TW201144384A - Liquid crystal alignment agent, method for producing liquid alignment film and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent which has exellent properties in coating and printing on a panel with minute concavo-convex, is able to provide an exellent liquid crystal alignment (pretilt angle expression) by a photo-alignment method with a few exposure of radiation, and furthermore provides a liquid crystal alignment film with exellent property in burning. The liquid crystal alignment agent comprise poly organ-siloxane and at least one of polymer selected from a group comprising polyamic acid and polyimide made from cyclodehydrating polyamic acid, wherein polyamic acid is obtained by reacting tetracarboxylic acid dianhydride with diamine which comprises an amin with C1-4 alkyl, C4-20 alkoxy, a group with a structure conneting with two or more 6 membered rings, a group with steroid structure and diamine with carboxyl group.

Description

201144384 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a crystal Hp a + , a Ba-like recording agent, a liquid crystal alignment film, and a liquid crystal display device. [Prior Art] /3⁄4日日示示 ^ ^半由. In the T 兀 ’ ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” ” The liquid crystal alignment film is broadcasted by a method of rubbing in one direction (wiping method) on the surface of the organic film formed on the surface of the substrate by using a cloth such as rayon. This is also the same in the horizontal electric field type liquid crystal display element; and: if the liquid crystal alignment film is formed by the rubbing treatment, there is a lower: dust or static electricity is easily generated in the rubbing step, so dust adheres to the surface of the alignment film. It is the cause of poor display. In addition, in the case of a substrate having a TFT (Thin Film Thunder, Due to Electrolytic Body) element, due to the generated static electricity, there is also c ^ α Φ ^ The circuit of the TFT device of the skin edge causes a problem that the yield is lowered and the m ratio is lowered.曰 曰 南 南 ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为Thus, the optical alignment method can be found in the patent document in the step. With uniform liquid crystal alignment. Dust or static electricity is formed, and in addition, as a liquid crystal display element, an STN (super twisted nematic) type or the like is used. The level alignment mode of the TM (turn-to-column) type, the nematic liquid crystal has a positive dielectric divergence using a liquid crystal display element having a negative dielectric # I Λ , ", and a negative "electric anisotropy" The vertical 201144384 (Homeotropic) alignment of the nematic liquid crystal. In this mode of operation I is tilted in a direction parallel to the substrate in the (vertical alignment) type liquid crystal display element:: 仏刀子魂Θ _日 a &gt ; /λ + f The liquid knives must be tilted from the normal direction of the substrate in a certain direction. This method can be used, for example, to set the protrusion on the surface of the substrate. You can go to the transparent electrode. The method of setting the stripe stripe on the straw, the use of the struts, and the alignment film, thereby tilting the liquid crystal molecules, is directed by the method in which the normal direction of the substrate faces one direction (pretilt) in the plane of the substrate. The above-mentioned light-aligning side, the present At _仏曰_ _ / is used as a method of controlling the tilting direction of the liquid-day eight-day-day molecular molecule in the liquid-day display element of the vertical alignment mode. By means of light distribution The control ability and the pretilt angle reflect the vertical alignment of the 渰θ 〕 night day alignment film, so that the liquid crystal molecules can be evenly tilted when the voltage is applied (Patent Documents 2 and 4 to 6). It is supplied by a light-aligning method to a liquid crystal alignment film. It can be effectively applied to various liquid crystal display elements. Miao ^ ^ ^ , heat and 'in order to impart liquid crystal alignment ability to the organic film by photo-alignment method, must be taken In the case of a strong radiation of 〇〇〇j/m2 or more, the problem of performance due to molecular scission of the organic thin film is caused by the 'other' which may cause deterioration of the radiation irradiation device over time (for example, light irradiation of an ultraviolet lamp) The deterioration of the strength with time is problematic from the viewpoint of reducing the manufacturing cost of the liquid crystal element. Further, it is pointed out that the liquid crystal alignment film formed by the photoalignment method sometimes has a pretilt angle embodying property at the initial stage, and sometimes It will change over time and requires improvement. When using the photo-alignment method, you or γ, λΑ is a good liquid crystal g with very little radiation exposure. A new liquid crystal alignment film material with daily alignment properties, reported as a liquid crystal alignment of a material composed of polyglycine 201144384 or polyamidiamine in the molecular region of the 暮人# + β ^ ^ Λ 疋The agent [boxes can be formed by the shots to form a good material, and the responsiveness of the recent years). The requirement of the property is higher than that of the liquid crystal alignment film which is increased before g, and it is desired to improve the difference in luminance generated on the surface of the film. As described above, the liquid crystal alignment agent is not known to be provided. The amount of line irradiation advantageously reflects the image sticking property improved by light and the prior art document patent documents (Patent Documents 7 to 9). In these documents, 500 to 3, 〇〇〇J/m2 emission, liquid crystal alignment liquid crystal alignment film, and high definition of liquid crystal display elements, and it is necessary to continue to improve. Therefore, it is not bad on the substrate surface, and the coating property to the liquid crystal alignment agent is large in the difference portion. In addition, in the presence of the light-receiving element, there is a residual image and a mark. In particular, due to the above-mentioned pretilt angle, the observer may consider it to be a branding, and the liquid crystal alignment agent may be used according to a small amount. The advantage of the alignment method and the ability to form a liquid crystal alignment film with imprinting characteristics. [9] Japanese Patent Application Laid-Open No. Hei. No. Hei. No. 2004-163646. It is a high-speed, good-quality, and it is possible to avoid the problem of the printing to the law. Patent document 1: Patent document 2 Patent document 3 Patent document 4 Patent document 5 201144384 Patent document 6: JP-A-2003-1 1443 No. 7 Patent Document 7: w020〇9/2 5385A1 Patent Document 8: WO2009/25386A1 Patent Document 9: W02009/253 88A 1 Patent Document 10: JP-A-63-291922, Non-Patent Document 1 J. The present invention has been made in view of the above circumstances, and it is an object of the invention to provide an excellent coating property or printability on a panel having fine concavities and convexities. At the same time, a liquid alignment method which imparts a good liquid crystal alignment property (pretilt angle embodyability) and a liquid crystal alignment film excellent in branding characteristics can be imparted by a photo-alignment method of a small amount of radiation irradiation. Eighth Another object of the present invention is to provide a liquid crystal display element having a liquid crystal alignment excellent in the imprinting characteristics of the upper 3? Excellent Phase I I Reliability Another object and advantage of the present invention can be achieved by the above-mentioned objects and advantages of the present invention. A solution, which comprises: a liquid crystal alignment of the stomach (A) having the structure represented by the following formula (A1), FV t organic oxoxane,

(A1) v' va is an integer of 4,

J In the formula (A 1), r is a fluorine atom or a cyano group represents a linkage, and 201144384 (B) is derived from poly-branched acid*, and § ̄ ̄ ̄ acid acid dehydrated 瑗 纠 纠 纠 纠 纠The fresh towel, s, and at least one polyglycolic acid selected from the polyethylidene is a tetracarboxylic acid dimer, wherein the polyfluorene is reacted with an amine, and each _ &; a diamine having a carboxyl group. The diamine preferably further includes; b-: includes (10) having: a carbon atom having a carbon number of 4 to 2 fluorene, a carbonogen ()-amine, an oxy group, having a bond of two members, being = A group that burns an alcohol structure. * Blade storm group or have a solid

The upper stream B of the present invention achieves the object and the advantage, and the second is that the liquid crystal alignment agent is formed by a liquid crystal ligand having the crystal lattice of the above-mentioned night crystal alignment film, such as a few pieces. To "M1丨 is coated on a panel with excellent embossing properties or excellent printability, π + ,, and a small amount of radiation alignment method can give light to the rays of the ray It is possible to impart afterimage and branding (pre-detection angle ancestry), and right-handedly "excellent liquid crystal alignment film. % of the liquid crystal alignment agent having the sleep of the present invention a a liquid crystal display of the present invention The liquid crystal alignment film is excellent in properties and can be reliably deteriorated over a long period of time even if it is improved for a long period of time. Therefore, the present invention (4) h-sexuality is not used in the device, for example, ^ can be effectively used in various 1^ seasons.锗, 0T 4隹丄, word processor, notebook computer, '· game console, text guide system, photography 趟, terminal, digital camera, action', portable information display device. ° Liquid daily TV [Embodiment] Hereinafter, the present invention will be described in detail. As described above, the liquid crystal alignment agent of the present invention contains: (Α) /, a hydroorganosiloxane having a structure represented by the above formula (Α), and

CH=CH—C—^ X4j—C—CH=CH c II o 201144384 (B) Poly-imine from poly(pro-imine) (hereinafter, sometimes referred to as “$ and dehydration ring closure of the polyplysine” The selected one of the group consisting of "polyimine (B)"), wherein the polyamine is tetrazoic acid and diamine, and the diamine comprises (b2) a diamine having a carboxyl group. The above-mentioned bi (bi) diamine has an alkoxy group having 4 to 20 carbon atoms and 4 to 20 carbon atoms, a group having two or more groups of 6 groups or having a steroid structure. <Polyorganooxane (A)> The polyorgano-oxygen (A) in the present invention is a polyorganosiloxane having a structure. As a in the above formula (A1), preferably 〇 or j, as the structure represented by the above formula (A 1), a structure which can be formed by a group represented by (A1-1) and (A1-2) is preferable: R1—X1-^R2 (Α1·molenic acid (B)”) 4, sometimes referred to as at least one polymerization reaction, the amine is preferably an alkyl group or a carbon atom ring structure. (A1) means more preferably 0. The examples are as follows: R3 —x3-^-r4-

(A1-2) In the formulae (Al-1) and (A1_2), r, a and "*" are defined the same; r1 in the formula (A1-1) is a hydrogen atom, and the number of rings containing the moon is 3 a monovalent organic group or a carbon atom group of ～40, wherein a part or all of the nitrogen atoms of the above alkyl group and a carbon atom of the above formula (A1) group are 1 to 40, which can be taken as a fluorine atom by 201144384. X is a single bond, an oxygen atom, + -COO - or + -〇c〇_ (the above "+" linkage is bonded to R1), and R2 is a divalent aromatic group and a divalent alicyclic ring. a heterocyclic group of a formula or a divalent fused cyclic group, X2 being a single bond, an oxygen atom, + -COO - or + -〇c〇_ (the above "+" linkage is bonded to R2 b is an integer of 0 to 3; R3 in the formula (A1-2) is a hydrogen atom, a monovalent organic group having a carbon atom number of 3 to 40 containing an alicyclic group, or a carbon atom number ~々. Wherein a part or all of the hydrogen atom of the above alkyl group, and the alkane X3 of the atom of j攸 are an oxygen atom or a divalent aromatic group, and the divalent ring R4 is a divalent aromatic group, and the divalent group a heterocyclic group of a alicyclic group or a divalent fused cyclic group, X4 is a single bond, an oxygen atom, + -C00- or + · 0 (: 〇 (the above "+" linkage bond and R4 bonding), C is an integer of 0 to 3. In the above two formulas (Α1-1), ν Τ «-J - , an alicyclic group having 3 carbon atoms, an i-valent organic group, for example a cholene-alkenyl group, a cholesteryl group, an adamantyl group, etc. The alkyl group having the number of carbon atoms of the group R3 is an alkyl group, and the group is a group of, for example, a carbon number of 1 to 20, wherein The base of the alkyl group, or the argon atom may be replaced by a halogen atom. Examples of the alkyl group include n-pentyl group, -10-201144384 n-hexyl group, n-heptyl group, n-octyl group, and anthracene group. Base, n-decyl, positive laurel is twelve-burning base, positive thirteen-burning base, positive fourteen burning base, positive fifteen burning positive sixteen burning base, positive seventeen burning base, positive eighteen burning base, positive ten Nine courtyards are eicosyl, 4,4,4-three Fluorobutyl, 4,4,5,5,5-pentafluoropenta 4.4.5.5.6.6.6- heptafluoroalkyl, 3,3,4,4,5,5,5-heptafluoroheptyl, 2 Trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, :fluorooctyl)ethyl, 2-(perfluorodecyl)ethyl, etc. . Examples of the aromatic group of R2 in the above formula (A1-1) and R4 in the above formula (A1-2) include, for example, 1,4-phenylene group, 2-fluoro-1,4-yl group, and 3 -fluoro-1,4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene, etc.; as a divalent alicyclic group of R2 and R4, for example, a cyclohexyl group , 2-fluoro-1,4-cyclohexylene, 3-fluoro-1,4-cyclohexyl 2.3.5.6-tetrafluoro-1,4-cyclohexylene, etc.; divalent heterocyclic group as R2 and R4 For example, a 10 Å base group, a 2,5 - yt ratio sigma group, and a 1,4 - sigma fluorenyl group are mentioned. Examples of the divalent condensed ring group of R 2 and R 4 include a naphthyl group and the like. The group represented by the above formula (A 1 -1) may be a group represented by the following formula, etc.; a group, a group, a group, a group, a 2,2-(all divalent benzene 1,4- group) ,, 4-Asian, for example, -11 - 201144384

Ric〇〇-〇^co -12- 201144384 C5H11 ο coo

C5Hh

CO· coo

Co- cf3—c3h6

Coo

CO· f3c-c2h4

Coo

CO- CF3C3H6

CF3C2H4·

CO- CF3CH2

CO-本 cf3c3h6-o

In the above formula, R1 and "*" are respectively the same as the definition of the formula (A 1 -1), and d is an integer of 1 to 10 0. The group represented by the above formula (A 1-2) may, for example, be a group represented by the following formula. 201144384

