TW201007304A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The object of the present invention is to provide a liquid crystal alignment agent having good heat resistance and light resistance, particularly the voltage holding ratio reduce less while irradiating with high light intensity and excellent performance of electrostatic leakage under high temperature. The solution of the present invention is to provide a liquid crystal alignment agent comprising a certain polyorganosiloxane having a epoxy, which with 50 to 10000g/mol of epoxy equivalent and 1000 to 100000 of conversion weight average molecular weight of polystyrene measuring with gel permeation chromatography.

Description

201007304 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element. More specifically, it relates to a liquid crystal alignment of a liquid crystal alignment film which can form an electrical property such as a voltage holding ratio without using an electric property such as a voltage holding ratio even if it is used under a severe environment such as high light and high temperature or driven for a long time. And a liquid crystal alignment film formed therefrom and a liquid crystal display element having the liquid crystal alignment film. [Prior Art] As a liquid crystal display element, a TN type liquid crystal display element having a so-called TN type (twisted nematic) liquid crystal cell is known, which is formed of an organic resin or the like on the surface of a substrate on which a transparent conductive film is provided. The liquid crystal alignment film is used as a substrate for a liquid crystal display element, and two of the substrates are opposed to each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a liquid crystal cell having a sandwich structure, and the liquid crystal molecules are long. The shaft is continuously twisted by 90° from one substrate to the other (Patent Document 1). In addition, an STN (Super Twisted Nematic) liquid crystal display element (Patent Document 2) capable of achieving high contrast compared to a TN type liquid Φ crystal display element has been developed, and an IPS (in-plane switching) type liquid crystal having a small viewing angle dependency has been developed. Display element and VA (vertical alignment) type liquid crystal display element (Patent Document 3), an optical compensation bending (OCB) type liquid crystal display element (see Non-Patent Document 1), which is excellent in viewing angle dependence and high in video response. The working principles of these various liquid crystal display elements are divided into two types: transmissive and reflective. The transmissive liquid crystal display element is displayed by a change in the transmitted light intensity of the backlight source from the back surface of the element when the element is driven. The reflective liquid crystal display element does not use a light source for backlight, but displays the change in the intensity of reflected light of external light such as sunlight when the element is driven. Since it consumes less power than the transmissive type, it recognizes It is especially advantageous for outdoor use. In the transmissive liquid crystal display device, the liquid crystal alignment film provided is irradiated with light from the backlight source for a long time. In particular, in commercial applications and in recent years, as a liquid crystal projector having a large demand for home theater, a light source having a very high irradiation intensity such as a metal halide lamp is used. Further, it is conceivable that the temperature of the liquid crystal display element itself φ rises during driving as high-intensity light is irradiated. The reflective liquid crystal display element is conceived to be used outdoors, in which case it uses sunlight containing strong ultraviolet light as a light source. Also, in the reflective type, in principle, the distance of light passing through the inside of the element is longer than that of the transmission type. Further, the transmissive liquid crystal display element and the reflective liquid crystal display element also have a tendency to be popularized in, for example, a private car, and the use mode of the liquid crystal display element is realized at a high temperature compared with the previously considered manner. surroundings. Ο In the manufacturing steps of the liquid crystal display element, from the viewpoint of shortening the manufacturing process and improving the yield, the liquid crystal dropping method, that is, the ODF (One Drop Fill) method is preferred. The ODF method is different from the conventional method of injecting liquid crystal into an empty liquid crystal cell assembled with a thermosetting sealant in advance, and after applying a UV curable sealant to a necessary portion of a single-sided substrate coated with a liquid crystal alignment film, The liquid crystal is dropped by the necessary portion, and the other substrate is bonded to each other, and then the entire surface is irradiated with ultraviolet light to cure the sealing agent to produce a liquid crystal cell (Patent Document 4). The ultraviolet light irradiated at this time usually has a strength of several tens of J/m2 or more. That is, when the 0DF method is employed, the liquid crystal alignment film is subjected to such strong ultraviolet light irradiation together with the liquid crystal in the manufacturing step of the liquid crystal display element 201007304. Such a liquid crystal display element is required to withstand high-intensity light irradiation, a high-temperature environment, long-time driving, and the like, which are not expected to be severe, and are required even if the performance thereof is improved, such as versatility, improvement of manufacturing steps, and the like. In such an environment, electrical properties or display properties such as liquid crystal alignment property and voltage retention ratio are still superior as compared with the prior art, and liquid crystal display elements are required to have a longer life. As a material of the liquid crystal alignment film constituting the liquid crystal display element, organic resins such as polyimine, polylysine, polyamine, and polyester are known according to the present invention. In particular, polyimine is used in many liquid crystal display elements because it exhibits excellent physical properties in terms of heat resistance, affinity with liquid crystals, mechanical strength, and the like in an organic resin (Patent Document 5). However, these organic resins are not materials which are supposed to be developed for use in the above-mentioned harsh environment, and their durability in such an environment is not good enough. At present, a liquid crystal alignment agent capable of forming a liquid crystal alignment film having sufficiently good heat resistance and light resistance in a very severe manufacturing environment and a use environment and having excellent electrostatic discharge performance is not known. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent 8] Japanese Patent Laid-Open No. Hei 5-107544 (2010) [Non-Patent Document 1] "SID' 94 Digest", P927 (1997) [Invention] The present invention has been made in view of the above circumstances, and an object thereof is to provide formation capable of forming A liquid crystal alignment agent of a liquid crystal alignment film which is excellent in heat resistance and light resistance, particularly in a high-temperature environment, which has a small decrease in voltage retention rate upon high-intensity illumination and excellent electrostatic leakage performance. Another object of the present invention is to provide a liquid crystal alignment film having various excellent properties as described above using the liquid crystal alignment agent of the present invention. Further, another object of the present invention is to provide a liquid crystal display element excellent in heat resistance and light resistance. Other objects and advantages of the invention will be apparent from the description which follows. According to the present invention, the above objects and advantages of the present invention are attained by a liquid crystal alignment agent comprising a polyorganosiloxane having a repeating unit represented by the following formula (S-1), a hydrolyzate thereof, and At least one of the group consisting of the hydrolysis condensate (wherein the epoxy equivalent is 50 to 10000 g/mol, and the amount of the polystyrene-converted weight average molecule measured by gel permeation chromatography is 1 000 to 100,000) , X " --Si—Ο-- .YJ (S-1) (In the formula (S-1), 'X is a monovalent organic group having an epoxy group, γ is 201007304, and the number of carbon atoms is 1. An alkoxy group of ～10, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms). The above objects and advantages of the present invention are attained by a liquid crystal alignment film formed of the above liquid crystal alignment agent, and thirdly by a liquid crystal display element having the above liquid crystal alignment film. When the liquid crystal alignment agent of the present invention is used, it is possible to obtain a liquid crystal alignment film which exhibits superior heat resistance and light resistance as compared with the prior alignment film, particularly in a high-temperature environment, and a high-intensity light irradiation rate. It also does not have a liquid crystal alignment film with a drop in m and excellent electrostatic leakage performance. Therefore, such a liquid crystal alignment film can be applied to various liquid crystal display elements. The liquid crystal display element of the present invention having the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention can be applied to, for example, a computer, a watch, a desk clock, a counter display panel, a word processor, a personal computer, a car navigation system, a liquid crystal television, and the like. [Embodiment] The liquid crystal alignment agent of the present invention contains at least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the above formula (S-1), a hydrolyzate thereof, and a hydrolysis condensate thereof ( Hereinafter referred to as "polyorganosiloxane having an epoxy group"). <Polyorganooxane having an epoxy group> The polyorganosiloxane having an epoxy group contained in the liquid crystal alignment agent of the present invention is selected from the group consisting of repeating units represented by the above formula (S-1) At least one of the group consisting of an organic siloxane, a hydrolyzate thereof, and a hydrolysis condensate thereof. The epoxy group contained in X in the above polyoxyorganosiloxane having an epoxy group means an epoxy group or a 1,2-epoxy group. As X, a group represented by the following formula (X-1) or (χ-2) is preferably 201007304.

