TW200911884A - Liquid crystal aligning agent, liquid crystal alignment film, method for producing the same, and liquid crystal display device - Google Patents

Abstract

Disclosed is a liquid crystal aligning agent containing at least one polymer (A) selected from the group consisting of polyamic acids and polyimides, and a compound (B) having a photosensitive group which is crosslinked or isomerized by light having a wavelength of 200-400 nm and an epoxy group. The liquid crystal aligning agent is used for forming a liquid crystal alignment film which is capable of aligning liquid crystals through irradiation of polarized or unpolarized radiation without performing a rubbing process.

Description

200911884 IX. Description of the Invention [Technical Field] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a method for forming the same, and a liquid crystal display element. More specifically, it relates to a liquid crystal alignment agent which can be used to form a liquid crystal alignment film which imparts a liquid to a liquid which is not subjected to rubbing treatment by irradiation of polarized light or non-polarized light, and forms a liquid crystal alignment agent from the liquid crystal alignment agent. It is accompanied by a method of producing a liquid crystal alignment film which generates dust or static electricity, and a liquid crystal display which exhibits excellent quality. [Prior Art] In the past, a positive dielectric anisotropic nematic liquid crystal system has a substrate sandwich structure in which a transparent electrode having a liquid crystal alignment film is added, and if necessary, the long axis of the liquid crystal molecules is between the substrates. A liquid crystal display element having a liquid crystal cell such as a TN (torsional nematic) type, an STN (super twisted nematic) type, or an IP (in-plane switching) type is known to be formed by continuously twisting at 0 degrees (refer to Japanese Patent Laid-Open No. 56). -9 1 277 and JP-A-10-1 20528). In these liquid crystal cells, in order to align the liquid crystal in a certain direction with respect to the substrate surface, it is necessary to provide a liquid crystal alignment film on the surface of the substrate. The liquid crystal alignment film is usually formed by a method (rubbing method) of reciprocating rubbing of the surface of the organic film formed on the surface of the substrate in a certain direction with a cloth such as a crucible. However, when the liquid crystal alignment film is formed by the rubbing treatment, dust is generated in the process and static electricity is generated. Therefore, dust adheres to the surface of the alignment film, which causes a display failure. In particular, in the case of a substrate having a TFT (Thin Film Transistor) device, the circuit of the TFT element 200911884 is damaged due to the generated static electricity, which is also a cause of a decrease in yield. Further, in the liquid crystal display device which is gradually higher in precision, unevenness is generated on the surface of the substrate in order to increase the density of the pixel, so that it is difficult to perform uniform rubbing treatment, and other methods for aligning the liquid crystal in the liquid crystal cell are used. It is known that a polarizing film or a non-polarizing radiation which is formed of a polyethylene laurate, a polyimide, an azobenzene derivative or the like formed on a surface of a substrate is irradiated with a polarized or non-polarized radiation. Orientation method. According to this method, static electricity or dust does not occur, and a uniform liquid crystal alignment can be achieved (refer to Japanese Laid-Open Patent Publication No. Hei 6-2-8 7453, Japanese Patent Application Laid-Open No. Hei No. Hei. No. Hei. Japanese Unexamined Patent Publication No. Publication No. JP-A No. 2000- 144 136, JP-A-2000-319510, JP-A-2000-28 1 724, JP-A-9-2973, No. 3, No. 2003-307736 Japanese Laid-Open Patent Publication No. 2004-163646 and JP-A-2002-25 0924. However, in a liquid crystal cell such as a TN (torsional nematic) type or an STN (super twisted nematic) type, it is necessary for the liquid crystal alignment film to have a pretilt characteristic in which liquid crystal molecules are obliquely aligned 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 is usually imparted by inclining the incident radiation from the substrate normal to the incident direction of the substrate surface. Further, as an operation mode different from the above-described liquid crystal display, a vertical (homeotropic) alignment mode VA (which is a vertical alignment of liquid crystal molecules having a negative dielectric anisotropy with a substrate) is also known. Vertical alignment type liquid crystal cell. This operation mode applies a voltage between the substrates. When the liquid crystal molecules are tilted in a direction parallel to the substrate, it is necessary to tilt the liquid crystal molecules from the normal direction of the substrate toward one of the substrate faces. As for the method for this, there are proposed, for example, a method of providing a protrusion on a surface of a substrate, a method of providing a stripe on a transparent electrode, and tilting a liquid crystal molecule from a normal direction of the substrate toward a direction in the plane of the substrate by using a rubbing alignment film ( The method of making the pretilt). It is also known that the above-described photoalignment method is also useful as a method of controlling the tilt direction of liquid crystal molecules in a liquid crystal cell of a vertical alignment mode. In other words, it is known that the tilting direction of liquid crystal molecules when a voltage is applied can be uniformly controlled by using a vertical alignment film which imparts an alignment control force and a pretilt angle by a photo-alignment method (refer to Japanese Patent Laid-Open Publication No. 2003-3 0773 No. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Thus, the liquid crystal alignment film produced by the above-described photoalignment method is effective for various liquid crystal display elements. However, in the past, the light alignment film had to be irradiated with a large amount of radiation if it had to obtain a large pretilt angle, for example, it has been reported in a light alignment film containing an azobenzene derivative, in order to obtain a sufficient pretilt angle. Irradiation of 1 〇, 〇00 J/m2 or more of its optical axis tilted from the substrate normal (see JP-A-2002-25 0924, JP-A-2004-83810, and J_ of the SID 11/3, 2003) , p.579). SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and its object is to provide a liquid crystal alignment film which can be used to form a liquid crystal alignment energy by irradiating a polarized or non-polarized -6-200911884 radiation without performing a rubbing treatment. Liquid crystal alignment agent. Another object of the present invention is to provide a method of forming a liquid crystal alignment film which is not accompanied by generation of dust or static electricity from the liquid crystal alignment agent. Still another object of the present invention is to provide a liquid crystal alignment film excellent in liquid crystal alignment and a liquid crystal display element excellent in display quality. Still other objects and advantages of the present invention will become apparent from the following description. According to the present invention, the above objects and advantages of the present invention are first achieved by the following liquid crystal alignment agent: (A) a polymer selected from at least one group consisting of polyacrylic acid and polyamidiamine And (B) a compound having a photosensitive group and an epoxy group which are subjected to a crosslinking reaction or an isomerization reaction by light having a wavelength of from 200 to 400 nm. The above objects and advantages of the present invention are achieved by a liquid crystal alignment film formed from the above liquid crystal alignment agent, and the third system is formed by applying a coating film on the substrate to form a coating film to polarize the coating film. Or a method of forming a liquid crystal alignment film in the step of non-polarizing radiation. Further, the above objects and advantages of the present invention are attained by the liquid crystal display element including the above liquid crystal alignment film. [Embodiment] Hereinafter, the present invention will be described in detail. The liquid crystal alignment agent of the present invention contains (A) at least one polymer selected from the group consisting of polylysine and polyimine. 200911884 <(A) Polymer> The above polylysine can be synthesized by reacting a tetracarboxylic dianhydride with a diamine. The above polyimine can be synthesized by dehydrating a poly-proline. [Tetracarboxylic dianhydride] The tetracarboxylic dianhydride used in the synthesis of the above polyamic acid can be exemplified by, for example, butyl tetracarboxylic dianhydride; 1,2,3,4-cyclobutanetetracarboxylic acid Anhydride, 12-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, hydrazine, 3 dimethylcyclobutylene tetraphthalic acid dianhydride, 1,3 -dichloro-: , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1.2.3.4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-ring Pentane tetracarboxylic dianhydride, 1,2,4,5·cyclohexane tetracarboxylic dianhydride, 3,3,4,4,-dicyclohexyltetracarboxylic dianhydride, 2,3,5- Tricarboxycyclopentyl acetic acid dianhydride '2.3.4.5- Tetrahydrofuran tetracarboxylic dianhydride, 1,3,3^4,5,91)_hexahydro-5-(tetrahydro^^-dioxo-furan Rhodium-naphtho-(i-)-furan-^-dione, l,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo -3-furanyl)-naphtho[l,2-c]-purine-1,3-dioxin, l,3,3a,4,5,9b-hexaamine-5-ethyl-5-( Tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro- 7-Methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, l,3,3a, 4,5,9b- Hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-yanoyl)-naphtho[l,2-c]-furan-l,3-dione, l, 3,3a,4,5,9b-hexahydro-8-methyl·5-(tetrahydro-2.5-dioxo-3-furanyl)-naphtho[1,2-(:]-furan-1 ,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1] ,2-〇]-furan-1,3-dione '1,3,3&,4,5,913-hexahydro-5,8-a-8- 200911884 methyl-5-(tetrahydro-2, 5-dioxo-3-furanyl)-naphtho[1,24]-furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene-2,3,5,6- Tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2,5,-dione), 5- (2) ,5-dioxotetrahydro-3-furan)-3 -methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethyl borneol Alkane-2: 3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.02,6]undecane-3,5,8,10-tetraone, the following formula (TI) and (T-II) an aliphatic or alicyclic tetracarboxylic dianhydride such as a compound,

〇 R4 R4 〇

A^r3—VA (In the formulae (TI) and (T-II), R1 and R3 are each a divalent organic group having an aromatic ring, and R2 and R4 are each a hydrogen atom or an alkyl group, and plural R2 and R4 are present. Can be the same or different); pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid Anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride , 3,3',4,4'-dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3, 4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxylic acid phenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyl 200911884 Phenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropene Diphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) Phenylphosphine oxide dianhydride, p-phenylene bis(triphenylphthalic acid) dianhydride, meta-phenylene bis(triphenylbenzene) Formic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, B Glycol-bis(anhydrous benzene trimellitate), propylene glycol-bis(anhydrous benzene trimellitate), 1,4-butanediol-bis(anhydrous benzene trimellitate), :1,6-hexane Alcohol-bis(anhydrous benzene trimellitate), 1,8 octanediol-bis(anhydrous benzene trimellitate), 2,2-bis(4-hydroxyphenyl)propane-bis(anhydrous benzotricarboxylic acid) Ester), an aromatic tetracarboxylic dianhydride of a compound such as the following formula (T-1) to (T-4): 0

COO

-10- 200911884

-11 - 200911884

These tetracarboxylic dianhydrides may be used alone or in combination of two or more. The benzene ring of the aromatic tetracarboxylic dianhydride may also be substituted by one or more alkyl groups having 1 to 4 carbon atoms (preferably methyl groups). The above-mentioned four-residual acid dianhydride used in the synthesis of the polyamic acid exhibits good liquid crystal alignment. The above preferably comprises a compound selected from the group consisting of tetrabutyl phthalic acid dianhydride, 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, hydrazine, 3· dimethyl _ 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, hydrazine, 2,3,4-cyclopentanyltetradecanoic acid Dihydride, 2,3,5-trimethylcyclopentyl acetic acid dianhydride, 1,3,33,4,5,913-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl )_Naphtho[1,2-(:]-furan-1,3-dione, 1,3,3&,4,5,91>-hexahydro-8-methyl-5-(tetrahydro- 2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5, 8-Dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2^]-furan-1,3-dione, bicyclo[2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran · 2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride , 3,5,6-tricarboxy-2-carboxymethyl-formane-2: -12- 200911884 3,5:6-dianhydride, 4,9-dioxatricyclo[5.3 .1.02'6]undecane-3,5,8,10-tetraketone, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ',4,4'-biphenylfluorene tetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride The compound represented by the following formula (T-5) to (T-7) in the compound represented by the above formula (T-1): Ο 〇

(T-7) and a compound represented by the following formula (8) in the compound represented by the following formula (T-II):

At least one of them (hereinafter referred to as "specific tetracarboxylic dianhydride"). The preferred tetracarboxylic dianhydride is exemplified by at least one selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxy-13 - 200911884 Cyclopentyl acetic acid dianhydride, l,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2-3-pyranyl)-naphtho[1,2-c]-furan -1,3-diketone, 1,3,3a hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene c]-furan-1,3 -dione, 3-oxabicyclo[3.2.1]octane-2,4-dif 3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetra Hydroxy)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 3,5,6-tricarboxymethylnorbornane-2 : 3,5 : 6 -dianhydride, 4,9-dioxy[5.3.1.0''6]undecane-3,5,8,10-tetraone, pyromellitic dianhydride; a compound represented by g(T-5). The tetracarboxylic dianhydride used in the synthesis of the polyamic acid, the tetracarboxylic dianhydride preferably contains 20 mol% or more of the above tetracarboxylic dianhydride, and more preferably 50 mol% or more. And contain 80% of the person. The diamine used in the synthesis of the above polyamic acid can be exemplified by p-p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl 4,4'-diaminodiphenyl. Ethane, 4,4'-diaminodiphenyl sulfide diaminodiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, aminobenzamide , 4,4'-diaminodiphenyl ether, 1,5-diamine 2,2 '-dimethyl-4,4 '-diaminobiphenyl, 5-amino-1 - ( 4 ' -amine)-1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl)trimethylindan, 3,4'-diaminodiphenyl ether , 3,3'-diamino ketone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 5-dioxo, 4,5,9b-[ 1,2-wide 6-spiro--3-furancarboxyl-2-heterotricyclic. The above formula: for the whole description, it is preferably a column, etc.: methane, 4, 4, -4, 4, _ diyl Naphthalene, phenyl-1,3,3-diphenyl 2,2-bis-14- 200911884 [4-(4-Aminophenoxy)phenyl]propane, 2,2-bis[4-( 4-aminophenyl)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, bis[4-(4-aminophenoxy)phenyl]indole, I 4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis(4-aminophenoxy)benzene, 1, 3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diaminopurine, 9,9-dimethyl- 2,7-Diaminopurine, 9,9-bis(4-aminophenyl)anthracene, bis(4•amino-2-chlorophenyl)methane, 2,2',5,5'-four Chloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy -4,4'-diaminobiphenyl, 4,4'-(p-phenylene diisopropylidene)diphenylamine, 4,4'-(m-phenylene diisopropylidene) double Aniline, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-3,3'-bis ( Trifluoromethyl)biphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl) Aromatic diamines such as phenoxy]-octafluorobiphenyl, compounds represented by the following formula (Dl) ~ (D-5):