The polyorgano-oxygen (A) of the present invention preferably has a structure of 0.2 to 6 mmol/g, and more preferably has a structure represented by the above formula (A1) of 0.3 to 5 mmol/g. The polyorganosiloxane (Α) has a weight average molecular weight of Μ00~5〇〇, _' more preferably 2, _~2〇〇, as measured by gel permeation chromatography. The above polyorganosiloxane (Α) is preferably in the above range: has a structure represented by the above formula (Α 1), and can be formed by any method, for example, A mixture of a decane compound of a hydrolyzable group (hereinafter referred to as "decane compound (1)") and a cyclane compound are subjected to hydrolysis condensation in the presence of an organic solvent, water and a catalyst, and first, a polycondensation having an epoxy group is synthesized. An organic siloxane (hereinafter referred to as "precursor of polyorganosiloxane"), which is then represented by the above formula (A 1 ) by making the polyorgano oxime disk a compound having a structure and a group reactive with an epoxy group (hereinafter referred to as "compound (A1)"), Synthesis. -14- 201144384 In this case, the compound (A 1) may be used in combination with the following compound (hereinafter referred to as "other reaction, biochemical substance"), and the compound has no structure represented by the above formula (4)) a group reactive. Examples of the above-mentioned Shi Xi Yuan compound (1) include 3-glycidoxypropyl dimethoxy decane, 3-glycidoxypropyl triethoxy decane, and 3-glycidoxypropyl group. Dioxadecane, 3 glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropylmonomethyloxyoxydecane, 3-glycidoxypropyldidecyl Oxylate... glycidyloxyethyltrimethoxy sulphate, 2 glycidoxyethyl triethoxy decane, 2-glycidoxyethylmethyldimethoxy decane' 2_glycidoxy Ethylmercaptodiethoxydecane, 2. glycidoxyethyldimethoxymethoxydecane, 2-glycidoxyethyldimethylethoxydecane, 4-glycidoxybutyl Trimethoxydioxane, 4-glycidoxybutyltriethoxydecane, 4-hydrazine: butyl butyl methyl dimethoxy decane, 4-glycidoxy butyl dioxy decane, 4-shrink Glyceroxybutyl dimethyl methoxy oxime: ethoxyglycidoxy butyl dimethyl ethoxy decane, 2 - (3, deuterocyclic 4-yl) ethyl Methoxydecane, 2-(3,4-epoxycyclohexyl)ethyl=% decyl decane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane bis=ethoxy epoxide ring For hexyl)propyltriethoxydecane, etc., it is possible to use a decane compound which is used for the synthesis of a polyorganosiloxane (Α) precursor from the agricultural (3, 4 or more). It may be composed of a decane compound (丨) as described above, and may contain other decane compounds a _ .LA ' other than the alkyl compound (1), and may be referred to as "alkane compound (2)"). -15- 201144384 As the decane compound (2) which can be used therein, for example, tetraoxane, tetradecyloxydecane 'tetraethoxydecane, tetra-n-propoxymide 1, tetraisopropoxy zeshi , tetra-n-butoxy-stone, four-N-T----butoxybutane, trioxane, trimethoxy decane, triethoxy decane, di-n-nooxy decane, triisopropyl Oxydecane, tri-n-butoxy-oxan, second-order butoxy-decane, trichlorodecane fluoride, trimethylsulfanyl fluoride, rhodium-ethoxylate, tri-n-propoxy fluoride Crushed, fluorescein-s oxydiisopropylidene hydride, fluorinated tri-n-butoxy decane, fluorinated tri- or two-butoxy alkane, methyl trioxane, methyl trimethoxy decane, hydrazine Triethoxy oxime, decyl tri-n-propoxy decane, methyl triisopropoxy fluorene, methyl di-n-butoxy decane, decyl tri- or 2-butoxy decane, r earth) ethyl Trichlorodecane, 2-(trifluoromethyl)ethyltrimethoxy oxalate, difluoromethyl)ethyltriethoxydecane, 2-(trifluoromethyl)ethyltri-n-propoxydecane , 2-(Trifluoromethyl)ethyl triisopropoxy decane, 2 (trifluoromethyl)ethyl tri-n-butoxy decane, 2-(trifluoromethyl)ethyl tri-n-butylbutane decane , (2-perfluoro-n-hexyl)ethyltrichlorodecane, (2. perfluoro-n-yl)ethyl bis-oxyxanthine, (2-perfluoro-n-hexyl)ethyltriethoxylate, (2 - Perfluoro-n-hexyl)ethyltri-n-propoxy-Xiyuan, (2_perfluoro-n-hexyl)ethyltriisopropoxydecane, (2-perfluoro-n-hexyl)ethyltri-n-butane-based gas, (2-Perfluoro-n-hexyl)ethyltri-n-butoxy oxane, (2_Wang-fluoro-n-octyl)ethyltrioxazole, (2 _perfluoro-n-octyl)ethyltrimethoxylate (2-perfluoro-n-octyl)ethyltriethoxydecane, (2-perfluoro-n-octyl)ethyltri-n-propoxydecane' (2-perfluoro-n-octyl)ethyltriisopropyl Gas-based crushed alkane, (2-perfluoro-n-octyl)ethyltri-n-butoxydecane, (2 _ all-gas n-octyl) ethyl tri-n-butoxy decane, hydroxymethyl trioxane, - 16 - 201144384 Hydroxymercaptotrimethoxydecane, Hydroxymethyltriethoxydecane, Hydroxyl Mercapto tri-n-propoxy decane, hydroxydecyl triisopropoxy decane, hydroxymethyl tri-n-butoxy decane, hydroxymethyl tri- or 2-butoxy decane, 3 (fluorenyl) propylene oxy propylene Trioxane, 3-(methyl)propenyloxypropyltrimethoxydecane, 3-(indenyl)propenyloxypropyltriethoxydecane, 3-(methyl)propenyloxypropane Tri-n-propoxy decane, 3 (meth) propylene methoxy propyl triisopropoxy decane, 3 - (meth) propylene oxy propyl ' yl - n - butoxy decane, 3 - (fluorenyl) Propylene methoxypropyl tri-n-butoxy decane, 3-mercaptopropyl tri-dioxane, 3-mercaptopropyl trimethoxy decane 3 -mercaptopropyl triethoxy decane, 3-mercaptopropyl propyl N-propoxy decane, 3-mercaptopropyltriisopropoxy decane, 3-mercaptopropyltri-n-butoxy decane, 3-mercaptopropyltri-n-butoxy decane, decylmethyltrimethoxyl Decane, mercaptomethyltriethoxydecane, vinyltrioxane, vinyltrimethoxydecane, vinyltriethoxydecane, vinyltri-n-propoxylate, and vinyl Propoxy decane, vinyl tri-n-butoxy oxalate, vinyl tri-n-butoxy decane, allyl trioxane, allyl trimethoxy decane, allyl triethoxy decane, olefin Propyl tri-n-propoxy alkane, allyl triisopropoxy decane, allyl tri-n-butoxy oxan, allyl tri-n-butoxy decane, phenyl trioxane phenyl Dimethoxydecane, phenyltriethoxydecane, phenyltri-n-propoxylate, phenyltriisopropoxydecane, phenyltri-n-butoxydecane, phenyldi-butoxy Decane, decyl dioxane, decyl dimethoxy oxalate, mercapto diethyl decane, methyl di-n-propoxy decane, decyl diisopropoxy decane, decyl di-n-butoxy Decane, methyl di- or two-butoxybutanthine, dimethyl dioxet, dimethyl dimethoxy oxime, two-17- 201144384 methyl diethoxy decane, dimethyl di-n-propyl Oxy decane, dimethyl diisopropoxy decane, dimethyl di-n-butoxy decane, dimethyl di- or di-butoxy group > 5 kiln, (methyl) [2 (Wang Niu Zhengxin Ethyl]dichlorite, (methyl)perfluoro-n-octyl)ethyl]dimethoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]diethoxy Decane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-propoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]diisopropoxydecane, ( Mercapto)[2-(perfluoro-n-octyl)ethyl]di-n-butoxydecane, (methyl)[2·(all-gas n-octyl)ethyl]di- or 2-butoxybutane, (A) (3) benzyl propyl dioxane, (fluorenyl) (3-mercaptopropyl) dimethoxy decane, (fluorenyl) (3-mercaptopropyl) diethoxy decane, Mercapto) (3-mercaptopropyl) di-n-propoxy oxalate, (methyl) (3-mercaptopropyl) diisopropoxy oxime, (methyl) (3-mercaptopropyl) n-Butoxydecane, (fluorenyl) (3_mercaptopropyl) di-2-butoxydecane, (fluorenyl)(vinyl)dioxane, (fluorenyl)(vinyl)dimethoxydecane , (Methyl) (vinyl) diethoxy oxime (indenyl) (ethenyl)-n-propoxy XI Xiyuan, ( Mercapto) (vinyl) _ isopropoxy decane, (methyl) (vinyl) di-n-butoxy decane, (methyl) (vinyl) di- or two-butoxy decane, divinyl two gas矽, divinyl dimethoxy decane, divinyl diethoxy decane, divinyl di-n-propoxy decane, divinyl diisopropoxy decane, divinyl di-n-butoxy decane, Divinyl di-2-butoxy decane, dipyridyl-chlorite sulphur 'di-p-styl-methoxy sulphur, diphenyldiethoxy sulphite 'diphenyldi-n-propoxy decane' Diphenyldiisopropoxydecane, diphenyldi-n-butoxydecane, di-p-butyl di-butoxybutane, dimethyl decane chloride, methoxy dimethyl decane 'ethoxy 2 Methyl decane, vaporized trimethyl decane, trimethyl decane bromide, iodotridecyl decane, -18- 201144384 methoxy trimethyl ketone, ethoxy trimethyl μ, n-propoxy A Methyl...isopropoxy trimethyl sulphate, n-butoxy; succinyl butoxy trimethyl, ternary butoxy 3:, gasification) (ethylene) diterpenes I'm ((methoxy)(ethinyl)dimethyl(milyl)(ethoxy)(vinyl)dimethyl, (gasification)(曱烧,(methoxy)(methyl)二a decane compound having a ruthenium atom such as a phenyl residue or an (ethoxylated fluorenyl) dioxin, such as KC-89, KC-89S, Χ-21-5842, Χ-21-5843, Χ-21-5846 , Χ-21-5847, Χ-22-170Β, Χ-22-170ΒΧ, Χ-22-176Β 'X-22-176D > Χ-40-2308, Χ-40-2651, Χ-40-2672, Χ-40-9220, Χ-40-9246, Χ-40-9247, Χ-41-1053, Χ-41-1056, KF6001, KF6002, KF6003, in addition, the trade name can also be listed, for example, Χ-21-3153 > Χ-21-5841 Χ-21-5844 ' Χ-21-5845 Χ-21 -5848 ' X-22-160AS X-22-170D, X-22-170DX X-22-176DX ' X-22- 1 76F Χ-40-2655Α, Χ-40-2671 Χ-40-9225 'Χ-40-9227 Χ-40-9250 ' Χ-40-9323 Χ-41 -1 805 ' Χ-4 1 -18 1 0 KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above is manufactured by Shin-Etsu Chemical Co., Ltd.) 〇1 & 88 1 ^ 8111 (Showa Denko (shares) manufactured); 3 > 1804,811805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (of Toray Dow above

Coring Silicone Co., Ltd.; -19- 201144384 FZ371 1. FZ37 22 (above is manufactured by UNICAR UNICAR); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS -S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (above Chisso (stock) manufacturing);

Methyl silicate M S51, Methyl silicate MS56 (above is manufactured by Mitsubishi Chemical Corporation);

Ethyl silicate 28, Ethyl silicate 40, Ethyl silicate 48 (manufactured by Colcoat Co., Ltd.); Partial condensate of GR100, GR650, GR908, GR95 0 (above, manufactured by Showa Denko). Among these compounds (2), tetradecyloxydecane, tetraethoxy zeoxime, decyltrimethoxydecane, methyltriethoxydecane, and 3-(meth)acrylofluorene are preferred. Oxypropyl trimethoxy decane, 3-(indenyl) propylene oxypropyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy sulphur, allyl trimethoxy decane , allyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, 3 - decyl propyl dimethoxy decane, 3 - decyl propyl triethoxy decane, fluorenyl Methyltrimethoxydecane, mercaptomethyltriethoxydecane, dimethyldimethoxycarbazide or dimercaptodiethoxydecane. The precursor of the polyorganosiloxane (A) used in the present invention is preferably a ring oxime equivalent of 1 〇〇 to 1 〇〇〇〇 g/m 〇 1, more preferably 150 〜1, 〇〇〇g/mol, especially good for 15〇~3〇〇^瓜〇1. Therefore, in the synthesis of the precursor of the aqueous organic oxane (A), it is preferred to set the decane compound (work) -20- and the ring 矽 not have a 列 〇〇

Ethyl alcohol is in the same amount as (4) of U 201144384, so that the obtained oxygen equivalent is within the above range. In synthesizing the precursor of the oxane (A) of the present invention, it is preferred to use only other decane compounds. Examples of the organic solvent capable of synthesizing the polyorganosiloxane (A) include a hydrocarbon, a ketone, and an ester. Examples of the hydrocarbon include, for example, anthracene and the ketone, and examples thereof include anthranilone-n-pentanone. And diethyl ketone, cyclohexanone, etc.; for example, ethyl acetate, n-butyl acetate, decyl acetate acetate, 3-decyloxybutyl acetate, and the above ether, for example, ethylene glycol Ethyl ether, tetrahydrofuran, dioxane, etc.; as the above-mentioned alcohol, for example, 丨-hexanol, diol monodecyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl, propylene glycol monomethyl hydrazine, propylene glycol monopropyl ether 4. Among them, the company is a water-insoluble solution. These organic solvents can be used singly or in combination. The amount of the organic solvent used is preferably from 10 to 10,0 parts by weight with respect to the weight of 100%, and more preferably, all of the decane is tested in the production of the polyorgano oxy- (A) precursor. The compound ' is preferably 〇5~1〇〇30 times mole. The polyorgano-delta compound (1) used in the polyorganocene oxy-combustion, the ether, the alcohol, and the like used in the precursor. Xylene, etc.; methyl isobutyl ketone, which is the above ester 'isoamyl ester, propylene glycol ethyl lactate, etc.; dimethyl ether, ethylene glycol * 4 -methyl-2-nonanol, mono-n-propyl ether , diethyl ether, propylene glycol single agent. For the above-mentioned catalyst, an alkali metal compound or an organic base can be used as the above catalyst, in which the two or more mixed portions are all decylated islands 50 to 1, and the amount of hydrazine is used in the amount of hydrazine, more preferably 21-201144384. , titanium compounds, wrong compounds, and the like. Examples of the metal compound described above include, for example, sodium hydroxide, potassium hydroxide, sodium decoxide, decyl alcohol, ethanol, ethanol, and the like. As the above organic test, for example, an organic primary or secondary amine such as ethylamine, diethylamine, piperidine, piperazine, pyrrolidine or pyrrole; such as diethylamine, tri-n-propylamine, tri-n-butylamine, and α ratio can be cited. An organic tertiary amine having a bite, 4 dimethyl dimethyl pyridine or diazabicyclononene; an organic quaternary amine such as tetramethyl oxidized. Preferred in these organic tests are, for example, diethylamine, tri-n-propylamine, tri-n-butylamine, η ratio sigma, and 4-monomethylamino group. An organic tertiary amine such as an organic quaternary amine such as tetradecyl ammonium hydroxide. The catalyst is preferably an alkali metal compound or an organic base in the production of a polyorganosiloxane (ruthenium) precursor. By using an alkali metal compound or an organic base as a catalyst, a side reaction such as ring opening of an epoxy group is not generated, and a target polyorganosiloxane is obtained at a hydrolysis rate and a condensation rate south of the crucible, and the production stability is good. Good for. Further, the liquid crystal containing the polyorganosiloxane (4) which is synthesized by using a base compound or an organic base as a catalyst and which is produced from a precursor is excellent in liquid crystal compatibility, and therefore is promoted by 鲈占丸社社Forming a ternary structure, it can be used to form a hexanol group with a relatively small proportion of arm organooxane. That is, the extraction of J ♦ ^ . pushes the organic oxane (A) due to the low content of decyl alcohol | & Excellent storage stability. -22- 201144384 As a catalyst, it is especially preferred as an organic base. The organic test uses different types of organic bases, temperature and other reaction conditions, etc., and the settings are made, for example, relative to all decane compounds = more than 0 moles, more preferably 0_05 to 1 moles.乂为〇.〇1~3 Hydrolysis or hydrolysis into the reaction of producing a polyorganosiloxane (A) precursor, preferably dissolving the compound having an epoxy group and the decane compound as needed in an organic solvent This solution is mixed with water and heated by, for example, an oil bath. In the hydrolysis and condensation reaction, the heating temperature is preferably 13 Torr. 〇 More preferably 40 to 100 ° C, preferably heated on 2, gentry J mouth keeper 'better 1 to 8 hours. The mixture may be stirred while being heated, or may be carried out under reflux. After completion of the reaction, the organic solvent layer separated from the reaction liquid is preferably washed with water. At the time of the washing, it is more (4) because it is easy to clean the operation by washing with water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2% by weight. After washing, the water screen after washing is neutral, and then the organic solvent layer is dried with a desiccant, which is required to be anhydrous calcium sulfate, molecular hydrazine, etc., and then the solvent is removed, thereby obtaining the target polyorganism. A siloxane (A) precursor. & For the precursor of polyorganosiloxane (A), the polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography is preferably 1,000 to 1,000,000, more preferably 1 500 to 300,000. . In the present invention, as the precursor of the polyorganosiloxane, a commercially available polyorganosiloxane having an epoxy group can be used. Examples of the commercially available product include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (the above are manufactured by Chisso Co., Ltd.). -23- 201144384 The above formula (A1) shows that the compound (A丨) used in the present invention is a compound having a structure and an epoxy group-reactive group. (A1) ' is a compound represented by each of the formulae (A1-1C) and (A1-2C) having a structure represented by the above formula (VIII).

