TW201100930A - Method for producing liquid crystal display element - Google Patents

Abstract

Provided is a method for producing a liquid crystal display element which is capable of high-speed response with high luminance while has excellent electrical properties. The method for producing a liquid crystal display element is characterized by having the following step: a polymer film with a specific structure represented by the following formul (I-1-2) is formed on a substrate; nematic liquid crystal having negative dielectric anisotropic is held between each film of two substrates; a voltage is applied among each transparent pixel electrode of the two substrates; the liquid crystal is aligned, and then a light is irradiated under such state.

Description

201100930 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of manufacturing a liquid crystal display element. More specifically, it relates to a method of manufacturing a liquid crystal display element which is particularly suitable for use in a liquid crystal display element of an MVA type which is excellent in liquid crystal alignment and electrical characteristics. [Prior Art] Conventionally, as a liquid crystal display element, a liquid crystal alignment film is formed on a surface of a substrate on which a transparent conductive ruthenium film is provided, and a substrate for a liquid crystal display element is formed, and the two substrates are arranged to face each other and formed in a gap therebetween. A nematic liquid crystal layer having positive dielectric anisotropy is formed into a cell of a sandwich structure, and has a so-called TN type in which the long axis of liquid crystal molecules is continuously twisted by 90° from one substrate to another substrate (twisted direction) Column type, Twisted Nematic) TN type liquid crystal display element of liquid crystal cell (Patent Document 1). In addition, a high-contrast STN (Super Twisted 〇 Nematic) type liquid crystal display element (Patent Document 2) can be realized, and the viewing angle dependency is small and the image screen is highly responsive as compared with the TN liquid crystal display element. Excellent optical compensation bending (OCB) type liquid crystal display element (Patent Document 3), VA (Vertical Alignment) type liquid crystal display element using nematic liquid crystal having negative dielectric anisotropy (Patent Document 4) An IPS (In-Plane Switching) type liquid crystal display element (Patent Document 5) in which a liquid crystal molecule is defined to have a small viewing angle dependency in a horizontal plane of the substrate. Among these, it is known that in the VA type liquid crystal display device, the alignment control structure such as a linear protrusion or a slit structure is provided on the substrate 201100930, and the liquid crystal alignment direction can be controlled in a plurality of directions when a voltage is applied. In the pixel, a liquid crystal display element of a MVA (Multi-domain Vertical Alignment) type having a wide viewing angle is realized (Patent Document 6). The Μ V A type liquid crystal display element has an advantage of excellent viewing angle characteristics, but has a drawback that white brightness is low and display is dark. The main reason for this disadvantage is that the region on the alignment control structure becomes a division limit of the liquid crystal alignment, and this region is optically dark, so that the light transmittance of the entire pixel is considered to be low. In order to improve the situation, it has been proposed to control the interval of the structure for alignment control to be very wide. However, since the number of structures for alignment control is relatively small, the time required for the alignment to be stabilized becomes long, and the response speed becomes slow. Therefore, there is a limit to the improvement of the countermeasure. In order to realize an MVA liquid crystal display element which can respond at high speed with high brightness, a method of specifying a pretilt angle of liquid crystal molecules and an oblique direction at the time of voltage application using a polymer has been proposed (Patent Document 6). Patent Document 6 describes a method in which a liquid crystal composition in which a monomer or a liquid crystal which is polymerized by light or heat is mixed is sealed between two substrates, and a voltage is applied between the substrates to tilt the liquid crystal molecules and determine the alignment. A technique of applying light or heat to the liquid crystal layer to thereby polymerize a monomer to prepare a polymer, which fixes the alignment direction and pretilt angle of the liquid crystal molecules. However, according to the technique of Patent Document 6, the unreacted polymerizable monomer may remain in the liquid crystal, or a part of the polymerizable monomer may be decomposed by light or heat, and the polymerizable monomer and/or its decomposition product may be in the liquid crystal. Medium diffusion will cause side effects of lower voltage retention, and it is expected to improve on 201100930. In recent years, a method of improving some of the disadvantages of the technique of Patent Document 6 has been proposed (Patent Document 38). This technique is to sandwich liquid crystal molecules between liquid crystal alignment films having crosslinkable sites, apply an electric field thereon, irradiate ultraviolet light in a state in which liquid crystal molecules are aligned, and crosslink the crosslinkable sites, thereby fixing liquid crystal molecules. Techniques for alignment direction and pretilt angle. According to this technique, it is possible to eliminate the problem caused by the residual of the polymerizable monomer, but the problem that the response speed of the liquid crystal molecules existing at the time of ΟΝ/OFF is slow except for the large amount of ultraviolet irradiation required for crosslinking is severe in performance. It is not practical in the field of current liquid crystal display elements. CITATION LIST Patent Literature Patent Literature No. JP-A No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Application Laid-Open No. Hei 8- No. Hei No. Hei 8- No. Hei No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. Japanese special Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 0-237075. Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 〇72626 公告 Patent Document 37 Japanese Patent Laid-Open Publication No. 2001-192657 Patent Publication No. 2009/032545 No. 3 Patent Application Publication No. Patent Document Non-Patent Document 1 TJ Scheffer et al., J. Appl. Phys ν · 19 19 19 3 3 Ο Ο Ο Ο Ο Ο Ο Ο 鉴于 鉴于 本 本 本 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In particular, a method of manufacturing a liquid crystal display element of the MV A type. Means for Solving the Problems The above object and advantages of the present invention are achieved by the following aspects: A method of manufacturing a liquid crystal display element, characterized in that the following steps are performed: forming on the transparent pixel electrode of a substrate having a transparent pixel electrode a film having a polymer structure having a structure represented by the following formula (I), wherein a nematic liquid crystal having a negative dielectric anisotropy is sandwiched between each of the two substrates forming the film, and each of the two substrates is transparent. A voltage is applied between the pixel electrodes to illuminate the light in a state in which the liquid crystal is aligned, X201100930 R1—(-A2—Z1-)^-A1—((I)

Y • A3- (In the formula (I), one of A1 and A3 is an alkyl group having a carbon atom number of 1 to 12 and an alkoxy group having a carbon number of (a halogen atom, a cyano group, a nitro group) ( One or more substituted phenyl groups selected from the group consisting of alkyl and alkoxy groups each substituted with a halogen atom, or pyridine-2,5-diyl, pyrimidine, 2,5-fluorene V a 1,4-thiophenediyl, 2,5-furanyl or CH group which may be substituted by a nitrogen atom, a 1,4-naphthyl group or a 2,6-anthranyl group, and the other may be a halogen atom. One or more substituted phenyl groups selected from the group consisting of cyano and nitro groups, or pyridine-2,5-diyl, pyrimidine-2,5-diyl, 2,5-thiophenediyl, 2, 5-furanyl, CH-substituted 1,4-azinophthyl or 2,6-anthranyl or *-000-, *-(:01^- or *-CO-E- (above) The bond of the band is bonded to -CH=CH-, and E is one or more substituted 1,4-phenylene groups, or pyridine-2, which may be selected from the group consisting of a halogen atom, a cyano group and a nitro group. 5-diyl, pyrimidine, 2,5-diyl, 2,5-thiophenediyl, 2,5-furfuranyl or CH-substituted hydrazine 4_strandyl or 2,6-naphthyl); A2 is a 1,4-phenyl group which may be substituted with one or more selected from the group consisting of a halogen atom, a cyano group and a nitro group, or Des-2,5-diyl, pyrimidine-2,5-diyl, 2,5-thiophenediyl, 2,5-extended furyl, anticyclohexyl, trans-1,3-dioxane- 2,5-diyl or 1,4-piperidinyl; 201100930 ζ1 represents a single bond, *-CH2CH2-, *-C00., *_〇c〇., ^cH2., *-ch2〇-, *- c three c-, *-(CH+-, *-0(CH2)k (ch small or trans-form *-och2ch=ch-, *-ch=chch2〇-, *_(CH2)2CH=CH_ Or -CH = CH(CH2)2-(the above-mentioned linkage is linked to A2); Ο R is a hydrogen atom, a halogen atom, a cyano group, a nitro group or a 1 group; or a 3 group or a carbon number of 1 to 12 The alkyl group 'the alkyl group may be substituted with fluorine, and one or two of the non-adjacent -CH2- groups may be substituted by an oxygen atom, -COO-, -oco- or _c◦-'-CHUCH2. -CH = CH-substitution, or a group having a steroid skeleton; X and Y each independently represent a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 12 carbon atoms, and the alkyl group may be substituted with a fluorine atom , one Or two non-adjacent -CH2- groups may be substituted by an oxygen atom, -COO-, -OCO- or -CO-; η is an integer of 0 to 4, and when η is 0, R1 is not a hydrogen atom). Provided is a method of manufacturing a liquid crystal display element which is capable of high-speed response at high luminance and excellent in electrical characteristics. The liquid crystal display element manufactured by the method of the present invention is particularly suitable for use in an MVA type liquid crystal display element. [Embodiment] The method for producing a liquid crystal display device of the present invention is characterized in that the film is sandwiched between two substrates of a film formed of a polymer having the structure represented by the above formula (I). A nematic liquid crystal having a negative dielectric anisotropy is applied between the transparent pixel electrodes of the two substrates, and the light is irradiated in a state in which the liquid crystal is aligned. -10-00900930 The structure shown in the above formula (I) is preferred. A structure that is isomerized or dimerized by light or thermal energy. A1 and A3 in the above formula (1) are preferably one of which may be a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. One or more substituted phenyl groups selected from the group consisting of (the alkyl groups and alkoxy groups may each be substituted with a halogen atom), or a pyridine-2,5-diyl, pyrimidine-2,5-diyl group , 2,5-thiophenediyl, 2,5-extended furyl, 1,4-naphthyl or 2,6-anthranyl,

G is another one which may be selected from a group consisting of a halogen atom, a cyano group and a nitro group, or a *-COO- or *-CO-E- (with a "link" -CH = CH-linkage, and E is one or more substituted 1,4-phenylene groups which may be selected from the group consisting of a halogen atom, a cyano group and a nitro group. Each of the above formula (I) is preferably Z1 is a single bond, *-CH2CH2-, *-COO_, *_OCH2-, *-(CH2)4-, *-〇(CH2)3- or *-(CH2)3〇-(the above 〇" The bond is bonded to A2); R1 is a hydrogen atom, a halogen atom, a cyano group or a nitro group or an alkyl group having a carbon number, and the alkyl group may be substituted with fluorine. One or two non-adjacent _CH2_ groups may be oxygenated. Atom, -C00- or -OCO-substituted, -CH2Ch2- group may be substituted by -CH=CH-, or a group having a steroid skeleton; X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, The compound may be substituted with a fluorine atom; Y is a hydrogen atom, and the cyano group has an alkyl group having 1 to 6 carbon atoms. However, the -11 - 201100930 may be substituted with fluorine or -COO-alkyl. The number of carbon atoms in the alkyl group is 3 ° above (1) The structure shown is more preferably in the above formula (1), and A1 is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, and a oxy group having 1 to 12 carbon atoms (such alkyl groups) And alkoxy groups, each of which may be substituted by a halogen atom, may be selected from the group consisting of a substituted phenyl group, or a pyridine-2,5-diyl group, a pyrimidine 2,5-diyl group, 2,5 - thiophenediyl, 2,5-extended furyl, 0 1,4-naphthyl or 2,6-naphthyl; A3 is one or more selected from the group consisting of a halogen atom, a cyano group and a nitro group Substituted phenyl, or *-C00 - or *-C0-E- (except that the above bond with " is bonded to -CH = CH-, E is a group of halogen atoms, cyano and nitro The structure of one or more substituted 1,4-phenylene groups selected in the group (hereinafter referred to as "structure (1-1)"), or in the above formula (I), A1 may be derived from a halogen atom, a cyano group, and One or more substituted 1,4-phenylene groups selected from the group consisting of nitro groups, or *-C00- or *-C0-E- (except that the above bond with hydrazine is linked to -CH=CH-, E is a group which can be composed of a _ atom, a cyano group and a nitro group. One or more substituted 1,4-phenylene groups selected; A3 is an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms (such alkyl groups and alkoxy groups) One or more substituted 1,4-phenylene's or pyridine-2,5-diyl, pyrimidine-2,5-diyl, 2,5- selected from the group consisting of halogen atoms. The structure of a thiophenediyl group, a 2,5-extended furanyl group, a 1,4-naphthyl group or a 2,6-anthranyl group (hereinafter referred to as "structure (1-2)"). When at least one of A1 and A3 in the above formula (I) is a phenylene group (including the case of -12-.201100930 generation), the phenylene group may be 1,2-phenylene, 1,3- A phenyl group or a 1,4-phenylene group is preferred, and among them, a 1,4-phenyl group is preferred. The group having a steroid skeleton of R1 in the above formula (I) may, for example, be a cholestyl-3-yl group, a cholest-5-en-3-yl group, or a cholest-24-en-3-yl group. Bile-5,24-en-3-yl, lanostan-3-yl and the like. When R1 is a group having a steroid skeleton, η is preferably 0. Examples of the above configuration (1-1) include, for example, the following formula

R1

Η (1-1-2) R1- c-coo-

H

(1-1-5) -13- 201100930

(1-1-7)

Ο (In the above formula, R1, a2, Ζ1 and η are the same as those in the above formula (I), respectively. 'R2 is a halogen atom, an amino group, a nitro group, a hydrocarbon group having 1 to 12 carbon atoms or a carbon ruthenium atom. An alkoxy group of 1 to 12 (the alkyl group and the alkoxy group may each be substituted by a halogen atom), and m is an integer represented by 〇~4), and the like, as an example of the above structure (I·2) For example, the following formula (1-2-1) R1——(A2-Z1)n can be cited.

(1-2-1) Η (In the formula (1-2-1), R1, A2, Ζ1 and η are the same as those in the above formula (I), respectively, and R2 is a halogen atom, a cyano group, a nitro group or a carbon atom. Alkyl-14-201100930 having a number of 1 to 12 or a hospitaloxy group having 1 to 12 carbon atoms (such a hospital base and a hospitaloxy group may each be substituted by a halogen atom), and m is an integer of 0 to 4) The structure of the representation, etc. The group yjAtZ1)!!- on the benzene ring in the above formula (1-1-1) may be in the 2-position, 3-position or 4-position with respect to -CH = CH-COO-, and particularly preferably in the 4-position. The structure represented by the above formula (I) is more preferably a structure represented by the above formula (I-1-1) and the above formula (1-2-1), and particularly preferably the following formula (I and II) )~ (I-2-1-4)

(I-1-1-3) -15- 201100930

(In the above formula, R1, & 2 and m are respectively the same as those in the above formula (Io) or (1-2-1)). Such a polymer film having a structure represented by the above formula (I) is preferably at least one selected from the group consisting of: (meth)acrylic acid derived having the structure represented by the above formula (I) (co)polymer of a styrene derivative, a vinyl ether, a vinyl vinegar or an unsaturated nicotinic acid derivative; a polyorganic shale having the structure represented by the above formula (I); and having the above formula (I) The polystyrenic acid of the structure shown and its brewed imidized polymer. -16-201100930 The polyorganoleoxasiloxane having the structure represented by the above formula (I) may be, for example, a hydrolysis of a decane having a structure represented by the above formula (I) and a group capable of hydrolyzing 'condensation. The reaction product of the condensate or the polyorganosiloxane having an epoxy group and the carboxylic acid having the structure represented by the above formula (I) is the latter. The polyamic acid having the structure represented by the above formula (I) and its quinone imidized polymer may, for example, be a tetracarboxylic dianhydride and a diamine containing a tetracarboxylic dianhydride having the structure represented by the above formula (I). The polylysine obtained by reacting the polylysine and its ruthenium iodide polymer or tetradecanoic acid dianhydride and the hydrazine diamine including the diamine having the structure represented by the above formula (1) The polymer is preferably the latter. Among these, a (co)polymer of a (meth)acrylic acid derivative having a structure represented by the above formula (I), a polyorganosiloxane having an epoxy group, and a compound of the above formula (I) are preferred. A reaction product of a carboxylic acid of the structure and at least one of a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine having a structure represented by the above formula (I) and a ruthenium iodide polymer thereof. The (co)polymer of the (meth)acrylic acid derivative having the structure represented by the above formula (I) may be a (meth)acrylic acid derivative having the structure represented by the above formula (1) or having the above formula ( I) A mixture of a (meth)acrylic acid derivative of the structure shown and another monomer is obtained by polymerization. The (meth)acrylic acid derivative having the structure represented by the above formula (I) can be exemplified by methacryloxyethyl 3-(E)-[4-cyano-4'-biphenyl] Acrylate, methacryloxyethyl 3-(E)-[3-cyanophenyl]acrylate, methacryloxyethyl 3-(E)-[4-chlorophenyl]propene酸酸-17- 201100930 Ester, methacryloxyethyl 3-(E)-[4-methoxyphenyl]acrylic acid vinegar, methacryloxyethyl 3-(E)-[ 3 -Nitrophenyl]acrylate, 3-methylpropyl succinylpropyl (E)-3-[4-cyanophenyl]propanol, ι_[Bu[(E)-3-( 4-methoxy-phenyl)-propenyl]-piperidin-4-yloxycarbonyl]-1-methyl-ethylene, methacryloxyethyl 3-(E)-biphenyl For example, a compound or the like described in Patent Document 7 (JP-A-6-287453) can be suitably used. Examples of the other monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, and fumaric acid; , itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, methyl fumaric acid and the like unsaturated dicarboxylic acid and unsaturated carboxylic anhydride; more than 3 yuan unsaturated polycarboxylic acid and more than 3 yuan Unsaturated polycarboxylic anhydride; mono(2-propenyloxyethyl) succinate, mono(2-methylpropenyloxyethyl) succinate, mono(2-propene phthalate) Mono(2-propenyloxyethyl) ester of non-polymeric dicarboxylic acid such as oxyethyl) ester, mono(2-methylpropenyloxyethyl) phthalate and non-polymerizable Mono(2-propenyloxyethyl) ester of a dicarboxylic acid; ω·carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, etc. Saturated monomer; styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyl toluene, p-chlorostyrene, o-methoxy Styrene, -18- 201100930 methoxystyrene, p-methoxystyrene, p-vinylbenzyl p-vinylbenzyl glycidyl ether, such as aromatic vinyl hydrazine, 1-methyl hydrazine Bismuth and its derivatives; methyl acrylate, methyl methacrylate, ethyl ethacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, methyl butyl Ester, isobutyl acrylate, isobutyl methacrylate, propyl ester, butyl methacrylate, butyl acrylate, ternary butyl acrylate, allyl acrylate, allyl methacrylate , benzyl methacrylate, phenyl acrylate, methyl ester, methoxy diethylene glycol acrylate, methacrylic acid glycol ester, methoxy triethylene glycol acrylate, methyl propyl phthalate Alcohol ester, methoxydipropylene glycol acrylate, methyl propylene dipropylene glycol ester, glycerin monoacrylate, unsaturated carboxylic acid ester of glycerol monomethyl propyl; 2-hydroxyethyl acrylate acrylate, 2-hydroxy methacrylate 2-hydroxypropyl enoate, 2-hydroxy propyl methacrylate Ester, propyl propyl ester, 3-hydroxypropyl methacrylate, 2-hydroxybutyl 2-hydroxyacrylate, 3-hydroxybutyl acrylate, methyl butyl acrylate, 4-hydroxybutyl acrylate, methacrylic acid 4 -hydroxy)5-hydroxypentyl acrylate, 6-hydroxyethyl 7-hydroxyheptyl (meth)acrylate, 9-hydroxydecyl 8-hydroxyoctenoate (meth)acrylate, (meth)acrylic acid 10 -hydroxy oxime ester, methyl ether, base compound; ester, methyl propyl, acrylic acid decanoic acid secondary butylated methacrylic acid, benzyl methacrylate benzyloxy diacetate methoxy trienoic acid methoxy Ethyl esters such as ethyl esters, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, (meth), (methyl), (methyl) propyl (meth) propylene-19- 201100930 Acid 11-transester 11-ester ester, (meth)acrylic acid ι 2 hydroxydodecyl ester, (methyl) acrylic acid 2-(6-ylethylhexyl hexyloxy) ethyl ester, (A 3-(6-Cycylethylhexyloxy)propyl acrylate, 4-(6-hydroxyethylhexyloxy)butyl vinegar (meth)acrylate '(5-Hydroxyethylhexyloxy). (meth)acrylic acid, 6-(6-hydroxyethylhexyloxy)hexyl (meth)acrylate, (meth)propionic acid 2-(3-transyl-2,2·dimethyl-propoxycarbonyloxy)-ethyl ester, (methyl)propionic acid 3-(3-hydroxy-2,2-dimethyl- Propyloxycarbonyloxy)·propyl ester, 0 (methyl)propanoic acid 4·(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-butyl ester '(meth)acrylic acid 5-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-pentyl vinegar, 6-(3-hydroxy-2,2-dimethyl-propoxycarbonyl (meth)acrylate Oxy)-hexyl ester, 4-hydroxy-cyclohexyl (meth)acrylate, 4-hydroxymethyl-cyclohexylmethyl acrylate, 4-hydroxyethyl-cyclohexylethyl (meth)acrylate, 3-hydroxy-bicyclo[2.2.1]hept-5-en-2-yl (meth)acrylate, 3-hydroxymethyl-bicyclo[2.2.1]hept-5-ene (meth)acrylate -2-ylmethyl ester, 3-hydroxyethyl-bicyclo[2.2.1]hept-5-en-2-ylethyl (meth)acrylate, 8-hydroxy-di(meth) acrylate Ring [2.2.1]hept-5-en-2-yl ester, (meth)acrylic acid 2- Base-octahydro-4,7-methyl bridge-nod-5-yl ester, 2-hydroxymethyl-octahydro-4,7-methyl bridge-indol-5-ylmethyl (meth)acrylate, 2-hydroxyethyl-octahydro-4,7-methyl bridge·indol-5-ylethyl methacrylate, 3-hydroxyl-adamantan-1-yl (meth)acrylate, (methyl) An unsaturated carboxylic acid hydroxyalkyl ester such as 3-hydroxymethyl-adamantane-indenylmethyl acrylate or 3-hydroxyethyl-adamantan-1-ylethyl (meth)acrylate; acrylic acid 2-Aminoethyl ester, 2-aminoethyl methacrylate, propylene-20- 201100930 2-dimethylaminoethyl enoate, 2-dimethylaminoethyl methacrylate , 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, acrylic acid 3- Amino propyl ester, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, unsaturated carboxylic acid amine Alkyl ester; glycidyl (meth)acrylate, glycidyl acrylate alpha-ethyl acrylate, C Acid glycidyl α-n-propyl ester, glycidyl acrylate α-n-butyl ester, (meth)acrylic acid-3,4-epoxybutyl ester, (meth)acrylic acid-6,7- Epoxyheptyl ester, α-ethyl acrylate-6,7-epoxyheptyl ester, methyl glycidyl (meth)acrylate, (meth)acrylic acid / /3-ethyl glycidyl Ester, propyl glycidyl (meth)acrylate, /3-methylglycidyl α-ethyl acrylate, 3-methyl-3,4-epoxybutyl (meth)acrylate , 3-ethyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, (meth)acrylic acid-5 -^ Methyl-5,6-epoxyhexyl ester, (meth)acrylic acid-hydrazine-methylglycidyl ester, 3-methyl-3,4-epoxybutyl (meth)acrylate An unsaturated carboxylic acid glycidyl ester; a vinyl carboxylate such as vinyl acetate, vinyl propionate, vinyl butyrate or vinyl benzoate; vinyl methyl ether, vinyl ethyl ether, Allyl glycidyl ether, methyl allyl glycidyl An oleyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, an unsaturated ether such as p-vinylbenzyl glycidyl ether-21-201100930; acrylonitrile, methacryl A vinyl cyanide compound such as nitrile, chloroacrylonitrile or vinyl cyanide; acrylamide, methacrylamide, α-chloropropenylamine, hydrazine-2-hydroxyethyl decylamine, hydrazine-2- Unsaturated guanamine such as hydroxyethyl methacrylamide, hydrazine-hydroxymethyl acrylamide, hydrazine-hydroxymethyl methacrylamide; Ν-cyclohexylmaleimide, Ν-phenyl Maleimide, fluorene-o-hydroxyphenylmaleimide, hydrazine-m-hydroxyphenylmaleimide, hydrazine-p-hydroxyphenylhydrazone maleimide, fluorene-o-methylphenyl Maleidin, Ν-m-methylphenylmaleimide, Ν-p-methylphenylmaleimide, Ν-o-methoxyphenylmaleimide, Ν-M. Anthracene-substituted maleimide such as oxyphenylmaleimide or fluorenyl-p-methoxyphenylmaleimide; 1,3-butadiene, isoprene, and chloroprene An aliphatic conjugated diene such as a diene. The synthesis of the (co)anthracene polymer having a (meth)acrylic acid derivative having the structure represented by the above formula (I) can be carried out according to a known radical polymerization method, and is preferably, for example, in a suitable solvent. In the presence of a polymerization initiator, a (meth)acrylic acid derivative having the structure represented by the above formula (I) or a (meth)acrylic acid derivative having the structure represented by the above formula (I) and other monomers The mixture is reacted to obtain. The solvent which can be used herein may, for example, be diethylene glycol methyl ethyl ether or propylene glycol methyl ether acetate. The solvent is preferably used in a proportion of 150 to 300 -22 to 201100930 parts by weight based on 100 parts by weight of the total of the monomers used. Examples of the polymerization initiator which can be used herein include radical polymerization of isobutyronitrile (hereinafter generally referred to as "AI BN" by a person skilled in the art) and azobis(2,4-dimethylvaleronitrile). Initiator. The proportion of use of the polymerization is preferably 0.5 to 10 parts by weight based on the total amount of 100 parts by weight. The polymerization temperature is preferably from 70 to 100 ° C, and the polymerization time is preferably from 3. The (meth)propionic acid derivative ruthenium polymer having the structure represented by the above formula (I) is determined by gel permeation chromatography and converted to a polyphenylene weight average molecular weight, preferably 1,000 to 1,000,000. More 5,000~100,000. The (meth)acrylic acid derivative polymer having the structure represented by the above formula (I) is preferably a homopolymer of a methyl 3-acid derivative having a structure represented by the above formula (I), particularly preferably used. Poly(methacrylofluorene 3-(E)-[4-cyano-4'-biphenyl]acrylate), poly(methylpropenylethyl 3-(E)-[ 3-cyano Phenyl]acrylate, poly(methylpropylethyl 3-(E)-[4-chlorophenyl]acrylate), poly(methacrylethyl 3-(E)-[4-methoxy Phenyl phenyl] acrylate), poly(methylpropylethyl 3-(E)-[3-nitrophenyl]acrylate), poly(3-methylaminopropyl (E)-3 -[4-cyanophenyl]propenylamine), poly[[(E)-3-(4-methoxy-phenyl)-propenyl]-piperidin-4-yloxy-bu-methyl- At least one selected from the group consisting of ethylene and poly(methacryloxyethyl 3-(E)-alenoate. Azo 2,2'-initiator body, smaller than ~10 (co) propylene (ethyl) propylene oxime oxime oxy oxy oxy oxy oxime 醯 1-[ 1-; carbonyl] phenyl -23- 201100930 a polydecane compound having a structure of the above formula (I), preferably a decane compound of a decane compound of an oxy group and a hydrolyzable group, hydrolyzed and condensed in the presence of an organic solvent, water and a catalyst, first epoxy The polyorganosiloxane is then synthesized by reacting the carboxylic acid of the structure represented by the formula (I) with the polyorganooxane. The decanolation having the above epoxy group and a hydrolyzable group can be exemplified by 3-glycidoxypropyltrimethoxydecane glyceryloxypropyltriethoxydecane, 3-glycidyloxyhydrazine. Dimethoxy decane, 3-glycidyloxypropyl methyl dioxane, 3-glycidyloxypropyl dimethyl methoxy decane, oleyloxy propyl dimethyl ethoxy Decane, 2-(3,4-epoxydecyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethyl, etc., one or more of them may be used. The epoxy group-containing polyorganosiloxane may be composed only of the above-mentioned oxime having an epoxy group and a hydrolyzable group, or may contain other substances in addition to the above-described decane compound. a decane compound such as methyltrichlorodecane, methyltrimethoxydecane, methyltriethoxyphenyltrichlorodecane, phenyltrimethoxydecane, phenyltriethoxymethyldichlorodecane, methyl dimethyl Oxy decane, methyl diethoxy dimethyl dichloro decane, dimethyl dimethoxy decane, dimethyl Decane, diphenyldichlorodecane, diphenyldimethoxydecane, preferably containing a ring in the synthesis and having an upper compound, for example, 3-hydrhydrylpropylmethylethoxy oxime 3-condensed The decane compound of the hexyl ethoxylated oxime compound can be exemplified by a decane, a decane, a decane, a diethoxy group, a hydrazine--> - this S - -24- 201100930 ethoxy group Decane, chlorodimethyl decane, methoxy dimethyl decane, ethoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, iodine trimethyl oxalate, methoxy trimethyl decane, Ethoxytrimethyldecane, 3-(methyl)propoxydecyloxypropyltrichlorodecane, 3-(methyl)propenyloxypropyltrimethoxysilane, 3-(methyl)propene oxime Oxypropyl propyl triethoxy decane, vinyl chlorosilane, vinyl trimethoxy decane, vinyl triethoxy decane, allyl trichloro decane, allyl trimethoxy decane, allyl tri One or more selected from the group consisting of ethoxy oxane and the like. The decane compound for synthesizing a polyorganosiloxane having an epoxy group, preferably containing 50 mol% or more of a decane compound having an epoxy group and a hydrolyzable group as described above with respect to all of the decane compound. More preferably, it contains 60% to 100% by mole. The organic solvent which can be used in the synthesis of the polyorganosiloxane having an epoxy group may, for example, be a hydrocarbon, a ketone, an ester, an ether or an alcohol. Examples of the hydrocarbon include toluene, xylene, and the like; ^ as the ketone, for example, methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentanone, diethyl ketone, cyclohexanone, or the like; as the above ester, for example, acetic acid Ethyl ester, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc.; as the above ether, for example, ethylene glycol dimethyl ether , ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc.; as the above alcohol, for example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol-25- 201100930 monomethyl ether, ethylene Alcohol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and the like may be used. Among them, it is preferred to use a solvent which is not water-soluble. The organic solvent is preferably used in an amount of 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight per 100 parts by weight of the total of the decane compound. The amount of water used in the synthesis of the polyorganosiloxane having an epoxy group is preferably from 0.5 to 100 moles, more preferably from 1 to 30 moles, per mole of the total of 1 mole of the decane compound. As the catalyst, for example, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound or the like can be used, and among them, an alkali metal compound or an organic base is preferably used. By using an alkali metal compound or an organic base as a catalyst, formation of a three-dimensional structure can be promoted, and a polyorganosiloxane having a small content of a stanol group can be obtained. Therefore, in the reaction with a carboxylic acid to be described later and a liquid crystal alignment agent containing the reaction product, it is preferable to obtain a liquid crystal alignment agent having excellent storage stability in order to suppress the condensation reaction between the stanol groups. Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide. As the above-mentioned organic base, for example, a primary or secondary organic amine such as ethylamine, diethylamine, piperazine, piperidine, lysine, or pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4 a tertiary organic amine such as dimethylaminopyrrolidine or diazabicycloundecene; -26- 201100930 tetramethyl, preferably aminoaminopyridine quaternary organic amine as a catalyst base The type is preferably, for example, an ear, more preferably 0 ^. The synthetic material is preferably an organic compound, and is appropriately hydrolyzed by 40 to 100 ° C > Reaction solvent layer. Contain a small amount of salt to wash. The cleaning is carried out as needed, and the quaternary organic amine or the like which is obtained by the ammonium hydroxide is removed. These organic bases are tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethyl; and a catalyst such as tetramethylammonium hydroxide is particularly preferably an organic base. The amount of the organic base to be used varies depending on the reaction conditions such as the temperature and the like, and can be appropriately set, and is 0.01 to 3 moles of 0.05 to 1 mole per 1 mole of the decane compound. The hydrolysis condensation reaction in the polyorganosiloxane having an epoxy group is carried out by dissolving the decane compound in the solvent and other decane as needed. The solution is mixed with an organic base or water, for example, by heating using an oil bath apparatus. The heating temperature at the time of the reaction is preferably 1 3 (TC or less, more preferably 0.5 to 12 hours, more preferably 1 to 8 hours). The mixture may be mixed without stirring or mixed. After being placed back, it is preferably separated from the reaction mixture by washing with water. In the case of the cleaning, it is preferable to use a water, for example, an aqueous solution of ammonium nitrate of about 0.2% by weight, etc., to be cleaned. The aqueous layer is neutral, and then an organic solvent layer: an anhydrous desiccant such as anhydrous calcium sulfate or a molecular sieve, to obtain a desired polyorganosiloxane having an epoxy group. The oxane is then preferably obtained by reacting a carboxylic acid having the structure represented by the above formula (I) in the presence of a catalyst and an organic solvent in the presence of a catalyst of -27 to 201100930 to obtain a polyorganic organic compound having the structure represented by the above formula (I). The carboxylic acid having the structure represented by the above formula (I), as the structure having the formula (1-1-1), can be exemplified by the following formula (1-1-(:-1)~ (1-1-(:-5) respectively indicated compound;

CbH2b+i

(in the above formula, a is an integer of from 1 to 12, and b is an integer of from 0 to 12). As a product having the structure represented by the above formula (I - 2 -1), for example, the following formula (I-2-Cl) can be cited. )~(I-2-C-5) respectively represent the compound; -28- 201100930 Η

CaH2a+1——OCO——C,

•OCO—C2H4"~COOH (I-2-C-1)

H

OCO-C \\

H

•OCO—C2H4—COOH (I-2-C-2) Ο

ChH bn2b+1

OCO-Cx

H

H c

~OCO-C2H4-COOH (I-2-C-3)

ChH bn2b+1

OCO-Cs

H c- OCO—C2H4—COOH (1-2CA)

H ❹ H CbH2b+1

Oco—c \ OCO—C 2 H 4 —COOH H (I-2-C-5) (In the above formula, 3 is an integer from 1 to 12, and b is an integer from 0 to 12). The use ratio of the carboxylic acid having the structure represented by the above formula (I) is preferably 0.1 to 0.8 mol, more preferably 0.2, per 1 mol of the epoxy group of the polyorganosiloxane having an epoxy group. ~0.7 moles. As the above catalyst, a known compound can be used as a so-called curing accelerator for promoting the reaction of an organic base or an epoxy compound and an acid anhydride. As the above organic base, for example, a primary or secondary organic amine such as ethylamine, diethylamine, pipe trap, piperidine, pyrrolidine or pyrrole; -29- 201100930 triethylamine, tri-n-propylamine, tri-n-butylamine , a ternary organic amine such as pyridine, 4-dimethylaminopyridine, diazabicyclo-carbene; a quaternary organic amine such as tetramethylammonium hydroxide; and the like. Among these organic bases, preferred are tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine; tetramethylammonium hydroxide and the like. Grade organic amine. Examples of the curing accelerator include tertiary amines, imidazolium compounds, organophosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds, quaternary ammonium salts, boron compounds, and metal halogens. As the compound or the like, a known latent curing accelerator can also be used. The catalyst is preferably 100 parts by weight or less, more preferably 0. 01 to 1 part by weight, still more preferably 0 to 1 to 20 parts by weight, per 100 parts by weight of the polyorganosiloxane having an epoxy group. Proportional use. Examples of the organic solvent include a hydrocarbon, an ether, an ester, a ketone, a decylamine, an alcohol, and the like. Among them, the solubility of the raw materials and products and the ease of purification of the product are preferred, and are preferably ethers, esters or ketones. In the solvent, the solid content concentration (the ratio of the weight of the component other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, more preferably 5 to 50% by weight. The reaction temperature is preferably from 0 to 200 ° C, more preferably from 50 to 150 ° C. The reaction time is preferably from 0.1 to 50 hours, more preferably from 0.5 to 20 hours. Preferred tetracarboxylic dianhydrides for synthesizing polylysine having the structure represented by the above formula (I) and its quinone imidized polymer, for example, an aliphatic tetracarboxylic dianhydride or an alicyclic tetracarboxylic acid Specific examples of the acid dianhydride and the aromatic tetracarboxylic dianhydride, -30-201100930 As the aliphatic tetracarboxylic dianhydride or the alicyclic tetracarboxylic dianhydride, for example, 1, 2, 3, 4 can be cited. Butane tetracarboxylic dianhydride, ethylene maleic acid dianhydride, iota, 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2 , 3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane alkyl acetate dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 4·(2, 5-tertiary oxytetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5-(2,5-di-oxo-tetrahydrofuran-3-yl)-3·methyl-3-cyclohexene -1,2-dicarboxylic anhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-0 tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3 , 5,6-tetracarboxylic dianhydride, 1,8-dimethylbicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, etc.; Examples of the carboxylic acid dianhydride include pyromellitic dianhydride, 3, 3', 4, 4 - benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-diphenyl maple tetracarboxylic dianhydride, 1,4, 5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenyldecanetetracarboxylic dianhydride, 3 , 3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy Diphenyl sulfide di-w anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium anhydride, 4,4, bis(3,4-dicarboxyphenoxy) Diphenylpropane dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, ethylene glycol bis(trimellitic acid) dianhydride, 4,4'-(1,4-stretch Benzene) bis(phthalic acid) dianhydride, 4,4,-(1,3-phenylene)bis(phthalic acid) dianhydride, 4,4'-(hexafluoroisopropylidene) di-ortho Phthalic anhydride, 4,4'-oxybis(1,4-phenylene)bis(phthalic acid) dianhydride, 4,4,-methylenedifluorene, 4·benzene) double Phthalic acid) dianhydride and the like. The -amine having the structure represented by the above formula (1) has the above formula 1-1) The structure shown in 201100930 is, for example, 3,5-diaminobenzoic acid 6-[3-(3-methoxy-4-butoxy) Phenyl phenyl) propylene fluorenyloxy] hexyl ester, 2-(2,4-diaminophenyl)ethyl (2E) 3-indole 4-[(4-(4,4,4,-trifluoro) Butoxy)benzhydryl)oxy]phenyl}acrylate; etc.; having the structure represented by the above formula (1-2-1), for example, has the following formula (I-2-D-1) to (I-2) -D-5) Compounds and the like respectively indicated, and these can be selected using at least one of them.

-32- 201100930

(I-2-D-1)

NH

Cfc>H2b+l

IK:

OCO-C

H \

H

OCO 0

CbH2b+i

H OCO—Q,

H

OCO

(I-2-D-4)

ChH bn2b+1 X:

OCO-C

H

H

OCO

(I-2-D-5) (In the above formula, ugly is an integer from 1 to 12, and b is an integer from 0 to 12) as a second used for synthesizing the above polylysine and its quinone imidized polymer As the amine, only a diamine having a structure represented by the above formula (I) or a diamine having a structure represented by the above formula (I) of -33 to 201100930 may be used in combination with other diamines. Ο

G, as another diamine which can be used here, an aliphatic diamine, an alicyclic diamine, and an aromatic diamine can be mentioned, and a specific example ' as an aliphatic diamine or an alicyclic diamine' can be mentioned, for example. Ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, Μ-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-decanediamine, 1,10-decanediamine, M1-undecanediamine, 1,12-dodecanediamine, α,α'-diamino-m-xylene, α,α '-Diamino-p-xylene, (5-amino-2,2,4-trimethylcyclopentyl)methylamine, ι,2-diaminocyclohexane, 4,4'-di Aminodicyclohexylmethane '1,3-1,3-(methylamino)cyclohexane, 4,9-dioxadecane-1,12-diamine, etc.; as an aromatic diamine, for example, 3,5-diaminobenzoic acid methyl ester, 3,5-monoaminobenzoic acid hexyl ester, 3,5-diamino benzoic acid lauryl ester, 3,5-diamino benzoic acid Propyl ester, 4,4,-methylenediphenylamine, 4,4'-ethylenediphenylamine, 4,4'-diamino-3,3,-dimethyldiphenylmethane' 3,3 ',5,5'-tetramethylbenzidine, 4,4 , diaminodiphenylphosphonium, 4,4,-monoamino-phenyl ether, 1,5-diaminonaphthalene, 3,3,-dimethyl-4,4'-diaminobiphenyl , 3,4'-diaminodiphenyl ether, 3,3,-diaminobenzophenone, 4,4, monoamino-benzophenone, 4,4'-diamine 2,2'-Dimethyldiphenyl, bis[4-(4-aminophenoxy)phenyl]anthracene 1,4-bis(4.aminophenoxy)benzene, anthracene-bis ( 4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,7-diaminoguanidine, 9,9-bis(4-aminophenyl)anthracene, 4,4,-methylenebis(2-chloroaniline), 4,4, bis(4-aminophenoxy)biphenyl, 2,2',5,5'-tetrachloro-4,4 '_Diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5,-dimethoxybiphenyl, 3,3'-di-34- 201100930 A Oxygen·4,4′-diaminobiphenyl, 4,4′-(1,4-phenylisopropylene)diphenylamine, 4,4′-(1,3-phenylene isopropylidene Diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenylpropane, 2,2-bis[3-(4.aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-methylphenyl]hexafluoropropane, 2,2-bis(4- Aminophenyl) hexafluoropropane, 2,2,-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4,-diamino- 2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-2,3,5,6,2 ',3',5',6'-octafluorobiphenyl hydrazine having a structure represented by the above formula (I) in combination with another diamine, the diamine having the structure represented by the above formula (I) is relatively It is preferable to use 10 mol% or more, and more preferably 20 mol% or more of all diamines. The above polyamic acid and its quinone imidized polymer can be synthesized according to a known method. For example, the polylysine is preferably obtained by reacting a mixture of a tetracarboxylic dianhydride and a diamine as described above at 40 to 100 ° C for 1 to 6 hours in a suitable solvent, thereby obtaining a polydecylamine. The above-mentioned quinone imidized polymer can be obtained by amidation of the acid by dehydration ring closure. The dehydration ring closure reaction for synthesizing the ruthenium iodide polymer can be carried out, for example, by heating (preferably at 60 to 250 ° C for 2 to 6 hours) or at a suitable dehydrating agent (for example, acetic anhydride, propionic anhydride, orthophthalic acid). In the presence of a formic anhydride, trifluoroacetic anhydride, etc.) and a dehydration catalyst (for example, trimethylamine, triethylamine, tributylamine, pyridine, hydrazine, hydrazine-dimethylaniline, lutidine, trimethylpyridine, etc.) It is preferably carried out easily at a temperature of from 90 to 120 ° C for 2 to 4 hours. When the polyamic acid and the polyimine obtained as described above are each made into a solution having a concentration of 10 -35 to 201100930% by weight, it is preferably a solution viscosity of 20 to 800 mPa·s, more preferably 30 to 500 mPa. s solution viscosity. The solution viscosity (mPa·s) of the polyamic acid and the polyimine is each a good solvent (for example, γ-butyrolactone, Ν-methyl-2-pyrrolidone, etc.) of the polymer, and the concentration is 1〇. % by weight of polymer solution 'The polymer solution was measured for enthalpy at 25 t using a Ε-type rotational viscometer. In the method for producing a liquid crystal display device of the present invention, first, a polymer film having the structure represented by the above formula (I) obtained as described above is formed on the substrate. For example, the pixel electrode having the azimuth direction of the regular tilted liquid crystal which is represented by the stripe pattern electrode structure described in Patent Document 9 (JP-A-2007-28664 1) is exemplified. Structure of the substrate. The structure of a preferred liquid crystal display element is shown in Figures 1 and 2. Fig. 1(a) is a schematic cross-sectional view showing the structure of the pixel 2 on the substrate surface in the normal direction, and Fig. 1(b) is a partial cross-sectional view taken along line AA of Fig. 1(a), and Fig. 2 is along the line A partial cross-sectional view taken along line BB of Fig. 1(a). The pixel electrode of the liquid crystal display element of the first (a) diagram is such that an η-channel TFT 16, a gate bus 6, a gate bus 4, and connection electrodes 12 and 14 are formed on the array substrate including the glass substrate 20. Stripe electrodes 8. A color filter layer 28 and a counter electrode 26 are formed on the opposite substrate including the glass substrate 30. As the substrate material, for example, a glass substrate having a thickness of about 0.7 mm can be cited. The plurality of stripe-shaped electrodes 8 are formed by extending from the central portion of the pixel to four directions (upper right, lower right, upper left, left -36 - 201100930). The electrode width L of the stripe electrode 8 is, for example, 3 // m, and the width S of the spacer 1 例如 is, for example, 3 /z m. The process of forming a polymer film on the substrate may be, for example, a solution in which a polymer having the structure represented by the above formula (I) is dissolved in a suitable solvent to form a solution (liquid crystal alignment agent), which is coated on the substrate. After that, the method of removing the solvent. The liquid crystal alignment agent used herein may contain, in addition to the polymer and the solvent having the structure represented by the above formula (I), other polymers, functional decane compounds, epoxy compounds, and the like, insofar as the target properties are not impaired. The other polymer is a polymer having no structure represented by the above formula (I), and examples thereof include polylysine having no structure represented by the above formula (I), and a ruthenium iodide polymer thereof, polyamine. Acid esters, polyesters, polyamines, polyorganosiloxanes, cellulose derivatives, polyacetal derivatives, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, poly As the (meth) acrylate derivative or the like, one or more kinds thereof can be appropriately selected and used. 〇 As the other polymer in the present invention, at least one selected from the group consisting of polylysine and its quinone imidized polymer and polyorganosiloxane is preferred. The polyamic acid which does not have the structure represented by the above formula (I) can be obtained by reacting a tetracarboxylic dianhydride with the above other diamine. By dehydrating and ring-closing the polyamic acid, a ruthenium iodide polymer having no structure represented by the above formula (I) can be obtained. The polyorganosiloxane having no specific structure can be obtained by hydrolyzing and condensing at least one selected from the group consisting of a decane compound having an epoxy group and a hydrolyzable group as described above and another decane-37-201100930 compound. . Those skilled in the art are aware that their synthesis can be carried out based on the above examples. The preferred use ratio of the other polymers differs depending on the kind of the polymer having the structure represented by the above formula (1). The polymer having the structure represented by the above formula (I) is a (meth)acrylic acid derivative, a styrene derivative, an ethyl cyanoether 'vinyl ester or an unsaturated carboxylic acid derivative having a structure represented by the above formula (1). In the case of the (co)polymer, the ratio of use of the other polymer to the total weight of the polymer having the structure represented by the above formula (I) and the total weight of the other polymer is preferably 30% by weight or less, more preferably 15% by weight. the following. When the polymer having the structure represented by the above formula (1) is a polyorganosiloxane having the structure represented by the above formula (1), the ratio of use of the other polymer to the polymer having the structure represented by the above formula (I) and other polymers The total weight is preferably 95% by weight or less, more preferably 90% by weight or less, and particularly preferably 75% by weight or less. In this case, the other polymer ' is preferably at least one of the polyaminic acid and the quinone imidized polymer having the structure represented by the above formula (1). The polymer having the structure represented by the above formula (1) is at least one selected from the group consisting of polylysine having a structure represented by the above formula (1) and a brewed imidized polymer I, and other polymers. The total weight of the polymer and other polymers having a structure represented by the above formula (1) is preferably 5 〇m or less, more preferably 2 重量% or less, and particularly preferably no other polymer is used. -38- 201100930 The above functional decane compound and epoxy compound can be used to improve the adhesion to the substrate surface of the polymer film, respectively. As such a sex decane compound, for example, 3-aminopropyltrimethoxyindole-3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecylaminopropyltriethoxylate can be cited. Base decane, N-(2-aminoethyl)-3-aminopropyloxydecane, N-(2-aminoethyl)-3-aminopropylmethyl dimethyl oxide, 3 - Acid urea-propyl dimethoxy sand, 3 - propyl propyl triethoxy sand N-ethoxycarbonyl-3-aminopropyl trimethoxy decane, N-ethoxycarbonyl; hydrazine Propyltriethoxydecane, N-triethoxycarbamidopropyltritriamine, N-trimethoxycarbamidopropyltriethylenetriamine, ι〇_trimethylformamidin-1,4, 7-Triazadecane, 10-triethoxymethane alkyl-1 triazanonane, 9-trimethoxycarbamido-3,6-diazoguanidinic acid 9-diethoxymethyl院-3,6-N-N-mercaptoacetic acid vinegar, N-nodal 3-propyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecanephenyl-3-amine Propyltrimethoxydecane, N-phenyl-3-aminopropyltridecyldecane, N-bis(oxyethylene)-3-aminopropyltrimethoxydecane (Oxyethylene) -3-aminopropyl triethoxy silane-like. Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol glyceryl ether, propylene glycol diglycidyl ether, tripropylene glycol dimethyl condensate, and polypropylene glycol diglycidyl ether. , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5, 6-tetrahydro-glycol-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, monofunctional alkane', 2-trimethyldecane, m-3 - Vinyloxy, 4,7-ester, Amine, N-ethoxy N-dual diglycidyl glycerol: Ether, oil base 1,3- -39- 201100930 Bis(N,N-diglycidylamine Methyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl) Aminopropyltrimethoxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, and the like. The blending ratio of the functional decane compound and the epoxy compound is preferably 40 parts by weight or less, more preferably 40 parts by weight or less, based on 100 parts by weight of the polymer having the structure represented by the above formula (I) and other polymers. It is 1.1~30 parts by weight. When the polymer is a (co)polymer having a (meth)acrylic acid derivative having a structure represented by the above formula (1), examples of the solvent used herein include alcohols, ethers, glycol ethers, and ethylene glycol alkyl groups. Ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate 'propylene glycol alkyl acid propionate, aromatic hydrocarbon, ketone, ester, and the like. Specific examples thereof include, as the alcohol, methanol, ethanol, benzyl alcohol, phenethyl alcohol, 3-phenyl-fluorene-propanol, etc.; hydrazine as an ether, for example, tetrahydrofuran; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.; as ethylene glycol alkyl ether acetate, for example, methyl sesaacetic acid vinegar, ethyl serosu acetate, ethylene glycol monobutyl Ether acetate, ethylene glycol monoethyl ether acetate, etc.; as diethylene glycol, for example, diethylene glycol monomethyl ether 'diethylene glycol monoacetic acid, - ethylene glycol dimethyl ether, diethylene glycol two Ethyl ether, diethylene glycol ethyl methyl ether, etc.; -40- 201100930 as dipropylene glycol 'for example, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl As the propylene glycol monoalkyl ether, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.; as propylene glycol alkyl ether propionate, for example, propylene glycol methyl ether acetate Ester, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, Propylene glycol butyl ether acetate or the like; as propylene glycol alkyl ether acetate, for example, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionic acid Examples of the aromatic hydrocarbons include toluene, xylene, and the like; and the ketones are, for example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and the like; , ethyl acetate, propyl acetate, butyl acetate, ethyl 2-propionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, hydroxyacetic acid Methyl ester, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-propylpropionate, ethyl 3-hydroxypropionate, 3-hydroxypropyl Propyl propyl ester ' 3 butyl cyanopropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, methoxyacetic acid Butyl ester, ethoxyacetic acid methyl vinegar, ethoxyacetic acid ethyl ester, ethoxy propyl acetate, butyl ethoxy acetate, methyl propoxyacetate, propoxyacetic acid , propoxy-41- 201100930 propyl acetate, butyl oxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, acetic acid 3- Methoxybutyl ester, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2-ethoxy Methyl propyl propionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxy Ethyl propyl propionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methyl Propyl oxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3- Butyl ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3- Esters such as methyl butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate. Among them, preferred are ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether or propylene glycol alkyl ether acetate, of which particularly preferred is diethylene glycol dimethyl ether. , diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate or 3-methoxybutyl acetate. The above solvents may be used singly or in combination of two or more. The polymer is a polyorganosiloxane having the structure represented by the above formula (I), which does not contain another polymer, or when the other polymer is a polyorganosiloxane having no structure represented by the above formula (1), as the above organic solvent, for example Examples thereof include 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl-42-201100930 ether, Dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl race), ethylene glycol Monopentyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl sarprosone acetate, ethyl stilbene acetate, propyl ceramide acetate, butyl succinate Ester, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propanol acetate, isopropanol acetate, n-butanol acetate, isobutanol acetate, diacetate acetate Alcohol, n-pentyl acetate, secondary pentanol acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, vinegar

Q acid 2-ethylhexyl ester, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate, N-methyl-2-pyrrolidone, r-butyrolactone , ethylene glycol-n-butyl ether (butyl siroli) and the like. The polymer is at least one selected from the group consisting of polylysine having a structure represented by the above formula (I) and a quinone imidized polymer thereof, or the polymer is represented by the structure represented by the above formula (I) When the polyorganosiloxane and the other polymer are at least one selected from the group consisting of polylysine having a structure represented by the above formula (I) and a quinone imidized polymer thereof, as the above organic solvent, for example Examples thereof include N-methyl-2-pyrrolidone, r-butyrolactone, r-butyrolactam, ν, ν-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, 4-hydroxyl -4·methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, 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 monomethyl ether, diethylene glycol monoethyl ether, -43- 201100930 diethylene glycol monomethyl ether acetate, two Ethylene glycol monoethyl ether acetate, 3 -butoxy-indole, hydrazine-dimethylpropanamide, 3-methoxy-hydrazine, hydrazine-dimethylpropanamide, 3-hexyloxy-oxime, hydrazine-dimethylpropanamide, etc. . Among them, from the viewpoint of exhibiting good printability, 3-butoxy-oxime, Ν-dimethylpropanamide, 3·methoxy-oxime, Ν-dimethylpropanamide, 3-hexyl group are particularly preferable. Oxy-indole, hydrazine-dimethylpropanamide.

The solid content concentration in the liquid crystal alignment agent (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) is preferably from 1 to 15% by weight, more preferably from 1 to 10% by weight. The liquid crystal alignment agent may be applied to the substrate by a suitable coating method such as a spin coating method, an offset printing method, a dipping method, a dropping method, or an inkjet printing method. Then, the solvent is removed by heating to form a film made of a polymer on the substrate. The heating performed here can be, for example, pre-baked at 50 to 12 (TC for 0.1 to 5 minutes), and for example, at 80 to 300 ° C, preferably 120 to 250 ° C, for example, 5 to 200 minutes, preferably. It is post-baked for 10 to 100 minutes. The post-baking is preferably carried out using a circulating cleaning oven, an IR oven or a hot plate. After the majority of the solvent in the liquid crystal alignment agent is removed in the above prebaking, after passing through The baking film can completely remove the solvent. The film thickness of the coating film formed here is preferably 0.001 to 1 # m, more preferably 0.005 to 0.5; α m. Therefore, two substrates having a polymer film are prepared, and then An example in which a nematic liquid crystal having a negative dielectric anisotropy is sandwiched between the respective films of the two substrates as a nematic liquid crystal-44 - 201100930 which can be used here as a negative dielectric anisotropy, for example, The liquid crystals described in Patent Documents 10 to 37 and the like. The nematic liquid crystal having a negative dielectric anisotropy is sandwiched between the polymer films of the two substrates, and can be, for example, a vacuum injection method or a liquid crystal dropping method. Liquid crystal is dropped on the substrate and then bonded to another substrate The gap of the polymer film, that is, the thickness of the liquid crystal layer is preferably 2 to 6 μm, more preferably 3 to 5 # m. Next, 'a voltage is applied between the transparent pixel electrodes of the two substrates. The liquid crystal cell can be produced by irradiating light in a state in which the liquid crystal is aligned. The voltage applied here varies depending on the dielectric anisotropy of the liquid crystal used, for example, 10 to 50 V. The voltage applied here may be a direct current voltage. It may also be an alternating voltage. As the irradiated light, a high-pressure mercury lamp or a metal halide or the like is preferably used as a light source for the unpolarized ultraviolet light, and more preferably it includes a bright line of ultraviolet light in a wavelength range of 2 80 to 3 50 nm. The amount of irradiation at a wavelength of 313 nm is preferably 1,500 Å/m 2 or more, less than 10 Å, 〇〇 0 Å/m 2 , and more preferably 1,000 50,000 50,000 J/m 2 . In the method described in the Patent Application Publication No. 2009/03 2545, it is necessary to irradiate light of about 10,000,000 J/m 2 , but in the method of the present invention, the amount of light irradiation is 50,000 Å/m 2 or less, and further, 10 000 The desired liquid crystal display can be obtained below J/m2 In addition to reducing the manufacturing cost of the liquid crystal display device, it is also possible to avoid a decrease in electrical characteristics caused by strong light irradiation and a decrease in long-term reliability. The temperature at the time of light irradiation is preferably less than the isotropic temperature of the liquid crystal - 45-201100930 Irradiation at a temperature of, for example, 20 to 60 ° C, preferably 25 to 50 ° C. The liquid crystal display element of the present invention can be obtained by disposing a polarizing plate on both surfaces of a liquid crystal cell produced in this manner. In addition to the polarizing plate, a wavelength plate, a light-scattering film, a driving circuit, and the like can be further mounted on the liquid crystal display element. The liquid crystal display element of the present invention produced as described above is excellent in liquid crystal alignment property and electrical characteristics, and is suitably used in various types of devices, such as a moving image display device typified by a liquid crystal television or the like. EXAMPLES Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited to the examples. The weight average molecular weight in the following examples is a polystyrene-converted oxime measured by gel permeation chromatography according to the following conditions.

Column: TSKgelGRCXLII manufactured by Tosoh Co., Ltd. Solvent: tetrahydrofuran® Temperature: 40 ° C Pressure: 68 kgf/cm 2 The epoxy equivalent is determined according to the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105. <Synthesis of diamine having the structure represented by the above formula (I)> 3,5-diaminobenzoic acid 6-[3-(3-methoxy-4-butoxy) used in the following synthesis examples Phenyl phenyl) propylene fluorenyl oxy hexyl acrylate (compound represented by the following formula) is synthesized by the method described in JP-A-2003-520878-46-201100930. Ch3o' ch3(ch2)3o

C Η

H

C-COO-(CH2)6〇CO

Synthesis Example 1 A compound (D-1) was synthesized according to the first scheme of the following synthesis scheme.

-47- 201100930

HOCO—CH NO, bh3*thf hoch2ch2 N02 NO, Ο cf3(ch2)3o_

CF3(CH2)3〇. ~O~c〇0

H

, C-COOH

C〇〇~〇-<H

H c-coo-ch2ch2

NO, NO, (D_1a)

Zn, FeCl3a6H2〇 Ο CF3(CH2)3〇 '~0^c〇〇O_((

H c-coo-ch2ch2

NH, NH, (D_1) Synthetic route Figure 1 Dissolve 22.6 g (100 mmol) of 2,4-dinitrophenylacetic acid in 150 mL of tetrahydrofuran, and add 300 mL of borane containing 1.0 mol/L in 2 hours. A THF solution of THF (tetrahydrofuran) complex (in terms of the amount of borane THF complex equivalent to 300 mmol). After stirring at 25 t for 3 hours, 200 mL of water was slowly added. Ethyl acetate was added to the obtained solution for extraction, and the organic layer was washed with water -48-201100930, dried over sodium sulfate, and concentrated on a rotary evaporator and dried to give a crude product. The obtained crude product was used as a developing solvent using a mixed solvent of toluene:ethyl acetate=1:1 (volume ratio), and purified by a column packed with 400 g of tannin, and further by a mixed solution of ethyl acetate and hexane. Recrystallization gave 20.7 g of 2-(2,4-dinitrophenyl)ethanol (yield 98%). 2.5 g (11.8 mmol) of 2-(2,4-dinitrophenyl)ethanol obtained above, 4.65 g (11.8 mmol) of (2 £) 3-{4-[(4-(4,4, 4,-Trifluorobutoxy)benzhydryl)oxy]phenyl}acrylic acid and 144 mg (1.2 mmol) of 4-dimethylaminopyridinium were dissolved in 30 mL of dichloromethane and cooled to 0 °C. At this temperature, 2.48 g (13.0 mmol) of the hydrochloride salt of N-(3-dimethylaminopropyl)-indole-ethylcarbodiimide was added thereto, followed by stirring at 0 ° C for 1 hour. . Then, the reaction mixture was warmed to room temperature, and stirred at room temperature for 22 hours to carry out a reaction. Methylene chloride and water were added to the obtained reaction solution for extraction and washing, and the organic layer was washed with water, dried over sodium sulfate, and then concentrated and evaporated to give a crude product. The obtained crude product was purified by using a mixed solvent of toluene:ethyl acetate=95:5 (volume ratio) as a developing solvent through a column packed with 200 g of tannin, using a mixed solution of ethyl acetate and hexane. Recrystallization, 4.93 g of compound (D-la) (2-(2,4-dinitrophenyl)ethyl(2E)3-{4-[(4-(4,4,4,-trifluoro)) Butoxy)benzhydryl)oxy]phenyl}acrylate) (yield 71%). 4.93 g (8.38 mmol) of the compound (D-la) obtained above was dissolved in a mixed solution of 50 mL of N,N-dimethylformamide and 6 mL of water. At this time, 13.9 g (51.4 mmol) of ferric chloride hexahydrate-49-201100930 and 5.6 g (85.7 mol) of zinc powder were added in portions over 60 minutes, and the reaction was carried out for 2 hours. Ethyl acetate and water were added to the reaction mixture, and after extraction and washing, impurities were removed by filtration to separate an organic layer. The organic layer was washed with water, dried over sodium sulfate, and then evaporated and evaporated. The obtained crude product was purified by using a mixture of toluene:ethyl acetate = 1:3 (volume ratio) as a developing solvent, with a column packed with 200 g of tannin, and further mixed with ethyl acetate. The solution was recrystallized to obtain 3.01 g of compound (Dl) (2-(2,4aminophenyl)ethyl(2E)3-{4-[(4-(4,4,4,-trifluorobutoxy) Benzyl hydrazino]phenyl} acrylate). Synthesis Example 2 Synthesis of Compound (D-2) according to the following synthesis scheme 2 (1) and (2) 5 5 Cyclone and Oxygen

-50- 201100930 Synthetic Route 2 (1) Ο

Into a 1 L three-necked flask equipped with a thermometer, a drip Shanghai, a hopper and a nitrogen introduction tube, 49 g of a compound (D-2A), 33 g of potassium carbonate, 6.4 g of tetrabutylammonium bromide, 200 mL of water and 100 mL of tetrahydrofuran were added. At 5. (: The following was ice-cooled. A solution of 60 mL of tetrahydrofuran and 19 g of acrylonitrile chloride was added dropwise with a dropping funnel over 30 minutes while stirring, and the reaction was further stirred for 1 hour. After the reaction was terminated, ethyl acetate was added to the reaction mixture. The obtained organic layer was washed once with dilute hydrochloric acid, washed with water three times, dried over magnesium sulfate, and then evaporated under reduced pressure - 51-201100930 to obtain a solid of 60 g of compound (D-2B). 60 g of this compound (D-2B) was added to a 3 L three-necked flask of the introduction tube and the cooling tube, and further, 44 g of 4-iodophenol, 2 L of N,N-dimethylformamide, 28 mL of triethylamine and 4.6 g of tetrakistriphenylphosphine palladium was stirred at 90 ° C for 2 hours. After cooling to room temperature, hydrazine was added, ethyl acetate was added to the filtrate, and the obtained organic layer was washed once with dilute hydrochloric acid, using water. After washing three times, it was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to give a crude product of compound (D-2C). The crude product was recrystallized from a mixed solvent of ethanol and tetrahydrofuran to obtain 55 g. The compound (D-2C) was white crystals. A 1 L three-necked flask equipped with a thermometer, a nitrogen introduction tube and a dropping funnel was charged with 55 g of the compound (D-2C)' and further added 23 g of potassium carbonate, 4.5 g of tetrabutyl bromide, 100 mL of tetrahydrofuran and 200 mL of water. , ice-cold at below 5 ° C. While stirring, use a dropping funnel to add 32 g of a solution of 3,5-dinitrobenzidine and tetrahydrofuran in a solution of 15 〇m L for 30 minutes or more, and stir for 1 Ο. After the reaction is terminated, the organic layer obtained by adding ethyl acetate to the reaction mixture is washed once with dilute hydrochloric acid, and washed three times with water. After drying with magnesium sulfate, the solvent is removed under reduced pressure. Crude product of the compound (D-2D). The crude product 'recrystallized from a mixed solvent of ethanol and tetrahydrofuran' gave pale yellow crystals of 65 g of compound (D-2D). 65 g of the compound (D-2D) was added to a 2 L eggplant-shaped flask, and 250 g of tin chloride dihydrate and il acetate B-52-201100930 ester were added to carry out the reaction under reflux for 4 hours. After the reaction was terminated, the reaction was carried out. Wash the reaction mixture twice with potassium fluoride solution, use After washing three times, the solvent was removed under reduced pressure to obtain a crude product. The crude product was recrystallized from a mixed solvent of ethanol and tetrahydrofuran to obtain 23 g of a white crystal of compound (D 2 ). Synthesis of Carboxylic Acid of Structure (I) > Synthesis Example 3

The compound (c_u) was synthesized according to the third scheme of the following synthetic scheme.

〇Synthesis Route Figure 3 In a three-necked flask of a 10 mL flask equipped with a reflux tube and a nitrogen introduction tube, 7.8 g of the compound obtained in the same manner as in the above-mentioned Synthesis Scheme 2 (Fig. 2) was added (D- 2C), 4.0 g of succinimide anhydride, 0.30 g of hydrazine, hydrazine-dimethylaminosuccinic acid, 4 〇mL of ethyl acetate and 3.4 mL of triethylamine were reacted under reflux for 8 hours. The reaction was washed once with dilute hydrochloric acid and then washed three times with water. The mixture was dried with magnesium sulfate. The solvent was removed under reduced pressure to give a crude product. -53-201100930 This crude product was recrystallized from ethyl acetate to give white crystals of 7.9 g of Compound (C-1). &lt;Synthesis of polyorganic electrification chamber having epoxy group&gt; Synthesis Example 4 Adding 100-0 g of 2-(3,4-ring) in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux cooling tube Oxycyclohexyl)ethyltrimethoxydecane, 500 g of methyl isobutyl ketone and 1 〇g of triethylamine were cooled to room temperature. Then, i〇〇g of deionized water was added dropwise thereto over 30 minutes using a dropping funnel, and the mixture was refluxed and reacted at 80 ° C for 6 hours. After the reaction was terminated, the organic layer was taken out from the reaction mixture, and washed with a 0.2% by weight aqueous solution of ammonium nitrate until the water after washing was neutral, and the solvent and water were distilled off under reduced pressure to obtain an epoxy group-containing polycondensation liquid. Organic germanium oxide EPS-1. The polyorganooxynonane EPS-1 was subjected to 1H-NMR analysis, and the theoretical strength of the peak was determined based on the epoxy group in the vicinity of the chemical shift (5) = 3.2 ppm, and it was confirmed that the epoxy group was not caused in the reaction. reaction. The polyorganooxynonane EPS-1 had a weight average molecular weight Mw of 2,200 and an epoxy equivalent of 186 g/mole. &lt;Synthesis of a polymer having the structure represented by the above formula (I)&gt; Synthesis Example 5 0.500 g (1.032 mmol) of 3,5-diaminobenzoic acid 6-[3-(3) was dissolved in 3.1 mL of tetrahydrofuran. -Methoxy-4-butoxyphenyl)propenyloxy]hexyl ester, at which time 182.1 mg (〇.9285 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added. Stir at 0 ° C for 2 hours. Next, -52-201100930 20.2 mg (0.1 030 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was further added and reacted at room temperature (23 ° C) for 22 hours. To the obtained reaction mixture, 3.5 mL of tetrahydrofuran was added, and all of them were added to 200 mL of diethyl ether, and the resulting precipitate was recovered. The obtained precipitate was redissolved in 10 mL of tetrahydrofuran, reprecipitated with 600 mL of water, and dried at room temperature for 24 hours under reduced pressure to obtain 0.61 g of polylysine (Polymer A) having the structure represented by the above formula (I). powder. Synthesis Example 6 Instead of 3,5-diaminobenzoic acid 6-[ 3-(3-methoxy-4-butoxyfluorene&quot;phenyl)propenyloxy]hexyl ester, except that the above synthesis example was used. In the same manner as in the above Synthesis Example 2, except that 〇.545 g (1.032 mmol) of the compound (D-1) obtained in 1 was obtained, 0.63 g of a polylysine (polymer B) powder having the structure represented by the above formula (I) was obtained. . Synthesis Example 7 Into a 200 mL three-necked flask equipped with a reflux tube, 10 g of the polyorganooxane EPS-1 having an epoxy group obtained in the above Synthesis Example 4, and 13 g of the (Cl) obtained in the above-mentioned oxime synthesis example 3 were added. 92 g of methyl isobutyl ketone and 1.0 g of tetrabutylammonium bromide were reacted at 8 (TC for 12 hours. After the reaction was terminated, the reaction mixture was poured into a large amount of methanol, and the resulting precipitate was recovered and dissolved therein. In the ethyl acetate, the obtained solution was washed three times with water, and the solvent was removed under reduced pressure to obtain a polyorganosiloxane (Polymer C) having the structure represented by the above formula (I). Synthesis Example 8 30 g was used. The compound (D-2) obtained in the above Synthesis Example 2 of 2,3,5-tricarboxycyclopentylacetic acid dianhydride of tetracarboxylic dianhydride and 7 g of diamine is dissolved in -55-201100930 400 g of N -methyl-2-pyrrolidone in which 'reaction at 60 ° C for 6 hours' yields a solution containing 20% by weight of polylysine (Polymer D) having the structure represented by the above formula (I). The solution viscosity of the acid solution was UOOmPa·3 ° &lt;Synthesis of other polymers&gt; Synthesis Example 9 196 g (l. 〇mol) was used as the tetracarboxylic acid 1,2,3,4-cyclobutanetetracarboxylic dianhydride of anhydride and 212 g (1.0 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl as diamine The reaction was carried out in 3,67 Og of N-methyl-2-pyrrolidone at 40 ° C for 3 hours to obtain a solution containing 10% by weight of other polymer, polylysine (polymer r). The solution viscosity of the solution was 170 mPa·s. &lt;Preparation of liquid crystal alignment agent and production and evaluation of liquid crystal display element&gt; Example 1 [Preparation of liquid crystal alignment agent] The polymer A synthesized in the above Synthesis Example 5 was dissolved in In N-methyl-2-pyrrolidone and butyl sarprosone, the solvent composition is N-methyl-2-pyrrolidone: ® butyl 赛路苏 = 50:50 (weight ratio), and the solid concentration is 3.0. A solution of a weight %. The solution was filtered through a filter having a pore size of 1 Am to prepare a liquid crystal alignment agent. <Evaluation of Liquid Crystal Display Element (1)&gt; [Manufacture of Liquid Crystal Display Element] ITO film structure with a stripe pattern The liquid crystal alignment agent prepared in the above embodiment was coated on the transparent electrode surface of the glass substrate of the transparent electrode by a spin coater, and was preliminarily prepared under a hot plate of 8 (TC). After calcination for 1 minute, it was heated at 200 ° C for 1 hour in an oven in a furnace by a nitrogen gas to form a polymer film (liquid crystal alignment film) having a film thickness of 0.1 μm. The same operation was repeated. A pair of (two pieces) of a substrate having a liquid crystal alignment film is obtained. On the outer periphery of the surface of the liquid crystal alignment film having one of the above substrates, epoxy bonding of alumina balls having a diameter of 5.5 /zm is applied by screen printing. After the agent, the two substrates were placed so that the liquid crystal alignment film faces of the pair of substrates faced each other, and the pressure was applied, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, _ negative liquid crystal (manufactured by Merck Corporation, trade name "MLC-6608") was placed in the gap between the two substrates through the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy-based adhesive. Further, in order to remove the flow alignment during liquid crystal injection, the film was heated at 150 ° C until it was gradually cooled to room temperature, and then a DC voltage of 32 V was applied thereto, and a high-pressure mercury lamp was used to irradiate the unpolarized ultraviolet light to form a liquid crystal. On the outer side surfaces of the substrate, two polarizing plates were bonded to each other so that the polarization directions thereof were perpendicular to each other, and a liquid crystal display element was produced. The liquid crystal display element was evaluated as follows. The evaluation results are shown in Table 1. (1) Evaluation of liquid crystal alignment property In the liquid crystal display device produced as described above, a region where there is no abnormality in brightness and darkness when the voltage of 5 V is 〇Ν·OFF (applied/released) is visually observed. When the voltage is OFF, no light leakage is observed from the cell, and the cell drive region is white when the voltage is applied. In the case where there is no light leakage in the other region, the liquid crystal alignment is "good", and when the voltage is OFF, the light leakage or voltage is observed from the cell. When the on is observed, the light leakage is observed from the area other than the cell drive region as the liquid crystal-57-201100930. (2) Evaluation of voltage holding ratio On the liquid crystal display element manufactured above, a voltage of 5 V was applied at 60 ° C for an application time of 60 μsec and an interval of 167 msec, and then the measurement was released from 1 6 7 . The voltage holding ratio after milliseconds. The voltage holding rate measuring device was manufactured by TOYO Corporation, and the model was "VHR-Γ. When the voltage holding ratio was 98% or more, the voltage holding ratio was evaluated as "good". When it was 98% or less, it was evaluated as "bad." 〇_ &lt;Evaluation of liquid crystal display element (2) &gt; Using the liquid crystal alignment agent prepared above, changing the pattern of the transparent electrode (two kinds) and the amount of ultraviolet irradiation (three kinds of levels), a total of six liquid crystal display elements were produced. [Evaluation of the liquid crystal cell having a transparent electrode without a pattern] Using a liquid crystal alignment film printer (manufactured by Nippon Photoprint Co., Ltd.), a transparent electrode surface of a glass substrate having a transparent electrode made of an IT0 film The liquid crystal alignment agent prepared above was coated on a hot plate at 80 ° C for 1 minute (prebaked). After removing the solvent, it was heated on a hot plate at 150 ° C for 10 minutes (post baking) to form an average film thickness. Coating film of 600 A. The coating film was rubbed by a friction machine having a roll with a crepe roll at a roll speed of 40 rpm, a layer moving speed of 3 cm/sec, and a pile length of 〇.lmm. Then, ultrasonic cleaning was performed for one minute in ultrapure water, and then dried in a TC cleaning oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two pieces) having The liquid crystal is supplied to the substrate of the film. In addition, the rubbing treatment may be a weak rubbing treatment by controlling the liquid crystal to be poured in a simple manner, and then the weak rubbing treatment may be performed on one of the pair of substrates. On the outer edge of the surface of the liquid crystal alignment film, an epoxy resin adhesive having a diameter of 5.5/m is applied, and the liquid crystal alignment film surfaces of the pair of substrates are relatively overlapped and pressurized to make the adhesive. Then, a nematic liquid crystal (MLC-6608, manufactured by Merck) was placed between a pair of substrates close to the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic acid photocurable adhesive to produce a liquid crystal cell. The above operation was repeated to manufacture three liquid crystal cells having a transparent electrode without a pattern, and one of them was supplied as it is to the pretilt angle evaluation described later. For the remaining two liquid crystal cells, The following method provides light to a pretilt angle in a state where a voltage is applied between the conductive films, and is supplied to the pretilt angle. For each of the liquid crystal cells obtained above, an alternating voltage of 10 V is applied between the electrodes at a frequency of 60 Hz, in the liquid crystal. In the driven state, the light source is irradiated with an ultraviolet irradiation device of a metal halide lamp with an ultraviolet ray of 10,00 (U/m2 or 100,000)/m2. The irradiation amount is based on a wavelength of 365 nm. Measurement of 値 measured by the illuminometer - Evaluation of pretilt angle - For each of the liquid crystal cells manufactured as described above, based on Non-Patent Document 1 (TJ Scheffer et al., J. Appl. Phys. νο. 19, p. 2013 (1980) The method described in the method of using He-Ne laser, the 値 of the angle at which the substrate surface of the liquid crystal molecules measured by the crystal rotation method is inclined is used as the pretilt angle. -59- 201100930 The pretilt angles of the liquid crystal cells which were not irradiated with light, the liquid crystal cell having an irradiation amount of 1,000 J/m 2 , and the liquid crystal cells having an irradiation amount of 1,00,00 0 J/m 2 are shown in Table 1. [Production of Liquid Crystal Cell Having Patterned Transparent Electrode] On each electrode surface of two glass substrates each having an ITO electrode (the electrode is patterned in a slit shape as shown in FIG. 3 and partitioned in a plurality of regions) The liquid crystal alignment agent prepared above was applied by using a liquid crystal alignment film printing machine (manufactured by Japan Photo Printing Co., Ltd.), and heated on a hot plate at 80 ° C for 1 minute (prebaked) to remove heat and heat at 150 ° C. The plate was heated for 10 minutes (post-baked), and Ο λ formed a coating film having an average film thickness of 600 Å. The coating film was subjected to ultrasonic cleaning for 1 minute in ultrapure water, and then dried in a 10 (TC cleaning oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two pieces). a substrate having a liquid crystal alignment film. Next, an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is applied to one of the pair of substrates on the outer edge of the surface having the liquid crystal alignment film, and then The liquid crystal alignment film surfaces of the pair of substrates are opposed to each other, and the adhesive is cured to cure the adhesive. Then, after nematic liquid crystal (Mell-6, MMC-6608) is filled between a pair of substrates close to the liquid crystal injection port, The liquid crystal cell was fabricated by sealing the liquid crystal injection port with an acrylic photocurable adhesive. The above operation was repeated to fabricate three liquid crystal cells having an imaged transparent electrode, and one of them was supplied as it is to the evaluation of the response speed described later. Two liquid crystal cells are passed through the same method as in the above-described liquid crystal cell having a transparent electrode having no pattern, and 10,000 J/m 2 or 100,000 J/ is applied in a state where a voltage is applied between the conductive films. The irradiation amount of m2 is supplied to the evaluation of the response speed of -60-201100930 after the light irradiation. - Evaluation of the response speed - Each liquid crystal cell manufactured above is sandwiched between a pair of polarizing plates arranged on a crossed Nicols mirror, Then, first, the visible light lamp was irradiated without applying a voltage, and the brightness of the light transmitted through the liquid crystal cell was measured with a light multimeter, and the enthalpy was used as a relative transmittance of 0%. Then, a 60 V alternating voltage was applied between the electrodes of the liquid crystal cell for 5 seconds as described above. The transmittance at the time of the clock is as a relative transmittance of 1%. At this time, when a 60 V AC voltage is applied to each liquid crystal cell, the time from the transition of 10% to 90% is determined as the time of the transmittance. The response speed was evaluated. The liquid crystal cell which did not emit light, the irradiation amount l〇, 〇〇 (the liquid crystal cell of H/m2 and the respective response speed of the liquid crystal cell of the irradiation amount of 100,000 J/m 2 are shown in Table 1. Example 2 In the preparation of the liquid crystal alignment agent and the polymer A, the liquid crystal alignment was prepared in the same manner as in the above Example 1 except that the polymer B synthesized in the above Synthesis Example 6 and the polymer D^ synthesized in the above Synthesis Example 8 were used, respectively. Agent' use them Various liquid crystal display elements were produced and evaluated. The evaluation results are shown in Table 1. Example 3 The solution containing the polymer r obtained in the above Synthesis Example 9 was equivalent to 90 parts by weight in terms of the polymer r. One part by weight of the polymer C' synthesized in the above Synthesis Example 7 was further added, and N-methyl-2-pyrrolidone and butyl sirolimus were added to prepare a solvent composition of N-methyl-2-pyrrolidone. : butyl 赛路苏苏 = 50:50 (weight ratio), a solid concentration of 3.0% by weight of the solution. The -61-.201100930 solution was filtered with a filter having a pore size of l / / m to prepare a liquid crystal alignment agent. The liquid crystal alignment agent prepared above was produced by evaluating various liquid crystal display elements. The evaluation results are shown in Table 1. Example 5 In the above Example 3, a liquid crystal alignment agent was prepared in the same manner as in Example 3 except that the amounts of the polymer r and the polymer C described in Table 1 were used. Various liquid crystal display elements were produced using this liquid crystal alignment agent, and evaluation was carried out. The evaluation results are shown in Table 1. Comparative Example 1 This comparative example is a comparative example based on Patent Document 6 (JP-A-2002-23199). In the production of a liquid crystal display device, a commercially available product manufactured by JSR Corporation, trade name ULIS-684) is used as a liquid crystal alignment agent, and liquid crystal sandwiched between a pair of substrates is used, in addition to liquid crystal O "MLC6608" manufactured by Merck. Various liquid crystal display elements were produced and evaluated in the same manner as in Example 1 except that a product of a compound represented by the following formula was mixed in an amount of 0.3% by weight. The evaluation results are shown in Table 1.

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Evaluation result evaluation (2) I $ _ 1 i 113⁄4 , response speed (milliseconds) UV exposure (J/m2) § 8 νη cn \〇cn cn CO cn cn 1 CO CO ο ΓΛ cn § g moth mg B 灿 ms 蚺m mK ϋ 1 Pretilt angle (degrees) UV exposure (J/m2) i 8 l ·Η 88.8 88.9 r &lt; 〇〇00 οό oo 1 1 88.2 88.3 10,000 89.2 1—^ 〇\ oo 88.5 οό oo i 88.6 89.4 ο 89.7 ί 89.7 89.8 89.7 89.8 89.8 Ί 电压 Good voltage retention rate 1 i Good "Good 1_ Γ Good poor liquid crystal alignment good Γ Good good Good good Good liquid crystal alignment agent ___1 I Other polymer amount (parts by weight) 〇ο Ο Ο JALS-684 Category 1 I Polymer r • Polymer r S 尔 姬 ms ms 擗m thief volume (parts by weight) 〇ι-*Η 8 t-Η 〇Ο % Η sm itfmt Polymer A Polymer B Polymer C Polymer D Polymer D Example 1 Example 2 Example 3 Example 4 Example 5 201100930 From the results of Table 1, it is understood that in the method of the present invention, the pretilt angle obtained by controlling the ultraviolet irradiation amount to 100,000 J/m 2 is obtained. Too much extent, at 10, ΟΟΟΙ/m2 or A suitable pretilt angle can be obtained at the following irradiation amount, and a sufficiently rapid response speed can be obtained even when the irradiation amount is small, and the voltage holding ratio is also excellent. Further, the use of the above-described Examples 1 to 5 is used. Each of the polymer compositions was changed and patterned in the same manner as in Example 1 except that the pattern of the ITO electrode included in the glass substrate was changed. When any of the polymer compositions was used, the pattern shown in Fig. 1 and Fig. 4 were used. Both of the illustrated patterns can achieve the same effects as those of the first to fifth embodiments. [Simplified description of the drawings] Fig. 1(a) is a schematic view showing the structure of the pixel 2 on the substrate surface in the normal direction, first (b) Fig. 2 is a partial cross-sectional view taken along line BB of Fig. 1(a). Fig. 2 is a partial cross-sectional view taken along line BB of Fig. 1(a). Fig. 3 is a view showing a transparent conductive film in a liquid crystal cell manufactured in the embodiment. Fig. 4 is a view showing the pattern of the transparent conductive film in the liquid crystal cell produced in the embodiment. [Description of main element symbols] 2 pixels 4 bungee bus bar 6 bungee bus bar 8 stripe electrode 10Sheet-64-201100930 12 and 14 Connecting electrode 16 TFT 18 Accumulating capacitive busbar 20 Array substrate side glass substrate 22 Insulating film 24 Liquid crystal layer 24a Liquid crystal molecules 26 Counter electrode 28 Color filter layer 30 Counter substrate side glass substrate 32 And 34 alignment film d cell gap 100 ITO electrode 200 slit portion 300 light shielding film

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Claims (1)

201100930 VII. Patent application scope: 1. A method for manufacturing a liquid crystal display device, comprising the steps of: forming a polymer having a structure represented by the following formula (I) on the transparent pixel electrode of a substrate having a transparent pixel electrode; In the film formed, a nematic liquid crystal having a negative dielectric anisotropy is sandwiched between the respective films of the two substrates on which the film is formed, and a voltage is applied between the transparent pixel electrodes of the two substrates, and the liquid crystal is aligned. Illuminating light, (In the formula (I), one of A1 and A3 may be an alkyl group selected from a halogen atom, a cyano group, a nitro group, a carbon number of 1 to 12, and an alkoxy group having 1 to 12 carbon atoms ( a phenyl group substituted with one or more groups in the group consisting of such an alkyl group and an alkoxy group each substituted with a halogen atom, or a pyridine 2,5-diyl group, a pyrimidine-2,5 -diyl, 2,5--phenenthryl, 2,5-extended furyl, or a 1,4-naphthyl or 2,6-naphthyl group, A1 and A3, wherein the CH group may be substituted by a nitrogen atom The other one is a phenyl group which may be substituted with one or more selected from the group consisting of a halogen atom, a cyano group and a nitro group, or a pyridinium 2,5-diyl group, a stagnation-2,5-two group. 1,4 -thiophenediyl, 2,5 -anthracenyl, 1,4 -anaphthyl or 2,6-naphthyl or *-COO-, *-CONH -or *-CO-E- (except that the above-mentioned linkage is linked to -CH=CH-, E is a group which can be selected from a group consisting of a halogen atom, a cyano group, and a -66 - 201100930 nitro group) Above substituted fluorene, 4_phenylene' or acridine-2,5-diyl, pyrimidine-2,5-diyl, 2,5-thiophenediyl, 2,5-extended a 1,4-naphthyl group or a 2,6-anthranyl group which may be substituted by a nitrogen group or a CH group: A2 may be one or more selected from the group consisting of a halogen atom, a cyano group and a nitro group. Substituted 1,4-phenylene, or pyridine-2,5-diyl, pyrimidine-2,5-diyl, 2,5-thiophenediyl, 2,5-extended furyl, trans-1,4 - cyclohexyl, trans-1,3·dioxane-2,5-diyl or 1,4-piperidinyl; 〇Ζ1 represents a single bond, *-CH2CH2-, *-COO·, *-〇CO -, *-OCH2-, *-CH2〇-, *-C=C-, *-(CH small-, *-〇(CH2)3- or *-(CH small 0- or trans-form *- OCH2CH = CH-, *-CH = CHCH2〇-, *-(CH〇2CH = CH- or -CH = CH(CH2)2- (except that the above-mentioned linkage is linked to A2); R1 is a hydrogen atom a halogen atom, a cyano group, a nitro group or an NCS group or an alkyl group having 1 to 12 carbon atoms, but the alkyl group may be substituted with fluorine, or a non-adjacent-Cii2- group of two or It may be substituted by an oxygen atom, -C〇0., _〇c〇_ or -CO-'. The _CH2ch2- group may be substituted by -CH=CH-, or R1 is a group having a steroid skeleton; X and Y are independently Represents a hydrogen atom, a halogen atom, a cyano group or a carbon source The alkyl group having a number of from 1 to 12 can be substituted with a fluorine atom, and one or two non-adjacent -CH2- groups can be replaced by an oxygen atom, -c〇〇_, -0C0- or -CO. - Substitution; η is an integer of 〇~4, except that when η is 〇, R1 is not a hydrogen atom). 2. The manufacturing method of the liquid crystal display element of claim 1, wherein the structure represented by the above formula (1) in -67-201100930 is the structure R1 - (-A2 - OCO-(R) represented by the following formula (Ι_2_ι) m Η (1-2-1 (in the formula (1-2-1), R1, A2, Ζ1 and η are the same as in the above formula (1), and R2 is a halogen atom, a cyano group, a nitro group, a carbon atom. The alkyl group having 1 to 12 or an alkoxy group having 1 to 12 carbon atoms (the alkyl group and the alkoxy group may each be substituted by a halogen atom), and m is an integer of 〇4 to 4). 3. The method for producing a liquid crystal display device according to the first aspect of the invention, wherein the structure represented by the above formula (I) is a group represented by the following formula (1-1-1). its (In the formula (1-Bu 1), R^A^Z1 and η are the same as those in the above formula (I), and R2 is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms or An alkoxy group having 1 to 12 carbon atoms (such an alkyl group and an alkoxy group may each be substituted with a halogen atom), and m is an integer of 0 to 4). 4. The method for producing a liquid crystal display device according to the invention, wherein the polymer is at least one selected from the group consisting of: (meth)acrylic acid having the structure represented by the above formula (I) a (co)polymer of a derivative, a styrene derivative, a vinyl ether, a vinyl ester or an unsaturated carboxylic acid derivative; a polyorganosiloxane having the structure represented by the above formula (I); -68-201100930 having the above Formula (I) represents a polylysine of the structure. 5. The manufacturing method according to any one of claims 1 to 4, wherein the light is unpolarized ultraviolet light having a wavelength of from 80 to 80. And the liquid crystal display element of the ruthenium iodide polymerization thereof is contained in the range of 350 nm -69-