'-(tetrazo-α-furan-2 ',5,-diindole), 5-(2,5-di-oxotetrahydro-3-furanyl)-3-indolyl-3-cyclohexyl Alkene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxydecylnordecane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxyl double Cyclo[3_3.0]octane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0''6]undecane 201221554 -3,5,8,10-tetraketone, etc.; as an aromatic tetracarboxylic dianhydride, such as pyromellitic acid di PMDA), 3,3,,4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4,dibenzophenone tetracarboxylic dianhydride, 1,4,5,8- The tetracarboxylic dianhydride described in JP-A-2010-97188 can also be used as the naphthalenetetracarboxylic dianhydride or the like. Further, the above tetracarboxylic dianhydrides may be used singly or in combination of two or more. The tetracarboxylic dianhydride used for the synthesis of the above polyamic acid preferably contains PMDA, and more preferably contains cyclobutanetetracarboxylic dianhydride. As a tetra-orthoacid dianhydride, when a mixture of aliphatic or alicyclic tetra-acid dianhydride and aromatic tetracarboxylic dianhydride is used, the ratio of the ratio of the aliphatic or alicyclic tetracarboxylic dianhydride is relative to the tetracarboxylic acid. The total amount of the acid dianhydride is preferably from 10 to 95 mol%, more preferably from 20 to 80 mol%. When the liquid crystal alignment film is formed by the above range, high voltage holding ratio, printability, and excellent storage stability can be exhibited in a balanced manner. [Diamine] The diamine used for the synthesis of the poly-proline in the present invention is preferably a compound represented by the above formula (2) (hereinafter, also referred to as a diamine.). In the case of 2), Ri is an alkyl group having 1 to 6 carbon atoms, a fluorene group or a gas-burning group, and when it is an integer of 2 to 4, each may be the same, and may be different. The number of carbon atoms is 1 to 6 The alkyl group may be linear or branched, and specifically, may be exemplified by methyl group, propyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or secondary butyl group. ??? 201221554 butyl, n-decyl, ruthenium, bauxite, neopentyl, n-hexyl, irihexene as a carbon atom number i~., hexyl, etc. The fluoroalkyl group can be 歹1j t Ffl S KS substituting as the above-mentioned carbon atom number, 歹 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举 举The number is 1 to 6 = an oxy group, and the number of carbon atoms is 6; the group of 6 is bonded to an oxygen atom; and the alkyl group is an ethoxy group, an ethoxy group, etc. m in the above formula (2) is a 〇~4 effect, more preferably 〇. The number 'is preferably 0 to 2, and the integer n is an integer of 1 to 3' is preferably 。. Β is a single bond, _〇_, _c〇〇 or _

It may or may not be the same as the two B U in the 4(2). In A of the above formula (2), 'as a carbon atom, it may be linear, and '42' is an alkyl group, a propyl group, and a second propyl group. ^ y , 4 · butyl butyl and the like; as the stretching naphthyl group, it can be exemplified by 1 &gt; 4 • stretching phenylene, etc.; as a stretching pyridyl group, can be listed as soil, 5 · stretching good base, etc.; As a pyrimidyl group, it can be listed as a pomelo n 竿2,5·an pyrimidinyl group; Μ 4 can be exemplified by 2,4_extension: a substitution of a group thereof Base, _ — listen to the base. As such a dentate atom, a cyano group, in addition to::. Such as a wind atom or a chlorine atom exemplified base. Further, the above R 1 may be mentioned, and as A, preferably a % is a substituted or unsubstituted stretched phenyl group. -10-201221554 In the case of the present invention, the present compound (hereinafter, in the crystal alignment, the interaction, the substitutable diphenylene diamine) is preferably represented by the above formula (3). Diamine (D-1-1)). At this time, the liquid formed by the ruthenium tends to cause a better alignment with the benzene ring of the liquid crystal molecules to make the liquid crystal alignment property. Preferably, hydrazine is a hydrazine-substituted amine group in which A is a substituted or unsubstituted phenyl group, and is preferably bonded to B at a position of 4 Å. Further, when the substituent is a substituted phenyl group, the substituent (the & R2 in the formula (3)) may be exemplified as the above-mentioned R1. As the diamine (D-1), specifically, a preferred group) is a trans-cyclohexane, a 2-methyl bis(4)amine, an amphoteric benzene 2 c. „ ^ ^ amidoxime base) ring Hexane, '5--methylbis(4-aminophenyl)cyclohexanthene, w: such that at least one of these compounds is introduced into the benzene ring-ring appearance on the primary bond of poly-aracine Benzene ring _,, structure. It is considered that the pretilt stability on the film can be improved, in particular, the pretilt stability before and after the application of the voltage can be further improved. The diamine of the amine acid may be a compound represented by the above formula (2), and the compound of the above formula may be used in combination with another diamine. Only U) may be used as the other diamine which can be used herein. Examples of the aliphatic diamine, the alicyclic diamine, the organic oxime, and the like, and specific examples thereof include, for example, hydrazine, 1 dimethyldiphenylene diamine, and 1,3. Known as amine, diamine as aliphatic diamine, &lt;-propylenediamine, tetramethylene&gt; 201221554 amine, pentamethylenediamine, hexamethylenediamine, etc.; The amine as the alicyclic diamine may, for example, be an anthracene, a 4:diaminocyclohexyl fluorenyl bis(cyclohexylamine 込^ bis(amino fluorenyl)cyclohexene i-based T, etc. The amine may, for example, be o-p-diamine, m-phenylenedi-p-phenylenediamine, 4,4'-diaminodiphenylnonane, 4,4,-diaminodiphenylthioindole or diamine-based , 2,2, _ bis-yl _4,4, _diamine benzene, 4,4'-diamino 2,2, bis (tris-yl)biphenyl '2,7-diamine Base, 4,4'-diaminodiphenyl ether, 2,2_bis[4_(4-aminophenoxy)phenyl]propane 9'9 (4-month female base) , 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4,_(p-benzene Diisopropylidene)bis(aniline), 4,4,-(m-phenyleneisopropylidene)bis(aniline), 1,4-bis(4-aminophenoxy)benzene, 4,4, - bis(4_aminophenoxy) conjugate, 2,6-diamino n-bite, 3,4-diamino η than bite, 2,4-diamine-based bite, 3,6- Monoamine. Cough, 3,6-diamino. Carben, Ν-Methyl_3,6-Diamine-based saliva, heart ethyl, 3,6-diamino fluorene ,]--phenyl-3,6-diamino. Card. Sit, Ν, Ν-bis(4-aminophenyl)benzidine, ν, Ν'-bis(4-amine-stupyl)- Ν,Ν'-dimercaptobenzil' i,4-bis(4-aminophenyl)piperidinium, 3 5 -diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, Tetradecanooxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2-,4-diaminobenzene, octadecyloxy -2,4-diaminobenzene 'dodecyloxy-2,5-diaminobenzene, tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5- Diaminobenzene, cetyloxy-2,5-diamino stupid, octadecyloxy-2,5-diamino stupid, cholestyloxy-3,5-diaminobenzene, Bile oxy-oxy-3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholestyloxy-2,4-diaminobenzene, 3,5_2 Amino benzoic acid cholesteryl ester, 3 -12- 201221554