R, R1, R2 in the above formula (A1-1C), R, R3, R4, χ3, X1 X4 in the above formula (A1-2C) are the same as defined in the formula (Α1-1) or (Α1-2) X5 in the above formula (Al-1C) is a single bond, a methyl group, an alkylene group having 2 to 10 carbon atoms, an alkenylene group or a divalent aromatic group, X2, a and b, and a and c is a single bond with an upper oxygen atom, a sulfur atom, and a sub- < atomic number of 2 to 10, when X5 is a single bond, e is 1 and R5 is a hydrogen atom, and X5 is a methylene group, a decyl group, an alkenylene group. Or a divalent aromatic group, wherein e is 0 or 1, and R5 is a carboxyl group, a hydroxyl group, _SH, _Nc〇, -NHR (wherein the above R is a hydrogen atom or an alkyl group having a carbon number of 6), -CH=CH2 *_S〇2Cl ; R6 in the above formula (A1-2C) is a divalent aromatic group, a divalent heterocyclic group or a divalent fused cyclic group, and X6 is An oxygen atom, _c〇〇_ + or -OCO- + (wherein the above bonding bond giving "+" is bonded to r6), -24- 201144384 f is an integer of 〇~3, and R7 is a carboxyl group, a hydroxyl group, - SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH = CH2 or -S02C, and X7 is a single bond, + -〇-(CH2)j_+ (wherein, 1 and j are integers of 〇~1 0, respectively, and a bond of "+" is bonded to R7) as a compound represented by the above formula (Al -1 C) In the above formula (Ai _ 1 c), a compound in which X5 is a single bond, R5 is a carboxyl group, or a compound in which X5 is a fluorenylene group, a stretching group or a divalent aromatic group, and R5 is a carboxyl group; The compound represented by the formula (A1-2C) is preferably a compound of the above formula (A1_2C) wherein r7 is a carboxyl group. Hereinafter, the compound (A1) having a carboxyl group is referred to as "carboxylic acid (A1)". The carboxylic acid (A1) is more preferably a compound represented by the above formula (A1C), and each of the compounds represented by the following formula: -25- 201144384

COOH

COOH

C〇〇_^_. \_

COOH

R1COO

R1 R10

R -o v

COO-(CH2)d-COOH

COO——CH2——COOH

V R1 R10

COO-CH2-COOH coo coo

COOH

COOH R1C00-

V

COOH -26- 201144384 c5h” coo

C5H”

COOH COO

COOH cf3-c3h6

Coo

COOH F3C—C2H4-

Coo

COOH CF3C3He

COOH CF3C2H4-

COOH CF3CH2

COOH

CF3C3H6—O

In the above formula, R1 is the same as the formula (Al-1), and d is an integer of 1 to 10; and as the compound represented by the above formula (A 1-2), the compounds represented by the following formulas and the like can be respectively listed; -27- 201144384

In the above formula, R3 is the same as defined in the formula (A1-2). The above-mentioned other reactive compound is preferably a compound having a carboxyl group as a group capable of reacting with an epoxy group, and a carboxylic acid having a pretilt angle-conforming structure (hereinafter referred to as "other carboxylic acid (1)")) a carboxylic acid having at least one of a structure in which a radical is generated by light irradiation and a structure having a photo-sensitizing function (hereinafter referred to as "other carboxylic acid (2)"), and other carboxylic acids other than the above ( The following 'referred to as 'other carboxylic acid (3)), etc.' may be selected from at least one of them. The so-called pretilt emissive structure in the above other carboxylic acid (1) may, for example, be an alkyl group or alkoxy group having 8 to 20 carbon atoms, a fluorinated alkyl group having 1 to 2 carbon atoms or fluorine. A structure consisting of an alkoxy group or a monovalent organic group having an alicyclic group and having 3 to 40 carbon atoms. Examples of the other carboxylic acid (1) having such a structure include compounds represented by the following formulas (匕1) to (C-4), respectively, -28- 201144384

ChF hF2h+"CiH2i-COOH (C-1)

Ππ2η+1 (C-3)

COOH (C-4)

CnH In the formula (C-1), h is an integer of u, 丨 is an integer of 3 to 18; j in the formula (C-2) is an integer of 5 to 2 ;; , k in 弋(3) is 1 An integer of 〜3, 〇, in addition, a positive number m is an integer of 〇~18; and n in the formula (C-4) is an integer of 丨18. Preferably, the eighth is preferably the above formula (C-2), (C_3), and (c_ compound, more than #A self-expressed, the L is as the above formula (C_2), and the 4-(n-pentyl) cage field is represented. Therefore, the mouthpiece 'can be listed as a base group') benzate, 4-(n-hexyl)benzoic acid, 4-(n-octyl, -m*4_(n-heptyl)benzene (octyl)-formic acid, 4_(正壬Benzoic acid, 4-Γτ: hail, 4-(n-decyl)undecyl)benzoic acid, 4-(n-octadecyl & et al; butyl octadecyl) benzoic acid as the above formula (C_3) The compound represented by the formula (C-3-l)~ic^± is J, for example, the compound represented by (L_3-3), etc. · -29- 201144384

C2F5—C3H6—ο

COOH (C-3-3 ) As a compound represented by the above formula (C_4), for example, 4 Butoxy)benzoic acid, 1 w TM & , 'n-(n-pentyloxy)benzonic acid, 4-( n-Hexyloxy) benzoic acid, 4_(n-heptyloxy)benzoic acid, 4-(n-octyloxy)benzoic acid, 4 (n-decyl)benzoic acid, 4_(n-decyloxy)benzoic acid, 4_(n-dodecyloxy oxime) benzoic acid, 4-(n-octadecyloxy)benzoic acid, or the like, one or more selected from the group consisting of two or more. The photo-sensitizing function of the carboxylic acid in the above other acid-inducing (2) means that after the light-irradiation forms a heavy-excited state, the inter-term intersection is quickly caused, and the double-term excited state is transferred, in the triple item. In the excited state, by changing to the excited state by the collision with other molecules, the function of returning to the basal state is self-recovering. The light sensitizing function can also coexist with the function of generating free radicals by the shot. The structure of at least one of a structure which generates a radical by light irradiation and a structure having a right " nine sensitizing function, and the structure of the second stupid structure 9,10-two-sided oxydihydroanthracene, 丨, 3_2 Nitrobenzene structure 1,4 - di-side cyclohexan-2,5-diene structure, that is, the structure of the following formula (1) ~ (4) respectively, -30- 201144384 〇N〇2 0 N〇 2 〇

O (3)

o (4) Can be at least one structure selected from. Examples of the other carboxylic acid (2) having such a structure include 3-benzoin benzoic acid, 4-benzoin benzoic acid, and 3-(4-diethylamino-2-hydroxybenzoin). Benzoic acid, 4-(2-hydroxybenzoin) benzoic acid, 3-(2-hydroxybenzoin) benzoic acid, 2-(2-hydroxybenzoin) benzoic acid, 4-(4- Methyl benzoin) benzoic acid, 4-(3,4-dimercaptobenzoin) benzoic acid, 3-(4-benzoin-phenoxy)propionic acid, 9,10-two side Oxyhydroindoline-2-carboxylic acid (indole-2-carboxylic acid), 3-(9,10-di-oxo-9,10-dihydroindol-2-yl)propionic acid, [3-(4) ,5-dimethoxyoxy-3,6-di-oxocyclohexyl-1,4-dienyl)propoxy]acetic acid, 3,5-dinitrobenzoic acid, 4-mercapto- 3,5-ditriphenylbenzoic acid, 3-(3,5-dinitrophenoxy)propionic acid, 2-methyl-3,5-dinitrobenzoic acid, and the like. Examples of the other carboxylic acid (3) include formic acid, acetic acid, propionic acid, and benzoic acid. -31 - 201144384 The use ratio of the carboxylic acid (A 1 ) used in the production of the polyorganosiloxane (A) of the present invention, relative to the epoxy group of the precursor of the lm〇l polyorganosiloxane (A) It is preferably 0.001 to im 〇l, preferably OHm 〇丨 more preferably 0.2 to 0.9 mol. The ratio of use of the other carboxylic acid (1) used in the production of the polyorganosiloxane (A) of the present invention is preferably 〇 with respect to 1 mol of the precursor of the polyorgano oxy (A) precursor. 5mol or less, more preferably 〇〇1~〇3m〇i. The ratio of use of the other carboxylic acid used in the production of the polyorganosiloxane (A) of the present invention is preferably 〇.3 mol or less, relative to the epoxy group of the precursor of 1 mol of the polyorganooxime (4). Good for 〇〇〇〇i~〇im〇i. The ratio of the other carboxylic acid (3) used in the clothing &amp; Benming Bin organic oxane (A), relative to the epoxy group of the precursor of lm〇1 polyorgano oxy (A) Preferably, it is O.-, more preferably 〇〇〇〇ι~〇2(4): when producing the polyorganosiloxane (4) of the present invention, in addition to the carboxylic acid (4)), in the case where other carboxylic acids are used in combination, the carboxylic acid (4)) It is preferred to use 10 m〇1% or more with respect to the total amount of all the carboxylic acids. Further, in the case of using other slow acid (7), in order to ensure better residual image characteristics, the use ratio is preferably 3 〇m〇i% or less, more preferably 1 5 or less, based on the total amount of total oxic acid. m ο 1 % or less. In the production of the polyorgano-oxygen (4) of the present invention, the total acid-suppressed acid is used in an example, and the epoxy of the precursor of the 1 mGl polyorganism (4) is preferably used in an amount of 0.11 to 1 mol. Good for 〇 w〗. The precursor of the organic siloxane (A), in the presence of a suitable catalyst, preferably in a suitable organic solvent, in the presence of a suitable carboxylic acid. • 32- 201144384 As a catalyst to be used therein, a known compound which promotes a ring-like curing accelerator can also be used. An aerobic compound and a test can be used, and the above-mentioned organic base can be exemplified as the above-mentioned organic base by the carboxylic acid. For example, an organic-grade, two, such as B, 呢, 、, 1, B, 哜, 唆, 唆, 唆Amines; ^ ethylamine, di-n-propylamine, tri-n-butylamine, pyridine, 4 decyl-based female quinone, aza-bicyclononene organic tertiary amine; methyl oxidized money organic quaternary Amines, etc. In these organic tests, it is preferably, for example, diethylamine, tri-n-propylamine, tri-n-butylamine, a specific bite, or a 4-dimethylamino group. As the organic tertiary amine of the pyridine, and the organic quaternary amine such as tetramethylammonium hydroxide, one or more selected from them can be used. The curing accelerator may, for example, be a tertiary amine such as benzyldimethylamine, 2,4,6-glycol(didecylaminofluorenyl)phenol, cyclohexyldidecylamine or diethanolamine; 2_methylimidazole, 2-n-butylimidazole, 2-n-dodecyl imidazole, 2-phenyl oxazole, 2-phenyl-4-methylimidazolyl-2-methylimidazole, 1- Mercapto-2-phenylimidazole, 1&gt;2-dimercaptoimidazole, 2 ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-ethylimidazole, 1 (2 cyanoethyl) Base)_2_n-dodecyl imidazole, cyanoethyl)_2_phenylimidazole, 丨-(2 cyanoethyl)-2-ethyl_4_mercaptoimidazole, 2 phenylmethyl$hydroxyl Mercaptoimidazole, 2-phenyl-7,5-bis(hydroxyindenyl)imidazole, 1-(2-cyanoethyl)-2_phenyl+5-bis[(2,-cyanoethoxy) Methyl] Weijun, 1(2-cyanoethanedi)2-n-undecylimidazolium trimellitate, cyanoethyl)_2_phenylmethane benzoate phthalate, ^(2 cyanide Base ethyl) 2 ethyl _ 4 fluorene-based sputum sulphuric acid trimellitic acid vinegar, 2,4 diamino _6_[2, decyl imidazole _ (1,)] -33- 201144384 ethyl _s- Triazole, 2,4-diamino _6_(2,_n-dodecyl Ethyl monozolium, 2,4·diamino-6-[2'-ethyl-4,-methylimidazolium-(r)]ethyl-s-diiso-imidazole Acid ester adduct, isocyanurate adduct of 2-phenylimidazole, 2,4·diamino _6_[2,_methylimidazolium_(ι,)]ethyl-s-diazole Imidazole compound of isocyanurate adduct; organic phosphorus compound such as diphenyl phenyl, diphenyl phosphine, triphenyl phosphite; such as benzyl dicarbyl gasification scale, tetra-n-butyl desert媾 媾, 曱 三 笨 笨 漠 、 、, ethyl triphenyl bromine scale, n-butyl triphenyl bromide, tetraphenyl desert scale, ethyl triphenyl cesium iodide, ethyl three Phenylacetate scale, tetra-n-butyl scale, ruthenium, osmium-diethyl dithiophosphate, tetra-n-butyl phenanthro-bisoxazolate, tetra-n-butyl squall tetrafluoroborate, tetra-n-butyl a quaternary phosphonium salt of a sulfonium salt of a tetraphenylphosphonate or a tetraphenylphosphonium tetraphenylborate; for example, 1,8-diazabicyclo[5.4.indole]undecane-7, an organic acid thereof a diazabicycloalkane of a salt; an organometallic compound such as a octanoic acid, a tin octoate, or an aluminum acetone aluminum complex; such as tetraethyl bromide a four-stage salt of tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium hydride; a boron compound such as boron trifluoride or tribasic borate; such as zinc sulfide or chlorine a metal halide of stannous; a high-melting point-dispersion latent curing accelerator such as an amide derivative such as dicyanodiamine or an amine and a cyclic oxime resin; and the above-mentioned imidazole compound and organophosphorus compound璇 capsule type latent curing accelerator whose surface is cured by polymer, such as quaternary salt and salt; amine salt type latent curing accelerator; -34- 201144384 Lewis, Bronsted A latent curing accelerator such as a pyrolysis type thermal cationic polymerization latent curing accelerator such as an acid salt. Among them, preferred are tetra-ammonium salts such as tetraethyl bromide, tetra-n-butyl bromide, tetraethylammonium hydride, and tetra-n-butylammonium chloride. The catalyst is preferably 100 parts by weight or less, more preferably 〇〇1 to 1〇〇, with respect to 100 parts by weight of the precursor of the polyorganosiloxane (A). Further preferably 〇·1 Use a ratio of ~2 〇 by weight. The organic/troreal agent used in the reaction of the precursor of the polyorganosiloxane (A) with a carboxylic acid can be, for example, a smoke compound, a hydrazine compound, a condensed compound, a ketone compound, a guanamine compound, an alcohol compound or the like. Among them, from the viewpoint of the solubility of the raw materials and products and the ease of purification of the products, it is preferred to test compounds, ester compounds, and ketone compounds. The solid content concentration of the solvent (the ratio of the total amount of the components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, and more preferably 5 to 50% by weight. The reaction temperature is preferably 〇~2〇〇. (:, more preferably 50 to 150 ° C. The reaction time is preferably from 0.1 to 50 hours, more preferably from 5 to 20 hours. The preferred polyorganosiloxane (A) in the present invention has a ring. The polyorganosiloxane of the oxy group is used as a raw material, and the structure represented by the above formula (A1) is introduced by ring-opening addition of an epoxy group. The production method is simple and convenient, and in particular, the above formula (A1) can be improved. It is a very good method from the viewpoint of the introduction rate of the structure shown. <Polyuric acid (B)&gt; The poly-proline (B) in the liquid crystal alignment agent of the present invention can be made by making tetracarboxylic acid The acid dianhydride is obtained by reacting a diamine including (b2) a diamine having a carboxyl group (hereinafter referred to as "diamine-35- 201144384 (b2)"). The above diamine preferably further comprises (b 1) a diamine. And having an alkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group linking two or more 6-membered ring structures, or a group having a steroid structure. Examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, and the like. Specific examples of the aliphatic tetracarboxylic dianhydride include, for example, butyric acid dianhydride; and examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid. Dihydride, 2,3,5-tricarboxycyclopentylcarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxo-3 Furyl)-naphthalene [1,2-(:]furan-1,3-dione, 1,3,33,4,5,91)-hexahydro-8-mercapto-5-(tetrahydro-)2 , 5-dioxa-3-furanyl)-naphthalene [l,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-di-oxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1 ,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxyindenyl-semi-alkyl-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3 ·3·0]octane-2:3,5:6-dianhydride, 4,9-di-side oxytricyclo[5_3.1.02,6]undec-3,5,8,10-tetraketone, etc. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and the like. The tetracarboxylic acid dianhydride described in Japanese Patent Application No. 2009-157556 can be used. As the tetrahydro acid dianhydride for synthesizing the polyamic acid (B), it is preferred to contain an alicyclic tetracarboxylic dianhydride, and more preferably a 2,3,5-tricarboxycyclopentene acetic acid. The dianhydride or the 1,2,3,4-cyclobutanetetracarboxylic dianhydride, particularly preferably contains 2,3,5-tricarboxycyclopentene acetic acid dianhydride. -36- 201144384 As the tetracarboxylic dianhydride for synthesizing polyamic acid (B), it is preferable to contain 2,3,5_3 of 1〇m〇1% or more with respect to all tetracarboxylic dianhydrides. Carboxycyclopentene acetate dianhydride or 1,2,3,4-cyclobutane tetracarboxylic dianhydride, more preferably 20 mol% or more, most preferably only 2,3,5 tricarboxycyclopentane It is composed of an enedic acid dianhydride or a 1,2,3,4-cyclobutane tetracarboxylic dianhydride. The above diamine (bi) is an alkyl group having 4 to 2 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group having two or more 6 membered ring structures, or a group having a steroid structure. Group of diamines. As the diamine (b1), the diamine containing a group linking two or more 6-membered ring structures or a group having a steroid structure may further have an alkyl group having a carbon number of * to (9) and having a carbon number of 4 to 20 in the alkoxy S group having a fluorinated alkyl group having 4 to 2 Å, 4 乍 is a group having a steroid structure, and examples thereof include choline-3-yl group and cholestane _5_ Alkene group, cholestane·24-alkenyl group, chalylene-5'24-diene+ group, lanostane-3-yl group and the like. The diamine (8) in the present invention may, for example, be fluorene-bis(4-((amino basic)methyl)phenyl)-4-pyrenecyclohexane, phenyl) phenyl) phenyl) -The combination of 戸3 ^ 幻^, 丨, 1-double (4·((amine-based oxy-oxygen, bis(4-(heptylcyclohexyl)cyclohexane, the following formula (8)))