(X-1) (X-2) Examples of the alkoxy group having 1 to 20 carbon atoms of Y include, for example, a methoxy group, an ethoxy group, an octadecyloxy group, and the like; The alkyl group of -20 may, for example, be methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecane. Base, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a butoxyphenyl group; and a polyorganosiloxane having an epoxy group, the epoxy equivalent of which is 50 to 10000 g/mol, preferably 50 to 5000 g/mol, more preferably 100 to 1000 g/mol, most preferably 150 to 500 g/mol. Further, the polyorganosiloxane having an epoxy group has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) of from 1,000 to 100,000, preferably from 1,500 to 50,000, more preferably 2000~1 0000. The polyorganosiloxane having an epoxy group may be preferably a mixture of a decane compound having an epoxy group or a decane compound having an epoxy group and a 201007304 decane compound thereof in a suitable organic solvent, The hydrolysis is carried out by hydrolysis or hydrolysis in the presence of water and a catalyst. Examples of the above decane compound having an epoxy group include, for example, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-glycidoxypropyl group. Methyldimethoxydecane, 3_glycidoxypropylmethyldiethoxydecane, 3·glycidoxypropyldimethylmethoxydecane, 3-epoxypropoxypropyl Methyl dimethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxy decane, 2-(3,4-epoxycyclohexyl) φ ethyltriethoxy decane, and the like. Examples of the other decane compound include tetrachloromethane, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, and tetra-di-butyl Oxy decane, trichlorodecane, trimethoxy decane, triethoxy decane, tri-n-propoxy decane, triisopropoxy decane, tri-n-butoxy decane, tri- or 2-butoxy decane, fluoro Trichlorodecane, fluorotrimethoxydecane, fluorotriethoxydecane, fluorotri-n-propoxy decane, fluorotriisopropoxy decane, fluorotri-n-butoxy decane, fluoro Tri- or two-butoxybutane, methyltrichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltriisopropoxydecane, methyltri n-Butoxydecane, methyl tri- or 2-butoxybutane, 2-(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl)ethyltrimethoxydecane, 2-(trifluoro Methyl)ethyltriethoxydecane, 2-(trifluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl)ethyltriisopropoxyfluorene , 2-(trifluoromethyl)ethyltri-n-butoxydecane, 2-(trifluoromethyl)ethyltri-n-butoxypropane, 2-(perfluoro-n-hexyl)ethyltrichloromethane, 2-(Perfluoro-n-hexyl)ethyltrimethoxydecane, 2-(perfluoro-n-hexyl)ethyltriethoxy-10-201007304 decane, 2-(perfluoro-n-hexyl)ethyltri-n-propoxy Decane, 2·(perfluoro-n-hexyl)ethyltriisopropoxydecane, 2-(perfluoro-n-hexyl)ethyltri-n-butoxyoxynonane, 2-(perfluoro-n-hexyl)ethyltri-n-butyl Oxydecane, 2-(perfluoro-n-octyl)ethyltrichlorodecane, 2-(perfluoro-n-octyl)ethyltrimethoxydecane, 2-(perfluoro-n-octyl)ethyltriethoxy Decane, 2-(perfluoro-n-octyl)ethyltri-n-propoxydecane, 2-(perfluoro-n-octyl)ethyltriisopropoxydecane, 2-(perfluoro-n-octyl)ethyltri n-Butoxydecane, 2-(perfluoro-n-octyl)ethyltri- or 2-hydroxybutoxydecane, methylol trichloromethane, hydroxymethyltrimethoxysulfonium alkane, hydroxyethyltrimethoxydecane, Hydroxymethyl tri-n-propoxy decane, methylol triisopropoxy decane, hydroxymethyl tri-n-butoxy Alkane, hydroxymethyl tri- or two-butoxy decane, 3-(methyl) propylene methoxy propyl trichloro decane, 3-(methyl) propylene methoxy propyl trimethoxy decane, 3- (a) Acryloxypropyltriethoxydecane, 3-(meth)acryloxypropyltri-n-propoxyoxydecane, 3-(methyl)propenyloxypropyltriisopropoxy Decane, 3-(methyl)propenyloxypropyltri-n-butoxydecane, 3-(methyl)propenyloxypropyltri-n-butoxypropane, 3-mercaptopropyltrichlorodecane , 3-mercaptopropyltrimethylsulfonyloxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropyltri-n-propoxyoxydecane, 3-mercaptopropyltriisopropoxydecane , 3-mercaptopropyltri-n-butoxydecane, 3-mercaptopropyltri-n-butoxybutane, mercaptomethyltrimethoxydecane, mercaptomethyltriethoxydecane, vinyl three Chlorodecane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tri-n-propoxy decane, vinyl triisopropoxy decane, vinyl tri-n-butoxy decane, vinyl tri-second Butoxy decane, allyl trichloride Decane, allyltrimethoxydecane, allyltriethoxydecane, allyltri-n-propoxydecane, allyltriisopropoxydecane, allyltri-n-butoxydecane, 11-201007304 Allyl tri-n-butoxy decane, phenyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl tri-n-propoxy decane, phenyl triisopropoxy Base decane, phenyl tri-n-butoxy decane, phenyl tri-n-butoxy decane, methyl dichlorodecane, methyl dimethoxy decane, methyl diethoxy decane, methyl di-n-propoxy Base decane, methyl diisopropoxy decane, methyl di-n-butoxy decane, methyl di- or 2-butoxy decane, dimethyl dichloro decane, dimethyl dimethoxy decane, dimethyl Diethoxydecane, dimethyldi-n-propoxy decane, dimethyldiisopropoxydecane, dimethyldi-n-butyl oxy decane, dimethyl di- or 2-butoxy decane, (A) (2-(perfluoro-n-octyl)ethyl]dichlorodecane, (methyl)[2-(perfluoro-n-octyl)ethyl]dimethoxydecane, (methyl)[2-( Perfluoro-n-octyl Ethyl]diethoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-propoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl] Diisopropoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-butoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di Butoxy oxane, (methyl) (3 decyl propyl) dichloro decane, (methyl) (3-mercaptopropyl) dimethoxy decane, (methyl) (3-mercaptopropyl propyl) Diethoxy decane, (meth) K3-mercaptopropyl) di-n-propoxy decane, (methyl) (3-mercaptopropyl) diisopropoxy decane, (methyl) ( 3-mercaptopropyl)di-n-butoxydecane, (methyl)(3·mercaptopropyl)di-2-butoxydecane, (methyl)(vinyl)dichlorodecane, (methyl) (vinyl)dimethoxydecane, (meth)(vinyl)diethoxydecane, (methyl)(vinyl)di-n-propoxydecane, (methyl)(vinyl)diisopropyl Oxy decane, (methyl) (vinyl) di-n-butoxy decane, (methyl) (ethylene Di-2-butoxydecane, divinyldichlorodecane, divinyldimethoxydecane, divinyldiethoxydecane, divinyldi-n-propoxydecane, divinyldiisopropyl Oxydecane, divinyl di-n--12- 201007304