Benzoic acid bile retention combenyl alkenyl, diaminobenzoic acid wool-retained alkyl hydrazine, 4~aminobenzhydryloxy)cholane, 3,6-bis (4-aminophenoxy) Bile, 4_(4,·trifluoromethoxybenzoquinoneoxy)cyclohexyl-3,5_1&gt; 曰4-(4-difluoromethylbenzylideneoxy)cyclohexyl 3,5 -January female-based alum ate ', 丨 bis(a)...aminophenyl) fluorenyl) phenyl oxime, butyl cyclohexene, U-bis(4_((aminophenyl)methyl)benzene 4) S ring pit, 1,1-bis(4_((amino)oxy)methyl)phenyl)-4-heptyl U, K bis(4_((amino)phenyl)methyl Phenyl hydrazine, ·heptylcyclohexanediyl, 3 amine-amino group _N,N•diallyl aniline, 4·amino ketone “yl” benzene (,, 4 basic base)..., acid, 4_ (吗烧,,~ 丨, 3-bis(N-(4-aminophenyl)piperidinyl)propan 01-)-aminophenyl phenylene and the following formula (Α)) 丨^)^-χ 丨-R 丨-χ&quot; h2n

CcH2c" (A-1) (in the case of ad, XI and χΙΙ are each a single bond, m(10) or -oco- (only with ''*,, the connection key is connected with two), W is a single bond, Number of bases or carbon atoms: 2 basic groups or R consecutive::: or h...~2 integers ^: two: when: '...1 and ~ are single bonds) two as diamines (four) burned' In the case of the above, the diamine described in JP-A-2010-971 88 can be used. -13 - 201221554 is a divalent group represented by -Χ^ΚΛχ11- in the above formula (Al), preferably a methylene group, an alkylene group having 2 or 3 carbon atoms, *-0-, * -COO- or *-0-CH2CH2-0- (only the linking bond is bonded to the diaminophenyl group). Specific examples of the group CcH2e+1- group include, for example, methyl group, ethyl group, and n-propyl group. Base, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-fifteen烧基,正六院基基,正七烧烧基,正十八烧基,正十九烧基,正二Further, the two amine groups in the diaminophenyl group are preferably the 2,4-position or the 3,5-position relative to the other groups. Specific examples of the compound represented by the above formula (A-1) For example, a compound represented by each of the following formulas (A-1-1) to (A-1-3) can be mentioned.

(A*M) (A-1-2) (A-1-3) The ratio of the compound represented by the above formula (2) is considered from the viewpoint of exhibiting a more stable pretilt angle on the liquid crystal alignment film, and The total amount of the diamine is preferably from 10 to 100% by mole, more preferably from 20 to 90% by mole, particularly preferably from 40 to 70% by mole. &lt;Molecular weight modifier&gt; -14- 201221554 In synthesizing polyamic acid, together with the tetrazoic acid di-hepatic and diamine as described above, a suitable molecular weight modifier can be used to synthesize a terminal-modified polymer. By forming such a terminal-modified polymer, the coating property (printing property) of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention. The "molecular weight modifier" may, for example, be an acid anhydride, a monoamine compound, a monoisocyanate compound or the like. Specific examples thereof include, as the acid anhydride, maleic anhydride, phthalic anhydride, itaconic acid, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl phenolic anhydride, and positive examples. Cetyl succinic anhydride or the like; as the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc.; For example, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned. The use ratio of the molecular weight modifier is preferably 2 parts by weight or less, and more preferably 1 part by weight or less, based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine to be used. <Synthesis of Diamine (D-1-1)&gt; The compound diamine (d_i_i) represented by the above formula (3) can be suitably produced by a usual method of organic chemistry, specifically, B is a single bond. In the case of the compound of η-1, for example, first, the magnesium metal is allowed to act on the compound (M-1) represented by the following formula in an ether solvent, and then the unsubstituted cyclohexane-indole, 4-dione is reacted. The intermediate (M-2) was obtained (refer to the following reaction formula (1)). 201221554

(wherein γ is a halogen atom JV Κ., m and r are the same as defined for R1, R, m and r in the above formula (3), respectively.) The i atom of Y is exemplified by a desert atom, a gas atom, and a hard Atom, fluorine atom, etc. Among them, from the viewpoint of reactivity, it is preferably an adipose atom. The reaction temperature of the reaction formula (I) can be appropriately determined according to the reaction method, and more preferably 〇~1〇〇t. The ether solvent to be used in the reaction may, for example, be diethyl ether or tetrahydrofuran. Next, the intermediate (M-2) is subjected to reduction of a nitro group and reduction of a hydroxy group under contact reducing conditions. Thus, the compound diamine (1^) represented by the above formula (3) can be obtained (refer to the following ^

A, , m and r are respectively the same as the definitions of Ri, 'm and r in the above formula (3). The reaction of the reaction formula (π) is carried out in the presence of nickel, ruthenium-carbon, Pt 〇2, pd (p. catalyzed catalyst, preferably at -20 to 15 (r, more preferably, 〇~12) (Continued under TC. As a solvent used in the reaction, for example, from the use of tetrahydrofuran, hydrazine, N, N-: methylcarbamide, n, n-dimercaptoacetamide, 1-methyl-2 - In addition, when η is 2 or 3, the above formula can be obtained by using a compound represented by the following formula (4), -16, 201221554, instead of cyclohexane-1,4-dione. (3) The compound represented (only B is a single bond and η is 2 or 3). (?1)m (yR,)m

0 (4) (where k is 〇 or 1. The scales 1 and m are respectively the same as the definitions of R1 and m in the above formula (3).) On the other hand, when B is *·〇_, *-C00- or *-0C0-hour (only the linkage is attached to the aminophenyl group) can be suitably synthesized using a conventional method. Specifically, if n=l is taken as an example, the compound 'for example B' can be dehydrogenated by dehydrogenating hydrogenation of 1,4-cyclohexanediol and nitrobenzene, and then reducing the nitro group. And get it. The compound wherein B is *-C〇〇- can be obtained, for example, by carrying out an esterification reaction of hydrazine, hydrazine-cyclohexanediol and nitrocrackin chloride, followed by hydration. a compound in which the month B is * - 〇 C 〇 -, for example, can be carried out by esterification of ruthenium, 4 · cyclohexane, sulphuric acid vapor and nitrophenol, followed by reduction

Basically. 'P &lt;Synthesis of Poly-Proline&gt; The polyamine of the present invention may be a diamine containing a compound represented by the above formula (2), preferably a compound represented by the above formula (3) And obtained by reacting with the above tetracarboxylic dianhydride. The ratio of use of the tetracarboxylic dianhydride and the diamine to the polyamic acid synthesis reaction is 'relative to the amine oxime equivalent of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride is preferably 0.2 to 2 equivalents. 0 · 3 to 1.2 equivalents. -17- 201221554 The synthesis reaction of polylysine is preferably carried out in an organic solvent. The reaction temperature at this time is preferably from -20 ° C to 150 ° C, more preferably from 0 to 100 ° C. Further, the reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours. Here, examples of the organic solvent include an aprotic polar solvent, a phenol and a derivative thereof, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, and the like. Specific examples of the organic solvent include, as the aprotic polar solvent, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylhydrazine. An amine, dimethyl sulfoxide, γ-butyrolactone, tetradecyl urea, trimethylamine hexamethyl phosphate, etc.; examples of the phenol derivative include m-nonyl phenol, diphenyl benzene, halogenated benzene, and the like. Examples of the alcohol include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, and the like; Examples of the ester include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the ester include ethyl lactate, butyl lactate, decyl acetate, ethyl acetate, butyl acetate, and decyloxypropane. An acid ester, ethyl ethoxypropionate, diethyl oxalate or diethyl malonate; and examples of the ether include diethyl ether, ethylene glycol monoterpene ether, ethylene glycol ethyl ether, and ethyl acetate. Glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl Ether acetate, diethylene glycol dioxime ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether B-18-201221554 Acid s, tetrahydrogen sulphide, etc.; as the above-mentioned southern hydrocarbons, for example, ethylene ethane dichloride, trichloroethane, benzene = pit gas; "As the top! Smoke, for example, burned, burned, burned: - A, isoamyl propionate, isoamyl isobutyrate, - lyl ether, etc.. 0 - off In the organic solvent, it is preferred to use an organic solvent selected from the group consisting of a non-quality phenol and a derivative thereof, or an organic solvent selected from the group consisting of a non-toxic agent and a phenol and a derivative thereof. The first group of organic solvent species consists of yeast, ketone, vinegar, shout, letter and smoke, and the mixture of y and above selected in the second group of organic solvents In the case of the second group of organic solvents, the &quot;: juice for the organic solvent of the first group and the organic solvent of the second group is preferably 50% by weight or less' more preferably 4 The amount of use of the organic solvent (a) is preferably such that the total amount of the tetracarboxylic dianhydride and the diamine (b) is 〇" to 5 相对 with respect to the total amount of the reaction solution (&amp; + 13). The amount by weight%. As described above, a reaction solution formed by dissolving polyamic acid can be obtained. The reaction solution may be directly supplied to the liquid crystal alignment agent, or the polylysine contained in the reaction solution may be separated first and then supplied to the liquid crystal alignment back 1 or the separated polyamic acid may be purified. The preparation of the liquid crystal alignment agent is further supplied. The separation and purification of polylysine can be carried out according to a conventional method. &lt;Yourly aminated polymer&gt; The ruthenium iodide polymer (polyimine) in this month can be obtained by dehydration of the above-mentioned synthesized polyamidamine by -19-201221554 Get it. At this time, the reaction solution formed by dissolving polylysine may be directly supplied to the dehydration ring-closure reaction, or the polyamic acid contained in the reaction solution may be separated and supplied to the dehydration ring closure reaction. Alternatively, the separated polyamic acid may be purified and then supplied to a dehydration ring closure reaction. The polyimine in the present invention may be a complete sulfhydryl imide obtained by dehydration ring closure of the proline structure of the polyglycolic acid of the precursor thereof, or may be a part of the dehydration ring closure of only the proline structure. The resulting proline structure and a portion of the quinone imine compound coexist. The polyimine in the present invention has a ruthenium amination ratio of preferably 30% or more, more preferably 50 to 99%, particularly preferably 65 to 99%. The ruthenium imidization ratio is expressed as a percentage of the total amount of the quintonimine ring structure relative to the total amount of the phthalic acid structure of the polyimine and the number of the quinone ring structure. Here, a part of the quinone ring may also be an isoindole ring. Dehydration ring closure of polylysine, preferably by heating poly-proline, or dissolving poly-lysine in an organic solvent, called τ and into the solution