-37- 201144384 In formula (b 1-1), ^ or 3 alkyl, 4 early bond, fluorenylene, carbon number is 2 -COO- or + -OCO ·, where 'x respectively + -0_, + The left side of the formula (3 small 1) indicates that the connection key to which it is applied is toward the alkyl group, and "~' R ' is an integer of 〇~2 of carbon number A2 or 3, respectively, and n2 is ": The bond is bonded to a diaminophenyl group, and nl is a hydrogen atom. When the number of carbon atoms is 2 or more in nl + n2, "is a fluorinated group, nl + : 2 is ~ 2, or a carbon number. It is a fluorinated alkyl group of 20. The alkyl group or the fluorene atom of 勹4 20 is 4 to 20, and the alkyl group and the decyl group in the above formula (bl) are preferably linear. In the present invention, the diamine (10) is preferably a compound represented by the above formula (μ(1), and specific examples thereof include, for example, n-dodecyloxy-2, diaminophenylbenzene, and tetradecyl. Alkoxy 2,4·diaminobenzene, n-pentadecanyloxy: 2,4-diaminobenzene, n-hexadecyloxy-24-diaminobenzene, n-octadecyloxy- 2'4-diamino stupid, n-dodecyloxy-2,5-diamino stupid, n-tetradecyloxy-2,5-diaminobenzene, n-pentadecane-2-, 5_Diaminobenzene, n-dec/, alkoxy-2,5-diaminobenzene, n-octadecyloxy-2,5-diaminobenzene, cholestyloxy-3,5- Diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholestyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diamino benzoic acid cholesteryl ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5_2 Alanine alkyl benzoate, 3,6-bis(4-aminophenyloxy) choline, -38- 201144384 3,6-bis(4-aminobenzoinoxy) A group represented by a cholestene, a formula (bl-1-1) to (bl-1-7), and the like. C5H”

Nh2

NH2 (b1-1-2)

C7H

Nh2 (b1-1-3)

(b1-1-4)

NH2 (b1-1-5) -39 201144384

(b1-1-6)

(b1-1-7) A liquid crystal containing a polyamine (B) synthesized using a diamine containing a diamine (bl) as described above, and a polyimine (B) obtained by dehydration of the polyglycine The alignment agent is particularly preferably used for the liquid VA type liquid crystal display element. The above diamine (b2) is a diamine having a carboxyl group. The diamine (b2) is preferably a compound represented by the following formula (b2-1). H2n-

/R'COOH^ 丨COOH)x\ •X1· Λ -NHc (b2-1) In the formula (b2_1), y is an integer of 0 to 2; and X is an integer of 0 to 4, respectively, where When a plurality of x are used, each X may be the same or different; each is a single bond, a methylene group, a group having 2 to 6 carbon atoms or a cyclohexylene group, and the above-mentioned stretching group of It can also be interrupted by a puzzle bond or an ester bond in the chain; -40- 201144384 X1 is a single bond, a methylene alkylene group, a carbon atom number a adenylene group, a carbon number of 2 to 4 groups, * -C00-, i〇c〇2~4, a fluorinated alkyl group, an oxygen atom, and a carbonyl group represent a linking chain ^H-, *-CONH-, *-NHCO' ("*

(X 〖-l) represents a group, RnCOOH is oriented to the left of (b2-l) or the following formula (X1-

I In the formula (X1-:!), Han 11 is an alkylene or cycloalkyl group of π, and its single bond, anthracene *, and the number of carbon atoms are 2 to 6 interrupted by an ether bond or an ester bond; The above alkylene group can also be in the chain

Rnl is a hydrogen atom, carbonogen-R]vCOOH (wherein, the number of Rlv曰^ subunits is 1 to 6 or the group 疋 early bond, the sub-alkyl group or the cyclohexylene group of the Yatian I mountain, r storm, carbon The number of atoms is 2~6, medium, upper '+* / l is interrupted by ether bond or ester bond), and the presently extended alkyl group can also be in the chain. In addition, the carboxyl group in formula (...) is used as the above formula (b2-l). The R1 and the number in the middle are integers of 1 to 4. An alkyl group having an atomic number of 2 to 5. ^ is preferably methylene or carbon as at least one of the above formula X is 1, the base is not a car and is preferably a compound of the above formula (b2-i), or in the above formula (b2-i) Inclusion = The above formula (χΙ-1) represents a compound of the group (ΧΜ) indicating a group. The king is 0, and the group X1 is the above formula. The compound formula (b2-b1) to (b2-l-5) represented by the above formula (b2-l) is preferably #, for example, the following table 7 compound of. 201144384

H2N

(b2-1-2)

H2N

Nh2 (b2-1-2')

H2N

(CH2)zCOOH -C

Nh2 (b2-1-3)

H2N

(CH2)2COOH (CH2)zC〇OH

Rni

H2N

Nh2 (b2-1-4)

Nh2 (b2-1-5) In the above formula, X1 is the same as X1 in the above formula (b2-l); R111 is an alkyl group having 1 to 6 carbon atoms; and X is an integer of 1 to 4, respectively. ; z is an integer from 1 to 5, and d is an integer from 1 to 4. x and d in the above formulae (b2-l-1), (b2-l-2), and (b2-l-5) are each preferably 1. The compound represented by the above formula (b2-l) is preferably a compound represented by (b2-ll), (b2-l-2) or (b2-l-5), as its preferred specific -42-201144384 For example, 3,5-diaminobenzoic acid, a compound represented by each of the following formulas (b2-1-2-1) and (b2-1-5-1) can be cited.

COOH

COOH /Λ.

NH 2 (b2-1-5-1 ) as the diamine in the present invention may be a substance consisting only of the above-mentioned diamine (1) and diamine (2), or may be a diamine (1) and In addition to the diamine (2), a diamine other than the above (hereinafter referred to as diamine (3)) is also contained. As the diamine (3) which can be used, for example, an aliphatic diamine other than the diamine (1) and the diamine (2), an alicyclic diamine, an aromatic diamine, a diamine organic decane oxide can be used. Wait. Specific examples thereof include, as the aliphatic diamine, isophthalamide, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, and 1,6-hexanediamine. And as the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-arylene bis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane An alkane or the like; examples of the aromatic diamine include p-phenylenediamine, 4,4′-diaminodiphenylnonane, 4,4′-diaminodiphenyl sulfide, and 1,5-diamine. Naphthalene, 2,2'-dimercapto-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoro-43- 201144384 methyl)biphenyl , 2,7-diaminopurine, 4,4,-diaminodiphenyl ether, 2,2· and [4 (4aminophenoxy)phenyl]propane, 9,9-bis (4 _Aminophenyl)anthracene, '2^^[4 (4-aminophenoxy)phenyl]hexafluoropropane, (4-aminophenyl-)fluoropropane 4,4-(p-phenylene diiso) Propyl) bis(aniline) '4,4,-(m-phenylenediisopropyl)bis(aniline), 1,4-bis(4-aminophenoxy)benzene, 4,4,_bis ( 4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4•diaminopyridine, 2,4- Diaminopyrimidine, 3,6.diaminopyridinium, 3,6-diaminocarbazole, alumina, 6-aminocarbazole, anthracene-ethyl-3,6-diaminocarbazole, anthracene -Phenyl-3'6-diamine σ卡卡, Ν, Ν, _ bis (4_Amino phenyl), bismuth, bis (4-aminophenyl) Ν, Ν, 曱Benzyl aniline, μ-bis-(4-aminobenzophenone) piperazine 4-(4-difluoromethoxybenzhydrazide)cyclohexyl_3,5-diaminophenylhydrazine, 4-( 4'-difluoromethylbenzhydryl)cyclohexyl_3,5-diaminophenyl phthalate; etc.; as the diamine organooxane, for example, 1,3-bis(3-aminopropyl) In addition to the diamines described in Japanese Patent Application No. 2,091,556, the diamines (1) and the diamines (2) may be used in addition to the diamines and the diamines (2). The diamine used for the synthesis of poly-proline (yttrium) is preferably contained in an amount of 10% or more, such as the above-mentioned diamine (1), more preferably 3 to 70 m〇1%, based on the entire diamine. Preferably, it contains 35 to 6 〇m 〇 1%; preferably 丨〇% or more with respect to all diamines, and more preferably contains 3 〇 to 7 〇m 〇 1%, as described above. The step preferably contains 40 to 65 mol%. The diamine used for the synthesis of the polyamic acid (B) may contain, in the range of 80 mol% or less, the diamine (3) as described above, preferably 5 Contains ~40m〇l% of the range. -44- 201144384 The diamine used to synthesize poly-branched acid (B), the funeral right contains the amine (1) in the above range, so that the obtained liquid crystal alignment can be obtained. ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, In the case of the meat, there is a diamine (2) in the above target, so that the liquid crystal is matched with your gem. ★ The good printability of the agent and the electrical properties of the formed liquid crystal alignment film (especially electricity) It is preferable that the balance is excellent. The fluorinated acid (B) of the fluorination retention ratio can be synthesized by reacting an amine as described above. The ratio of the use of the monoanhydride to the two synthetic reactions for the poly (proline) (B) is preferably: with respect to 1 equivalent of the diamine:: anhydride, the acid needle of the liver of the diamine is 〇.2~ 2 equivalents, more preferably 〇3: The synthesis reaction of dimercaptoic acid dimercaptoic acid is preferred in the presence of solvent? proportion. -20 〇C~150 °C, contending from * 戍, stimulant, preferably at i 'more preferably 〇 ~ 1 〇 (rc, ^ hours, more preferably 0.5 to 12 hours. For the organic solvent, a solvent, a phenol, a hair, a hair, a cockroach, a cockroach, a cockroach, a cockroach, a cockroach, a cockroach, a cockroach Specific examples of the hydrocarbon, hydrocarbon-organic & gluten-based granules, as a solvent, can be listed as a non-protonic enthalpy, for example, N-mercapto-2-pyridinamide, N N--Tan Ganyu Ming, N,N-dimercaptolactone, tetraterpene iN, iN-methylformamide, diterpene, urea, hexamethylphosphonium triamine, etc.; Halogenated phenol or the like; j-terresin and dimethyl as the above-mentioned alcohol' may, for example, be decyl alcohol, cyclohexanol, ethylidene, isopropanol, ^G-indole, propylene glycol, 1,4·d2 Alcohol, - ^-ol mono-mystery, etc.; 1-ethoxyethanol, B-45- 201144384 as butyl ketone as ethyl ethyl ethane as ethylene glycol butyl ether, methyl ether, ether, tetrahydro oxime Burning toluene, ether, etc. The above ketones can be listed, for example, acetone, cyclohexanone, etc.; ketones, methyl groups are the above esters, and may be listed, for example, ethyl lactate, esters, ethyl acetate, " Extremely butyl butyl ester, acid, alcohol isopropyl bond, 7 ethylene glycol acetate g, _ 7 ethylene glycol monomethyl bond, -7 - ethylene glycol glycol monoethyl M r ^ dry G 鞑 acetic acid G butyl acrylate, decyl methoxy oxyl propoxylate, oxalic acid _ lactop propionate, ethyl acrylate, malonic acid - for the above ether, can look at Y, one ethyl sulfonium, etc.; 1J, for example, diethyl ether, diethyl ether, ethylene glycol n-propyl ether, ethyl phthalate oxime ether ethylene glycol dimethyl _, 7 ethylene glycol ethylene diethylene glycol diethyl hydrazine, _ ethylene diethylene glycol single scream Acetate, di-anthing, etc.; for the above-mentioned i-hydrocarbon, 矸, J is exemplified by, for example, dioxane, 1,4-dichlorobutane, = &gt; milk pit, 1, fluoroethane, gas stupid, Adjacent to the above hydrocarbons, it can be listed as one of the following xylenes, propionic acid octane octane, hydrazine, isoamyl isobutyrate, diisomeric in these organic solvents, solvent and benzoquinone and its derivatives. Λ 4 use selected from In the aprotic pole or using the above-mentioned first-right organic/mixing agent, more than one kind, drunk, _, ..., dentate and hydrocarbon (second ancient: above and selected from the above conjugates). In the latter case, the ratio of one example of the solvent to the first organic solvent and the second organic solvent is 50% by weight or less, more preferably 40% by weight. Preferably, the weight of the organic solvent is (a) preferably four total straight (b) relative to the total amount of the reaction solution (a + b醆). The -46-' of the dianhydride and the diamine is 50% by weight. 201144384 A reaction solution in which polylysine (B) is dissolved can be obtained as above. The reaction solution can be directly used for preparation of a liquid crystal alignment agent, and is used for preparing a liquid crystal alignment agent after separating the polyamic acid (B) contained in the reaction solution, or after separating the separated polyamic acid (B). For the preparation of liquid crystal alignment agents. In the case where the poly (proline) acid (B) is dehydrated and closed to form a polyimine (B), the above reaction solution can be directly supplied to the dehydration ring closure reaction, and the polylysine contained in the reaction solution can be contained. (B) Separation; ^, supplied to the dehydration ring closure reaction, or may be supplied to the dehydration ring closure reaction after refining the separated poly-@-acid (B). The separation and purification of poly-proline (β) can be carried out according to a known method. &lt;Polyimine (B)&gt; The polyimine (B) of the present invention can be obtained by subjecting the polyamic acid (B) synthesized as described above to dehydration ring closure and imidization of ruthenium. The polyimine (B) in the present invention may be a fully acid imide which dehydrates and closes all of the indoleamine structure of the polyglycolic acid (B) as a precursor thereof, or may be only a proline A part of the structure is dehydrated and closed, and the proline structure and the quinone imine structure coexist. The polyimine (B) in the present invention preferably has a quinone imidization ratio of preferably 10 to 90%, more preferably 20 to 80%. The ruthenium imidization ratio is expressed as a percentage of the number of ruthenium ring structures relative to the sum of the number of ruthenium ring structures of the polyimine and the number of quinone ring structures. Wherein, a part of the quinone ring may be an isoindole ring. The dehydration ring closure of poly-aracine (B) is preferably a method of heating poly-proline (B) or dissolving poly-proline (b) in an organic solvent, adding a dehydrating agent and a dehydration ring in the solution. The catalyst is carried out according to a method of heating as needed. Among them, the latter method is preferred. -47- 201144384 In the method of adding a dehydrating agent and a dehydrated closed-loop catalyst to the solution of the polyamic acid (B), an acid anhydride such as acetic acid, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 〇.〇1 to 2〇m〇1 with respect to the proline structure of 1 mol of polylysine. As the dehydration ring-closing structure, for example, pyridine or tridecylpyridyl can be used. A tertiary amine such as dimethylpyridine or triethylamine. The amount of the dehydration ring-closure catalyst to be used is preferably 〇.01 to 1〇m〇1 with respect to 1 mol of the dehydrating agent to be used. The organic solvent to be used in the dehydration ring-closure reaction is exemplified as the organic solvent exemplified as the solvent used for the synthesis of the polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 〇18 〇t:, more preferably 1 Torr to 150 °C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours. Thus, a reaction solution containing the brewinide (B) was obtained. The reaction solution can be directly used for the preparation of the liquid crystal alignment agent, or the liquid crystal alignment agent can be prepared on the basis of removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and can also be used for liquid crystal alignment after separating the polyimine (B). The preparation of the agent, or the purification of the isolated polyimine (B), is used for the preparation of a liquid crystal alignment agent. These purification operations can be carried out according to a known method. &lt;Other components&gt; The liquid crystal alignment agent of the present invention contains at least the above-mentioned polyorganosiloxane (A) and at least one selected from the group consisting of polyamic acid (B) and polyimine (b). A polymer may contain any other components as long as it does not impair the effects of the present invention. Examples of the other component that can be used therein include a polymer other than the above polyorganophosphonium (A), polylysine (B), and polyimine (B) (hereinafter referred to as "other polymer"). ), -48- 201144384 Mouth-state curing catalyst, curing accelerator. v A compound with a hydroxyl group The above other polymers can be used to further improve the solution characteristics of the presenting agent and the electrical properties of the obtained day-to-day alignment film. As a polymer, you can use it on the 丨 · ' ' ' 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 =external acid (hereinafter referred to as "polyimine other than other polyimine (B)) I醯S乂: ^ A will be combined with other polyimine I), polyphthalate, poly Vinegar, polyfluorene, ... female cellulose derivative, polyacetal, 2', poly(styrene-phenylmaleimide) derivative, terracotta acrylate, etc. For other organic decane, other poly-araminic acid, potted # ” he polyimine, one or more selected from the pot may be used. The above other polyorganosiloxane may be obtained by hydrolysis-condensation of at least one selected from the group consisting of decane-forming: (1) and (2). A polyorgano oxo-fired (4) precursor can also be used as the other polyorganisms described therein. For the other polyorganic oxy-oxygenation in the present invention, the average molecular weight of the heavy enthalpy of the ethylene-modified sulphide is preferably 500~1 by gel permeation chromatography. 0,000' is preferably 500 to 1 0,000. The synthesis reaction and separation and purification of other polyorganosiloxanes can be carried out according to the example of polyorgano oxo (4), which will be apparent to those skilled in the art. -49 · 201144384 Other polyamic acid can be obtained by reacting a tetracarboxylic dianhydride with at least one diamine selected from the above diamines (b1) and (b3), or a tetracarboxylic acid and an anhydride The above diamines (b 2) and (b 3) are reacted with at least one of the diamines to obtain the other polyi-imines, which can be obtained by hydrazine imidation by dehydration of the other polyamic acid as described above. The polyamidimide has a ruthenium imidation ratio of preferably 30 ° / ◦ or more and more preferably 40 to 80 〇 / 〇. The synthesis, separation and purification of other polyaminic acids and other polyimines can be carried out according to the examples of polyamic acid (B) or polyimine (B). [Curing Agent and Curing Agent Catalyst and Curing Accelerator] In order to more firmly carry out the crosslinking reaction of the polyorganosiloxane (A), the above-mentioned curing agent and curing catalyst may be contained in the liquid crystal alignment agent of the present invention. In order to accelerate the curing reaction of the curing agent, the above-mentioned curing accelerator may be contained in the liquid crystal alignment agent of the present invention. As the curing agent, a curing agent which is usually used as a curable compound having an epoxy group or a curable composition containing a compound having an epoxy group can be used, and examples thereof include a polyamine, a polycarboxylic acid needle, and a polyvalent compound. Carboxylic acid, etc. The polyvalent carboxylic acid anhydride may, for example, be a phthalic anhydride of cyclohexanetricarboxylic acid or another polyvalent carboxylic acid anhydride. Examples of the acid anhydride of the above cyclohexanetricarboxylic acid include cyclohexane, 3,5·di-hyaloacid-3,5-anhydride, and cyclohexane-1,2,3-tricarboxylic acid _2 3-anhydride. Examples of the other polybasic acid anhydrides include, for example, 4-methyltetrahydrophthalic acid, succinic acid, methylnormene anhydride, dodecene succinic anhydride, succinic anhydride maleic anhydride, phthalic anhydride, trimellitic anhydride, and lower Compound represented by the formula, and -50- 201144384