Butoxy decane, divinyl di-2-butoxy decane, diphenyl dichloro broth, diphenyl dimethoxy sand, diphenyl diethoxy sand, diphenyl. Propoxy decane, diphenyl diisopropoxy decane, diphenyl di-n-butoxy decane, diphenyl di-n-butoxy decane, chlorodimethyl sand, methoxy dimethyl Decane, ethoxy dimethyl decane, chlorotrimethyl chopping, bromotrimethyl decane, iodotrimethyl decane, methoxy trimethyl sand, ethoxy trimethyl decane, positive Propyl trimethyl decane, isopropoxy trimethyl decane, n-butoxy trimethyl decane, secondary butoxy trimethyl sand, φ tertiary butoxy trimethyl decane, (chlorine (vinyl) dimethyl decane, (methoxy) (vinyl) dimethyl decane, (ethoxy) (vinyl) dimethyl sand, (chloro) (methyl) diphenyl decane And a decane compound having one ruthenium atom such as (methoxy)(methyl)diphenyl decane or (ethoxy)(methyl)diphenyl decane, and other commercially available names For example, KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21_ 5845, X-21- 5846, X — 21—5847, X- 21 - 5848, X- 22-160AS, X- 22 — 170B, X—22-❹ 170BX 'X- 22 - 170D, X - 22 — 1 70DX, X - 22 - 1 76B , X — 22 — 176D' X — 22 — 176DX' X — 22 — 176F' X — 40 — 2308 ' X — 40 — 2651, X — 40 — 2655A, X — 40 — 2671, X — 40 — 2672, X - 40 - 9220, X - 40 - 9225, X - 40 - 9227, X - 40 - 9246, X - 40 - 9247, X - 40 - 9250, X - 40 - 9323, X - 41 - 1053, X - 41 — 1056, X - 41- 1805, X - 41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR3H, KR401N, KR500, KR510, KR5206 , KR5230, KR5235, KR9218, KR9706 (above -13-201007304 produced by Shin-Etsu Chemical Co., Ltd.); gurasurejin (produced by Showa Denko (share)); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406 , SR2410, SR241 1, SR2416 SR24 20 (above produced by Toray Dow Corning); FZ3711, FZ3722 (above, produced by UNICAR, Japan), DMS-S12, DMS-S15' DMS-S21, DMS-S27, DMS-S3 Bu DMS-S32, DMS - S33, DMS - S35, DMS - S38, DMS - S42, DMS - S45, DMS - S5, DMS - 227, PSD - 0332, PDS - 1615, PDS - 9931, XMS - 5025 (above 0 Chisso) Methyl citrate MS51, methyl decanoate MS56 (above produced by Mitsubishi Chemical Co., Ltd.); ethyl citrate 28, ethyl citrate 40, ethyl citrate 48 (above produced by Corde); GR100, Partial condensates such as GR650, GR908, and GR950 (produced by Showa Denko Co., Ltd.). Among these other decane compounds, preferred are tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, 3-(methyl) propylene methoxy propyl trimethoxy. Base decane, 3-(meth) propylene methoxy propyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy φ decane, allyl trimethoxy decane, allyl triethyl Oxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, mercaptomethyltrimethoxydecane , mercaptomethyltriethoxydecane, dimethyldimethoxydecane or dimethyldiethoxydecane. The polyorganosiloxane having an epoxy group used in the present invention, when a polyorganosiloxane having an epoxy group is synthesized due to the equivalent epoxy group as described above, a decane compound having an epoxy group and the like The use ratio of the decane compound 'should be set such that the epoxy equivalent of the obtained polyorganosiloxane is adjusted to the range of -14,070,07304 within the above range. The organic solvent which can be used in the synthesis of the polyorganosiloxane having an epoxy group may, for example, be a hydrocarbon, a ketone, an ester, an ether or an alcohol. Examples of the hydrocarbons include toluene and xylene. Examples of the ketones include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone. Examples of the esters include ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, and the like. Examples of the class 0 include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, and dioxane. Examples of the alcohol include 1-hexanol and 4-methyl-2-pentanol. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Among them, a water-insoluble solvent is preferred. These organic solvents may be used singly or in combination of two or more. The amount of the organic solvent is preferably from 10 to 10,000 parts by weight, more preferably from 50 to 1 part by weight, per 100 parts by weight of the total of the decane compound. 水 When preparing a polyorganosiloxane having an epoxy group, water The amount is preferably from 0.5 to 100 moles, more preferably from 1 to 30 moles per mole of the total decane compound. As the catalyst, a base metal compound, an organic base, a titanium compound, a zirconium compound or the like can be used. Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide. The organic base may, for example, be a primary or secondary organic amine such as ethylamine, diethylamine, piperidine, piperidine, pyrrolidine or pyrrole, a triethylamine, a tri-n--15-201007304 propylamine or a tri-n-butylamine. An organic tertiary amine such as pyridine, 4-dimethylaminopyridine or diazabicycloundecene, or an organic quaternary ammonium salt such as tetramethylammonium hydroxide. Among these organic bases, organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine, and organic tertiary ammonium hydroxide such as tetramethylammonium hydroxide are preferred. As the catalyst for preparing the polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferred. By using an alkali metal compound or an organic base, side reactions such as ring opening of an epoxy group do not occur, and the target polyorganosiloxane can be obtained at a rapid Φ hydrolysis/condensation rate, so that the production stability is excellent, and thus Preferably. As the catalyst, an organic base is particularly preferred. The amount of the organic hydrazine to be used varies depending on the type of the organic base, the reaction conditions, and the like, and is appropriately set. For example, it is preferably 0.01 to 3 moles, more preferably 0.05 to 1 mole, based on the total of the decane compound. The hydrolysis or hydrolysis/condensation reaction in the preparation of the polyorganosiloxane having an epoxy group is preferably carried out by dissolving a decane compound having an epoxy group and other decane compounds as required in an organic solvent. It is mixed with organic hydrazine and water and heated by an oil bath or the like. In the hydrolysis/condensation reaction, the heating temperature is preferably 130 ° C or lower, more preferably 40 to 100 ° C, preferably 0.5 to 12 hours, more preferably 1 to 8 hours. The mixture may be stirred during heating or may be placed under reflux. After completion of the reaction, it is preferred to wash the organic solvent layer separated from the reaction liquid with water. At the time of the washing, it is preferable to use a water containing a small amount of salt, for example, an aqueous solution containing about 0.2% by weight of ammonium nitrate-16-201007304, from the viewpoint of facilitating the washing operation. The washing is carried out until the water property after washing is carried out. Then, the organic solvent layer is dried with anhydrous calcium sulfate and a suitable desiccant as necessary, and then the solvent is removed to obtain a polyorganosiloxane having an epoxy group. In the present invention, a commercially available product is also used as the polyorganosiloxane having an epoxy group. As such a commercially available product, for example, elbows 3_DMS-E12, DMS-E21, EMS-32 (above, Chisso, etc.) are used. 其他 <Other components> The liquid crystal alignment agent of the present invention contains a ring as described above. The oxyalkylene oxide is an essential component, and may contain other components without impairing the advantages and disadvantages of the present invention. As such other components, for example, a polymerization other than polyorganosiloxane having an epoxy group is called "Other polymer"), having at least one epoxy group in the molecule (except for polyorganosiloxane having an epoxy group, hereinafter referred to as an oxy compound), a functional decane compound, etc. 〇 [Other polymers The above other polymer may be used in order to further improve the solution properties of the agent of the present invention and the electrical properties of the obtained liquid crystal alignment film, and as such other polymer, for example, a group selected from the group consisting of polyamidimide may be mentioned. At least one polymer, polyphthalate, polyimine, cellulose derivative, polyacetal, polystyrene derivative ethylene-phenyl maleimide), Among the (meth) acrylates, a seed polymer selected from the group consisting of polylysine and polyimine. The layer is a neutron sieve and the like can be used to make a polymerization of -Ε01 '. If it is effective, it can be used. (The following compounds are combined with "cyclocrystalline liquid crystals." and polyfluorene polyester, poly(benzene, etc. at least one of -17-201007304. The above poly-proline can be obtained by using tetracarboxylic dianhydride. Synthesis by reaction with diamine. Monocarboxylic dianhydride 1. As the tetracarboxylic dianhydride used in the synthesis of the above polyamic acid, for example, butane tetracarboxylic dianhydride, 1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3 , 4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane φ tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ',4,4'-Dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2 ,3,4,5-tetrahydrogen Furan tetracarboxylic dianhydride, l,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c] -furan-1,3-dione, 1,3,3&amp;,4,5,91)-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl )-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5- Dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,33,4,5,91)-hexahydro-7-methyl-5 -(tetraφ hydrogen 2,5·dioxofuranylnaphthalene [l,2-c]-furan-I,3·dione, 1,3,3&amp;,4,5,913-hexahydro-7-B 5-(4-hydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&amp;,4,5 , 91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan -1,3-dione, 1,3,3&amp;,4,5,91)-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furan -Naphthalene [l,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2- Dicarboxylic anhydride, bicyclo[2.2.2]-oct-7-ene-2,3, 5,6-tetracarboxylic dianhydride, 3-oxabicyclo-18-201007304 [3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran·2',5'- Diketone), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxyl 2-carboxymethylnorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0''6]undecane-3,5,8,10-tetra An aliphatic or alicyclic tetracarboxylic dianhydride such as a ketone or a tetracarboxylic dianhydride represented by the following formulas (TI) and (T-II);

(In the formulae (T-Ι) and (T-II), R1 and R3 are each a divalent organic group having an aromatic ring, and each of R2 and R4 is a hydrogen atom or an alkyl group, and each of a plurality of R2 and R4 may be present. The same or different) pyromellitic dianhydride, 3,3,,4,4,-benzophenonetetracarboxylic dianhydride, 3,3,,4,4,_diphenylphosphonium tetracarboxylic acid Dihydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene tetraresidic acid dianhydride, 3,3,,4,4,-diphenyl ether tetracarboxylic acid Dihydride, 3,3',4,4,-dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3,4,4,-tetraphenylnonanetetracarboxylic dianhydride, 1,2, 3,4-furantetracarboxylic dianhydride, 4,4,-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4,-bis(3,4.dicarboxybenzene Oxy)diphenyl succinic anhydride, 4,4,-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3,4,4,- -19- 201007304 perfluoro Isopropylene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, double ( Phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) , m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid) )-4,4'·diphenylmethane dianhydride, ethylene glycol-bis(hydroper trimellitate), propylene glycol-bis(hydrogen trimellitate), 1,4-butanediol-double ( Dehydrated trimellitate), 1,6-hexanediol-bis(anhydrotrimellitic acid ester), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2,2-double φ (4-Hydroxyphenyl)propane-bis(hydrogen trimellitate), 2,3,2',3'-biphenyltetracarboxylic dianhydride, the following formula (T-1)~(T-4 An aromatic tetracarboxylic dianhydride such as a compound represented by each. They may be used alone or in combination of two or more.

-20- 201007304

CH3

ο

/CH3, Η3 σ-4) a tetracarboxylic dianhydride for synthesizing the above polyamic acid, preferably containing butane tetracarboxylic dianhydride selected from the above, 1,2,3,4-cyclobutane Alkane tetracarboxylic acid di•21- 201007304 anhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid Dianhydride, 2,3,5·tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furan -Naphthalene [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5 -dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&amp;,4,5,91)-hexahydro-5,8- Dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, bicyclo[2.2.2]-octyl -7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2 ',5'-dione), _ 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3, 5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0''6]undecane-3,5,8 , 10-tetraketone, pyromellitic dianhydride, 3, 3', 4 , 4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride And 1,4,5,8-naphthalenetetracarboxylic dianhydride, a compound represented by the following formula (T-5) to (T-7) in the compound represented by the above formula (Τ-I), and the above formula ( The tetracarboxylic dianhydride of at least one of the groups represented by the following formula (T-8) in the compound represented by the following formula (T-8) (hereinafter referred to as "specific tetracarboxylic dianhydride"). -22- 201007304