-15- 200911884 ch3 ,ch3

Nh2

(D-5) (wherein y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5); 1, 1 - p-xylylenediamine, 1, 3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethyl-16-200911884 bisamine, jiapaya Diamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentanedienediamine, hexahydro-4,7-methyl bridge Diamine, tricyclo[6.2.1.02'7]-exedecyldimethyldiamine, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl) An aliphatic or alicyclic diamine such as cyclohexane, l,4-bis(aminomethyl)cyclohexane; 2,3-diaminopyridine, 2,6-diaminopyridine, 3, 4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopiperidine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)piperidine, 2,4-diamino-6- Isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl- 1,3,5-three Pyrazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl- S-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethylurea, 3,5-di Amino-1,2,4-triazole, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperidine, 3,6-diaminoacridine, N,N '-Bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-di Amino oxazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, anthracene, Ν'-bis(4-aminobenzene a compound represented by the following formula (D-1): -N,N'-dimethyl-benzidine:

(In the formula (D-1), R5 is a monovalent organic group selected from the group consisting of ruthenium, sulfonate, triple exposure, piperidine and piperazine having a nitrogen atom-containing ring structure, and X1 represents 2-17-200911884 The valence organic group, R6 is an alkyl group having 1 to 4 carbon atoms, and al is 0 to 3, and the compound represented by the following formula (D-II) has two groups and a nitrogen other than the primary amine group. Amine diamine: number), ~-amine (R8) a2

(R8)a2

(D-II) (In the formula (D-II), R7 is a divalent organic group having a ring structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, anthracene and piperazine, and χ is a divalent organic group, and the plural is present X 1 1 may be the same or different alkyl groups having a carbon number of 1 to 4, and a2 is an integer of 0 to 3, respectively; and the compound of the following formula (D-III) is monosubstituted (R11) a3 OR9 —R10 (D-III) L nh2 (in the formula (D-III), r9 is -〇-, -COO-, -OCO-, -CONH- or -CO-, and R1Q has a structure selected from steroids, three a valence of a skeleton or a base of a phenyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group, or an alkyl group having a carbon number of 6 to 30, and R1 1 is an alkyl group having 1 to 4 carbon atoms, an integer of 0 to 3) The diamine group of the compound represented by the following formula (Dl IV ), piperidinium 1 respectively, R8 minute #diamine-NHCO-fluoromethylorgano group a3 is a gas oxime-18- 200911884 alkane: R12 R12 H2N -fCH2^Si—(-〇-Si^-CH3^NH2 R12 R12 (D-IV) (In the formula (D-IV), R12 is a hydrocarbon group having a carbon number i~12, and the plural R12 may be the same or Different, p is an integer of 1 to 3, and q is an integer of 1 to 2 0. The diamines may be used alone or in combination. The above-mentioned aromatic diamine benzene ring may be substituted by one or two or more alkyl groups having 1 to 4 carbon atoms (preferably methyl groups). The above formulas (DI), (D-II) and In the case of D-ΠΙ), R6, R8 and R1 1 are each preferably a methyl group, and al, a2 and a3 are preferably 〇 or 1 ' and more preferably 0. The above formula (D-ΙΠ) is r1() The steroid skeleton is a skeleton composed of a cyclopentane polyhydrophenanthrene nucleus or one or two or more carbon-carbon bonds thereof, which is a double bond. The R1 () one-valent organic group having such a steroid skeleton is preferably carbon. The number is from 17 to 51, more preferably from 17 to 29 carbon atoms. Specific examples of R1() having a steroid skeleton can be exemplified by, for example, cholestane-3-yl, cholest-5-ene-3, and biliary甾-2 4 ene-3-yl, cholest-5,2 4 -dien-3-yl, wool broth-3, and the like. The diamine used to synthesize the above polyamic acid is preferably included Select at least one of the following groups (hereinafter referred to as "specific diamines"): in the above-mentioned p-phenylenediamine, 4,4'-diaminodiphenylcarbamate, 4, 4, -diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl--19- 200911884 4,4'-Diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,7-diaminopurine, 4,4'- Diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-double [4-(4-Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene diiso) Propyl)benzidine, 4,4'-(m-phenylenediisopropylidene)benzidine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis (4- Aminophenoxy)biphenyl, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamino), 1,3-bis(aminomethyl)cyclohexane a compound represented by the above formula (D-1) to (D-5), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6- Diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole ,Ν,Ν'-bis(4-aminophenyl)-benzidine, anthracene, Ν'-bis(4-aminophenyl)-indole, Ν'-dimethylbenzidine, above formula (D- 1 ) The compound represented by the following formula diagram (D-6) Compound:

A compound represented by the following formula (D-7) in the compound represented by the above formula (D-II):

(D-7) -20- 200911884 Dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene in the compound represented by the above formula (D-III) , cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-aminobenzene, fifteen courtyard oxygen Base-2,5--•amine basic, hexamethyleneoxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, respectively, of the following formula (D-8)~ Compound represented by (D -1 5 ):

H2n— nh2

-21 - 200911884

And at least one selected from the group consisting of 1,3-bis(3-aminopropyl)-tetramethyldioxane in the compound represented by the above formula (D-IV) (hereinafter, referred to as "specific two Amine" is preferred. The diamine used for the synthesis of the above polyamic acid preferably contains 20 mol% or more of the specific diamine as described above, and more preferably 50% or more of the -22-200911884. It is best to contain more than 80% by mole. <Synthesis of Polylysine> The polyglycolic acid in the liquid crystal alignment agent of the present invention can be obtained by reacting a tetracarboxylic dianhydride as described above with a diamine. The ratio of the tetracarboxylic dianhydride to the diamine used in the polyamine acid synthesis reaction is preferably from 0.2 to 2 equivalents based on the amine group of one equivalent of the diamine. More preferably, it is a ratio of 0.8 to 1.2 equivalents. The synthesis reaction of poly-proline is preferably carried out in an organic solvent 'and preferably at -2 0 ° C to 150 ° C, more preferably at a temperature of 0 to 1 ° C, preferably 0. 1~2 4 hours, better 0.5~1 2 hours. The organic solvent is not particularly limited as long as the synthetic polyaminic acid can be dissolved. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N, Aprotic polar solvent such as N-dimethylformamide, dimethyl hydrazine, γ-butyrolactone, tetramethyl urea, hexamethylphosphoric acid triamide; m-cresol, dimethylhydrazine, hydrazine A phenolic solvent such as a halogenated phenol. The amount (a) of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is from 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution. Further, when the organic solvent is used in combination with a weak solvent to be described later, the amount (a) of the above organic solvent can be understood to mean the total amount of the organic solvent and the weak solvent. The organic solvent may be an alcohol, a ketone, a vinegar, an ether, a halogenated hydrocarbon, a hydrocarbon or the like which has a polyacetic acid as a weak solvent in a range in which the produced polyaminic acid is not precipitated. Specific examples of the weak solvent include, for example, methanol, ethanol 'isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 〗 〖, 4-butanediol, triethyl-23-200911884 diol, ethylene glycol monomethyl Ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, Ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl Ether 'ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol single Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane Alkane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, isoamylpropionate, isoammine Isobutyrate, diisoamyl ether . When the organic solvent and the weak solvent are used, the ratio of the weak solvent to be used may be appropriately set within a range in which the polyamic acid is not precipitated, but it is preferably 50% by weight or less, more preferably 4 0, based on the total amount of the solvent. It is below weight%, and is preferably 30% by weight or less. As described above, a reaction solution in which polylysine is dissolved can be obtained. The reaction solution can be used for preparing a liquid crystal alignment agent, and can also be used for preparing a liquid crystal alignment agent after the polyamic acid contained in the reaction solution is separated, or the isolated polyamic acid can be purified. Modulation of liquid crystal alignment agent. The separation of the polyamic acid can be carried out by injecting a large amount of the above reaction solution into a weak solvent to obtain a precipitate, drying the precipitate under reduced pressure, or distilling off the reaction solution under reduced pressure in an evaporator. In addition, the poly-proline can be re-dissolved in an organic solvent, followed by precipitation in a weak solvent, or by the step of -24-200911884 one or several times of evaporation of the evaporator under reduced pressure. Purification of proline. <Polyimine> The polyimine in the liquid crystal alignment agent of the present invention can be obtained by subjecting the polylysine as described above to dehydration ring closure and hydrazine imidization. The polyimine contained in the liquid crystal alignment agent of the present invention may be a fully ruthenium imide formed by dehydration ring closure of the proline structure of the raw material polyphthalic acid, or may be only a proline One part of the structure is dehydrated and closed to form a partial yttrium imide of the proline structure and the quinone ring structure. The polyimine in the liquid crystal alignment agent of the present invention preferably has a ruthenium iodide ratio of 30% or more, more preferably 50% or more, and most preferably 80% or more. The sulfhydrylation ratio is the ratio of the number of decanoic acid structures to the total number of quinone imine ring structures, and the proportion of the quinone imine ring structure expressed as a percentage. A part of it may also be an isoindole ring. Such a ruthenium imidization rate can be known from the 'h-nmr of polyimine. The dehydration ring of polylysine is preferably (i) a method of heating polylysine or (Π) by dissolving polylysine in an organic solvent, adding a dehydrating agent and dehydrating ring in the solution. Catalyst, and depending on the method of heating. The reaction temperature in the above method (i) for heating the polyglycolic acid is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. When the reaction temperature is less than 50 °C, it is difficult to sufficiently carry out the dehydration ring-closure reaction, and the reaction temperature exceeds 2 °C to lower the molecular weight of the obtained ruthenium iodide polymer. The reaction time is preferably from 1 to 0 to 2 4 to 25 to 200911884 hours, more preferably from 1.0 to 12 hours. On the other hand, in the above method of adding a dehydrating agent and a dehydration ring-closing catalyst to the polyaminic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent, depending on the desired imidization ratio, is 1 mol per mol of the glycine acid of the polyglycolic acid, preferably 0.01 to 20 mol. Further, as the dehydration ring-closing catalyst, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 1 mol with respect to the dehydrating agent used for 1 mol. The dehydration rate may be higher as the amount of the above dehydrating agent and dehydration ring-clogging agent is used. The organic solvent used in the dehydration ring-closure reaction can be exemplified by an organic solvent exemplified for use in the synthesis of polylysine. The reaction temperature of the dehydration ring closure reaction is preferably from 〇1 to 18 ° C, more preferably from 10 to 150 ° C. The reaction time is preferably from 1 to 11 to 12 hours, more preferably from 2.0 to 30 hours. The polyimine obtained in the above method (i) may be prepared by the liquid crystal alignment agent, or may be obtained by subjecting the obtained polyimine to a liquid crystal alignment agent. On the other hand, a reaction solution containing polyimine can be obtained in the above method (i i ). The reaction solution can be prepared for the preparation of the liquid crystal alignment agent, or can be prepared by the liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, or can be used for liquid crystal after being separated from the polyimide. Modulation of the alignment agent' or the preparation of the liquid crystal alignment agent after purification of the isolated polyimine. The dehydrating agent and the dehydration ring-closing catalyst are removed from the reaction solution, and a method such as solvent replacement can be suitably used. The separation and purification of the polyimine can be carried out by performing the same operation as the separation and purification method of the above polyamic acid to carry out the -26-200911884-end modified type polymer - which is contained in the liquid crystal alignment agent of the present invention. The polyaminic acid or polyimine may also be a molecularly modified terminal modified polymer, respectively. By using the terminal modified polymer ', the coating characteristics and the like of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention. These terminal modified polymers can be carried out by adding a molecular weight modifier to the polymerization reaction system in the synthesis of polyamic acid. The molecular weight modifier may, for example, be an acid 1, a monoamine compound, a monoisocyanate compound or the like. The above acid anhydride may, for example, be, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride or the like. The above monoamine compound can be exemplified by, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, and positive ten Monoalkylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-eighteen Alkylamine, n-icosylamine, and the like. The above monoisocyanate compound may, for example, be phenyl isocyanate, naphthyl isocyanate or the like. The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyamic acid. -Solid viscosity - -27- 200911884 The poly-proline and polyimine obtained as described above preferably have a solution viscosity of 2 〇 to 800 mPa · s, respectively, as a solution having a concentration of 10% by weight, respectively. It has a solution viscosity of 30 to 500 mPa.s. The solution viscosity (mPa*s) of the above polymer is a polymerization of a concentration of 10% by weight prepared by using a good solvent of the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). The solution was measured at 25 ° t using a Ε-type rotary viscometer. <(B) Compound> The compound (B) contained in the liquid crystal alignment agent of the present invention is a compound having a photosensitive group and an epoxy group which can generate a crosslinking reaction or an isomerization reaction by light having a wavelength of 200 to 400 nm. . The compound (B) is not particularly limited as long as it has the above properties. For example, the compound may be a compound having the following groups: an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, and a cyclohexyl group having An alkylcyclohexyl or alkylphenyl group having an alkyl group having 1 to 20 carbon atoms, a fluorine-based cyclohexyl group having a carbon number of 1 to 20 or a phenyl group, or a hospital having a carbon number of 4 to 20 a oxy group, a fluoroalkyloxy group having 1 to 20 carbon atoms, a cyclohexyloxy group, an alkyloxycyclohexyl group having an alkyloxy group having 1 to 20 carbon atoms or an alkyloxyphenyl group having carbon a fluoroalkylcyclohexyl group or a fluoroalkyloxyphenyl group of a fluoroalkyl group having 1 to 20 or a group having a carbon number of 17 to 51 having a steroid skeleton and an epoxy group, and a group represented by the following formula (1) ° -28- 200911884

y—CH=CH—CO— (1) The compound (B) is preferably a compound represented by the following formula (1-1): (AW)—X—(Ep)n (1-1) (Formula (1-) In 1), A is a group represented by any one of the following formulas (Al) to (A-8), and W is a group represented by any one of the following formulas (W-1) to (W-4), and X is the following formula; A tetravalent group represented by any one of (X-1) to (X-5), Ep is a group represented by the following formula (Ep-1) or (Ep-2), m is an integer of 1 to 3, and η is 4 -m ):

(In the formula (A-1), R1 is independently an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, and an alkyl group having an alkyl group having 1 to 20 carbon atoms. a hexyl or a phenyl group, a gas-based cyclohexyl group or a fluoroalkyloxyphenyl group having a carbon number of 1 to 20, or a carbon number of 17 to 5 1 having a steroid skeleton, X1 being a single a bond, an oxygen atom, a sulfur atom, -COO-, -NHCO-, -C0NH- or -CO-, X2 is a single bond or a formula of any of the following formulae (X2-l)~(X2-3):

C00— (X2-1) -29 - 200911884

OrΟ- (Χ2-2) (Χ2-3) (In the above formula, "*" indicates the side of the bonding key X1 attached thereto). X3 is a single bond, *-〇-(CH2)a-, *-0-(CH2)a-C0-, *-(CH2)a-OCO-(CH2)a-, or a base represented by the following formula:

Cyo (where a is an integer of 1 to 6 independently, "*" means that the key with the key is located at -CH = C Η - C Ο - side), but the adjacent two keys are single bonds When these can be together as a single button),

R1—X4—X5—CO—CH=CH (A-2) (In the formula (A-2), R1 has the same meaning as R1 in the above formula (Al). X4 is a single bond, an oxygen atom, a sulfur atom, -C〇〇_, -OCO-, -NHCO-, -CONH- or -CO-, X5 is a single bond or a phenyl group, and X6 is a single bond or a formula represented by the following formula (X6-;!):

•OCO

(X6-1) -30- 200911884 (in the formula (X6-l), "*" indicates that the key with the key is located on the X7 side), X7 is a single bond, *-〇CO-(CH2)a-, *-OCO-(CH2)a-CO- or the base represented by the following formula (X7-l): (X7-1)

*-OCO (in the above, a is an integer from 1 to 6, and "*" indicates that the key with the key is located on the X6 side)). However, when two adjacent keys are single keys, these may be together. Become a single button),

R1—OCO—CH=CH

—CH=CH—CO— (A-3) (In the formula (A-3), R1 has the same meaning as R1 in the above formula (A-1)),

-31 - 200911884

(In the formulae (A-4) to (A-6), R1 has the same meaning as R1 in the above formula (A-1), and X8 is a single bond, an oxygen atom, a sulfur atom, or -COO-, respectively.

(In the formulae (A-7) and (A-8), R1 has the same meaning as R1 in the above formula (A-1), and X9 is a single bond or *-(CH2)a-COO- (where a An integer of 1 to 6, "*" indicates that the key with the key is located on the -CO- side),

OH —Ο—CH2-CH——CH2——* (W-1) ———Ο HO——CH2-CH—CH2——* (W2) -32- 200911884

HO

(W-3)

O

HO

CH2— * (W-4) (In the above formula, “*” means that the key with the key is on the X side).

-33 - 200911884

(In the above formula, γ horse single bond, -Ο-, -S-, -CH2-, -C(CH3)2- or the formula represented by the following formula (y-1):

R is an alkyl group having 1 to 6 carbon atoms which may be substituted by a fluorine atom, or a fluorine atom 'b is an integer of 0 to 4),

In the above formulas (A-ι) to (A-8), the substituents such as the 〇-〇 bond are not allowed to be combined. The groups of carbons 4 to 20 of R1 in the above formulas (A-1) to (A-8) can be exemplified by, for example, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, and positive ten. A fluoroalkyl group having 1 to 20 carbon atoms such as a dialkyl group, a n-hexadecyl group, an n-octadecyl group or a n-icosyl group can be exemplified by, for example, a trifluoromethyl group, a perfluoroethyl group, and 3,3. , 3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4-5,5,5-pentafluoropentyl, 4,4-5,5-6,6,6-hexafluorohexyl, etc.; 34- 200911884 An alkylcyclohexyl group having a carbon number of 1 to 20 alkyl groups may be exemplified by, for example, 4-methylcyclohexyl group, 4-n-butylcyclohexyl group, 4-n-pentylcyclohexyl group, 4-n-hexylcyclohexyl group. And the alkylphenyl group having a carbon number of 1 to 20 alkyl groups may be exemplified by, for example, 4-n-butylcyclohexyl group, 4-n-pentylphenyl group, etc.; fluorocarbon having a carbon number of 1 to 2-fluoroalkyl group; The cyclohexyl group can be exemplified by, for example, 4-trifluoromethylcyclohexyl group; and the fluoroalkylphenyl group having a carbon number of 1 to 2 fluorinated fluoroalkyl group can be exemplified by, for example, 4-trifluoromethylphenyl group or the like. The steroid skeleton in R1 is a skeleton composed of a cyclopentane polyhydrophenanthrene nucleus or a skeleton in which one or two or more carbon-carbon bonds are double bonds. The one-valent organic group of R1 having such a steroid skeleton is preferably a carbon number of 17 to 29. Specific examples of R1 having a steroid skeleton can be exemplified by, for example, cholestane-3-yl, cholest-5-en-3-yl, cholestyl-2-en-3-yl, cholestyl-5,24-di Alk-3-yl, lanostan-3-yl and the like. The two nitrogen atoms in the above formula (X-1) are respectively located in the meta or para position. ♦ The two nitrogen atoms in the above formula (X-2) are respectively located at the 4, 4'-position; The two nitrogen atoms in X-3) are located at the L3-position or the 1,4-position, respectively; the two N-substituted methylene groups in the above formula (X-4) are respectively at the I, the position or the 1 , wherein the two N-substituted methylene groups in the above formula (X-5) are preferably located in the meta or para position. ~ 35 - 200911884 The compound (B) as described above can be obtained by, for example, Χ·(Ερ)4 (wherein X and Ερ have the same meanings as described in the above formula (1-1)) and the compound Α-ΟΗ ( Among them, a mixture of a lanthanide series and the same meaning as described in the above formula (1-1) is preferably synthesized by heating in a suitable organic solvent in the presence of a desired catalyst. Specific examples of the compound X-(Ep) 4 can be exemplified as follows: If the group X is the above formula (X-1), for example, the following formula (X-1-1) and (X-1-) can be exemplified. 2) a compound or the like which is represented by the above formula; wherein, if the group X is the above formula (X-2), it is, for example, a compound represented by the following formulas (XH) to (X-2-6); (X-3) is, for example, a compound represented by the following formulas (χ_3_ι) and (Χ-3-2); and if the base X is the above formula (Χ-4), it is, for example, the following formula (χ-n) And a compound represented by the following formula (X-5), and a compound represented by the following formula (X-5-2).

(Χ-2-1) (Χ-2-2) -36- 200911884

(Χ-4-2)

Examples of the compound A-OH can be exemplified as follows: those represented by the above formula (A-1) are, for example, represented by the following formulas (A-1-1) to (A-1-30) -37- 200911884, respectively. The compound represented by the above formula (A-2) is, for example, a compound represented by the following formulas (A-2-1) to (A-2-15); and the base A is represented by the above formula (A-3). For example, the compounds represented by the following formulas (A-3 - 1) to (A-3-42), respectively, wherein the base A is represented by the above formula (A - 4 ) are, for example, the following formula (A - 4- 1 ) to The compound represented by (A-4-3); the base A is a compound represented by the following formula (A-5-1), and the base A is represented by the above formula (A-6). For example, the compound represented by the following formula (A-6-1); the base A is a compound represented by the following formula (A-7), for example, represented by the following formula (A-7-1); the base A is the above formula (A- 8) The compounds represented by the following formulas (A-8-1) and (A-8-2), respectively. -38- 200911884

CH=CH—COOH

Coo CH=CH—COOH (A-1-3)

Coo <y CH=CH—COOH (A-1-4)

R^OO—CQ〇-^~^—CH=CH-COOH (A-1-5)

CH=CH-COOH

Ri〇^G^°-^y CH=CH—COOH (A-1-7) (A-1-6)

R^OO—CH=CH-COOH (A-1-8) R^OO—CH=CH—COOH (A-1-9)

R1—CH=CH—COO-(CH2)a-QH (A-1-10) -39- 200911884

CH=CH—COO-(CH2)a-OH (A-1-11)

R^OO-^^—CH=CH—COO—(CH2)a-〇H

R1—^~y~CH=CH—COO-(CH2)a-COOH (A-1-13)

R

CH=CH—COO—(CH2)a—COOH (A-1-14)

RiCOO

COO-(CH2)a-COOH (A-1-15)

Rl-〇-COO-^~~^>—CH=CH—COO-(CH2)a-OH COQ-^~^—CH=CH—COQ-(CH2)a-QH

R!COO COO-^^—CH=CH-C00-(CH2)a-0H

*~Qr COO-^~^—CH=CH—COO-(CH2)a-COOH (A-1-19) COO-^~^—CH=CH—COO-(CH2)a-COOH (A-1 -20) -40- 200911884

R^OO—COO--^~~^—CH=CH—COQ-(CH2)a-COOH (A-1-22)

rIO^ COO-^~~^—CH=CH-C0-CH2-0C0(CH2)a~0H

rI〇hQ- COO-^~^—CH=CH-C0-CH2-0C0(CH2)a-0H (A-1-23)

R^OO—COO-(^~^)—CH=CH-C0-CH2-0C0(CH2)a-0H (A-1-24) rI-0Ό*

CH=CH-C〇-(CH2)a-〇H (A-1-25)

R^COO-^"^-CH=CH-CO-(CH2)a-OH (A-1-26)

Coo J〇T CH=CH—COOH (A-1-27) )_〇- CH=CH—C0-<\ />-COOH (A-1-28)

CH=CH—CO COOH (A-1-29)

R^OQ—^~~^~CH=CH—CO—COOH (A-1-30) -41 - 200911884

R!0C0—CH=CH OH (A-2-1)

R1C〇-CH=CH

Bu OH (A-2-2)

R!0C0-CH=CH-"OCO classification H (A-2-3) F^CO—CH=CH -o- oco O~oh ‘ (A-2-4)

RI0C0-CH=CH OCO <y OCO - (CH2)a-OH (A-2-5)

R1OC〇-CH=CH—OCO—(CH2)a-COOH (A-2-6)

RIC〇-CH=CH—OCO O~ OCO-(CH2)a—OH (A-2-7)

RICO-CH=CH—OCO J〇T OCO - (CH2)a-COOH (A-2-8)

CO-CH=CH OH (A-2-9) rI〇^0~ CO-CH=CH -^\)r OH (A-2-10) CO_CH=CH <y (A-2-11) OC 〇-(CH2)a-〇H (A-2-12) -42- 200911884

C〇-CH=CH

COOH (A-2-13)

C〇-CH=CH~(\ /)—COOH (A-2-14)

COOH (A-2-15) -43 200911884

CgHn-O-C Ο

C-OH u Ο (A-3-1) 〇 6 latch 12 〇 -?

(A-3-2)

CgH-j/-〇_C II ο

C-OH II Ο (A-3-3) C1〇H2i-O-Co

C-OH II O (A-3-4) 6

C-OH u O (A-3-5)

〇16Η33 one 〇_C

(A-3-6)

Ci8H37_〇—C

(A-3-7) cf3—o-c

(A-3-8) CF3(CH2)2_〇_Co

C-OH IIo (A-3-9) C2F5-o~c ^ 3 II o

C-OH II 0 (A-3-10) C2F5-O-C 〇

C-OH II 〇 (A-3-11) -44 - 200911884

O F 〇 (A-3-15) (A- 3-12) (A each 13) (A.3-14) (A-3-16) C16H33 - 〇_c 6

(A-3-17)

(A-3-18) C18H37_〇~C o

(A-3-19) CF3(CH2)2-〇-C o

(A-3-20)

(A-3-21)

(A-3-22) 45- 200911884 CHF2CF2CH2 - 〇-ρ

Ο C-OH 11 Ο (Α-3-23)

C-OH Η Ο (Α-3-24)

CsFi7-〇-C Ο

(Α-3-25) C5H”—y~ ceHi3—o-c II Ο O-C II ο

C-OH n Ο (A-3-26) C-OH II Ο (A-3-27) CF3

(A-3-28) C5H11

(A-3-29) cf3

(A-3-30)

(A-3-31)

(A-3-32) -46- 200911884 CHF2CF2CH2-0-Brother~"

(Α-3-33)

CsFi7-011 C

(A-3-34)

(A-3-35) C5H”

(A-3-36)

CeHi3—^-0-0

(A-3-37) cf3 KD-°-

(A-3-38)

CsH^-^jKO-C

(A-3-39) CF3

(A-3-40)

47- 200911884 ο

CH=CH—COOH (A-4-1) ο

CH=CH—COOH (A-4-2)

R!-S

CH=CH—COOH O (A-4-3)

Rl-OCO

CH=CH-COOH (A-5-1)

Rl~0

CH=CH—COOH O (A-6-1)

O HOCO

CH=CH—COOR O (A-7-1) -48- 200911884

(In the above formula, R1 has the same meaning as R1 in the above formula (Al), and a and X3 in the above formula (A-1), X7 in the formula (A-2), or the formula (A-). 8) The meaning of a in the definition of X9 is the same). In the above formulas (A-3-1) to (A-3-42), the double bonds on both sides of the benzene ring are respectively described in trans form, but it should be understood that both are cis-form and single The trans form and the other is a compound of the cis form. Among these, (A-1-1), (Al-2), (A-1-3), (A-1 -4), (Al-27), (A-3-1)~ (A-3-7), (A- 3-12)~(A-3-18), (A-3-26) ~ (A-3-29), (A-3- 36)~(A The compounds represented by -3-39) and (A-4-1) are preferred from the viewpoints of productivity and liquid crystal alignment and UV absorbability of the formed liquid crystal alignment film. The compound A-OH as described above can be synthesized by appropriately combining the laws of organic chemistry. For example, the compound represented by the above formula (A-1 - 1 ) can be obtained by heating a reaction between malonic acid and benzaldehyde having an alkyl group corresponding to R1 in the presence of a suitable base such as piperazine. The compound represented by the above formula (A-1 - 2 ) can be obtained by heating, for example, a hydroxy laurel-49 - 200911884 citric acid and a halogenated alkyl group having an alkyl group corresponding to R1 in the presence of a suitable base such as potassium carbonate. It is obtained by hydrolysis of an alkaline aqueous solution containing a suitable base such as sodium hydroxide. The compound represented by the above formula (A-1 - 3 ) can be obtained by, for example, benzoic acid derivative having an alkyl group corresponding to R1 in the presence of ruthenium chloride in sulfinium chloride, in the presence of a suitable base such as potassium carbonate. It is obtained by reacting with hydroxycinnamic acid at o °c to room temperature. The compound represented by the above formula (A-1 - 4 ) can be obtained by, for example, using a methyl or hydroxybenzoate with a halogenated alkyl group having an alkyl group corresponding to Ri or an alkyl group of p-toluene in the presence of a suitable base such as potassium carbonate. After the reaction is carried out at a temperature of from room temperature to 100 ° C, it is hydrolyzed with an aqueous alkaline solution containing a suitable base such as sodium hydroxide, and then converted to ruthenium chloride with sulfinium chloride, in the presence of a suitable base such as potassium carbonate. It is obtained by reacting with hydroxycinnamic acid at a temperature of from °C to room temperature. The compound represented by the above formula (A-1 - 27) can be formed by, for example, forming potassium chloride with a 4-alkylcyclohexylcarboxylic acid having an alkyl group corresponding to R1 by using sulfinium chloride. It is obtained by reacting with hydroxycinnamic acid at a temperature of from 〇 ° C to room temperature in the presence of a base. The compound represented by the above formula (A-2-1) can be subjected to a coupling reaction using a palladium catalyst by, for example, phenol iodide and an alkyl acrylate having an alkyl group corresponding to R1 (this reaction is generally referred to as "Heck" reaction). And get. The compound represented by the above formula (A-2-6) can be obtained by adding a compound represented by the above formula (A-2-l) to a compound represented by the following formula: -50- 200911884

(in the above formula, 'a has the same meaning as described in the above formula (A-2-6)). The compounds represented by the above formulas (A-3-1) to (A-3_42) can be respectively obtained by using, for example, 4-bromocinnamic acid or 4-bromo cinnabarin chloride with an alcohol, a phenol or an alkyl halide having a desired group. After the group, the halogenated aryl group or the alkylamine is reacted to form 4-bromocinnamate, it is synthesized by adding acrylic acid thereto by a Heck reaction. The compound represented by the above formula (A - 4 -1 ) can be refluxed in acetic acid by, for example, an acid anhydride derivative having a desired R1 group and 4-amino cinnamic acid, or in toluene or xylene, in sulfuric acid, three It is synthesized by refluxing in the presence of an appropriate catalyst such as ethylamine. The compound represented by the above formula (A-4-2) can be obtained by, for example, an alkyl iodide or a brominated alkyl group having a desired R1 group and a methyl or ethyl ester of malic acid in the presence of a suitable catalyst such as silver oxide. After the reaction is carried out, the ether is hydrolyzed by a base, and the acid anhydride is dehydrated and closed to form an acid anhydride derivative having R1 - 〇-, which is used as a raw material by the same method as the synthesis of the compound represented by the above formula (A_4-1). synthesis. The compound represented by the above formula (A-4-3) can hydrolyze the maleimide by, for example, a Michael Addition having a desired R1 group on the maleimide. Subsequently, it is synthesized by the same method as the synthesis of the compound represented by the above formula (A-4) by using a dehydration ring closure. The compound represented by the above formula (A-5-1) is obtained by, for example, using sulfite-51 - 200911884 chlorine to form a hydrogen addition product of a partial diacid to ruthenium chloride, and an alcohol having a desired rI group. 'Reacted into an ester in the presence of a suitable appropriate base such as triethylamine' and synthesized as a raw material in the same manner as the synthesis of the compound represented by the above formula (A-4-1). The compound represented by the above formula (A - 6 -1 ) is obtained by subjecting, for example, hydroxyphthalic anhydride to dehydration and ring closure, and refluxing it with 4-aminocinnamic acid in acetic acid' or in toluene or xylene, in sulfuric acid The quinone imine compound is synthesized by refluxing in the presence of a suitable catalyst such as triethylamine, and then reacted with a halide having an alkyl group corresponding to R1 in the presence of a base such as potassium carbonate. The compound represented by the above formula (A - 7 - 1 ) is, for example, obtained by reacting 4-nitrocin cinnamic acid with an alkyl halide having a desired R1 group in the presence of a suitable base such as potassium carbonate to form an ester. After the tin is reduced and the nitro group is converted into an amine group to obtain an intermediate, the intermediate is refluxed with acetic acid in cyclohexane tricarboxylic acid anhydride, or in toluene or xylene, in a suitable contact with triethylamine or the like. The medium is synthesized by refluxing. The compound represented by the above formula (A-8-1) can be substituted with cyclohexanetricarboxylic anhydride by using trimellitic anhydride in the synthesis of the compound represented by the above formula (A-7-1) to be as in the above formula (A). The synthesis of the compound represented by -7-1) was synthesized in the same manner. The compound represented by the above formula (A - 8 - 2 ) is obtained by, for example, reacting 4-nitrocin cinnamic acid with an alkyl halide having a desired R1 group in the presence of a suitable base such as potassium carbonate to form an ester. After the tin is reduced and the nitro group is converted into an amine group to obtain an intermediate, the intermediate is refluxed with hydroxy phthalic anhydride in acetic acid, or in toluene or xylene, in triethylamine or the like -52 - 200911884 The catalyst is refluxed in the presence of a catalyst, and then the product is added to the product to form an acid anhydride. When the compound X-(Ep)4 is reacted with the compound A-OH, it is preferably used in an amount of 1 to 3 moles, more preferably 1 to 2 moles, per mole of the compound X-(EP) 4' compound A_0H. The organic solvent which can be used when the compound Χ-(Ερ)4 is reacted with the compound A-OH can be preferably an aprotic organic solvent. For the convenience of preparation of the liquid crystal alignment agent, a specific example thereof is preferably exemplified, for example. Ν_Methyl-2-pyrrolidone, γ-butyrolactone, hydrazine, hydrazine dimethyl dimethyl acetamide, hydrazine, hydrazine dimethyl carbamide, dimethyl hydrazine, tetramethyl urea And hexamethylphosphoric acid triamide or the like 'but an organic solvent similar to the organic solvent used as a solvent for the liquid crystal alignment agent can also be used. When a mixed solvent is used as the organic solvent of the liquid crystal alignment agent, one of the organic solvents constituting the mixed solvent is preferably selected as the organic solvent. The ratio of use of the organic solvent is preferably such that the solid content concentration (the ratio of the total weight of the compound Χ-(Ερ) 4 to the compound Α-ΟΗ to the reaction solution) is 1% by weight or more, and the ruthenium is more preferably The ratio of 5 to 50% by weight. The catalyst which can be used for the reaction of the compound Χ-(Ερ)4 with the compound Α-ΟΗ is exemplified by a base, and specific examples thereof include imidazole and tetrabutylammonium bromide. The use ratio of the catalyst is preferably 20 parts by weight or less, more preferably 5 parts by weight or less, per 100 parts by weight of Χ-(Ερ)4. The reaction temperature is preferably from 20 to 250 ° C, more preferably from 50 to 180 ° C. The reaction time is preferably from 1 to 24 hours, more preferably from 1 to 6 hours. -53- 200911884 The compound represented by the above formula (1 -1 ) thus obtained may be used as a single compound alone or in combination of the types A, D, X and Ep in the above formula (1-1) and m. Two or more compounds different from one or more of η. The use ratio of the (Β) compound in the liquid crystal alignment agent of the present invention is preferably from 1 to 200 parts by weight, more preferably from 5 to 100 parts by weight, per 1 part by weight of the (?) polymer. <Other components> The liquid crystal alignment agent of the present invention may contain, as an essential component, the above-mentioned (A) polymer and (B) compound, but may contain other components as needed. These other components may, for example, be a thermosensitive crosslinking agent or a functional decane compound. The heat-sensitive crosslinking agent is contained in the liquid crystal alignment agent of the present invention in order to further improve the stability of the pretilt angle of the liquid crystal alignment film to be formed and the film strength. The heat-sensitive crosslinking agent may, for example, have one molecule. A compound of two or more epoxy groups (except for the compound (B), which is hereinafter referred to as "epoxy compound"), and specific examples thereof are preferably, for example, the above formula (X-1-). 1), (Xl-2), (X-2- 1) ~(X-2-6), (X-3-1), (X-3-2), (X-4-1), ( Compounds represented by X-4-2), (X-5-1) and (X-5-2), ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, Propylene glycol diglycidyl ether 'polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, propylene-54- 200911884 alcohol diglycidyl ether, trimethylol Propane triglycidyl ether neopentyl glycol diglycidyl ether, N,N-diglycidylbenzyl diglycidylaminomethylcyclohexane, hydrazine, hydrazine-diglycidylamine, and the like. The epoxy compound in the liquid crystal alignment agent of the present invention is preferably 40 parts by weight or more, more preferably 25 parts by weight or less per 100 parts by weight of the (?) polymer. The functional decane compound is contained in the liquid crystal of the present invention for the purpose of further improving the adhesion between the alignment film and the substrate, and the functional decane compound is exemplified by, for example, 3-trimethoxydecane or 3-aminopropyl. Triethoxy decane, 2-amine methoxy decane, 2-aminopropyl triethoxy decane, Ν-(2-)_3_aminopropyltrimethoxy decane, Ν-(2-amino group Ethyl propyl methyl dimethoxy decane, 3-ureidopropyl trimethoxy oxapropyl triethoxy decane, hydrazine-ethoxycarbonyl-3-aminopropyl decane, hydrazine-ethoxy Carbocarbonyl-3-aminopropyltriethoxyphosphonium ethoxylated alkylpropyltriethylethylamine, bismuth-trimethoxysulfonium triethylidene triamine, 10-trimethoxydecyl-1 ,4,7-triazo 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethyl-3,6-diazaindolyl acetate, 9-trimethyl Oxyalkylalkyl-3-mercaptoacetate, methyl 9-triethoxydecyl-3,6-diazepine trimethoxydecyl-3,6-diazepine, 9- Methyl triethyl-3,6-diazepine, Ν-benzyl-3-aminopropyltrioxane, Ν-benzyl-3-aminopropyl Ratio of triethoxy decane, fluorenyl-phenyltrimethoxydecane, fluorenyl-phenyl-3-aminopropyltriethoxy.2,2-dibromoamine, hydrazine, fluorenylcyclohexyl In the liquid crystal alignment agent, the aminopropyl propyl tri-aminoethyl)-3-aminoalkyl, 3-ureidotrimethoxy, N-trialkylpropyl oxane, oxygen Pyrantane, 6-diazamethyl ester, 9-oxydecane methoxyindole-3-aminopropane, condensed -55- 200911884 hydroglycidoxymethyltrimethoxydecane, glycidoxymethyl Triethoxy decane, 2-glycidoxyethyl trimethoxy oxime, 2 · glycidoxyethyl triethoxy decane, 3-glycidoxypropyl trimethoxy decane, 3-shrink Glyceroxypropyltriethoxydecane, and the like. The proportion of the functional decane used in the liquid crystal alignment agent of the present invention is preferably 2 parts by weight or less or more preferably 0.2 parts by weight or less based on 100 parts by weight of the (A) polymer. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention contains the above-mentioned (A) polymer and (B) compound as essential components, and may further contain any of the other components described above, and is preferably dissolved in the above components. Modulation in the state of the solvent. The solvent which can be used in the liquid crystal alignment agent of the present invention is preferably an organic solvent which can dissolve the above components but does not react with them. Examples thereof can be exemplified, for example, as the above-exemplified organic solvents for users in the synthesis of polyglycine. Wait. Those used in the synthesis of polyaminic acid can also be used with the exemplified weak solvents. These organic solvents may be used singly or in combination of two or more. The solvent composition is preferably a composition obtained by combining the above solvents, and the composition of the liquid crystal alignment agent is not analyzed, and the surface tension of the liquid crystal alignment agent is set to be in the range of 25 to 40 mN/m. The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the liquid crystal alignment agent other than the solvent to the total weight of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, etc., but is preferably 1~ A range of 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate table -56 to 200911884 to form a coating film as a liquid crystal alignment film. However, when the solid content concentration is less than 1% by weight, the coating film thickness is too small. It is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film because the film thickness of the coating film is too large. Further, when the viscosity of the liquid crystal alignment agent is too large, coating properties may be insufficient. The optimum solid concentration range will vary depending on the coating method used to coat the liquid crystal alignment agent on the substrate. For example, in the case of the spin coating method, a particularly preferable range is 1.5 to 4.5% by weight. In the case of the printing method, the solid content concentration is in the range of 3 to 9 % by weight, and accordingly, the solution viscosity is preferably in the range of 12 to 50 mPa · s. In the case of the ink jet method, the solid content concentration is in the range of 1 to 5 % by weight, and accordingly, the solution viscosity is preferably in the range of 3 to 15 mPa·s. The temperature of the liquid crystal alignment agent of the present invention is preferably from 0 ° C to 100 ° C, more preferably from 10 ° C to 40 ° C. <Liquid Crystal Alignment Film> A method of forming the liquid crystal alignment film of the present invention will be described below. The method for forming a liquid crystal alignment film of the present invention comprises the steps of: coating a liquid crystal alignment agent on a substrate to form a coating film, and irradiating the coating film with a polarized or non-polarizing radiation. First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then a coating film is formed on the substrate by heating the coated surface. When a TN type, STN type or VA type liquid crystal display element is manufactured, two substrates having a patterned transparent conductive film are provided as a pair on the surface of the transparent conductive film, for example, by lithography or spinning. The inkjet printing method 'coats the liquid crystal alignment agent of the present invention, and then coats the surface to form a coating film. Here, as the substrate, a glass such as float glass or a transparent substrate made of polyethylene terephthalate, polyphenylene glycol ester, polyether oxime, polycarbonate, or poly(alicyclic hydrocarbon) can be used. A transparent conductive film provided on one surface of the substrate is, for example, a NESA film made of tin oxide (SnO 2 ) (registered trademark of the company), and a patterned transparent conductive film is obtained from indium oxide-tin oxide (ITO film formed of 203η 203 -). When a patterned transparent conductive film is used, a transparent conductive film is formed by patterning a uranium engraved pattern, and when an alignment agent having a desired pattern is used, the substrate surface and the transparent conductive film are more favorable. After coating the pre-coated functional decane compound or the functional titanium compound 〇 liquid crystal alignment coating agent on the surface of the substrate to form a coating film, pre-heating (pre-baking) is preferably performed in order to prevent the coating from flowing. The pre-baked 30~200°C 'better is 40~150°C, preferably 40~100°C, preferably 0.25~10 minutes, more preferably 0.5~5 minutes. Complete solvent removal, etc. The baking (post-baking) step (post-baking) temperature is preferably 80 to 300 ° C, more preferably 1 2 baking time is preferably 5 to 200 minutes, more preferably 1 〇 ~ (A) a polymer contained in a liquid crystal alignment agent of the present invention has and is transparent in each The transfer coating method or the structure of the plastic film by heating each of the glass and the sodium sulphate dicarboxylic acid can be used, for example, in the formation method, in the method. On the interface between the liquid crystal and the coating film, it is preferred to treat the liquid of the alignment agent before the application. When pre-baking, then, in order to delay. The firing is 250. . . After the minute. In the case of the proline acid structure of the present invention -58-200911884, the deuteration of the proline structure by the heating described above may be used to form a ruthenium imide coating film. The film thickness of the formed coating film is preferably 〇.001 to 1 Pm, more preferably 0 0.5 μπι 〇. On the other hand, when the IPS type liquid crystal display element is manufactured, the conductive layer of the substrate having the comb-shaped transparent conductive film is provided. The film forming surface and the surface of the counter substrate not provided with the electric film are preferably coated with the liquid crystal alignment agent of the present invention by a lithography method, a rotary method or an inkjet printing method, respectively, and then each coated surface is heated to form a coating layer. membrane. The substrate used in this case and the material of the transparent conductive film 'transparent conductive patterning method, substrate pretreatment, addition after application of the liquid crystal alignment agent, and preferred film thickness for forming a coating film, and manufacturing of the above TN type, STN VA type liquid crystal The same is true for display elements. Then, the coating film formed as described above is irradiated with a linearly polarized light or a partially polarized radiation or a non-polarized radiation, depending on the case, and further heat-treated at a temperature of 150 to 250 ° C for 1 to 120 minutes to form a film. Liquid crystal alignment film for liquid crystal alignment. Among them, the radiation can be ultraviolet light and visible light such as light having a wavelength of from 15 〇 nm to 800 nm, but is ultraviolet light having a wavelength of from 300 nm to 400 nm. When the radiation is polarized or partially polarized, the irradiation is performed in a direction perpendicular to the surface of the substrate, and the pretilt angle may be applied from the direction of the tilt, and the same may be performed. When the radiation of the unpolarized light is irradiated, the irradiation direction is inclined. The irradiation angle when irradiated from the oblique direction is preferably 20 to 70° with respect to the normal line, more preferably 30 to 60, and the water is closed. 005- The coated coating is coated by the hot square of the film or the light is good. In the case of the coating, it is preferable to carry out the necessary coating film-59-200911884. The light source used is, for example, a low-pressure mercury lamp, a metal halide lamp, a xenon resonance lamp, a gas lamp, and a UV of a preferred wavelength range. The light source is obtained by means of the means. The irradiation amount of the radiation is preferably U/m2, more preferably 100 to 3,000 J/m2. Further, it is necessary to irradiate the irradiation amount of the coating liquid J/m2 or more formed by the known liquid crystal alignment agent. However, the irradiation amount of the alignment agent and the photo-alignment method may further lower the manufacturing cost of the liquid crystal display element by 1 or less, 〇〇〇J/m2 or less. The liquid crystal alignment film thus formed has an advantage in that the response speed of the liquid crystal is fast as compared with the conventional liquid crystal display element. <Liquid crystal display element> The liquid crystal display element of the present invention will be described below. The liquid crystal display element of the present invention is provided with a liquid crystal alignment film. The liquid crystal display device of the present invention is exemplified by a method for producing a liquid crystal cell on both sides of a liquid crystal cell in which a liquid crystal cell is formed by arranging a liquid crystal alignment film as a substrate, for example, the first method is a conventionally known method. . Tube pressure mercury lamp, xenon lamp, excimer laser, etc. When the above-mentioned sheet, grating, etc., and the above-mentioned optical alignment method of less than 10,000 J/m2 are used for the conventional alignment, 1 〇, 〇〇〇, if the liquid crystal of the present invention is used, it is 3,000 J/m 2 or less. The liquid crystal alignment property is used for, for example, a liquid crystal alignment film of a vertical alignment type, and the liquid crystal alignment agent of the present invention is provided in a pair of two-piece (two-piece) shape. The following two methods. First, each of the liquid crystal alignment films -60-200911884 is disposed opposite to each other with a gap (cell gap) disposed therebetween, and a sealant is used to bond the portions around the two substrates to distinguish the surface of the substrate from the sealant. After the inside of the liquid crystal cell gap is injected and filled with the liquid crystal, the injection hole is sealed to constitute the liquid crystal cell, thereby manufacturing the liquid crystal cell. The second method is called the ODF (Drip Charge) method. Applying, for example, an ultraviolet curable sealing material to a predetermined position on one of the two substrates on which the liquid crystal alignment film is formed, and further adding a liquid crystal to the liquid crystal alignment film, and then bonding the liquid crystal alignment film to the other substrate in a relatively opposed manner Then, the sealing agent is cured by irradiating all of the substrate with ultraviolet rays, thereby manufacturing a liquid crystal cell. Even if it is carried out by any method, it is preferred to further heat the liquid crystal cell produced as described above to a temperature at which the liquid crystal used is in the same phase, and then slowly cool to room temperature, thereby eliminating the flow alignment property at the time of liquid crystal injection. Next, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. Among them, as the sealant, for example, a hardener and an epoxy resin containing alumina balls as a separator can be used. For the liquid crystal, for example, a nematic liquid crystal or a smectic liquid crystal can be used. Among these, nematic liquid crystals are preferred. In the case of the VA 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 liquid crystal, or an azo can be used. An azoxy liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, or the like. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic liquid crystal having positive dielectric anisotropy is preferable, for example, a biphenyl liquid crystal, a phenyl cyclohexene-61 - 200911884 alkyl liquid crystal, or an ester liquid crystal. And a terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a Cubane liquid crystal, or the like. In the liquid crystals, cholesteric acid liquid crystals such as cholesteryl chloride, cholesteryl phthalate, and cholesteryl carbonate may be further added; or sold under the trade names C-15 and CB-15 (manufactured by Merck). It is used as a palmitic agent; a strong dielectric liquid crystal such as p-norbyoxyalkyl bromide-p-amino-2-methylbutyl laurate. The polarizing plate which is bonded to the outer surface of the liquid crystal cell may, for example, be a polarizing film called a "ruthenium film" which is obtained by stretching and aligning polyvinyl alcohol while absorbing iodine, and a polarizing plate held by a cellulose acetate protective film or a film itself. A polarizing plate is constructed. The present invention is more specifically illustrated by the following examples, but the present invention is not limited by the examples. Synthesis Example 1 (Synthesis of Compound (A -1 - 2 -1 )) The compound (A -1 - 2 -1 ) was synthesized according to the following Reaction Scheme 1: -62- 200911884

CH=CH - COOH K2CO3 〇5Η·|·)Βγ 'r

NaOH/H2〇

C5H11 - O--COOH (A-1—2-1) Reaction Procedure 1 In a 1 liter pear-shaped reaction flask, 82 g of p-hydroxycinnamic acid, 3 4 g of potassium carbonate and 400 ml of N-methyl were fed. -2-pyrrolidine oxime, after 1 hour of turbulence at room temperature τ, '1 6 6 gram of 1 - indigo pentoxide was added and spoiled at 1 〇〇〇c for 5 hours. The solvent was then distilled off under reduced pressure. 48 g of sodium oxychloride and 400 ml of water were added thereto, and refluxed for 3 hours to carry out a hydrolysis reaction. After the completion of the reaction, the reaction system was neutralized with hydrochloric acid, and the resulting precipitate was recovered and recrystallized from ethanol, whereby 80 g of a white crystal of the compound represented by the following formula (A-1-2-1) was obtained. Synthesis Example 2 (Synthesis of Compound (A-1-2-2)) In the above Synthesis Example 1, 'except that 262 g of 1-iodo-4,4,4-trifluorobutane was used instead of 1-bromopentane' Synthesis Example 2 was carried out in the same manner to obtain 85 g of a white powder of the compound (Compound (a-1-2-2)) represented by the following formula (A-1-2-2): -63- 200911884 CF3-C3H6 - ο

CH=CH-COOH (A-1-2-2) Synthesis Example 3 (Synthesis of Compound A-1 - 4 - 1 ) The compound (A-1-4-1) was synthesized according to the following reaction procedure 2 HO~^ ^ ~COOCH3 K2C〇3 CgHuBr

Na0H/H20

C5H-, COOH (A-1-4-1A) SOCI2

T K2C〇3

HO-<Q>-CH=CH-COOH ▼

CsHn-0 hQ-coo-h^- CH=CH—COOH (A-1-4-1) Reaction procedure 2 (Synthesis of compound (A-1-4-1A)) Feed in a 1 liter pear type reaction flask After adding 91.3 g of methyl 4-hydroxybenzoate-64 - 200911884, 182.4 g of potassium carbonate and 3 20 ml of N-methyl-2-pyrrolidine at room temperature for 1 hour, 99.7 g of 1-bromopentane was added. The reaction was carried out by stirring at 100 ° C for 5 hours. After the reaction was completed, it was precipitated with water. Next, 48 g of sodium hydroxide and 400 ml of water were added to the lake and refluxed for 3 hours to carry out a hydrolysis reaction. After the completion of the reaction, the resulting precipitate was recrystallized from ethanol to obtain white crystals of the compound (A-)-4-1A. (Synthesis of Compound (A-1-4-1)) 52 g of the compound (Al-4-lA) was placed in the reaction, and 200 ml of sulfinium chloride and 0.2 ml of hydrazine, hydrazine-difluorene were added thereto. The amine was stirred at 80 ° C for 1 hour. Subsequently, the mixture was evaporated under reduced pressure, dichloromethane was added and washed with aqueous sodium hydrogencarbonate, and the organic layer was dried over magnesium and concentrated, and then tetrahydrofuran was added to the solution. Next, 4-hydroxycinnamic acid, 69 g of potassium carbonate, 2.4 g of tetrabutylammonium, liter of tetrahydrofuran and 500 ml of water were fed into the above-mentioned other 500 ml three-necked flask. The aqueous solution was cooled with ice, and a reaction product of the compound (A-1-4-1 A) and sulfinium chloride in tetrahydrofuran was added, followed by stirring for 2 hours. After completion of the reaction, the mixture was neutralized with EtOAc. EtOAc (EtOAc)EtOAc. Synthesis Example 4 (Synthesis of Compound (A -1 · 4 - 2 )) The ketone was slowly and dropwisely precipitated in methyl sulfonium chloride at 37 g of sulfuric acid in a chlorination vessel. Addition of concentrated white-65-200911884 According to the following reaction procedure 3, compound (A - 1 - 4 - 2 ) COOCH3 K2C03 CF3C3H6I Na0H/H20 CF3C3He-〇-COOH (A-1-4-2A) SOCI2 K2C03

H0-(\ />-CH=CH-COOH

CF3C3H6Q—^~^-COO-^~y-CH=CH-COOH (A-1-4-2) Reaction procedure 3 (synthesis of compound (A-1-4-2A)) in 1 liter pear type reaction flask The solution of 82 g of methyl 4-hydroxybenzoate, 166 g of potassium carbonate and 400 ml of N,N-dimethylacetamide was stirred at room temperature for 1 hour, and then 95 g of 1,1,1 was added. -Trifluoro-4-iodobutane' and the reaction was carried out by stirring at room temperature for 5 hours. After the reaction was completed, reprecipitation was carried out with water. Next, 32 g of sodium hydroxide and 400 ml of water were added to the precipitate and refluxed for 4 hours to carry out a hydrolysis reaction. After completion of the reaction, the resulting precipitate was recrystallized with hydrochloric acid to give 80 g of a white crystal of compound (A_ 1-4-2A). -66- 200911884 (Synthesis of Compound (A-1-4-2)) 46. 4 g of the compound (A-1-4_2A) was placed in a reaction vessel, and 200 ml of sulfinium chloride was added thereto. 2 ml of hydrazine, hydrazine-dimethylformamide, and stirred at 80 ° C for 1 hour. Then, sulfite chloride was distilled off under reduced pressure, and dichloromethane was added thereto, and the organic layer was washed with aqueous sodium hydrogencarbonate. The organic layer was dried over magnesium sulfate and concentrated, and then tetrahydrofuran was added to a solution. Next, 36 g of 4-hydroxycinnamic acid, 55 g of potassium carbonate, 2-4 g of tetrabutylammonium, 200 ml of tetrahydrofuran and 400 ml of water were fed into the above other 2 liter three-necked flask. The aqueous solution was ice-cooled, and the above tetrahydrofuran solution containing the reaction product of the compound (A-1-4-2A) and sulfinium chloride was slowly added dropwise, followed by stirring for 2 hours. After completion of the reaction, the mixture was neutralized with hydrochloric acid, extracted with ethyl acetate, dried over magnesium sulfate, concentrated, and then recrystallized from ethanol to obtain white powder of 39 g of cinnamic acid derivative (A-!-4-2). crystallization. Synthesis Example 5 A compound (A - 4 -1 -1 ) was synthesized according to the following reaction procedure 4: -67- 200911884

Ο C10H2i CH=CH—COOH 〇(A-4-1-1) Reaction Procedure 4 Feed in a 1 liter pear-shaped reaction flask with a reflux tube, a nitrogen inlet tube, and a Dean-Stark tube. 72 g of anhydrous decyl succinate, 49 g of decyl cinnamic acid, 70 ml of triethylamine, 500 ml of toluene and 200 ml of tetrahydrofuran were reacted under reflux for 36 hours. After the completion of the reaction, the reaction mixture was washed successively with dilute hydrochloric acid and water, dried over magnesium sulfate, concentrated, and then recrystallized from a mixed solvent of ethanol and tetrahydrofuran, whereby 72 g of a compound (A-4-1-1) was obtained. ) white crystals. Synthesis Example 6 Synthesis of Compound (A - 5 -1 -1 ) according to the following Reaction Scheme 5 -68- 200911884

SOCI2

C2F5C3H6-OH

Reaction Procedure 5 198 g of 1,2,4-cyclohexanetricarboxylic anhydride, 500 ml of sulfinium chloride and 2 ml of n,n. dimethylform were fed into a 2 liter pear-shaped reaction flask equipped with a reflux tube. The guanamine was refluxed at 80 ° C for 1 hour to carry out the reaction. After the completion of the reaction, the thiocyanine chloride was removed under reduced pressure. The chloroform was added to the residue, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and water, then dried over sodium sulfate and concentrated to dryness. Add 500 ml of tetrahydrofuran. On the other hand, the apparatus was provided with a dropping funnel, a thermometer and a nitrogen introduction tube of 200911884 liters of pyridine and 1.5 liters of tetrahydrofuran, and was cooled in a water bath. The tetrahydrofuran solution containing the above-mentioned reactant of 1,2,4-cyclohexanetricarboxylic anhydride and sulfinium chloride was slowly added dropwise thereto, and the mixture was stirred at room temperature for 4 hours to carry out a reaction. After the reaction was completed, extraction was carried out with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, and purified on a silica gel column to obtain 26 8 g of compound (A-5-l-la) (synthesis of compound (A-5-1-1)) - a 200 ml pear-shaped reaction flask of a Stark tube was fed with 241 g of the compound obtained above (A-5-l-la), 109 g of 4-aminocinnamic acid, 190 ml of triethylamine, 16 g of 4- Dimethylaminopyridine, 1 liter of toluene and 2 liters of tetrahydrofuran were reacted under reflux for 24 hours. After the reaction is completed, the monkey reaction mixture is washed with dilute hydrochloric acid and water. The organic layer was dried over magnesium sulfate and then recrystallized from methanol to afford 78 g of Compound (A-5-1-1). Synthesis Example 7 Compound (A-6-1-1) was synthesized according to the following Reaction Scheme 6: -70- 200911884 H°xx

COOH COOH h2n

CH=CH a COOH CH=CH—COOH (A-6-1-1a)

O K2C03

cf3c3h6—I

HCI o cf3c3h6- o CH=CH-COOH (A-6-1-1) Reaction procedure 6 (synthesis of compound (A-6-l-la)) with reflux tube, D-Stark tube and nitrogen A 2-liter three-neck reaction flask of the introduction tube was fed with 90 g of 5-hydroxyphthalic acid and 500 ml of diethylbenzene, and refluxed for 1 hour. Next, 80 g of 4-amino cinnamic acid and 500 ml of tetrahydrofuran were added thereto, and the reaction was carried out under reflux for 12 hours. After completion of the reaction, the reaction mixture was washed successively with dilute hydrochloric acid and water, and then dried over magnesium sulfate, and then concentrated, and then recrystallized from ethyl acetate and tetrahydrofuran-71-200911884 solvent, thereby obtaining 95 g of the compound (A - 6 -1 -1 a ). (Synthesis of Compound (A - 6 -1 -1 )) In a 500 ml pear-shaped reaction flask, 75 g of the compound (A-6-l-la) obtained above, 70 g of potassium carbonate and 150 ml of N- were fed. Methyl-2-pyrrolidone was stirred at room temperature for 1 hour, then 5 9 g of 4,4,4-trifluoro-1 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ After the reaction was completed, 1 liter of water was added and the precipitate was recovered. The precipitate was treated with ethyl acetate and hexane as a solvent, and after purifying on a silica gel column, the solvent was removed to obtain 50 g of a mixture (A-6-1-1). Synthesis Example 8 A compound (A-7-1-1) was synthesized according to the following Reaction Scheme 7: -72- 200911884 o2n

CH=CH a COOH K2C03 cf3c3h6-i 〇2N—^^-CH=:CH—COO-C3H6CF3 (A-7-1 -1 a)

SnCI2 H2N—^ CH=CH—COO—C3H6CF3 (A-7-1-1b)

HOOC

CH=CH—COO-C3H6CF3 (A-7-1-1) Reaction procedure 7 (Synthesis of compound (A-7-l-la)) Feeding 9_7 g in 300 ml of three tubes equipped with thermometer and nitrogen inlet tube 4-Nitrocinnamic acid, 12 g of 4,4,4-trifluoro-, 14 g of potassium carbonate and 50 ml of hydrazine-methyl-2-pyrrolidone were stirred for 1 hour to carry out a reaction. After the end of the reaction, the acetic acid mixture was added and extracted. The organic layer was washed with water, and the mixture was stirred in a magnesium sulfate neck, 1-iodobutane, and after de-drying at 50 t of ethyl ester, and concentrated at -73 to 200911884 to remove the solvent, thereby obtaining 14 g of a compound ([7-^ 1 a (Synthesis of Compound (A-7-l-lb)) In a 300 ml three-neck reaction flask of a device thermometer and a nitrogen introduction tube, 14 g of the compound (A-7-l-la) obtained above, 53 The reaction mixture was stirred at 70 ° C for 1 hour, and the reaction mixture was poured into ice water, neutralized with 2M aqueous sodium hydroxide solution, and then added with ethyl acetate. Precipitate. Ethyl acetate was added to the filtrate and extracted to give an organic layer. The organic layer was washed with water, dried over magnesium sulfate, and concentrated to remove solvent to give 12 g of compound (A - 7 - ; l - 1 b (Synthesis of Compound (A-7-1-1)) Into a 200 ml pear-shaped reaction flask equipped with a reflux tube and a nitrogen introduction tube, 12 g of the compound obtained above (A-7-l-lb) was fed. ), 8.7 g of 1,2,4-cyclohexanetricarboxylic anhydride and 1 ml of acetic acid, and the reaction was carried out under reflux for 1 hour. After completion, the reaction mixture was extracted with ethyl acetate to obtain an organic layer. The organic layer was washed with water, dried over magnesium sulfate, concentrated, and solvent was removed, and recrystallized from a solvent mixture of ethyl acetate and hexane. 11 g of a white crystal of the compound (A-7-1 -1 ) was obtained. Synthesis Example 9 The compound (A - 3 - 2 6 ) was synthesized according to the following reaction procedure 8: -74- 200911884

HOOC—CH=CH SOCI2

CICO—CH=CH (i ) C5H” -〇-〇h C5H1

i~^ ^-~〇〇C~~CH—CH

Br (ii)

Pd(OAc)2

CH2=CH—COOH CH=CH—COOH (A-3-26)

CsH"-OOC-CH=CH- Reaction procedure 8 (Synthesis of compound (i) (4-bromo cinnabarin chloride)) 107 g (0.47 mol) of 4-bromocinnamic acid was refluxed in 83 g of sulfite chloride After 4 hours, a red transparent solution was obtained. Then, after the unreacted sulfinium chloride was distilled off, the residue was recrystallized from toluene and washed with n-hexane, whereby 85 g (yield 74%) of compound (i) was obtained. White crystals. (Synthesis of compound (Π) (4-bromocinnamic acid (4-aminocyclohexyl))) 25.0 g (0.147 mol) of 4-aminocyclohexanol was dissolved in 25 -75- 200911884 ml of pyridine. The temperature of the solution was maintained at about 3 ° C, and 43.3 g (0.176 mol) of the above-obtained compound (i) in 350 ml of pyridine suspension was added dropwise, followed by a reaction for 3 hours. The obtained reaction mixture (suspension) was poured into 1 kg of hydrochloric acid acidic ice water, and the resulting precipitate was filtered, washed with water and dried, whereby 50 g (yield 85 %) of compound (ii) was obtained. Crude product (milky powder). (Synthesis of compound (A-3-26)) In nitrogen, 125 ml (0.9 mol) Anhydrous triethylamine was added to a crude product containing 50 g of the compound (ii) obtained above, 0.28 g (1.25 mmol) of palladium acetate and 1 to 52 g (5 mmol) of tris(o-toluene)phosphine. The reaction was carried out in the mixture. After the crude product of the compound (ii) was completely dissolved, 1 〇·8 g (0.55 mol) of acrylic acid was injected through a syringe, followed by continuing the reaction at 95 ° C for 2 hours. The green reaction mixture was poured into 1.3 kg of hydrochloric acid acidic ice water, and the resulting precipitate was recovered by filtration. The precipitate was dissolved in 500 ml of ethyl acetate, followed by 1N hydrochloric acid and 5 wt% sodium hydrogen carbonate solution. After washing, the organic layer was recovered and dried over magnesium sulfate, and evaporated to give the crude product (yellow solid) of 56 g of compound (A-3-26). The crude product was recrystallized from ethanol to obtain 30 g ( Yield 5 5 %) of a yellow powder of the compound (A - 3 - 2 6 ). Synthesis Example 1 〇~1 6 In the above Synthesis Example 9, the compounds listed in Table 1 were each used -76-200911884 0.1 47 Moore replaced 4_aminocyclohexanol, and the rest with Example 5 The compound represented by the above formula (A-3-1) to (A-3-7) is synthesized (wherein the double bonds on both sides of the benzene ring are trans-forms. Hereinafter, the compounds are respectively referred to as compounds ( A - 3 -1 ) ~ ( A - 3 - 7 )). Table 1 Compound type Product synthesis Example 10 n-pentanol compound (A-3-1) Synthesis Example 11 Synthesis of n-hexanol compound (A-3-2) 12-n-octanol compound (A-3-3) Synthesis Example 13 N-nonanol compound (A-3-4) Synthesis Example 14 Normal monolauryl alcohol compound (A-3-5) Synthesis Example 15 Normal-cetyl group Alcohol compound (A-3-6) Synthesis Example 16 n-Stearyl alcohol compound (A-3-7) Synthesis Examples 17 to 24 In the above Synthesis Examples 9 to 16, each of 0.47 mol 2 -fluoro-4 was used. - bromocinnamic acid was used in the same manner as in the above Examples 5 to 12 except that 4-bromocinnamic acid was replaced, and the above formula (A-3-36) and (A-3-12) to (A - 3 -1 8 were synthesized. a compound represented by the formula (wherein the double bond on either side of the benzene ring is a trans form, the following 'these compounds are respectively referred to as the compound (A-3 - 36) or the compound (A-3-12) ~ (A -3-18)). Synthesis Example 2 5 The compound (a - 2 - 1 4 - 1 ) was synthesized according to the following reaction procedure 9: -77- 200911884 ch3-c ° II o

OH

Br—CsH-n ch3-ch^V-oc5h o N^/ 11 (A-2-14-1A)

COOH

C5H-11O

Reaction Procedure 9 In a 1-liter three-necked reaction flask, 27_2 g of 4-hydroxyacetophenone, 27.6 g of potassium carbonate, 1.0 g of potassium iodide and 500 ml of acetone were fed, and the mixture was stirred at room temperature for 30 minutes, and then added 30.2 g of 1- Bromopentane' and refluxing under nitrogen for 5 hours. After the reaction was completed, the reaction solution was poured into water to precipitate a product. The resulting precipitate was recovered and recrystallized from acetone to obtain 35 g of white crystals of 4-pentyloxyacetophenone (compound (A-2-14-1A)). 20.6 g of the above-obtained 4-pentyloxyacetophenone, 15.0 g of 4-methylmercaptobenzoic acid, 8.0 g of sodium hydroxide and 150 ml of ethanol were fed into a 500 ml three-necked reaction flask, and The reaction was carried out under reflux for 6 hours. After completion of the reaction, it was allowed to stand to cool to room temperature, and 2 〇 ml of water was added -78-200911884' to stir until the solution was uniformly obtained. The resulting solution was placed in a 1 liter beaker, stirred and concentrated hydrochloric acid was added dropwise to ρ Η 7 or less. The resulting precipitate was recovered and recrystallized from ethanol, whereby 25 g of white crystals of 4-carboxy-4,-pentyloxybenzenepropenebenzene (compound (Α-2-1 4-1 )) were obtained. Synthesis Example 2 6 In the same manner as in Synthesis Example 1, except that 47.6 g of 1-iodo-4,4,4-trifluorobutanol was used instead of 1-bromopentane, 28 g of the following formula was obtained (白色-2-14-2) A white powder of the compound (compound (Α-2-14_2)):

(Α-2-14-2) Synthesis Example 2 7 A compound was synthesized according to the following reaction procedure 10 (Α-1·29·1): -79- 200911884

Br—CsH” 0 (Α-1-29-1Α)

(Α-1-29-1) 27.6 In the backwater, by)) benzene oxidation reaction procedure 10 Ling 1 liter three-neck reaction flask was fed with 24.4 g of 4-hydroxybenzaldehyde, gram of potassium carbonate, 1.0 g of potassium iodide and After 500 ml of acetone was stirred at room temperature for 30 minutes, 30.2 g of 1-bromopentane was added, and the reaction was carried out under nitrogen for 5 hours. After the reaction was completed, the reaction solution was poured to precipitate a product. The recovered precipitate was recovered from acetone to obtain 33 g of 4-pentyloxybenzaldehyde (the compound (white crystal of Α-1-29-1 A). The cold 500 ml three-necked reaction flask was injected into the above. 19.2 g of 4-pentyloxy P aldehyde, 16.4 g of 4-acetic benzoic acid, 8.0 g of hydrogen ft and 150 ml of ethanol, and reacting under reflux for 6 hours. Anti-80-200911884 should be finished After standing to cool to room temperature, 200 ml of water was added, and the mixture was stirred until homogeneously obtained. The obtained solution was placed in an i liter beaker, stirred and concentrated hydrochloric acid was added dropwise to pH 7 or less. The precipitate was recrystallized from ethanol to obtain white crystals of 29 g of 4-pentyloxy-4,-carboxyphenylpropene benzene (compound (A-1-29-1)). In the above Synthesis Example 27, except that 47.6 g of hydrazine-iodo-4,4,4-trifluorobutane was used instead of 1-bromopentane, the same procedure as in Synthesis Example 27 was carried out.

CF3(CH2)3-0_^_/-§Oc〇〇H (A-1-29-2) Obtained 30 g of the compound represented by the following formula (Al-29-2)) (compound (A-1-29-) 2)) White powder. <Synthesis of the compound represented by the above formula (B)> Example 1 23.4 g (0.10 mol) was fed as a compound a-OH in a 500 ml three-necked reaction flask equipped with a thermometer, a stirrer and a nitrogen introduction tube. The compound (Al-2-l) obtained in the above Synthesis Example 1 and 47.1 g (0.10 mol) of the compound represented by the above formula (x-2-4) of the compound χ_(Ερ)4 and 188.4 g of fluorene-methyl group 2-pyrrolidone (solid content concentration: 27% by weight), and the reaction was carried out under a nitrogen stream at 14 ° C for 5 hours to obtain a solution containing the compound (B-1). -81 - 200911884 Next, the above solution was measured by liquid chromatography (ODS column, acetonitrile: water = 80:20), and it was confirmed that all the compound (A-1 - 2 -1 ) used was consumed. Examples 2 to 40, except that the kinds and amounts listed in Table 2 were used as the compound A-OH and the compound X-(Ep) 4, respectively, and the amount of N-methyl-2-pyrrolidone used was adjusted. In the same manner as in the above Example 1, the reaction was carried out at a solid concentration of 27% by weight to obtain a solution containing the compounds (B-2) to (B-40), respectively. Each solution was measured by liquid chromatography (ODS column, acetonitrile: water = 80: 20), and it was confirmed that the compound A-OH used in all of Examples 2 to 40 was consumed. Table 2 A-0] X-(Ep, U Compound name type (A) Type (ά) Example 1 A-1-2-1 0.1 X-2-4 0.1 Β-1 Example 2 A-1-2 -1 0.1 X-4-2 0.1 Β-2 Example 3 A-1-2-1 0.1 X-5-2 0.1 Β-3 Example 4 A-1-2-2 0.1 X-2-4 0.1 Β -4 Example 5 A-1-2-2 0.1 X-4-2 0.1 Β-5 Example 6 A-1-2-2 0.1 X-5-2 0.1 Β-6 Example 7 A-1-4 -1 0.1 X-2-4 0.1 Β-7 Example 8 A-1-4-1 0.1 X-4-2 0.1 Β-8 Example 9 A-1-4-1 0.1 X-5-2 0.1 Β -9 Example 10 A-1-4-2 0.1 X-1-1 0.1 Β-10 Example 11 A-1-4-2 0.2 X-1-1 0.1 Β-11 Example 12 A-1-4 -2 0.1 X-2-1 0.1 Β-12 Example 13 A-1-4-2 0.1 X-2-2 0.1 Β-13 -82- 200911884 Table 2 (continued) A-0 Η χ-(Ερ) 4 Compound name type (mole) Species (mole) Example 14 A-1-4-2 0.1 Χ-2-4 0.1 Β-14 Example 15 A-1-4-2 0.1 Χ-4-2 0.1 Β-15 Example 16 A-1-4-2 0.1 Χ-5-2 0.1 Β-16 Example 17 A-4-1-1 0.1 Χ-2-4 0.1 Β-17 Example 18 A-5- 1-1 0.1 Χ-2-4 0.1 Β-18 Example 19 A-6-1-1 0.1 Χ-2-4 0.1 Β-19 Example 20 A-7-1-1 0.1 Χ-2-4 0.1 Β-20 Example 21 A-3-26 0.1 Χ-2 -4 0.1 Β-21 Example 22 A-3-1 0.1 Χ-2-4 0.1 Β-22 Example 23 A-3-2 0.1 Χ-2-4 0.1 Β-23 Example 24 A-3-3 0.1 Χ-2-4 0.1 Β-24 Example 25 A-3-4 0.1 Χ-2-4 0.1 Β-25 Example 26 A-3-5 0.1 Χ-2-4 0.1 Β-26 Example 27 A -3-6 0.1 Χ-2-4 0.1 Β-27 Example 28 A-3-7 0.1 Χ-2-4 0.1 Β-28 Example 29 A-3-36 0.1 Χ-2-4 0.1 Β-29 Example 30 A-3-12 0.1 Χ-2-4 0.1 Β-30 Example 31 A-3-13 0.1 Χ-2-4 0.1 Β-31 Example 32 A-3-14 0.1 Χ-2-4 0.1 Β-32 Example 33 A-3-15 0.1 Χ-2-4 0.1 Β-33 Example 34 A-3-16 0.1 Χ-2-4 0.1 Β-34 Example 35 A-3-17 0.1 Χ -2-4 0.1 Β-35 Example 36 A-3-18 0.1 Χ-2-4 0.1 Β-36 Example 37 A-2-14-1 0.1 Χ-2-4 0.1 Β-37 Example 38 A -2-14-2 0.1 Χ-2-4 0.1 Β-38 Example 39 A-1-29-1 0.1 Χ-2-4 0.1 Β-39 Example 40 A-1-29-2 0.1 Χ-2 -4 0.1 Β-40 In the above Table 2, the abbreviations of the compound A-OH and the compound X-(Ep)4 have the following meanings, respectively. (Compound A-OH) -83-200911884 A-1-2-1: Compound (Al-2-1) obtained in the above Synthesis Example 1 A-1-2-2: Compound obtained in the above Synthesis Example 2 ( A-1-2-2) A-1-4-1 : Compound (A-1-4-1) A - 1 - 4 - 2 obtained in the above Synthesis Example 3: the compound obtained in the above Synthesis Example 4 ( A -1 - 4 - 2 ) A-7-1-1 : Compound (A-7-1-1) A - 5 -1 -1 obtained in the above Synthesis Example 5: the compound obtained in the above Synthesis Example 6 ( A - 5 -1 -1 ) A-6-1-1 : Compound (A-6-1-1) obtained in the above Synthesis Example 7 A-7-1-1: Compound obtained in the above Synthesis Example 8 ( A-7-1-1) A - 3 - 2 6 : Compound (A - 3 - 2 6 ) A-3-1 obtained in the above Synthesis Example 9: Compound (A_3_l) A obtained in the above Synthesis Example 10. 3 - 2 : Compound (A - 3 - 2 ) A-3-3 obtained in the above Synthesis Example 11: Compound (A_3_3) obtained in the above Synthesis Example 12 A-3-4 : Compound obtained in Synthesis Example 13 above (A-3-4) A-3-5 : Compound (A-3-5) A - 3 - 6 obtained in the above Synthesis Example 14 : Compound (A - 3 - 6 ) obtained in the above Synthesis Example 15. A-3-7: Compound (A-3-7) obtained in the above Synthesis Example 16 A-3-36: the above combination Compound (A-3-36) A-3-12: Compound (A-3-12) obtained in the above Synthesis Example 18 A-3-13: Compound obtained in the above Synthesis Example 19 ( A-3-13) A-3-14: Compound (A-3-14) A-3-15 obtained in the above Synthesis Example 20: Compound (A-3-15) A- obtained in the above Synthesis Example 21. 3-16: Compound (A-3-16) A-3-17 obtained in the above Synthesis Example 22: Compound (A-3-17) A-3-18 obtained in the above Synthesis Example 23: Synthesis Example 24 above Compound (A-3-18) -84- 200911884 A-2-14-1. Compound (A-2-14-1) obtained in the above Synthesis Example 25 A-2-14-2: Synthesis as described above Compound (A-2-14-2) A-1-29-1 obtained in Example 26: Compound (A-1-29-1) obtained in Synthesis Example 27, Al-29_2: obtained in Synthesis Example 28 above Compound (A-1-29-2) (Compound X-(Ep)4) X-2-4: Compound X-4-2 represented by the above formula (X-2-4): Formula (X-4) -2) Compound X-5·2: Compound X-1:1 represented by the above formula (X-5-2): Compound X-2-1 represented by the above formula (X-1 -1): Compound X-2-2 represented by (X-2-1): compound represented by the above formula (X-2-2) <polyamine Synthesis of Synthesis Example 29 19.6 g (0.1 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride and 21.2 g (0.1 mol) as a diamine were used. 2,2'-Dimethyl-4,4 '-diaminobiphenyl was dissolved in 3 6 7 g of N-methyl-2-pyrrolidone, and reacted at 4 (TC for 3 hours to obtain 4 0 7 g of a solution containing 10% by weight of polyaminic acid (PA-1). The solution viscosity of the polyaminic acid solution was -85-200911884 1 70 mPa · so Synthesis Example 30 22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride And 14.23 g (0.1 mol) of cyclohexane bis-1,3-(methylamine) as diamine dissolved in 3 29.3 g of N-methyl-2-pyrrolidone and carried out at 60 ° C The reaction was carried out for 6 hours, whereby 3 6 5 g of a solution containing 10% by weight of poly-proline (PA-2) was obtained. The solution viscosity of the polyaminic acid solution was 110 mPa·s. <Synthesis of Polyimine> Synthesis Example 3 1 22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 9.73 g as a diamine (0.09 mol) p-phenylenediamine and 5.23 g (〇_〇ι Moule) The diamine represented by the compound represented by the above formula (D-10) is dissolved in 336.2 g of N-methyl-2-pyrrolidone. The reaction was carried out at 6 ° C for 4 hours, whereby a solution containing 1% by weight of poly-proline was obtained. The solution viscosity of the polyaminic acid solution was 1 2 6 mP a · s ο Next, 3 4 8 g of Ν-methyl-2-pyrrolidone was added to add 7.9 g of pyridine and 1 于 in the obtained poly-proline solution. 2 g of acetic anhydride, and dehydration ring closure was carried out for 4 hours under 丨丨〇〇c. After the dehydration ring-closure reaction, the solvent in the system is replaced by a new N-methyl-2-bendrolone (the pyridine and acetic anhydride used in the dehydration ring-closing reaction in this operation are excluded from the system, the same applies hereinafter) From -86 to 200911884, about 230 grams of a solution of a polyamidiamine (Ρ I -1 ) containing 6.1% by weight of a ruthenium iodide of about 54% was obtained. A small amount of the polyimine solution was added to add a solution of ruthenium-methyl-2-pyrrolidone to a polymer concentration of 1% by weight. The solution viscosity was determined to be 75 mPa·s. Synthesis Example 3 2 The solution containing the polyamic acid (pa-2) obtained in the above Synthesis Example 30 was converted to a polyacetic acid (PA-2) equivalent to an amount of 17.5 g, and 23 2.5 was added thereto. N-methyl-2-pyrrolidone, gram pyridine and 4.9 g of acetic anhydride' were dehydrated and closed at 1 1 ° C for 4 hours. After dehydration ring closure reaction, by replacing the solvent in the system with a new N-methyl-2-pyrrolidone solvent, about 81 g of polyimine containing about 14.8% by weight of hydrazine imidization (about 50%) was obtained ( PI-2) solution. A small amount of the polyimine solution was added to add N-methyl-2-pyrrolidone to a polymer concentration of 10% by weight. The solution had a solution viscosity of 6 9 m P a · s. Example 4 1 <Preparation of Liquid Crystal Aligning Agent> As a (A) polymer, a solution containing the polylysine (PA-1) obtained in the above Synthesis Example 25 was converted into polylysine (PA_i). The amount of the compound (B-1) obtained as the compound (B-1) obtained in the above-mentioned Example 1 is added to the compound (B-1) in an amount equivalent to 50 parts by weight, and is equivalent to 50 parts by weight. The amount, further added methyl-2-pyrrolidone and butyl cellosolve, the solvent composition of N-methyl-2-[] ratio slightly -87- 200911884 ketone: butyl cellosolve = 50: 50 (weight ratio) It became a solution having a solid concentration of 2.5% by weight. This solution was filtered through a filter having a pore size of 1 μm to thereby modulate the liquid crystal alignment agent (S -1 ). Examples 42 to 89 The liquid crystal alignment agents (S - were prepared in the same manner as in the above Example 4 except that the types listed in Table 3 and the amounts listed in the same table were used as the (A) polymer and the (B) compound, respectively. 2) ~ (S - 4 9 ). Further, the (A) polymer and the (B) compound are each supplied to the liquid crystal alignment agent by the above-mentioned a or the solution obtained in the above examples, and the amount in Table 3 is converted into the respective solutions. (Α) Polymer 戍 4Β ) The amount of a substance. Ώ

200911884 Table 3 (continued) (A) Polymer (B) Compound Liquid crystal alignment agent Name Type (parts by weight) Species (parts by weight) Example 55 PA-2 100 B-15 50 S-15 Example 56 PI- 2 100 B-16 50 S-16 Example 57 PI-1 100 B-10 50 S-17 Example 58 PI-1 100 B-11 50 S-18 Example 59 PI-1 100 B-12 50 S- 19 Example 60 PI-1 100 B-13 50 S-20 Example 61 PI-1 100 B-14 50 S-21 Example 62 PI-1 100 B-14 25 S-22 Example 63 PI-2 100 B-15 50 S-23 Example 64 PI-2 100 B-16 50 S-24 Example 65 PA-1 100 B-17 50 S-25 Example 66 PA-1 100 B-18 50 S-26 Implementation Example 67 PA-1 100 B-19 50 S-27 Example 68 PA-1 100 B-20 50 S-28 Example 69 PA-1 100 B-21 50 S-29 Example 70 PA-1 100 B- 22 50 S-30 Example 71 PA-1 100 B-23 50 S-31 Example 72 PA-1 100 B-24 50 S-32 Example 73 PA-1 100 B-25 50 S-33 Example 74 PA-1 100 B-26 50 S-34 Example 75 PA-1 100 B-27 50 S-35 Example 76 PA-1 100 B-28 50 S-36 Example 77 PA-1 100 B-29 50 S-37 Example 78 PA-1 100 B-30 50 S-38 Example 79 PA-1 100 B-31 50 S-39 Example 80 PA-1 100 B-32 50 S-40 Example 81 PA-1 100 B-33 50 S-41 Example 82 PA-1 100 B-34 50 S-42 Example 83 PA-1 100 B -35 50 S-43 Example 84 PA-1 100 B-36 50 S-44 Example 85 PI-1 100 B-14 100 S-45 Example 86 PA-1 100 B-37 50 S-46 Example 87 PA-1 100 B-38 50 S-47 Example 88 PA-1 100 B-39 50 S-48 Example 89 PA-1 100 B-40 50 S-49 -89- 200911884 Example 90 Using the above implementation The VA type liquid crystal display element was produced in the same manner as the liquid crystal alignment agent prepared in Example 4, and the evaluation of the liquid crystal alignment property was performed. &lt;Production of VA type liquid crystal display element&gt; The above-mentioned liquid crystal alignment agent was provided with a transparent glass substrate composed of an ITO film by a spin coater, and dried on a hot plate at 80 ° C. Minutes were pre-supplied and replaced with nitrogen and post-baked at 20 (TC) for 1 hour ί. ίμιη coating on the surface of the coating using Hg-Xe lamp (Gian-Taylor) 稜鏡, self-coating The normal line of the film is irradiated with a polarized ultraviolet ray having a thickness of 130 J/m 2 and a 133 nm light line at 40°. This operation is repeated to obtain a pair of (two pieces) substrates on the transparent electro-optical liquid crystal alignment film. After forming a surface of each of the liquid crystal alignment films, an epoxy having a diameter of 5.5 μm is added, and then the substrate is superposed and pressed in a direction opposite to the ultraviolet light axis toward the substrate surface, at 150 t. The mixture was heated for 1 hour, and then filled with a liquid crystal injection port between a pair of substrates, manufactured by Merck Co., Ltd., MLC-66 08), and sealed with an epoxy-based crystal injection port. Next, in order to eliminate the liquid crystal injection, it was heated at 150 ° C and then slowly cooled to room temperature. S - 1, after the directionality and voltage S -1 are applied to the surface of the bright electrode, in the oven, the film thickness and the direction of the gradient of the Glan-Thai are formed, and the outer surface of the liquid crystal matching surface has a mesh resin. The agent is applied to the parallel side to make the adhesive hard-type liquid crystal (the agent then aligns the liquid flow, and then the polarizing plate is bonded on both sides of the base of the base-90 - 200911884, so that the polarization directions thereof are orthogonal to each other and the liquid crystal alignment film The VA type liquid crystal display element was manufactured by the ultraviolet light axis toward the substrate surface projection direction at an angle of 45. <Evaluation of liquid crystal alignment property> For the VA type liquid crystal display element manufactured as described above, DC 5V was observed by an optical microscope. When the voltage is turned on and off (applied or released), an abnormal block is generated. When the liquid crystal display element is not observed to have an abnormal block, the liquid crystal alignment property is described as "good". <Evaluation of voltage maintenance rate> Applying a voltage of 5 V to the VA type liquid crystal display device manufactured above at 60 ° C for a period of 60 μsec, and after the interval of 167 ms is applied, the voltage maintenance of 167 ms after the release of the application is measured. rate In the measurement device, the VHR-1 manufactured by Toyo Technic is used. When the voltage maintenance rate is 90% or more, the voltage maintenance rate is evaluated as "good", and the other is evaluated as "poor", and the liquid crystal display element is used. The voltage maintenance ratio was "good." Examples 91 to 114, 116, 118 to 135, 138, and 139 In addition to the use of the liquid crystal alignment agents listed in Table 4, respectively, and the polarized ultraviolet irradiation amounts of the liquid crystal display elements were respectively The va liquid crystal display element was produced in the same manner as in the above Example 90 except that the liquid crystal alignment property and the voltage maintenance ratio were evaluated. The results are shown in Tables 4 - 91 - 200911884. Example 1 1 5 The liquid crystal alignment agent S-26 prepared in the above Example 66 was used to produce a TN liquid crystal display element, and the liquid crystal alignment property and the voltage maintenance ratio were evaluated. <Production of TN liquid crystal display element> Using spin coating The above-prepared liquid crystal alignment agent S-26 was coated on a transparent electrode @ of a glass substrate provided with a transparent electrode composed of an ITO film, and dried on a hot plate of 8 (TC) for 1 minute for prebaking. The oven was replaced with nitrogen and post-baked at 2 Torr for 1 hour to form a film having a film thickness of ί. ίμιη. Hg-Xe lamp and Gülen-Taylor were used on the surface of the film. A polarized ultraviolet ray having a 313 nm illuminating line of 1,000 I/m 2 is irradiated in a direction inclined at 40° to the normal line of the substrate, thereby forming a liquid crystal alignment film imparting liquid crystal alignment energy. The same operation as above is repeated to produce a pair (two a glass substrate having a liquid crystal alignment film on a surface of the transparent conductive film. A portion of the surface of each of the pair of substrates on which the liquid crystal alignment film is formed is screen-printed and coated with a ring of alumina having a diameter of 5.5 μm After the oxy-resin adhesive, the substrate was superposed and pressed in a direction orthogonal to the direction in which the polarized ultraviolet rays were irradiated, and the adhesive was cured by heating at 150 ° C for 1 hour. Next, a positive nematic liquid crystal (manufactured by Merck Corporation 'MLC-622 1 ' is added to the palm powder) from the liquid crystal injection port in the gap between the substrates, and the liquid crystal is bonded to the liquid crystal-92-200911884. The entrance is sealed. Next, in order to eliminate the flow alignment at the time of liquid crystal injection, it was heated at 150 ° C for 1 〇 minute and slowly cooled to room temperature. Then, a polarizing plate is bonded to both surfaces of the outer surface of the substrate so that the polarization directions thereof are orthogonal to each other and parallel to the direction of polarization of the liquid crystal alignment film, whereby a TN liquid crystal display element is manufactured. &lt;Evaluation of Liquid Crystal Alignment&gt; Regarding the TN liquid crystal display device manufactured as described above, whether or not an abnormal block was generated when an ON voltage of 5 V was turned on and off (applied/released) by an optical microscope was observed. If the display element has an abnormal block, it is judged that the liquid crystal alignment property is "good". &lt;Evaluation of Voltage Maintaining Rate&gt; A voltage of 5 V was applied to the TN liquid crystal display device manufactured above at 60 ° C for 60 μs, and after the interval of 丨 6 7 ms was applied, the measurement was performed after the application was released. 67 milliseconds voltage maintenance rate. The measuring device used VHR-1 manufactured by Dongyang Technic. When the voltage holding ratio is 90% or more, the voltage holding ratio is evaluated as "good" and "other than" is evaluated as "poor", and the voltage holding ratio of the liquid crystal display element is "good". Examples 117, 136 and 137 Except that those listed in Table 4 were used as the liquid crystal alignment agent, respectively, and the amount of polarized ultraviolet rays at the time of manufacture of the liquid crystal display element was respectively -93-200911884 listed in Table 4, and the above examples In the same manner, a TN liquid crystal display device was produced in the same manner, and liquid crystal alignment properties and voltage maintenance ratios were evaluated. The results are shown in Table 4. Table 4 Liquid crystal alignment agent name polarized light irradiation amount (J/m2) Display mode liquid crystal alignment voltage maintenance rate Example 90 S-1 1,000 VA Good good example 91 S-2 1,000 VA Good good example 92 S-3 1,000 VA Good good example 93 S-4 1,000 VA Good good example 94 S-5 1,000 VA Good good example 95 S-6 1,000 VA Good good example 96 S-7 1,000 VA Good good example 97 S-8 1,000 VA Good Good Example 98 S-9 1,000 VA Good Good Example 99 S-10 1,000 VA Good Good Practice 100 S-11 1,000 VA Good Good Practice 101 S-12 1,000 VA Good Good Practice 102 S-13 1,000 VA Good good example 103 S-14 1,000 VA Good good example 104 S-15 1,000 VA Good good example 105 S-16 1,000 VA Good good example 106 S-17 1,000 VA Good good example 107 S-18 1,000 VA Good Good Example 108 S-19 1,000 VA Good Good Practice 109 S-20 1,000 VA Good Good Practice 110 S-21 1,000 VA Good Good Practice 111 S-22 1,000 YA Good Good Example 112 S-23 1,000 VA Good Good Practice 113 S-24 1,000 VA Good Good Practice 114 S-25 1,000 VA Good Good Practice 115 S-26 1,000 TN Good Good Practice 116 S-27 1,000 VA Good good example 1Π S-28 1,000 TN Good good example 118 S-39 1,000 VA Good good-94- 200911884 Table 4 (continued) Liquid crystal alignment agent name polarized radiation exposure (J/m2) Display mode liquid crystal alignment Voltage Maintainance Example 119 S-30 1,000 VA Good Good Example 120 S-31 1,000 VA Good Good Practice 121 S-32 1,000 VA Good Good Practice 122 S-33 1,000 VA Good Good Practice 123 S-34 1,000 VA Good Good Example 124 S-35 1,000 VA Good Good Example 125 S-36 1,000 VA Good Good Practice 126 S-37 1,000 VA Good Good Practice 127 S-38 1,000 VA Good Good Practice 128 S-39 1,000 VA Good Good Example 129 S-40 1,000 VA Good Good Example 130 S-41 1,000 VA Good Good Practice 131 S-42 1,000 VA Good Good Practice 132 S-43 1,000 VA Good Good Practice 133 S-44 1,000 VA Good Good Practice 134 S-21 200 VA Good Good Practice 135 S-45 1,000 VA Good Good Practice 136 S-46 3,000 TN Good Good Practice 137 S-47 3,000 TN Good Good Example 138 S-48 3,000 VA Good Good Practice 139 S-49 3,000 VA Good and Good [Effect of the Invention] The liquid crystal alignment agent of the present invention, as can be specifically understood from the above examples, can be used as It is suitable for the liquid crystal alignment agent of the photo-alignment method, and can form a liquid crystal alignment film which exhibits good liquid crystal alignment and high voltage retention by a radiation irradiation amount smaller than before. Therefore, when such a liquid crystal alignment film is used for a liquid crystal display device, a liquid crystal display element excellent in display quality can be manufactured more expensively than ever. -95- 200911884 The liquid crystal display element of the present invention having the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention has good display quality. Therefore, the liquid crystal display element of the present invention can be effectively used in various devices, for example, it can be preferably used in a desktop computer, a watch, a clock, a coefficient display panel, a digital processor, a personal computer, or a liquid crystal television. -96 -

Claims (1)

200911884 X. Patent application scope 1. A liquid crystal alignment agent characterized by comprising: (A) a polymer selected from at least one group consisting of polylysine and polyamidiamine, and (B) having a wavelength A light-emitting group of 200 to 400 nm is subjected to a crosslinking reaction or an isomerization reaction. 2. The liquid crystal alignment agent of claim 1, wherein the compound (B) is a compound having the following groups: an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a cyclohexyl group, An alkylcyclohexyl group or an alkylphenyl group having an alkyl group having 1 to 20 carbon atoms, a fluoroalkylcyclohexyl group or a fluoroalkylphenyl group having a fluoroalkyl group having 1 to 20 carbon atoms, and a carbon number of 4 to 20 An alkyloxy group, a fluoroalkyloxy group having 1 to 20 carbon atoms, a cyclohexyloxy group, an alkyloxycyclohexyl group having an alkyloxy group having 1 to 20 carbon atoms or an alkyloxyphenyl group; a fluoroalkylcyclohexyl or fluoroalkyloxyphenyl group having a fluoroalkyl group having 1 to 20 carbon atoms, or a group having a carbon number of 17 to 51 having a steroid skeleton, and an epoxy group and the following formula (1) Base: 3. The liquid crystal alignment agent of claim 2, wherein the compound (B) is a compound represented by the following formula (1·1): (AW)-X-(Ep)n (1-1) (formula In 1-1), A is the following formula (A-1) to (A-8) -97- 200911884. The formula of the formula 'W is the following formula (W-1) to (W-4) In the formula, X is a tetravalent group represented by any one of the following formulae (X-1) to (X-5), and Ep is a group represented by the following formula (Ep-1) or (Ep-2), m is The integer '1 to 3' is 4-m), rI—x1—X2 }—CH==CH—CO—X3— ^ (A-1) (In the formula (Al), R1 is independently an alkyl group having 4 to 2 carbon atoms, a fluorine compound having a carbon number of 1 to 2, and a ring. a hexyl group, an alkylcyclohexyl group having a carbon number iDO or a phenyl group, a fluoroalkylcyclohexyl group having a fluoroalkyl group having a carbon number, or a fluorine-based base group, or a carbon number having a steroid skeleton; The radical X of ～51 is a single bond, an oxygen atom, a sulfur atom, _c〇〇_, _NHC〇_, _c〇NH_ or -CO_, and X2 is a single bond or a formula represented by any of the following formulas (~(χ2_3): (X2-1) (X2-2) (X2_3) indicates that the bonding key attached to it is located on the χ 1 side) -98- 200911884 X3 is a single key, *-〇-(CH2)a-, *-0-( CH2)a-C0_, *-(CH2)a-〇CO-(CH2)a-, or a base represented by the following formula: c=o (wherein a is independently an integer of 1 to 6, and "*" indicates attached There is a key on the -CH = CH-CO- side), but when two adjacent keys are single-key, these can become a single bond together, R1—X&quot; CO——CH= CH--X6-X7- (A-2) (In the formula (A-2), R1 has the same meaning as R1 in the above formula (A-1) 'X4 is a single bond, an oxygen atom, a sulfur atom, -COO -, -OCO-, -NHCO-, -CONH- or -CO-, X is a bond or a phenyl group, and X6 is a single bond or a group represented by the following formula (X6-1): -OCO (X6·!) indicates that the bond key attached thereto is on the X7 side) X7 is a single bond, *-〇C〇-(CH2)a-' *-OCO-(CH2)a-CO- or the following formula (X7) -1 ) indicates the base: -99- 200911884 孝oco- (χ7-υ (in the above, a is an integer from 1 to 6, "*" means that the key with the key is located on the X6 side)), but, When the two adjacent keys are single bonds, these can become a single bond together, R1—OCO—CH=CH —CH=CH—CO— (A-3) (In the formula (A-3), R1 has the same R1 as in the above formula (A-1) -100- 200911884 (In the formulae (A-4) to (A-6), R1 has the same meaning as R1 in the above formula (A-1), and X8 is a single bond, an oxygen atom, a sulfur atom, or -COO-, respectively. (In the formulae (A-7) and (A-8), R1 has the same meaning as R1 in the above formula (A-1), and X9 is a single bond or *-(CH2)a-COO- (where a An integer of 1 to 10, "*" indicates that the bonding key attached thereto is located on the -CO- side), OH - Ο - ch2-ch - CH2 - * (W-1) - Ο HO - CH2 - CH—CH2— * (W2) HO O -CH2— (W-3) -101 - 200911884 Ο HO CH2- * (W-4) (In the above formula, "*" indicates that the key with the key is on the X side) Or the base represented by the following formula (Y-1): -102- 200911884 The alkyl group or the fluorine atom R11 is a carbon number of 1 to 6 which can be substituted by a fluorine atom, and b is an integer of 0 to 4), (Ep-1) Ο (Ep-2) 4. The liquid crystal aligning agent compound according to item 2 of the patent application can be compounded with the compound X-(Ep)4 (wherein, the same meaning as described in the formula (1-1)) A mixture of Α-ΟΗ (same meaning as described in the above formula (1-1)) is added with an I 5 _ liquid crystal alignment film which is formed by the liquid crystal alignment agent of any one of the patents. 6. A method for forming a liquid crystal alignment film, which is characterized by coating a liquid crystal coating film according to any one of claims 1 to 4, and irradiating the coating film with polarized or non-polarizing radiation. A liquid crystal display device characterized by having a liquid crystal alignment film of five applications. 8. The liquid crystal display element of claim 7 is a negative liquid crystal. A compound characterized by having a photosensitive group and an epoxy group which are subjected to a crosslinking reaction or an isomerization reaction at a wavelength of 200 -, wherein (Β) Ερ is obtained separately from the above. The range of the first to fourth ranges has a step of forming a substrate alignment agent. The scope of the patent is the use of -400 nm light -103 - 200911884 1 0. The compound of claim 9 wherein the above compound has the following groups: carbon number 1 to 2 0 alkyl group, carbon number 1~ a fluoroalkyl group, a cyclohexyl group, an alkylcyclohexyl group or an alkylphenyl group having an alkyl group having 1 to 20 carbon atoms, a fluoroalkylcyclohexyl group having a fluoroalkyl group having 1 to 20 carbon atoms or a fluoroalkane a phenyl group, an alkyloxy group having 4 to 20 carbon atoms, a fluoroalkyloxy group having 1 to 20 carbon atoms, a cyclohexyloxy group, an alkyloxy group having an alkyloxy group having 1 to 20 carbon atoms a hexyl or alkyloxyphenyl group, a fluoroalkylcyclohexyl group or a fluoroalkyloxyphenyl group having a fluoroalkyl group having 1 to 20 carbon atoms, or a group having a carbon number of 17 to 51 having a steroid skeleton, and a ring An oxy group and a group represented by the above formula (1). 1 1 method for producing a compound of claim 9 or 10, characterized in that the compound Χ-(Ερ)4 (wherein X and Ερ are respectively of the same meaning as described in the above formula (1-1) And heating with a mixture of the compound Α_0Η (wherein the 'A system has the same meaning as described in the above formula (1-1)). -104- 200911884 Nothing to say that there is no simple Jane.. No. is a map of the map element on behalf of the map: the table pattern represents the present generation /-N set one or two days Sw / eight, if there is a chemical formula in this case, please reveal the most Chemical formula that can show the characteristics of the invention: none