CrriH2m+*l wherein in the above formula, m is an integer of 1 to 2 〇. In addition to the tetracarboxylic dianhydride which is usually used for the synthesis of polylysine, an alicyclic ring having a common double bond such as α-terpinene or AU〇〇cimene may be mentioned. Diels-Alder reaction product of maleic anhydride and maleic anhydride, hydrogenated product thereof and the like. As the curing catalyst, for example, a hexafluoride compound, a male hexafluoride compound, triacetic acid acetic acid or the like can be used. These catalysts can catalyze the cationic polymerization of an epoxy group by heating. The curing accelerator may, for example, be a pyridinium compound; a quaternary scaly compound; a quaternary compound; a diazabicyclo ring such as 1,8-diazabicyclo[5.4.0] decaene 7 and an organic acid salt thereof. Olefin; such as zinc octoate, octane tin [organic metal compound of acid aluminoacetate complex; such as trifluoride shed, rotten acid three stupid duck shed compound; such as gasification, gasification of stannous metal complex High-melting-point-dispersion type, such as the addition of a di-cyanodiamine ammonium amine to an epoxy resin, and a high-melting-point-dispersion type of latent curing, which promotes the coating of the surface of the tetra-, and &amp; salt-coated microcapsules A latent curing accelerator, an amine salt type latent curing accelerator; a latent curing accelerator such as a Lewis acid salt, a pyrolysis-based thermal cationic polymerization type latent curing accelerator, and the like. [Epoxy compound] -51- 201144384 The above epoxy compound is a compound having at least one epoxy group in the molecule, but does not include the above-mentioned polyorganooxane (A) or other polyorganooxane. . The liquid crystal alignment agent of the present invention may contain the epoxidation as the epoxy compound from the viewpoint of further improving the adhesion of the formed liquid crystal alignment film to the surface of the substrate. Examples thereof include ethylene glycol diglycidyl ether and polyethylene glycol. Glycidyl ether, propylene glycol diglycidyl ether, tripropanol diglycidyl mystery, polypropanol diglycidyl hydrazine, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol Glycidyl bond, 2,2-dibromopentaerythritol diglycidyl 1,1,3,5,6-tetraglycidyl-2,4-hexanol, N,N,N',N ,-tetraglycidyl-m-dimethyldiamine, 1,3-bis(&gt;ί,Ν-diglycidylaminomethyl)cyclohexane, M,N,N,,N'·four Glycidyl-4,4'-diaminodiphenylnonane, n,n-diglycidyl-benzylamine, N,N-diglycidyl-aminomercaptocyclohexene, etc. are preferred Substance. In the case where the liquid crystal alignment agent of the present invention contains a bad oxygen compound, in order to carry out the crosslinking reaction efficiently, a base catalyst such as 丨-benzyl-2-methyl-flavor may be used in combination. [Functional decane compound] In order to improve the adhesion of the obtained liquid crystal alignment film to the substrate, it is possible to

Oxydecane, decane, NU t as a functional decane compound, oxydecane, 3-aminopropyltriethoxy decane, 2-aminopropyltriethyl (2-aminoethyl) 3-Aminopropyltrimethoxydecane, -52- 201144384 N-(2-Aminoethyl)-3-aminopropylmethyldimethoxyoxycarbazone, 3,ureidodimethoxy矽, 3-醯 urea propyl triethoxy decane, ... Ethyl-based 3-aminopropyltrimethoxy decane, N-ethyl decyl _3 amine octyl ethoxy decane , N-diethoxydecyl propyl triethylene tri-n-N-decyloxy decyl propyl diethylene triamine, 1 〇 trimethoxy carbitol L 4 '7 - diazadecane, 10 _ Triethoxy decyl-1,4 7 oxazepine, 9-trimethoxymethyl sulfonyl-3,6-diazaindoleyl-acid S0 9-diethoxy decane Base_3,6-diazaindolyl acetate, benzyl-3-aminol-based trimethoxy-xanthine, N-pyro-3-aminopropyltriethoxy oxane, N- Phenyl-3-aminopropyltrioxoxime. Face Benjamin J. Two soil triethoxydecane, Ν-bis(oxyvinyl)-3-aminopropyl = A Oxydecane, N-bis(oxyvinyl bromide 3-aminopropyltriethoxylate)3, glycidylpropyltrimethoxyoxane, 2-(3,4-epoxyoxyl) And a reaction product of a tetracarboxylic anhydride and a decane compound having an amine group, etc., as described in the patent document 1 (Japanese Unexamined Patent Publication No. SHO 63-291 922). [Surfactant] Examples of the above surfactant include a nonionic interface biocide, an anionic surfactant, a cationic surfactant, a bisexual boundary, a tongue growth agent, a polyoxyalkylene surfactant, and a polycondensation agent. An alkylene oxide surfactant, a fluorine-containing surfactant, etc. [Photosensitizer] Examples of the photosensitizer include, for example, tetramethylbenzene, benzonitrile, hydrazine, acetophenone, acetophenone, N-xanthone, 4-methoxyacetophenone, 3-methoxyphenylacetophenone, anthrone, benzaldehyde, 4,4,-dimethoxybenzophenone, -53- 201144384 benzophenone, anthracene, hydrazine Three stupid, Lianben, 9-oxosulfur sigma sigma, lean, bis(diethylamino) dioxin ^ palpitations, 4,4 _ benzophenone, 2-block Tsai, Γ, Phenyl bromide (tetra), 4_phenylindole-naphthalene nitrile, ... stupid: e), 2 · naphthalene nitrile, ^ 峨 naphthalene, shovel smashing: this, the base, burning f, $ pyridine, 蒽, and Tetraphenyl, 2-methyl 4, Benzene, 2 Benzene oxime, 吖 氧 i i-naphthalene, I4-dicyano extract, 9 惫 笛, 9,1 〇-dicyanoguanidine, 2, 6 9 1〇 "Achieve 9 - chaotic basis" y, 1 0 - tetracyanoquinone, etc. &lt;Proportion of use of each component&gt;

The ratio of use of each component in the liquid crystal alignment check Φ long + human k I ^ ^ M of the present invention is as follows. In the case where the liquid crystal human 1π π A - to J 3 of the present invention has at least _ ^ ^ species selected from other polyglycines and other polyamidiamines, these other poly groups. The ratio of use of the substance is better than that of 氐^ and (ie, e P for the total 2 of poly-proline and polyimine, ie, 'poly-polyglycine (8) and poly-polyglycine and other arm Μ π^ The weight used is / m ^ "total. The same as the following", which is 90 mil / 〇 or less, more preferably 7 〇 wt% or less. The liquid crystal alignment of the present invention is close to the ancient polyamine 舻mu job β organic 矽复 ( quot A A 以及 以及 以及 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( m m m m m m m m m m m m The ratio of polyorganooxane (Α) to if, ^ ^ ^ 乂酝 amidoxime and polyimine

τ, the car father is 0.1 to 1 〇〇 〇〇 佟, trial child * 1J step more Duda c 垔 伤 injury, more preferably 1 to 5 parts by weight, into - preferably 5 to 15 parts by weight. The funeral is owned by the owner #—only the surname is wrong and the ratio of the use of the 5H range is good, and the good liquid crystal alignment agent can be used as a good tk. This is a good coating and printing property. It is preferable to see an appropriate pretilt angle embodiment.贯;: Brothers 纟 ^ month liquid helium alignment agent contains other polyorganooxanes 'the use ratio relative to her bucket〗 π Λ 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚The brewing imine is preferably 1 〇〇 heavy Λ under Λ 4 ,, and &; 堇 伤 以下, more preferably 50 parts by weight or still more preferably 20 parts by weight or less. -54- 201144384 In the case where the liquid crystal alignment agent of the present invention contains a curing agent, it is used in a proportion of not more than 100 parts by weight of polyorganooxime (A), preferably i 重量 part by weight or less. In the case where the liquid crystal alignment agent of the present invention contains a curing catalyst, the use ratio thereof is preferably 2 parts by weight or less based on 100 parts by weight of the polyorganosiloxane (A). In the case where the liquid crystal alignment agent of the present invention contains a curing accelerator, the use ratio thereof is preferably 10 parts by weight or less based on 100 parts by weight of the polyorganosiloxane. In the case where the liquid crystal alignment agent of the present invention contains an epoxy compound, the use ratio thereof is preferably 40 parts by weight or less, more preferably 〇1, based on the total amount by weight of the polyglycolic acid and the polyamidimide. ~3〇 parts by weight. Further, in the case where the base catalyst is used together with the epoxide, the estimated ratio is less than 1 〇〇 by weight, and preferably less than 1 〇 by weight. Share. In the liquid crystal state of the present invention, the ratio of use thereof, and polyimine, are preferably as follows. The compounding agent containing a functional decane compound is preferably used in an amount of 50 parts by weight or less, more preferably 20 parts by weight, based on 100 parts by weight of the polyamidamine, and is preferably used in the case of a surfactant, preferably in the case of a surfactant. The liquid crystal of the present invention having all of the liquid crystals of the present invention is one part by weight or less. In the case where the ratio is relative to the 丨00 light sensitizer, the summer 彳 is divided into the right 4 parts by weight or less, more preferably the organic siloxane (A), preferably 勹1 〇 or less by weight. -55- 201144384 &lt;Liquid Crystal Aligning Agent&gt; The liquid crystal alignment agent of the present invention contains the polymer as described above and any other components, and is preferably prepared in the form of a solution composition which is dissolved in a suitable organic solvent. As an organic solvent which can be used for preparing the liquid crystal alignment agent of the present invention, it is preferably selected from the group consisting of polyorgano-oxygen (A), poly-proline (B) and polyimine (B). At least one kind of polymer and any other component that is used, does not react with it. The organic solvent which can be preferably used in the liquid crystal alignment agent of the present invention is exemplified as used in the synthesis of polyorganohydrogenane (A), polyamic acid (B) and polyaniline (b). The organic solvent to be exemplified above may be one or more selected from the group consisting of the organic solvents exemplified above. In the preparation of the liquid crystal alignment agent of the present invention, it is preferred that the solvent is contained in one of the above organic solvents, or two or more of the above organic solvents are combined, in the preferred solid bottle concentration concentration described below. The components of the liquid crystal alignment agent 3 are not precipitated, and the surface tension of the liquid is slightly in the range of 25 to 45 mN/m. The solid component of the liquid crystal alignment agent of the invention 澧 々 丨 取 knife, morning, that is, liquid crystal alignment agent

The ratio of the weight of all the components other than the medium to the granules to the total weight of the liquid B 6 /Night 曰 alignment agent can be selected in consideration of viscosity, volatility, etc., and is preferably in the range of 1% by weight. The liquid crystal alignment agent of the present invention forms a coating film as a liquid crystal alignment film by coating on a substrate, and when the solid content concentration is less than 1 篁/〇, the film of the coating film may be 犋^The child is too small to obtain a good liquid daily alignment film. On the other hand, in the case where the concentration of the solid ^ ^ 瓸 attack is more than 10% by weight, the film thickness of the coating film is too large, and it is difficult to obtain a good alignment film of the liquid crystal-56-201144384, and in addition, the dot property of the liquid crystal alignment agent is 0. ^ &amp; large, sometimes insufficient coating properties. : The range of good solid content concentrations varies depending on the method used on the substrate (4) when the liquid crystal is aligned. In the case of the case, the extra good $5~4,5 in the 耧 by: more in the 〇/〇 of her circumference. In the case of the printing method, it is particularly preferable that the solid concentration is in the range of 3 to 9 wt%, and the solution viscosity is in the range of 12 to 50 mPa. In the case of the Hemo method, it is particularly preferable that the solid content concentration is 5 weight. /. Within the range of 'the solution viscosity is in 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 1 ° C to 6 ° C. &lt;Method of Forming Liquid Crystal Alignment Film&gt; The liquid crystal alignment agent of the present invention is preferably used for forming a liquid crystal alignment film by a photo-alignment method. The method of forming the liquid crystal alignment film by the liquid crystal may be, for example, a method of forming a coating film on the liquid crystal alignment film of the present invention, and then applying a liquid crystal force to the coating film: soil polarized or non-polarized radiation '(8). . The second film i is applied to the transparent alignment of the substrate on which the pattern-shaped transparent conductive film is provided, and the liquid crystal alignment of the present invention is applied by a coating method such as a roll coating method, a spin coating method, a printing method, an inkjet method, or the like. Agent, then apply the coating