(Τ-5) (Τ-6) (Τ-7) As a specific tetracarboxylic dianhydride, it is particularly preferably selected from 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4 ,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, l, 3, 3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3 -dione, φ 3-oxabicyclo[3.2.1]octane-2,4-dione·6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2, 5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane -2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0''6]undecane-3,5,8,10-tetraone and 2,3,2', At least one of the group consisting of 3'-biphenyltetracarboxylic dianhydride. The tetracarboxylic dianhydride for synthesizing the above polyamic acid preferably contains 50 mol% or more of the specific tetracarboxylic dianhydride as described above, more preferably 60 mol per mol of the total tetracarboxylic dianhydride. More than %, particularly preferably contains more than 75 mol%. -23-201007304 - Diamine-1 As the diamine for synthesizing the above polyamic acid, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4, 4 may be mentioned. '-Diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'-dimethyl-4,4 '-Diaminobiphenyl, 4,4'-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl -4,4'-diaminobiphenyl, 2,2, bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4, 4'-diaminobiphenyl, 5-amino-1-(4'-aminobenzene)-1,3,3-trimethylammonium, 6-amino-1-(4'-aminobenzene )-1,3,3·trimethylindan, 3,4′-diaminodiphenyl ether, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone , 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxyl) Phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-pile, 1,4- Bis(4-aminophenoxy)benzene, 4,4'-bis(4-amine Phenyloxy)biphenyl, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminobenzene )-10-hydroquinone, 2,7-diaminopurine, 9,9-dimethyl-2,7-diaminopurine, 9,9-bis(4-amine Φ benzene) fluorene, 4,4 '-Methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4' -diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-(p-phenylene diiso) Propylene)diphenylamine, 4,4'-(m-phenylene diisopropylidene)diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy) Phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl) Aromatic diamines such as phenoxy]-octafluorobiphenyl; 1,1-m-xylylenediamine, 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine , octanediamine, decanediamine, 4,4-diaminoheptyldiamine, 1,4-di-24- 201007304 aminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene Amine, hexahydro•4,7-methylene quinone dimethylene diamine, tricyclic [ 6.2.1.02'7] undecyldimethyldiamine, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, 1,4 An aliphatic or alicyclic diamine such as bis(aminomethyl)cyclohexane; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2, 4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyridine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6 - dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)piped, 2,4-diamino-6-isopropoxy-1,3, 5-three tillage, φ 2,4-diamino-6-methoxy-1,3,5-three tillage, 2,4-diamino-6-phenyl-1,3,5-three tillage , 2,4-diamino-6-methyl-s-three tillage, 2,4-diamino-1,3,5-three tillage, 4,6-diamino-2-vinyl-s - three tillage, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-di Amino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4- Diaminopiperidine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole, indolemethyl-3,6-diaminehydrazine , 1 ethyl-3,6-diaminocarbazol, N-phenyl-3,6-diaminocarbazol, N,N,-bis(4-guanidinobenzene)benzidine, N, N'-bis(4-aminophenyl)-N,N'-dimethyl-benzidine, a compound represented by the following formula (D-I),

(M) (In the formula (D-I), R5 is a monovalent organic group having a nitrogen atom-containing cyclic structure selected from the group consisting of pyridine, pyrimidine, tritrap, piperidine, and pipe trap, and X1 is a divalent organic group, R6 is an alkyl group having 1 to 4 carbon atoms, -25 to 201007304 al is an integer of 0 to 3), and a compound represented by the following formula (D-π) has two molecules in the molecule. a primary amine group and a diamine of a nitrogen atom other than the amine group,

(D-Π) (In the formula (D-II), R7 is a divalent organic group 0 group having a nitrogen atom-containing cyclic structure selected from the group consisting of pyridine, pyrimidine, tri-till, piperidine and piperazine. Χ2 is a divalent organic group, and a plurality of X2 groups may be the same or different, each of R8 is an alkyl group having 1 to 4 carbon atoms, and each a2 is an integer of 0 to 3); a monosubstituted phenylenediamine such as a compound represented by (D-III),

(In the formula (D-III), R9 is a divalent organic group selected from the group consisting of -0, -COO-, -OCO-, -NHCO-' ® -CONH- and -CO-, Rl (&gt; is a monovalent organic group having a skeleton or a group selected from the group consisting of a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group, Or an alkyl group having 6 to 30 carbon atoms, R11 is an alkyl group having 1 to 4 carbon atoms, and a3 is an integer of 0 to 3); a diamine-based organic compound such as a compound represented by the following formula (D-IV); Oxane, -26- 201007304 R12 f〇—Si4-V | yq R12

(D-IV) R12 H2N—(—CH2-)—Si— R12 (In the formula (D-IV), R12 each represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R12 groups may be the same or may be the same. Different from each, P is an integer of 1 to 3, and q is an integer of 1 to 20); a compound represented by the following formulas (D-1) to (D-5), etc.

-27- 201007304

O^〇~fc2H4-〇^^NH (D-4)

(Y in the formula (D-4) is an integer of 2 to 12, and the redundancy in the formula (D-5) is an integer of _ to 5). z 1 The above-mentioned aromatic diamine and the present ring of the compound represented by the above formula (D_丨) to (D-5) may be optionally one or two or more alkyl groups having 1 to 4 carbon atoms ( It is preferably substituted with methyl). R6, R8 and R11 in the above formulae (1) to (1) and (1) to 111 are each preferably a methyl group, and each of al, a2 and a3 is preferably 0 or 1, more preferably m-amine may be used alone or in combination of two or more. Used in combination. The diamine for synthesizing the above polyamic acid preferably contains p-phenylamine, 4,4,diaminodiphenylmethane, 4,4,-diaminodiphenylsulfide selected from the above ® Ether, 1,5-diaminonaphthalene, 2,2,-dimethyl-4,4,diaminobiphenyl, 22,_(difluoromethyl)_4,4,-diaminobiphenyl , 2,7-diaminopurine, 4,4,-diamino-phenylene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-double (4·Aminobenzene)苟, 2,2_bis[4_(4-aminophenoxy)phenyl]hexafluoropropyl] 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4 , _(p-phenylene diisopropylidene)diphenylamine, 4,4'-(m-phenylene diisopropylidene)diphenylamine, 1,4-bis(4-aminophenoxy)benzene , 4,4'-bis(4-aminophenoxy)biphenyl, anthracene, 4-cyclohexyl diamine, 4,4'-methylenebis(cyclohexylamine), ^-bis (amino group) Methyl)cyclo- 28- 201007304 hexane, 4,4,-diaminodiphenyl milling, 2,2-bis[4-(4-aminophenoxy)phenyl] maple, the above formula (D — 1)~(D-5) each represented by the compound 2,6-diaminopyridine, 3,4·diaminopyridine, 2,4-diaminopyrimidine, 3,6-di Amino 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)-indole, Ν'-dimethyl-benzidine, The compound represented by the following formula (3) to 6) in the compound represented by the above formula (D-I), the anthracene compound represented by the following formula (D-7) in the compound represented by the above formula (D-II),

(D-7) Dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecane in the compound represented by the above formula (D-III) Oxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecyloxy-2, 5. Diaminobenzene, hexadecyloxy-2, 5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, the following formula (D-8)~(D-16) a compound represented by each of them and at least a group consisting of 1,3 -bis(3-aminopropyl)-tetramethyldioxane in the compound -29-201007304 represented by the above formula (D-IV) A diamine (hereinafter referred to as "specific diamine").

