TW200922974A - Liquid crystal-aligning agent, and method for production of liquid crystal alignment film - Google Patents

Abstract

Disclosed is a liquid crystal-aligning agent comprising at least one polymer selected from the group consisting of a polyamic acid produced by reacting a tetracarboxylic acid dianhydride with a diamine compound including specific compounds typified by a compound represented by the formula (1-1), and a polyimide produced by imidizing the polyamic acid. Wherein R1 represents an alkyl group having 1 to 20 carbon atoms or an alicyclic group having 5 to 50 carbon atoms; and b represents an integer of 0 to 20. The liquid crystal-aligning agent enables to produce a liquid crystal alignment film having good aligning properties and excellent seizing properties by a photo-alignment method at a lower irradiance level.

Description

200922974 IX. EMBODIMENT OF THE INVENTION [Technical Field] The present invention relates to radiation irradiation by polarized polarization without performing rubbing alignment treatment. Even a small amount of exposure can form excellent liquid crystal alignment energy and excellent afterimage characteristics. The liquid crystal of the liquid crystal alignment film and the method for producing the liquid crystal alignment film. [Prior Art] In the prior art, a nematic crystal having a positive dielectric anisotropy is formed into a three-layer structure with a substrate having a transparent electrode having a liquid crystal alignment film, and if necessary, the long axis of the liquid crystal molecules is continuous between the substrates. A liquid crystal display element having a crystal cell such as a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, or an IPS (In Plane Switching type) which is formed by twisting a ground (Japanese Patent Publication No. 56-9 1 277) No. 1 - 1 2 0 5 2 8 bulletin). In such a liquid crystal cell, in order to make the liquid crystal molecules in a predetermined direction with respect to the substrate, a liquid crystal alignment film must be disposed on the surface of the substrate; the liquid crystal alignment film imparts liquid crystal alignment energy, usually by forming an organic film on the surface of the substrate. The surface is formed by rubbing a cloth such as a thread in one direction (friction alignment method). However, the formation of the liquid film by the rubbing alignment treatment is likely to cause dust or static electricity in the step, and the TFT (Thin Film Transistor) element is provided in addition to the adhesion of dust on the surface of the alignment film to cause display failure. The substrate may also have a broken circuit or a non-conformity to the liquid crystal of the TFT element due to the static electricity generated. When there is a problem with the crystal lattice of the base method, the 200922974 becomes a cause of the decrease in the yield, and the liquid crystal display element of the future is more refined because of the higher density of the pixels. Inevitably, irregularities are generated on the surface of the substrate, and it becomes difficult to uniformly perform the rubbing alignment treatment. As another means for aligning the liquid crystal in the liquid crystal cell, it is known to irradiate a polarizing film or a non-polarizing light to a photosensitive film such as polyethylene cinnamate, polyiminoimide or azobenzene derivative formed on the surface of the substrate. Radiation, a light alignment method that imparts alignment energy to a liquid crystal. According to this method, uniform liquid crystal alignment can be achieved without occurrence of static electricity or dust (Japanese Unexamined Patent Application Publication No. Hei No. Hei No. Hei 6-2 8 745 3, No. 1 0-25 1 646) Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In liquid crystal cells such as TN (T wisted N ematic ) type and STN (Super T wisted N ematic ) type, the liquid crystal alignment film must have a pretilt characteristic for tilting the liquid crystal molecules at a predetermined angle with respect to the substrate surface. When the liquid crystal alignment film is formed by the photo-alignment method, the pretilt angle expression is usually imparted by inclining the incident direction of the irradiated radiation toward the substrate surface from the substrate normal. On the other hand, as an operation mode of the liquid crystal display element different from the above, it is known that a liquid crystal molecule having a negative dielectric anisotropy is vertically aligned to a homeotropic alignment mode of the substrate. In this operation mode, when a voltage is applied between the substrates to tilt the liquid crystal molecules in a direction parallel to the substrate, it is necessary to tilt the liquid crystal molecules from the normal direction of the substrate toward a direction of -6-200922974 in the plane of the substrate. As such a means, for example, a method of providing a protrusion on a surface of a substrate, a method of providing a strip shape on a transparent electrode, and a method of using a rubbed alignment alignment film to tilt liquid crystal molecules from a normal direction of the substrate toward a direction inside the substrate surface are proposed ( Make it pre-tilt) method. The photoalignment method is known as a method for controlling the tilt direction of liquid crystal molecules in a liquid crystal cell in a vertical alignment mode, that is, it is known to impart alignment regulation energy and pretilt expression verticality by a photo-alignment method. The aligning film' can uniformly control the tilting direction of the liquid crystal molecules when the voltage is applied. (Japanese Laid-Open Patent Publication No. 2003-307736, JP-A-2004-163646, JP-A-2004-83810, JP-A-H09-211468, and Open 2003- 1 1 443 7 bulletin). As described above, the liquid crystal alignment film produced by the photo-alignment method can be effectively applied to various liquid crystal display elements. However, in the prior art photo-alignment film, a large amount of radiation irradiation is required in order to obtain a large pretilt angle. problem. For example, when a film containing an azobenzene derivative imparts a liquid crystal alignment energy by a photo-alignment method, in order to obtain a sufficient pretilt angle, it is necessary to irradiate an optical axis of 10,000 J/m 2 or more with oblique radiation from the substrate normal. The report (JP-A-2002-25 0924, JP-A-2004-8 3 8 1 0 and J. Of the SID 11/3, 2003, p579). However, with the development of recent pictures or the development of highly animated recording technology, users have become more and more strict with the display performance of liquid crystal display elements, and liquid crystal display elements are required to have better electrical characteristics and display characteristics. In particular, there is a strong demand for improvement in afterimage characteristics, and in the industry, it is eagerly desired to respond to the requirements related to the liquid crystal alignment film. 200922974 SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. The object of the present invention is to provide a liquid crystal alignment of a liquid crystal alignment film having excellent liquid crystal alignment energy and excellent afterimage characteristics even when the amount of exposure is small by irradiation with polarized or non-polarized radiation without performing rubbing alignment treatment. And a method of forming the liquid crystal alignment film. Further objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above objects and advantages of the present invention, the first aspect is characterized by containing a tetracarboxylic dianhydride and containing the following formula (1) R1_R2^R3_R4

CH=CH—C—S—(CH2)b—R5—(ΟΗ2)〇 =yNH2

-8- 200922974 A divalent heterocyclic group; R6 is a fluorine atom, a methyl group or a cyano group; a is an integer of 0 to 3; b is an integer of 〇~20; c is an integer of 0 to 4; d is 0. An integer of ~4. At least one polymer selected from the group consisting of a polyaminic acid obtained by reacting a diamine compound of the compound and a polyimine obtained by subjecting the polyamic acid to ruthenium iodide It is achieved by a liquid crystal alignment agent. The above object and object of the present invention are attained by a method of forming a coating film by applying the above liquid crystal alignment agent onto a substrate, and irradiating the coating film with a radiation liquid crystal alignment film. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The liquid crystal alignment agent of the present invention contains a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine compound containing the compound represented by the above formula (1), and subjecting the polyamic acid to a ruthenium At least one polymer selected from the group consisting of aminated amidines. <tetracarboxylic dianhydride> The tetracarboxylic dianhydride used in the production of the polyproline in the present invention may, for example, be 2,3,5-tricarboxycyclopentyl acetic acid dianhydride or butane tetracarboxylate. Acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-12,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3& ,4,5,91)-hexahydro,5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene 200922974 [1,2-c]-furan-1,3-dione ,l,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-8-methyl-naphtho[l,2-C] -furan-l,3-dione, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]- Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, the following formula (T-1)~(Τ_14)

(Τ-Χ) (Τ-2)

(Τ-8) (Τ-9)

(Τ-4) (Τ-5)

(Τ-10) (T-U) (Τ-12) -10- 200922974

(Τ-13) An aliphatic or alicyclic tetracarboxylic dianhydride such as tetracarboxylic dianhydride represented by each of (TU); pyromellitic dianhydride, 3,3', 4,4'· Benzene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl Ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3 ',4,4 '-tetraphenylnonane tetracarboxylic dianhydride, 1, 2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis (3,4 -Dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoro Isopropyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-double (three Phenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, double Triphenylphthalic acid) _4,4'-diphenylmethane dianhydride, the following formula (T-15)~(T-18) 200922974

The aromatic tetracarboxylic dianhydride etc., such as tetracarboxylic dianhydride shown by each. The tetracarboxylic dianhydride used in the production of polyproline in the present invention is the above 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo -3-furanyl)-naphtho[l,2-c]-furan-l,3-dione, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5 -dioxo-3-furanyl-8-methyl-naphtho[l,2-c]-furan·l,3-dione, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride Butane tetracarboxylic dianhydride ' -12- 200922974 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, l, 2, 3 4, 4' lycopene Tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3,4,4,-biphenylene, tetra-trans-acid anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2, 3,6,7-naphthalene tetraterpene - phthalic anhydride and 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and the above formula (T_1} (Τ-2) and (Τ-15) At least one selected from the group consisting of tetracarboxylic dianhydrides represented by ~(τ-18) is preferred. The diamine compound used in the synthesis of polylysine in the present invention contains the above formula. (1) The compound represented by the formula (1) is preferably a group having 1 to 20 carbon atoms or an alicyclic group having 5 to 5 carbon atoms as R1, and the alkyl group or alicyclic group. a portion of a hydrogen atom may be substituted by a fluorine atom; R1 is an alkyl group having 1 to 20 carbon atoms, a cholesteryl group or a cholesteryl group, preferably hydrogen of the alkyl group, cholesteryl group or cholesteryl group. A part of the atom may be substituted by a fluorine atom. Specific examples of R1 include, for example, η-butyl, η-pentyl, η-hexyl, η-heptyl, η-octyl, η-fluorenyl, η-癸. Base, η-lauroyl, η-twelfth base 'η- thirteen yards, η-tetradecyl, η-pentadecyl, η-hexadecyl, η-heptadecyl, η - octadecyl, η-nonadecyl, η-eicosyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 4,4, 5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluorohexyl, cholesteryl, cholesteryl, etc. As R2 and R4, each independently is a single The bond, -0-, -COO- or -Ο C 0 - is preferred. Specific examples of R3 include, for example, 1,4-phenylene, 1,3-extension-13-200922974 phenyl, 1,4 -cyclohexyl, 1,3-cyclohexyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 2,5-thiophenediyl, 2,5-furfuranyl or CH-based 1,4-naphthyl or 2,6- substituted by a nitrogen atom The naphthyl group is preferably 1,4-phenylene. As R5 when b is 0, it is preferably -COO', -CONH-**, -NHCO', -COS-* or -NHCOO-*. , -COO-* is better (only the key with "*" attached above is -(CH2). -side). R5 in the case where b is an integer of 1 to 20 is preferably -〇-, -COO- or -OCO-. A is preferably 〇 or 1. It is preferable that b is an integer of 1 to 10. c is preferably 〇, 1 or 2. The bonding position of the radical 1^-112-(尺3-民4)3- is relative to -(^ = (:11-c (= 〇;> - s - is preferably the alignment. 2 amine groups) The bonding position is preferably 2, 5-position or 3, 5-position. As a preferred example of the diamine compound of the present invention, the following formula (1-1)-(1-12) can be cited.

-14- 200922974 NH2

r1—COO -〇-c〇°- CH=CH—C—S—(CH2)b—〇CO-o (1-4) NH2 nh2 r1-

CH=CH—C—S—(CH2)b-〇—(CH2)-O (1-5) NH2 nh2 R1—COO- CH=CH—C—S—(CH2)b-〇—(CH2)co (1-6) nh2 nh2 r1_0 CH=CH—C—S—(CH2)b-〇—(CH2)co (1-7) nh2 nh2 R1-COO- CH=CH—C—S — (CH2)b -0-(CH2)c 0 (1-8) NH2 CH=CH—C—S—(CH2)b-〇—(CH2)i

NH2 NH2 (1-9) nh2

R1—COO CH=CH—C—S—(CHjb—0—(CH2)5~o (1-10) nh2 R1-0- "c〇〇^0~' CH=CH—C—S—( CH2)b-

(1-11) 200922974

R1—COO

(1-12) A compound represented by each of R1, R and c in the formula (1-1) to (i-12), which are the same as those in the above formula (1). In the above formula (1-1)-(1-12), R1' is an alkyl group having a carbon number of i-20, a cholesteryl group or a cholesteryl group, and a thiol group, a stilbene group or a cholesteryl group of Ri. A part or all of the hydrogen atom of the decyl group may be substituted by a fluorine atom. b is preferably 2 to 10, and 'c is preferably 〇, 1 or 2. In the case of producing a polyaminic acid in the present invention, the compound represented by the above formula (1) may be used as the diamine compound, or the compound represented by the above formula (1) and another diamine compound may be used. In the present invention, as the other diamine compound which can be used together with the compound represented by the above formula (1), for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodi Phenylmethane, 4,4,-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'- Dimethyl-4,4'-diaminobiphenyl, 4,4,-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino-b (4'-aminophenyl)-1,3,3-trimethyl-p- 6-amino-1-(4'-aminophenyl)-1,3,3 -trimethylindan, 3,4'-diaminodiphenyl ether, 2,2-bis(4-aminophenoxy)propane, 2,2-bis[4-(4-aminobenzene) Oxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2 ,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 14-bis(4-aminophenoxy-16-200922974) benzene, 1,3-bis(4-aminobenzene) Oxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diaminoguanidine, 9 , 9-double (4- Aminophenyl)anthracene, 4,4'-methyl-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2, 2'-Dichloro-4,4,diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4 '-(p-phenylisopropylene) phenylaniline, 4,4'-(m-phenylisopropylene)diphenylamine, 2,2-bis[4-(4-amino-2-tris) Fluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino) -2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 6-(4-arylpropenyl aralkyloxy)hexyloxy (2,4-diaminobenzene), 6-(4 '-Fluoro-4_aryl propylene oxime aryloxy) hexyloxy (2,4-amino-amine), 8-(4-aryl); (3⁄4 aryl oxy) octyloxy (2,4-diaminobenzene), 8-(4'-fluoro-4-arylpropene fluorene aryloxy) octyloxy (2,4-diaminobenzene), 1-12 Alkyloxy-2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecyloxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy Base-2,4-diaminobenzene, 1-cholesteryloxy-2,4-diaminobenzene, 1-cholestyloxy-2,4-diaminobenzene, dodecyloxy (3,5-diaminobenzimidamide), tetradecyloxy (3,5-diaminobenzimidamide), pentadecyloxy (3,5-diaminobenzimidamide) ), hexadecyloxy (3,5-diaminobenzimidamide), octadecyloxy (3,5-diaminobenzimidamide), cholesteryloxy (3,5-di) Amido benzamidine), cholesteryloxy (3,5-diaminobenzimidamide), (2,4-diaminophenoxy)palmitate, (2,4-diamino group) Phenoxy)stearate, (2,4-diaminophenoxy)-4-trifluoromethylbenzoate, the following formula (ϋ-ΐ)~(D-5) -17- 200922974

(D-D

An aromatic diamine such as a compound represented by each; an aromatic diamine having a hetero atom such as a diaminotetraphenylthiophene; m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine , pentamethyldiamine, hexamethylenediamine, heptaethylenediamine, octamethyldiamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrogen Dicyclopentadiene diamine, hexahydro-4,7-methanoindanylenedimethylenediamnine, tricyclic [6.2.1.02,7] -18- 200922974 An aliphatic or alicyclic diamine such as undecyl dimethyl diamine or 4,4′-methylene bis(cyclohexylamine); a diamine group such as diamino hexamethyldioxane Organic oxirane and the like. Preferred among these are p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 15-diaminonaphthalene, 2,7-diaminoguanidine, 4,4. '-Diaminodiphenyl ether, 4,4,-(p-phenylisopropylene)diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-Diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-eight Fluorobiphenyl, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholesteryloxy-2,4 -diaminobenzene, 1-cholestyloxy-2,4-diaminobenzene, hexadecyloxy (3,5-diaminobenzimidamide), octadecyloxy ( 3,5-diaminobenzimidamide), cholesteryloxy (3,5-diaminobenzimidamide), cholesteryloxy (3,5-diaminobenzimidamide) or the above formula The compound represented by each of (Dl) to (D-5). These may be used alone or in combination of two or more. The diamine compound to be used in the production of polylysine in the present invention contains the compound represented by the above formula (1), but the proportion of the compound represented by the above formula (1) in the total diamine compound is used. It is more preferably 30% by weight or more, and more preferably 60% by weight or more. By using the compound represented by the above formula (1) in the relevant ratio, it is possible to easily obtain a liquid crystal alignment agent which forms a liquid crystal alignment film which exhibits excellent alignment properties and more excellent afterimage characteristics by a small amount of radiation irradiation. Preferably. -19- 200922974 &lt;Synthesis of Polyproline&gt; The ratio of use of the tetracarboxylic dianhydride to the diamine compound for the synthesis reaction of polyproline is 1 equivalent to the amine group contained in the diamine compound. The acid anhydride group of the tetracarboxylic dianhydride is preferably a ratio of from 0 to 2 to 2 equivalents, more preferably from 0.3 to 1 to 2 equivalents. The synthesis reaction of poly-proline is preferably carried out in an organic solvent at a temperature of -20 to 150 ° C, more preferably 〇 1 to 1 ° C, preferably 0.5 to 24 hours, more preferably For 2 to 10 hours. Among them, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylacetamide, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylimidazolidinone, dimethyl sulfoxide An aprotic polar solvent such as γ-butyrolactone, tetramethyl urea or hexamethylphosphoric acid triamide; a phenol solvent such as m-cresol, xylenol, phenol or halogenated phenol. The amount of the organic solvent used (a: when the organic solvent is used and the weak solvent described later, it is called the total amount used), and the total amount of the tetracarboxylic dianhydride and the diamine compound (b) is relative to the reaction solution. The total amount (a + b) is preferably from 0.1 to 50% by weight, more preferably from 5 to 30% by weight. In the above organic solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon or the like which is a weak solvent of polyglycine can be used insofar as the produced polyamine does not precipitate. Specific examples of the related weak solvent include methanol, ethanol, isopropanol, cyclohexanol 'ethylene glycol, propylene glycol, 1,4-butanediol, and triethylene glycol 'ethylene glycol monomethyl ether. , ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, -20- 200922974 ethyl acetate, butyl acetate, methyl methoxy propyl Sour vinegar, ethyl ethoxy propionate, oxalic acid diethyl acetonate, diethyl malonate, ethyl ketone, ethyl alcohol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl Ether, ethylene glycol small propyl ether, ethylene glycol-η-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl acetate vinegar, diethylene glycol dimethyl ether, monoethyl _ Ethyl acid, monoethyl alcohol monomethyl ether, diethylene glycol monoethyl ether, monoethyl alcohol monomethyl acid acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, two Chloroform, 1,2-dichloroethane, 1,4 -dichlorobutyl, dichloroethane, gas, 0-chlorobenzene, hexane, heptane, octane, benzene, toluene, xylene Wait. In the production of polylysine, when a weak solvent such as the above is used in an organic solvent, the ratio of use can be appropriately set within a range in which the produced polyamine does not precipitate, preferably in a total solvent. 50% by weight or less. According to the above method, a reaction solution in which polylysine is dissolved can be obtained. The reaction solution can be directly supplied to the liquid crystal alignment agent, and the polyamine acid contained in the reaction solution can be supplied to the liquid crystal alignment after isolation. The modulation of the agent or the purification of the isolated polylysine to the liquid crystal alignment agent. For the isolation of polylysine, a precipitate may be obtained by injecting the above reaction solution into a large amount of a weak solvent, and the precipitate may be dried under reduced pressure, or the reaction solution may be distilled off under reduced pressure using an evaporator. The method is carried out. Further, the poly-proline may be purified by dissolving the polylysine in an organic solvent, followed by precipitation with a weak solvent, or by a step of distilling off under reduced pressure with an evaporator. . &lt;Polyimine&gt; -21 - 200922974 In the present invention, the polyimine can be produced by subjecting the proline structure of the polyamic acid obtained as described above to dehydration ring closure and then imidization In this case, all of the proline structure can be dehydrated by ring closure and then completely imidized, or only a part of the proline structure can be dehydrated and closed to form a proline structure and a quinone imine structure. Part of the quinone imide. The polyimine contained in the liquid crystal alignment agent of the present invention preferably has a ruthenium iodide ratio of 30% or more, more preferably 40 to 90%. a dehydration ring-closing reaction of poly-proline, for example, by (i) heating poly-proline, or (Π) dissolving poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution. It is carried out by heating if necessary. The reaction temperature in the method for heating poly-proline in the above (i) is preferably 50 to 200 ° C, more preferably 60 to 17 〇t:, and the reaction temperature is lower than 50 ° C, the dehydration ring closure reaction is not sufficiently performed. When the reaction temperature exceeds 200 ° C, the molecular weight of the obtained ruthenium-imided polymer may be lowered. The reaction time in the method of heating the polyamic acid is preferably from 0.5 to 48 hours, more preferably from 2 to 20 hours. On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the solution of the above (ii) in polylysine, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used; The amount of the dehydrating agent to be used is preferably 1 Torr to 1 Torr, relative to 1 mole of the polyamic acid structural unit. Further, as the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridoxine, trimethyl-d-butyl, dimethylpyridine or triethylamine can be used, but it is not limited thereto; the amount of the dehydration ring-closing catalyst is used. It is preferably 0 _ 0 1~1 相对 Moel relative to the dehydrating agent used. The organic solvent -22-200922974 used as a dehydration ring-closure reaction is exemplified as the organic solvent exemplified by the synthesis of polyglycine. The reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C ', more preferably from 10 to 150. (:, the reaction time is preferably from 0.5 to 20 hours, more preferably from 1 to 8 hours. The polyimine obtained in the above method (i), which can be directly supplied to the liquid crystal alignment agent, or The obtained polyimine may be purified and supplied to a liquid crystal alignment agent. On the other hand, a reaction solution containing polyimine may be obtained in the above method (Π), and the reaction solution may be directly supplied to the liquid crystal. The preparation of the alignment agent may also be prepared by removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and then supplying the liquid crystal alignment agent to the liquid crystal alignment agent, or may be supplied to the liquid crystal alignment agent after separation, or may be purified and isolated. After the polyimine is supplied to the liquid crystal alignment agent, the dehydrating agent and the dehydration ring-closing catalyst are removed from the reaction solution, and for example, a method such as solvent replacement can be applied. Separation and purification of the polyimine can be carried out by the above. The same procedure is carried out for the isolation and purification of polylysine. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention contains at least 1 selected from the group consisting of polylysine and polyimine as described above. Polymerization The liquid crystal alignment agent of the present invention may contain, if necessary, at least one polymer selected from the group consisting of polylysine and polyimine. Other components, for example, other polymers other than the above-mentioned polyaminic acid or polyimine (hereinafter referred to as "other polymerization-23-200922974"), heat-sensitive crosslinking agent, and functional group are mentioned. The above-mentioned other polymer' can be used for improving the solution property and the electrical property. Examples of the other polymer related to the above include, for example, a tetracarboxylic dianhydride and a compound not represented by the above formula (1). Polylysine obtained by the reaction of a diamine compound (hereinafter referred to as "other poly-proline"), and polyimine which is obtained by imidating the other polyamine acid (hereinafter referred to as " Other polyimine"), polyphthalate, polyester, polyamine, polyoxyalkylene, cellulose derivatives, polyacetal, polystyrene derivatives, poly(styrene-phenyl horse) Derivatives of acid Poly(methyl)propionate or the like, but other polyphthalic acid is preferred from the viewpoint of heat resistance and electrical properties. When the liquid crystal alignment agent of the present invention contains another polymer, its ratio is 'relative' a polylysine obtained by reacting a tetracarboxylic dianhydride with a diamine compound containing the compound represented by the above formula (1), and a polyimine obtained by subjecting the polyamic acid to ruthenium iodide A total of 100 parts by weight, preferably 5,000 parts by weight or less, more preferably 100 to 2,000 parts by weight, more preferably 300 to 1,000 parts by weight. The above heat-sensitive crosslinking agent can be used for stabilization of the pretilt angle and improvement of film strength. As a thermosensitive crosslinking agent, for example, a polyfunctional epoxy compound is effective 'a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a cyclic aliphatic epoxy resin, A glycidyl ester epoxy resin, a glycidyl diamine epoxy resin, a heterocyclic epoxy resin, an epoxy resin having an epoxy group, etc., and as such a commercial item, EPOLIGHT400E and the same 3002 ( Gongrongshe Chemical (stock) system, EPIKOTE 828, 152, epoxy phenol -24- 200922974 aldehyde varnish 180S (made by Nippon Epoxy Co., Ltd.). When a polyfunctional cyclic compound is used as the thermosensitive crosslinking agent, an alkali catalyst such as 1-benzyl-2-methylimidazole can be used in order to efficiently cause crosslinking. The functional decane compound can be used for the purpose of improving the adhesion to the substrate of the liquid crystal alignment film to be obtained. Examples of the functional decane article include 3-aminopropyltrimethoxydecane and 3-aminopropylethyl. Oxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyloxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxyphthalate (2_ Aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureido-dimethoxysulfate, 3-ureidopropyltriethoxylate, N-ethoxy- 3-Aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminotriethoxydecane, N-triethoxycarbenylpropyltriethylenetriaminetrimethoxycarbamidyl Propyltriethylenetriamine, 10-trimethoxymethyl-1,4,7-triazadecane, 10-triethoxycarbamido-1,4,7-heterodecane, 9- Trimethoxycarbamido-3,6-diazepine acetic acid-branched triethoxycarbamido-3,6-diazaindolyl acetate, N-benzylpropyltrimethoxydecane , N-benzyl-3-aminopropyltriethoxyethane, N-phenyl-3-aminopropyltrimethoxydecane, K-phenyl 3-aminotriethoxydecane, fluorene-bis(oxyethylidene)-3-ylaminopropyltrimethylnonane, fluorene-bis(oxyethylidene)_3-aminopropyltriethoxydecane, Examples of the oxypropyloxypropyltrimethoxydecane, the 2-(3,4-epoxycyclohexyl)ethoxymethoxydecane, and the tetracarboxylic dianhydride of JP-A-63--29 1 922 A reactant or the like with a decane compound having an amine group. As a liquid crystal alignment used in the preparation of the present invention in a solution state: oxidation of the resulting compound tris, tris, n-propylcarbonylpropyl 'N-decane, triazide, 9--3-aminoindenyl When the propoxy 3-ring-based three-post carrier is used -25-200922974, the solvent 'dissolves at least one polymer selected from the group consisting of the above poly-proline and polyimine, and any other contained therein The component is not particularly limited as long as it is an organic solvent that does not react with these. As such a solvent, for example, an organic solvent exemplified as a user of the synthesis of polyglycolic acid may be mentioned, and in this case, a weak solvent exemplified as a compound for use in the synthesis of polylysine may be used. These organic solvents may be used singly or in combination of two or more. The preferred solvent to be used for the preparation of the liquid crystal alignment agent of the present invention is one or a combination of two or more of the above organic solvents, and the components contained in the liquid crystal alignment agent are not contained in the preferred solid content concentration described below. The surface tension of the liquid crystal alignment agent is in the range of 25 to 40 mN/m. The solid content concentration of the liquid crystal alignment agent of the present invention, that is, the total weight of all components other than the solvent in the liquid crystal alignment agent, is based on the total weight of the liquid crystal alignment agent, and is selected in consideration of viscosity, volatility, etc., but is preferably selected. 1 to 1 0% by weight range. The liquid crystal alignment agent of the present invention is applied onto the surface of the substrate to form a coating film which becomes a liquid crystal alignment film. However, when the solid content concentration is less than 1% by weight, it is difficult to obtain an excellent liquid crystal alignment when the film thickness of the coating film is too small. In the case of a film, on the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film is too large, and it is difficult to obtain an excellent liquid crystal alignment film. Further, when the viscosity of the liquid crystal alignment agent is increased, there is insufficient coating property. Case. The range of the particularly preferable solid content concentration differs depending on the method used for coating the liquid crystal alignment agent on the substrate, and is particularly preferably in the range of I·5 to 4.5% by weight by the spin method; In the method, the solid content concentration is in the range of 3 to 9 wt%, whereby the viscosity of the solution is 12 to 50 mPa, and the range of s is particularly -26-200922974; when the inkjet method is used, the solid concentration is 1 The range of ~5 wt%' is particularly preferable in that the viscosity of the solution is in the range of 3 to 15 mP a · s. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 〇 ° C to 200 t: and more preferably 20 ° C to 60 ° C. &lt;Method of Forming Liquid Crystal Alignment Film&gt; The liquid crystal alignment agent of the present invention can be suitably used to form a liquid crystal alignment film. The method of forming the liquid crystal alignment film may, for example, be a method of forming a coating film of the liquid crystal alignment film of the present invention on a substrate, and then applying a radiation to the coating film to impart a liquid crystal alignment energy to the coating film. First, the liquid crystal alignment agent of the present invention is suitably coated, for example, by a roll coating method, a spin method, a printing method, an inkjet method, or the like on the side of the transparent conductive film of the substrate on which the transparent conductive film is formed. The coating method is applied, and after the application, it is preferably subjected to heating (prebaking) for the purpose of preventing liquid dripping of the applied liquid crystal alignment agent. The prebaking temperature is preferably from 30 to 2 0 〇 ° C, more preferably from 40 to 150 ° C, particularly preferably from 4 0 to 1 〇〇 ° C; and the prebaking time is preferably 0 · 1 ~1 0 minutes, more preferably 0.5 to 5 minutes. Then, a firing (post-baking) step is carried out for the purpose of completely removing the solvent or the like. Thereafter, the baking temperature is preferably 80 to 300. (:, more preferably 1 2 0 to 2 5 0 t; post-baking time ' is preferably 1 to 300 minutes, more preferably 2 to 120 minutes. The film thickness of the coating film formed here is preferably 〇. 〇〇1~1μιη' is more preferably 〇.〇〇5~〇5μηι 〇 as the substrate, for example, glass of float glass, soda lime glass, such as polyethylene terephthalate, poly pair Benzene phthalate -27- 200922974 A transparent substrate made of a plastic of a polyester, a polyether fluorene or a polycarbonate. As the transparent conductive film, a NESA film made of Sn02 is used, and the In203-Sn〇2 is used. For forming a transparent conductive film such as an ITO film or the like, a light etching method or a method of using a mask when forming a transparent conductive film can be used. When a liquid crystal alignment agent is applied, a substrate or a transparent conductive material is used. The adhesion between the film and the coating film is more excellent, and a functional decane compound, a titanate compound, or the like can be applied to the substrate and the transparent conductive film in advance. Next, the coating film is irradiated with radiation, and if necessary, 1 500. -25 0 °C temperature is preferably 1 to 1 20 minutes heat treatment, giving liquid crystal alignment energy Here, the radiation may be a linearly polarized or partially polarized radiation or a non-polarized radiation. As the type of radiation, for example, ultraviolet light and visible light having a wavelength of 150 to 800 nm may be used to contain 300 to 40. The ultraviolet light of the wavelength of 0 nm is preferably used. When the radiation to be used is linearly polarized or partially polarized, the irradiation may be performed in a direction perpendicular to the surface of the substrate, or may be performed from the oblique direction in order to impart a pretilt angle, or may be combined. When the non-polarized radiation is irradiated, the direction of the irradiation must be the direction of the slope. As the light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a heavy hydrogen lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, or a quasi-aluminum can be used. In the above-mentioned preferable wavelength region, the light source can be obtained by, for example, a filter or a diffraction grating, etc. The irradiation amount of the radiation is preferably U/m2 or more. And less than 10,000 J/m2, more preferably from 1 〇 to 3,000 J/m2. Further, the prior art known from -28 to 200922974 is formed by a liquid crystal alignment agent. When the coating film imparts liquid crystal alignment energy by the photo-alignment method, it is necessary to irradiate the radiation amount of 〇J/m2 or more. However, when the liquid crystal alignment agent of the present invention is used, the radiation irradiation amount in the photo-alignment method is less than 10,000. J/m2' is preferably 3,000 J/m2 or less, and particularly preferably Loooj/n^ or less, and even if it is 800 J/m2 or less, excellent liquid crystal alignment property can be imparted, which contributes to reduction in manufacturing cost of the liquid crystal display element. In the present invention, the "pretilt angle" is an angle at which liquid crystal molecules are inclined in a direction parallel to the substrate surface. <Method for Producing Liquid Crystal Display Element> Liquid crystal display element formed using the liquid crystal alignment agent of the present invention, for example It can be manufactured according to the following method. A pair of (two) substrates in which the liquid crystal alignment film is formed by the above-described method is prepared, and the liquid crystal alignment film which is provided is opposed to each other at a predetermined angle when the polarization direction of the irradiated linearly polarized radiation is at a predetermined angle. The peripheral portion is sealed with a sealant, injected and filled with liquid crystal, and the liquid crystal injection port is closed to constitute a liquid crystal cell. Next, it is desirable to heat the liquid crystal cell until the liquid crystal to be used is at the temperature of the isotropic phase, and then cool to room temperature to remove the flow alignment at the time of injection. Then, the polarizing plate is bonded to the alignment direction of the liquid crystal alignment film which becomes the substrate in the polarizing direction on both surfaces thereof at a predetermined angle, thereby forming a liquid crystal display element. When the liquid crystal alignment film is horizontally aligned, the angle between the polarized light direction of the linearly polarized radiation and the angle of each substrate and the polarized light -29-200922974 is adjusted by the two substrates on which the liquid crystal alignment film is formed. A liquid crystal display element having a TN type or STN type liquid crystal cell can be obtained. On the other hand, when the liquid crystal alignment film has a vertical alignment property, the substrate in which the liquid crystal alignment film is formed is formed in parallel in the direction in which the alignment is easy, and the polarizing plate is easily aligned in the polarization direction and the alignment. When it is bonded at an angle of 45°, it can be a liquid crystal display element having a vertical alignment type liquid crystal cell. As the sealant, for example, an epoxy resin containing an alumina 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 crystal can be used. When it is a TN type liquid crystal cell or an STN type liquid crystal cell, it is preferable to use a nematic liquid crystal having positive dielectric anisotropy. Biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, ditrim liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cuba LCD and so on. Further, in the liquid crystal, a cholesteric liquid crystal such as cholesterol chloride, cholesteryl phthalate or cholesteryl carbonate may be further added; a chiral molecular agent sold under the trade names of C-15 and CB-15 (manufactured by MELC) (Chiral agent); a strong dielectric liquid crystal such as p-methoxy group or p-amino-2-methylbutyl cinnamate or the like. On the other hand, in the case of a vertical alignment type liquid crystal cell, a nematic liquid crystal having a negative dielectric anisotropy is preferable, and for example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, a Schiff base type liquid crystal, or an oxidation can be used. An azo-based liquid crystal, a biphenyl-based liquid crystal, a phenylcyclohexane-based liquid crystal, or the like. The polarizing plate used for the outer side of the liquid crystal cell is a polarizing plate which is a polarizing film called a "ruthenium film" which is obtained by absorbing a iodine while extending a cellulose acetate protective film while absorbing iodine. A polarizing plate made of the enamel film itself. [Embodiment] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to the Examples. &lt;Synthesis of the compound represented by the above formula (1)&gt; Example 1 According to the following scheme 1 - 31 - 200922974 Scheme 1 COOCH3 cf3c3h6i I K2C〇3

Na0H/H20 CF3C3H6-〇——COOH (1-3-1-1) 2

SOCI ΗΟΗ0~

CH=CH-COOH K2C03 (1-3-1-2) Dicyclohexylcarbodiimide N,N-Dimethylaminopyridine Ο

Cf3c3h6-o coo ~Qr CH=CH-COOH

HS-C3H6-CI

CF3C3Hg~〇~^》~COO~^ CH=CH-C-S~C3Hg-CI (1-3-1-3) -32- 200922974 Flow 1 (continued) — _ Ο CF3〇3H6&quot;〇&lt;y Coo-^~^-ch=ch-cs-c3h6

Cl (1-3-1-3)

Nal N02 HOOC-^) NO, K2C03 O , N02 CF 3C3H6··〇 o coo CH=:CH—C—S—CsHg-OCO-“jj (1-3-1-4)

NO 2

SnCI2.2H20

O NH2

Cf3c3h6-o coo ~Qr ch=ch-c-s-c3h6-oco -Q

NH 2 \ , synthesis of compound (1-3-1). [Synthesis of Compound (1 - 3 -1 -1)] In a 1 L Japanese eggplant type flask, 82.2 g of methyl 4-hydroxybenzoate, 165.9 g of potassium carbonate, and hydrazine, hydrazine-dimethylacetamide were charged. After 400 mL of the mixture was stirred at room temperature for 1 hour, 1-iodo-4,4,4-trifluorobutane 95. lg ' was added and stirred for 5 hours to carry out a reaction. After the completion of the reaction, the precipitate obtained by reprecipitation with water was added to 32 g of sodium hydroxide and 400 mL of water, and the mixture was refluxed for 3 hours to carry out a hydrolysis reaction. After the reaction was completed, the mixture was neutralized with hydrochloric acid to form a precipitate. The precipitate was recrystallized from ethanol to obtain 80.4 g of a white crystal of compound (1-3-1 -1). [Synthesis of Compound (1-3-1-2)] In a 30 mL mL Japanese eggplant type flask, 46.4 g of the compound (l-3-ll) obtained above was used, and sulfurous chloride was added thereto. 150 mL and N,N-dimethylformamide 〇 2 m L were reacted at 80 Torr for 1 hour. After the completion of the reaction, the thionyl chloride was distilled off under reduced pressure, and the residue was extracted with methyl chloride. After extraction, the organic layer was washed with aqueous sodium hydrogencarbonate and dried over magnesium sulfate. After concentration, tetrahydrofuran was added. 〇m L. On the other hand, in a 500-mL three-necked flask, hydroxycinnamic acid 36-lg, potassium carbonate 55.2 g, tetrabutylammonium bromide (2.41 g), tetrahydrofuran 200 mL, and water 400 mL were placed, and the aqueous solution was ice-cold, and the above-mentioned was slowly dropped. The tetrahydrofuran solution of the reaction product of the compound (1-3-1-1) and thionyl chloride was further stirred for 2 hours to carry out a reaction. After the completion of the reaction, the mixture was neutralized with hydrochloric acid, and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, and then concentrated, and then recrystallized from ethanol to obtain 38.5 g of a white crystal of compound (u-u). [Synthesis of Compound (1 - 3 -1 - 3 )]

In a 1 L Japanese type flask, '30 g of the compound (l-3-l-2) obtained above, N,N-dimethylaminopyridinium.92 g, dichloromethane 3 50 mL -34- 200922974 And 10 g of 3-chloropropanethiol, which was ice-cooled and then added to a pre-prepared dichloromethane solution containing 16.09 g of dicyclohexylcarbodiimide in dichloromethane, for 1 hour in an ice bath, and then stirred at room temperature. The reaction was carried out for 3 hours. After completion of the reaction, the insoluble material was filtered, and the filtrate was washed with aqueous sodium hydrogen carbonate solution, and then washed with water three times, dried over magnesium sulfate, concentrated, and recrystallized from ethanol to obtain 25.5 g of compound (1-3) -1-3). [Synthesis of Compound (1-3-1-4)] In a Japanese-style flask of 500 mL, the above-obtained compound (l-3-l-3) 22.02 g, sodium iodide 34.0 was charged. g and methyl ethyl ketone 14 OmL were refluxed under nitrogen for 6 hours to carry out a reaction. After completion of the reaction, the mixture was extracted with EtOAc. EtOAc was evaporated. Next, 14.0 g of potassium carbonate, 9.76 g of 3,5-dinitrobenzoic acid, and 140 mL of 1-methyl-2-pyrrolidone were added to the above-mentioned dry solid, and the reaction was carried out by stirring 5 hours under nitrogen for 5 hours. After the completion of the reaction, the mixture was extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogencarbonate and dried over magnesium sulfate, and then the solid obtained by concentration under reduced pressure was recrystallized from ethanol to give 21 g of compound ( 1-3-1-4) [Synthesis of Compound (Bu3-1)] In a 200 mL three-necked flask equipped with a thermometer, 20.15 g of a compound (1-3-1-4) and tin chloride 2 hydrate were added. The reaction was carried out by stirring 67.7 g of ethanol and 150 mL of ethanol at 70 ° C for 1 hour. After the reaction was completed, add -35-200922974 to neutralize with an aqueous solution of sodium hydrogencarbonate, and add flurtzite and ethyl acetate to filter the brucite. Next, the filtrate was purified by column chromatography and recrystallized from ethanol to obtain 3.1 g of the compound (1 - 3 -1). &lt;Polyuric acid and polyimine Synthesis> Example 2 (Synthesis of Polylysine) 2,3,5-Tricarboxycyclopentylacetic acid dianhydride 〇68 g and the above Example 1 1.82 g of the obtained compound (l-3-l) was dissolved in 7.5 g of N-methyl-2-pyrrolidone, and allowed to react at room temperature for 6 hours. Then, a large amount of the reaction mixture was excessively injected into methanol to cause a reaction. The resultant precipitated, and then washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to give 2.3 g of polylysine (PA-1). Example 3 (Synthesis of Polyimine) 1 g of the polylysine (PA-1) obtained above was added thereto, and 9.0 g of N-methyl-2-pyrrolidone, 0.19 g of pyridine and 0.25 g of acetic anhydride were added thereto to obtain 1 2 0. The dehydration ring-closing reaction was carried out for 4 hours. Then, the reaction mixture was poured into a large amount of excess methanol to precipitate the reaction product. The precipitate was washed with methanol and dried by decompression for 15 hours. 9 g of polyimine (PI -1) 'The polyamidimide (PI -1) has a ruthenium iodide ratio of 51%. &lt;Synthesis of other polymers&gt; Synthesis Example 1 (Other polyfluorene) Synthesis of aminic acid) -36- 200922974 Cyclobutane tetracarboxylic dianhydride 19.6 lg (0.1 mol) and 4,4,-diamino-2,2'-monomethylbiphenyl 21_23 g (〇. l旲耳)' Dissolved in 367.6 g of N-methylpyrrolidone and allowed to react at room temperature for 6 hours. Then, a large amount of the reverse eagle mixture was excessively injected into methanol to precipitate the reaction product, and the precipitate was washed with methanol, by The i 5 Xiaori Temple was dried at 40 t under reduced pressure to obtain 35 g of other polylysine (pa-Ι). Synthesis Example 2 (Synthesis of Other Polylysine) 2,3,5-Tricarboxycyclopentane 22.4 g of acetal dianhydride (〇.i Mo) and the following formula (n) ch3 synthesized according to JP-A-2003-52〇878

2 nh2 C4H9—0 \_ch=ch-coo--c6h12-〇co (d-1) Compound 4 8.4 6 g (ο 1 mol) is dissolved in N _methyl-2 _pyrrolidone 2 8 3.4 g, it was allowed to react at room temperature for 6 hours. Next, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product, and the precipitate was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain 67 g of other polyamine. Acid (pa_2). &lt;Preparation of Liquid Crystal Aligning Agent&gt; Example 4 -37-200922974 Into 100 parts by weight of the polylysine (PA·1) obtained in the above Example 2, the other polyfluorene obtained in the above Synthesis Example 1 was added. 400 parts by weight of aminic acid (pa-1), dissolved in N-methyl-2-pyrrolidone and butyl cellosolve, and the solvent composition is N-methyl-2-pyrrolidone: butyl cellosolve = 5 0 · 5 〇 ( Weight ratio), a solution having a solid concentration of 3.0% 'filtered by using a filter having a pore size of 1 μm' to prepare a liquid crystal alignment agent 1 ° Example 5 Polyimine obtained in the above Example 3 ( ρ I -1) 1 part by weight of the other polyglycine (pa - 1 ) obtained by the above Synthesis Example 1 was added in an amount of 400 parts by weight, and N-methyl-2-pyrrolidone and butyl cellosolve were added thereto. Dissolved, the solvent composition is N-methyl-2-pyrrolidone: butyl cellosolve = 5 0: 50 (weight ratio), which becomes a solution with a solid concentration of 3.0% 'by using this solution with a pore size of 1 μ m The filter is filtered to modulate the liquid crystal alignment agent 2. Comparative Example 1 After dissolving N-methyl-2-pyrrolidone and butyl cellosolve in the other polylysine (P a -2) obtained in the above Synthesis Example 2, the solvent composition was N_methyl-2. Pyrrolidone: butyl cellosolve = 50:50 (weight ratio), a solution having a solid concentration of 3.0%, and the liquid crystal alignment agent 3 was prepared by filtering the solution with a filter having a pore size of 1 μm. Example 6 &lt;Production of Vertical Alignment Type Liquid Crystal Display Element&gt; -38 - 200922974 The liquid crystal alignment agent 1 prepared above was applied to a glass substrate having a transparent electrode formed of an ITO film using a spin coater. The surface of the transparent electrode was prebaked on a hot plate at 80 ° C for 1 minute, and then baked at 180 ° C for 1 hour to form a coating film having a film thickness of 0.1 μm. On the surface, using a Hg-Xe lamp and a Glan Taylor prism, the polarized ultraviolet ray i, 〇〇〇j/m2 of the bright line containing 313ηηα is irradiated in a direction inclined by 40° from the substrate normal line to impart liquid crystal alignment energy. A liquid crystal alignment film is formed. The same operation as above was repeated to prepare one pair (two sheets) of a glass substrate having a liquid crystal alignment film on the surface of the transparent conductive film. In the peripheral portion of the pair of substrates on which the liquid crystal alignment film is formed, an epoxy resin adhesive containing an oxidized spheroidal ball having a diameter of 5·5 μm is applied by screen printing, and then reversed in the direction of polarized ultraviolet light irradiation. The substrate was pressed in parallel and pressed, and heated at 150 ° C for 1 hour to thermally cure the adhesive. Then, the liquid crystal injection port was injected into the gap of the substrate to charge the nematic liquid crystal (manufactured by MELC Corporation, MLC-660 8). After that, the liquid crystal injection port is closed with an epoxy-based adhesive and 'in order to remove the flow alignment during liquid crystal injection, it is heated at 15 ° C for 1 minute, then slowly cooled to room temperature, and then, on the substrate. On both sides of the outer side, the polarizing plates are orthogonal to each other in the direction of polarization, and are 45 in the direction of polarization of the ultraviolet rays irradiated to the liquid crystal alignment film. Lamination is performed at the angle of 'making a vertical alignment type liquid crystal display element. The evaluation of the liquid crystal display element was carried out as follows. The results are shown in Table-39-200922974. [Evaluation of liquid crystal alignment property&gt; The liquid crystal display element manufactured as described above was turned ON at a voltage of 5 V (additional release) When there is an abnormal region in the change of brightness and darkness, it is observed by an optical microscope that 'there is no abnormal region. &lt;Evaluation of Pretilt Angle&gt; Regarding the liquid crystal display element manufactured as described above, according to Ding···

Scheffer et. al. J. Appl. Phys. vol. 19, p20 1 3 (1 980), the pretilt angle is measured by a crystal rotation method using He-Ne laser light, and the pretilt angle is 89.5 to 85°. When the liquid crystal display element manufactured above was applied with a voltage of 60 microseconds and a span of 167 milliseconds, a voltage of 5 V was applied, and the measurement was released from the external application. The voltage holding ratio after the 167 milliseconds was measured using "VHR-1" manufactured by TOYO Corporation, and the voltage holding ratio was 90% or more. &lt;Avatar image&gt; In the liquid crystal display device manufactured as described above, a rectangular wave of 30 Hz '5 V with a DC of 5 V was applied at an ambient temperature of 60 ° C for 2 hours, and the liquid crystal cell remaining after the DC power was cut off. The voltage (residual DC voltage) is obtained by the scintillation erasing method. The residual DC voltage is less than 100 mV, and the residual image is "good", and the residual image "bad" is defined as 1 〇〇mV or more. -40-200922974 Example 7 and Comparative Example 2 In the above-described Example 6, 'the vertical alignment type liquid crystal display element was produced and evaluated in the same manner as in Example 6 except that the liquid crystal alignment agent was used as the liquid crystal alignment agent. 'Results are shown in Table 1. Table 1 Liquid crystal alignment agent name Evaluation result of liquid crystal display element Liquid crystal alignment pretilt voltage retention rate afterimage Example 6 Liquid crystal alignment agent 1 Good good example 7 Liquid crystal alignment agent 2 Good good good example 2 Liquid crystal alignment agent 3 Liangliangliang Defects It is clear from the above examples that the liquid crystal alignment agent of the present invention can form excellent liquid crystal alignment energy and excellent pretilt characteristics and excellent afterimage by a light alignment method with a small amount of light exposure. The liquid crystal alignment film of the characteristics can provide a liquid crystal display element which exhibits excellent liquid crystal alignment and high display characteristics. Advantageous Effects of Invention The liquid crystal alignment agent of the present invention can provide a liquid crystal alignment film by a photo-alignment method. Compared with a liquid crystal alignment agent known in the prior art, the display can be formed by a photo-alignment method with a small amount of radiation exposure. A liquid crystal alignment film excellent in alignment performance and excellent afterimage characteristics. Therefore, when this liquid crystal alignment film is applied to a liquid crystal display element, a liquid crystal display element which exhibits superior performance and electrical characteristics superior to the prior art can be manufactured at a lower cost than the prior art. -41 - 200922974 A liquid crystal display element comprising a liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention can be effectively applied to various devices, and can be suitably applied to, for example, a desktop computer, a watch, a clock, a counting display panel, and a word processing. Devices such as personal computers and LCD TVs.

Claims (1)

200922974 X. Patent application scope ί. A liquid crystal alignment agent characterized by containing tetracarboxylic dianhydride and containing the following formula (1) CH=CH—C—S—(CH2)b—R°—(CH2)c =yNH2 in nh2 (1 (in the formula (1), R1 is a substituent having a carbon number of 1 to 20 or an alicyclic group having a carbon number of 5 to 50, a part of the hydrogen atom of the alkyl or alicyclic group or All may be substituted by a fluorine atom, a cyano group or an aryl group; R2, R4 and R5 are each independently a single bond, -0-, -S-, -coo-, -OCO-, -CONH-, -NHCO-, ί -COS-, -SCO-, -O-CO-O-, -NH-C00- or -O-CO-NH-; R3 is a divalent aromatic group having a carbon number of 6 to 20, and a carbon number of 5 to 30 a divalent alicyclic group; a divalent group having a condensed ring having 6 to 30 carbon atoms; or a divalent heterocyclic group having 5 to 30 valence; R6 being a fluorine atom, a methyl group or a cyano group; An integer of 0 to 3; b is an integer of 0 to 20; c is an integer of 0 to 4; d is an integer of 0 to 4) Polyamine obtained by reacting a diamine compound of the compound represented and a polymer of at least one selected from the group consisting of polyamidiamines obtained by hydrazylation of a polyamine. The liquid crystal alignment agent of the first aspect of the invention, wherein the aforementioned tetracarboxylic acid The anhydride is composed of 1,3,3&amp;,4,5,91)-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]- Furan-1,3-diketone, l, 3, 3a, 4, 5, 9b- A hydrogen-5-(tetrahydro-2,5-dioxo-3-furanyl)-8-methyl-naphtho[l,2-c]-furan-1,3-dione, 2,3 ,5-tricarboxycyclopentyl acetic acid dianhydride, butane tetracarboxylic acid-43- 200922974 dianhydride, 1,3-dimethyl-12,3,4-anthracene tetracarboxylic dianhydride, 1,2 , 3,4-cyclobutane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-biphenylfluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalene At least one selected from the group consisting of carboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride. 3. The liquid crystal alignment agent according to the first aspect of the invention, wherein the ratio of use of the diamine compound represented by the above formula (1) is 30% by weight or more based on the total diamine compound. A method for forming a liquid crystal alignment film, which is characterized in that the liquid crystal alignment agent of any one of the first to third aspects of the invention is applied to form a coating film, and the coating film is irradiated with radiation. 5. The method for forming a liquid crystal alignment film according to item 4 of the patent application scope, wherein the irradiation amount of the radiation is lJ/m2 or more and less than l〇, 〇〇〇j/m2 〇6. It is formed by the liquid crystal alignment agent of any one of Claims 1 to 3. 7 · A liquid crystal display element characterized by a liquid crystal alignment film of 6 patents. 8 - a polyphthalic acid obtained by reacting a tetracarboxylic dianhydride with a diamine compound represented by the above formula (1) or a polyimine obtained by subjecting the polyamic acid to ruthenium iodide . 9. A diamine compound represented by the above formula (1). -44 - 200922974 VII. Designation of Representative Representatives (1) The representative representative of this case is: No (2). The symbol of the representative figure of this representative figure is simple: No. 8. If there is a chemical formula in this case, please reveal the best display. Chemical formula of the inventive feature: none