The addition of a dehydrating agent and a dehydration ring-closing catalyst are carried out according to the method of heating. Among them, it is better to use the latter method. In the method of correcting and dehydrating the ring-closing agent, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, an acid anhydride or trifluoroacetic anhydride may be mentioned. The amount of the dehydrating agent used, preferably the poly-amic acid structural unit of the mole, is preferably 】 •. As a dehydration ring-closing catalyst, for example, a secondary amine such as pyridine or kelin can be used. The use of the dehydration-blocking catalyst is β I, relative to -20-201221554 Mo = the dehydrating agent used, preferably Q Q1~i Q mole. The organic solvent used in the dehydration % reaction can be exemplified as the organic solvent exemplified in the synthesis of polylysine. The reaction temperature of the dehydration ring-closing reaction is preferably from 0 to 180 ° C, more preferably from 10 to 15 (TC, the reaction time is preferably from 1.0 to 120 hours, more preferably from 2 to 3 hours). The reaction solution may be directly supplied to the liquid crystal alignment agent, or may be supplied from the reaction solution to the dehydrating agent and the dehydration ring-closing catalyst before being supplied to the liquid crystal compound. Moreover, the polyimine may be separated and then supplied to the liquid crystal alignment j, or the separated polyimine may be refined and then supplied, and the liquid sa is prepared by the alignment agent. The conventional method is carried out. &lt;Solid viscosity of polymer&gt; The polyglycolic acid or quinone imidized polymer of the present invention obtained as above (hereinafter, also referred to as a specific polymer) is formed to have a concentration of 1 When the weight % of the gluten solution is used, it is preferably a solution viscosity of 20 to 800 mPa·s, preferably a solution viscosity of 3 〇 5 〇〇 mPa s. In addition, the solution viscosity of the above polymerization ( mPa.s) is a good solvent for the use of this polymer (9) Γ 〇 Γ: The concentration of the polymer solution prepared in 5% by weight of vinegar, Ν 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 A 25C &lt;Other Additives&gt; The liquid crystal alignment agent of the present invention contains the specific polymerization as described above to contain other components as needed. As such a component, for example, a polymer other than a specific polymer or a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy--21 - 201221554"), A functional decane compound or the like. [Other polymers] Other polymers can be used to improve solution properties and electrical properties. The other polymer is a polymer other than the specific polymer, and, for example, polylactoic acid obtained by reacting a diamine and a tetrabasic acid dianhydride which do not contain the compound represented by the formula (2) (hereinafter referred to as 'the following' It is a poly-imine (hereinafter referred to as "other polyimine") formed by dehydration and ring closure of the other poly-proline, a polyphthalamide, a polyester, Polyamide, polyoxin, cellulose derivatives, polyacids, polystyrene derivatives, poly(styrene-stupyl maleimide) derivatives, poly(meth)acrylates, etc. Wherein 'preferably other poly-proline or other polyimine, and more preferably other poly-proline. In addition, used as a tetracarboxylic dianhydride for the synthesis of other poly-proline or other polyimine. The diamine may be a compound for synthesizing a specific polymer. When a other polymer is added to the liquid crystal alignment agent, the compounding ratio thereof is preferably 5% by weight or less based on the total amount of the polymer in the liquid crystal alignment agent. 'More preferably 〇.1~4〇% by weight' is particularly good for 〇·ι~3〇% by weight [Epoxy compound] Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl bond, tripropylene glycol diglycidyl ether, and polypropylene glycol. Di-glycidyl / by neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl mystery, propylene glycol diglycidyl ether, trihydrocarbyl propane triglycidyl ether, 2,2_2> stinky Neopentyl glycol diglycidyl ether, hydrazine, hydrazine, hydrazine, hydrazine, -tetraglycidyl-m-dimethyldiamine, 1,3-bis(indole, hydrazine-diglycidylamino) -22- 201221554 Cyclohexane, N,N,N',N'-tetraglycidyl_4,4'-diaminodiphenylcarbamate, n,n-diglycidyl-benzylamine, N , N_ diglycidyl-aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine, etc. When such an epoxy compound is added to a liquid crystal alignment agent, the compounding ratio 'relative to liquid crystal The total amount of the polymer contained in the alignment agent is preferably 40 parts by weight or less, more preferably 0 to 1 to 30 parts by weight. [Functional decane compounding As the above-mentioned functional decane compound, for example, 3-aminopropyldioxyxanthene-3-aminopropyltriethoxy-xanthene, 2-aminopropyltrimethoxydecane, 2 -Aminopropyltriethoxydecane, Ν-(2••aminoethyl)-3-aminopropyltrimethoxydecane, Ν-(2-aminoethyl)_3_aminopropyl A Dimethoxy oxime, 3-methoxypropyl trimethoxy oxime, 3-ureidopropyltriethoxy decane, Ν-ethoxycarbonyl-3-aminopropyltrimethoxy zeshi , Ν-ethoxy oxo-3-aminopropyl triethoxy sulphur, yttrium-triethoxy sulfonium propyl tridecyl diamine, Ν-dimethoxy decyl propyl Ethyl triethylamine, 10-trimethoxymethoxycarbamimidyl-1,4,7-triazadecane, 10-triethylmercaptoalkyl-1,4,7-triazaindene Alkane, 9-trimethoxymethoxymethylalkyl-3,6-diazaindolyl acetate, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-triethyl Oxyalkyl decyl-3,6-diazaindolyl acetate, 9-trisethoxy fluorenyl-3,6-diazepine decyl ester, 9-triethoxy fluorene Methyl-3,6-diazepine, Ν-benzyl-3-aminopropyltrimethoxy decane, Ν-benzyl-3-aminopropyltriethoxy decane, hydrazine- Phenyl-3-aminopropyltrimethoxydecane, fluorenyl-phenyl-3-aminopropyltriethoxydecane, glycidyloxymercaptotrimethoxydecane, glycidyloxydecyltriethyl Oxygen stone, 2_ -23- 201221554 glycidoxyethyl trimethoxy decane, 2-triethoxy decane, 3-glycidoxy propyl triglycidoxy propyl triethoxy decane Wait. The addition ratio of these functional groups is preferably 0.02 to 0.2 parts by weight based on 100 parts by weight or less of the polymer of the liquid crystal alignment agent. [Organic solvent] The liquid crystal alignment agent of the present invention contains a specific concentration. Other additives to be compounded are preferably dissolved. Examples of the liquid crystal alignment agent used in the present invention include, for example, N-fluorenyl-2-pyrrolidone, γ·butylene ν, ν-dimethylformamide, hydrazine, hydrazine-dimethylacetamide. 