-30- 201007304

oc〇-Of (D-16) The diamine used for the synthesis of the above polyamine, preferably containing more than 50 mol% of the specific diamine as described above, more preferably 75 mol, relative to the entire diamine. More than %, especially preferably contains more than 90% by mole. -31 - 201007304 - Synthesis of poly-proline - The ratio of use of tetracarboxylic dianhydride to diamine for the synthesis of poly-proline, preferably with respect to 1 equivalent of amine contained in the diamine The acid anhydride group of the acid dianhydride has a ratio of 0.5 to 2 equivalents, more preferably 0.7 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at a temperature of from -20 to 150 ° C, more preferably from 0 to 100 ° C. The reaction time is preferably from 2 to 24 hours, more preferably from 2 to 12 hours. Here, the organic hydrazine solvent is not particularly limited as long as it is a solvent capable of dissolving the synthesized polyaminic acid, and examples thereof include N-methyl-2-pyrrolidone and N,N-dimethylacetamide. , aprotic polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, r-butyrolactone, tetramethylurea, hexamethylphosphonium triamine; m-methylphenol, dimethyl A phenolic solvent such as phenol, phenol or halogenated phenol. Further, the amount (a) of the organic solvent is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is from 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution. Further, when the organic solvent is used in combination with the poor solvent described below, the amount U) of the above organic solvent is understood to mean the total amount of the organic solvent and the poor solvent. In the organic solvent, a solvent alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, or the like may be used in combination with a polyglycine in a range in which the produced polyamine is not precipitated. . Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4, butanediol, triethylene glycol, ethylene glycol monomethyl ether, and lactic acid. Ethyl ester, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethoxy-32 - 201007304 Ethyl propyl propionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, B Glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-di Chlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like. The use ratio of the φ poor solvent is preferably 80% by weight or less, more preferably 50% by weight or less, and most preferably 40% by weight or less based on the total amount of the organic solvent and the poor solvent. As described above, a reaction solution in which polylysine was dissolved was obtained. The reaction solution may be directly supplied to the liquid crystal alignment agent, or the polyamic acid contained in the reaction solution may be separated and supplied to the liquid crystal alignment agent, or the separated polyamic acid may be refined. The preparation of the liquid crystal alignment agent is supplied. The separation of the polyamic acid can be carried out by introducing the above reaction solution into a large amount of a poor solvent to obtain a precipitate, and then drying the precipitate under reduced pressure, or by subjecting the reaction solution to distillation under reduced pressure using an evaporator. get on. Further, poly-proline can be purified by a method in which the polyproline is redissolved in an organic solvent and then precipitated with a poor solvent, or a step of performing one or several steps of distillation under reduced pressure using an evaporator. - Synthesis of Polyimine - The above polyimine can be synthesized by dehydrating and blocking the polylysine obtained as above. At this time, it may be a complete brewed imine compound in which the proline structure is completely dehydrated and closed, or it may be a part of the structure of only the proline acid dehydration-33-201007304. The closed-loop portion of the proline structure and the quinone imine structure coexist. Yttrium imide. The ruthenium imidization ratio of the polyimine is preferably 403⁄4 or more, more preferably 80% or more. Here, the "rhodium imidization ratio" means the total amount of the structure of the guanidine structure and the number of the quinone ring structure, and the ratio of the number of the quinone ring structure is expressed by a percentage. At this time, a part of the quinone ring may also be an isoindole ring. The dehydration ring closure reaction of polylysine may be carried out by (i) heating the polyamic acid or (ii) by dissolving the polyaminic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the hydrazine solution. And according to the method of heating required. The reaction temperature in the method of heating poly-proline in the above (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 °C, the dehydration ring-closure reaction does not proceed sufficiently. If the reaction temperature exceeds 200 ° C, the molecular weight of the obtained polyimine will decrease. The reaction time in the method of heating the polyamic acid is preferably from 0.5 to 48 hours, more preferably from 2 to 20 hours. Further, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyamic acid solution of the above (ii), an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent is preferably 0.01 to 20 moles per 1 mole of the polyamic acid structural unit. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, dimethylform or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst is preferably from 0 01 to 10 mol per mol of the dehydrating agent used. The organic solvent used in the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as a solvent used in the synthesis of polyglycine. Des. 34 - 201007304 The reaction temperature of the water ring closure reaction is preferably 0 to 180 ° C, more preferably ° C, and the reaction time is preferably 0. 5 to 20 hours, more preferably 1 to 8 in the above method (i) The obtained polyimine may be formulated as a direct crystal alignment agent, or may be supplied to a liquid crystal alignment agent. Further, in the above method (ii), a reaction solution containing a polyimine. The reaction solution may be prepared by preparing a liquid crystal alignment agent, or may be supplied to a liquid crystal alignment agent after removing the dehydration ring-closing catalyst from the reaction solution, or may be supplied to the liquid crystal alignment agent after separation of the φ imine, or may be separated. After the polyimine is refined, it is supplied to a liquid crystal alignment agent. The dehydrating agent and the dehydration ring-closing catalyst are removed from the liquid, and a method such as exemplification can be employed. The separation and purification of polyimine can be carried out in the same manner as described in the separation and purification methods of poly-proline. The end-modified polymer - the poly-proline and the poly-imine, each of which can also be used. It is a feed-modified end-modified polymer. The terminal-modified poly(TM) is synthesized by adding a single compound, a monoisocyanate compound or the like to the reaction system during the synthesis of the polyamic acid. Here, for example, maleic anhydride, phthalic anhydride, and itacon are mentioned. Acid succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl-p-hexadecyl succinic anhydride, and the like. As the monoamine compound, it may be aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, and Tetradecaneamine, n-pentadecylamine, n-hexadecylamine, amine, n-octadecylamine, n-icosylamine, and the like. As a monoguanidine isocyanate 10 ~ 150 hours. After the supply liquid is refined, it is obtained by directly supplying the liquid agent and removing the polycondensation from the reaction solution such as a solvent. The molecular compound may be an anhydride, a monoamine is a monoanhydride, an anhydride, a ruthenium anhydride, a exemplified by, for example, an amine, an n-octyl-n-tridecyl heptadecane compound, and -35-201007304, for example, benzene isocyanate. Ester, naphthyl isocyanate, and the like. The use ratio of the molecular weight modifier is preferably 5 or less, and more preferably 2% by weight or less based on the total amount of the tetracarboxylic dianhydride and the diamine used in the synthesis polymerization. - Ratio of use of other polymers - When the liquid crystal alignment agent of the present invention contains a polymer other than a polyalkene having an epoxy group, the use as a polymer is more than 100 parts by weight of a polyorganoquinone having an epoxy group. The oxane is preferably 5% by weight or less, more preferably 200 to 50,000 parts by weight, most preferably 20,000 parts by weight, particularly preferably 2,000 to 10,000 parts by weight. [Epoxy group] The liquid crystal alignment agent of the present invention may contain an upper compound from the viewpoint of further improving the surface property of the formed liquid crystal alignment film. Further, although the polyorganofluorene having the above epoxy group is a compound having at least one epoxy group in the molecule, the epoxy compound herein is different from the epoxy group-organosiloxane in that the molecular weight is less than 1,000. Preferred examples of such an epoxy compound include diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol dioleate, tripropylene glycol diglycidyl ether, and polypropylene glycol diethylene glycol neopentyl glycol. Glycidyl ether, 1,6-hexanediol diglycidyl ether diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1, diglycidyl-2,4-hexanediol, ^^州'-tetraglycidyl 3 dimethylamine, 1,3 -bis(N,N-diglycidylaminomethyl) ring ^State'-tetraglycidyl-4,4'-diamine Diphenyldiphenylmethane phthalic acid weight% machine argon oxygen rate, phase 50000 1 000 ~ the adhesion of the epoxy oxide is also called the base polyethylene glycol glycidyl ether, glycerol 3,5,6-S - m-Benzylene, N, N--36-201007304 diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, and the like. The mixing ratio of these epoxy compounds is preferably 40 parts by weight based on the total amount of 100 parts by weight of the polymer (refer to the total amount of the polyorganosiloxane having an epoxy group and the other polymer, the same applies hereinafter). Hereinafter, it is more preferably 0.1 to 30 parts by weight. The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyl. Triethoxy decane, N-(2-aminoethenyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyl dimethyl Oxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl- 3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecane- 1,4,7-triazanonane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindole Acetate, 9-triethoxydecyl-3,6-diazaindolic acid acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-amine Propyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxyhydrazine , N- bis (oxyethylene) -3-aminopropyl trimethoxy Silane, N - bis (oxyethylene) -3 - aminopropyl triethoxy silane-like. The mixing ratio of these functional decane compounds is preferably 2 parts by weight or less, more preferably 0.2 parts by weight or less, based on 100 parts by weight of the total amount of the polymer. &lt;Liquid crystal alignment agent&gt; -37-201007304 The liquid crystal alignment agent of the present invention is preferably formulated as a polyorganosiloxane having an epoxy group as described above and optionally other components dissolved in a suitable organic solvent. The state of the solution. The organic solvent which can be used in the liquid crystal alignment agent of the present invention may, for example, be a solvent exemplified as a solvent used in the synthesis reaction of polyglycine. Here, it is also possible to appropriately select a poor solvent which can be exemplified by a combination of a poor solvent in the synthesis reaction of polylysine. The preferred organic solvent to be used in the liquid crystal alignment agent of the present invention is a solvent obtained by combining one or more kinds of β in the above organic solvent, and is a liquid crystal alignment agent which does not have a preferable solid content concentration as described below. Each of the components was analyzed, and the surface tension of the liquid crystal alignment agent was set to a solvent in the range of 20 to 50 mN/m. The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is selected in consideration of viscosity, volatility, and the like. A preferred solid content concentration is in the range of 1 to 20% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film as a liquid crystal alignment film. When the solid content is less than 1% by weight, the thickness of the coating film is too small to obtain a good liquid crystal alignment. When the solid content concentration exceeds 20% by weight, the thickness of the coating film is too thick, and it is also difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent is increased, resulting in deterioration of coating properties. The particularly preferable solid content concentration range differs depending on the method used to apply the liquid crystal alignment agent to the substrate. For example, when the spin coating method is employed, it is particularly preferably in the range of 1.5 to 6 · 0% by weight. When the printing method is employed, it is particularly preferable to set the solid content concentration to a range of 3 to 20% by weight, so that the solution viscosity can be made to fall within the range of 12 to 50 rnPa.s. When the ink jet method is employed, it is particularly preferable that the solid content concentration of -38 to 201007304 is in the range of 1 to 5 wt%, so that the solution viscosity can be made to fall within the range of 3 to 15 mPa·s. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 0 ° C to 200 ° C, more preferably from 20 ° C to 60 ° C. &lt;Liquid Crystal Display Element&gt; The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention as described above. The liquid crystal display element of the present invention can be produced by, for example, the following method. (1) First, the liquid crystal alignment agent of the present invention is applied onto a pair of substrates, and a solvent is removed to form a coating film. Here, when the display mode of the liquid crystal display element to be manufactured is a vertical electric field mode such as TN type, STN type, or VA type, a substrate having two patterned transparent conductive films on one surface is used as a pair of substrates. In addition, when the display mode of the liquid crystal display element to be manufactured is a lateral electric field method known as the IPS method, a substrate provided with a transparent conductive film having a comb-tooth pattern and a substrate without a transparent conductive film are used as a pair of substrates. use. In either case, a liquid crystal alignment agent is applied on the substrate (when a transparent conductive film is provided on the substrate, it is coated on one side of the substrate having a transparent conductive film). As the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether maple, polycarbonate, poly(alicyclic olefin) can be used. ) Plastic transparent substrates. As the transparent conductive film provided on one surface of the substrate, tin oxide (NESA film manufactured by SnOO (registered trademark of PPG, USA), indium oxide-tin oxide (IT2 film made of In2 (h-Sn〇2), etc.) can be used. These patterned transparent-39-201007304 conductive films can be obtained by a method of forming a pattern by photolithography after forming a transparent conductive film without a pattern, and a method of using a mask having a desired pattern when forming a transparent conductive film. A method of directly forming a patterned transparent conductive film, etc. The liquid crystal alignment agent is applied onto a substrate, and can be applied by a suitable coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method. In order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional decane Φ compound, a functional titanium compound, or the like may be applied to the surface to be coated of the substrate. After application, in order to prevent application of the alignment agent For the purpose of liquid sagging, etc., preheating (prebaking) is preferred. The prebaking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, particularly preferably 40 to 100 ° C. The prebaking time is preferably from 1 to 15 minutes, more preferably from 1 to 10 minutes, and then a post-heating (post-baking) step is carried out for the purpose of completely removing the solvent, etc. The post-baking temperature is preferably 80. ~300 ° C, more preferably 120 to 250 ° C. The post-baking time is preferably 5 to 120 minutes, more preferably 0 to 60 minutes. ® (2) When the display mode of the liquid crystal display element to be manufactured is VA type In this case, the coating film formed as described above may be used as the liquid crystal alignment film as it is, or may be subjected to the following rubbing treatment as needed. On the other hand, the display mode of the liquid crystal display element to be manufactured is a vertical electric field method other than the VA type and horizontal In the electric field mode, the formed coating film surface is subjected to a rubbing treatment. The rubbing treatment can be carried out by rubbing in a certain direction with a roll wrapped with a cloth made of a fiber such as nylon, rayon, cotton or the like. The alignment of the liquid crystal molecules can be made into a liquid crystal alignment film. Further, the coating film after the rubbing treatment is carried out, for example, in Patent Document 6 (Japanese Laid-Open Patent Publication No. Hei-40-201007304 No. Hei. The process of changing the pretilt angle of a portion of the liquid crystal alignment film that irradiates a part of the ultraviolet alignment film, as shown in the Japanese Patent Laid-Open Publication No. Hei No. Hei. After forming a resist film on a part of the resist film, the process of removing the resist film after rubbing treatment in a different direction from the first direction has different liquid crystal alignment energy in each region of the film, so that the field of view performance of the liquid crystal display element can be obtained. Prefabricating two substrates which form a liquid crystal alignment film as described above, and arranging liquid crystal between the two substrates to produce a liquid crystal cell. When the film is subjected to a rubbing treatment, the two substrates are patterned at a predetermined angle such as vertical or reverse. The production of the liquid crystal cells in parallel and oppositely, for example, the following two first methods are known, and are conventionally known methods. First, the substrates are relatively disposed through the gaps (cell gaps) so that the respective opposing faces are filled with the liquid crystal in the cell gap surrounded by the sealant bonding surface and the sealant. A liquid crystal cell is produced. The second method is called the 0DF (One Drop F method. A part of the two substrates forming the liquid crystal alignment film is coated with, for example, an ultraviolet curable sealant material, and the liquid crystal is dropped onto the film surface. The other substrate is opposite to the liquid, and then the entire surface of the substrate is irradiated with ultraviolet rays to make the liquid crystal cell. In any case, the liquid crystal may be passed through the line such as -28 1 937. Specialized, in front of the liquid crystal rubbing treatment, so that the liquid crystal is matched enough to improve the pass through in the opposite direction, when the rubbing direction is mutually entangled. By placing two liquid crystal alignment films, the holes are closed to the substrate, i 1 1 ) The rule on the substrate is further solidified in the liquid crystal alignment film, and the liquid cell 41-201007304 can be further heated until the liquid crystal used is at an isotropic phase temperature, and then slowly cooled to room temperature to eliminate the liquid crystal. Flow alignment during injection. Then, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. Here, as the sealant, for example, an epoxy resin containing alumina balls as a curing agent and a separator can be used. The liquid crystal may, for example, be a nematic liquid crystal or a disk-shaped liquid crystal. When a liquid crystal display element having a TN type liquid crystal cell, an STN type liquid crystal cell or an IPS type liquid helium cell is produced, a liquid crystal having positive dielectric anisotropy in a nematic liquid crystal is preferable, and for example, a biphenyl liquid crystal can be used. , phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal, etc. . Further, in these liquid crystals, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl phthalate, and cholesteryl carbonate may be further added; chiral agents sold under the trade names of C-15 and CB-15 (manufactured by Merck & Co.) It is used for ferroelectric liquid crystals such as decyloxybenzylidene-p-amino-2-methylbutylcinnamate. Further, in the case of a VA type liquid crystal cell, a liquid crystal having a negative dielectric anisotropy in a nematic liquid crystal is preferable, which is also generally referred to as a negative type liquid crystal. For example, a diamino benzene liquid crystal, a quinone liquid crystal, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal or the like can be used. The polarizing plate to be bonded to the outer surface of the liquid crystal may be a polarizing plate obtained by sandwiching a polarizing film called a "ruthenium film" obtained by stretching a polyvinyl alcohol and simultaneously absorbing iodine, in a cellulose acetate protective film, or a crucible. The film itself is made of -42-201007304 into a polarizing plate. [Examples] Hereinafter, the present invention will be further illustrated by the examples, and the present invention is not limited to the examples. The polyorganic average molecular weight Mw having an epoxy group in the following synthesis examples is a polystyrene-equivalent oxime which passes through a gel under the following conditions. Pipe column: manufactured by Tosoh Co., Ltd., TSK-GEL Φ Solvent: tetrahydrofuran

