TW201245356A - Method for producing liquid crystal display element, liquid crystal display element and polymer composition - Google Patents

Abstract

The present invention provides a method for producing liquid crystal display element having a wide vision angle, a fast-speed response of liquid crystal molecules and excellent display properties and long-term reliability. The above-mentioned method is characterized by passing through the following steps: coating a polymer composition, which comprises (A) at least one polymer selected from the group consisting of a polyamide, a polyvinyl alcohol derivate and a poly(meth)acrylate and (B) a polymeric unsaturated compound, on conductive films, which are on a pair of substrates, respectively to form a coating; a pair of substrates on which the coating is formed are disposed so that the coatings face each other through a liquid crystal layer to form a liquid crystal cell; and illuminating the liquid crystal cell by light in the case of applying voltage between the conductive films which are on a pair of substrates.

Description

201245356, invention: TECHNICAL FIELD The present invention relates to a method for producing a liquid crystal display device, a liquid crystal display device, and a polymer composition. More specifically, it relates to a new method for producing a liquid crystal display element having a phase, a wide angle of view, and a fast response speed. [Prior Art] In the liquid crystal display device, as a vertical alignment mode, the MVA (Multi-Domain Vertical Alignment) type panel which is currently known is formed by forming protrusions in the liquid crystal panel. The tilt direction of the liquid crystal molecules, thereby expanding the viewing angle. However, according to the one-way method, it is inevitable that the projections cause insufficient light transmittance and contrast, and thus have a problem that the response speed of the liquid crystal molecules is slow. In recent years, in order to solve the above-mentioned substrate and gap of the V A type panel compound stable film or the gap between the conductive films of the substrate, it is a technique of polymerization. By means of the structure, the MVA profile is expanded. The illumination is generated. The liquid crystal is separated by the PSA (Polymer Sustained Alignment) method. The PS A mode is formed by sandwiching a substrate containing two patterned conductive films on a substrate formed by a substrate having a patterned conductive non-patterned conductive film. The liquid crystal composition is irradiated with ultraviolet rays in a state of applying a voltage to combine the polymerizability to exhibit a pretilt property, and the liquid crystal alignment direction is controlled. By using the technique, the conductive film can be made to have a specific viewing angle and the liquid crystal molecules can be made to respond. High-speed, it can also solve the inevitable light transmittance and the problem of the degree. However, in order to polymerize the above-mentioned polymerizable compound, a large amount of ultraviolet rays such as 100,0 Å/2, therefore, in addition to the problem of decomposition of 201245356, it is known that the unreacted compound which does not polymerize by irradiation of ultraviolet rays remains in the liquid crystal. In the layers, or in combination with their 'generating display spots', the voltage retention is adversely affected, or the long-term reliability of the panel causes problems. In response to these problems, Non-Patent Document 1 proposes a method of using a liquid crystal alignment film formed of a polyimine-based liquid crystal alignment agent containing a reactive mesogen. According to Non-Patent Document 1, the response of the liquid crystal molecules of the liquid crystal display element having the liquid B aligning film which is obtained by the method is idling. However, in the non-patent literature, there is no description as to which reactive liquid crystal cell should be used in what amount, and the necessary ultraviolet irradiation is still much, and the display property, particularly the voltage holding property, is still not eliminated. Worried. However, in recent years, the trend of enlargement of liquid crystal display elements has become remarkable, and at the same time, it is required to reduce the weight of large-sized substrates. In order to meet this requirement, an attempt was made to use a substrate made of a part of synthetic resin. However, the liquid crystal alignment ruthenium material having a liquid crystal cell site described in Non-Patent Document 1 has poor solubility, and therefore, in order to prepare it as a composition of a solution, it is necessary to make 2 specific high-boiling solvents (for example, N-fluorenyl- 2-pyrrolidinium). A has a saying

The high-boiling solvent liquid crystal alignment agent is required to carry out the high-temperature heating of the degree of complete evaporation of the high-purine printing solvent to be used in the step of removing the solvent from the S-coated S-soil. This heating temperature occasionally exceeds the softening temperature of a conventional resin, and thus hinders the use of the PS A mode and the resinous substrate therein. /, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Japanese Patent Publication No. 2009-169224, JP-A-201-76065, Y.J. Lee et al., SID 09 DIGEST, p. 666 (2009) Non-Patent Document 2 TJ Scheffer et al, J. Appl. Phys. Vol. 48, p. 1783 (1977) Non-Patent Document 3 F. Nakano et al, JPN, J. Appl. Phys, Vol. 19, p. 2013 (1980) [Problem to be Solved by the Invention] The present invention has been made in view of the above problems, and an object thereof is to provide a method for manufacturing a liquid crystal display element which has a wide viewing angle, a liquid crystal molecule having a high response speed, and excellent display properties and long-term reliability. Further to the above liquid crystal display element of the present invention, it is preferable to provide a production method which does not require high-temperature heating. [Means for Solving the Problem] According to the present invention, the above-described problem of the present invention is achieved by a method for displaying a component of a liquid-liquid display device, such as a radish + 丄-search method, which is characterized by έ Step · ▲ On the conductive film of the pair of substrates of the conductive cesium, respectively, the right polymer, the coating, and the coating are formed, and the polymer composition is selected from The extract contains at least one polymer of terrasin, a polyvinyl alcohol derivative, and a poly(methyl ketone group) propylene J 纰 , and -6 - 201245356 (B) a polymerizable unsaturated compound; a layer of the liquid crystal molecules interposed between the pair of substrates on which the tantalum coating is formed, and the coating film is disposed to face each other to form a liquid crystal cell; and the conductive layer of the pair of substrates is described When the voltage is applied between the films, the liquid crystal cell is irradiated with light. [Effect of the invention] The liquid crystal display element manufactured by the method of the present invention has a fast response speed of liquid crystal molecules, exhibits sufficient light transmittance, and This degree 'excellent in display properties, even if Continuous operation for a long time...loss of display properties. In addition, by the method of the present invention, it is possible to reduce the illumination; the amount of light required 'helps to reduce the manufacturing cost of the liquid crystal display element. This is the polymerization used in the method of the month. Composition does not need to be made

The use of the intermediate/folk point solvent is particularly suitable for use in a resin substrate lacking heat resistance.

At this reason, the liquid crystal display element manufactured by the method of the present invention is superior to the currently known liquid crystal display device in terms of both the surface and the cost, and is suitable for various uses. [Complex method] [Formation for carrying out the invention] <Polymer composition> = The polymer composition used in the method includes: acid 冓 selected as V: bismuth, diethyl sterol At least one polymer of the derivative and the poly(indenyl) propyl group and the t) polymerizable unsaturated compound. 201245356 [(A) polymer] (A) The polymer is a polymer selected from the group consisting of polyamines, polyvinyl alcohol derivatives, and poly(meth)acrylates, preferably selected from the group consisting of the following: At least one compound in the group: a group having a quinone structure, a group represented by the following formula (A-0)

/ y--CcH2c+1 'Ά (Α-Ο) (in the formula (A-Ο), a is 0 or 1, b is an integer of 0~2' where a and b are not 0 at the same time, c is 1~ An integer of 20), a carbon atom of 〜4 to 40 (wherein the group represented by the above formula (A-Ο) is removed), and a gas group having a carbon number of 4 to 40 ( Hereinafter, it is referred to as "pretilt-developing group". (A) The polymer is excellent in the response speed of the liquid crystal by having a pretilt-developing group '.疋 乂 乂 烯基 烯基 作为 作为 作为 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基 烯基The wool is left in the base. As the above formula (A-Ο), the United States! Specific examples of the τ丞 map CcH2c+1 - may, for example, be a mercapto group, an ethyl group, a j U column η-propyl group, an η-butyl group, an n-pentyl group, an η-heptyl group, an η-octyl group, η Μ 匕 壬 壬 ' 'n-fluorenyl, η-dodecyl, dialkyl, η-tetradecyl, ten ^ ^, η pentadecyl, η-hexadecyl, + Burning base, η - 18 yard base, 17 "±. 19-burning base, η_20-burning base (in the upper female +, "η-" means straight chain). The above-mentioned composition of the above formula (A - 0) is exemplified by, for example, the following formulas. (Formula (A-〇-l) and (Α-0-2) respectively represent the base ' 8 - 5 201245356

Including the above, particularly preferably, the alkyl group having 4 to 40 carbon atoms (in the case of a group represented by argon = (A-0)), preferably a linear carbon number of 8 〜 20 linear alkyl groups. The alkyl group having 4 to 40 carbon atoms is preferably a straight chain. Specific examples of the fluoroalkyl group as the pretilt angle-developing group include, for example, 3-(difluoromethyl)propyl group and 4-(trifluoromethyl)butyl group. In the present invention, the '(A) polymer is preferably in a ratio of 0.05 to 0.7 mmol/g-polymer. More preferably, the ratio of 〇M 5_〇1/g•polymer has the above-described pretilt angle developability. Group. - Polyamide - In the present invention, the polyamine can be obtained by subjecting a dicarboxylic acid or a dicarboxylic acid to a polycondensation reaction with a diamine. The polystyrene in the present invention preferably has such a pretilt appearance group as described above. The polyamine having a pretilt-developing group can be obtained by, for example, a polycondensation reaction of a slow acid or a bis-acid, and a diamine having a pretilt appearance. The dicarboxylic acid used for the amine, the one having the alicyclic structure, and the polyfluorene used for the synthesis of the present invention, for example, oxalic acid, aliphatic diacid acid 201245356, having a waxy ring structure and an aromatic acid acid having an aromatic A dicarboxylic acid or the like of both of the ring-shaped i-group rings. Examples of the aliphatic dibasic acid include a dibasic acid in which a di(tetra)yl group is bonded to a saturated fluorenyl group having a carbon number of 20, and a di(4-) group bonded to an unsaturated smoky group having 2 to 20 carbon atoms. The two slow acid. Examples of the former include, for example, malonic acid, dimethyl..., succinic acid, glutaric acid, adipic acid, and 2-methyladipate: acid: hept: acid, 2, 2_2 Methyl glutaric acid, 3,3-diethyl sulphate (tetra), sulphonium sulphate, azelaic acid, suberic acid, etc.; - Examples of the latter include, for example, fumaric acid muconic acid. Among them, it is preferred to use two stagnation acids in which the number of carbon atoms is 丨~12 and the two slow bases are combined. The diacetyl acid having an alicyclic structure can be exemplified by the following examples; acid = dicarboxylic acid, hydrazine, 2-cyclopropanedicarboxylic acid, 1 small ring Ding Xuan " dimethyl, dingyuan II Formic acid, α-cyclobutane dicarboxylic acid, U-cyclobutyl sulfonium, "-: 二,丨_cyclobutene_3,4·dicarboxylic acid, W-cyclopentane dicarboxylic acid, 2·% decanedicarboxylic acid, 13 -cyclopentanedioic acid, U·capric acid, 1,2-cyclohexanedicarboxylic acid,! 3 * % dimethyl dimethyl decane didecanoic acid, 1,4-cyclohexyl; [V=4_(2-lower formic acid, degraded dicarboxylic acid, acid, 1Γ1,4·didecanoic acid, bicyclo [2·2·2] Xin... Diterpenic acid::: Oxygen 10 4-bicycloindole. 2] Xinchao dicapric acid, ^ dicarboxylic acid, i 3 side oxygen-1'3 Jin Guang said - Jia Jun 2,6·Snail [3.3] Geng-burning T驮I3·adamantane diacetic acid, camphoric acid, etc.; 201245356 decanoic acid, 5-tris-butyl-isophthalic acid, 5-aminoisophthalic acid, 5 -hydroxyisophthalic acid, 2,5-dimercaptophthalic acid, tetramethylterephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-anthracedicarboxylic acid, 1,4-nonyl didecanoic acid, 2,5-biphenyl dinonanoic acid, 4,4'-biphenyl Diterpenic acid, 1,5-biphenyldicarboxylic acid, 4,4''-terphenyldicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenylethane Formic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 4,4 '-diphenyl ether dicarboxylic acid, 4,4 '-bipyridine Citrate, 4,4 '-stilbene dicarboxylic acid, 4,4'-acetylene dibenzoic acid, 4,4'-carbonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3'-p-phenylenedipropionic acid, 4-carboxycinnamic acid , p-phenylenedicarboxylic acid, 3,3'-[4,4'-(indenyldi-p-phenylene)dipropionic acid, 4,4'-[4,4'-(oxy pair Phenyl)]dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)]dibutyric acid, (isopropylidene dip-phenylenedioxy)dibutyric acid , bis (p-carboxyphenyl) decyl decane, 1,5-(9-side oxindole) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4 , 5-thioxadicarboxylic acid, 1,2,5-° stopper 2. Sodium- 3,4-dicarboxylic acid, 1,2,5-oxadi(s), sit- 3,4-didecanoic acid, 2,3 -π ratio biting diterpenic acid, 2,4 - ° ratio, diterpenic acid, 2,5 -. ratio dicarboxylic acid, 2,6 -. ratio diterpenic acid, 3,4 -. Didecanoic acid, 3,5-, bis-dicarboxylic acid, 3,6-0, D-dicarboxylic acid, etc.; as the dicarboxylic acid having both the alicyclic structure and the aromatic ring, for example, 3 ,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-.cyclobutanedicarboxylic acid, 3,4- (2-hydroxyphenyl)-1,2-cyclobutanedicarboxylic acid, 2,4-bis(2-hydroxyphenyl)-1,3-cyclobutanedicarboxylic acid, etc. 45356 It·ί门&lt The composition of the ninth and the aliphatic dicarboxylic acid is one or more selected from the group consisting of oxalic acid and an aliphatic dicarboxylic acid. The acid may be exemplified by the above-exemplified di-and-fat 雉. It is particularly preferred to use a material selected from the group consisting of oxalic acid. Further, one or more kinds of vapors in the group consisting of carboxylic acid or a diamine of polyamine in the present invention may be exemplified by organic helium. The diamine diamine 'aromatic diamine and diamine group may, for example, be a diamine having a pretilt angle of a dodecyloxydiamine: preferably a polyamine of a polyamine, preferably comprising a group of two Amine. 'Diamine of the earth mass. As a pre-dip angle-developing group, as a T JL, it is an aromatic diamine-based compound having a pretilt-developing group, and a pentadecyloxy-2,4-diamine octadecyloxy-2,4 -diaminetetradecyloxy-2,5-diaminehexadecyloxy-2,5-diamine cholestyloxy-3,5-diamine cholestyloxy-2,4-di Amine 3,5-diaminobenzoic acid, cholyl phenyl, phenylphenyltetradecyloxy-2,4-diaminophenyloctadecyloxy-2,4-diaminobenzene Dodecyloxy-2,5-diaminophenylpentadecyloxy-2,5-diaminophenyloctadecanoyloxy-2,5-diamine-based succinyl-leastyloxy-3, 5-diaminophenylcholestyloxy-2,4-diaminobenzoic acid vinegar, 3,5-diaminobenzoic acid biliary vinegar, 3,5-diaminobenzoic acid wool留院基@,, 3'6_bis(4-aminobenzylideneoxy)choline, 3,6-bis(4-aminophenoxy)cholyl, phenyl)methyl) Phenyl)-4-butylcyclohexane, u_:(4_((aminophenyl)methyl) phenyl)-4-heptylcyclohexanide 1,1-di(4-((aminophenyl) Oxy)methyl)phenyl-12- 201245356 ,_(4_((indolyl)methyl)phenyl)-4-(4) -heptyl-dehexyl) hexane, H2N-- oxime formula (A·1), etc. Plant /==\ Ί Γ /-VI X1—R1—-χ11·heptylcyclohexane , 1 1 ^

C〇^2c+1 (^(Al)t , χΙ . γΠ χ (Α_1) by *-oc〇- (which makes \ single bond, *_◦·, *_co〇- or methylene or carbon atom Number: 2=: The two formulas and the shy/alkyl group in the above formula (A-Ο), a, ^〇C respectively) the same meaning of τ).佳为=说(4) The group is more than *-〇ch2CH2.0_ (its * is ^3* of the stretching base, *·〇_, WOO-, , ^ *" is connected to the diamine basic soil The two amines X of the diamine-based group are 2,4-position or 3,5-position of the ketone-glycan +a. 1-Amino group is preferably the other group: the above formula (A.1) Specific examples of the compounds shown are represented by the following formula (4), U.(4)), and (Ι5ΓΓ二==

201245356 (in the above formula, n-CsHu- and η-^Η, 5 respectively represent a linear pentyl group and a linear heptyl group), and a diamine having a pretilt-developing group, preferably used, Free cetyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diamino stupid, cholestyloxy-3,5, diamine stupid Base-3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholestyloxy-2,4-diaminobenzene, 3,5·diaminobenzoic acid A cholesteryl group, a 3,5-diaminobenzoic acid cholestyl group, and one or more of the above formula (constituted by the compound represented by AD). As a polyamine which is used in the synthesis of the present invention The diamine may be formed only of a diamine having a pretilt-developing group, or may be a mixture of a diamine having a pretilt-developing group and a diamine having no pre-tilt-developing group. Examples of the diamine of the developing group include an aliphatic diamine having no pretilt-developing group, an alicyclic diamine, an aromatic diamine, a diamine-based organodecane, etc. No pretilt appearance group Group of diamines, respectively Examples of the aliphatic diamine include, for example, isophthalamide, hydrazine, 3-propylenediamine, i,4-butanediamine, 1,5-pentanediamine, iota, hexamethylenediamine, and the like; The alicyclic diamine may, for example, be 1,4-diaminocyclohexanone, 4,4'-fluorenylene di(cyclohexylamine), hydrazine, 3-bis(aminomercapto)cyclohexane. The aromatic diamine having no pretilt-developing group, for example, as the aromatic diamine, for example, o-p-diamine, m-phenylenediamine, p-diphenylamine, 4,4,-diamino group Diphenylmethane, 4,4,-diaminodiphenyl descaling, 1,5-diaminonaphthalene, 2,2,-dimethyl-4,4'-diamine linkage, 4, 4,_ -14- 201245356 Diamino-2:,2'-bis(trifluoromethyl)biphenyl, 27-diamino, 4,4,-diaminodiphenyl_, 2,2_ Bis[4_(4-aminophenoxy)phenyl]propane, 9 bis(4-aminophenyl)m[4_(4-aminophenoxy)phenyl]hexapropane 2,2 _ (4 aminophenyl) hexafluoropropane, 4,4,-(p-phenylenediphenylene)bis(aniline), 4,4,-(inter)phenyldiisopropylidene) Aniline) phenoxy)benzene, 4 , 4'-bis(4)aminophenoxy)biphenyl, 2,6-diaminopyridinium, 3 4 - η* s, 4-monoaminopyridine, 2,4-diaminopyrimidine, '6 —Based on D疋, 3,6-diaminocarbazole, hydrazine methyl-3,6-diaminopyrene, hydrazine-ethyl-3,6-diamino. Card. Sit, &; phenyl _3,6-diamino oxazole, hydrazine, hydrazine, bis(4-aminophenyl)-benzidine, anthracene, fluorene, -di(4-aminophenyl)_Ν'Ν _ Methyl benzidine, bis-(4-aminophenyl)-slightly, 3,5-aminobenzene-f-acid, 4·(4,-trifluoromethoxybenzyl methoxy) hexyl hexyl -diamine-based acid vinegar, 4-(4,trifluoromethylbenzyloxy)cyclohexyl-3,5-diaminobenzoic acid ester, 2,4-diamino-based ν, ν, ·Diallyl benzidine 4'-aminobenzylamine, 3-aminobenzylamine, 1-(2,4-diaminophenyl) 0-well-4-carbazine, 4-(味琳_4_yl)benzene L3 diamine, fluorene-bis(ν·(mono)·aminophenyl)piperidinyl)propane, α-amino 1 aminophenylalkylene group, etc. 9 as no pretilt appearance group The diamino-based organooxane of the group can be exemplified by, for example, 1 3 , & , J + —(3-aminopropyl)_tetra Silicon two siloxane groups and the like in Patent Document 2 (Japanese Laid-Open Patent Publication No. 88 971 2〇1〇) noted planted diamine. As the diamine having no pretilt-developing group, it is preferably selected from the group consisting of p-phenylenediamine, 4,4, diaminodiphenylmethane, 2,2, dimercapto~4,4'-di Aminobiphenyl, 4,4,diamino-2,2,bis(trifluoromethyl)biphenyl 201245356, 4,4'-diaminodiphenyl ether, 2,2-di[4- (4-Amino-p-oxy)phenyl]-propyl, 1,4-di-(4-aminophenyl)-D-bottom and 3,5-diaminobenzoic acid More than one type. The diamine for synthesizing the polyamine in the present invention preferably contains 1 mol% or more, more preferably 5 to 40 m〇1%, and further contains 1 to 3 mmol%, based on the total amount of the diamine. A diamine having a pretilt-developing group. The polyamine in the present invention is synthesized by subjecting the above dicarboxylic acid or halogenated acid to a polycondensation reaction, preferably in the presence of a suitable condensing agent, preferably in a suitable solvent. The ratio of use of dicapric acid or halogenated dicarboxylic acid to diamine is preferably 〇-9~1.1111〇1, based on the ratio of diamine to 1 mol of dicarboxylic acid or dicarboxylic acid. For 〇95~1〇5111〇1. Preferred condensing agents vary depending on the use of the dicarboxylic acid or the use of a carboxylic acid. As the condensing agent', when a dicarboxylic acid is used, for example, (PhO)3p '(ph〇) PCl2, PhP〇Cl2, (C3H7)3P(0)〇, p〇Cl3, SOCl2/Et3N, Ph3P/ are preferably used. C2Cl6, SiCl4, Me2SiC14; Further, in the case of using a dilute dicarboxylic acid, for example, triethylamine, pyridine, N,N-didecylaniline or the like is preferably used. The ratio of the condensation cut is preferably from 2 to 4 parts by weight, more preferably from 0 to 4 parts by weight, more preferably as an organic solvent, and is preferably used, for example, for 1 part by weight of the dibasic dicarboxylic acid. Four H South, H toluene, gas imitation, dimethylformamide, dimethyl-branched amine-mercapto-hardened 'N_mercapto n. Fixed and so on. The solvent is preferably used in an amount of from 400 to 重量 parts by weight, more preferably from about 7 parts by weight, based on the total hydrazine portion of the hydrazine or the halogenated monocarboxylic acid and the diamine. -16- 201245356 The temperature of the polycondensation reaction is preferably from 25 to 200 ° C, more preferably from 60 to 10 (Γ. The time of the polycondensation reaction is preferably from 2 to 1 hour, more preferably from 3 to 6 hours. The polyamine of the present invention can be synthesized. The polyamine thus synthesized is preferably purified by a known method. - Polyethanol derivative - The polyvinyl alcohol derivative of the present invention is selected, for example, from polyethylene. Among the polymers obtained by modifying alcohols, vinyl alcohol/ethylene copolymers, and the like, preferably, the polyethyl alcohol having the pretilt-developing group described above can be esterified by polymerization after vinyl acetate. The saponification member can be obtained by saponifying the ester bond of the repeating unit derived from vinyl acetate by copolymerizing vinyl acetate and ethylene. Polyvinyl alcohol derivative having a pretilt-developing group The material can be obtained by, for example, substituting at least one of the hydrogen atoms of the vinyl acetate with a group having a pretilt-developing group (referred to as 'pretilt angle' Display group substituted acetic acid a method for homopolymerization of vinyl ester ") (method 1); polymerization of a pre-tilt-developing group of cyclamate and ethylene, followed by vinyl acetate (method 2); And saponification with at least one mixture selected from the group (the saponification of the ester bond of the total repeating unit), the oxime-vinyl alcohol followed by the & After the formation of the hydroxyl group on the JL right box 偭# soil reactivity, after the method of the group name W group having a pre-dip angle-developing group (method 3) # 201245356 the above-mentioned vinyl squaric acid alcohol can be formed into three 'Addition to vinegar in the method of acetic acid B 2~60mol%, 10 0~3 0 m ο 1% lOmol% or more of the homopolymerization of the above aryl ester,: ester and the copolymer selected from the species, the homopolymerization of the ester Ester and Ethyl as the polymerization, solution, in the method of dissolving and radically aggregating the mixture, preferably according to the need of the side or the copolymer as the upper: the pretilt angle of the alcohol burning base used in the method 1 and 2 The vinegar substituted by the group is revealed by, for example, having a pretilt angle first. The fluorononionate of the group is synthesized by the method of C=C double bond carbon of the acid vinyl vinegar under the heck reaction condition. 2 'pre-dip angle-developing group relative to all monomers Preferably, the dilute vinegar is used in an amount of 2 mol% or more, more preferably 5 to 40 mol%, more preferably used. In the method 3, it is preferably used in comparison with all monomers. ～9〇mol% vinyl acetate. The group consisting of vinyl acetate 曰 'ethylene ester and ethylene substituted by pretilt angle-developing group in vinyl acetate left-hand method 2 substituted by pre-dip angle-displaying group in method 1 At least 1 of the methods and the vinyl acetate for obtaining polyvinyl alcohol in the method 3 are used for obtaining a vinyl alcohol/ethylene copolymer of vinyl acetate, respectively, by a known radical polymerization method. White is legally obtained by taking soil, and a suitable method such as bulk Α & emulsion polymerization or suspension polymerization can be used, and the car is preferably a solution polymerization method. : when the polymerization method is carried out by radical polymerization, the desired monomer or monomer is 5 Torr in the presence of a suitable solvent σ initiator, more preferably at a temperature of 6 〇 1 〇〇 1 ,, 1. Stirring with ethylene, the desired polymerization enthalpy can be obtained: the solvent can be exemplified by alcohol, mystery, glycol ether, ethylene-2, hydrazine alkyl ether, propylene glycol monoalkyl Ether, C--18-201245356 monool alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone, ester. As the solvent for the radical polymerization, an alcohol such as methanol, ethanol or isobutanol is preferably used. The use ratio of the solvent is preferably from 100 to 900 parts by weight, more preferably from 6 to 8 parts by weight, based on the total mass of the monomer. Examples of the above-mentioned radical polymerization initiator include azo-isobutyronitrile, azobis-2,4-dimethylvaleronitrile, and azobis(4methoxy-2,4-dimethylpentyl). Azo compound such as nitrile; acetonitrile peroxide, benzammonium peroxide, oxidized laurel, acetal cyclohexylsulfonyl vortex & w - earth peroxide, 2,4,4- a peroxide such as trimethylpentyl-2_peroxyphenoxyacetate; octapropylperoxydicarbonate, :2-ethylhexyl carbonate, diethoxy X 7^ Percarbonate sigma compound such as ethyl peroxydicarbonate, peracetic acid tertiary butyl citrate, peroxy neodecanoic acid neodecanoic acid tertiary butyl lysate, etc.; azo two (The other than the other polymerization initiators such as quinazoline (methoxy oxime), etc., have a ratio of 胄/monomer totaling 1 〇. parts by weight of 'free radicals 0.05 to 2 parts by weight. Preferably, it is 1 to 5 parts by weight, more preferably free radically polymerized 睹pg 0 'between 2 to 10 hours, more preferably 3 to 5 hours, the reaction system is subcooled, and the polythermal temperature is terminated. Can be an example Preferably, the polymerization is carried out after a small polymerization of 1 ° C or higher, and the saponification after the polymerization is carried out at 50 C, preferably 2 〇 to 201245356 for termination of polymerization, which can be obtained by (total) The polymer is subjected to an experimental condition. Therefore, it is preferred to contact the (co)poly(8) with a basic compound in a suitable solvent. Examples of the solvent used for the saponification include an alcohol. For example, decyl alcohol, ethanol, butanol, etc. may be mentioned. For 100 parts by weight of (co)polymer, the solvent is preferably used in a proportion of 25 to 900 parts by weight, more preferably 5 to 6 parts by weight. The basic compound used for saponification is preferably an alkali metal compound such as sodium, sodium formaldehyde, sodium acetal or potassium acetal, or a catalyst such as an alcoholate. Compared with the 1〇〇1 (co)polymerization #有四四酸乙四的 unit's use of the compound ratio is more than 0.001 ~ O.Olmo Bu is better than 〇〇〇 2 ~ 〇〇〇 8m〇i. The temperature is preferably 1〇~7〇t:, more preferably 3〇~4〇. The time is preferably 0.5 to 4 hours, more preferably 2 hours. According to the composition of the (co)polymer, the saponification reaction may be gelled when saponification is carried out. In this case, the smash is properly smashed. After all the pulverization of the reaction body is completed, the incipientization reaction is continued. After the saponification reaction, it is desirable to use the neutralizing agent for each of the fields to form the reaction system and, as the neutralizing agent used herein,

Ah ^ ^ U lists, for example, hydrochloric acid 4 . The neutralization system is carried out under conditions of a pH of preferably 5 to 9, more preferably 6. The neutralization temperature is t. C, better for 20~

In 沄i and Method 2, it is possible to obtain a polyethylene derivative of the car in the J* month by ^ m cb. -20- 201245356 In Process 3, a precursor polymer of a preferred polyvinyl alcohol derivative of the present invention, that is, a polyvinyl alcohol or a vinyl alcohol/ethylene copolymer can be obtained by the above method. In the method 3, a preferred polyethylene in the present invention can be obtained by adding the polyvinyl alcohol or the vinyl alcohol/ethylene copolymer (precursor polymer) to a group having a pretilt angle to exhibit a green group. Alcohol: Creature. More specifically, first, a group having a pretilt-developing group and a compound having a retardation group (hereinafter, referred to as "a pre-tilt-developing slow-halogenation-type halogenating agent to form a bismuth halide" will The acid hydrazine flood polymer is preferably synthesized by a cooling reaction in the presence of a suitable condensing agent in a suitable solvent. To exemplify the pre-tilt angle carboxylic acid, it can be classified as a steroid. The structure A _ 乂 exemplifies, for example, a group having a sub-number of ".: two; a group represented by the above formula (Α·〇), a group of carbon atoms; (Α-0) shows a phytic acid: as a deuterium (four) group having a gas "having a gas-burning group having a carbon number of 4 to 4 Q"; and V 2 ' can be exemplified by, for example, a succinic acid (3, ( 7_ 物等. ) 化 is represented by the following formula (Μ)~((一)) respectively - 2 - 201245356

(5-3)

C〇〇H C2F5 - C3H6 one (5-4)

As the above-mentioned agent, a sulfhydryl group gas is preferably used, and as a specific example thereof, for example, (Ph0)Pcl2, PhPOCl2, P〇Ci3, SOCl2/Et3N, Ph3P/C2Cl6, SiCl4, Me2SiCl2 (above 'P' It is a stupid base, Et is an ethyl group, Me is a mercapto group, and the like. The ratio of use of the developing carboxylic acid' as a halogenating agent to 100 parts by weight of the pretilt angle is preferably 2 to 1 part by weight, more preferably 3 to 6 parts by weight. The halogenation reaction is preferably carried out in the presence of a suitable solvent-22-201245356' such as dichloromethane, gas, hydrazine-monomethylformamide, etc., for example, 20~1〇〇t# 〇~8〇c, for example, 0.5 to 5 hours, preferably 1 to 2 hours. The use of the material and the pre-dip angle of the halide of the carboxylic acid. The ratio of the use of the decanoic acid (tetra) to the 1 mol of the precursor polymer is preferably from 0.95 to 1. 5 mol. As the above condensing agent, for example, triethylamine, pyridine, N,N-methylaniline or the like is used. It is inclined to the tongue β. The ratio of the use of the resetting agent to the condensing agent is preferably 2〇〇~4〇〇. 400 parts by weight, more preferably 220 to 300 parts by weight as the above solvent, preferably ^, horse using organic gluten, suitable for use, for example, four simmering, two simmering, simmering imitation, dimethyl Indoleamine, monomethylacetamide, dimethyl sulfoxide, decylamine is used in the precursor polymer and pre-dip...bicronidone. The solvent is preferably used in a ratio of gamma and more than 100 500 to 700 parts by weight relative to the parts by weight. w 文住局 The temperature of the esterification reaction is preferably 35~2 ′ Wen Jia is 5〇~innr. The time for the esterification reaction is preferably from 3 to 10 hours, and the horse is allowed to live for 3 to 6 hours. The polyvinyl alcohol derivative which can be obtained as a desired polyvinyl alcohol derivative as described above is preferably used by a known method to obtain a di-(poly(decyl)acrylic acid-t-butyl group. The hydrazine (mercapto) acrylate in the present invention is a copolymer of a copolymer of a methyl methacrylate or a copolymer, which is also a copolymer of a vinylene acrylate, and is known to be flat and humiliated. The above-mentioned description of the present group. J. Dip angle -23- 201245356 The (mercapto) acrylate's described herein contain the concept of both acrylate and methacrylate. The same concept of both acrylic acid and f-based acrylic acid. Poly(fluorenyl) acrylate having a pretilt-developing group, for example, a homopolymer of (meth) acrylate having a pretilt-developing group Alternatively, a copolymer of a (meth) acrylate having a pretilt-developing group and a copolymerizable monomer other than the above may be used. Here, as another copolymerizable monomer, for example, no pretilt angle appears. a (mercapto) acrylate, a (meth)acrylic acid, a maleimide compound, a vinyl aromatic compound, etc. as a (fluorenyl) acrylate having no pretilt-developing group, List A (meth) acrylate having a cyclic ether structure and other (meth)acrylic acid having no pretilt-developing group other than the above. As the above-mentioned (fluorenyl) acrylic having a pretilt-developing group Examples of the ester include, for example, (meth)acrylic acid 3_cholesteryl ester, (meth)acrylic acid 3-cholestyryl ester, (meth)acrylic acid 3_ergolinel ester, (decyl) Acrylic acid 3- ergoline alkyl ester, (mercapto)acrylic acid 3 bean-retained alkenyl vinegar, (meth)acrylic acid 3-doban alkyl ester '(meth)acrylic acid n-octadecane vinegar, (mercapto) For the 4-(4-n-pentylcyclohexyl)phenyl acrylate, one or more selected from them may be used. Examples of the (fluorenyl) acrylate having a cyclic ether structure include (meth)acrylic acid. Glycidyl ester, (meth)acrylic acid 2 _ (glycidoxy) ethyl ester, (meth)acrylic acid 3_(3,4 epoxycyclohexyl) propyl ester, etc.; -24- 201245356 as the above without pretilt angle Other (meth)acrylic acid vinegar of a developing group may, for example, be ytterbium (meth)acrylate Ester, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, benzyl (meth) acrylate, etc.; Examples of the butenylene imine compound ', for example, N-phenylcis-7-enediamine, N-cyclohexylmethyleneimine, and the like; and the vinyl aromatic compound may, for example, be benzene. Ethylene, α-mercaptostyrene, p-methyl styrene, anthracene, p-hydroxystyrene, or the like, one or more selected from the group consisting of them and (meth)acrylic acid; and Patent Document 3 (Japanese Patent Laid-Open No. 2009-) In the case of synthesizing the poly(meth)acrylate of the present invention, the ratio of use of poly(meth)acrylic acid vinegar having a pretilt angle-developing group to all monomers is higher. Preferably, it is 2〇1〇1% or more, more preferably 2~6〇, then 1%, further preferably 5~4〇m〇1%, and particularly preferably 1〇~3〇m〇i%. The poly(meth) acrylate in the present invention is obtained by a known radical reaction method. The synthesis of the poly(meth) acrylate of the present invention can be carried out by radical polymerization in the presence of a suitable polymerization initiator (IV), preferably in a suitable month. By its s i 14 poly. The initiator ' can be used without limitation as a polymerization initiator known as a self-introduction, and examples thereof can be used: azo m guess, 2 azobis-(2,4·dimethylvaleronitrile..., _ soil 2, Azo compound such as 4_monomethylvaleronitrile; -25- 201245356 Peroxidized benzoate μ τ醯, oxidized laurel, peroxypivalic acid tri-butyl, ι,ι,-~_ 'Ordinary peroxidized hydrogen peroxide such as mono(tertiary butyl peroxy)cyclohexane. As the above-mentioned, hexa-p- ing granules, for example, an alcohol, an ether, a glycol ether, an ethyl ether alkyl hexanoate, a stone, a diethylene glycol alkyl ether, a propylene glycol monoalkyl ether Monool alkyl ether? Oven, lion & ester, propylene glycol alkyl ether propionate, aromatic > di-, ester, etc.; a, -7 _, among them, preferably ethylene glycol alkyl ether acetate Ethylene glycol alkyl group, acid ester, β-propanediol single-base puzzle, propylene glycol alkyl shouting B 1 inch, preferably i __ ether, C-diethylene glycol dimethyl ether 'diethylene glycol B Ketone-alcohol methyl ether,

Methyl methoxypropionate. —Alcohol Ether, Propylene Glycol Methyl Ether Acetate or 3-Poly(S)-formed Poly(A)-based acrylate can be polymerized by a known method. (A) Polymer _ (A) Polymerization in the Invention An enol derivative and a poly(methyl', a polyamine, or a polyethylene. The at least one of the oxime groups of ~a olefinic acid esters may be used to extend the polymer f, where ^ It is preferable to use a mixture of two or more types of cuts. As the (A) compound in the present invention, it is preferable to use polyspores, 妒r抡, and succinic acid to be used alone, and one of them is The other polymers described later are used in combination. 4 UB) polymerizable unsaturated compound] (B) used in the present invention: Α Α Α Α 不 不 不 不 含 含 含 含 含The group of the carbon double bond 〇^n6C _ In the knives, a compound having at least two of the monovalent groups of the following formula is called). -26- 201245356

R (B-I) CH2=4h3— (In the formula (B; -l), ^ Si m ^ 虱 atom or fluorenyl group, Y and Y3 each dig a ruthenium atom or a sulfur atom). The compound of the formula (B-II) of the above-mentioned formula (B-II) is preferably two, and the number of the compounds (B) of the mussel group is preferably two. In the molecular order, at least one of the divalent groups shown by ^ atom is further contained, and the following formula (Bn) -X'-Y'-X2. (Β-ΙΙ) (in the formula (Β-ΙΙ), Χΐ and Χ2 are each independently, 独立-extension base or 丨4 stretch % hexyl, γ ΐ is a single bond, carbon homicide, 4-sub, sulfur atom or W, wherein 'the above 22 is a hydrocarbon group The alkyl group having an oxo group having a carbon atom number of 4, a carbon atom and a ruthenium may be substituted by one or more subunits or a gas group.) '"1 to 4 of an alkoxy group and a fluorocarbon as the above formula (Β-ΙΙ) In the carbon atomic cylinder, a divalent hydrocarbon group having a number of 1 to 4, for example, a divalent group represented by an anthranylene group or a dimethyl group (Β Τ .. fluorenyl group, etc. as the above formula (7)·11) may be mentioned. The group can be distinguished from (τ, Ττ., for example, the following formula a~ul)~(Β-ΙΙ-6) respectively, etc. -27- 201245356

(B-II-1)

(Β-ΙΙ-5)

(β'ΙΙ-6) The benzene ring and the cyclohexanthene in each of the above formulas (Β-ΙΙ-1) to (Β-ΙΙ-6) may be respectively an alkyl group having a anatomical number of 1 to 4 and carbon. A grafting oxy group, a fluorine atom or a cyano group having an atomic number of 14 is substituted. The compound (B_丨) used in the present invention may, for example, be a di(meth)acrylic acid ester having a bonded structure (Y2 and Y3 in the above formula (B_I) are each an oxygen atom, and the above formula ( The divalent group represented by Β-Π) is a group represented by the above formula (Β-π-丨), and the di(meth)acrylic acid S§ having a benzene-cyclohexyl structure (the above formula (4) ^ 丫 2 And 丫3 are each an oxygen atom, a divalent group represented by the above formula (Β-Π), a β 1 (f), a group represented by the above formula (Β-ΙΙ-2), having 2, 2 - 2 Phenylpropane crusting. The bis(indenyl) acrylate (the above-mentioned '28-.201245356), Y2 and Y3 in the formula (Β-I) are each an oxygen atom, and the divalent group represented by the above formula (B-II) is the above formula (Β) a group represented by -ΙΙ-3), a di(meth)acrylate having a diphenylnonane structure (Υ2 and Υ3 in the above formula (Β-Ι) are each an oxygen atom, and the above formula (Β- The divalent group represented by ΙΙ) is a group represented by the above formula (Β-ΙΙ-4), and a disulfide (meth) acrylate having a diphenyl sulfide structure (the above formula (Β-Ι) In the middle, Υ2 is an oxygen atom, Υ3 is a sulfur atom, the divalent group represented by the above formula (Β-ΙΙ) is a group represented by the above formula (Β-ΙΙ-5), and other compounds (Β-1) . Specific examples thereof include di(indenyl)acrylate having a biphenyl structure, and examples thereof include 4'-acryloxy-biphenyl-4-yl-acrylate and 4'-mercaptopropyl. Dilute oxy-biphenyl-4-yl-methacrylate, 2-[4'-(2-propenyloxy-ethoxy)-biphenyl-4-oxy]-ethylpropanoic acid Ethylene oxide addition of vinegar, 2-[4'-(2-mercapto acrylate-ethoxy)-biphenyl-4-oxy]-ethyl (methyl acrylate), biphenyl a diacrylate of an ethylene oxide adduct of diphenyl, a diacrylate of an ethylene oxide adduct of biphenyl, a diacrylate of a propylene oxide adduct of biphenyl, a dimethylene of a propylene oxide adduct of biphenyl Acrylate or the like; as the di(meth)acrylate having a phenyl-cyclohexyl structure, for example, 4-(4-propenyloxy-phenyl)-cyclohexyl acrylate, 4-(4-A) Acryloxy-phenyl)cyclohexyl-methacrylate; -29-201245356 As a di(meth)acrylate having a 2,2-diphenylpropane structure, for example, 4-[1 -(4-propenyloxy-stupyldibu-methyl-ethyl) Alkyl acrylate, 4-[1-(4-methacrylate-phenyl)-indole-yl-ethyl]-phenyl-methylpropionic acid, ethylene oxide a diacrylate of a product, a dimercapto acrylate of an ethylene oxide adduct of bisphenol A, a diacrylate of a propylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A Dimethacrylate or the like; as the di(meth)acrylate having a diphenylnonane structure, for example, a diacrylate of an ethylene oxide adduct of bisphenol F or a ring of bisphenol F a dimercapto acrylate of an oxyethylene adduct, a diacrylate of a propylene oxide adduct of a double F, a dimethyl acrylate of a propylene propylene oxide adduct of a double F; The other compound (B-1) may, for example, be 2,5-di{4-(3-propenyloxy-propoxy)-benzoic acid ruthenium toluene or the like; and Patent Document 4 (曰本特开20) The compound described in the above-mentioned compound (B-1) can be obtained by a conventional method in which organic chemistry is appropriately combined, and can also be obtained from a commercially available product. Compound (B-1) The commercially available product can be exemplified by, for example, jgishydroxyethoxy BP Diacrylate, Bishydroxyethoxy Bis-A Diacrylate (manufactured by Honshu Chemical Industry Co., Ltd.); ARON1XM-208, M-21〇 (manufactured by East Asia Synthetic Co., Ltd.); SR-349, SR- 601, SR-602 (manufactured by Sartomer), KAYARAD R-712, R-551 (manufactured by Sakamoto Chemical Co., Ltd.)·' -30- 201245356 NKesterBPE-1 00 ' NKesterBPE-200 ' NKesterBPE-5 00 , NKester BPE - 1 300, NKester A-BPE-4 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Actilane 420 (manufactured by Saka Hegner Co., Ltd.);

Light Ester BP-2EM 'Light Acrylate BP-4EA ' Light Acrylate BP-4PA ' Epoxy Ester 3000M ' Epoxy Ester 3000A (made by Kyoeisha Chemical Co., Ltd.); V#54〇, V#7〇〇 (Osaka Organic Chemistry) Industrial (stock) manufacturing); FA-321M (manufactured by Yuli Chemical Industry Co., Ltd.); ^^31\^ (manufactured by Sumitomo Seika Co., Ltd.); RIPOXYVR-77 (manufactured by Showa Polymer Co., Ltd.). The compound (B-1) to be used in the present invention is preferably at least one selected from the group consisting of the compounds exemplified above. As the W polymerizable unsaturated compound, only the compound (4) can be used. Alternatively, the compound (B_1} and the oxime-unsaturated compound can be used. The Z-deuterium unsaturated compound is based on a pretilt angle of approximately 90. Λ本本本本本(四)Μ#@ The polymer composition of the invention contains a compound which has a carbon-carbon saturating bond in the present, and is a compound which is more conjugated to the scorpion unsaturated compound. Specific examples of having one γ-stone double bond and the above formula π 〃, minus one stone anti-stone compound can be used as such other unsaturated-based vinegar and methyl acrylate Compound (B)) - " hexyl _4_ group) stupid and so on. ^) When the test of the undesired compound + is (9) a polymerizable unsaturated compound, the use of a compound unsaturated compound is relative to the king of (Β). k is preferably 80% by weight or less, more preferably -31-201245356 50 is 50% by weight or less. The amount of the other unsaturated compound relative to the total amount of the (b) polymerizable unsaturated compound can be expected to be obtained by using 2% by weight or more. M is a total of 100 parts by weight of the polymer (referred to as (A) polymer and the arbitrarily used, the total amount of the ruthenium 5, the same applies hereinafter), as the polymer composition used in the original month ( B) The use ratio of the polymerizable unsaturated octa is preferably from 1 to 100 parts by weight, more preferably from 5 to 50 parts by weight per [other components] and . The polymer composition used in the present invention and the (A) polyfluorene delta unsaturated compound are required as an essential component, and may be a component within a range not deteriorating the effects of the present invention. The other components used as W' and ’' may be 屮η other polymers m η, and examples thereof include a precursor initiator, a radical scavenger, and the like. ~ 庀 庀 庀 • • 匕 匕 • 匕 匕 匕 * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * The ruthenium complex is a polymer other than the (A) polymer, and one or more of the guanamine, the polyethylene derivative, and the poly(indenyl) acrylate. Specific examples of the other polymer include, for example, poly-proline, 9A, 5, polyphthalic acid, polyorgano-oxygen, IS, cellulose derivatives, wherein (4) Two ethylene derivatives (m in the case of (A) 1 & matter), poly(styrene-phenyl cis-butanthene-SE imine) derivatives, and the like. When the ruthenium polymer is used, it is preferable to use τ as a group selected from the group consisting of poly-branched acid, poly-imine, and poly-32-201245356 organic oxy-oxygen. More preferably, it is more preferably used in a group selected from the group consisting of polylysine and polyanilin. The polymer composition of the present invention has a ratio relative to the polymer when other polymers are contained. The total amount is 祛Α θ. The hand 乂隹 is 50% by weight or less, more preferably 3% by weight or less. - Photopolymerization initiator - The above photopolymerization initiator is based on the response speed of the obtained liquid crystal display element The polymer composition of the present invention may contain 0 as a photopolymerization initiator, and may, for example, be an α-diketone, a keto alcohol, a keto alcohol ether, a benzophenone compound, an acetophenone compound, or the like. a hydrazine compound, a halide, a mercaptophosphine oxide, an organic peroxide, etc., as specific examples thereof, each of which is an α-diketone, and examples thereof include benzoin, hydrazine, and the like; For example, benzoin and the like; as an alcohol ketone ether, For example, benzoin a mystery, 1 ^ benzoin ethyl ether, benzoin isopropyl ether, etc.; as a class A compound ' can be exemplified by e plug < 1 ton, 2 4 diethyl thiophene Tons of ketone, thioxanthone-4-heteroic acid, benzophenone, 4 4, _ _ methylamino) diphenyl fluorenone, 4,4'-di(diethylamino) diphenyl hydrazine Ketone, benzyl-(4-p-tolylsulfanyl-phenyl)-methanone, etc.; as the acetophenone compound, for example, acetamidine, +, p-dimethylaminoethyl benzene, 4 -(α,α'-dimethoxyacetoxy m ^ J - fluorenone, 2,2'-dimethoxy-2-phenylethyl benzene, p-methoxy acetophenone, 2 _曱基>-2-味琳代_ι_(4-曱thiophenyl)-1-propanone, 2-n-phenyldimethylamino-1-(4-porphyrinylphenyl)-butyl -1-ketone, etc.; soil-33-201245356 As the ruthenium compound, for example, 蒽醌'1,4-naphthoquinone or the like can be mentioned as an i-form, and examples thereof include acetophenone and tribromodecyl phenyl stone. Tris(trichloromethyl)-s-secondary, etc., as the deuterated phosphine oxide, for example, 2,4,6-trimercaptobenzylidene diphenylphosphine , bis(2,6-dimethoxyphenylhydrazino)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethyl adenyl) benzene For the organic peroxide, for example, a di-tertiary butyl peroxide or the like can be used, and one or more selected from the group consisting of them can be used. As the photopolymerization initiator, a commercially available product can be used. For example, IRGACURE-124, IRGACURE-149, IRGACURE-184, IRGACURE-369, IRGACURE-500, IRGACURE-651, IRGACURE-819, IRGACURE-907 'IGGACURE-1000, IRGACURE-1700, IRGACURE-1 800, IRGACURE-1850 , IRGACURE-2959, Darocur-1116, Darocur-1173, Darocur-1664, Darocur-2959, Darocur-4043 (above, manufactured by Ciba specialty chemicals); KAYACURE-BMS, KA Y ACURE-DETX, KAYACURE-MBP ' KAYACURE- DMBI > KAYACURE-EPA, KAYACURE-OA (above, manufactured by Sakamoto Chemical Co., Ltd.); LUCIRIN TPO (manufactured by BASF); VICURE-10, VICURE-55 (above, manufactured by STAUFFER); TRIGONALPl (AKZO) Manufacturing); -34- 201245356 SANDORAY 1000 (manufactured by SANDOZ);卩£八卩 (eight? : [0111^Manufactured by the company); QUANTACURE-PDO, QUANTACURE-ITX, QUANTACURE-EPD (above, manufactured by WARD BLEKINSOP). As the photopolymerization initiator, a benzophenone compound is preferably used from the viewpoint of high thermal stability. The use ratio of the photopolymerization initiator is preferably 30 parts by weight or less, more preferably 0% by weight, and particularly preferably 5% by weight to 5 parts by weight based on 100 parts by weight of the (B) polymerizable unsaturated compound. - Radical scavenger - The above-mentioned radical scavenger is applied to a substrate to form a coating film. The polymerizable unsaturated compound is produced in a liquid crystal alignment agent. It is avoided that in the case of the polymer group of the present invention, it is preferable to carry out the reaction of the base trapping agent of the present invention by heating, and to exemplify, for example, pentaerythritol tetra[3_ (3,5_二二护_#, __hydroxyphenyl)propionate], thio-extension ethyl bis-3-Π s "ester", , _--, and butyl _4-hydroxybenzene Propionate i 3 5 - trial two 丞 4- 4- 4- 4- 4- 4- 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙-hydroxybenzyl N,N'-hexane_丨,6-diylpropionamine), -butyl-4-hydroxybenzene 3,3',3",5',5"-six three Butyl triyl) three pairs of alpha, alpha, alpha, alpha - (mesitylene-2,4,6--35-201245356 4.6-bis(octylthiomethyl)o-nonylphenol, 4.6-two ( Dodecyl sulfonyl) o-nonylphenol, ethyl bis(oxyalkylene) bis[3-(5-tris-butyl-4-hydroxy-m-phenyl) propionate, 1,6 - hexyl bis[3-(3,5-ditributyl-4-hydroxyphenyl)propionate], 1,3,5-di(3,5-di-tributyl-4-one Basal base)-1,3,5-triple-2,4,6(1H,3H,5H)-trione, 1 3,5-tris[(4-tert-butyl-3-hydroxy-2,6-quinolinyl)methyl]_1,3,5-tritero-2,4,6(111,311,511)-trione , 2,6- >-secondary butyl-4-(4,6-di(octylthio)-1,3,5-tri-p-yl-2-ylamine)phenol, etc., which can be selected from them One or more of them may be used. As the radical scavenger, a commercially available product may be used, and for example, Adekastab AO-20, Adekastab AO-30 'Adekastab AO-40, Adekastab AO-50, Adekastab AO manufactured by ADEKA Co., Ltd., for example, is preferably used. -60, Adekastafc丨AO-70, Adekastab AO-80, Adekastab AO-330, Sumitomo Chemical GM, sumilizer GS, sumilizer MDP-S, sumilizer BBM-S, sumilizer WX-R 'sumilizer GA-80 »

IRGANOX1010, IRGANOX 1 035, IRGANOX 1 076, IRGANOX1 098, IRGANOX1 135, IRGANOX1330, IRGANOX1 726, IRGANOX1425WL, IRGANOX1 520L, IRGANOX245, IRGANOX259, IRGANOX31 14 , IRGANOX5 65 , IRGAMOD295 ; -36- 201245356 API by Ciba Japan Co., Ltd. Yoshinox BHT manufactured by Corporation

Yoshinox EiB, Yoshinox 2246G, Yoshinox 425 'Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshinox 9 1 7, Yoshinox 3 1 4, etc. The use ratio of the radical scavenger in the polymer composition of the present invention is preferably i 〇 part by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the (B) polymerizable unsaturated compound. [Polymer composition] The polymer composition used in the invention is preferably (A) poly-b-i on the j- and (B) polymerizable unsaturated compound and optionally dissolved in the 匕' additive. In the organic solvent, the solvent is used as a solution. I Ϊ organic solvent ' can be cited as a high boiling point solvent and its t 1 8 Ω ° Γ ·, A / Fu point solvent is atmospheric pressure (1.013 gt; < 105Pa) under the 180 ° C) boiling point j 钱Examples of the internal enthalpy include exemplified by 'methyl-acid B s, bis:: butyl Sa, methoxypropionate s, ethoxy ρ and the above-mentioned high-boiling-capacity V cellosolve). The above other organic solvents having different solvent strengths may, for example, be 2-pentanone, B-I, methyl acetamide, 4, yl + A,

Alcohol monomethyl ether, lactic acid butyl, acetic acid J 201245356 The (A) polymer in the present invention has a high solubility in a relatively common organic solvent, so that it can be prepared as a solution even if the above-mentioned high boiling point solvent is not used. Composition. Therefore, as a solvent containing the composition of the present hair cockroach compound, by using no high-boiling solvent, it is only used as a solvent and can be removed after the application of the polymer composition. In the step of firing 1, the solvent can be easily removed from the coating film even if the heating temperature is low. Therefore, the method of the present invention is also suitable for use in a synthetic resin substrate having a low heat resistance temperature. . The ratio of use as an organic solvent is preferably a solid content concentration of the polymer complex (the ratio of the total weight of the components other than the organic solvent in the polymer composition to the total weight of the polymer composition) is 1 to 2 The ratio of % is better than the ratio of 1 · 5 to 8 weight 0 / 〇. <Manufacturing Method of Liquid Crystal Display Element> The method for producing a liquid crystal display element of the present invention is characterized in that the above-described polymerization is applied to the conductive film of a pair of substrates having a conductive film by a knife a composition of the composition forms a coating film, and a pair of substrates on which the coating film is formed are interposed between the liquid crystal molecules, and the coating film is disposed opposite to each other to form a liquid crystal cell; The liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films. Here, as the substrate ', it is possible to use, for example, a glass such as float glass or soda glass; from polyethylene terephthalate, polyethylene terephthalate, g-butyl phthalate, polyether sulfone, polycarbonate. A transparent substrate formed of a synthetic resin such as polyethylene naphthalate, polyethyleneimine, a polyether resin, or a triacetyl cellulose (TAC). -38-201245356 As the transparent conductive film, a transparent conductive film is preferably used, and for example, a NESA film (registered trademark) formed of SnCh, an ITO film formed of In2〇3-Sn〇2, or the like can be used. Each of the conductive films is preferably a patterned conductive film divided into a plurality of regions. By applying a voltage between the conductive films for such a conductive film structure (described later), by applying different voltages to the respective regions, the direction of the pretilt angle of the liquid crystal molecules in the respective regions can be changed, whereby the viewing angle property can be broadened. When the polymer composition is applied to the conductive film of such a slab, it can be suitably applied by a coating method such as a roll coating method, a spin coating method, a printing method, or an ink jet method. After coating, the coating surface is pre-heated (pre-baked), and then post-baked (post-bake into a coating film. Pre-baking conditions such as 仏 5 minutes at ° C) are preferably used for baking conditions (10) ~3 ah, better 120~2,) 0C, especially good for 15〇~18〇t under the minute, better for 1〇~1〇〇 minutes.人# ’ 使 When the high-boiling solvent is not contained. The composition of the composition is post-baked at a temperature of 18 generations or less, and the method of the present invention is suitably used to: "spray the effect of the present invention". After baking, the film is _factor=low synthetic resin substrate is used 〇—(4) thickness is preferably 〇·〇〇ι plus better Μ Μ 罝 罝 造 造 造 造 造 造 造 , , , , , , , The rubbing treatment should be performed before the xk respect cell of the step described later. The old block is subtracted from the first hand. The hand rub is treated as a pair of coatings. - Nylon, rayon, and cotton enamel face are wrongly wound. The 4 fiber shape Λ Μ + friction is performed. Among them, the roller of the cloth such as s is described in the slogan of the slogan, and the slogan is published in the slogan of the slogan. 1 3 9 - 201245356 After forming a photoresist film, and then rubbing it in a different direction from the previous rubbing treatment, the photoresist film is removed. By performing such a treatment, different rubbing directions are formed for each region, which can be further improved. The viewing angle property of the obtained liquid crystal display element. Next, 'the pair of substrates on which the coating film is formed is interposed with the liquid crystal molecules interposed therebetween, and the coating film is opposed to each other to form a liquid crystal cell. As the liquid crystal molecules used herein, It is preferably a nematic liquid crystal having a negative dielectric orientation and twinning, and for example, a dicyanobenzene liquid crystal, a liquid crystal, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl may be used. The liquid-like layer aa, the phenylcyclohexane-based liquid crystal, etc. The layer of the liquid crystal molecule is preferably 1 to 5 μm. In order to produce the liquid crystal cell using the liquid crystal, two methods may be mentioned. Liquid crystal alignment film pair The two substrates are placed facing each other in the gap of the setter (the gap of the cells), and the peripheral portions of the sealed I:::: block substrate are bonded together, and after the filling liquid crystal is injected into the surface of the substrate and the sealing; Sealing the injection hole, which can be applied to the two substrates of the film: at a predetermined position where the liquid crystal is provided with the ultraviolet curable seal / i, the liquid crystal is applied at several positions, for example: the specification of the crystal alignment film surface The film is facing, at the same time, the nightingale/I-substrate and the liquid crystal is aligned to the entire surface to illuminate the ultraviolet light: the whole surface is spread out 'then' after the substrate. 2. The sealing agent is hardened, and the liquid crystal cell can be manufactured. Next, the liquid crystal cell irradiation light is applied to the conductive voltage applied to the substrate by the front cymbal. -40- 201245356 The voltage applied here may be, for example, a direct current or an alternating current voltage of 5 to 5 〇V. Ultraviolet rays and visible light including light having a wavelength of, for example, 15 〇 to 8 〇〇 ππ may be used, preferably ultraviolet rays containing light having a wavelength of 3 〇〇 to 4 〇〇 nm. As a light source for illuminating light, for example, a low voltage may be used. mercury High-pressure mercury lamp, heavy hydrogen lamp, metal-chemical lamp, argon resonance lamp, xenon lamp, excimer laser, etc. The above-mentioned preferred wavelength region of ultraviolet light can be combined by illuminating the aforementioned light source and, for example, a filter, a diffraction grating, and the like. The amount of light to be used is preferably 1,000 J/m 2 or more and less than 1 〇〇, and 〇〇〇j/m 2 ' is more preferably 1 ·, 000 to 50,000 J/m 2 . Currently known PSA mode In the manufacture of a liquid crystal display device, it is necessary to irradiate light of 1 〇〇, 〇〇〇J/m2, but in the method of the present invention, even if the amount of light irradiation is 5 〇, 〇〇〇J/m2 or less, and further When it is 10,000 J/m2 or less, a desired liquid crystal display element can be obtained, and in addition to contributing to reduction in the manufacturing cost of the liquid crystal display element, it is also possible to avoid deterioration of electrical properties due to strong light irradiation and low long-term reliability. Then, a liquid crystal display element can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell after the above-described treatment. The polarizing plate used herein may be a polarizing plate formed by stretching a polyvinyl alcohol by a polarizing film which is called a "ruthenium film" while sandwiching a polyvinyl alcohol protective film. A polarizing plate formed by the ruthenium film itself or the like.

[Synthesis Example J < Synthesis of (Α) Polymer> Synthesis Example Α-1 -41-201245356 In a 2000 mL three-necked flask, 83.07 g (0,50 m〇l) of benzene was used as the dicarboxylic acid. Citrate, 54.07g (0.40mol) of p-phenylenediamine and (-3-1〇m〇1) 3 5 -diaminobenzoic acid-3-cholestylalkyl ester as a diamine and 31〇〇g (〇 5〇m〇i) triphenyl phosphite, 42.4g (1.0 0mol) gasification chain, 250m bbit bite and 500ml of N-mercapto-2-pyrrolidinium, at l〇〇°c The reaction was carried out by stirring for 3 hours. After the reaction, the reaction mixture was poured into a large amount of ethanol, precipitated again, and 90 g of the polymer (A-1) (polyamide) was recovered by filtration. A small amount of the obtained polymer (A-1) was dissolved in N-methyl-2-pyrrolidone to form a solution having a polymer concentration of 1% by weight, and the measured solution viscosity was 60 mPa-s. Synthesis Example A-2 (1) Synthesis of vinyl monomer having a pretilt appearance site The compound (a-2) was synthesized according to the following Synthesis Scheme 1. -42- 201245356

(a-2-anhydride, in, in, in a 2000 mL three-sigma flask, 384, 64 g (1.00 mol) of 7-dehydrocholesterol, 33 8.56 g (1.20 mol) of the formula 0) The fluorosulfonium sulfonate and 202.2 g (2.0 mol) of triethylamine were dissolved in a nitrogen atmosphere in 840 mL of di-methane, and the mixture was stirred at -301 for 1 hour to carry out a reaction. Then, a small amount of distilled water was added to the reaction mixture each time. The reaction was stopped, and 300 niL of ethyl acetate was added thereto, followed by washing with dilute hydrochloric acid and distilled water. After the organic layer was dehydrated with magnesium sulfate, the solvent was removed to give a solid. -43- 201245356 In a 500 mL three-necked flask, the above solid and 0.112 g (0.0005 mol) of palladium acetate, 〇.608 g (0.002 mol) of tris(o-phenylphenyl)phosphorus, 100 mL of dimercapto B were placed under a nitrogen atmosphere. A mixture of decylamine (dehydrated product), 27.7 mL (0.20 mol) of diethylamine (dehydrated product) and 51.65 g (0.6 mol) of vinyl acetate was stirred at 1 15 ° C for 8 hours to carry out a reaction. After the reaction, 300 mL of ethyl acetate was added to the reaction mixture, followed by washing with dilute hydrochloric acid and distilled water. After dehydrating the organic layer with magnesium sulfate, the solvent was removed to give a solid. The obtained solid was recrystallized from ethanol to obtain white crystals of 3 7 3.4 g of the compound of formula (a - 2). (2) Synthesis of polyvinyl alcohol derivative In a 20 〇〇mL three-necked flask, 46 7 g (〇1πι〇ι) and 77 5 g (〇) in the white crystal of the compound represented by the above formula (a_2) were obtained. 9m〇1) After the acetic acid was dissolved in 5 〇〇mL of decyl alcohol, 5 〇〇nig azo-isobutyronitrile was added thereto, and stirred at 60 ° C for 5 hours to carry out radical polymerization. After the reaction, '25 rnL of the specified sodium hydroxide water was added to the reaction mixture, and the gluten solution was saponified at 4 rc for 1 hour, and then the reaction liquid was poured into the water to precipitate the product. The solid content was determined by filtration. The recovery was carried out and dried under reduced pressure to give 58 g of a polymer polyvinyl alcohol derivative. The solution of the smectic polymer (A_2) was dissolved in N_mercapto-2-pyrrolidone to form a solution having a polymer concentration of 丨〇% by weight, and the measured solution viscosity was 60 mPa·s ° -44 - 201245356 Synthesis Example A -3 In a 3〇〇mL four-necked flask equipped with a stir bar, a three-way wide and a thermometer, 15 g (〇.〇33 mol) of cholesteryl thioglycolate and 13 g (0.090 mol) of methacrylic acid were added. Glyceryl ester ' 7 2g (〇〇 84mol) methacrylic acid, 7.2g (〇_〇69mol) styrene and 7.2g (0.044mol) N-hexyl cis hydrazide dilute imide' then add 5 3 g as solvent Ethanol, 2.2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator, and 0.96 g of α-methylstyrene dimer as a molecular weight regulator. This was boiled in a nitrogen stream for about 10 minutes. After replacing the nitrogen in the system, the reaction was carried out at 70 ° C for 5 hours under a nitrogen atmosphere to obtain a solution containing 48% by weight of the polymer (A - 3 ). . Synthesis Example A-4 (1) Synthesis of precursor polymer In a 10,000 mL four-necked flask equipped with a stir bar, a three-way valve, and a thermometer, 42 〇g (5 mol) of vinyl acetate was added at 8 Torr. The lower part was searched and boiled by a nitrogen stream for about 10 minutes to replace the nitrogen in the system. Then, 12,512 kPa of ethylene gas was sealed in the flask, followed by addition of 5 〇g of 2,2'-azobis(2,4-quinolyl valeronitrile) as a polymerization initiator. The temperature in the flask was raised to 80 ° C, the temperature was maintained at 3 ° C. After the copolymerization reaction, the mixture was cooled to 30 ° C to stop the reaction. After the equivalent amount, after the reaction was stopped, 250 ml of a 1 N aqueous sodium hydroxide solution was added to the reaction mixture, and the mixture was stirred at 40 ° C for 1 hour to carry out saponification. The saponified reaction mixture was poured into an excess of water to precipitate a product. The precipitated product was recovered by filtration and dried under reduced pressure to give 288 g of a polyethylene/ethylene copolymer (the content of vinyl alcohol = 5 〇m 〇 1%). -45- 201245356 (2) Pre-tilt-developing carboxylic acid synthesis In a 5,000-mL three-necked flask, 389 g (1 mol) of 7-dehydro-3-cholesterol, 200 g (2 mol) of leucovorin needle, 2.0 L of acetic acid B were added. Vinegar, 1.47 g (12.0 mmol) of a decylamino group 0 to 0 and 167 mL (1.2 mol) of triethylamine were mixed, and stirred under reflux conditions at 80 ° C for 8 hours. About half of the stirred mixture was transferred to a separatory funnel and 700 mL of tetrahydrogen was added. After the muffle, it was washed twice with 250 mL of dilute hydrochloric acid and 3 times with 25 mL of distilled water. The remaining half of the mixture was also subjected to extraction washing in the same manner as in the above. The washed organic layers were combined and dried over magnesium sulfate. Thereafter, after filtering magnesium sulfate, it was concentrated by an evaporator to a liquid amount of about 1.2 L. The concentrated solution was allowed to stand at room temperature for about 1 hour to precipitate crystals. The crystals were collected by filtration. After carefully washing with ethyl acetate, solvent was evaporated under reduced pressure to give white crystals of (266.5 g (54.5 mmol) of succinic acid mono(3-(7-dehydro)cholenyl) ester. The rate is 54.5%). (3) Halogenation of pretilt angle developing carboxylic acid 4 89 g (1 〇 mm 〇 1) of the above-obtained mono(3-(7-dehydro)cholestyl succinate obtained in a 100 mL three-necked flask was taken out. Add 1^,;^-dimercaptocarbamide bath containing 0.6 54 § (5_5〇1111〇1) sulfite gas, and stir at 80 C for 6 minutes to carry out halogenation reaction. . After the reaction, the solvent and the remaining sulphur sulphur gas were removed using a pumping gas to obtain 4.56 g of a solid succinic acid mono(3-(7-de-, Β&p#, this μ-produced w w too) biliary Alkenyl) ester helium. (4) Synthesis of polyvinyl alcohol derivative All of the succinic leucovorin (3-(7--dehydro) choline alkenyl) obtained by the above (3) is dissolved in 25 tetrahydrofuran. 454, 9_〇1) and -46-201245356 into a solution, mixing 1.82 g (18 mmol) of triethylamine and 0.648 g of the precursor polymer obtained in the above (1) (equivalent to vinyl alcohol monomer equivalent) The reaction was carried out by stirring at room temperature for 2 hours at 9 mm. After the reaction, 150 mL of ethyl acetate was added to the mixture of i and washed with distilled water. The organic layer was dehydrated by magnesium sulfate, and the solvent was removed under reduced pressure to give 3 & A small amount of the obtained polymer (Α_4) was dissolved in Ν_methyl_1. A solution having a polymer concentration of 丨〇% by weight in the ketamine was measured to have a solution viscosity of 60 mPa·s. Example 1 <Preparation of Polymer Composition> The polymer (A-1) obtained as the above Synthesis Example A-1 of the (A) polymer was dissolved in butyl sirosu, in which j was To the above-mentioned (A) polymer, 1 part by weight of a compound represented by the following formula (B-1-1) which is (B) a polymerizable unsaturated compound is added to form a solid content concentration of 〇 by weight. / 〇 solution. The solution was filtered using a filter of pore size 丨μπι to prepare a polymer composition. <Manufacturing and Evaluation of Liquid Crystal Cell> Using the polymer composition prepared above, changing the pattern of the transparent electrode

In the case of the case (3 types) and the amount of ultraviolet irradiation (3 standards), a total of 9 liquid crystal cells were produced and evaluated as follows. Μ L

[Production of Liquid Crystal Cell Having a Patternless Transparent Electrode] The above preparation was applied to a transparent electrode surface of a glass substrate having a transparent electrode formed of a ruthenium film using a liquid crystal alignment film printer (manufactured by Nippon Photoprint Co., Ltd.). The polymer composition was heated on a hot plate of 8 Torr for 1 minute (prebaking), and after removing the solvent, it was heated on a hot plate at 150 ° C for 10 minutes (post-baking) to form an average film. A coating of 6 厚 people. -47-201245356 The coating film was subjected to a rubbing treatment using a rayon cloth wound at a roll rotation speed of 400 rpm and a table moving speed of 3 cm/s and 0·1 mm. Thereafter, ultrasonic cleaning was performed in y minutes, followed by a clean minute at 1 ° C to obtain a substrate having a liquid crystal alignment film. A pair (two pieces) of a substrate having a liquid crystal alignment film was obtained. Next, an oxygen resin adhesive having a diameter of 5 · 5 μm was applied to the outer edge of one of the pair of substrates, and then the liquid crystal alignment film surface was pressure-bonded to cure the adhesive. Next, a nematic liquid crystal was filled between the liquid crystal injection plates (manufactured by Merck, Inc., 'The liquid crystal was injected with an acrylic light-curing adhesive. The above operation was repeated, and three of the liquid crystal cells having a picture were used to directly use one of them. The two liquid crystal cells of the pretilt angle described later are subjected to light irradiation in the state of the conductive film by the following method, respectively, and thereafter, for evaluating the pretilt rate 〇 for two of the liquid crystal cells obtained above, respectively, at a frequency of 60 Hz. 〇V AC voltage, the amount of ultraviolet ray 10,000 J/m2 or i 〇〇, 〇0〇j/m2 used for the operation of the liquid crystal using a metal halide lamp as the light source. The irradiation amount is measured by the wavelength of 365 nm. The roller of the roller is woven into the length of 1 pure water for 1 to dry in a water box. 1 Repeat this operation, the liquid crystal alignment film of the aluminum ball of the epoxy pair of substrates overlaps the mouth 'on the pair of base MLC-6608) Mouth, the evaluation of the transparent electrode of the liquid crystal case. The remaining voltage and voltage applied between the electrodes remain in the state of application between the electrodes' using a grating device to UV. In addition, the value measured by the meter -48 - 201245356 [Evaluation of the pretilt angle] Each of the liquid crystal cells manufactured as described above is based on Non-Patent Document 2 (T j

Scheffer et al. J. Appl. Phys_ Vol. 48, p. 1783 (1 977)) and Non-Patent Document 3 (F. Nakano et al., JPN. J. Appl. Phys. Vol. 19, p. 2013 (1980) In the method described in the above, the value of the angle from the liquid crystal molecule to the substrate surface is measured by a crystal rotation method using He-Ne laser light, and the value is a pretilt angle. The pretilt angles of the liquid crystal cells which were not irradiated with light, the irradiation amount of l〇, the liquid crystal cell of 〇〇〇j/m2, and the liquid crystal cell of the irradiation amount of 100,000 J/m2 are shown in Table 2. [Evaluation of Voltage Retention Rate] Each of the liquid crystal cells manufactured as described above was applied with a voltage of 5 V at an interval of 60 μsec and a time of 167 msec at 23 ° C, and then the measurement was applied from the release to 1 6 voltage retention after 7 ms. As the measuring device, VHR-1 manufactured by τ 〇 γ 〇 Technica Co., Ltd. was used. The respective voltage holding ratios of liquid crystal cells irradiated with enthalpy of 10,0 0 0 J / m 2 and liquid crystal cells having an irradiation amount of 100,000 J/m 2 are shown in Table 2. [Manufacturing (1) of Liquid Crystal Cell Having Patterned Transparent Electrode] Each of the glass substrates a and B each having a slit-like pattern as shown in FIG. 1 and a ΪΤΟ electrode divided into a plurality of regions On the electrode surface, a liquid crystal alignment film printer (manufactured by Japan Photoprinting Co., Ltd.) was applied, and the polymer composition prepared above was coated on a hot plate of 801 by heating for 丨 minute (prebaking). After removing the solvent, at 1 On a hot plate at 50 °C, heat for 1 〇 minutes (post-baking) to form a coating film with an average film thickness of 600 people. After the coating film was subjected to ultrasonic cleaning for 1 minute in ultrapure water, it was dried in a clean room of 1 〇 1 for 1 〇 -49 - 201245356 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of (two pieces) substrates 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 the outer edge of one of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film faces are relatively opposed. Substrate overlap crimping 'hardens the adhesive. Next, a nematic liquid crystal (manufactured by Merck Co., Ltd., MLC-6608) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal cell was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell. Three liquid crystal cells having patterned transparent electrodes were fabricated. One of them is directly used for the response speed evaluation described later. The remaining two liquid crystal cells are "by 10,000 J/m2 or i" in a state where a voltage is applied between the conductive films by the same method as in the manufacture of the liquid crystal cell having the transparent electrode having no pattern. The irradiation amount of 〇j/m2 is used to evaluate the response speed after the light is irradiated. Further, the electrode pattern used herein is the same pattern as the electrode pattern in the PSA mode. [Evaluation of Response Speed] The visible light was applied to each of the liquid crystal cells produced as described above without applying a voltage, and the shell of the light transmitted through the liquid crystal cell was measured by a photo multimeter, and the value was relative transmittance 〇 %. Then, the light transmittance when a voltage of 6 交流V was applied between the electrodes of the liquid crystal cells for 5 seconds was measured in the same manner as above, and this value was made into a relative light transmittance of 1%. At this time, when a voltage of 6 〇V was applied to each liquid crystal cell, the time at which the relative light transmittance was changed from 10% to 9〇% was measured, and this time was defined as the music response speed. 3 - 50 - 201245356 The liquid crystal cell which is not irradiated with light, the irradiation amount is 丨〇, the liquid crystal cell of 〇〇〇J/m2 and the response speed of the liquid crystal cell having an irradiation amount of 100,000 j/m2 are shown in Table 2. [Production of Liquid Crystal Cell Having Patterned Transparent Electrode (2)] In addition to using the polymer composition prepared above, a glass substrate 分别 having a ruthenium electrode each having such a fishbone pattern as shown in Fig. 2 was used. In the same manner as in the production (1) of the liquid crystal cell having the above-described patterned transparent electrode, the liquid crystal cell which is not irradiated with light, the liquid crystal cell having an irradiation amount of 100 Å, and the JJ/m 2 and the irradiation amount are 1 〇〇, 〇 The liquid crystal cells of 〇〇J/m2 were used to evaluate the response speed in the same manner as described above. The evaluation results are shown in Table 2. Example 2 '4, 5 and 7 and Comparative Example 1 In addition to the above-mentioned Example 1, the types and amounts of the (A) polymer and (B) polymerizable unsaturated compound were respectively described as illusory, and were carried out. Example ^ A polymer composition was prepared in the same manner, and various liquid crystal cells were produced using the same. In addition, in the preparation of the polymer composition, the oxime-unsaturated compound in the coat of the type and amount of the stand-off A shown in Example 1 is used together with (B) the poly-incorporation and the compound, and the η is not saturated. In Example 7, except for Ύ f @ in addition to (A) poly 5 and (B) polymer, 佶田t, β - 丨王未化Γ More uses the types and amounts shown in Table 1 & The result of the evaluation of the polymerization property of the non-saturated compound in Comparative Example 1 is shown in Table 2. 201245356 Example 3 <Preparation of polymer composition> In a solution containing the polymer (AI-3) obtained as the above-mentioned Synthesis Example A-3 of the (A) polymer, butyl 赛路苏' was added. Diluted, in which 15 parts by weight of the compound (B-1-2-1) as the (B) polymerizable unsaturated compound is added to 100 parts by weight of the above (A) polymer to form a solid content concentration of 5 · 0 % by weight solution. This solution was filtered using a filter having a pore size of 丨μπι to prepare a polymer composition. <Production and Evaluation of Liquid Crystal Cell> Various liquid crystal cells were produced and evaluated in the same manner as in Example i except that the polymer composition prepared above was used. The evaluation results are shown in Table 2. Example 6 <Preparation of Polymer Composition> In a solution containing the polymer (A-3) obtained as the above-mentioned Synthesis Example A-3 of the (A) polymer, butyl sarbuta was added and diluted therein. 1 part by weight of a compound represented by the following formula (B-1-1) which is (b) a polymerizable unsaturated compound is added to 100 parts by weight of the above (A) polymer, and then the above (A) is based on 100 parts by weight. The polymer was added with 5 parts by weight of hydrazine-based hydrazine-based hydrazine-based phthalocyanine-3-formyl ester to form a solution having a solid content concentration of 5.0% by weight. The solution was transitioned using a filter having a pore size of 1 μm to prepare a polymer composition. <Production of Liquid Crystal Cell> Various liquid crystal cells were produced and evaluated in the same manner as in Example 除了 except that the polymer composition prepared above was used. -52- 201245356 The results of the evaluation are shown in Table 2. Example 8 <Preparation of Polymer Composition> A solution containing the polymer (A-4) obtained as the above Synthesis Example A 4 of the (A) polymer was dissolved in butyl sirosu, in which To the above (A) polymer, 5 parts by weight of a compound represented by the following formula (B-1 -1) as a polymerizable unsaturated compound was added to the (A) polymer to form a solution having a solid content concentration of 5.0% by weight. This solution was filtered using a filter having a pore size of 1 μm to prepare a polymer composition. <Production of Liquid Crystal Cell> Various liquid crystal cells were produced and evaluated in the same manner as in Example 1 except that the polymer composition prepared above was used. The evaluation results are shown in Table 2. Comparative Example 2 <Preparation of Polymer Composition> The compound represented by the following formula (Β-1 -1) which is a (Β) polymerizable unsaturated compound was dissolved in the butyl group without using a (ruthenium) polymer. In the road Su, a solution having a concentration of 15% by weight was formed. The solution was filtered using a transition vessel of pore size ημηι to prepare a polymer composition. <Production of Liquid Crystal Cell> In addition to the use of the polymer composition prepared above, various liquid crystal cells were produced in the same manner as in Example ,, and when the polymer composition was applied, coating pits were generated in a large amount, and it was impossible to produce a liquid crystal cell which can be evaluated. . -53- 201245356 Table 1 (A) Polymer (B) Polymerizable unsaturated compound Photopolymerization initiator Compound (B-1) Other unsaturated compound type (parts by weight) Type (parts by weight) Type (parts by weight) Type t (parts by weight) Example 1 A-1 100 B-1-1 10 — — — — Example 2 Λ-2 100 BM 15 — — — — Example 3 A-3 100 B-1-2- 1 15 — — — — Example 4 A-1 100 B-1-2-2 8 — — — — Example 5 A-2 100 B-1-2-1 10 B-2-1 5 — — Example 6 A-3 100 B-1-1 10 B-2-2 5 — — Example 7 A-1 100 B-1-3 15 — — C-1 0.1 Example 8 A-4 100 B-1-1 15 — — — — Comparative Example 1 A-1 100 — — — — — — Comparative Example 2 — — B-1-1 100 — — — — Liquid crystal cell having a patterned liquid crystal cell having a patterned electrode (1 Liquid crystal cell with electrode forming a round case (2) Pretilt angle (°) Voltage retention rate (%) Response speed (msec) Response speed (msec) Amethyst line exposure (J/m2) UV exposure (J /m2) Ultraviolet light 1 amount (J/m2) Ultraviolet irradiation t (J/m2) 0 10,000 100,000 1 0,000 100,000 0 10,000 100,000 0 10,000 100,000 Example 1 89.8 88.8 82.6 99.5 99.3 51 32 27 51 32 28 Example 2 89.9 86.1 79.5 99.6 99.2 51 29 24 51 29 24 Example 3 89.8 86.8 80.1 99.6 99.2 51 29 26 51 28 25 Example 4 89.9 88.8 82.5 99.5 99.3 51 32 28 51 32 28 Example 5 89.8 85.:> 79.2 99.2 98.9 51 27 22 51 28 22 Example 6 89.9 853 79.3 99.3 97,5 51 27 22 51 27 22 Example 7 89.9 82.6 75,2 99.2 97.6 51 26 21 51 26 22 Example 8 89.8 86.0 79.4 99.6 99.2 51 29 25 51 30 24 Comparative Example 1 89.7 89.7 89.6 99.4 96.1 52 52 52 52 52 52 Comparative Example 2 Evaluation In the above Table 1, the abbreviations of the respective components in the polymer composition are respectively the following meanings. -54- 201245356 [(B) Polymer Unsaturated Compound] Compound (B-1) B-1-1 : Compound B-1-2-1 represented by the following formula (B-1-1): In (B-1-2), η is a mixture of compounds of 2 to 4 Β-1-2-2: in the following formula (Β-1-2), the average value of the total amount of two η is 2.6 Mixture Β-1-3: a compound represented by the following formula (Β-1-3)

[Other unsaturated compounds] Β-2-1: 4-(4'-phenyl-dicyclohexyl-4-yl)phenyl hydrazide hydrazide-2-2: decyl acrylate-5 ξ-cholane -3-yl ester [photopolymerization initiator] C -1 ·Phenyl-(4-p-phenylene thiol-phenyl)-曱酉同-55- 201245356 [Simplified illustration] Figure 1 Description of the transparent conductive film pattern in the liquid crystal cell having the patterned transparent conductive film produced in the examples and the comparative examples Fig. 2 is a view showing the transparent conductive film having the pattern formed in the examples and the comparative examples. Explanation of the transparent conductive film pattern in the liquid crystal cell 〇 [Main component symbol description] 1 ITO electrode 2 slit portion 3 light shielding film - 56-

Claims (1)

201245356 VII. Patent application scope: The manufacturing method is characterized by the following steps: 1. The preparation of the liquid crystal display element: In the cloth having the conductive film, a polymer composition is (A) selected from the group consisting of polyamine, acid An unsaturated compound in the group formed; - a coating film is formed on the conductive film of the substrate, and the polymer composition contains at least one polymer of a polyvinyl alcohol derivative and poly(meth) propylene And (B) polymerizability is a layer in which a pair of substrates forming the coating film are interposed between liquid crystal molecules, and is disposed opposite to each other to form a liquid crystal cell; *In the month, the conductive layer of the substrate is The liquid crystal cell is irradiated with light in a state where a voltage is applied between the films. 2. The method for producing a liquid crystal display device according to claim 1, wherein the extract has a group selected from the group consisting of: a group having a retention structure; a group represented by the following formula (A-0), an alkyl group having 4 to 4 fluorene atoms (in the case where a group containing the above formula (Α·〇) is removed), and a carbon number of 4 ~40 fluorine L base, & (Formula (A-0) Let 'a' be 0 or 1 'b is an integer of 〇~2, where 3 and 匕 are not 0' 〇 are 整数~2〇 integers). -57-.201245356. A method for producing a liquid crystal display device according to claim 1 of the patent application has a T (B) polymerizable unsaturated compound ^ 佘 ... 佘 has the following formula in the molecule (BI () at least 2/(" of the compound (B-1), (BI) CH〇-C-C-Y" Y2 and γ3 are each independently (in the formula (BI), r is a hydrogen atom) Or a methyl group is an oxygen atom or a sulfur atom. The method for producing the element, the step of which comprises the following formula (Β-Π) 4. The above compound (B-1) is in the molecule in the liquid crystal display of claim 3 Further, at least one of the divalent groups shown, -x'-Y'-x2-(B-II} (in the formula (B-II), X1 and X2 are each,,,,,,,,,, , 4-phenylene or 1, stretched hexyl, γ1 is a single bond, the number of carbon atoms ^, the product 2 has a T sip as i~4 of a divalent hydrocarbon group, a subunit, a sulfur atom or -C00-, wherein The above χ> χ2 may be substituted by a group having 1 or a group of atoms having a carbon number of 4, an alkoxy group having a carbon number of 4, a fluorine atom or a cyano group.) The manufacture of a liquid crystal display element of claim 4 The compound (Β -1) is at least one compound selected from the group consisting of bis(meth) acrylate having a biphenyl structure having a biphenyl structure, having 2, 2 - Diphenylpropenyl bis(indenyl) acrylate, bis(indenyl) enoate having a diphenylnonane structure, and disulfo(indenyl) acrylate having a diphenyl sulfide structure The method for manufacturing a liquid crystal display device according to the first aspect of the invention, wherein the conductive film is a patterned conductive film divided into a plurality of regions, respectively. The method for producing a liquid crystal display device according to any one of claims 1 to 6, wherein the polymer composition is characterized by comprising: (A) selected from the group consisting of polyamines and polyethylenes. At least one polymer selected from the group consisting of an alcohol derivative and a poly(fluorenyl) acrylate, and (B) a polymerizable unsaturated compound.