Pre-bake 1 ° heat (pre-bake), then simmer (post-baking) to form a coating film. The condition of the bait bar is 0.1 to 5 minutes at, for example, 40 to 12 ° C, and the latter is preferably 12 to 3 ° C, more preferably 150 to 25 (TC P, pregnant father) Jiayan, after ht b is carried out for 5 to 200 minutes, more preferably for 10 to 100 minutes, and the film thickness after I baking &amp; u is preferably 〇〇〇1~, more preferably 〇〇5 〜 0.5_. -57- 201144384 As the upper ifi I &gt; soil plate can use glass such as float glass or soda glass; for example, the aggregate m ^ κ pair of ethylene diacetate, polybutylene terephthalate A transparent substrate made of a plastic such as an ester, an ether, a polycarbonate or a cyclic olefin resin. The transparent conductive film may be, for example, a film of Sn02, or an IT0 made of In2〇3_Sn〇2. Membrane and the like. A well-known method can be used in order to pattern the $-transparent conductive film. When the liquid crystal alignment agent is applied, in order to make the adhesion between the substrate or the transparent conductive film and the coating film, 2, or -r, 丄4+, it is preferable to pre-print the substrate or the transparent conductive film.丨生石夕烧化合物, titanium vinegar compound, etc. Then, the liquid crystal alignment ability is imparted by irradiating linearly or partially polarized radiation or non-polarized radiation to the coating film. Here, as the radiation, for example, ultraviolet rays and visible rays containing light having a wavelength of 15 〇 nm to 8 〇〇 nm can be used, and it is preferable to include the external line of the "please". In the case where the radiation to be used is linearly polarized or partially polarized, the irradiation may be performed in a direction perpendicular to the substrate surface, and may be performed from the oblique direction in order to impart the pretilt angle, or may be combined. In the case of irradiating non-polarizing radiation, the direction of irradiation must be a direction of inclination. The irradiation amount of the radiation is preferably 1 J/m2 or more, and less than 1 &quot;〇〇 J/m2' is more preferably 10 to 3, _ J/m 2 . In addition, in the conventional coating film formed of a liquid crystal alignment agent, when the optical alignment capability is given by the light alignment (four), the sag_丨〇〇〇〇T/m 2 , , , The amount of radiation exposure. However, according to the liquid crystal alignment agent of the present invention, even when the amount of radiation irradiation in the photo-alignment method is 3, _J/m2 or less, and further 1, _j/m2 or less, -58-201144384 can impart good liquid crystal alignment ability. , can reduce the manufacturing cost of liquid crystal. &lt;Manufacturing Method of Liquid Crystal Display Element&gt; The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the agent of the present invention. It is preferable that the liquid crystal alignment agent crystal alignment film of the present invention can exert its advantageous effects to the utmost extent in the liquid crystal display for the vertical alignment type. The liquid crystal display element of the present invention can be produced, for example, by preparing two substrates in which a liquid crystal alignment film is formed as described above, and liquid crystal is provided between the plates to produce a liquid crystal cell. For the production of the liquid, for example, the following two methods are listed. In order to produce a liquid crystal cell using the liquid crystal, an exemplary method can be cited. In the first method, the two substrates are placed by the gap (cell gap), the liquid crystal alignment films are opposed to each other, and the two peripheral portions are partially bonded by using a sealant, and the liquid crystal is filled into the liquid crystal by the substrate surface and the sealant. After that, the method of sealing the injection hole is thereby united. The second method is a method called 0 DF (drop, Ο ne D r ο p. In a predetermined portion of the two substrates in which the liquid crystal alignment film is formed, for example, by applying ultraviolet curable Then, the liquid crystal is dropped onto the liquid crystal alignment film, and then adhered to the other base crystal alignment film, and then the entire surface of the substrate is irradiated with a violet sealant to be cured, thereby producing a liquid crystal cell. When the liquid element formed by the liquid crystal alignment of the display element is displayed, The two base cells can be made as follows: the cell gap of the two substrates facing the substrate can be made into a liquid filling method, the plate is sealed on the substrate, and the liquid is made external, so that -59- 201144384 no matter which method 'Next, It is preferred to heat the liquid crystal cell to a temperature at which the liquid crystal is formed into a phase, and then slowly cool to room temperature to remove the flow alignment at the time of liquid crystal filling. Further, the liquid crystal display element of the present invention is obtained by laminating a sheet of light on the outer surface of the liquid crystal cell. In the case of the vertical alignment of the liquid crystal alignment film, the constituent unit is configured to form a liquid crystal alignment film: the alignment between the two substrates is easy to be parallel to the direction of the axis, and the alignment is made on the opposite side to make the polarization direction and alignment easier. Shaft &amp; 45. The angle is formed from a liquid crystal display element having a vertical liquid crystal alignment type liquid crystal cell. As the above-mentioned sealant, it is preferable to use j, for example, an epoxy resin containing a spacer, an alumina ball, and a curing agent. In the case where the liquid crystal germanium is the above liquid crystal, it is preferable to use a nematic liquid crystal or a smectic isoform = unit, and it is preferable to have a dielectric alternating liquid system. (4) For example, a 4-based benzene liquid crystal, a crystal, or a A phenanthrene-based liquid crystal, an oxidized azo-based liquid crystal, a biphenyl-based liquid, or a non-hexene-ene liquid crystal. "Ή膜" „The polarizing plate used outside the unit cell is exemplified by the diffraction and absorption of polyethylene glycol; and:: holding the polarizing plate by the protective film, etc. η 卫 and iodine’ or Η The display characteristics of the liquid crystal display element which can be used for the period of the 驭 itself, and the long-term embodiment of the present invention: Please refer to the embodiment for a more pure description of the present date, but it is not limited thereto. - -60- 201144384 The weight average molecular weight Mw in the examples is a polystyrene-converted value measured by gel permeation chromatography (GPC) under the following conditions: Column: manufactured by Tosoh, TSKgelGRCXLII Solvent: tetrahydrofuran Temperature: 40 ° C Pressure: The epoxy equivalent of 68 kgf/cm 2 was measured in accordance with "hydrochloric acid-methyl ethyl ketone method" of JIS C2 195. The solution viscosity of the polymer is a polymer solution (solvent: N_methyl 2 pyrrolidone) which is 20% by weight of the polymer concentration indicated in each synthesis example' using an E-type viscometer at 25 ° C The value measured below. The ruthenium imidization ratio of the polyimine is obtained by adding a polyimine solution obtained in each synthesis example to pure water, and drying the obtained precipitate under a sufficient pressure at room temperature, and then dissolving in a heavy hydrogenated dimethyl hard. The H_NMR spectrum measured at room temperature by tetramethyl ♦ burning as a reference material was calculated by the following mathematical formula (1). Ruthenium amination rate (%) = (1 -Α'/Α2χα)χ 1 00

In the mathematical formula (1), the near-occurring mass area of the sulfhydryl group, Α indicates the peak area from the aureus at a chemical shift of 10 ppm, and A2 is the relative proton from the other protons relative to the —/, — polymer precursor ( The ratio of the number of other protons of the ruthenium matrix in poly-proline. In addition, the following is repeated according to the following synthesis scale, and the synthesis of the raw material compound and the human compound Α, 5 is repeated as needed to ensure the necessary amount for use in the following synthesis. -61· 201144384 Synthesis of Polyorganosiloxane (Polyorganic Oxygen (A)&lt;&gt; Moon 1J Drive with Epoxy Group)&gt; Synthesis Example E-1 has a reaction vessel internal oxydecane, Mix down. Then, the water is washed, and then the liquid is washed, and the solvent and the oxy group are directly removed. The addition of the polymixer, the 1 degree meter, the dropping funnel and the reflux condensation camp (10).0g# 2·(3, 4-epoxycyclohexyl)ethyltrimethyl WOg methyl isobutyl ketone and 1G Gg triethylamine were added to the mixture under reflux for 30 minutes by dropping into the funnel over 30 minutes. And reacted at 8 (TC for 6 hours.), the organic layer was taken out, dissolved in water by 0.2% by weight of ammonium nitrate until the washed water was neutral, and then the remaining water was distilled under reduced pressure to obtain a thick layer. In the form of a transparent liquid with cyclopentane (EPS-1). The organic oxirane (EPS-1) was subjected to 1H-NMR analysis, and the theoretical strength was obtained based on the chemical shift (δ) = 3.2 ppm. The peak of the epoxy group was confirmed to not cause a side reaction of the epoxy group in the reaction. The polyorganosiloxane (EPS-1) had a weight average molecular weight Mw of 2,200 &gt; an epoxy equivalent of 186 g/mol. Synthesis of Carboxylic Acid (A1) In the following synthesis examples, the following formula (A_1) to (A-8) -62- 201144384 were synthesized.

n-C5H

OCO-CH=CH

Λ—CH=CH—COOH (A-3)

CF3(CH2)3—O

y~CH=CH—COOH (A-4)

(A-6) n-C7Hi5

^—CH=CH—COOH (A-7)