Column temperature: 40 °C Pressure: 80 kg f/cm2 Epoxy equivalent is determined by the solution of the solution of polylysine solution and polyimine solution measured by the ketone method described in JIS C 2105. The polymer solution was an E-type viscosity meter. ® The ruthenium imidization rate of polyimine is determined by measuring 1H-NMR at room temperature by drying in each of the polydimethyl hydrazines after drying at each temperature. ) Find.醯 imidization rate AWA2xa ) χ 100 (In formula (1), A1 is the peak area of the chemical shift of 10 ppm NH proton, and A2 is derived from other protons in the polyimine precursor (polyproline) The ratio of the number of his protons). The description of the body, but the monomethyl viscosity of hydrochloric acid determined by the weight-penetration chromatography of decane is determined by the bis-imine in each room at 25 ° C. The protons appearing near the following formula (1) originating from the peak area, α is the phase thiol group, and -43-201007304 &lt;Synthesis of polyorganosiloxane having an epoxy group&gt; Synthesis Example 1 Stirring 2-(3,4-epoxycyclohexyl)ethyltrimethoxy sand court 100.Og, methyl isobutyl ketone 500g and three were added to the reaction vessel of the thermometer, the dropping funnel and the reflux condenser. Ethylamine i〇〇g was mixed at room temperature. Then, 'i〇〇g deionized water was added dropwise thereto through a dropping funnel over 30 minutes', and reacted at 80 ° C for 6 hours under reflux stirring. After completion of the reaction, the organic layer was washed with a 0.2% by weight aqueous solution of ammonium nitrate until the washed water® was neutral, and the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group ( EPS — 1) Viscous transparent liquid. 1H-NMR analysis of the polyorganosiloxane having an epoxy group was carried out, and a theoretical peak derived from an epoxy group was obtained at a chemical shift (&lt;5) = 3.2 ppm, and it was confirmed that no epoxy group occurred in the reaction. side effects. The weight average molecular weight Mw and epoxy equivalent of the polyorganooxynonane (EPS-1) having an epoxy group are shown in Table 1. Synthesis Examples 2 to 3 ® In the same manner as in Synthesis Example 1, except that the raw materials to be added were as shown in Table 1, respectively, polyorganooxiranes (EPS - 2 ) and (EPS - 3) having an epoxy group were obtained. Viscous transparent liquid. The weight average molecular weight Mw and epoxy equivalent of these polyorganosiloxanes having an epoxy group are shown in Table 1. Further, in Table 1, the abbreviations of the starting decane compounds are respectively the following meanings. ECETS: 2-(3,4-Epoxycyclohexyl)ethyltrimethoxydecane MTMS: methyltrimethoxydecane-44-201007304 PTMS: phenyltrimethoxydecane Table 1 Synthesis Example 1 Raw-alkane compound Amount of (g) polyoxyalkylene having a cyclooxy group ECETS MTMS PTMS name Mw epoxy equivalent (g/mol) 100 0 0 EPS-1 1 3500 180 Synthesis Example 2 64 36 0 EPS-2 2200 240 Synthesis Example 3 55 0 45 EPS-3 3800 301 &lt;Synthesis of polyglycine&gt; ® Synthesis Example 4 1,2,3,4-cyclobutanetetracarboxylic dianhydride 2 〇 2 as tetracarboxylic dianhydride (0.1 mol), 2,2'-dimethyl-4,4'-diaminobiphenyl as a diamine 21 g (0.1 mol) dissolved in 37 g of N-methyl-2-pyrrolidone and 330 g r - The mixed solvent of the lactone composition was subjected to a reaction at 40 ° C for 3 hours to obtain a solution containing 10% by weight of polyglycine (A-1) in an amount of about 400 g. The solution had a solution viscosity of 160 mPa.s. Synthesis Example 5 1,8,3,4,4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride, 9.8 g (0.05 mol) and pyromellitic dianhydride 11 g (〇.〇5 mol) ; 4,4'-diaminodiphenylmethane 20 g (0.1 mol) as a diamine is dissolved in a mixed solvent of 23 g of N-methyl-2-radolithone and 210 g of r-butyrolactone. After reacting at 40 ° C for 3 hours, I35gr - butyl vinegar was added to obtain about 390 g of a solution containing 10% by weight of poly-aramidic acid (A - 2 ). The solution viscosity of the solution was 125 roPa * s. Example 6 -45-201007304 28 g (0 09 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 28 g of 1,2,3,4-cyclobutane tetracarboxylic dianhydride (〇〇1 Mo) Ear), 3.0 g (0.02 mol) of p-phenylenediamine as diamine and 23 g (0.08 mol) of 44,-diaminodiphenyl acid are dissolved in 3 23 g of Ν·methyl-2-pyrrolidone. The reaction was carried out for 3 hours to obtain about 380 g of a solution containing 15% by weight of polyglycolic acid (Α-3). The solution viscosity of the solution was 380 mPa·s. &lt;Synthesis of Polyimine&gt; Synthesis Example 7 Φ 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride, llg (0.05 m) and 1,3, 3&,4,5,91)-hexahydro-8-methyl-5-(tetrazine-2,5-dioxo-3-furanyl)-naphthalene[1,2-indole:]-furan- 1,3_2嗣16g (0.05m), p-phenylenediamine as a diamine 9.4g (〇.〇87 mole), 1,3-bis(3-aminopropyl)-tetramethyl Bismuth 2.5g (〇.〇l Mo) and 3,6-bis(4-aminobenzylideneoxy)cholane 0.96 (0.0015 mol), and octadecyl as a monoamine 0.81 g (0.0030 mol) of the amine was dissolved in 96 g of N-methyl-2-pyrrolidone (NMP), and the reaction was carried out at 60 ° C for 6 hours to obtain a polyaminic acid solution. A small amount of the obtained polyaminic acid solution was added, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was 60 mPa·s. Then, 270 g was added to the obtained polyaminic acid solution. NMP was further added with 40 g of pyridine and 41 g of acetic anhydride, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring-closure reaction, the solvent in the system is replaced with a new r-butyrolactone (by the solvent replacement operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system). A solution containing 15% by weight of a polyamidimide (B-1) having a ruthenium iodide ratio of about 95% is about -46 to 201007304 240 g. A small amount of this solution was added, and r-butyrolactone was added to prepare a solution having a polyimine concentration of 10% by weight. The viscosity of the solution was determined to be 7 〇 mP a.s. Synthesis Example 8 As a tetracarboxylic dianhydride, 3,5-tricarboxycyclopentyl acetic acid dianhydride 11 g (0.050 mol), as a diamine p-phenylenediamine 4.3 g (〇〇4〇m) And 5.2 g of 3-(3,5-diaminobenzylideneoxy)cholestane dissolved in 83 g of NMP, and reacted at 60 ° C for 6 hours to obtain polyfluorene. Amino acid solution. A small amount of the obtained polyaminic acid solution was added, and NMP was added to prepare a solution having a polyamine amine acid concentration of 10% by weight, and the solution viscosity was determined to be 60 mPa·s. Then, 'add 190 g of NMP to the obtained poly-proline solution, and then add 4.0 g of pyridine and 5.1 g of acetic anhydride' to carry out a 4-hour dehydration ring-closure reaction under U (after dehydration ring closure reaction) by using a new solvent in the system. The NMp is subjected to solvent replacement to obtain a solution containing about 15% by weight of a polyanilin (B-2) having a ruthenium iodide ratio of about 50%. A small amount of the solution is added, and NMP is added to form a polyimine concentration. For a 10% by weight solution, the solution viscosity was determined to be 4 7 mPa·s. 合成© Synthesis Example 9 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride llg (0.050 m) , as a diamine, p-phenylenediamine 3.8g (〇.〇35 mole), 4,4'-diaminodiphenylmethane 2.0g (〇.〇i Moer) and 3_(3,5-two Aminobenzhydryloxy) 2.6 g (0. 〇〇5 mol) was dissolved in 80 g of NMP, and reacted at 60 ° C for 6 hours to obtain a polyaminic acid solution. The proline solution 'added to NMP' was formulated into a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was 60 mPa·s. Then, 18 μg of NMP was added to the obtained polyaminic acid solution, and then In-47-201007304 8.0g pyridine and l〇g acetic anhydride, 4 hours dehydration ring closure reaction at 110 °c. After the dehydration ring closure reaction, the solvent in the system was replaced by a new r-butyrolactone solvent. A solution containing 15% by weight of a polyamidimide (B-3) having a ruthenium iodide ratio of about 80% was obtained, about 1 l〇g. A small amount of the solution was added, and r-butyrolactone was added to form a polyazide. The solution having an amine concentration of 10% by weight has a solution viscosity of 87 mPa*s. Synthesis Example 1 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride 22 g (0.10 Mo) Ear), 8.7 g (0.08 mol) of p-phenylenediamine as diamine, 2.0 g (0.01 mol) of 4,4'-diaminodiphenylmethane and 4,4'-diamino-2, 3.2 g (0.01 mol) of 2'-bis(trifluoromethyl)biphenyl was dissolved in 25.6 g of NMP, and the reaction was carried out at 60 ° C for 6 hours to obtain a solution containing 1% by weight of polyglycine. The solution viscosity of the polyaminic acid solution was 40 mPa·s. Then, 208 g of NMP was added to the obtained polyaminic acid solution, and 15 g of pyridine and 20 g of acetic anhydride were further added, and the dehydration ring-closing reaction was carried out at U 〇 ° C for 4 hours. Dehydration After the ring reaction, a solvent containing 15% by weight of a polyamidimide (B-4) having a ruthenium iodide ratio of about 80% is obtained by solvent-replacement of a solvent in the system with a new r-butylene ester. A small amount of this solution was taken at 23 gg, and r-butyrolactone was added to prepare a solution having a polyethylenimine concentration of % by weight. The viscosity of the solution was determined to be 57 mPa·s. Synthesis Example 1 1 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 16.8 g (0.075 mol) and 1,3,3&amp;,4,5,9-hexahydro-hexahydro 5-5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione 7.9 g (〇.〇) 25 mol), p-phenylenediamine as diamine 4.3 g (0.04 mo-48-201007304 ears), bis[4-(4-aminophenoxy)phenyl]ether 117 g (〇〇4 mol) And 2.2-bis[4-(4-aminophenoxy)phenyl]indole 8_6 g (0.02 mol) dissolved in 260 g of NMP' was reacted at 60 ° C for 6 hours to obtain a polyaminic acid solution. A small amount of the obtained polyaminic acid solution was added to NMP to form a solution having a polyglycine concentration of 10% by weight, and the viscosity of the solution was determined to be 92 mPa·s. Then, 350 g of NMP was added to the obtained polyamic acid solution, and then 40 g of pyridine and 31 g of acetic anhydride were added to carry out a dehydration ring-closure reaction for 4 hours under not. After the dehydration ring closure reaction, the solvent in the system was replaced with a new r-butyrolactone solvent to obtain 11% by weight of hydrazine. A solution of polyamidolimine (B-5) having an imidization ratio of about 92% is about 415 g. A small amount of the solution is taken. A solution of 7-butyrolactone was prepared in a concentration of 1% by weight of polyimine, and the measured solution viscosity was 123 mPa·s. Synthesis Example 1 2 2, 3, 5_ as tetracarboxylic dianhydride Tricarboxycyclopentyl acetic acid dianhydride I4.6g (0.06 5 moles), 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo 3-3-furyl)-naphthalene [1,2-(:]-furan-1,3-dione Φ 7.9 g (0.025 mol) and 2,3,2',3'-biphenyltetracarboxylic acid Dihydride 2.9 g (0.010 mol), p-phenylenediamine as diamine 4,3 g (0. 〇4 mol), bis[4-(4-aminophenoxy)phenyl]ether u.7 g (0.04 mol) and 2.2-bis[4-(4-aminophenoxy)phenyl]indole 8.6 g (0.02 mol) were dissolved in 260 g of NMP and reacted at 60 ° C for 6 hours to obtain a poly Proline acid solution. Take a small amount of the obtained polyaminic acid solution, add NMP, and prepare a solution with a polyglycine concentration of 10% by weight, and measure the viscosity of the solution to 103 mP as. Then, to the obtained poly-proline solution Add 3 50g NMP, add 4〇g pyridine and 31g acetic anhydride, and carry out 4 hours dehydration ring closure at ll〇°C for anti-49- 201007304. After dehydration ring closure reaction, pass the system The solvent in the solvent was replaced with a new r-butyrolactone to obtain a solution containing 10% by weight of a polyamidimide (B-6) having a ruthenium iodide ratio of about 90%. About 420 g» Solution viscosity of the solution 113 raPa·s 〇 Synthesis Example 1 2 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 22.4 g (0-1 mol), p-phenylenediamine as diamine .8g (0.1 mole) was dissolved in 300 g of NMP and reacted at 60 ° C for 6 hours to obtain a polyfluorene φ amino acid solution. A small amount of the obtained polyaminic acid solution was added, NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was 103 mPa·s 0 . Then, 380 g of NMP was added to the obtained polyamic acid solution. Further, 40 g of pyridine and 31 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new r-butyrolactone to obtain a solution containing 10% by weight of a polyamidimide (B-7) having a ruthenium iodide ratio of about 90%. The solution viscosity of the solution of 320g» is ^ 113 mP a · s. &lt;Preparation of Liquid Crystal Aligning Agent&gt; Example 1 100 parts by weight of the polyorganooxynonane EPS-1 having an epoxy group obtained in Synthesis Example 1 is equivalent to being converted into polyimine (B-1) 5000 parts by weight of the polyiminoimine (B-1)-containing solution prepared in Synthesis Example 8 was mixed, and 500 parts by weight was added thereto (the total amount equivalent to 9.8 by weight relative to 100 parts by weight of the polymer) As an epoxy compound, ^ Chuan'-tetraglycidyl-4,4'-diaminodiphenylmethane (molecular-50-201007304 is about 400), and then added to the r-butin Ester (BL), N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC), the solvent composition is BL: NMP: BC=45:45:10 (weight ratio), solid content concentration is 4 % by weight solution. The solution was filtered through a vessel having a pore size to prepare a liquid crystal alignment agent. Various evaluations were carried out using the liquid crystal alignment agent as follows. The evaluation results are shown in Table 2. &lt;Production of Liquid Crystal Cell&gt; Using a liquid crystal alignment film printer (manufactured by 写本写真印刷), Φ The liquid crystal alignment agent prepared above was applied onto a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film. The film was heated on a hot plate at 80 ° C for 1 minute, and further heated on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 800 Å. The coating film is polished by a grinding machine equipped with a roller wound with a rayon cloth at a roller speed of 500 r pm, a table moving speed of 3 cm/sec, and a fluffing length of 〇.4 mm. A liquid crystal alignment film is formed. Then, it was ultrasonically washed in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C for 10 minutes. This operation was repeated to produce a pair of (two pieces) substrates having a liquid crystal alignment film on the surface of the transparent electrode. Then, an epoxy resin adhesive having an alumina ball having a diameter of 5·5 μm is applied to each outer edge of the pair of substrates having a liquid crystal alignment film, and then the liquid crystal alignment film faces are opposed to each other and overlapped and pressed. In combination, the polishing directions of the liquid crystal alignment films are antiparallel to each other to cure the adhesive. Then, a nematic liquid crystal (manufactured by Merck & Co., MLC-6 221) was charged between a pair of substrates through a liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell. -51-201007304 &lt;Evaluation of liquid crystal cell&gt; The above operation was repeated to produce a plurality of liquid crystal cells. The evaluation of the heat resistance and the evaluation of the light resistance were carried out using the respective liquid crystal cells. [Evaluation of Voltage Retention Rate] A voltage of 5 V was applied to the liquid crystal cell manufactured above at 60 ° C for a time span of 167 msec, the application time was 60 μsec, and then the voltage from the voltage release to 167 msec was measured. Retention rate. When the voltage holding ratio is 98% or more, the voltage holding ratio can be evaluated as good.

0 In addition, the voltage holding ratio measuring device uses VHR-1 manufactured by Dongyang TECHNICA. [Evaluation of heat resistance] The liquid crystal cell produced above was measured for the voltage holding ratio (initial voltage holding ratio) under the same conditions as the above-described evaluation of the voltage holding ratio. Then, after the liquid crystal cell was allowed to stand in an oven at 100 ° C for 1 000 hours to cause thermal stress, the voltage holding ratio (voltage holding ratio after generating thermal stress) was measured again under the above conditions, and investigation was made to generate thermal stress. The rate of change of the voltage holding ratio with respect to the initial electric pressure holding ratio. When the rate of change is less than ± 2%, the heat resistance can be evaluated as good. [Evaluation of light resistance] The liquid crystal cell produced above was measured for the voltage holding ratio (initial voltage holding ratio) under the same conditions as the above-described evaluation of the voltage holding ratio. Then, the liquid crystal cell was statically placed at a distance of 5 cra under a 40 watt white fluorescent lamp, and after irradiating for 100 hours to generate a light stress, the voltage holding ratio was measured again under the above conditions (the voltage retention after the generation of the optical stress) Rate) The rate of change of the voltage holding ratio after the generation of the optical stress with respect to the initial voltage holding ratio was investigated. When the change rate -52 - 201007304 is less than ± 2%, the light resistance can be evaluated as good. [Measurement of Electrostatic Leakage Performance] A voltage of 120 V was applied to the liquid crystal cell produced above at 25 ° C for 5 minutes to accumulate static electricity in the cell. Then, the time from the release of the applied voltage to the disappearance of the accumulated voltage was measured on a scale of 5 minutes, and when the time was within 60 minutes, the electrostatic leakage performance was evaluated as good. Examples 2 to 18 and Comparative Examples 1 to 3 In the same manner as in Example 1, except that the types and amounts of polyorganosiloxane and other polymers having an epoxy group were as shown in Table 2, respectively. Liquid crystal cells were prepared for each liquid crystal alignment agent and evaluated. The evaluation results are shown in Table 2. Further, 'other polymers were respectively supplied to the liquid crystal alignment agent in the form of a polymer solution prepared in the above Synthesis Example, and the amounts in Table 2 were respectively calculated as the amounts of the polymers contained in the respective solutions. In Examples 13 to 18 and Comparative Example 2, each of the examples used two other polymers. -53-

Claims (1)

201007304 Table 2 Liquid crystal alignment agent Liquid crystal cell Cyclohexane with cyclopolyorganooxy group Other polypyrene voltage retention ratio (%) Heat resistance Light resistance Electrostatic leakage performance Type (parts by weight) _ Amount (parts by weight) Rate of change (%) Rate of change (%) Time of disappearance (minutes) Example 1 EPS-1 100 B-2 5000 99 1.1 0.8 45 Example 2 EPS-1 100 B~3 5000 99 1.0 0.7 55 Example 3 EPS-1 100 B~5 5000 99 0.8 0.5 50 Example 4 EPS — 1 100 B-6 5000 99 0.8 0.5 45 Example 5 EPS-2 100 B-2 5000 99 1.1 0.8 45 Example ό EPS — 2 100 B — 3 5000 99 1.0 0.7 55 Example 7 EPS-2 100 B-5 5000 99 0.8 0.5 50 Example 8 EPS-2 100 B — 6 5000 99 0.8 0.5 45 Example 9 EPS-3 100 B-2 5000 99 1.1 0.8 45 Example 10 EPS- 3 100 B-3 5000 99 1.0 0.7 55 Example 11 EPS-3 100 B — 5 5000 99 0.8 0.5 50 Example 12 EPS-3 100 B-6 5000 99 0.8 0.5 45 Example 13 EPS-1 100 A-1 1000 98 1.2 1.0 30 B~1 4000 Example 14 EPS-1 100 A-2 1500 98 1.9 1.5 20 B-1 1500 Example 15 EPS-1 100 A-3 2000 98 1.7 1.3 15 B-4 3000 Example 16 EPS-1 100 A — 1 1500 98 1.5 1.2 35 B-1 3500 Example 17 EPS—1 100 A—2 1000 98 1.7 1.4 25 B— 1 4000 Example 18 EPS-1 100 A — 3 2000 98 1.5 1.1 20 B-4 3000 Comparative Example 1 /fm- /\\\ 0 B-2 5000 98 5.0 2.5 40 Comparative Example 2 No 0 A-1 1000 97 6.5 3.3 30 B— 1 4000 Comparative Example 3 4rrr. m 0 B -7 5000 99 0.8 0.5 90 [Simple description of the diagram] None. [Description of main component symbols] None 0 - 54 - 201007304 7. Patent application scope: 1. A liquid crystal alignment agent characterized by containing a polyorganosiloxane having a repeating unit represented by the following formula (s-1), At least one of the group consisting of a hydrolyzate and a hydrolysis condensate thereof, wherein the epoxy equivalent weight is from 50 to 10,000 g/mol', and the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography is from 1000 to 100,000. , μ* X φ--Si—Ο-- _ YJ (S-1) In the formula (s—i), x is a monovalent organic group having an epoxy group, y is a hydroxyl group, and the number of carbon atoms is 1~ An alkoxy group of 20, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. 2. The liquid crystal alignment agent of claim 1, wherein X in the above formula (S-1) is a formula (X-1) or (X-2) (X-1) The group represented by (X-2). 3. The liquid crystal alignment agent according to claim 1 or 2, which further comprises at least one poly-55-201007304 compound selected from the group consisting of polylysine and polyimine. 4. The liquid crystal alignment agent of claim 3, wherein at least one polymer selected from the group consisting of polylysine and polyimine is selected from the group consisting of poly-brenic acid and the poly-proline At least one polymer of a group consisting of polydecimide formed by dehydration ring closure, the polyamic acid containing 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, l, 3, 3a, 4, 5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-l,3-dione, l,3,3a ,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furan-yl)-naphthalene[1,2-c]-furan-1,3 -dione, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5 -dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane- 2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.02'6]undecane-3,5,8,10-tetraketone and 2,3,2',3 A tetracarboxylic dianhydride of at least one of the group consisting of '-biphenyltetracarboxylic dianhydride is reacted with a diamine. 5. The liquid crystal alignment agent of claim 3, wherein the content ratio of at least one polymer selected from the group consisting of polyφ valine and polyimine is selected from 100 parts by weight relative to 100 parts by weight At least one of the group consisting of the polyorganosiloxane having the repeating unit represented by the above formula (S-1), the hydrolyzate thereof, and the hydrolysis condensate thereof is from 200 to 50,000 parts by weight. 6. A liquid crystal alignment film formed by the liquid crystal alignment agent of any one of claims 1 to 5. A liquid crystal display element characterized by having a liquid crystal alignment film according to item 6 of the patent application. -56- 201007304 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None.