2-pentanone, ethylene glycol monomethyl ether, butyl lactate, methyl propyl propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, 2 基赛路苏), ethylene glycol diterpene ether, ethylene glycol ethyl glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol early ether 'diethylene glycol monomethyl ether acetate , acetic acid @旨, -_g -p «·- — butyl butyl hydrazine, isoamyl propionate, iso-, pentyl ether, vinyl acrylate, propylene carbonate, etc., or may be used in combination of two or more. The solid content concentration of the liquid crystal alignment agent (liquid crystal 酉: the total weight of the components accounts for the total weight of the liquid crystal alignment agent), and the volatility is appropriately selected, and is preferably a glyceroloxyethyl group. - when the compound is fired, the total of 1 is preferably 2 conjugates and, if necessary, in an organic solvent, an organic solvent, γ-butyrolactam, 4-alkyl-4, butyl phthalate,曱 基 _, ethylene glycol ethyl i 1 alcohol n-butyl bond (butyl sulphate acetate, diethanol monomethyl test, diethyl ethane glycol monoethyl ether taucan acid g, two. These can be used alone The solvent is in the ratio of t, and the range of % by weight is considered. -24- 201221554 In other words, 'the liquid crystal alignment agent of the present invention' is coated on the surface of a substrate to be described later by heating, preferably to form a liquid crystal alignment. The coating film of ruthenium or the coating film constituting the liquid crystal alignment film. However, when the solid content of the solid content is less than 1% by weight, the film thickness of the coating film is too thin to obtain a good liquid crystal alignment film. On the other hand, when solid When the concentration of the component exceeds ίο重量%, the film thickness is too thick. However, it is difficult to obtain a good liquid crystal alignment film and the viscosity of the ruthenium alignment agent is increased, which may result in deterioration of coating characteristics. The range of the solid content concentration is particularly based on the method used to apply the a-aligning agent on the substrate. For example, the concentration of the solid component of the spin coating method is particularly preferably 丨5 to 6. 〇% by weight. When the printing method is employed, the solid content concentration is particularly preferably in the range of 3 to 9% by weight, whereby the solution viscosity is made The range of i2 to 50 mPa s. When the inkjet method is employed, the solid content concentration is particularly preferably in the range of 1 to 5 wt%, and thereby the solution viscosity is in the range of 3 to i5 mPa.s. The temperature at the time of the liquid crystal alignment agent is preferably 丨〇 50 C ' or more preferably 20 to 3 CTC. &lt;Liquid crystal alignment film and liquid crystal display element &gt; The liquid crystal alignment film of the month is formed of the above liquid crystal alignment agent. The liquid crystal display element of the present month has a night BS alignment 形成 formed by the above liquid crystal alignment agent. Regarding the operation mode of the liquid crystal display element, it can be adapted to a horizontal alignment called a 4 IPS type, a TN type or an STN type. D, I are used for VA type vertical alignment type, but horizontal alignment type is preferred. Among them, it is more preferably applied to TN type. η ' The following description of the manufacturing method of the liquid crystal display element of the present invention will also be described with respect to the liquid crystal alignment film of the present invention. Manufactured - 25 - 201221554 The liquid crystal display device of the present invention can be produced, for example, by the following processes (1) and (3). In the process (1), the substrate to be used is different depending on the desired mode. (2) and (3) are common to each operation. ' [Process (1): Formation of coating film] First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then the coated surface is coated on the substrate by heating. A coating film is formed thereon.曰 (1-1) When manufacturing a TN type, STN type or VA type liquid crystal display element, 'two sheets of a substrate on which a patterned transparent conductive film is provided are used as a pair, and each of the transparent conductive film forming surfaces is coated with the same The liquid crystal alignment agent of the invention 'preferably uses a lithography method, a spin coating method, a roll coating method or an ink printing method, followed by heating each coated surface (preferably preheating (prebaking and firing (post baking) A two-stage heating is formed to form a coating film. Here, as the substrate ', for example, glass such as float glass or soda glass; polyethylene terephthalate or polybutylene terephthalate may be used. a transparent substrate formed of a plastic such as a poly bond, a polycarbonate, or a poly(alicyclic olefin), etc. As a transparent conductive film provided on one side of the substrate,

J, using a NESA film formed of tin oxide (Sn〇2) (registered trademark of ppG VIII, USA), an ITO film formed of indium oxide-tin oxide (In2〇3_Sn〇2), etc., to obtain a pattern For the transparent conductive film, for example, a method of forming a pattern by photolithography after forming a transparent conductive film without a pattern, a method of using a photomask having a desired pattern when forming a transparent conductive film, or the like can be employed. When the liquid crystal alignment agent is applied, in order to make the adhesion between the surface of the substrate and the transparent conductive film and the coating film better, the surface on which the inner coating film is to be formed on the surface of the substrate may be coated with a functional decane compound. - 201221554 Pretreatment of energetic titanium compounds, etc. Next, the coating surface of the liquid crystal alignment agent is applied by preheating (prebaking), followed by baking (post baking) to form a coating film. The pre-baking conditions are, for example, 40 to 12 (0.1 to 5 minutes under TC, post-baking conditions, preferably 120 to 300 C', more preferably 150 to 250 ° C, and particularly good at 5 to 2 〇〇. Minutes, preferably in the range of 1 〇 to 100 minutes. The film thickness of the coating film formed is preferably 0.001 Ι Ι μηι, more preferably 0 005 〜 〇 6 μιη. (1-2) On the other hand, the ips type liquid crystal display is manufactured. In the case of the element, the liquid crystal alignment agent of the present invention is applied to the surface of the conductive film forming surface of the substrate patterned with the comb-shaped transparent conductive film and the opposite substrate of the non-X conductive film, respectively, by Each coated surface is heated to form a coating film. The substrate used in this case, the material of the transparent conductive film, the coating method, the heating conditions after coating, the patterning method of the transparent conductive film, the pretreatment of the substrate, and the preferred film for forming the coating film. In the case of any of the above (1-1) and (1_2), after the liquid crystal alignment agent is applied onto the substrate, the organic solvent is removed to form a coating film which becomes an alignment film. At this time, when the polymer contained in the liquid crystal alignment agent of the present invention is a poly The amine I or a brewed iminated polyδ material having a structure of an imine ring structure and a proline structure can be further heated by forming a coating film to form a more imidized coating. [Process (2): Rubbing Treatment] When manufacturing a ΤΝ-type, STN-type or IPS-type liquid crystal display element, a coating formed by winding a fiber such as nylon, rayon, cotton, or the like is used. The film is rubbed by rubbing in a certain direction. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film, thereby forming a liquid crystal alignment film of -27-201221554. Further, a part of the liquid crystal alignment film is irradiated with ultraviolet rays to make the liquid crystal pretilt angle. The changed process 'or after the anti-surname film is formed on the liquid crystal, 'after rubbing treatment with the previous rubbing line' and then the visor of the liquid crystal display element obtained by removing the resist film having different liquid crystal matching on each region In addition, the coating film formed by the VA type liquid crystal display is directly subjected to rubbing treatment as a liquid crystal alignment film. [Process (3): Construction of liquid crystal cell] The liquid crystal alignment film gap has been formed as described above. (Cell gap) is disposed oppositely, so that the two substrates are oriented orthogonally or anti-parallel, and the sealant is adhered to 'on the outer surface of the liquid crystal cell formed by the substrate surface and the sealant filling liquid crystal' sealed injection hole to be polarized The liquid crystal display element can be obtained by the rubbing direction of the liquid crystal alignment film which is formed by the moon. As the sealing agent, for example, an epoxy resin containing alumina balls containing the material can be used. For the nematic liquid crystal, for example, an azo liquid crystal, a biphenyl liquid crystal, or a phenyl ring film can be processed in a different direction by a part of the surface of the alignment film which is directed to a partial region of the liquid crystal. The treatment can change the liquid crystal alignment direction, so that when the device can be modified, the above-mentioned pair can be used, but the pair of substrates described above can be implemented, and the periphery of the two substrates can be divided by the friction of the liquid crystal alignment film therebetween. Intracellular space is injected. Then, by bonding in the liquid light direction and the substrate uniformly or perpendicularly, there is a hardener and a smectic liquid crystal as a spacer f. Among them, there are Schiff liquid crystal, oxygen L-liquid crystal, and ester liquid. 28- 201221554 Γ 1 t-benzene liquid crystal, biphenyl cyclohexyl (tetra) liquid crystal, (d) liquid crystal, external helium, f liquid helium, bicyclooctane liquid crystal, cubic liquid crystal. This &quot;x adds biliary liquid crystal such as choline chloride, cholesteric vinegar, cholesteric 55* a &gt; »c_15,, ester, etc. to these liquid crystals; as a commercial name, "CB-l5 Chiral reagent sold by ''(Merck); p-methoxyl-methylene-p-quinone. 竺# m-m-methyl-butyl cinnamate and other ferroelectric liquid crystal cellulose: The polarizer "attached to the extracellular surface" may be a polarizer formed by a polarizing film of an Ethylene plate or a ruthenium film itself, which is referred to as % 胄, which forms a polarizer which is agglomerated. Part B% absorbs the moth while stretching the alignment. The liquid crystal display of the present invention can be used, for example, for various types of notebook computers, various types of notebook computers, steam M/type (four) machines, word processors, machines, mobile phones, various types of dry: f% video recorders, PDAs, Digital phase embodiment 'Yi, LCD TV and other display devices. More specifically, the present invention is not limited to the embodiments by the examples. &lt;Synthesis of monoamine&gt; [Synthesis Example 1-1] According to the following Scheme 1, λ (diethylamine is 1,4-di(4-amino phenyl), also called diamine (D- Ij)). Rolling base)% -29- 201221554 o2n -α-

Pd/C

Mg

N〇2

Br +

NH2 Scheme 1 &lt;Synthesis of Polylysine&gt; [Synthesis Example 2-1] 19 g (80 mol%) of 1,2,3,4-cyclobutanetetracarboxylic acid as tetracarboxylic dianhydride Anhydride and 5.3 g (20 mol%) pyromellitic dianhydride, and 12 g (20 mol%) i,3_bis(&amp;(4-aminophenyl)piperidinyl)propene as diamine Calcined, 7.2 g (15 mol%) tetradecyloxy-2,4-diaminobenzene, l2 g (1,2 mol%) 3,6-bis(4-aminobenzhydryloxy) Cholesterane and 26 g (638 mol/〇) compound (D-1-2) 'dissolved in a mixed solvent of 320 g of N-methyl-2-pyrrolidone and 320 g of γ-butyrolactone The reaction was carried out for 3 hours under 4 Torr. Thus, a solution containing 1% by weight of poly-proline (p_i) was obtained. [Synthesis Examples 2-2 and 2-3, Comparative Synthesis Example i] In addition to the type and composition of the tetracarboxylic dianhydride and the diamine, as in the following Table 1, the composition was prepared in the same manner as in the synthesis example. A solution of weight % polyaminic acid (P-2), (p_3), (n). [Table 1] Polyfluorene tetracarboxylic dianhydride 丨 mol% l Diamine "mol% l Amino acid T-1 T-2 T-3 T-4 D-1-2 D-2-1 D-2-2 D-2-3 D-2-4 Synthesis Example 2_1 P-1 80 20 - 63.8 20 15 1.2 _ Synthesis Example 2-2 P-2 - - 100 68 20 10 2 • Synthesis Example 20 P-3 - - 100 59 ^ 20 20 1 _ Comparative Synthesis Example 1 R-1 80 20 - - - 20 13 1.5 65.5 -30- 201221554 In Table 1, the abbreviation 'tetracarboxylic dianhydride and diamine' respectively have the following meanings. [Tetracarboxylic acid II Anhydride] Tl: 1,2,3,4-cyclobutanine tetracarboxylic dianhydride (CB) T-2: pyromellitic dianhydride (pmdA) D-3.2,3,5-di-rebase Two needles of acetic acid T-4 : 2,4,6,8-tetracarboxybicyclo[3.3·〇]octane_2:4,6:8 dianhydride [diamine] D 2 1 . 1,3-1 (N -(4-aminophenyl)0 bottom-biting)propane-fired D-2-2:tetradecyloxy-2,4-diaminobenzene D-2-3 : 3,6-di(4- Aminobenzophenoxy)cholane D-2-4: Preparation of p-phenylenediamine &lt;liquid crystal alignment agent&gt; [Example 1] The polyglycine containing the synthesis product of the above Synthesis Example 2-1 (p_)), adding γ-butyrolactone (BL), N-mercapto-2-pyrene, _ (NMP) and butyl siroli (BC) and further adding Gather 1 part of the total amount of the residue, 20 parts by weight of n, N, N, N,-tetraglycidyl-4,4'-diaminodiphenylmethane as an epoxy compound, and stirred well, A solution having a solvent composition of BL:NMP:BC = 30:30:40 (weight ratio) and a solid content concentration of 6.0% by weight was formed, and the solution was filtered using a filter having a pore size of 1 μm to obtain a liquid crystal alignment agent. Examples 2 to 3 and Comparative Example 1 A liquid crystal was prepared in the same manner as in Example 1 except that the type of polyamic acid was changed to any of (P-2), (Ρ-3), and (R-1). 201221554 &lt;Production of Liquid Crystal Cell&gt; Each of the prepared liquid crystal alignment agents of Examples 1 to 3 and Comparative Example 1 was applied to a glass to which a transparent electrode formed of an IΤ film was applied by a spin coater. The transparent electrode surface of the substrate was heated and heated on a hot plate at ° C for 1 minute (prebaking) to remove the solvent, and then heated on a hot plate of 200 (for: 1 minute (post-baking) to form an average film thickness. It is a coating film of 600 A. By using a friction machine having a roller wound with rayon cloth, the number of rolls is 500 rpm, and the sample is moved. Speed of 3cm / sec, the length of villi pressed into 0.4mm, rubbing treatment of the coated film, imparting the liquid crystal alignment capability. Then, ultrasonic cleaning was carried out for 1 minute in ultrapure water, followed by drying in a 1 t clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two sheets) of substrates having a liquid crystal alignment film. Next, an epoxy resin adhesive containing a 5.5 μm diameter alumina ball is applied to the outer edge of any one of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film faces are opposed to each other and the rubbing directions of the respective alignment films are orthogonal. Perform overlapping presses' and harden the adhesive. Then, a nematic liquid crystal (MLC-6221, manufactured by Merck Co., Ltd.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell. &lt;Evaluation of liquid crystal cell&gt; (1) Evaluation of heat-resistant stability The liquid crystal cell produced as described above was subjected to 3 〇 Hz, 3 of 6.0 V alternating current (peak_peak) at a temperature of 7 (rc at ambient temperature for 500 hours). Rectangular wave of 〇v. The liquid crystal cell after 500 hours passed was visually observed, and the case where no display defect was observed was evaluated as heat resistance stability. "Good, and observation will be observed.

-32- 201221554 The case of poor performance was evaluated as "poor" in heat resistance stability. (2) Measurement of voltage holding ratio A voltage of 5 V was applied to the liquid crystal cell produced as described above at an application time of 60 μsec and an interval of 67 μm, and then the voltage holding ratio from the release of the application to 167 ms was measured. The measuring device used VHR-1 manufactured by TOYO corp〇rati〇n. The case where the voltage holding ratio was 95% or more was evaluated as "good", and the other cases were evaluated as "poor". (3) Measurement of initial pretilt angle For the liquid crystal cell produced above, according to "TJ S cheffere t. a 1., J. Appl. Phys., vol. 48, pl 783 (1977), and "F. Nakano, The method described in et. al., JP N. J. Appl. Phys., vol. 19, P2013 (1980), determines the pretilt angle by a crystal rotation method using He-Ne laser. The measurement system is performed after the application of the voltage after the liquid crystal cell is fabricated, and this is taken as the initial pretilt angle θίηί. (4) Evaluation of pretilt stability The pretilt angle (pretilt angle after driving eac) after driving at room temperature for 13 hours at AC9V was measured in the same manner as in the above (3). The pretilt angle change rate α [%] is calculated by the following formula (5). The case where the pretilt angle change rate α was less than 3% was evaluated as "good", and the case where the value was equal to or higher than the value was evaluated as "bad"' ° a = (0ac - 0ini) / 0 inixl 〇〇 [%] (5) The results of the above (1) to (4) are shown in Table 2 below. -33- 201221554 [Table 2]

As shown in Table 2, the liquid crystal cell of Example 3 was excellent in both H-form and voltage retention. Further, for the pretilt angle change rate α, it is 8 to 2 in the embodiment 3, and the pretilt angle does not change before the application of the voltage and after the application of the voltage is released. In contrast, in Comparative Example 1, 'α = 5.0%, and the change in the pretilt angle was large before and after the application of the voltage. [Simple description of the diagram] None. [Main component symbol description] No 0 -34-

Claims (1)

B-A-NH2 201221554 VII. Applicable Patent Range: L-type liquid crystal alignment agent, its aminated polymer &amp; two 12 has a group of φI composed of poly-proline and its cleavage At least one kind of polymerization which is acidified by the acid is obtained by reacting a tetracarboxylic acid dimer system with a monovalent L* and an amine to obtain a structure represented by the following formula (1). In the formula (1), R1 is an alkyl group, an arsenic or a fluoroalkane group having a carbon atom of 1-6, and a melon is an integer of 〇~.3, when m is 2 to 4' R1 is independently and in the same manner, and has the above definition, and η is 1 to 3. When η is 2 or 3, r and m each independently have the above-mentioned connection bond. 2. For example, in the patent application scope ^ ^ ^, Gu Di 1 liquid crystal alignment agent, wherein the second is a compound containing the following formula (2) household jin # - ), 醯 物, the polyoxygen The number of base integers, meaning, amine atom, extension of hydrogen C00-; or fluorine MR1 "η is -35- 1 2 (2) ten, A is independently a single bond 'arylene group, number is 2 〜6 alkyl, phenyl, anthranyl, anthranil, or a triad, and at least the atoms of the carbon atom can be substituted 'B are each independently a single bond, -0- , or - 0C0-, R is an alkyl group having 1 to 6 carbon atoms, and the oxyalkyl group 'm is an integer of 0 to 4, and when the melon is an integer 3 of 2 to 4, each independently has the above definition, An integer of 1 to 3, 201221554 2 or 3, R1 and m each independently have the above definitions. 3. The liquid crystal alignment agent of claim 2, wherein the A is independently phenyl or substituted A liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 3. 5. Liquid crystal display element , Which patent as having a range-based entries of the liquid crystal alignment film 6. 4 - Species compound represented by the following formula (3) represented. In the formula (3), B is each independently a single bond, -0-, -COO- or -OCO-, and R1 and R2 are each independently an alkyl group, an alkoxy group or a fluoroalkane having 1 to 6 carbon atoms. Further, m is an integer of 0 to 4, and when m is an integer of 2 to 4, R1 each independently has the above definition, and r is each independently an integer of 0 to 5, and when there are a plurality of R2, R2 is independent The ground has the above definition, η is an integer of 1 to 3, and when η is 2 or 3, R1 and m each independently have the above definition. 7. A polymer obtained by reacting a compound of the sixth aspect of the patent application with a tetrahydro acid dianhydride. -36- 201221554 IV. Designation of Representative Representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 〇 ί **, 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: