TW201125942A - Manufacturing method of LCD element, polymer composition and LCD element - Google Patents

Abstract

Present invention provides a manufacturing method of LCD element which has characteristics of wide angle-of-view, liquid crystal molecular with rapid response speed, highly property of display and highly reliable. In the method, it is characteristic by following step: separately coating at least one of polymer (A) selected from a group consisting of polyamic acid and polyimide, and polymer composition (B) which contains specific compound represented by di(meth)acrylate having vinyl structure onto conductive films which is on a pair of substrates; forming coating film; installing a pair of substrates to have the coating film in opposite directions by inserting a liquid crystal molecular layer; forming liquid crystal cell; and illuminating beam on the liquid crystal cell when voltage are applied on conductive films of the pair of substrates.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a liquid crystal display device, a polymer composition, and a liquid crystal display device. In more detail, there is a new method for manufacturing a liquid crystal display element having a wide viewing angle and a fast response speed. [Prior Art] In the liquid crystal display device, a MVA (Multi-domain Vertical Alignment) type panel which is known as a vertical alignment mode has been formed by controlling protrusions of liquid crystal molecules by forming protrusions in the liquid crystal panel. Direction, thereby expanding the angle of view. However, according to this method, it is inevitable that the projections cause insufficient transmittance and contrast, and further have a problem that the response speed of the liquid crystal molecules is slow. In recent years, in order to solve the problem of the above M VA type panel, a PSA (P〇lymer Sustained Algnment) mode has been proposed. The PSA method is a gap between a pair of substrates formed of a substrate having a patterned conductive film and a substrate having a patterned conductive film, or a gap between a pair of substrates formed by two substrates having a patterned conductive film. A liquid crystal composition containing a polymerizable compound is irradiated with ultraviolet rays in a state where a voltage is applied between the conductive films, and the polymerizable compound is polymerized, thereby exhibiting a pretilt property and controlling the alignment direction of the liquid crystal. By using this technique, it is possible to achieve a wide viewing angle and a high speed response of liquid crystal molecules by making the conductive film have a specific structure, and it is also possible to solve the problem of inevitable transmittance and contrast of the MVA type panel. However, in order to polymerize the above-mentioned polymerizable compound, it is necessary to irradiate a large amount of ultraviolet rays such as ?4-201125942 1 00,000 J/m2, and therefore, it is shown that in addition to the problem of decomposition of liquid crystal molecules, there are still unreacted compound residues which cannot be polymerized by ultraviolet irradiation. In the liquid crystal layer, 'the combination of them produces uneven display, which adversely affects the voltage holding property' or the long-term reliability of the panel is problematic, and it is still not practical. On the other hand, 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 liquid crystal. The response of the liquid crystal molecules of the liquid crystal display element 'the liquid crystal alignment film formed by the method of the non-patent document 1' is fast. However, in Non-Patent Document 1, there is no indication as to what kind of reactive liquid crystal precursor should be used in what amount, and the amount of ultraviolet radiation necessary is still large, and the problem of display properties, particularly voltage holding properties, cannot be excluded. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2010-97188 [Non-Patent Document] [Non-patent document 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) 201125942 [Disclosure] The present invention has been made in view of the above problems, and its object is to provide a wide viewing angle. A method of manufacturing a liquid crystal display element having a fast response speed of liquid crystal molecules, excellent display properties, and long-term reliability. [Means for Solving the Problems] According to the present invention, the above object of the present invention is achieved by a method for producing a liquid crystal display device, which comprises the steps of: coating a conductive film on a pair of substrates having a conductive film, respectively; A polymer composition comprising a coating film comprising (A) at least one polymer selected from the group consisting of polylysine and polyimine, and (B) in a molecule a compound having at least one of a divalent group represented by the following formula (Bd) and at least two of the monovalent groups represented by the following formula (B-II): -X 1 - Y 1 -X2- (BI) In the formula (BI), X1 and X2 are each independently a 1,4-phenylene group or a 1,4-cyclohexylene group, and Y1 is a single bond, a divalent hydrocarbon group having a carbon number of 1 to 3 'oxygen An atom, a sulfur atom or -COO-, wherein the above X1 and X2 may be one or a plurality of alkyl groups having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom or a cyano group. Replace.

R

CH2=C Γγ3~(Β-ΙΙ) Υ2 201125942 In the formula (Β-II), 'R is a hydrogen atom or a methyl group, and γ2 and γ3 are each independently an oxygen atom or a sulfur atom. a liquid crystal cell is formed by a layer of liquid crystal molecules formed on the substrate, and the liquid crystal cell is formed in a direction in which a voltage is applied between the conductive films of the pair of substrates. The cells illuminate the light. [Effect of the Invention] The liquid crystal display element manufactured by the method of the present invention has a high viewing angle, a liquid crystal molecule having a high response speed, and exhibits sufficient transmittance and contrast. The display property is excellent, and the display property is not deteriorated even if it is continuously operated for a long period of time. Further, by the method of the present invention, even if the amount of light necessary for the irradiation is reduced, it is possible to reduce the manufacturing cost of the liquid crystal display element. Therefore, the liquid crystal display element manufactured by the method of the present invention has both performance and cost. The aspect is superior to the currently known liquid crystal display elements' suitable for various uses. [Embodiment] <Polymer Composition> The polymer composition used in the method of the present invention comprises: (Α) at least one polymer selected from the group consisting of polyproline and polyimine. And (化合物) a compound having at least one of a divalent group represented by the above formula (Β-Ι) and at least two of the monovalent groups represented by the above formula (Β-II) in the molecule. 201125942 [(A) Polymer] The polymer contained in the polymer composition used in the present invention is at least one selected from the group consisting of polylysine and polyimine. The polylysine may be synthesized by, for example, a reaction of a tetracarboxylic dianhydride and a diamine, and the polyimine may be synthesized by subjecting the polyamic acid to dehydration and ring imidization. [Tetracarboxylic dianhydride] Examples of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic acid II. Anhydride, etc. Specific examples of the aliphatic tetracarboxylic dianhydride include, for example, butane-based tetracarboxylic dianhydride; and examples of the alicyclic tetracarboxylic dianhydride include, for example, 1, 2, and 3; , 4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,33,4,5,913-hexahydro-5-(tetrahydro-2,5 - Bis-oxo-3-furyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5 - (tetrahydro-2,5-dioxaxos-3-furyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]xin- 2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-di-oxotetrahydrofurfuryl)-3-methyl-3 - cyclohexan-1,2-dicarboxylic acid: 3,5,6-tricarboxy-2-carboxymethylnordecane-2:3,5:6-dianhydride, 4,9-dioxa Tricyclo[5.3.1.02,6]undeccarbon-3,5,8,10-tetraketone, etc.; as the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, etc.; and the use of patent documents 2 (Tetracarboxylic acid dianhydride described in Japanese Patent Laid-Open Publication No. Hei 2 0 1 0 - 9 7 1 8 8). -8- 201125942 As the tetracarboxylic dianhydride for synthesizing the above polyamic acid, among them, it is preferred to use only an alicyclic tetracarboxylic dianhydride or an alicyclic tetracarboxylic acid dioxane and an aromatic A mixture of tetradecanoic dianhydride. In the latter case, the alicyclic tetraphthalic acid dianhydride occupies a proportion of the total tetracarboxylic dianhydride, preferably 20 m ο 1 % or more, more preferably 40 m ο 1 % or more. [Diamine] As the diamine used for the synthesis of the above polyamic acid, a diamine (hereinafter referred to as "specific diamine") containing a diamine having a group represented by the following formula (D') is preferably used. R, |Z4RlIV)^^HcH2^r (□*) In the formula (D'), R1 is an alkyl group having 4 to 4 carbon atoms or a fluoroindenyl group having 4 to 40 carbon atoms, or a hydrocarbon group having a steroid skeleton having 17 to 51 carbon atoms; Z1 is a single bond, *_〇_, *-C〇0_ or *_〇c〇· (wherein the bond bond with * is the R1 side); R11 is a cyclohexylene group or a phenyl group; η 1 is 1 or 2: wherein 'n丨 is 2, two R" may be the same or different; η2 is 〇 or 1; Ζ11 is *-0-, *-COO- or wherein the bond with * is the R1 side); η3 is an integer of 〇~2; η4 is 0 or 1. -9- 201125942 The number of carbon atoms of R1 in the above formula (D') is The alkyl group of 4 to 40 is preferably an alkyl group having 6 to 4 Å, and specifically, for example, a hexyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group or an octadecyl group. And as a fluoroalkyl group having 4 to 40 carbon atoms, preferably a carbon source The fluoroalkyl group having a subnumber of 4 to 20 may specifically, for example, be a trifluoromethylpropyl 'trifluoromethylbutyl group, a trifluoromethylhexyl group or a trifluoromethyl fluorenyl 'pentafluoroethyl propyl group. And a hydrocarbyl group having a carbon number of 17 to 51 having a steroid skeleton, and examples thereof include a cholesteryl group, a cholesteryl group, and a lanthanyl group. The exocyclohexyl and phenyl groups of R11 in the above formula (D ') are preferably 1,4-cyclohexylene and 1,4-phenylene, respectively. In the above formula (D'), as the formula - The divalent group is preferably a preferred substance, and when n1 is 1, for example, 1,4-phenylene group, 1,2-cyclohexylene group or the like; and when η 1 is 2, it is exemplified For example, 4,4 '-biphenyl, 4,4 '-dibicyclohexyl, a group represented by the following formula, etc.

Η3 in the above formula (D') is preferably 2. The specific diamine in the present invention is preferably an aromatic diamine having a group represented by the above formula (D'), and specific examples thereof include, for example, -10-201125942 4-diaminobenzene, fifteen-epoxy-2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diamino Benzene, doxayloxy-2,5-diaminobenzene, fifteenth oxy-2,5-diaminobenzene,

I hexadecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestene oxygen Base-3,5-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, 3,5-diaminobenzoic acid As the lanthanum aryl ester or the like, it is preferred to use one or more of them. As the specific diamine in the present invention, it is preferred to use a compound selected from the group consisting of cetyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, and cholestyloxy group. At least one of the group consisting of -3,5-diaminobenzene and cholestyloxy-3,5-diaminobenzene. As the diamine used for the synthesis of the above polyamic acid, only the specific diamine shown above may be used, or a specific diamine may be used together with other diamines. Other diamines which may be used herein are diamines having no group represented by the above formula (D '), such as aliphatic diamines, alicyclic diamines, aromatic diamines, diamine-based organic oximes The alkane or the like is not equivalent to the diamine of the above specific diamine. As specific examples thereof, as the aliphatic diamine, for example, 1,1-m-xylenediamine, 1,3-propylenediamine, 1,4·butylamine, 1,5-pentane can be cited. Amine, 1,6-hexanediamine, etc.; as the alicyclic diamine, for example, 1,4 -diaminocyclohexane, 4,4,-methylenebis(cyclohexylamine), i, 3_bis(aminomethyl)cyclohexanthes, etc. 0 -11 - 201125942 As the aromatic diamine, for example, p-phenylenediamine, 4,4,-diaminodiphenylmethane, 4, 4, -diaminodiphenylsulfate, hydrazine, 5-diaminonaphthalene, 2,2,-dimethyl-4,4,-diaminobiphenyl, 4,4'-diamino-2,2 '-bis(trifluoromethyl)biphenyl' 2,7-diaminopurine, 4,4,-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy) Phenyl]propane, 9,9-bis(4-aminophenyl) fluorene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2_two (4.Aminophenyl)hexafluoropropane, 4,4,-(p-phenylenediphenylidene)bis(aniline), 4,4,(inter)phenyldiisopropylidene) (aniline), 1,4_bis(4-aminophenoxy)benzene, 4 ,4,-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diamine Acridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3 ,6-Diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N,-bis(4-aminophenyl)-N,N'-dimethyl Examples of the diamine-based organodecanes include, for example, 3-bis(3-aminopropyl)-tetramethyldioxane, and Patent Document 2 (Japanese Patent Laid-Open No. 2010-- The diamine described in No. 97188). The diamine used for synthesizing the polyamic acid is preferably contained in an amount of 2 mol% or more, more preferably 2 to 60 mol%, further preferably 5 to 40 mol%, particularly preferably 1 to 30 mol%, based on the total of the diamine. % specific diamine as indicated above. [Molecular weight modifier] When synthesizing the aforementioned polyaminic acid, a terminal modified type -12-201125942 polymer can be synthesized by using an appropriate molecular weight modifier together with the tetracarboxylic acid diamine and the diamine as shown above. By forming the terminal-modified polymer, the coating property (printability) of the polymer composition can be improved without impairing the effects of the present invention. The molecular weight modifier may, for example, be an acid monoanhydride, a monoamine compound or a monoisocyanate compound. Specific examples thereof include, as the acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl salicylic anhydride, n-dodecyl salicylic anhydride, and tetradecyl. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, and the like. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine. Examples of the monoisocyanate compound include, for example, phenyl isocyanate, naphthyl isocyanate, and the like. The use ratio of the molecular weight modifier is preferably 1 part by weight or less based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine to be used. [Synthesis of Poly-Proline] The ratio of use of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of poly-proline is compared with the amine group of one equivalent of the diamine, and the anhydride group of the tetracarboxylic dianhydride Preferably, the ratio is from 2 equivalents to 2 equivalents, more preferably from 0.3 equivalents to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at -20 ° C to 150 ° C. More preferably at 0 to 100 ° C, preferably for 1 to 24 hours, more preferably. Good for 0.5 to 12 hours. Here, examples of the organic solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl-13-. 201125942 Aachen' γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine and other non-polar solvents; m-cresol, xylenol, phenol, halogenated phenol and other agents. The amount (a) to be used as the organic solvent is preferably tetracarboxylic dianhydride and the total amount (b), and the total amount (a + b) of the reaction solution is 0.1 to 30. As described above, a reaction solution in which polylysine is dissolved can be obtained. The reaction solution can be directly used for preparing a liquid crystal alignment agent; it is also used to prepare a liquid after separating the polyamic acid contained in the reaction solution; or after the separated polyamic acid is refined, it is used for preparing a liquid. When the poly (proline) is dehydrated and closed to form a polyimine, the solution can be directly used for the dehydration ring-closure reaction; or the polylysine which is dissolved in the separation reaction can be separated and used for the dehydration ring closure reaction; or the polyamine can be used. After acid refining, it is used for the dehydration ring closure reaction. Polylysine is carried out according to a known method. [Synthesis of Polyimine] The above polyimine can be obtained by subjecting a polyamine which is synthesized as above to ring closure and ruthenium. The polyimine in the present invention may be a pro-imine structure in which the proline structure of the precursor as a precursor is completely dehydrated and closed. It may be only a part of the acid structure. Part of the quinone imine compound that coexists with the ring structure. The polyamidization rate in the present invention is preferably 40% or more. The ruthenium imidization ratio is an isolated acid-dehydrated lysine which can be separated from the crystal phase by the crystal phase distribution to the above-mentioned reverse liquid by the weight percentage of the proton phenol-soluble diamine; the percentage of the structure and the quinone imine - 14-201125942 Indicates the ratio of the number of quinone imine ring structures to the total amount of the guanidine structure of the polyimine and the total amount of the quinone ring structure. The dehydration ring closure of polylysine is preferably carried out by heating poly-proline, or dissolving poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as needed. get on. Among them, the latter method is preferably carried out. In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyamic acid solution, examples of the dehydrating agent include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. The amount of the dehydrating agent is preferably from 0.01 mol to 20 mol, based on the valeric acid structure of 1 mol of the polyaminic acid. The dehydration ring-closure catalyst may, for example, be a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine. The amount of the dehydration ring-closure catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. The organic solvent used in the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as a solvent used for synthesizing polyglycine. The reaction temperature as the dehydration ring-closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. The reaction time is preferably 1 · 0 to 1 2 0 hours, more preferably 2 · 0 to 3 0 hours. Thus, a reaction solution containing polyimine can be obtained. The reaction solution can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after removing a dehydrating agent and a dehydration ring-closing catalyst from the reaction solution; and can also be used for preparing a liquid crystal alignment agent after separating the polyimine. Or after the purification of the polyimine from -15-201125942, it is used to prepare a liquid crystal alignment agent. These purification operations can be carried out according to a known method. [(B) Compound] The compound (B) used in the present invention has at least one divalent group represented by the above formula (BI) and at least two of the above formula (B-II) in the molecule. A compound of a valence group. The number of the monovalent groups represented by the above formula (B-II) in the compound (B) is preferably two. The divalent hydrocarbon group having 1 to 4 carbon atoms in the above formula (B-?) may, for example, be a methylene group or a dimethylmethylene group. Examples of the divalent group represented by the above formula (B-1) include a group represented by the following formulas (B-1 to 1) to (B-1 to 6), and the like. -16- 201125942 (B-I-2)

--ο-

The benzene ring and the cyclohexane ring in the above formulas (BI-1) to (BI-6) may each be an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 4 carbon atoms, or a fluorine atom. Cyano substitution. As γ2 in the above formula (B-II), an oxygen atom is preferred. The (B) compound used in the present invention may be a di(meth)acrylate having a biphenyl structure (the divalent group represented by the above formula (BI) is represented by the above formula (bh) a group, Y2 and Y3 in the above formula (B-II) are each an oxygen atom), -17- 201125942 a di(meth)propionic acid vinegar having a phenyl-cyclohexyl structure (the above formula (BI)) The divalent group is a group represented by the above formula (BI-2), Y2 and Y3 in the above formula (B-II) are each an oxygen atom), and a di(a) having a 2,2-diphenylpropane structure Acrylate (the divalent group represented by the above formula (BI) is a group represented by the above formula (BI-3), and Y2 and Y3 in the above formula (B_II) are each an oxygen atom), having a diphenyl group A di(meth) acrylate having a methane structure (the divalent group represented by the above formula (H) is a group represented by the above formula (Β·ΐ-4), and Y2 in the above formula (B-II) And Y3 are each an oxygen atom), a di-thio(meth)acrylate having a diphenyl sulfide structure (the divalent group represented by the above formula (8-1) is a compound of the above formula (8-1-5) The group shown, Y2 in the above formula (8_11) is an oxygen atom, Y3 is a sulfur atom) and others (B) a compound. Specific examples thereof include, as a di(meth)acrylate having a biphenyl structure, for example, 4,-propenyloxy-biphenyl-4-yl-acrylate, 4'-methyl. Propylene methoxy-biphenyl-4-yl-methacrylate '2-[4-(2-propanyloxy-ethoxy)-biphenyl-4-yloxy]-ethyl acrylate , 2-[4'-(2-methylpropenyloxy-ethoxybiphenyl-4-yloxy)ethyl (methacrylate), dihydroxyethoxybiphenyldiacrylate,

C -18- 201125942 Di-based ethoxylated biphenyl dimethacrylate, 2-(2_{4'-[2-(2-propenyloxy-ethoxy)-ethoxy]-linked Benz-4-yloxy}-ethoxy)-ethyl acrylate, 2_(2·{4'-[2-(2-methylpropenyloxy-ethoxy)-ethoxylated Phenyl-4-yloxy}-ethoxy)-ethyl methacrylate, ethylene oxide adduct of biphenyl, di- acrylate of biphenyl's ethylene oxide adduct Diacrylate of propylene oxide adduct of acrylate, biphenyl, dimethacrylate of propylene oxide adduct of biphenyl, 2_(4'-acryloxy-biphenyl-4-yloxy Ethyl acrylate, 2-(4'-methacryloxyl-biphenyl-4-yloxyethyl methacrylate, etc.; as di(methyl) having a phenyl-cyclohexyl structure The acrylate may, for example, be 4-(4·acryloxy-phenyl)-cyclohexyl acrylate or 4-(4-methylpropenyloxy-phenyl)-cyclohexyl methacrylate. 2-{4-[4-(2-Propyloxy-ethoxy)-phenyl]-cyclohexyloxyethyl acrylate, 2-{4-[4_(2-methylpropene) Oxy-ethoxy)-phenyl]-cyclohexyloxy}-ethyl methacrylate, 2-[2-(4-{4-[2-(2-propanyloxy-ethoxy) () ethoxylated phenyl}-cyclohexyloxy)-ethoxy]•ethyl acrylate, 2-[2-(4-{4_[2-(2-methylpropenyloxy)- Ethoxy)-ethoxy]_ -19- 201125942 phenyl}-cyclohexyloxy)-ethoxy]-ethyl methacrylate, etc.; as a structure having a 2,2-diphenylpropane structure The (meth) acrylate ' can be exemplified by, for example, 4-[1-(4-propenyloxy-phenyl)-1-methyl-ethyl]-phenyl acrylate, 4-[1-(4- Methyl propylene oxide oxy-phenyl)-1-methylethyl]-phenyl-methacrylate, 2-(4-{1-[4-(2-propanyloxy)-B Oxy) phenyl]-1-methyl-ethyl}-phenoxy)-ethyl acrylate, 2-(4-{1-[4-(2-methylpropionyloxy)-B Oxy)-phenyl]-1-methyl-ethyl}-phenoxy)-ethylmethylpropanoic acid vinegar, diacetoxy-bisphenol A diacrylate, dihydroxyethoxy -bisphenol A dimethacrylate '2-{2-[4-(1-{4-[2-(2-propenyloxy-ethoxy)-ethoxy]-phenyl}-1 -methyl-ethyl)- Oxy]-ethoxydiethyl acrylate, 2-{2-[4-(1-{4-[2-(2-methylpropenyloxy-ethoxy)-ethoxy]-phenyl }-1-Methyl-ethyl)-phenoxy]-ethoxy}-ethyl methacrylate, diacrylate of ethylene oxide adduct of bisphenol A, epoxy of bisphenol A Dimethacrylate of ethane adduct, diacrylate of propylene oxide adduct of bisphenol A, dimethacrylate of propylene oxide adduct of bisphenol A, 2-(4-丨1-[4-(2-Propyloxy-propoxy)-phenyl]-1-methyl-ethyl-20- 201125942-}-phenoxy)-ι-methyl-ethyl acrylate, 2-(4-{1-[4-(2-methylpropenyloxy-propoxy)-phenyl]-1-methyl-ethyl}-phenoxy)-1-methyl-B Methyl methacrylate, 2-{2-[4-(1-{4-[2-(2-propenyloxy-propoxy)-propoxy]-phenyl) 1-methyl-1 -ethyl)-phenoxy]-1-methyl-ethoxy}-1-methyl-ethyl acrylate, 2- {2-[4-(1-{4-[2-(2 - Methyl propylene methoxy-propoxy)-propoxy]-phenyl}_1-methyl-1-ethyl)-phenoxy]-1-methyl-ethoxy}-1_methyl -ethyl methacrylate, 3- {4-[1- (3-{1-[4-(3-Propyloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl}-phenyl)-1-methyl-ethyl Phenoxy-2-hydroxy-propyl acrylate, 3_{4-[1-(3-{1-[4-(3-methylpropenyloxy-2-hydroxy-propoxy)-phenyl) ]-1-methyl-ethyl}-phenyl)-1-methyl-ethylphenoxy-2-hydroxy-propyl methacrylate, 3-(4-{1-[4-(3 -propenyloxy-2-hydroxy-propoxy)-3-cyclohexyl-phenyl]-1-methyl-ethyl}-2-cyclohexyl-phenoxy)-2-hydroxy-2-propane Acrylate, 3-(4-{1-[4-(3-methylpropenyloxy-2-hydroxy-propoxy)-3-cyclohexyl-phenyl]-1-methyl-ethyl }-2-cyclohexyl-phenoxy)-2-hydroxy-2-propyl methacrylate, 3-(5-U-[6-(3-propenyloxy-2-hydroxy-propoxy) )-biphenyl-21 - 201125942-3-yl]-1-methyl-ethyl-biphenyl-2-yloxy)-2-hydroxy-propyl acrylate, 3-(5-{1 -[6-(3-methacryloxy-2-hydroxy-propoxy)-biphenyl-3-yl]-1-methyl-ethyl-biphenyl-2-yloxy) 2-hydroxy-propyl methacrylate, 3-{4-[1-(4-{1-[4-(3-propenyloxy-2-hydroxy-propoxy)-3-methyl -bensyl-1-methyl-ethyl}-phenyl)-1-methyl-ethyl]-2-methyl-phenoxy-2-hydroxy-propyl acrylate, 3-{4- [1-(4-{1-[4-(3-Methylpropenyloxy-2-hydroxy-propoxy)-3-methyl-phenyl]-1-methyl-ethyl}-benzene ))-1-methyl-ethyl]-2-methyl-phenoxy}-2.hydroxy-propyl methacrylate, 3-(4-{1-[4-(3- propylene) Oxy-2-trans-propyl-propoxy)-benzyl]-1-methyl-ethyl}-phenoxy)-2-hydroxy-propyl acrylate, 3-(4-{1-[4 -(3-Methoxypropenyloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl}-phenoxy)-2-hydroxy-propyl methacrylate, 3 -[4-(1-{4-[3-(4-{1-[4-(3-Propyloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-Phenoxy)-2-hydroxy-propoxy-]-phenyl}-1-methyl-ethyl)-phenoxy]-2-hydroxy-propyl acrylate, 3-[4-( 1·{4-[3-(4-{1-[4-(3-Methylpropenyloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl}-benzene Oxy)-2-hydroxy-propoxy-]-phenyl}-1-methyl-ethyl)-phenoxy]-2-hydroxy-propyl methacrylate, 3-{4-[1 -(4-{3·[4-(1-{4-[3_(4-{1-[4-(3-acryloxy)基-22- 201125942 -2-Phenyl-propoxy)-phenyl]-1-methyl-ethyl}-phenoxy)_2-hydroxy-propoxy-]-phenyl}-1-A Benzyl-ethyl)-phenoxy]-2-hydroxy-propoxyphenyl}-1-methyl-ethyl)-phenoxy}_2· benzyl-propyl-acrylic acid vinegar, 3- {4-[1-(4-{3-[4-(1-{4-[3-(4-{1-[4-(3-Methylpropenyloxy-2-hydroxy-propoxy) )-Phenyl]-1-methyl-ethylphenoxy)_2-hydroxy-propoxy-]-phenyl}-1-methyl-ethyl)-phenoxy]-2-hydroxy- Propoxy-]-phenyl}-1-methyl-ethyl)-phenoxy}-2-yl-propylmethyl acrylate vinegar, 1- (2-{4-[1-( 4-{2-[2-hydroxy-3-(1-methylene-aryloxy)-propoxy]-propoxyphenyl)-1-methyl-ethyl]-oxy}-1 _Methyl-ethoxy)-3-(1-methylene-aryloxy)-propan-2-ol; etc.; as a di(meth) acrylate having a diphenylmethane structure, it is exemplified For example 4-(4-propenyloxy-benzyl)-phenyl acrylate, 4-(4-methylpropenyloxy-benzyl)-phenyl methacrylate, 2-{4-[4 -(2-propanyloxy-ethoxy)-benzyl]-phenylethyl benzoate, 2_丨4-[4-(2-methyl Acryloxy-ethoxy)-benzyl]-phenyl}-ethyl methacrylate, an ethylene oxide adduct of diacid F, a diacrylate, a double-brown F-epoxy Adducts of dimethacrylate 'Double-F, a diacetate-added diacrylate, a double-brown F-oxygen propylene compound adduct of dimethacrylate, 2 [2-(4 -{4-[2_(2_propanoximeoxy-ethoxy)-ethoxy]-indole-23- 201125942 base}-phenoxy)-ethoxy]-ethyl acrylate, 2- [2-(4-{4-[2-(2-Methylpropenyloxy-ethoxy)-ethoxy]-]}-phenoxy}-phenoxy)-ethane group]-ethylmethyl Acrylic acid vinegar, 2_{4·[4-(2-propenyloxy-propoxy)-benzyl-phenoxy}_丨-methyl-ethyl acrylate, 2-{4-[4 -(2-Methylpropenyloxy-propoxy)-benzyl-phenoxy}-1-methyl-ethyl methacrylate, 2_[2-(4-{4-[2-( 2-propenyloxy-propoxy)-propoxybenzylidene}-phenoxy)-1-methyl-ethoxy]-1-methyl-ethylethyl acrylate, 2-[2- (4-{4-[2-(2-Methylpropenyloxy-propoxypropoxyl}}-phenoxy)-1-methyl-ethoxy]-1-methyl-B Base ethyl a methacrylate or the like; as the di-thio(meth)acrylate having a diphenyl sulfide structure, for example, 4-(4-thiopropenyloxysulfanyl-phenylsulfanyl group) )-Phenyldithioacrylate, 4-(4-thiomethylpropenyloxysulfanyl-phenylsulfanyl)-phenyldithiomethacrylate, bis(4-methacrylofluorene) Examples of the other (B) compound include 2,5-bis{4-(3-propenyloxy-propoxy)-benzoic acid}toluene. The (B) compound can be obtained from commercial products in addition to being synthesized by a conventional method in which organic chemistry is appropriately combined. As a commercial product of the (B) compound, -24-201125942 may, for example, be dihydroxyethoxy BP diacrylate or bishydroxyethoxy Bis-A diacrylate (manufactured by Honshu Chemical Industry Co., Ltd.); ARONICS M- 208, M-210 (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.); NK ESTER BPE-100, NK ESTER BPE-200, NK ESTER BPE-500, NK ESTER BPE-1300, NK ESTER A-BPE-4 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Actilai 420 (made by Siber Hegner Co., Ltd.) ):

Light Ester BP-2EM 'Light Acrylate BP-4EA ' Light Acrylate BP-4PA, Epoxy Ester 3 0 0 0 M, Epoxy Ester 3 000A (manufactured by Kyoeisha Chemical Co., Ltd.); V# 540, V# 700 (Osaka Organic Chemical Industry Co., Ltd.; FA-32 1M (manufactured by Hitachi Chemical Co., Ltd.); MPSMA (manufactured by Sumitomo Seika Co., Ltd.);

Ripoxy VR-77 (made by Showa Polymer Co., Ltd.). The compound (B) used in the present invention is preferably at least one selected from the group consisting of the compounds exemplified above. The proportion of the compound (B) used in the polymer composition used in the present invention is preferably from 1 to 1 part by weight, more preferably from 5 to 50 parts by weight, per 100 parts by weight of the (A) polymer. . [Polymer Composition] The polymer composition used in the present invention is preferably prepared by dissolving the above-mentioned (A) polymerized -25-201125942 and (B) compound in a suitable organic solvent to form a solution. Examples of the organic solvent which can be used herein include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butylide, hydrazine, hydrazine-dimethylformamide, and hydrazine. Ν-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl Ethoxypropionate 'ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cyproterone), Ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether 'diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol single Ethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, two Isopentyl ether and the like. The ratio of use of the organic solvent is preferably a solid content concentration of the polymer composition (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 15% by weight. The ratio is preferably 1. 5 to 8 wt%. <Manufacturing Method of Liquid Crystal Display Element> The method of manufacturing a liquid crystal display element of the present invention is characterized by the following steps: coating the polymer composition as described above on the conductive film of a pair of substrates having a conductive film Forming a coating film, forming a pair of substrates on which the coating film is formed, and arranging the coating film in a direction opposite to each other by a layer of liquid crystal molecules to form a liquid crystal cell, -26-201125942 having conductivity in the pair of substrates In a state where a voltage is applied between the films, the light illuminates the liquid crystal cell. Here, as the substrate, for example, glass such as float glass or soda lime glass; plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime or polycarbonate can be used. A transparent substrate or the like formed. As the conductive film, a transparent conductive film is preferably used, and for example, a NESA film formed of Sn02, an ITO film formed of In2〇3-Sn02, or the like can be used. Each of the conductive films is preferably a patterned conductive film divided into a plurality of regions. By forming such a conductive film structure, when a voltage is applied between the conductive films (described later), by applying different voltages to the respective regions, the direction of the pretilt angle of the liquid crystal molecules in each region can be changed, thereby further expanding The nature of the perspective. The polymer composition may be applied to the conductive film of the substrate by a suitable coating method such as a roll coating method, a spin coating method, a printing method, or an ink jet method. After coating, the coated surface is formed by preheating (prebaking) and then firing (post baking). The prebaking conditions are, for example, 4 Torr to 12 (TC is carried out for 0.1 to 5 minutes; and the post-baking condition is preferably 120 to 300 ° C, more preferably 150 to 250 ° C, preferably 5 to 200 minutes, more preferably 1 〇 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001 to Ιμηι, more preferably 0.005 to 0.5 μηι. The coating film thus formed can be directly It is used in the production of liquid crystal cells in the following steps, or it may be subjected to rubbing treatment on the surface of the coating film as needed before the production of the liquid crystal cell. The rubbing treatment is performed by winding fibers such as nylon, artificial -27-201125942 silk, cotton, etc. The roll of the formed cloth is applied to the surface of the coating film. As described in the patent document Η曰本特开开报, after the rubbing treatment is performed, the resist film is formed, and then the rubbing treatment is performed. After the rubbing treatment, the treatment for removing the photoresist film is performed, and the obtained viewing angle properties can be further improved for different rubbing directions. Then, the pair of substrates on which the coating film is formed are arranged such that the coating film is opposed to each other to form a liquid crystal moon. The liquid crystal molecules used herein are preferably anisotropic liquid crystals, and for example, a dicyano group can be used. Liquid crystal, Schiff base liquid crystal, oxygen azo based liquid 曰 1 phenylcyclohexane liquid crystal, and the like. Layer 1 of liquid crystal molecules 〜5 μηι 〇 The liquid crystal cell is produced by using the liquid crystal, and a method can be cited. As a first method, each of the liquid crystal alignment film gaps (cell gaps) is disposed such that the two substrates are opposed to each other, and the peripheral portion of the dense plate is bonded, and after filling the liquid crystal by the surface of the substrate and the gap, Seal the injection hole from the cell. Alternatively, as a second method, a sealing agent is applied at a predetermined position on one of the substrates formed on the liquid substrate, and then liquid crystal is dropped on the liquid crystal alignment film surface to rub the surface of the public coating film ρ 5-107544 in a certain aspect. A part of the different directions is made by making the liquid crystal display elements of the respective regions 丨 liquid crystal molecules, 3 . Negative dielectric orientation: benzene liquid crystal, 嗒哄k, biphenyl liquid crystal, f thickness is preferably, for example, the following two sides [opposite, by means of a sealant, two base sealants By distinguishing between the two cells of the liquid crystal crystal alignment film, such as ultraviolet light curing, the liquid crystal alignment -28-201125942 film is bonded to the other substrate in the opposite direction. Then, the front surface of the substrate is irradiated with ultraviolet light, and the sealing is hardened. The agent can thereby produce a liquid crystal cell. Then, in a state where a voltage is applied between the conductive films of the pair of substrates, the liquid crystal cells are irradiated with light. The voltage applied here may be, for example, a direct current or an alternating current voltage of 5 to 50 volts. As the light to be irradiated, ultraviolet light and visible light containing light having a wavelength of 150 to 800 nm can be used, and ultraviolet light containing light having a wavelength of 300 to 400 nm is preferable. As the irradiation light source, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon resonance lamp, an excimer laser or the like can be used. The ultraviolet light in the above preferred wavelength region can be obtained by using the above-mentioned light source, for example, a mechanism used together with a filter, a diffraction grating, or the like. The irradiation amount of light is preferably 1,0 00 J/m2 or more and less than 100,000 J/m2, more preferably 1,000 to 50,000 J/m2. When manufacturing a liquid crystal display element of the PSA mode which is currently known, it is necessary to irradiate light of about 〇〇, 〇〇〇]/m2, but in the method of the present invention, even if the amount of light irradiation is 50, O00J/m2 or less Further, when it is 10,000 J/m 2 or less, a desired liquid crystal display element can be obtained, and in addition to contributing to reduction in manufacturing cost of the liquid crystal display element, it is possible to avoid deterioration of electrical properties due to irradiation of strong light and deterioration in 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 -29-201125942 polarizing plate used herein may be a polarizing plate polarizing plate in which a polyvinyl alcohol is stretched toward a '-acid cellulose protective film to sandwich an iodine-absorbing iodine called a "ruthenium film" or formed of a ruthenium film itself. Polarizer and the like. [Examples] Synthesis Example 1 110 g (0.50 mol) of 2,3,5-tripentylacetic acid dianhydride as a tetracarboxylic dianhydride, and 43 g (0.40 m 〇1) as a diamine of benzotriene 3 52 g ( 0.10 mol) of 3-(3,5-diaminobenzimidyloxy) cholesterane in 830 g of N-methyl-2.pyrrolidone was subjected to t at 60 °C. A small amount of the obtained polyaminic acid solution was added, and N. methyl ketone was added to form a solution having a polyglycine concentration of 10% by weight. The viscosity was measured to be 60 mPa_s. Next, l,9〇〇g-based 2-pyrrolidone was added to the obtained polyaminic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were added to carry out a dehydration ring-closure reaction for 4 hours. After the dehydration ring closure reaction, the body 3 was replaced with a new N-methyl-2-pyrrolidone solvent (the pyridine and acetic anhydride used in the ring closure reaction were removed to the outside of the system in this operation) to contain about 15% by weight of hydrazine. A polyimide solution having an imidization rate of about 50%. A small amount of the obtained polyimine solution was added, and N-methylrrolidone was added to form a solution having a polyamidimide concentration of 1% by weight. The viscosity of the release was 47 mPa_s. The tricarboxyl ring g diamine formed by using vinegar and the solution of N-methyl 1 10 〇C dissolved in the solution of »hour anti-2 -pyrrole are dehydrated to obtain (PI-1). Base-2 · pyridinium 1 solution -30- 201125942 Example 1 <Preparation of polymer composition> The polyaniline-containing amine (PI-1) obtained in the above Synthesis Example 1 as the (A) polymer In the solution, N-methyl-2-D is slightly added as an organic solvent (NMP) and butyl cyanidin (BC), and then the following formula (B-1) is added as the compound (B). The compound represented by the above-mentioned (A) polymer is 20 parts by weight, and the solvent composition Ν : P : BC = 5 〇: 5 〇 (by weight), and the solid content concentration of 6.0% by weight is formed. Solution. This solution was filtered using a sieve of pore size 1 to prepare a polymer composition.

Using the polymer composition prepared above, the pattern (two types) of the transparent electrode and the ultraviolet irradiation amount (three grades) were changed, and a total of six liquid crystal display elements were produced and evaluated as follows. [Production of liquid crystal cell having a transparent electrode without a picture] The liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.) was used to coat the above-prepared surface on the transparent electrode surface of a glass substrate having a transparent electrode formed of an ITO film. The polymer composition was heated on a hot plate at 80 ° C 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 thickness. 600 coats of film. The coating film was subjected to a rubbing treatment by a friction device having a roller for winding a rayon cloth at a roll rotation speed of 400 rpm, a table moving speed of 3 cm/s, and a pile press-in length of 0.1 mm -31 to 201125942. Thereafter, ultrasonic washing was performed for 1 minute in ultrapure water, and then dried in a loot cleaning oven for 10 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 each of the outer edges of the pair of substrates having the liquid crystal alignment film, and then pressure-bonded to overlap the liquid crystal alignment film surface to bond the liquid crystal alignment film. The agent hardens. Then, from the liquid crystal injection port, a nematic liquid crystal (manufactured by Merck, MLC-66 0 8) is filled between the pair of substrates, and then the liquid crystal injection port is sealed by an acrylic photo-curing adhesive to manufacture a liquid crystal cell. . The above operation was repeated to produce three liquid crystal cells having a transparent electrode without a picture. One of them is directly used for the pretilt angle evaluation described later. The remaining two liquid crystal cells were used to evaluate the pretilt angle and the voltage holding ratio after light irradiation in a state where a voltage was applied between the conductive films by the following method. Two of the liquid crystal cells obtained above were applied with an alternating voltage of 10 Hz at a frequency of 60 Hz between the electrodes, and in the state of driving the liquid crystal, an ultraviolet ray irradiation device was used, which irradiated the ultraviolet ray with a metal halide lamp as a light source, and the irradiation amount was 1 0,0 00J/m2 or 1 00,000J/m2. Further, the amount of irradiation is measured by a light meter measured using a wavelength of 3 6 5 nm. [Evaluation of Pretilt Angle] Each of the liquid crystal cells manufactured as described above is according to Non-Patent Document 2 (T. J. Scheffer et. al., J. Appl. Phys. vol. 48, p. 1783 (1977)) and non-patent. The method described in Document 3 (F. Nakano, et. al., JPN. J. Appl. Phys_ vol. -32-201125942 19, p_2〇13 (1980)), by crystal rotation using He-Ne laser The method 'measures the 値 from the angle at which the liquid crystal molecules are inclined toward the substrate surface, and the 値 is the pretilt angle. The pretilt angles of the liquid crystal cells having an unexposed light, the liquid crystal cell having an irradiation amount of 1,0 0 0 J / m 2 , and the liquid crystal cells having an irradiation amount of 1,100,000 J/m 2 are shown in Table 1. [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 an interval of 167 ms at 23 ° C, and then measured from the release of the voltage. The voltage holding ratio after milliseconds. As the measuring device, VHR-1 manufactured by TOYO Corporation was used. The respective voltage holding ratios of the liquid crystal cells of the 〇〇〇J/m2 and the liquid crystal cells having an irradiation amount of 100,000 J/m2 were as shown in Table i. [Production of Liquid Crystal Cell Having Patterned Transparent Electrode] Using the slit-like pattern shown in FIG. 1 to form a liquid crystal on each of the electrode faces of the glass substrates A and B each having an ITO electrode divided into a plurality of regions An alignment film printer (manufactured by Japan Photo Printing Co., Ltd.), coated with the polymer composition prepared above, and heated on a hot plate at 80 ° C for 1 minute (prebaking) 'after removing the solvent, at 1 50 The hot plate of °C was heated for 10 minutes (post-baking) to form a coating film having an average film thickness of 600A. The coating film was ultrasonically washed in ultrapure water for 1 minute, and then dried in a cleaning tank of 10 °C for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two pieces) of substrates having a liquid crystal alignment film. -33- 201125942 Next, after coating the outer edges of the pair of substrates having the liquid crystal alignment film, an epoxy resin adhesive having a diameter of 5 · 5 μm of alumina balls is applied, and then the pressure bonding is performed so that the liquid crystal alignment film faces are opposite. , harden the adhesive. then. From the liquid crystal injection port, a nematic liquid crystal (manufactured by Merck, MLC-660 8) was interposed between a pair of substrates, and then the liquid crystal cell was filled with an acrylic photo-curing adhesive to produce a liquid crystal cell. The above operation was repeated to fabricate three liquid crystal cells having a patterned transparent electrode. One of them is directly used for the response speed evaluation described later. The remaining two liquid crystal cells are irradiated with a dose of 10,000 J/m 2 or 100,000 J/m 2 in a state where a voltage is applied between the conductive films in the same manner as in the production of the liquid crystal cell having the above-described transparent electrode without a transparent electrode. Used to evaluate the response speed. Further, the electrode pattern used here is the same pattern as the electrode pattern in the PSA mode. [Evaluation of response speed] The liquid crystal cells manufactured as described above were not applied with a voltage, and the visible light was irradiated. The brightness of the light transmitted through the liquid crystal cell was measured by an optical multimeter, and the 値 was used as the relative transmittance 〇%. Then, when a voltage of 60 V was applied between the electrodes of the liquid crystal cell for 5 seconds, the transmittance was measured in the same manner as described above, and the enthalpy was used as a relative transmittance of 100 °/. . When 60 V ac was applied to each of the liquid crystal cells at this time, the time when the relative transmittance was shifted from 10% to 90% was measured, and this time was defined as the response speed and evaluated. -34- 201125942 The liquid crystal cell with an irradiation dose of 1 0, 0 00 j/m2, the irradiation amount is 100, and the response speed of each of the liquid crystal cells of 〇〇〇J/m2 is shown in Table 1. (Examples 2 to 5) A polymer composition was prepared in the same manner as in Example 1 except that the type and amount of the compound (B) were as described in Table 1, and various polymer compositions were used to produce various kinds. The liquid crystal cells were evaluated. The evaluation results are shown in Table 1. Comparative Example 1 A polymer composition was prepared in the same manner as in Example 1 except that the compound (B) was not used, and various liquid crystal cells were produced using the polymer composition for evaluation. The evaluation results are shown in Table 1. Comparative Example 2 <Preparation of Polymer Composition> The compound represented by the above formula (B-1) as the compound (B) was dissolved in the N-methyl group as an organic solvent without using the (A) polymer. In 2-pyrrolidone (NMP) and butyl cyanidin (BC), a solution having a solvent composition of NMP: BC = 50:50 (weight ratio) and a solid content concentration of 6.0% by weight was formed. This solution was filtered using a screening procedure having a pore size of 1 μm to prepare a polymer composition. -35-201125942 <Evaluation> Various liquid crystal cells were produced in the same manner as in Example 1 except that the polymer composition prepared above was used, and the voltage holding ratio was evaluated. The evaluation results are shown in Table 1. Further, since the crystal domain (d 〇 m a i η ) was generated in the liquid crystal cell produced in the comparative example, the evaluation of the pretilt angle could not be performed, and the evaluation of the response speed could not be performed. Comparative Examples 3 to 5 In the above Example 1, the respective compounds shown in Table 1 which are other compounds were used instead of the (Β) compound, and the amounts shown in Table 1 were used. A polymer composition was prepared in the same manner as in Example 1 except that the polymer composition was used to produce various liquid crystal cells for evaluation. The evaluation results are shown in Table 1. -36- 201125942 [I ¥ The evaluation result has the liquid crystal cell response speed (msec) of the patterned electrode Μ 陛鹱100,000 (Ν <η (Ν CM CN iT) not determined (N 10,000 *Τ) (Ν οο (Ν σ\ (Ν σ; CN not determined yn CN liquid crystal cell voltage retention rate with no pattern electrode (%) ή 〇 (Ν >Τ) ^Τ) CN Not determined Cvl 陛 state 铖〇〇〇*—Η 99.3 99.3 II 99.3 99.0 98.8 97.5 78.3 97.3 97.6 1—Η 〇\ Pretilt angle (.) ί| 〇〇Λ o' 99.6 99.5 99.5 99.4 99.2 99.4 99.3 99.3 99.4 100,000 76.0 1 81.2 83.5 83.5 83.8 ON CO Cannot be measured 〇 00 88.0 89.0 m 骧ο θ' 84.2 86.4 86.0 88.4 88.6 〇\ oo Cannot measure αί 00 88.0 89.0 ο Os 00 89.1 89,2 89.8 89.9 89.1 Cannot measure 〇\ 00 88.0 89.0 Polymer composition 1 ί 1 15 ^ ^ X 莩刍S 1 Μ gm quantity (parts by weight) another ο 〇 another type Β Β-1 Β-2 Β-3 Β-4 Β Β-1 «ό X) S3 (A) Polymer dan (parts by weight) ο ο ο ο ο o 〇ο 〇Ο Τ-Ν ΡΙ-1 I 1 Ε Λ CU ΡΙ-1 έ II CL, soil «"Η 2 CU 1 5: diCl, Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 - ζ ε - 201125942 The abbreviations of the compound names in Table 1 are respectively B-1: Compound B-2 represented by the above formula (B-1): a mixture of compounds wherein η is 2 to 4 in the following formula (B-2) Β-3: the following formula (Β-3) In the mixture, η is a mixture of compounds of 2 to 4 Β-4 : a compound b-Ι represented by the following formula (Β-4): a compound b-2 represented by the following formula (b-Ι): Compound b-3 shown in b-2): a compound represented by the following formula (b-3)

-38- 201125942 From the results of Table 1, it can be known that in the method of the present invention, the ultraviolet irradiation amount is selected to be 100,000 J/m 2 (which is the currently used enthalpy in the PSA mode), and the inclination angle of the pretilt angle obtained is excessive, at 1 At an irradiation dose of 0,000 J/m2 or less, an appropriate pretilt angle is formed. In addition, a sufficiently fast response speed can be obtained even when the amount of irradiation is small, and the voltage holding ratio is also excellent. Therefore, according to the method of the present invention, since the advantage of the PSA mode can be realized with a small amount of light irradiation, it is possible to manufacture a display unevenness which is not caused by the amount of high light irradiation, a low voltage holding ratio, and insufficient reliability, but a viewing angle. Wide liquid crystal display elements with fast response, high transmission coefficient, and high contrast. Further, each of the polymer compositions used in the above-mentioned Examples 1 to 5 was evaluated in the same manner as in Example 1 except that the ITO electrode pattern of the glass substrate was changed. When any of the polymer compositions are used, the same effects as in Examples 1 to 5 can be obtained in both the pattern shown in Fig. 2 and the pattern shown in Fig. 3. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view showing a transparent conductive film pattern of a liquid crystal cell having a patterned transparent conductive film produced in Examples and Comparative Examples. Fig. 2 is an explanatory view showing a transparent conductive film pattern of a liquid crystal cell having a patterned transparent conductive film produced in the example. Fig. 3 is an explanatory view showing a transparent conductive film pattern of a liquid crystal cell having a patterned transparent conductive film produced in the example. -39- 201125942 [Main component symbol] 1 : ITO electrode 2 : slit portion 3 : light shielding film -40-

Claims (1)

201125942 VII. Patent application scope: 1. A method for manufacturing a liquid crystal display device, characterized in that the following steps are performed: 'coating a polymer composition on the conductive film of a pair of substrates having a conductive film to form a coating a film comprising: (A) at least one polymer selected from the group consisting of polylysine and polyimine, and (B) having the formula (Β_ι) in the molecule 1 1 in the divalent group and at least 2 in the monovalent group represented by the following formula (B-II): 1Χ3; -Χ'-Υ'-Χ2- (Β-Ι) In the formula (Β-Ι), X1 and X2 are each independently I, 4-phenyl or cyclohexyl, Y1 is a single bond, a divalent hydrocarbon having 1 to 4 carbon atoms, an oxygen atom, sulfur An atom or -COO-, wherein the above X1 and X2 may be substituted by one or a plurality of alkyl groups having 1 to 4 carbon atoms, a grafting oxygen group having 1 to 4 carbon atoms, a fluorine atom or a cyano group, R CH2=CC-Y3-(B-II) Y2 In the formula (B-II), R is a hydrogen atom or a methyl group, and Y2 and Y3 are each independently an oxygen atom or a sulfur atom, and a pair of substrates which form the coating film are formed. By liquid crystal Sub-layer 'that the coating film opposite to $ arranged to form a liquid crystal cell; -41-201125942 voltage is applied between the conductive film has the pair of substrates, the liquid crystal cell of the irradiation light. 2. The method of producing a liquid crystal display element according to claim 1, wherein the compound (B) is selected from the group consisting of di(methyl)propyl ester having a biphenyl structure and di(methyl) having a phenyl-cyclohexyl structure. Acrylate, di(meth)acrylate having a diphenylpropane structure, di(meth)acrylate having a diphenylmethyl structure, and a substituted (meth)acrylate having a diphenyl sulfide structure A method of fabricating a liquid crystal display element according to claim 1 or 2, wherein the conductive film is a patterned electric film divided into a plurality of regions, respectively. 4. A polymer composition' which is a polymer composition for producing a liquid crystal display element according to the first aspect of the patent, which comprises: (A) selected from the group consisting of polyproline and polyruthenium At least one polymer of the group consisting of amines and (B) a compound having at least one of a divalent group represented by the above formula and at least two of the group represented by the above formula (B_n) in the molecule . The liquid crystal display element of the liquid crystal display element is characterized in that the olefinic acid 2,2-alkylene disulfide 3 ° is produced by the method for producing a liquid crystal display element according to any one of claims 1 to 3. Create a special group (BI) price base range -42-