n-C5H

y—CH=CH—COOH (A-8) -63- 201144384 The above formula (A-1) to (A-8) (A-8) and the like. Don't show the compounds separately. Hereinafter, the compound to be represented is referred to as "Compound Synthesis Example A-1. In a catechu-type sputum of 2 〇〇社 having a reflux tube, l2 g of n-decyl sylvestre if, 8 oxime of 4. amino cinnamic acid and (10) The acetic acid is reacted under reflux for 2 hours. After the reaction is completed, the acetic acid is extracted from the reaction mixture. The obtained organic layer is washed with water, dried over magnesium sulfate, and then subjected to column chromatography (filler: sulphur dioxide Glue, developing solvent: gas/methanol = 8/2 (volume ratio)) Refined 'recrystallized from ethanol and tetrahydroanthracene. South mixed aa solvent' to obtain a white knot of 1 g of compound (ai) Purity 98.0%). Synthesis Example A-2 In a 1 L eggplant type flask, 82 g of p-hydroxycinnamic acid, carbonic acid and 4 〇〇mL of N-methyl_2_ were added. Mix ι 'I hour' and then add 212g of 1-evolution simmer, and smash for 5 hours at 1 〇. Then, remove the solvent by distillation under reduced pressure. Add 48g of sodium hydride and 400mL of water to it. The hydrolysis reaction is carried out back to & 3 hours. After the reaction, the reaction system is neutralized with hydrochloric acid, and the formed precipitate is recovered, and then regenerated from ethanol. Crystals, thereby obtaining white crystals of 80 g of the compound (A 2 ). Synthesis Example A - 3 10 7 g of 4-bromocinnamic acid was refluxed in 8 3 g of sulfoxide for 4 hours to obtain a red transparent solution. The unreacted thionite-brewed chlorine was distilled off, and the residue was recrystallized with toluene, and the obtained crystal was washed with n-hexane to obtain white crystals of 85 g of cerium bromide sulphide. -64- 201144384 Then, 25 〇g (〇147111〇1) of heart-amine cyclohexanol was dissolved in 25 mL of pyridine. The temperature of the :海:· 谷谷液 was maintained at about 3. 〇, and it was dropped into 350 mL of pyridine to suspend 43.3 g. (〇176m〇1) of 4-bromo cinnabar hexafluoride, and further reacted for 3 hours. The obtained reaction mixture (suspension) was added to 1.3 kg of hydrochloric acid acidic ice water to recover the resulting precipitate, washed with water, and dried to obtain 50 g of 4 - crude brominated cinnamic acid 4_n-pentylcyclohexyl ester (cream powder). Crude 4 - bromocinnamate 4-n-pentylcyclohexyl ester obtained in 50 g of the above, 0.28 g of acetic acid In a mixture of palladium and mg ginseng (o-phenyl)phosphine, 'under a nitrogen atmosphere, add 1 25 mL of dry The reaction was carried out with dry triethylamine. After the crude 4-n-pentylcyclohexyl cinnamate was completely dissolved, 10 g of acrylic acid was injected with a syringe, and the reaction was continued at 95 ° C for 2 hours. 1·3 kg of hydrochloric acid in acidic ice water, the obtained dark green reaction mixture was added, and the resulting precipitate was recovered. The solution of the obtained solid was dissolved in 5 mL of ethyl acetate with 1 N hydrochloric acid and 5 wt./〇 sodium hydrogencarbonate. The solution was washed with a person, and then dried over magnesium sulfate, and the solvent was evaporated to give a crude compound (yellow solid) of the compound of the above formula (A-3). The crude product was recrystallized from ethanol to give 3 g (yield: 55%) of a yellow powder of Compound (A-3). Synthesis Example A-4 In a 1 L eggplant type flask, 91.3 g of 4,4-hydroxybenzoic acid vinegar, 182.4 g of potassium carbonate, and 320 mL of N-fluorenyl-2-pyrrolidone were added, and the mixture was stirred for 1 hour under coffee. Then, 1 5.7 · 1 g of 1 _ iodo _ 4, 4, 4 - trichomes was added and the reaction was stirred at 100 Torr for 5 hours. After the reaction was completed, the reaction mixture was added to water to carry out reprecipitation. Then, 48 g of sodium oxysulfide and 4 mL of water were added to the obtained squash-65-201144384 melon, and the hydrolysis reaction was carried out for 3 hours. After completion of the reaction, the reaction mixture was neutralized with hydrochloric acid, and the resulting precipitate was recovered and recrystallized from ethanol to obtain white crystals of 4-(4,4,difluorodifluorobutoxy)benzic acid of 11 (). 12.41 g of the 4_(4,4,4-tris-butoxy)benzoic acid was taken out from the reaction vessel, and 1 mL of sulfite gas and 77 Å of N,N_, fluorenylmethyl hydrazine were added thereto. Amine, at 80. . Stir for 1 hour. Then, sulfite gas was distilled off under reduced pressure, dichloromethane was added, and the organic layer was washed with aqueous sodium hydrogencarbonate, and dried over magnesium sulfate, and then solvent was evaporated. The resulting solid was dissolved in tetrahydrofuran to form a solution. Next, 7.39 g of 4-hydroxycinnamic acid, π...potassium carbonate, ο% tetrabutyl, a stinky chain, 50 mL of tetrahydrocyanate, and 1 加入 were added to another 5 烧 three-burning paper different from the above. 〇mL water. The solution was chilled, and the above tetrahydrofuran was slowly dropped, and the reaction was further stirred for 2 hours. After the completion of the reaction, hydrochloric acid was added to the reaction mixture for neutralization, and the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and then evaporated. The obtained solid was recrystallized from ethanol to obtain 1 g of a white crystal of (A-4). Synthesis Example A - 5 In a 5 mL mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube, 31 g of 1-bromo-4-(4-n-pentylcyclohexyl)benzene, palladium 23 palladium acetate was added. 1.2 g of cis (o-tolyl)phosphine, 56 mL of triethylamine, 82 mL of acrylic acid and 200 mL of N,N-dimercaptoacetamide at 12 Torr. The mixture was stirred for 3 hours. After the completion of the reaction, the reaction mixture was filtered, and 1 L of ethyl acetate was added to the obtained liquid crystals, and the obtained organic layer was washed with dilute hydrochloric acid for 2 - 66 - 201144384 times, washed three times with water, dried over magnesium sulfate, and then evaporated. The solvent was removed. The obtained solid was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain crystals of 15 g of Compound (A-5). Synthesis Examples A-6 and A-7 In the above Synthesis Example A-5, except that 28 g of 1-bromo-4-(4-n-propylcyclohexyl)benzene (Synthesis Example A-6) and 34 g, respectively, were used. 1- Desertified 4-(4-n-heptylcyclohexyl)benzene (Synthesis Example A-7) in place of 1-bromo-4-(4-n-pentylcyclohexyl)benzene, and Synthesis Example A-5 In the same manner, 13 g of the crystal of the compound (A-6) and 14 g of the compound (A-7) were respectively obtained. Synthesis Example A-8 In a 300 mL flask equipped with a reflux tube and a nitrogen introduction tube, 21 g of 4-n-pentyl-4'-carboxybicyclohexyl group, 80 mL of sulfoxide and mL·lmL of N,N-di were added. The mercaptoamine was stirred at 80 ° C for 1 hour. After the end of the reaction, the sulfite gas was distilled off from the reaction mixture, and then 150 ml of dioxane was added, and the resulting organic layer was washed three times with water. The organic layer was dried over magnesium sulfate, and then the solvent was evaporated under reduced pressure, and 400 mL of tetrahydrofuran was added to the obtained solid. On the other hand, in a 1 L three-necked flask having a dropping funnel and a thermometer, 16 g of p- cinnamic acid, 24 g of potassium carbonate, 〇 8 7 g of tetrabutyl desert, 2 0 0 was added. m L water and 100 m L tetrahydrogen cough, ice to below 5 °C. The above tetrahydrofuran solution was added dropwise over 3 hours, and then reacted under sandalwood for 1 hour. After the end of the reaction, the rare acid was added to the reaction mixture to adjust the pH to 4 or less, and then 3 L of hydrazine and 1 L of tetrahydrofurfuran were added, and the obtained organic layer was washed three times with water. After the organic layer was dried over magnesium sulfate, the solvent was removed under reduced pressure, and the obtained solid was recrystallized from a mixture solvent of ethanol and tetrahydrogen to obtain 2 1 g of the compound (a-8). -67- 201144384 &lt;Synthesis of Polyorganooxane (A)&gt; Synthesis Example S-1 In a 2 mL flask, a mixture of 5. 〇g of the above-mentioned Synthesis Example E-1 was obtained. The above-mentioned synthesis example a-Ι of the polyorganomethoxyane (Eps i), 46 4 g of methyl isobutyl ketone I, 1-4 g of carboxylic acid (A1) as a carboxylic acid (Al) (relative to EPS) -1 has an epoxy group, corresponding to 25 mol%) and 〇.13 g of tetrabutylammonium bromide, and the reaction is stirred at 8 (TC for 12 hours). After the reaction is completed, reprecipitation with methanol is carried out. The hall was dissolved in ethyl acetate to obtain a solution, and the solution was washed with water three times, and then the solvent was distilled off to obtain 2.3 g of a white powder of polyorganooxane (S-1) as polyorganooxane (A). Synthesis Example S-2 to S-33 In the synthesis example S·1, except that the type and amount of the carboxylic acid used were as described in Table 1, respectively, as shown in Synthesis Example S-1, Polyorganosiloxane (S-2)~(S-33). Among them, in the synthesis examples S-3~S-7, S-17 and S-21, the carboxylic acid (A1) Other carboxylic acids of the kind and amount described in Table 1. (1) In combination with the other carboxylic acid (2), in the synthesis examples S-31 to S-33, two acids are used as the carboxylic acid (A1). The amount of the carboxylic acid described in Table 1 is relatively The gas group of EPS-1 is mol% -68- 201144384 Table 1 Synthesis of polyorganosiloxane (A) List of carboxylic acid polyorganosiloxane (A) Name carboxylic acid (A1) Other carboxylic acids (1) • Other carboxylic acid (2) Addition amount (mol%) Type of addition (mol%) Type of addition (mol%) Synthesis example S - 1 A-1 25 - 0 - 0 S-1 Synthesis example S-2 A- 1 50 — 0 — 0 S-2 Synthesis Example S-3 A_1 50 B-1 5 C-1 0.2 S-3 Synthesis Example S-4 A-1 50 B-1 10 C-1 0.4 S-4 Synthesis Example S —5 A-1 50 B-1 15 C-1 0.6 S-5 Synthesis Example S-6 A-1 50 B-2 5 C-1 0.2 S-6 Synthesis Example S-7 A-1 50 B-3 5 C-1 0,2 S- 7 Synthesis Example S-8 A-1 75 A 0 0 0 S-8 Synthesis Example S-9 A-2 25 — 0 — 0 S-9 Synthesis Example S-10 A-2 50 — 0 — 0 S-10 Synthesis Example S-11 A-2 75 — 0 — 0 S-11 Synthesis Example S-12 A-3 25 — 0 — 0 S-12 Synthesis Example S-13 A-3 50 — 0 — 0 S-13 Synthesis Example S — 14 A-3 75 — 0 — 0 S-14 Synthesis Example S —15 A-4 25 — 0 — 0 S-15 Example S-16 A-4 50 - 0 - 0 S-16 Synthesis Example S-17 A-4 50 B-1 5 C-1 0.2 S-17 Synthesis Example S-18 A-4 75 — 0 — 0 S -18 Synthesis Example S-19 A_5 25 — 0 — 0 S-19 Synthesis Example S-20 A-5 50 — 0 — 0 S-20 Synthesis Example S—21 A-5 50 B-1 5 C-1 0.2 S -21 Synthesis Example S - 22 A-5 75 - 0 - 0 S-22 Synthesis Example S - 23 A-6 25 - 0 - 0 S-23 Synthesis Example S-24 A-6 50 - 0 - 0 S-24 Synthesis Example S-25 A-6 75 - 0 - 0 S-25 Synthesis Example S-26 A-7 25 A 0 - 0 S-26 Synthesis Example S-27 A-7 50 A 0 - 0 S-27 Synthesis Example S-28 A-7 75 — 0 — 0 S-28 Synthesis Example S — 29 A-8 25 — 0 — 0 S - 29 Synthesis Example S — 30 A-8 50 — 0 — 0 S-30 Synthesis Example S — 31 A-1 15 — 0 — 0 S-31 A-3 10 Synthesis Example S — 32 ATM5 15 — 0 — 0 S-32 A~8 10 Synthesis Example S — 33 A-4 25 — 0 — 0 S -33 A-5 25 -69- 201144384 The abbreviations of the carboxylic acids in Table 1 above have the following meanings. [Carboxylic acid (A1)] A-1 : Compound (A-1) obtained in the above Synthesis Example A-1 A-2: Compound (A-2) obtained in the above Synthesis Example A-2 A-3: Synthesis Example Compound (A-3) A-4 obtained by A-3: Compound (A-4) obtained in the above Synthesis Example A-4 A-5: Compound (A-5) A-6 obtained in the above Synthesis Example A-5 : Compound Yang (A-6) A-7 obtained in the above Synthesis Example A-6: Compound (A-7) obtained in the above Synthesis Example A-7 A-8: Compound obtained in the above Synthesis Example A-8 (A- 8) [Other carboxylic acid (1)] B-1: Stearic acid B-2: 1,4-succinic acid mono(3-cholestyl) ester B_3 : 4-(4,4,4-three Fluorobutoxy)benzoic acid [other carboxylic acid (2)] (:-1:3,5-dinitroindole acid <synthesis of polyimine (B)> Synthesis example P -1 to P_ 2 9 Use of Polyimide Tetracarboxylic Acid dianhydride In these synthesis examples, each of the polymers (B) was synthesized by the following procedure. As the monomers, the types and amounts of the anhydrides and diamines shown in Table 2 were used, respectively. The amount of each monomer used in Table 2 is shown in the unit of m ο 1 % in the case where the amount of tetracarboxylic acid is 100 μm ο 1 %, and the tetracarboxylic dianhydride and Monomer mixture of diamine The solution was dissolved in N-mercapto-2-pyrrolidone to form a solution having a monomer concentration of 2% by weight, and reacted at 60 C for 4 hours to obtain a solution containing 2% by weight of polyglycine. The solution viscosity of each polylysine solution is shown in Table 2. Then, N methyl-2-pyrrolidone was added to each of the obtained polyaminic acid solutions, and the polyamine concentration was diluted to 1 〇 by weight. %, further adding pyridine and acetic anhydride, respectively, relative to the methionine unit of im〇1 polyphthalic acid, which is the mole multiple of the description of Table 2 and then dehydration at 4 °: 4 hours Then, the solvent in the reaction system is replaced with a new &amp; methyl-2-pyrrolidone to obtain a polyimine which is about 2% by weight as a polyimine (B). Ρι_υ~(ρι_29). The ruthenium imidization rates of the respective polyfluorenes contained in these solutions are shown in Table 2. <Synthesis of Other Polylysine> Synthesis Example p -1 to P_ 5 In the synthesis of the above polyimine (B), in addition to the use of the types and amounts of the tetracarboxylic acid dioxins and diamines shown in Table 2, In the synthesis of the amine (B), 20% by weight of polylactoic acid, which is another poly-brenic acid, was also obtained. The viscosity of the solution was shown in Table 2. The dilution of the solution was shown in Table 2. Preparation. Some poly makeup 铋 瑕 瑕 瑕 瑕 N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N - 6~p - 8 In the synthesis of the above polyimine (B), in addition to the use of the types and amounts of tetracarboxylic dianhydride and diamine shown in Table 2, synthesis with polyimine (B) In the same manner, 20% by weight of each polylysine was obtained. The solution viscosity of each polyamine was shown in Table 2. Then, using each polyaminic acid solution, as in the synthesis of the polyimine (B), 20% by weight of polyimine (pi-1) to (pi-3) as another polyimine was obtained. ). The oxime imidization ratio of each polyimine contained in these solutions is shown together in Table 2. -72- 201144384 Table 2 Polymer composition at a glance Synthesis Example Tetracarboxylic dianhydride Diamine Polyamide solution Viscosity (mPa. S) Dehydration ring closure reaction Polymer name Diamine (1) Diamine (2) Diamine (3) Amount (mol%) Species (mol%) Species (mol%) Species (mol%) Pyridine (Pymol) Acetic anhydride (Momol) Ammonium amination rate (%) P-1 t1 100 a 40 e 60 - 1670 1.5 1.5 65 PI-1 P-2 t1 100 a 35 e 10 k 55 1800 2.0 2.0 75 PI-2 P-3 t1 100 b 45 e 20 ί 35 1500 1.0 1.0 50 PI-3 P-4 T1 100 b 40 e 60 - 0 1650 1.5 1.5 65 PI-4 P-5 t1 100 d 20 e 80 - 0 1910 1.0 1.0 50 PI-5 P-6 t1 100 d 10 e 90 - 0 2200 1.5 1.5 65 PI- 6 P-7 t1 100 c 10 e 90 - 0 2100 1.5 1.5 65 PI-7 P-8 t1 100 d 40 e 60 - 0 1400 1.5 1.5 65 PI-8 P-9 t1 100 a 40 f 60 - 0 1450 1.5 1.5 65 PI-9 P-10 t1 100 d 40 g 60 - 0 1400 1.5 1.5 65 PI-10 P-11 t1 100 b 40 e 25 i 25 1450 1.0 1.0 50 PI-11 I 10 1510 1.5 1.5 65 PI-12 P-12 t1 100 d 40 e 40 i 20 1.0 1.0 P-13 t1 100 d 40 f 10 i 20 1480 2.0 2.0 50 PI-13 j 30 1.5 1.5 P-14 t1 100 d 40 f 30 k 30 147 0 0.5 0.5 75 PI-14 P-15 t1 100 a 40 g 30 k 30 1380 1.0 1.0 65 PI-15 P-16 t1 100 b 70 e 10 k 20 900 1.5 1.5 30 PI-16 P-17 t1 100 c 30 e 70 - 0 1630 1.5 1.5 50 PI-17 P-18 t1 100 d 30 e 70 - 0 1780 1.5 1.5 65 PI-18 P-19 t1 100 a 30 f 70 - 0 1550 1.5 1.5 65 PI-19 P-20 T1 100 d 30 g 70 - 0 1610 1.5 1.5 65 PI-20 P-21 t1 100 d 60 e 40 - 0 880 1.5 1.5 65 PI-21 P-22 t1 100 d 50 e 50 - 0 1050 1.5 1.5 65 PI- 22 P-23 t1 100 d 50 f 50 - 0 980 1.0 1.0 65 PI-23 P-24 t1 100 b 40 g 30 h 30 1440 1.5 1.5 65 P b 24 P-25 t1 100 c 10 e 60 - 0 1490 1.0 1.0 50 PI-25 d 30 P-26 t1 100 c 10 f 60 - 0 1380 1.5 1.5 65 PI-26 d 30 P-27 t1 100 c 30 g 60 - 0 1290 1.0 1.0 50 PI-27 d 10 P-28 T1 100 c 20 f 20 i 20 1520 1.5 1.5 65 PI-28 d 20 j 20 P-29 t1 100 a 10 f 60 - 0 1420 1.0 1.0 50 PI-29 b 30 P-1 t2 100 - 0 - 0 m 100 990 0 0 0 pa-1 p-2 t2 50 - 0 - 0 m 100 850 0 0 0 pa-2 t3 50 p-3 t2 50 - 0 - 0 n 100 920 0 0 0 pa-3 t3 50 p-4 T2 50 - 0 - 0 i 100 870 0 0 0 pa-4 t3 50 p-5 t1 100 - 0 - 0 i 100 7 00 0 0 0 pa-5 p-6 t1 100 c 10 - 0 i 20 2010 1.5 1.5 65 pi-1 j 70 p-7 t1 100 c 20 - 0 j 80 1980 1.0 1.0 50 pi-2 p-8 t1 100 c 50 - 0 j 50 1700 0 0 0 pi-3 -73- 201144384 The abbreviations of the monomers in Table 2 above are respectively the following meanings. '[Tetracarboxylic dianhydride] tl: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride t2: 1,2,3,4-cyclobutane tetracarboxylic dianhydride t3: trimellitic acid dianhydride [Diamine]-diamine (1)_ a : Compound b represented by the above formula (bl-1-4): Compound c represented by the above formula (bl-1-7): 3,5-diaminophenylhydrazine Acid-3-cholesteryl d: 2,4-diamino-3-cholestyloxybenzene-diamine (2)-e : 3,5-diaminobenzoic acid f: 3 , 3'-dicarboxy-4.4'-diaminobiphenyl g: bis(4-aminophenyl)bis(2-carboxyethyl)decane-diamine (3) _ h : N-(2, 4-diaminophenyl)piperidinium i: 4,4'-diaminodiphenylmethane j: p-phenylenediamine k: 1-(4-aminophenyl)-2,3-dihydro- 1,3,3-tridecyl-1H-indole-5- 1 : N,N'-bis(4-aminophenyl)piped m: 2,2'-dimercapto-4,4'- Diaminobiphenyl η: 4,4'-diaminodiphenyl ether &lt;Preparation and evaluation of liquid crystal alignment agent&gt; Example 1-74-201144384 [Preparation of liquid crystal alignment agent] The above synthesis example Pq was contained. LW is obtained from a solution of polyimine (PI-1), and is added to the polypyridinium contained in the solution of π 松 &amp; 1 〇 by weight of the above combination, _ t. s, the polyorganooxy oxane (S-1) obtained as an example s-1 'addition of N_methyl-2 milk w W , Λ, &amp; χτ ratio Each pyridine _ and butyl cyanidin, the solvent composition is Ν-methyl-2-pyrrole 1 gluten ketone: butyl cyanidin = 40:60 (weight 1 ratio), forming a solid concentration of crying m 7| π n 0 G · 5 % by weight of the solution. This solution was also used to prepare a liquid crystal alignment agent for the evaluation of printability by using a 2 μ m sieve test program. In the same manner as above, a liquid crystal alignment agent for producing a liquid crystal display element was prepared in the same manner as described above except that the solid component _ &amp; 1 U m air knife spread was 3.5% by weight. [Evaluation of the printability] A resin sheet (manufactured by Sekisui Chemical Industry Co., Ltd., "Micro Pearl EX-0041-AC4") with a diameter of about 4·1 μm is dispersed on a 6-inch-inch Shih-hwa wafer. Heat treatment on a hot plate of 120 °C for 1 ' ° Prepare a stone wafer with an attached gasket. The liquid crystal alignment agent for printability evaluation prepared as described above was used to be aligned by liquid crystal. Printing (4) manufacturing), in the above-mentioned 塾 塾 勺 勺 勺 勺 上 上 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ), a coating film having a flat and uniform film thickness is formed. The coating film is observed under a microscope with a magnification of 2 G times, and the P brush is subjected to „f &amp;铴, there will be no observation of uneven printing and partial depressions. _ Test the strips of the gasket; the sub-mussels are excellent in printability, and little sputum α HP ^ will be observed, but there is basically no In the case where the above-described coating is not good, the gasket is partially recessed: it is evaluated as "poor" in the case where the printing is not hooked or attached. -75- 201144384 [Manufacture of liquid crystal display element] Having an ITO film On the glass substrate electrode surface of the transparent electrode, 'the liquid crystal alignment agent for liquid crystal display element prepared above was spin-coated on a hot plate at 80 ° C for 1 minute to bake' and then the chamber was replaced with nitrogen in an oven. 2 〇〇 1 hour 'forming film thickness 〇〇 8μηι Then, on the same surface, an HG-Xe lamp and a Gian_Tayl〇r prism were used to irradiate an outer line of 5 〇〇J/m2 containing a bright line of 313 nm from a direction inclined by 40. A liquid crystal alignment film was formed. The same operation was repeated. A substrate having a liquid crystal alignment film was obtained. One of the pair of substrates has a liquid crystal alignment film on the circumference of the liquid crystal alignment film by screen printing to apply a diameter of 5.5 μηι in the Lu ball of the oxy-resin adhesive, and then the liquid crystal facing the pair of substrates facing The pressure bonding was performed so that the projection directions on the ultraviolet light axis plane of each substrate were anti-parallel, and 1 at 50 ° C was used to thermally cure the adhesive agent. Then, a negative liquid crystal (manufactured by Merck, MLC-6608) was filled between the substrates by a liquid crystal injection port, and an epoxy-based adhesive sealed the liquid crystal injection port. In addition, in order to remove the incoming flow alignment, it can be heated to 1 5 01 and then to room temperature. Next, on both outer surfaces of the substrate, the bonding is biased so that the polarization directions thereof are perpendicular to each other, and the projection direction of the ultraviolet ray of the liquid crystal alignment film on the substrate surface is 45. The angle of the system is thus displayed. The liquid crystal display element was evaluated in the following manner. The composition and evaluation results of the agent are shown in Table 3. The transparent part is made of pre-baked and coated with a coated substrate. The polarized violet pair (the outer surface of the oxidized alignment film on both sides of the substrate is small, and then the liquid crystal is injected with a slow cold plate, and the line optical axis is made of liquid crystal liquid crystal. -76- 201144384 [Evaluation of Liquid Crystal Display Element] (1) Evaluation of Pretilt Angle The pretilt angle was measured by the method of the crystal rotation method described in the above-mentioned liquid crystal display 1 (TJ Scheffer et. p2013 (1980)) t. The display element can be based on Patent a1·J·Appl. Phys. vol· 19. 'Evaluation of voltage retention by using He-Ne misdirected junction (2) For the above-prepared liquid crystal display element, at ambient temperature of 纟, in (four) seconds The application time is applied, and then the span of ι 67 milliseconds is applied. Then, the voltage holding ratio after the release of the application to 67 ms is applied. The measuring device is manufactured by TOYO C〇rporati〇n (share), model "". (3) According to the evaluation of the imprinting characteristics of the difference in brightness, two liquid crystal display elements are prepared in the same manner as described above, and an alternating voltage of 1 〇v is applied to the element (component A) at 6 〇t, and the target is added to the other (element b). Turbulence voltage 1V, holding Then, when the applied voltage is switched to a DC voltage of 2.5 V, when the difference in luminance between the observed element a and the element β is expressed as 256 levels, the difference in luminance is 1 〇 or less, and the branding characteristic is "good". In the case of the above-mentioned Example 1, except that the type and amount of the polymer used were in Table 3, the case where the amount of the polymer was less than 1 评价 was evaluated as the inferiority of the branding characteristics 'poorness> and the examples 2 to 12 9 and the comparative examples 1 to 7. In addition to the above, the liquid crystal alignment agent for liquid crystal display element production and the liquid crystal alignment agent for printability evaluation were prepared in the same manner as in the examples. The evaluation results are shown in Table 3. -77- 201144384 Table 3 Liquid crystal alignment agent Composition and evaluation results Liquid crystal alignment agent Liquid crystal display element Polyorganosiloxane __(A)^ Polyimine (B) Other polymer solvent composition NMP/BC parts by weight) Printability pretilt angle (.) Voltage retention rate (%) Type of branding (parts by weight) Type (parts by weight) Type (parts by weight) Characteristic Example 1 S-1 10 PI-1 100 - 0 40/60 Excellent 89.2 98 Good Example 2 S-2 10 PI-1 100 - 0 40/60 Excellent 88.5 98 Good Example 3 S-8 10 PI-1 100 - 0 40/60 Good 88.1 98 Good Practice 4 S-3 10 PI-1 30 pa-1 70 40/60 Excellent 88.3 99 Good Practice 5 S-3 10 PI -1 30 pa-2 70 40/60 Excellent 88.0 99 Good Practice 6 S-3 10 PI-1 30 ps-3 70 40/60 Excellent 88.1 99 Good Practice 7 S-3 10 PI-1 30 pa-4 70 40/60 Excellent 88.1 99 Good Practice 8 S-3 10 PI-1 30 pa-5 70 40/60 Excellent 88.0 99 Good Practice 9 S-4 10 PI-1 30 pa-5 70 40/60 Excellent 88.3 99 Good example 10 S-5 10 PI-1 30 pa-5 70 40/60 Good 88.5 99 Good example 11 S-6 10 PI-1 30 pa-5 70 40/60 Good 88.4 99 Good example 12 S -7 10 PI-1 30 pa-5 70 40/60 Excellent 87.8 99 Good Practice 13 S-9 10 PI-2 100 - 0 45/55 Excellent 89.3 98 Good Practice 14 S-10 10 PI-3 100 - 0 40/60 Excellent 88.8 98 Good Practice 15 S-9 10 PI-4 100 - 0 40/60 Excellent 89.1 98 Good Practice 16 S-10 10 PI-4 100 - 0 40/60 Excellent 88.8 98 Good Practice 17 S-11 10 PI-4 100 - 0 40/60 Good 88.5 98 Good Practice 18 S-12 10 PI-5 100 - 0 50/50 Good 88.4 98 Good Practice 19 S-13 10 PI-5 100 - 0 50/50 Good 88.0 98 Good example 20 S-14 10 PI-5 100 - 0 50/50 Good 87.7 98 Good practice 21 S-15 10 PI-6 100 - 0 60/40 Good 88.5 98 Good practice 22 S-9 10 PI -7 100 - 0 60/40 Good 88.5 98 Good Practice 23 S-12 10 PI-7 100 - 0 60/40 Good 88.2 98 Good Practice 24 S-15 10 PI-7 100 - 0 60/40 Good 88.4 98 Good example 25 S-17 10 PI-8 100 - 0 40/60 Excellent 88.3 98 Good example 26 S-20 5 PI-8 100 - 0 40/60 Excellent 88.5 98 Good example 27 S-21 5 PI -8 100 - 0 40/60 Excellent 88.8 98 Good Practice 28 S-24 5 PI-8 100 - 0 40/60 Excellent 89.0 98 Good Practice 29 S-26 5 PI-8 100 - 0 40/60 Excellent 89.2 98 Good example 30 S-29 5 PI-8 100 - 0 40/60 Excellent 89.3 98 Good practice 31 S-16 5 PI-8 100 0 40/60 Excellent 88.2 Good S-20 5 y〇 Example 32 S -17 5 PI-8 100 0 40/60 Excellent 88.4 98 Good S-29 5 Example 33 S-17 10 PI-8 30 pa-1 70 40/60 Excellent 88.0 98 Good Practice 34 S-17 10 PI- 8 30 pa-2 70 40/60 Excellent 87.9 98 Good Practice 35 S-17 10 PI-9 100 - 0 40/60 Excellent 88.2 99 Good Practice 36 S-20 5 PI-9 100 - 0 40/60 Excellent 88.4 99 Good Practice 37 S-21 5 PI-9 100 • 0 40/60 Excellent 88.6 99 Good Practice 38 S-24 5 PI-9 100 - 0 40/60 Excellent 88.8 99 Good Practice 39 S-26 5 PI-9 100 - 0 40/60 Excellent 89.1 99 Good Practice 40 S-29 5 PI-9 100 - 0 40/60 Excellent 89.1 99 Good Practice 41 S-16 5 PI-9 100 0 40/60 Excellent 88.0 99 Good S-20 5 Example 42 S-17 5 PI-9 100 0 40/60 Excellent 88.1 Good S-29 5 yy -78- 201144384 Table 3 Composition and Evaluation Results of Liquid Crystal Aligning Agent (Continued) Example 43 S-17 10 PI-9 30 pa-3 70 40/60 Excellent 87.8 99 Good Practice 44 S-17 10 PI-9 30 pa-4 70 40/60 Excellent 87.6 99 Good Practice 45 S- 17 10 PI-9 30 pa-5 70 40/60 Excellent 87.7 99 Good Practice 46 S-15 10 PI-10 100 - 0 40/60 Excellent 88.7 98 Good Practice 47 S-16 10 PI-10 100 - 0 40/60 Excellent 88.2 98 Good Practice 48 S-18 10 PI-10 100 - 0 40/60 Good 87.8 98 Good Practice 49 S-19 5 PI-11 100 - 0 40/60 Excellent 88.9 98 Good Practice 50 S-20 5 PI-11 100 - 0 40/60 Excellent 88.5 98 Good Practice 51 S-22 5 PI-11 100 - 0 40/60 Good 88.2 98 Good Example 52 S-23 5 PI-12 100 - 0 40/60 Excellent 89.2 99 Good Practice 53 S-24 5 PI-12 100 - 0 40/60 Excellent 88.8 99 Good Practice 54 S-25 5 PI- 12 100 - 0 40/60 Good 88.5 98 Good Practice 55 S-26 5 PI-13 100 - 0 40/60 Excellent 88.5 98 Good Practice 56 S-27 5 PI-13 100 - 0 40/60 Good 88.0 98 Good Example 57 S-28 5 PI-13 100 - 0 40/60 Good 87.7 98 Good Practice 58 S-29 5 PI-14 100 - 0 45/55 Excellent 88.9 99 Good Practice 59 S-30 5 ΡΙ- Ϊ4 100 - 0 45/55 Good 88.4 99 Good Practice 60 S-13 10 PI-15 10 pa-5 90 40/60 Excellent 88.1 99 Good Practice 61 S-13 10 PI-15 20 pa-5 80 40/ 60 Excellent 88.0 99 Good Practice 62 S-13 10 PI-15 30 pa-5 70 40/60 Excellent 88.0 99 Good Practice 63 S-13 10 PI-15 40 pa-5 60 40/60 Excellent 88.2 99 Good implementation Example 64 S-13 10 ρμΐ5 50 pa-5 50 40/60 Good 88.3 98 Good Practice 65 S-13 10 PI-15 70 pa-5 30 40/60 Good 88.3 98 Good Practice 66 S-13 10 PI- 16 100 - 0 40/60 Good 88.9 98 Good Practice 67 S-3 10 ρμΐ7 100 - 0 45/55 Excellent 88.4 98 Good Practice 68 S-17 10 PI-18 100 - 0 45/55 Excellent 87.8 98 Good Practice 69 S-20 5 PI-18 100 - 0 45/55 Excellent 88.2 98 Good Practice 70 S-24 5 PI-18 100 - 0 45/55 Excellent 88.8 98 Good example 71 S-29 5 PI-18 100 - 0 45/55 Excellent 89.1 98 Good example 72 S-17 10 PI-18 30 pa-1 70 45/55 Excellent 87.6 98 Good example 73 S- 17 10 PI-18 30 pa-2 70 45/55 Excellent 87.5 98 Good Practice 74 S-3 10 PI-19 100 - 0 45/55 Excellent 88.0 99 Good Practice 75 S-10 10 PI-19 100 - 0 45/55 Excellent 88.2 99 Good Practice 76 S-13 10 PI-19 100 - 0 45/55 Excellent 87.9 99 Good Practice 77 S-16 10 PI-19 100 - 0 45/55 Excellent 88.0 99 Good Practice 78 S-4 10 PI-19 30 pa-3 70 45/55 Excellent 88.1 99 Good Practice 79 S-4 10 PI-19 30 pa-5 70 45/55 Excellent 88.0 99 Good Practice 80 S-3 10 PI- 20 100 - 0 45/55 Excellent 88.3 99 Good Practice 81 S-10 10 PI-20 100 - 0 45/55 Excellent 88.5 99 Good Practice 82 S-13 10 PI-20 100 - 0 45/55 Excellent 88.2 99 Good Example 83 S-16 10 PI-20 100 - 0 45/55 Excellent 88.3 99 Good Practice 84 S-2 5 PI-20 100 - 0 45/55 Excellent 87.9 99 S-27 5 Example 85 S-10 5 PI-20 100 - 0 45/55 Excellent 88.0 99 Good S-27 5 Example 86 S-16 5 PI-21 100 - 0 45/55 Excellent 88.6 99 Good S- 20 5 Example 87 S-17 10 PI-21 100 - 0 40/60 Excellent 88.7 99 Good Practice 88 S-20 10 PI-21 100 - 0 40/60 Excellent 88.4 99 Good Practice 89 S-16 10 PI -21 30 pa-1 70 40/60 Excellent 88.9 99 Good Practice 90 S-16 10 PI-21 30 pa-2 70 40/60 Excellent 88.8 99 Good-79- 201144384 Table 3 Composition and Evaluation Results of Liquid Crystal Aligning Agent (Continued) Example 91 S-16 5 PI-22 100 - 0 40/60 Excellent 88.8 99 Good S-29 5 Example 92 S-17 10 PI-22 100 - 0 40/60 Excellent 88.9 99 Good Practice 93 S-20 10 PI-22 100 - 0 40/60 Excellent 88.3 99 Good Practice 94 S-30 5 PI-22 100 - 0 40/60 Excellent 88.5 99 Good Practice 95 S-16 10 PI-22 30 pa- 1 70 40/60 Excellent 88.5 99 Good Practice 96 S-16 10 PI-22 30 pa-2 70 40/60 Excellent 88.4 99 Good Practice 97 S-3 10 PI-23 100 - 0 40/60 Excellent 88.3 99 Good Example 98 S-10 10 PI-23 100 - 0 40/60 Excellent 88.5 99 Good Practice 99 S-13 10 PI-23 100 - 0 40/60 Excellent 88. 2 99 Good example 100 S-16 10 PI-23 100 - 0 40/60 Excellent 88.3 99 Good example 101 S-2 5 PI-23 100 - 0 40/60 Excellent 88.2 99 Good S-13 5 Example 102 S-2 10 PI-23 30 pa-3 70 40/60 Excellent 88.0 99 Good Practice 103 S-2 10 PI-23 30 pa-4 70 40/60 Excellent 88.1 99 Good Practice 104 S-3 5 PI- 24 100 - 0 40/60 Excellent 88.8 98 Good Practice 105 S-3 10 PI-24 100 - 0 40/60 Excellent 88.4 98 Good Practice 106 S-3 15 PI-24 100 - 0 40/60 Good 88.2 98 Good Example 107 S-3 20 PI-24 100 - 0 40/60 Good 87.9 98 Good Practice 108 S-3 10 PI-25 100 - 0 40/60 Excellent 88.3 98 Good Practice 109 S-13 10 PI- 26 100 - 0 40/60 Excellent 88.1 98 Good Practice 110 S-17 10 PI-27 100 - 0 40/60 Excellent 88.4 98 Good Practice 111 S-24 5 PI-28 100 - 0 40/60 Excellent 88.6 98 Good Example 112 S-3 5 PI-29 100 - 0 40/60 Good 88.3 98 Good Practice 113 S-10 10 PI-29 100 - 0 40/60 Excellent 88.5 98 Good Practice 114 S-13 10 PI- 29 100 - 0 40/60 Excellent 88.7 98 Good Practice 115 S-16 10 PI-29 100 - 0 40/60 Excellent 88.3 98 Good Practice 116 S-20 5 PI-29 100 - 0 40/60 Excellent 88.6 99 Good Practice 117 S-24 5 PI-29 100 - 0 40/60 Excellent 88.9 99 Good Practice 118 S-30 5 PI-29 100 - 0 40/60 Excellent 88.8 99 Good Practice 119 S-13 10 PI-29 30 pa-3 70 40/60 Excellent 88.4 99 Good Practice 120 S-13 10 PI-29 30 pa-4 70 40/60 Excellent 88.3 99 Good Example 121 S-13 10 PI-29 30 pa-5 70 40/60 Excellent 88.4 99 Good Practice 122 S-31 5 PI-1 100 - 0 40/60 Good 89.0 99 Good Practice 123 S-33 5 PI-1 100 - 0 40/60 Good 88.2 99 Good Practice 124 S-32 5 PI-8 100 - 0 40/60 Excellent 88.6 98 Good Practice 125 S-33 5 PI-8 100 - 0 40/60 Excellent 88.2 98 Good Practice 126 S-31 5 PI-18 100 - 0 45/55 Excellent 88.5 98 Good Practice 127 S-33 5 PI-18 100 - 0 45/55 Excellent 87.9 98 Good Practice 128 S-32 5 PI-29 100 - 0 40/60 Excellent 88.7 99 Good Practice 129 S-33 5 PI-29 100 - 0 40/60 Excellent 88.1 99 Good Comparative Example 1 S-3 10 - 0 pi-1 100 60/40 Poor 88.0 97 Bad Comparative Example 2 S-3 10 - 0 pi-1 30 60/40 Bad 87.7 98 Bad pa-4 70 Comparative Example 3 S-3 10 - 0 pi-1 30 60/40 Good 88.8 98 Bad pa-5 70 Comparative Example 4 S-10 10 - 0 pi-2 100 50/50 Bad 88.1 98 Bad Comparative Example 5 S-13 10 - 0 pi-3 100 40/60 Good 88.8 96 Good Comparative Example 6 S-32 5 - 0 pa-1 100 50/50 Bad 88.7 97 Bad Comparative Example 7 S-33 5 - 0 pa-4 100 50/50 Bad 88.2 97 Bad -80- 201144384 In addition, in Example 31 In the 32, 41, 42, 84, 85, 86, 91 and 101, two polyorganosiloxanes (A) can be used, respectively, and in Comparative Examples 2 and 3, two other polymers are used, respectively. The abbreviations of the solvent composition block are the following meanings. NMP : N - mercapto-2-pyrrolidone BC : butyl cyanidin. In the above Table 3, it was confirmed that the liquid crystal alignment agent of the present invention of Examples 1 to 129 can also exhibit excellent surface of the substrate having fine unevenness. Printability. Further, the liquid crystal alignment film formed of these liquid crystal alignment agents of the present invention exhibits a good pretilt angle and a high voltage holding ratio, and has good branding characteristics. Thus, the liquid crystal display element having the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is excellent in display quality and excellent in long-term reliability, which can be easily estimated by those skilled in the art. On the other hand, the liquid crystal alignment agent belonging to the prior art prepared in the comparative example cannot satisfy all of the above characteristics at the same time. [Simple description of the diagram] None. [Main component symbol description] Benefits

-81 - S

Claims (1)

201144384 VII. Patent application scope: 1. A liquid crystal alignment agent comprising: (A) a polyorganosiloxane having a structure represented by the following formula (A*i), (R)a 〇(A1) in formula () Wherein R is a mouse atom or a cyano group, a is an integer of 0 to 4, "* represents a linkage; and (B) 彳 &amp; poly phthalic acid and a poly phthalocyanine obtained by dehydration of the poly phthalic acid At least one polymer selected from the group consisting of: the polyamic acid is obtained by reacting a tetracarboxylic dianhydride with a diamine, and the diamine comprises (b2) a diamine having a rebel group. The liquid crystal alignment agent of the above item 1, wherein the diamine advancement comprises (bl) a diamine having: an alkyl group having 4 to 20 carbon atoms; an alkoxy group having 4 to 20 carbon atoms; a group of 6 or more members having a steroid structure or a group having a steroid structure. 3. The liquid crystal alignment agent according to claim 1 or 2, wherein the above (A) organic oxane has an epoxy group. a reaction product of a polyorganosiloxane and a carboxylic acid having a structure represented by the above formula (A1). Compound alignment agent, Si in the above (b 2) a piece goods amine of the formula (b2-l) represented by, -82 201144384 "In the formula (b2_1)" is an integer of 〇~2; X is each 〇~4, where 'when there are multiple x, each X 叮 is the same or different; R1 is a single key The exocyclic group or the vinegar bond of the thiol group, the sulfhydryl group or the carbon atom having a number of 2 to 6 is interrupted; the alkyl group may also be an ether bond in the chain or X1 is: a single bond, a sub-product of the extension Base, carbon atom "[two: base, carbon number is 2~4, fluorinated, *-cn〇c〇, fluorinated alkyl, oxygen atom, among them, "* -NH·, *_C〇NH-, INHCO-, white. The linkage chain not imparted thereto is oriented to the left of (b2-l), or the group of the following formula (χ-υ, RnCO〇H, Rm (XM) is in the formula (X-1), RII is a single bond,士-甘4, fluorenyl, an extended or extended cycloalkyl group having 2 to 6 carbon atoms, wherein, ..^.. can also be ether-bonded in the chain or The vinegar bond is interrupted; R111 is a hydrogen atom, the number of carbon atoms is R, vrn〇M # ^ 1V is an alkyl group of 1 to 6 or a group -R COOH, wherein R is a single, methylene, carbon The alkylene group or the cyclohexyl group having an atomic number of 2 to 6 may be interrupted by an ether bond or an ester bond in the chain; and the total number of carboxyl groups in the formula (b2) is an integer of 1 m. 5. The liquid helium ^ θ _ night aligning agent according to item 3 of the patent application, wherein the (bi) diamine hydrazine comprises a diamine having a steroid structure. -83- 201144384 6. A method of forming an alignment film, which is characterized in that the liquid is formed into a coating film according to any one of the first to fifth aspects, and the coating film is irradiated with radiation. 7. A liquid crystal display element characterized by having For example, the liquid crystal alignment agent of any one of items 1 to 5 is formed into a film. The liquid crystal of the patent application is applied as a matching agent. -84- 201144384 IV. Designation of representative drawings: (1) The representative representative of the case is : No. (2) Simple description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: