TW201226445A - Liquid crystal alignment agent, liquid crystal alignment film, method for forming liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The object of the present invention provides a liquid crystal alignment agent which has an excellent radiation sensitivity and is capable of forming a liquid crystal alignment film having various properties such as a good liquid crystal alignment capacity and electrical property, etc. by a photo-alignment method with few exposure amounts. Also, the present invention provides a method for forming a liquid crystal alignment film using the liquid crystal alignment agent, and a liquid crystal alignment film and further provides a liquid crystal display element having the liquid crystal alignment film. The liquid crystal alignment agent comprises a polyamic acid and/or polyimide having a bicycle [2.2.2] octane skeleton. And further, the above polyamic acid has a structure unit represented by the following formula (1) and the above polyimide has a structure unit represented by the following formula (2).

Description

201226445 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal alignment film, and a liquid crystal display element which are suitable for light alignment. [Prior Art] Liquid crystal display (LCD) is widely used as a display element of an LCD in televisions and various monitors and the like. It is known to have a TN (Twisted Nematic) type; STM (Super Torsion Nematic) (Super Twisted Nematic)) i, IPS (In Piane Switching) type; changing the as-type electrode structure's FFS (Fringe FieM Switching) to increase the aperture ratio of the display element portion and thereby improve the brightness Liquid crystal cell of the type or the like (see Patent Documents 1 and 2). As a method of aligning the liquid crystal of the liquid crystal cell, it is known to form an organic film such as a liquid crystal alignment film on the surface of the substrate, and to rub the surface of the organic film in a single direction with a cloth such as rayon to perform a rubbing treatment; A method of obliquely steaming a oxidized stone; a method of forming a monomolecular film having a long-chain alkyl group by using the langmuir-blodgett method (LB method). Among them, a method of rubbing treatment is generally employed from the viewpoints of substrate size, alignment uniformity of liquid crystal, processing time, and processing cost. However, if the liquid crystal is aligned by the rubbing treatment, dust or static electricity is generated in the step, and dust is attached to the surface of the alignment film, which may cause display failure. In particular, in the case of a substrate having a TFT ('Thin Film Transistor) element, the static electricity generated may damage the circuit of the TFT element, which may cause a decrease in productivity. In addition, in the future, the increasingly finer liquid crystal -4 - 201226445 shows that the metamorphic embossing is caused by cinnamic acid, or by arbitrarily arranging radiation or ash. In the case where the processing method is insufficient, the density of the pixel is high, so that it is difficult to perform t on the surface of the substrate as a avoidance. , the tendency of friction treatment. F Feng's method of avoiding the above problems, ester and other senses Μ堉 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知 已知For the material of the photosensitive film, see Patent Documents 3 and 4). For the material of the obtained film, a liquid crystal method of poly(^^^ bromoamine resin) is used (see Patent Document 5). By deer 6t-a , it will not produce static dust, and it will be evenly distributed.

At . . ^ Day alignment. In addition, with friction treatment

The Lunar New Year is in the direction of Ren Si and the Jing Song secret batch & A tf controls the liquid crystal alignment direction. When the radiation is irradiated, the light-glycol stems, and the nine masks are used, so that the liquid crystal alignment direction can be formed on one substrate; π different fields. However, there is a case where it is necessary to heat up at the time of irradiation, and a large cumulative exposure amount is required. Further, the existing liquid crystal alignment by using a polyimide resin does not require heating even when irradiated with radiation, but there is a problem of sensitivity. In this case, it is desired to develop a liquid crystal alignment agent which can form a liquid crystal alignment film having good liquid crystal alignment by a low-emission photoalignment method and can form a liquid crystal display element having various properties such as excellent electrical characteristics. It is also strongly desired to develop a method for forming a liquid crystal alignment film using the liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film. [PATENT DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. A liquid crystal alignment agent which can form a liquid crystal alignment film which is excellent in radiation sensitivity and which has a good liquid crystal alignment property by a light irradiation method of low irradiation amount. In addition, a method of forming a liquid crystal alignment film using the liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element having the same electrical properties as those of the liquid crystal alignment film are also provided. [Means for Solving the Problems] The invention for solving the above problems is a liquid crystal alignment agent containing a polyphosphonic acid having a bicyclo [2.2.2] octene skeleton and/or a polyimine. The liquid crystal alignment agent of the present invention can improve radiation sensitivity by containing polyglycolic acid and/or polyimine having a bicyclo[2.2.2]octene skeleton, and therefore can be formed at a low irradiation amount. Good liquid crystal alignment liquid crystal alignment film. Further, the reason why the radiation sensitivity can be further improved by including the poly-proline and/or polyimine having a bicyclo [2.2.2] octene skeleton has not been clarified, and for example, the following estimation is made. It is considered that poly-proline or the like can cause decomposition of a main chain such as poly-proline and a bond between main chains by, for example, a Diels-Alder reaction by having a bicyclo[2.2.2] octyl skeleton. Dimerization, etc., thus causing light alignment by polarization. In this case, the portion which is considered to cause the decomposition reaction or the binding reaction is introduced into a steric structure as compared with, for example, polyglycine having a cyclobutane skeleton, and the structural change of the polymer before and after the reaction is larger as of 201226445. As a result, the light alignment can be performed with a smaller amount of irradiation. Thereby, the amount of radiation irradiation necessary for the optical alignment can be reduced, so that the liquid crystal alignment agent 1 can be reduced in cost. Further, when a liquid crystal alignment film formed of the liquid crystal alignment agent is used, a liquid crystal display element having excellent electrical properties and the like can be produced. Preferably, the polyamic acid has a structural unit represented by the following formula (1), and the polyimine has a structural unit represented by the following formula (2).

(In the formulae (1) and (2), R1 and R2 each independently represent a divalent organic group.) The liquid crystal alignment agent can have the above specific structure by allowing the above polyamic acid and polyimine. Light alignability with higher sensitivity. The liquid crystal alignment agent of the present invention is suitably used for photoalignment. The liquid crystal alignment agent is highly sensitive to radiation, and a liquid crystal alignment film having excellent liquid crystal alignment ability can be formed by radiation of a low irradiation amount. The method for forming a liquid crystal alignment film of the present invention comprises: 201226445 (1) a step of applying the present step on a substrate, and a liquid crystal alignment agent of a month to form a coating film (2) on the coating film. The ultraviolet ray of light and the liquid crystal distribution can also perform photoalignment in the formation method of the present invention, and the ^ ^ 1 Μ 4 @ (four) line irradiation is highly high, and can be reduced, and the liquid crystal alignment film is also produced to produce the present invention. It is also preferably included. A right-right alignment film formed of the liquid crystal alignment agent. The liquid crystal J of the present invention is formed by the liquid crystal alignment agent, so that the sensitivity to radiation is high, and the amount of .4 A soil is $, n in the forming step, by the amount of the handle Radiation, can impart liquid crystal, alignment ability, so the production efficiency is good, and the manufacturing cost can also be reduced." Shuangfengliang The liquid crystal alignment element of the present invention has the liquid crystal alignment film 曰 alignment film by the liquid crystal alignment agent of the present invention "日日J Since it is formed, it is possible to impart liquid crystal alignment ability by a small amount of radiation irradiation. Therefore, the liquid crystal display element having the liquid crystal alignment film can be made cheaper than the current ones: In addition, the liquid crystal display element of the present invention can also charge various properties.冤 冤 冤 冤 另外 另外 「 「 「 「 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 可见光 可见光 可见光 可见光 可见光 可见光 可见光 可见光 可见光 可见光 可见光 可见光 可见光 可见光 。 In addition, the term "radiation" includes the concept of "light" in addition to the electromagnetic wires and bundles. [Effects of the Invention] The liquid crystal alignment agent of the present invention has high radiation sensitivity, and can form a liquid 201226445 crystal alignment film having excellent liquid crystal alignment properties under low-radiation radiation irradiation, so that the production efficiency is high and Can reduce production costs. Further, the liquid crystal display element having the liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention is excellent in various properties such as electrical characteristics. [Embodiment] [Formation for Carrying Out the Invention] <Liquid Crystal Aligning Agent> The liquid crystal alignment agent of the present invention comprises polybrene acid having a bicyclo [2.2.2] octene skeleton and/or polyimine. A liquid crystal alignment film containing polyphosphoric acid having a bicyclo [2.2.2] octene skeleton and/or polyimine, radiation having improved radiation sensitivity, and emission at a low irradiation amount can be formed. Further, the respective members are described separately in terms of the properties of the electric properties and the like without damaging the effects of the present invention, other than proline and/or polyimine. [Polyuric acid] Excellent liquid crystal alignment under the line The liquid crystal display element of the liquid crystal alignment film is excellent. The liquid crystal alignment agent of the present invention may contain other components in addition to the above-mentioned aggregation as an essential component. The polylysine used in the following invention has a bicyclo [2.2.2] octene bone sympathetic bone and a sulfur in the sulphate:, and has a bicyclo [2.2_2] hibisin amide in its structure, there is no In particular, the polylysine can be made, for example, by having a double net? ★ The ruthenium [2.2.2] octene skeleton of tetracarboxylic acid dioxime is reacted with a compound in an organic solvent to synthesize it. As a four-glow g dianhydride with a double ring "2 9 ο 1 jL · lx •• anaerobic skeleton, it can be = such as double ring [2.2.2] 辛..., 3, 5, 6·丄^ [2 2 and 2^ 2·2·2] Xin·7wu 2,3,5,6. Four-salt acid di^6-based-bicyclic • ·] Xin: dilute _2,3,5,6_tetradecanoic acid double ring 201226445 [2.2. 2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 7-n-butyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid Acid dianhydride, 7-second butyl-bicyclo[2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1-indenyl-bicyclo[2.2.2] octane- 7-ene-2,3,5,6-tetracarboxylic dianhydride, 1-methyl-7-methyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid Acid dianhydride, 1-mercapto-7-ethyl-bicyclo[2_2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1-indolyl-7-n-propyl -bicyclo[2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1-methyl-7-n-butyl-bipolar [2_2.2] octa-7-thin - 2,3,5,6-tetradecanoic acid two-needle, 1-methyl-7-tert-butyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid A dianhydride or the like. Among them, a bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1-methyl-bicyclo[2.2.2]oct-7- is preferred. Alkene-2,3,5,6-tetracarboxylic dianhydride, 7-methyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetra Acid dianhydride, 1-mercapto-7-fluorenyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. Among them, more preferably bicyclo [2.2.2 Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 7-fluorenyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid The anhydride is particularly preferably a bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. The polyglycolic acid used in the present invention preferably has the above formula (1). By using the polyamic acid having a specific structure, by polarized ultraviolet light irradiation, liquid crystal molecules can be aligned in a certain direction with respect to a polarization direction, and can be uniformly and stably aligned. In the above formula (1), the divalent organic group represented by R1 is a group derived from a diamine. Specific examples of the diamine compound are as long as it is in the synthesis of a usual polyamine or polyimine. The primary diamine to be used is not particularly limited, and examples thereof include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diamine organic decane, and the like. -10- 201226445 As an aliphatic diamine For example, m-xylylenediamine, 13-propylenediamine 'tetradecyldiamine, and five Yue diamine, > methylene diamine. 'As an alicyclic diamine, for example, hydrazine, 4-diamine cyclohexane, 4,4'-methylene bis(cyclohexylamine), j 3 bis '-methane (methylamine) cyclohexane Wait. Examples of the diamine organooxosiloxane include hydrazine, 3-bis(3-aminopropyl)-tetramethyldioxane and the like. Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-diphenylamine, 4,4,-diaminodiphenylmethane, 4,4, and diaminodiphenyl sulfide. 1,5-Diamine naphthalene, 2,2,-dimercapto-4,4,-diaminobiphenyl, 4,4'-diamino 2,2,-bis(trifluoromethyl) Stupid, 2,7-diamino, 4,4'-monoaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9_ Diaminophenyl) 1,2,2-bis[4-(4-aminophenoxy)phenyl]hexaethoxypropane, 2,2-bis(4.aminophenyl)hexafluoropropane, 4,4,_(p-phenylenediisopropyl)bis(aniline), 4,4'-(m-phenylenediisopropyl)bis(aniline), ι,4-bis(4-amine-based oxy Benzo, 4,4,-bis(4-aminophenoxy)biphenyl, 2,6-monoaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine '3, 6-Diamino-based, 3,6-diaminocarbazole, N-mercapto-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N _stupyl-3,6-diaminocarbazole, n,n,_bis(4-aminophenyl)-benzidine, n,n,_bis(4-aminophenyl)_N,N, _Dimercaptobenzidine, 1,4· (4-Amino-phenyl)-piperidine, 3,5-diaminobenzoic acid, dodecyloxy 2,4-diaminobenzene, tetradecyloxy-2,4-diamine Stupid, fifteen alkoxy-2,4-diamino stupid, cetyloxy-2,4-diamino stupid, octadecyloxy-2,4-diaminobenzene, twelve Alkoxy-2*5-diamino group•11- 201226445 Benzene, tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, hexadecane Oxy-2,5-diamino stupid, octadecyloxy-2,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy·3, 5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholestyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteryl Ester, cholesteryl 3,5-diaminobenzoic acid, lanyl alkyl 3,5-diaminobenzoic acid, 3,6-bis(4-aminobenzyl methoxy) cholesteryl Alkane, 3,6-bis(4-aminophenoxy)cholane, 4-(4'-trifluorodecylphenyl)cyclohexyl-3,5-diaminobenzoic acid , 4-(4'-trifluoromethylphenyl)cyclohexyl-3,5-diaminobenzoic acid vinegar, 1,1-bis(4-((aminophenyl)methyl)phenyl )_4_ Cyclohexane, hydrazine, bis(4-((aminophenyl)indenyl)phenyl)-4-heptylcyclohexane, M.. bis(4_((aminophenyl)indenyl)benzene -4-heptylcyclohexane, bismuth (4-((aminophenyl) decyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, 2,4-diamine base-N,N-diallylaniline, 4-aminobenzylamine, %aminobenzylamine, 201226445

X1 — R3 — X2 1-(2,4-diaminophenyl)piperidine-4-carboxylic acid, 4-(sodium benzo-4-yl)benzene-anthracene, diamine, 1,3-bis(Ν -(4.Aminophenyl)piperidinyl)propane, an α-aminoaminophenylalkylene group, a compound represented by the following formula (A-indole), and the like. H2N^=

CcH2c+i (A -1 ) (In the formula (A_l), X1 and χ2 are each a single bond, *〇, *_c〇〇_ or c〇" in the connection key with 胄"*" in χ1 The diaminophenyl group binds/bonds to R3 in χ 2. R3 is a methylene group, an ethylene group or a propylene group. a is 0 or 1. 匕 is a bismuth of 〇~2. An integer of 1 to 20, wherein a and b are not simultaneously 〇., -12- 201226445 In the above formula (Al), 'divalent group represented by _χ1_κ3_χ2_, preferably methylene group, carbon number It is a 2 or 3 alkylene group, *-〇-, *-COO- or *_0-CH2CH2-0-, wherein a bond having a "*" bond is bonded to a diaminophenyl group. In 1), examples of the group represented by -CcH2c+1 include a mercapto group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, an n-octyl group, a n-decyl group, and a ruthenium. Base, n-dodecyl, n-tridecyl, n-tetradecyl, n-five-burning, n-five-family 'n-seventeen-burning base, n-octadecene base, positive nineteen-burning base, In addition, the two amine groups in the diamino benzene storm are 2,4 ·* or 3,5-position relative to the other groups.

Examples of the compound of the above formula (A-1) include a compound of the following formula (A-1, n, (A-1-2), (A-1-3), and the like.

C5H” C5^ii (A-1-2)

-13-201226445 As the diamine other than the above, a diamine described in JP-A-10-10 1978 can be used. Further, in the case of using a diamine represented by the above formula (A-1), a diamine having a side chain containing a long-chain acrylic side chain or a cholesteric skeleton, it is also suitable as a VA (Vertical Alignment). A liquid crystal alignment agent of a liquid crystal display element. Among these diamines, aromatic diamines are preferred. [Synthesis of Polylysine] The polylysine used in the present invention can be obtained, for example, by reacting a tetracarboxylic dianhydride having a bicyclo [2.2.2] octene skeleton with the above diamine compound in an organic solvent. . a proline structure derived from a tetracarboxylic [2.2.2] octene skeleton having a guanidine & I + y , i , δ ratio, as used in the present invention

Ten Yu Wang. The entire structural unit of the PV compound is preferably 〇.1 to 1 〇〇 mol%, more preferably s~μ.旯佳 is 5 to 95% by mole, and particularly preferably 50 to 90%. In the polylysine used in the present invention, the ring-shaped symplectic skeleton...the two needles are doubled with the other four. For example, 'as the other four acid-low-needle needles, it can be exemplified by the fat two: Xuan and dianhydride, alicyclic tetracarboxylic acid-舡^壬 伽 肪 面 绫 绫 〜 〜 〜 方 方 方 方 方 fang fang fang fang . ★ As a specific example of 匕, we can list aliphatic tetracarboxylic dianhydrides such as butyl hydrazine; carboxylic acid dianhydride 1,2,3,4-cyclobutane tetracarboxylic dianhydride, two acid two needles ...—nitrogen_5...yl)_naphtho[l,2-c]furan-丨3 _ gas-3-furanyl-5-(tetrahydro.25 _ gas 3, — ,,Μ,5,%- Hexahydro-I-methyl 2,5--oxygen_3·pyranyl)naphthoquinone π, 2 exogenous. South]丄二-14- 201226445 Ketone, 3-oxobicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-indolyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxyl Base decene-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2,4,6,8-dianhydride, 4,9- Dioxatricyclo[5.3.1.02'6]-!--carbon-3,5,8,10-tetraketone and other alicyclic tetracarboxylic dianhydride; aromatic tetracarboxylic acid such as pyromellitic dianhydride Further, the dianhydride may be a tetracarboxylic dianhydride described in JP-A No. 20 10-97 188. These other tetracarboxylic dianhydrides may be used alone or in combination of two or more. Examples of the organic solvent used in the synthesis of polylysine include an aprotic polar solvent, benzophenone and a derivative thereof, an alcohol, a ketone, a vinegar, a mystery, a hydrocarbon, a hydrocarbon, and the like. As specific examples thereof, N-mercapto-2-pyrrolidone, N,N-dimethylacetamide, hydrazine, hydrazine-dimethyl decylamine, dimethyl sulfoxide, 7- Aprotic polar solvent such as butyrolactone, tetramethyl urea, hexamethylphosphine tridecylamine; phenol derivative such as m-cresol, xylenol or halogenated phenol; methanol, ethanol, isopropanol, cyclohexane An alcohol such as an alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol or ethylene glycol monoterpene ether; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; Ethyl ester, butyl lactate, decyl acetate, ethyl acetate, butyl acetate, decyloxy propionate, ethyl epoxy propionate, diethyl oxalate, diethyl malonate, etc. Ester; -15- 201226445, ethylene glycol diethyl ether glycol ester, di-p-phenylhexyl ester, heterogeneous solvent or from the upper ketone, the ratio of the above phase is 50 or less. Ether, ethylene glycol, shouting, ethylene glycol oxime, ethylene glycol n-propyl ether, isopropyl sulfonate, ethylene glycol n-butyl (tetra), ethylene glycol dimethyl ether, ethylene bismuth Diethylene glycol dihexyl, diammonium ether, diethylene glycol monotopine, diethylene glycol monomethyl ether acetate ethylene glycol monoethyl ether acetate, tetrahydrogen. The mystery of Fu et al; gasification of methane, 1,2-dichloroethane, M•dichlorobutane, tri-ethane ethane, o-dichlorobenzene, etc.; Yuan Gengxuan • Xin Tong, benzene, A hydrocarbon such as stupid, xylene, isoamyl propionate, diisoamyl ether or the like. In the k-diorganic agent, it is preferred to use one or more selected from the group consisting of an aprotic electrode, a phenol and a derivative thereof, and an organic solvent selected from the group (1). a mixture selected from the group consisting of alcohols, ethers, dentate hydrocarbons, and hydrocarbons. In the latter case, the use of the organic solvent of (ii) is preferably less than or equal to the total of the organic solvent of (1) and the organic solvent of (ii), more preferably 40% by mass. /. In the following, it is particularly preferable that the amount of the organic solvent used is 3, and the total amount of the tetracarboxylic dianhydride and the diamine is preferably 〇 1 to 5 % by mass based on the total amount of the reaction solution. The reaction solution obtained by dissolving polylactoic acid in the above solvent can be directly used for the preparation of the liquid crystal alignment agent, and can also be used for the preparation of the liquid crystal alignment agent after separating the polylysine contained in the reaction solution. The purified polyamic acid is used for the preparation of a liquid crystal alignment agent. In the case of dehydration of poly-proline to form a polyimine, the above reaction solution may be directly used for the dehydration ring closure reaction, or after the polyamine acid contained in the reaction-16 - 201226445 solution is separated. It is used for dehydration ring closure reaction; or the separated polyamic acid can be refined and used for dehydration ring closure reaction. Further, the separation and purification of the poly-aracine can be carried out according to a known method. The ratio of the tetracarboxylic dianhydride to the diamine used in the polyamine acid synthesis reaction is preferably 0.2 to 2 equivalents based on 1 equivalent of the amine group of the diamine. Good is 0.3 to 1.2 equivalents. The temperature of the synthesis reaction is preferably from -20 ° C to 15 CTC, more preferably from 〇 to 1 00 ° C. The synthesis reaction time is preferably from 〇丨 to 24 hours, more preferably from 5 to 12 hours. In the synthesis of the above polyamic acid, a terminal modified type polymer can be synthesized by using a suitable molecular weight modifier in addition to the above tetracarboxylic acid di-needle and diamine. By forming the terminal-modified polymer, the coating property (printability) of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention. The above-mentioned molecular weight modifier "monoanhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned. Examples of the monoanhydride include maleic anhydride, liver of phthalic acid, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl group. Succinic anhydride and the like. The monoamine compound ' can be aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine or n-octylamine. Examples of the monoisocyanate compound' include phenyl isocyanate and naphthalene isocyanate. The tetracarboxylic dianhydride and the diamine used in the use ratio of the molecular weight modifier are preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on the total amount of i 〇 〇 by mass. -17- 201226445 [Polyimide] The polyimine used in the present invention has a bicyclo[2 2 2]octene skeleton. In the structure, it is not particularly limited as long as it is a substance having a bicyclo[2·2 2]octene skeleton. However, it can be obtained, for example, by dehydration ring closure of the polylysine synthesized as above and ruthenium ruthenium. The polyimine used in the present invention preferably has a structural unit represented by the above formula (2). The liquid crystal molecules are irradiated by polarized ultraviolet rays by the polyimine containing the specific structure, so that the liquid crystal molecules can be in a certain direction with respect to the polarized light. The sentence is steadily aligned. The polyimine in the present invention may be a poly-aracine which is used as a precursor thereof: a lysine structure in which all of the proline structures are dehydrated and closed, or a structure of only a proline- Partial dehydration ring closure, partial quinone imine compound with a proline structure and a quinone ring structure. The polyimine in the present month preferably has a sulfhydrylation ratio of 3 〇 % or more, more preferably 5 0 9 9 /〇', and more preferably 6 5 to 9 9 %. The ruthenium imidization ratio is a numerical value in which the ratio of the number of the quinone imine ring structure to the sum of the number of the ruthenium structure of the polyimine and the sum of the quinone ring structures is expressed as a percentage. The portion of the 'II imine ring' may be a racered imine ring. [Synthesis of Polyimine] The polyimine used in the present invention can be obtained by dehydrating ring-opening and hydrazine imidation of the polylysine synthesized as described above. The dehydration ring closure of the acesulfame is preferably a method of heating the poly phthalic acid or dissolving the polyaminic acid in an organic solvent, adding dehydration hydrazine and a dehydration ring closure catalyst to the solution, and heating as needed. get on. Among them, it is preferably carried out by a method described later. -18 - 201226445 In the above solution of polylysine, I am looking forward to the process of adding dehydrating agent and dehydration ring-closing catalyst. As a dehydrating agent, I can use, for example, acetic anhydride, propionic anhydride, trifluoroethane. An acid anhydride such as an acid anhydride. Dehydrated sword to the field 曰Λ 的 4 The amount of Ν 4 used relative to the 醯 耳 耳 耳 醯 醯 醯 , , , , , , , , , , , , , , , , , , , , , , As the dehydration ring-closing catalyst, for example, pyridinium, =Tian*, and T-storm D ratio can be used. A tertiary amine such as dimethylpyridine or triethylamine. The dehydration ring-closing catalyst is preferably used in an amount of from 1 to 1 mol per mol of the dehydrating agent used per 1 mol. The organic solvent used in the dehydration ring-closure reaction is exemplified as the solvent used in the synthesis of the polyamic acid, and the organic solvent exemplified. The reaction temperature of the dehydration ring closure reaction is preferably from 0 to 18 Torr.

1 Xuan 1 (J 1 5 QC. The reaction time is preferably ~ ^ hour, more preferably 2 〇 ~ 3 〇 〇 〇 〇 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有It can also be used for the preparation of liquid crystal alignment agent after removing the dehydrating agent and the dehydrated ruthenium catalyst from the reaction solution; it can also be used for the preparation of the liquid crystal alignment agent after separating the polyimine, or can be: Preparation of liquid crystal alignment agent after refining of quinone imine. These refining operations can be carried out by a known method. The poly-proline or polyimine obtained as above is formed at a concentration of 10% by mass. In the case of a solution, it is preferred that the solution viscosity of 2 〇 8 8 mPa s is more preferably a solution viscosity of 30 to 500 mPa·s. The solution viscosity (mPa . s) of the above polymer is for the use of the polymer. A polymer solution having a concentration of 10 mil % prepared by a good solvent (for example, 7 · butyrolactone, N-methyl-2-pyrrolidone, etc.), using a Ε-type rotational viscosity, a value measured at ° C. 25 -19 - 201226445 [Other Ingredients] The liquid crystal alignment agent of the present invention contains the above polyfluorene The amine acid and/or the polyimide may be an essential component, and may contain other components as needed. Examples of the other component include other polymers and compounds having at least one epoxy group in the molecule (hereinafter also referred to as It is an "epoxy compound j" or a functional decane compound. (Other polymers) The above other polymers can be used to improve solution characteristics and electrical properties. The other polymer is other than the above polylysine or the above polyimine. The polymer 'is, for example, a polyglycine which is obtained by reacting a tetracarboxylic dianhydride other than tetrareoxalic dianhydride having a bicyclo [2.2.2] octene skeleton with a diamine (hereinafter referred to as "other polyfluorene" Amino acid"), a polyimine obtained by dehydration of the above polylysine (hereinafter also referred to as "other polyimine"), polyglycolate, polyester, polyamine, polyoxyl An alkane, a cellulose derivative, a polyacetal, a polystyrene derivative, a poly(styrene-phenyl cis-butane) derivative, a poly(meth) acrylate, etc., wherein 'preferably Other polyaminic acid or other polyimine More preferably, it is another poly-proline. The tetra-hypo-dianhydride used for the synthesis of the above other poly-aramidic acid or other polyimine is exemplified as a tetracarboxylic acid for synthesizing the poly-proline used in the present invention. The acid dianhydride 'is the same as described above' but is preferably selected from the group consisting of 1,2,3,4-cyclobutane tetraphthalic acid dianhydride, pyromellitic acid dioxins, 2,3,5-two rebellion Base pentyl basal acid-if and i, 3 3a 4,5,91>-hexamil-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[nqfuran 4, At least one of the groups consisting of 3-diketones. • 20- 201226445 For the diamines of other poly-proline or other polyimine, it can be enumerated. The diamine used in the case of the poly-proline used in the present invention is at least one selected from the above-exemplified ones. As a diamine for synthesizing JL, /, poly-polyamine or other polyimine, it is preferred to use a base selected from 4 4, a ^ ^ ^ '4 - January female base, 2,2'-Dimethyl-4 4,- 'mono-Azate, Hit s-alcohol-2,4-diaminobenzene, 3,5-diaminobenzoic acid and 1,4 - 雔 η ('Aminophenyl) - Listen at least one of the groups formed. The ratio of use of ΧΛτ. and the complex is relative to the sum of the polymers (the sum of the above-mentioned poly sulfonium & amine SiL and/or other polymers. The same applies hereinafter.), preferably 50 哲θ ^Budong % or less, more preferably (^~ buckle mass. /., further more preferably 0. 1 to 30% by mass. (epoxy compound) 4 乍 is an epoxy compound, and examples thereof include ethylene glycol diglycidyl Jun, poly 7 ^, _ A-alcohol diglycidyl ether, propylene glycol diglycidyl ether, ~~ monool diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl alcohol wall > 1,6-hexanediol diglycidyl ether, glycerol diglycidyl _., dimethicone triglycidyl ether, 2:, 2-dibromo neopentyl glycol-starting u. Ether, N,N,N'N,-tetraglycidyl-m-diphenylene diamine, 〖2 μ χτ, 3_bis(Ν,Ν-diglycidylamino) hexane, ν , ν, ν, ΝΛ a 'tetraglycidyl-4,4,-diaminodiphenylmethane, hydrazine, hydrazine-glycidol 1 & @卷-卞-amine, hydrazine, hydrazine-bi-hydration Oil-amino-mercaptocyclohexene, Ν "Μ _ & glyceryl-cyclohexylamine, etc. as a preferred material. 14 Mixture ratio of the diepoxide compound relative to the sum of 1 〇〇 by mass of t The compound, the dying i & / Λ 0 曰 flat is preferably 40 parts by mass or less, more preferably 0.1 to 30 parts by mass. -21 - 201226445 (functional decane compound) as the above-mentioned functional stone smelting compound, can For example, 3-aminopropyldimethoxycarbazide, 3-aminopropyltriethoxymethane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane , N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)_3·aminopropylmethyldimethoxydecane, 3-urea Propyltrimethoxydecane, 3·ureidopropyltriethoxydecane, N_ethoxycarbonyl-3-aminopropyldimethoxydecane, N-ethoxycarbonyl-3-amine Propyltriethoxydecane, N-triethoxycarbamidopropyltriethylenetriamine, N-trimethoxymethyl decylpropyltriethylenetriamine, 1〇-trioxyloxydecane Base _i, 4, 7 · triazepine, 10-triethoxy Formyl-M,7-triazanonane, 9-methoxymethoxycarbazide-3,6-diazaindolyl acetate, 9-tridecyloxymethylalkyl-3, 6-diazaindolyl acetate, 9-triethoxymethylglycine 3'6-diazaindolyl acetate, 9-trimethoxymethylglycine _3,6-二 旨 旨 ' ' ' 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 3_Aminopropyl hydrazine diethoxy decane, N-phenyl-3-aminopropyl trimethoxy decane, nf group, 3-aminopropyl triethoxy decane, glycidoxymethyl dimethyl Stupid base, glycidyloxydecyl triethoxydecane' 2_ shrinking gas, ethyl tridecyloxydecane, 2-glycidoxyethyl: 'burned by you, 3-glycidoxy Propyl tridecyloxydecane, 3_water, urethane, triethoxy, and the like. 'Electricity The mixing ratio of these functional decane compounds is preferably 2 parts by mass or less, more preferably parts by mass, based on the polymer of the 1 Q fluorene compound. ., 〇.〇2~0.2 -22-201226445 <Preparation of Liquid Crystal Aligning Agent> The liquid crystal alignment agent of the present invention is preferably another component which is arbitrarily mixed as needed with the above polylysine or polyaluminum Dissolving organic solvent used in the liquid crystal alignment agent of the present invention, vinegar, hydrazine, for example, hydrazine methyl-2_° ratio acetophenone, butyl vinegar, ι butyl methyl-^-gu Monomethylmethamine ~ Mu... Dimercaptoacetamide ~ hydroxy hydroxy-4-oxo & naloxin, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl lactobionate ,ethyl ether, _ acetonitrile ethyl propionate, ethylene glycol methyl ether, ethylene glycol butyl phthalate = glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (J | Sai Su) , _ 1 ^ diol _ - yeast dimethyl _, ethylene glycol ethyl ether acetate, diethyl ether ~ ~ methyl ether, _ _ diol single 7 ,, - yeast diethyl ether, diethylene glycol monomethyl ether, Diacetate, ethylene glycol monomethyl hydrazine acetate, diethylene glycol monoethyl ether, two mornings, isobutyl ketone, isoamyl propionate, isoamyl isobutyrate Base key, #秘,μ separate Wei Rasp & vinyl ester, propylene carbonate and the like. These can be Π3 5 jL _ ± ^. Two or more types can be used in combination. The solid content concentration in the octagonal alignment agent other than the liquid hydrazine solvent of the present invention (the liquid crystal alignment agent takes into account the ratio of the total mass of the viscous knives to the total mass of the liquid crystal alignment agent) can be appropriately selected within the range of β, volatility, etc. Good at 1 to 10% by mass of 1%. In other words, the liquid crystal alignment agent of the invention is as described later, and it is preferable to form a liquid film on the substrate surface by heating to form a coating film as a liquid crystal alignment film or 'human 曰酉 曰酉 & 0 0 0 0 0 0 In the case of the film coating of the film, but the solid content concentration is less than 1 mass, the film thickness of the film is too small, the film thickness is too small to obtain a good liquid, in terms of coating, the solid content concentration exceeds 10%. . In addition, when the thickness of the crucible is too large, the viscosity of the crystal alignment agent which does not obtain a good liquid crystal alignment increases, and the coating property deteriorates. -23- 201226445 The range of particularly good solid content concentrations varies depending on the method used to coat the liquid crystal alignment agent on the substrate. For example, in the case of the spin coating method, the solid content concentration is preferably in the range of 15 to 45 mass%. In the case of the printing method, a concentration of solid content concentration of 3 to 9% by mass is particularly preferable. Thus, the solution viscosity is in the range of 12 to 5 QmPa s. In the case of the ink jet method, it is particularly preferable that the solid content concentration is in the range of 5% by mass, whereby the solution is cooled and the viscosity is in the range of 3 to 15 mPa·s to modulate the liquid crystal alignment of the present invention. When the agent is J Μ ", the degree of the dish is preferably 丨〇~5 〇, more preferably 20~30 °C. <Liquid Crystal Alignment Film> The liquid crystal alignment film of the present invention is formed of 兮, 曰, and 由 from 6 玄液日日. Therefore, in the forming step, the liquid crystal alignment ability can be imparted by the radiation of θ ' · ·, and the radiation 1. In addition, the heating step after the radiation irradiation and the solar ray irradiation is performed, and thus the production efficiency .... after shooting

Good and Reduced Manufacturing Cost Q <Formation Method of Liquid Day Alignment Film> The liquid crystal alignment agent of the present invention has a material suitable for use as a day alignment film according to the photoalignment method. In addition,

蜇 or STN type liquid crystal cell liquid 曰 - t is in, there is TN 咕 night and day, or IPS type, Fpq

The transverse electric field of the liquid crystal cell is changed to M t a - FFS wave crystal alignment film. The liquid a of the present invention is used as a day-to-day alignment agent, especially when the liquid crystals of the pear, FFS type liquid crystal cells have a liquid crystal g _ , /, and there are IPs, and the present invention can be used for the present invention. The effect is better. Further, the method for forming the liquid crystal alignment crucible of the present invention includes: -24-201226445 (1) a step of applying the liquid crystal alignment agent of the present invention to a substrate and forming a coating film (hereinafter, also referred to as "step (1)'") And (2) a step of irradiating the polarized ultraviolet light on the coating film and imparting a liquid crystal alignment ability (hereinafter also referred to as "step (2)"). Hereinafter, each step will be described in detail. [Steps In the case where the liquid crystal alignment agent of the present invention is applied to a liquid crystal display element having a TN type or STN type liquid crystal cell, two substrates each having a patterned transparent conductive film are provided as a pair, The liquid crystal alignment agent of the present invention is applied onto the transparent conductive film forming surface to form a coating film. On the other hand, an in-glass diacetate plate or the like of the opposite plate of the liquid crystal cell film. The composition is as above. When the liquid crystal alignment agent of the present invention is used for a liquid crystal display element having an lps type or an FFs type without forming a pattern, a substrate having an electrode on one side of a transparent conductive film or a zigzag pattern, and an electrode substrate not provided As a pair, the liquid crystal alignment agent of the present invention is applied to the formation surface of the zigzag electrode and the opposite base surface to form a coating film. All of the earth's It; brother's as the above substrate, 彳 used to use glass such as float, soda glass, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and other plastics As the transparent conductive film, for example, an In203-Sn02 IT tantalum film, a NESA (registered trademark) film made of Sn 2 , or the like can be used. For example, a film made of a metal such as chrome: a pattern of a conductive film and a metal film may be used, for example, a transparent conductive film may be used, followed by a method of photolithography, sputtering, etc. In the case of a conductive film, a method having a desired nine cover or the like is used. -25- 201226445 When the liquid crystal alignment agent is coated on the substrate, the adhesion of the high-conductivity film or the electrode to the coating film is obtained, ^ , At liL j 预先 pre-coating the 3b decane compound, titanate on the substrate and the electrode Wait. The liquid crystal alignment agent may be coated on the substrate. Preferably, the coated surface is pre-heated by a suitable coating method such as offset printing, spin coating, roll coating, or ink jet printing. Baking), and then firing (post-fire, roasting) to form the coating film 1 for baking conditions, for example, at 4 〇 to i2 (rc for 0.1 to 5 minutes; post-baking conditions are preferably at i2 〇 to 3 〇 ( Rc, more preferably 150 250 CT, preferably 5 to fan minutes, preferably ίο~1 〇〇 minutes. The film thickness of the film after post-baking is preferably 〇〇〇ι~ 'better It is 0.005 to 〇5μηι. [Step (2)] The liquid crystal alignment ability is imparted by irradiating the polarized radiation in the thus formed coating film. [As the radiation, for example, ultraviolet rays containing light having a wavelength of 150 to 800 nm can be used. The visible light line is preferably ultraviolet light containing light having a wavelength of from 200 nm to 400 nm. As the light source used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a heavy hydrogen mercury lamp, a metal hydride lamp, an argon resonance lamp, a xenon lamp, an excited molecular laser can be used. Etc. The above is preferred wavelength The ultraviolet ray of the domain can be obtained by a method in which the above-mentioned light source is used in combination with, for example, a filter, a diffraction lattice, etc. If the liquid crystal alignment agent of the present invention is used, it is usually required to irradiate ultraviolet rays of 10000 J/m or more, even if it is 8 Å. J/m2 can also impart good liquid crystal alignment ability, can improve the productivity of the liquid crystal display element, and reduce the manufacturing cost. ' 26 - 201226445 &lt;Liquid crystal display element&gt; The liquid crystal display element of the present invention has a liquid crystal alignment agent formed using the liquid crystal alignment agent The liquid crystal alignment film 'is therefore capable of imparting alignment ability to the liquid crystal at a lower irradiation amount than the present. Therefore, the liquid crystal display element having the liquid crystal alignment film can be manufactured at a lower cost than the current one. The liquid crystal display element of the present invention can be, for example, The liquid crystal cell having a structure in which liquid crystal is sandwiched between the pair of substrates is prepared as described above. The liquid crystal cell having a structure in which liquid crystal is sandwiched between the pair of substrates is prepared. For the production of the liquid crystal cell, for example, the following two methods are available. Known method. Set the two substrates oppositely by the gap (cell gap) to make the liquid crystal alignment films face each other. The peripheral portion of the two substrates is bonded together with a sealant, and after filling the liquid crystal into the interstitial space defined by the surface of the substrate and the sealant, the injection hole is sealed to prepare a liquid crystal cell. The second method is called ODF (liquid crystal instillation). Method of 〇ne Drop Fill). On a predetermined portion of one of two substrates forming a liquid crystal alignment film, for example, an ultraviolet curable sealing material is applied, and liquid crystal is dropped on the liquid crystal alignment film. Then, another substrate is bonded to face the liquid crystal alignment film, and then ultraviolet light is irradiated on the entire surface of the substrate to harden the sealant to prepare a liquid crystal cell. In any case, preferably The liquid crystal display element of the present invention can be obtained by heating the liquid crystal cell to a temperature at which the liquid crystal is formed to an isotropic (four) temperature, and then slowly cooling to room temperature to remove the liquid crystal. Flow alignment. The polarizing plate is attached to the surface, and thus, the angle of the polarizing plate of the linear polarized radiation which is formed by the liquid crystal distribution is 27-201226445, so that the angles of the light-incident direction can be appropriately adjusted in the two substrates of the film. Each substrate is a desired liquid crystal display element. As the above-mentioned sealant, for example, an epoxy resin containing an alumina-oxidized ball as a spacer and a curing agent can be used. As the liquid crystal ', for example, a nematic liquid crystal or a smectic liquid enthalpy can be used as a material having a positive dielectric anisotropy capable of forming a nematic liquid crystal, for example, a biphenyl liquid crystal or a phenylcyclohexene. Liquid crystal, turtle liquid crystal, biphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid M, monodecane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal, and the like. Further, in the liquid crystal, a cholesteric liquid crystal such as cholestane chloride, cholesteryl phthalate or cholesteryl carbonate may be further added; under the trade names "C·15" and "CB_15" (above) A chiral agent sold by Merck Co., Ltd.; a ferroelectric liquid crystal such as a nonoxybenzylidene-p-amino-2-methylbutyl cinnamate or the like. The polarizing plate used for the outer side of the liquid crystal cell may be a polarizing plate in which a polyvinyl alcohol is stretched and aligned, and a polarizing film called a "ruthenium film" which absorbs iodine is sandwiched by a cellulose acetate protective film, or the ? film itself A polarizing plate or the like is formed. The liquid crystal display element of the present invention thus produced is excellent in various properties such as display characteristics and electrical characteristics. [Examples] The present invention is specifically described by the following examples, but the present invention is not limited by the examples. -28 ^ 201226445 &lt;Synthesis of polyglycolic acid&gt; [Synthesis Example 1] In 373.26 g of N_methyl-2-°Bilobital _ dissolved 〇.1 mol (24.82 g) of bicyclo [2.2.2 Oct-7-keto-2,3,5,6-tetracarboxylic dianhydride and oxime" (41.05 g) 2,2-bis[4-(4-aminophenoxy)phenyl]propane , react at room temperature for 6 hours. Next, the reaction mixture was mixed with a very large excess of sterol to precipitate a reaction product. Then, it was washed with decyl alcohol and dried under reduced pressure of 4 Torr for 15 hours to obtain 658 polyacetic acid octa-1 (yield 98.7%). [Synthesis Examples 2 to 3] Polyphthalic acid polymers A-2 to A-3 were obtained in the same manner as in Synthesis Example 1 except that the diamine compound was the following D-2 to D-3. [Diamine compound] Dl : 2,2-bis[4-(4-aminophenoxy)phenyl]propane D-2 : p-phenylenediamine D-3 : 4,4'-diaminodiphenyl Base ether [Comparative Synthesis Example 1] Dissolve Moer U9.61g in 343.74g N-mercapto_2_〇 洛 洛 _ _ 1, 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride and 〇 1 Mo Ear (41 〇 5 §) The above D-1 compound was reacted at room temperature for 6 hours. Next, the reaction mixture was mixed with a very large excess of sterol to precipitate a reaction product. Then, it was washed with decyl alcohol and dried under reduced pressure of 40 for 15 hours to obtain a yield of 60 g of polyamidamine a~U (98.9%). [Comparative Synthesis Examples 2 to 3] Polyphthalic acid polymers a_2 to a_3 were obtained in the same manner as in Comparative Synthesis Example 1, except that the diamine compound was the above D-2 to D-3. -29-201226445 &lt;Preparation of liquid crystal alignment agent&gt; [Example 1] N-methyl-2-pyrrolidone (NMP) was added to the solution containing polyglycine (A_1} obtained in the above Synthesis Example 1. And butyl cyanidin (BC), and then add 2 parts by mass of N, N, N, N'-tetraglycidyl-4,4, diamino 2 to 100 parts by mass of the polymer. Phenylmethane is used as an epoxy compound and stirred sufficiently to form a solution having a solvent composition of NM:p:BC = 60:40 (mass ratio)' solid content concentration of 25% by mass. The lacquer liquid is filtered with a pore size Ιμπι The liquid crystal alignment agent (Β-1) was prepared by the transition. [Examples 2 to 3, Comparative Examples 1 to 3] In Example 1, except that the polymerizations obtained in Synthesis Examples 2 to 3 and Comparative Synthesis Examples 1 to 3, respectively. In the same manner as in Example 1, a liquid crystal alignment agent B - 2 to B - 3 and b -1 to b - 3 were prepared in the same manner as in Example 1 except that yttrium ruthenate Α 2 Α Α 、 、 、 a & & & & & & & & & & & & β β Applying the above-prepared liquid crystal alignment agent (Β-1 to Β-3, b-Ι) on a transparent electrode surface having a glass substrate with a transparent electrode composed of a ruthenium film using a spin coater B-3) 'Making the film thickness to 01 μηι, at 2 〇〇. (: drying for 1 hour, forming a film. Using H g - X &lt;; lamp on the surface of the film, illuminating 8,000 J from the normal direction of the substrate /m2, 1 〇, 〇〇〇j/m2 or 5 〇, 〇〇〇j/m2 contains polarized ultraviolet light of 254 nm light. Then, a pair of substrates subjected to the above light irradiation treatment are formed in the liquid crystal alignment film. The edge of the surface retains the liquid crystal injection port, and the epoxy resin adhesive of oxidized #吕球 with a diameter of 5 5 μηι is added by screen printing, and then the substrate is pressed and pressed to make the illumination direction -30-201226445 anti-parallel, 15 (The adhesive is thermally hardened for 15 hours under rc. Then, a nematic liquid crystal (manufactured by Merck's ZLM 565) is filled between the pair of substrates by the liquid crystal injection port, and then the liquid crystal injection port is sealed with an epoxy adhesive. Further, in order to remove the flow alignment during liquid crystal injection, it is heated to 150 ° C and then slowly cooled to room temperature. Then, the polarizing plates are attached to the outer sides of the substrate so that the polarization directions thereof are perpendicular to each other, and the liquid crystal alignment film is Polarized ultraviolet light optical axis substrate The projection direction of the surface was perpendicular to one direction and parallel to the other direction to prepare a liquid crystal display element. Each of the above liquid crystal display elements was subjected to the following evaluation. The results are shown in Table 1. <Evaluation> [Liquid alignment property] In the liquid crystal display device, 'there is an abnormal region when the voltage is turned on/off (applied or released) by a polarizing microscope, and the case where there is no abnormal region is judged as "good", and even if there is one abnormal region, it is judged as "poor". [Voltage Retention Rate] A liquid crystal display element prepared by polarizing ultraviolet light irradiation at 8,0 J/m2 was applied with a voltage of 5 V for 60 msec, applied at intervals of 167 ms, and then measured for voltage retention after 167 ms from the start of release application. rate. As the measuring device, vhR-Ι manufactured by T〇Y〇 Technica Co., Ltd. was used. The case where the voltage holding ratio is 9% or more is judged as "good", and the other case is judged as "bad". -31- 201226445 1 j ______ Liquid crystal alignment agent liquid crystal alignment pressure retention ratio (%) UV irradiation amount (J/cm 〇 first line irradiation amount (J/cm2) 8,000 10,000 50,000 ____ 8,000 Example 1 Β-1__ Good and good ___ 99 Example 2 Β-2 Good Good Good _____ 99 Example 3 Good Good Good _ 99 Comparative Example 1 b-1 Poor Good Good 98 Comparative Example 2 b-2 Poor Good Good 99 Comparative Example 3 b-3 ____ ^ Poor good and good 98 As shown in Table 1, the liquid crystal alignment agent containing the polyglycine having the bicyclo[2·2·2] skeleton has high sensitivity to radiation, even at a low irradiation dose of 8000 J/m 2 In the liquid crystal display device having the obtained liquid crystal alignment film, the liquid crystal alignment property was also good, and the voltage holding ratio was also good. In the comparative example, an abnormality was observed at a low irradiation amount of 8000 J/m 2 . In the above, it is known that the liquid crystal alignment agent of the present invention has high radiation sensitivity, and can form a liquid crystal alignment film having excellent liquid crystal alignment properties under low-radiation radiation irradiation. The liquid crystal alignment agent of the present invention has high radiation sensitivity, and can form a liquid crystal alignment film having excellent properties such as liquid crystal alignment property and electrical characteristics by a low-emission photoalignment method, and has the liquid crystal alignment film. The liquid crystal display element of the present invention can reduce the amount of radiation required for light alignment by the liquid crystal alignment agent of the present invention, so that cost reduction can be achieved. [Simplified description of the drawing] No. [Description of main component symbols] None. -32-

Claims (1)

201226445 VII. Patent application scope: 1. A liquid crystal alignment agent comprising polylysine and/or polyimine having a bicyclo[2.2.2]octene skeleton. 2. The liquid crystal alignment agent of claim 1, wherein the polyamic acid has a structural unit represented by the following formula (1), and the polyimine has a structural unit represented by the following formula (2) , (In the formulae (1) and (2), R1 and R2 are each independently a divalent organic group). 3. For the liquid crystal alignment agent of claim 1 or 2, it is used for photoalignment. A method for forming a liquid crystal alignment film, comprising: (1) a step of coating a liquid crystal alignment agent according to item 3 of the patent application and forming a coating film on the substrate, and (2) irradiating the polarizing film on the coating film. The step of ultraviolet light and imparting alignment ability to the liquid crystal. -33- 201226445 5. A liquid crystal alignment film formed by a liquid crystal alignment agent as disclosed in claim 1, 2 or 3. A liquid crystal display element having a liquid crystal alignment film as in the fifth aspect of the patent application. -34- 201226445 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: