TW201035037A - Liquid crystal alignment agent, method for forming liquid crystal alignment film, liquid crystal display element and the preparation method thereof - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent. The said liquid crystal alignment agent can form a liquid crystal alignment film having the excellent stability for pre-tilt angle during time. The above-mentioned liquid crystal alignment agent comprises a radiation-sensitive polyorganosiloxane having the structure represented by the compound of following formula (1): The above-mentioned radiation-sensitive polyorganosiloxane is preferably a reaction product of (a) polyorganosiloxane having epoxy and (b) a compound having the structure represented by the above-mentioned formula (1) and carboxy, or a compound having the group represented by the following formula (2) -C ≡ C-COOH (2).

Description

201035037 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent, a method of forming a liquid crystal alignment film, a liquid crystal display element, and a method of manufacturing a liquid crystal display element. [Prior Art] At present, liquid crystals having liquid crystal cells such as TN (Twisted Nematic) type and STN (Super Twisted Nematic) type IPS (In Plane Switching) type are known. a display element, wherein the liquid crystal display element is a nematic liquid crystal having a positive dielectric anisotropy, and a sandwich structure is formed using a substrate with a transparent electrode having a liquid crystal alignment film, and the long axis of the liquid crystal molecules is on the substrate as needed The continuous twist is formed by 0 to 3 60 ° (refer to Patent Documents 1 and 2). In such a liquid crystal cell, since liquid crystal molecules are aligned in a predetermined direction with respect to the surface of the substrate, it is necessary to provide a liquid crystal alignment film on the surface of the substrate. The liquid crystal alignment film is usually formed by a method of rubbing the surface of the organic film formed on the surface of the substrate with a rayon or the like and rubbing it in one direction (friction method). However, if the liquid crystal alignment film is formed by the rubbing treatment, dust and static electricity are likely to be generated during the process, and therefore dust is adhered to the surface of the alignment film, which causes a problem of poor display. In particular, in the case of a substrate having a TFT (Thin Film Transistor) element, there is a problem that the circuit of the TFT element is destroyed by the generated static electricity, which causes a decrease in yield. Further, in the liquid crystal display device having higher accuracy in the future, as the density of the pixels is increased, it is difficult to uniformly perform the rubbing treatment due to the unevenness generated on the surface of the substrate. As another method of aligning the liquid crystal in the liquid crystal cell, it is known that a photosensitive film such as polyvinyl cinnamate, polyimine or azobenzene formed on the surface of the substrate is irradiated with polarized or non-polarized radiation. A photo-alignment method that imparts an alignment energy to a liquid crystal. According to this method, static electricity and dust are not generated, and uniform liquid crystal alignment can be achieved (see Patent Documents 3 to 13). Among them, in liquid crystal cells such as TN type and STN type, the liquid crystal alignment film must have liquid crystal molecules obliquely aligned at a predetermined angle to the surface of the substrate, and has a pretilt property. When the liquid crystal alignment film is formed by the pupil alignment method, the pretilt angle is usually given by tilting the substrate surface of the radiation irradiated from the substrate normal to the incident direction. On the other hand, as an operation mode of the liquid crystal display element different from the above, it is also known that a vertical (Homeotropic) alignment mode VA (Vertical Alignment) in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned on a substrate. 'Vertical alignment' type liquid crystal cell. In this operation mode, when a voltage is applied between the substrates and the liquid crystal molecules are tilted in the direction parallel to the substrate, the liquid crystal molecules are inclined from one direction of the substrate to one direction in the substrate surface. As such a method, for example, a method of providing a protrusion on a surface of a substrate; a method of providing a stripe on a transparent electrode; and using a rubbing alignment film, tilting liquid crystal molecules from a normal direction of the substrate toward a direction in the surface of the substrate is slightly inclined (pre-tilt) method, etc. The aforementioned photoalignment method is known as a method for controlling the tilt of liquid crystal molecules as a liquid cell for a vertical alignment mode. In other words, it is known that the tilting direction of the liquid crystal molecules at the time of voltage application can be uniformly controlled by using the vertical alignment liquid crystal alignment film which imparts the alignment control energy and the pretilt angle 201035037 by the photo-alignment method (refer to Patent Document 1 1). ~ 1 2 and 1 4~ 1 6). Thus, the liquid crystal alignment film produced by the photoalignment method can be effectively applied to various liquid crystal display elements. However, the liquid crystal alignment film formed by these techniques exhibits a good pretilt angle even at the time of initial formation, and a phenomenon in which the pretilt angle appears to be absent with time, and the stability of the pretilt angle deficiency with time is pointed out. However, in order to expand the viewing angle of the liquid crystal panel in the vertical alignment mode, it is known that MVA (Multi-Domain Vertical Alignment) type is formed by forming protrusions in the liquid crystal panel, thereby restricting the direction in which liquid crystal molecules are poured. panel. However, in this case, the transmittance and contrast from the projections are inevitably insufficient, and there is a problem that the response speed of the liquid crystal molecules is slow. In order to solve the problem of such an MVA type panel, a PSA (Polymer Sustained Alignment) method has been proposed in recent years. The PSA method is a gap between a pair of substrates formed of a substrate having a patterned conductive film and a substrate having a patterned conductive film, or a gap between a pair of substrates formed by two substrates having a patterned conductive film. In the liquid crystal composition containing a polymerizable compound, a technique of controlling the alignment direction of the liquid crystal by irradiating the ultraviolet ray and polymerizing the polymerizable compound in a state where a voltage is applied between the conductive films. According to this technique, the conductive film can be made into a specific structure, the viewing angle can be enlarged, and the liquid crystal molecules can be speeded up, and the inevitable transmittance of the MVA type panel and the insufficient contrast of the 201035037 can be solved. However, in order to polymerize the above-mentioned polymerizable compound, it is necessary to irradiate a large amount of ultraviolet rays such as 100,000 J/m 2 , and therefore, it is shown that in addition to the problem of decomposition of liquid crystal molecules, an unreacted compound which cannot be polymerized by ultraviolet irradiation remains in the liquid crystal layer. They combine to produce a display mottled' that adversely affects the voltage holding properties, or the long-term reliability of the panel, which is currently not practical. On the other hand, Non-Patent Document 3 proposes a method of using a liquid crystal alignment film formed of a polyimine-based liquid crystal alignment agent containing a reactive liquid crystal element (m e s 〇 g e η). The non-patent document 3, the liquid crystal molecules of the liquid crystal display element having the liquid crystal alignment film formed by the method, is called a response very quickly. However, in Non-Patent Document 3, there is no indication as to what kind of reactive liquid crystal cell element should be used, and the amount of ultraviolet radiation necessary is still large. The problem of display properties, particularly voltage retention properties, cannot be excluded. . [Patent Document 1] Japanese Patent Laid-Open No. 5-6 - 9 1 2 7 7 Patent Document 2: Japanese Patent Laid-Open No. 2 〇 5 2 8 Patent Document 3: Japanese Patent Laid-Open No. 6-287453 Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. 5, No. 5, No. 5, No. 5, No. 5, No. 5, No. 5, No. 5, pp. 〇 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 Japanese Patent Laid-Open Publication No. Hei. No. 2004-163646. Patent Document No. JP-A-2004-163924. Patent Document 14: JP-A-2004-83810 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2003-114437. Patent Document No. JP-A No. 2003-114437. Patent Publication No. 5 - 1 0 7 5 4 No. 5 Non-Patent Document Non-Patent Document 1: Chemical Reviews, No. 95, P1409 (1995) Non-patent 2: TJ Sch effer et. al. J. Appl. Phys. Vol. 19, P20 1 3 (1 980) ❹ Non-Patent Document 3: Y.-J. Lee et. al., SID 09 DIGEST, P666 (2009) SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a pretilt angle which can be imparted by a photo-alignment method, and which provides excellent stability with respect to time due to a pretilt angle imparted thereto. A liquid crystal alignment agent for a liquid crystal alignment film. 201035037 Another object of the present invention is to provide a method of forming a liquid crystal alignment film from the above liquid crystal alignment agent. Still another object of the present invention is to provide a method of manufacturing a liquid crystal display element excellent in electrical properties and long-term reliability. Other advantages and objects of the invention are as follows. Means to solve the problem

C ❹ In accordance with the present invention, the above objects and advantages of the present invention are attained by a liquid crystal alignment agent comprising a radiation-sensitive polyorganosiloxane having a structure represented by the following formula (1). 'C=C' (1) The liquid crystal alignment agent can be suitably used for forming a liquid crystal alignment film of a liquid crystal display device having a known structure such as a ΤΝ type, an STN type, an IPS type or a VA type, by a photo-alignment method having a small exposure amount. It can also be used to manufacture new liquid crystal display elements that solve the problem of MVA panels. Therefore, the above objects and advantages of the present invention are achieved by a method of forming a coating film by irradiating the liquid crystal alignment agent with a coating film to irradiate the coating film to form a liquid crystal alignment film, and the third is by manufacturing a liquid crystal display element. According to the method, the method comprises the steps of: applying a coating film to the liquid crystal alignment agent on the conductive film of the pair of substrates having a conductive film, and forming the coating film on the pair of substrates on which the coating film is formed. When the liquid crystal molecular layer is opposed to each other, the liquid crystal cell 'forming the alignment structure is applied with a voltage of 201035037 between the conductive films of the pair of substrates, and the liquid crystal cell is irradiated with light in this state. According to the present invention, there is provided a liquid crystal alignment agent which can provide a pretilt angle by a photo-alignment method having a small amount of exposure, and which provides a liquid crystal alignment film which is excellent in stability with respect to time due to imparting a pretilt angle. 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 long-term reliability, and is therefore suitable for use in various display devices. Further, the liquid crystal display element manufactured by the above-described method for producing a liquid crystal display element of the present invention has a wide viewing angle, a high response speed of liquid crystal molecules, exhibits good electrical properties, and sufficient transmittance and contrast 'excellent display property, and even long The time is continuously driven without damaging the display properties. Further, according to the method of the present invention, since the amount of necessary light for irradiation is small, it contributes to the reduction of the manufacturing cost of the liquid crystal alignment film and the liquid crystal display element. [Embodiment] The liquid crystal alignment agent of the present invention contains a radiation-sensitive polyorganosiloxane having a structure represented by the above formula (1). <Rain-sensitive linear polyorganosiloxane. The radiation-sensitive polyorganosiloxane contained in the liquid crystal alignment agent of the present invention has a structure represented by the above formula (1). The content of the structure represented by the above formula (1) in the radiation-sensitive polyorganooxime-10-201035037 alkane contained in the liquid crystal alignment agent of the present invention is preferably 0.2 to 6 mmol/g-polymer, more preferably It is 0.3~5m mol/g-polymer. The radiation-sensitive polyorganosiloxane contained in the liquid crystal alignment agent of the present invention preferably has an epoxy group in addition to the structure represented by the above formula (1). In this case, the epoxy equivalent of the radiation-sensitive polyorganosiloxane is preferably 150 g/mol or more, more preferably 200 to 10,000 g/mole, still more preferably 20 0 to 2,0 00 g. / Mo Er. By using such a ratio of epoxy equivalent radiation-sensitive polyorganosiloxane, the liquid crystal alignment agent of the present invention does not impair the storage stability of the liquid crystal alignment agent, and can form a pretilt angle because of excellent liquid crystal alignment. A liquid crystal alignment film excellent in stability over time is preferable. The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of the radiation-sensitive polyorganosiloxane containing the liquid crystal alignment agent of the present invention is preferably 500 to 1,000,000, more preferably 1, 〇〇〇~ 1〇〇,〇〇〇, especially good for 2,00〇~50,000. 〇 <Synthesis of a radiation-sensitive polyorganosiloxane. The radiation-sensitive polyorganosiloxane contained in the liquid crystal alignment agent of the present invention is not limited to the above, and can be synthesized by any method. The method for synthesizing the radiation-sensitive polyorganooxane contained in the liquid crystal alignment agent of the present invention may be, for example, a hydrolyzable decane compound having a structure represented by the above formula (1), or the hydrolyzable decane compound and others. A method of hydrolyzing and condensing a mixture of hydrolyzable decane compounds, (a) a polyorganosiloxane having an epoxy group (hereinafter, referred to as "a polyorganosiloxane having an epoxy group of -11 - 201035037" And (b) a compound having a structure represented by the above formula (1) and a compound having a carboxyl group or a compound having a group represented by the following formula (2) (hereinafter, referred to as "compound (b)"), etc. . - c = c - COOH (2) Among them, from the viewpoint of easiness of synthesis of the raw material compound, ease of reaction, and the like, it is preferably carried out by the latter method. ❸

Hereinafter, a preferred method for synthesizing a radiation-sensitive polyorganosiloxane containing a liquid crystal alignment agent of the present invention, that is, a polyorganosiloxane having an epoxy group (a) and a compound (b) The reaction method is explained. [Polyorganooxane (a) having an epoxy group] The epoxy group in the polyorganosiloxane having an epoxy group (a) is preferably an oxyethylene skeleton or a 1,2-epoxycycloalkane skeleton directly The alkylene group which may be interrupted by an oxygen atom in the middle, is contained in the polyorganooxane in such a manner as to be incorporated into a group of a halogen atom (a group having an epoxy group). The group having such an epoxy oxime is preferably a group represented by the following formula (X^1) or (X1-), for example.

(In the formula (XM) or (χΐ_2), the connection key is respectively indicated). The polyorganosiloxane (a) having an epoxy group preferably has an epoxy equivalent of 100 to 10,00 Å/mole, more preferably 150 to 1,0 0 g/mole, still more preferably -12. - 201035037 1 50~300g/mole. The polyorganosiloxane having an epoxy group (a) preferably has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of 5 〇〇 1 〇〇, 〇〇〇, more preferably 1, 〇 〇〇~1〇, 〇〇〇, especially good is 1, 〇〇〇~5, 〇〇〇. The polyorganosiloxane having such an epoxy group can be, for example, a decane compound having an epoxy group or a mixture of a decane compound having an epoxy group and another decane compound, preferably in a suitable organic solvent, water and a catalyst. In the presence of hydrolysis, condensation synthesis. The oxime compound having an epoxy group as described above may, for example, be 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane or 3-glycidoxypropyl. Methyldimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyldimethylmethoxydecane, 3-glycidoxypropyldimethyl Ethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, and the like. 〇 As the above other decane compound, for example, tetrachloroguanidine, tetramethoxy sand, tetraethoxy sand, tetra-n-propoxy sand, tetraisopropoxy decane, tetra-n-butoxy Decane, tetra-second butoxy decane, trichlorodecane, trimethoxy decane, triethoxy decane, tri-n-propoxy decane, triisopropoxy decane 'tri-n-butoxy decane, three second butyl Oxy decane, fluorotrichloro decane, fluorotrimethoxy decane, fluorotriethoxy decane, fluorodi-n-propoxy group, fluorotriisopropoxy group, gas, tri-n-butyl Oxygen sand institute, fluorinated di-butoxylate sand, methyl trichloropurine, methyl-13· 201035037 trimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane , methyl triisopropoxy decane, methyl tri-n-butoxy decane, methyl tri-tert-butoxy decane, 2-(trifluoromethyl)ethyl trichlorodecane, 2-(trifluoromethyl Ethyltrimethoxydecane, 2-(trifluoromethyl)ethyltriethoxydecane, 2-(trifluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl)B Base three Isopropoxydecane, 2-(trifluoromethyl)ethyltri-n-butoxydecane, 2-(trifluoromethyl)ethyltri-t-butoxydecane, 2-(perfluoro-n-hexyl) Trichlorodecane, 2-(perfluoro-n-hexyl)ethyltrimethoxydecane, 2-(perfluoro-n-hexyl)ethyltridecylethoxydecane, 2-(perfluoro-n-hexyl)ethyltri-n-propyl Oxaloxane, 2-(perfluoro-n-hexyl)ethyltriisopropoxydecane, 2-(perfluoro-n-hexyl)ethyltri-n-butoxyoxane, 2-(perfluoro-n-hexyl)ethyltride Dibutoxydecane, 2-(perfluoro-n-octyl)ethyltrichlorodecane, 2-(perfluoro-n-octyl)ethyltrimethoxydecane, 2-(perfluoro-n-octyl)ethyltriethyl Oxydecane, 2-(perfluoro-n-octyl)ethyltri-n-propoxydecane, 2-(perfluoro-n-octyl)ethyltriisopropoxydecane, 2-(perfluoro-n-octyl) Tri-n-butoxy decane, 2-(perfluoro-n-octyl)ethyltri-t-butoxydecane, hydroxymethyltrichlorodecane, hydroxymethyltrimethoxydecane, hydroxyethyltrimethoxydecane , hydroxymethyl tri-n-propoxy decane, hydroxymethyl triisopropoxy decane, hydroxyl Methyl tri-n-butoxy decane, hydroxymethyl three-butoxy decane, 3-(methyl) propylene methoxy propyl trichloro decane, 3-(methyl) propylene methoxy propyl trimethoxy Base decane, 3-(meth) propylene methoxy propyl triethoxy decane, 3 · (meth) propylene methoxy propyl tri-n-propoxy decane, 3-(methyl) propylene decyloxy Propyl triisopropoxy decane, 3-(methyl) propylene methoxy propyl tri-n-butoxy decane, -14- 201035037 3-(methyl) propylene methoxy propyl tri-tert-butoxy Decane, 3-mercaptopropyltrichlorodecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropyltri-n-propoxydecane, 3- Mercaptopropyl triisopropoxy decane, 3-mercaptopropyltri-n-butoxy decane, 3-mercaptopropyltri-tert-butoxybutane, decylmethyltrimethoxydecane, fluorenyl Triethoxy decane, vinyl trichloro decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tri-n-propoxy decane, vinyl triisopropoxy decane, vinyl three N-butoxy decane, vinyl Second butoxy decane, decyl propyl trichloro decane, allyl trimethoxy decane, allyl triethoxy decane, allyl tri-n-propoxy decane, allyl triisopropoxy Decane, allyl tri-n-butoxy decane, allyl tri-tert-butoxy decane, phenyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl tri-n-propoxy Base decane, phenyl triisopropoxy decane, phenyl tri-n-butoxy decane, phenyl tri-tert-butoxy decane, methyl dichloro decane, methyl dimethoxy decane, methyl diethoxy Base decane, methyl di-n-propoxy decane, formyl diisopropoxy decane, methyl di-n-butoxy decane, methyl di-butoxy decane, dimethyl dichloro decane, dimethyl Dimethoxy decane, dimethyl diethoxy decane, dimethyl di-n-propoxy decane, dimethyl diisopropoxy decane, dimethyl di-n-butoxy decane, dimethyl di Second butoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]dichlorodecane, (methyl)[2-(perfluoro-n-octyl)ethyl]dimethoxydecane , Methyl)[2-(perfluoro-n-octyl)ethyl]diethoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-propoxyfluorene-15- 201035037 , (methyl) [2-(perfluoro-n-octyl)ethyl]diisopropoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-butoxydecane, ( Methyl)[2_(perfluoro-n-octyl)ethyl]di-t-butoxydecane, (methyl)(3-mercaptopropyl)dichlorodecane, (methyl)(3-mercaptopropyl) Dimethoxy decane, (methyl) (3-mercaptopropyl) diethoxy decane, (methyl) (3-mercaptopropyl) di-n-propoxy decane, (methyl) (3) -mercaptopropyl)diisopropoxydecane, (methyl)(3-mercaptopropyl)di-n-butoxydecane, (methyl)(3-mercaptopropyl)di-butoxybutane , (methyl) (vinyl) dichlorodecane, (methyl) (vinyl) dimethoxy decane, decyl (methyl) (vinyl) diethoxy decane, (methyl) (vinyl) Di-n-propoxy decane, (methyl) (vinyl) diisopropoxy decane, (methyl) (vinyl) two Butoxy decane, (methyl) (vinyl) di-butoxy decane, divinyl dichloro decane, divinyl dimethoxy decane, divinyl diethoxy decane, divinyl bis N-propoxy decane, divinyl diisopropoxy decane, divinyl di-n-butoxy decane, divinyl bis second butoxy decane, diphenyl dichloro decane, diphenyl dimethoxy Base decane, diphenyldiethylene methoxy decane, diphenyl di-n-propoxy decane, diphenyl diisopropoxy decane, diphenyl di-n-butoxy decane, diphenyl bis second Oxy decane, chlorodimethyl decane, methoxy dimethyl decane, ethoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, trimethyl decane iodide, methoxy Trimethyl decane, ethoxy trimethyl decane, n-propoxy trimethyl decane, isopropoxy trimethyl decane, n-butoxy trimethyl decane, second butoxy trimethyl decane , second butoxy trimethyl decane, (chloro) (vinyl) dimethyl decane, (methoxy) (vinyl) dimethyl decane, Ethoxy)(B-16 - 201035037 alkenyl) dimethyl decane, (chloro)(methyl)diphenyl decane, (methoxy)(methyl)diphenyl decane, (ethoxy) a decane compound having one ruthenium atom such as (methyl)diphenyl decane, and may be exemplified by a commercial name such as KC-89, KC-89S, X-21-3153, X-21-584, and X-21-. 5842, X-21-5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22- 1 60 AS, X-22- 1 70B, X-22- 1 70BX, X-22 - 1 70D, X-22- 1 70DX, X-22- 1 76B, X-22- 1 76D, X-22 - 1 7 6DX, 〇X-22 - 1 76F , X-40-23 0 8 , X-40-2 6 5 1 , X-40 -26 5 5A , X-40-267 Bu X-40-2672, X-40-9220, X-40 -9225, X-40-9227, X-40-9246' X-40-9247' X-40-9250' X-40-9323' X-41-1053 ' X-41-1056 , X-41-1805 , X-41-1810 , KF6001 , KF6002 , KF6003 , KR2 1 2 , KR-2 1 3 , KR-2 1 7 , KR220L , KR242A , KR27 卜 KR282 , KR300 , KR31 卜 KR401N , KR500 ' KR510 ' KR5 20 6 , KR5 2 3 0, KR5 2 3 5, KR9218, KR9706 (above, Shin-Etsu Q Chemical Industry) ) Manufacturing); Glass Resin (manufactured by Showa Denko); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406 > SR2410, SR2411, SR2416, SR2420 (above > Dow Corning Toray) ); FZ3711, FZ3 722 (above, manufactured by Sakamoto 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-03 32, PDS-1615, PDS-993 1 , XMS-5025 (above, -17- 201035037

Chisso (manufactured by Chisso); methyl decanoate MS51, methyl decanoate MS56 (above 'Mitsubishi Chemical Co., Ltd.); ethyl citrate 28, ethyl citrate 40, ethyl citrate 48 (above, Colcoat (manufactured by the company); part of the condensate such as GR100, GR6 5 0, GR90 8, GR9 5 0 (above, manufactured by Showa Denko). Among these other decane compounds, preferred are tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, 3-(methyl) propylene methoxy propyl trimethoxy. Baseline, 3-(meth)acryloxypropyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, allyltrimethoxydecane,allyltriethyl Oxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, mercaptomethyltrimethoxydecane , mercaptomethyltriethoxydecane, dimethyldimethoxydecane or dimethyldiethoxydecane. In the synthesis of the polyorganosiloxane (a) having an epoxy group of the present invention, it is preferred to formulate a Q ratio of a decane compound having an epoxy group and other decane compounds so that the obtained polyorganosiloxane can be used. The epoxy equivalent of the above is the above preferred range. The organic solvent used in the synthesis of the polyorganosiloxane (a) having an epoxy group may, for example, be a hydrocarbon, a ketone, an ester, an ether or an alcohol. Examples of the hydrocarbon include toluene and xylene; and examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, cyclohexanone, and the like; Examples of the ester include ethyl acetate, n-butyl acetate, -18-201035037 isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, and the like; Examples of the ethers include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, and dioxane. Examples of the alcohol include 1-hexanol and 4-methyl-2-pentane. Alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol single N-propyl ether and the like. Among them, those which are not water-soluble are preferred. These organic solvents may be used alone or in combination of two or more. The organic solvent is preferably used in an amount of from 1 Torr to 10% by weight based on 1 part by weight of the total of the sand compound, more preferably from 5 Å to 1 Å. When the polyorganosiloxane (a) having an epoxy group is produced, the amount of water is preferably from 5% to 10,000 moles, more preferably from 1 to 30 moles per mole of the total decane compound. As the above catalyst, for example, an acid, an alkali metal compound, an organic base, a titanium compound, a pin compound or the like can be used. Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide. The organic base may, for example, be a 1 to 2 organic amine such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine or pyrrole; such as triethylamine, tri-n-propylamine or tri-n-butyl A tertiary amine such as a sulfonamide, a sulphate, a 4-dimethylamino group B, a quinone, or a diazacycloundecene; a 4-grade organic amine such as tetramethylammonium hydroxide; Among these organic bases, preferred are tertiary organic amines such as triethylamine, tri-19-201035037 n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine; A grade 4 organic amine such as methylammonium. The catalyst is preferably an alkali metal compound or an organic base when the polyorganoles (a) having an epoxy group is produced. 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 desired polyorganosiloxane (a) can be obtained at a high hydrolysis rate and a condensation rate, so that the production stability is excellent. It is better. In addition, the liquid crystal alignment agent of the present invention containing a reaction product of an epoxy group-containing polyorganoles and a compound (b) synthesized using an alkali metal compound or an organic tester is extremely excellent in storage stability, so it is suitable. of. The reason is that, as indicated in Non-Patent Document 1 (Chemical Reviews > Vol. 95, P1409 (1995)), in the hydrolysis or condensation reaction, if an alkali metal compound or an organic base is used as a catalyst, it is presumed that it is formed. A random structure, a ladder structure or a basket structure cannot obtain a polyorganosiloxane having a small content of a stanol group. That is, since the content Q of the decyl alcohol group of the polyorganosiloxane is small, the present invention contains the radiation-sensitive polyorganosiloxane obtained from the polyorganosiloxane (a) having an epoxy group. In the liquid crystal alignment agent of the invention, it is presumed that the liquid crystal alignment agent of the present invention can suppress the radiation sensitivity when it contains other polymers to be described later. The condensation reaction of the decyl alcohol group of the polyorganosiloxane and other polymers is excellent in storage stability. Particularly preferred as the catalyst is an organic base. The amount of the organic base to be used varies depending on the kind of the organic base, the reaction conditions, and the like, and should be appropriately set. For example, the phase -20-201035037 is preferably 0.01 to 3 times moles, more preferably 005 M times, for all the decane compounds. ear. The hydrolysis and condensation reaction in the production of the polyorganic cermetsite (a) having an epoxy group preferably dissolves the decane compound having an epoxy group and other decane compounds as needed in an organic solvent, 'the solution and the organic base and The water is mixed, for example, by heating in an oil bath or the like. In the hydrolysis and condensation reaction, the heating temperature is preferably 130 ° C or less, more preferably 4 0 to 1 0 0 ° C. Preferably, the heating is 0 · 5 to 1 2 hours, more preferably 1 to 8 hours. . When heating, the mixture may be stirred or may be refluxed. After the completion of the reaction, the organic solvent layer separated from the reaction liquid is preferably washed with water. This washing is carried out by using water containing a small amount of salt, for example, 〇. 2 by weight. /. Washing with an aqueous solution of ammonium nitrate or the like is preferable in that the washing operation is easy. The washing is preferably carried out until the aqueous layer after washing is neutral. Thereafter, the organic solvent layer is dried with an anhydrous calcium sulfate, a molecular sieve or the like as needed, and then the solvent is removed to obtain a desired polyorganooxy group having an epoxy group. Alkane G (4). In the present invention, a polyorganosiloxane having an epoxy group can be used by a commercially available person. Examples of such a commercially available product include DM S-E01, DMS-E12, DMS-E21, and EMS-32 (above, Chisso). <Compound (b)> The compound (b) used in the present invention is a compound having a structure represented by the above formula (1) and a carboxyl group or a compound having a group represented by the above formula (2). When the compound (b) is a compound having a structure represented by the above formula (1) and a carboxyl group -21 - 201035037, the carboxyl group which the compound (b) has may have a structure represented by the above formula (1) on either side. The compound (b) used in the present invention is preferably a compound represented by the following formula (3) or (4).

(R1 in the formula (3) is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms or a carbon atom having an alicyclic group of 3 to 4; The monovalent organic group 'R2 of hydrazine is a single bond, an oxygen atom, a sulfur atom, *_c〇〇_, *-COS-, *-SCO- or *_oc〇- (wherein, in the above, the linkage The bond is bonded to R1) 'R3 is a divalent aromatic group, a divalent alicyclic group, a fluorene bivalent heterocyclic group or a divalent fused ring group, or a structure having a heterocyclic ring and an aromatic ring condensed structure 2 A valence group or a divalent group 'R4 having a structure in which a heterocyclic ring and an alicyclic ring are condensed are a single bond, an oxygen atom, a sulfur atom, *_c〇〇_, *_c〇s_, *_sc〇_ or *_〇C 〇 _ (where 'in the above, with "*,, the connection key and R3 connection" 'R5 is an oxygen atom or a cyano group, a is an integer of 〇~3, b is an integer of 〇~4, formula (4 R6 is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms or a carbon atom having an alicyclic group of -22 to 201035037 3 to 40. The monovalent organic group 'R7 is an oxygen atom or a divalent aromatic group, and R8 is an oxygen atom, -COO-* or - OCO -* (wherein, above, the linkage and R9 linkage) R9 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group. Or a divalent group having a structure in which a heterocyclic ring and an aromatic ring are condensed or a divalent group having a structure in which a heterocyclic ring and an alicyclic ring are condensed, R10 is a single bond, -〇CO-(CH2)e-* or -〇_ (CH2)f-* (wherein 'in the above, a linkage and a carboxyl linkage", wherein e and f 0 are each an integer of 1 to 10, R11 is a fluorine atom or a cyano group, and c is 0 to 3 In the integer of the formula (3), R1 has an alkyl group having 1 to 40 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, and more preferably has a carbon number of 4 to 20 alkyl groups. Examples of such a preferred alkyl group include, for example, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-decyl group, n-lauric group, and Dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n- 〇alkyl, etc. As a R1, the number of carbon atoms in the range of 1 to 40 A fluoroalkyl group having 1 to 20 carbon atoms, more preferably a fluoroalkyl group having 4 to 20 carbon atoms. As an example of such a preferred fluoroalkyl group, for example, 4 ,4,4-trifluorobutyl, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluorohexyl, 3,3,4,4 ,5,5,5-heptafluoropentyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 2 -(Perfluorooctyl)ethyl, 2-(perfluorodecyl)ethyl and the like. -23- 201035037 The monovalent organic group having 3 to 40 carbon atoms of the alicyclic group containing R1 may, for example, be a cholesteryl group, a cholesteryl group, an adamantyl group or the like. Is a single bond, an oxygen atom or *-COO- (wherein, with a "linkage and R1 linkage"; as R4 is preferably a single bond, an oxygen atom or *-COO- (wherein with a "link" and R3 connection). The divalent aromatic group of R3 may, for example, be 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2, 3,5,6-tetrafluoro-1,4-phenylene; etc.; as the divalent alicyclic group of R3, for example, 1,4-cyclohexylene or the like; and a divalent heterocyclic group of R3, For example, a 1,4-extended pyridyl group, a 2,5-extended pyridyl group, a 1,4-extended furyl group, a group represented by the following formula, and the like can be given.

(In the above formula, the linking bond is bonded to R4); the divalent fused ring group ' as R3' may, for example, be a naphthyl group or the like; a divalent group having a structure in which a hetero ring and an aromatic ring are condensed as R3. For example, a group represented by the following formula, etc., Ο

-24- 0 201035037 (The linkage bond carried in the above formula is a heterocyclic ring and an alicyclic ring of R3, and a group such as a group represented by the following formula is given] (in the above formula, a linkage bond is provided) (a) is preferably 0 or 1; b is a compound represented by the above formula (3), for example, the following formulas (3 - 1) to (3 - 1 9 ) respectively represent an I R4 linkage; Structure of the divalent group 'can

]R4 connection). Η圭 is 0. More specific examples, compounds that can be listed, etc.

-25- 201035037 R1· C III C—C〇OH (3-1) R1—0-

C=C—COOH (3-2)

R1-COO

C III C—COOH (3-3) Ο Μ Ι -C=C—COOH (3-4) R1—〇- —\ C=C—COOH (3-5) R1-CO〇- C=C—COOH (3-6)

-26- 201035037 R1- \ -coo- C=C—COOH (3-7) R1—O—— \ •c〇o- -c III C—COOH (3-8) R1-C〇0

•coo-

C=C—COOH (3-9) O R1- -coo

C III C—COOH (3-10) R1—0- -c〇o-

C=C—COOH (3-11)

R1-COO

-coo- -C III C-COOH (3-12) ❹ R1-

C III C—COOH (3-13) R1—0-

C=C—COOH (3-14) R1-C00- C=C—COOH (3-15) -27- 201035037

(3-17) (3-18)

Ο ❹ (In the above formula, ' Rl is the same as defined in the above formula (3)). The compound represented by the above formula (3) can be synthesized by a usual method in which organic chemistry is appropriately combined. For example, the compound represented by the above formula (3 _2) can be chlorinated on a palladium catalyst by a halogenated aryl compound having a desired group R1 and a propiolic acid as shown in Fig. 1 of the following synthetic route. The reaction is carried out by reacting cuprous with an amine compound. -28- 201035037 R1—Ο

X

+ CH III C - COOH amine Pd catalyst Cul R1-0

—C=C—COOH O Synthetic line Fig. 1 (In the above formula, R1 is the same as defined in the above formula (3), and X is a tooth atom). This reaction is referred to by those skilled in the art as "bacterial coupling". The alkyl group having 1 to 40 carbon atoms of R6 in the above formula (4), a fluoroalkyl group having 1 to 40 carbon atoms, and 1 valent carbon atom having an alicyclic group of 3 to 40 The organic groups are the same as defined in R1 in the above formula (3), respectively. R7 is preferably a single bond; ❹c is preferably 0; R1G is preferably -OCO-(CH2)e-* (wherein e is an integer of 1 to 10, with a linkage and a carboxyl linkage). A more specific example of the compound represented by the above formula (4), for example, a compound represented by the following formula (4-1). R6—Ο—C—C III C II 〇

=y^0C0—(CH2-)—COOH (4-1) -29- 201035037 (In the above formula, 'R6 is the same as defined in the above formula (4), and e is an integer of 1 to 10). The e is preferably 2 or 3. The compound represented by the above formula (4) can be synthesized by a conventional method in which organic chemistry is appropriately combined. For example, in the above formula (4-1), a compound in which e is 2 or 3 is first synthesized by ring-opening addition of succinic anhydride to 4-bromophenol (e=2) or glutaric anhydride (e=3). The intermediate can be obtained by coupling a propionate having a desired group R6 to its head. ❹ [Synthesis of Radiation-Tensible Polyorganosiloxane] The radiation-sensitive polyorganosiloxane used in the present invention is preferably an epoxy group-containing polyorganooxane (a) and a compound (b). The reaction is synthesized in the presence of a catalyst. The compound (b) herein is preferably used in an amount of from 0.001 to 10 moles, more preferably from 0.01 to 5 moles, more preferably from 0.01 to 5 moles per mole of the epoxy group of the 1 molar polyorganosiloxane. Moor. In the present invention, a part of the compound (b) may be used instead of the compound represented by the following formula (5) insofar as the effects of the present invention are not impaired. R12-R13-COOH (5) In the formula (5), R12 is an alkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, and a fluorinated carbon having 4 to 20 carbon atoms. An alkyl group or a fluoroalkoxy group having 4 to 20 carbon atoms or a monovalent organic group having an alicyclic group having 3 to 40 carbon atoms, and R13 is a single bond or a phenyl group, wherein R12 is In the case of an alkoxy group, R 13 is a phenyl group. -30- 201035037 In this case, the radiation-sensitive polyorganosiloxane may be obtained by reacting a polyorganosiloxane (a) having an epoxy group, a compound (1), and a compound represented by the above formula (5). The mixture is reacted to synthesize. R12 in the above formula (5) is preferably an alkyl group having a carbon number of 8 to 20 or an electrophilic group or a fluorinated or fluorinated alkoxy group having 4 to 21 carbon atoms as R13. It is preferably a single bond, 1,4-cyclohexylene or 1,4-phenylene. A preferred example of the compound represented by the above formula (5) is a compound represented by any one of the following formulae (5-1) to (5 to 4), and ChF2h+ "CiH2" COOH (5-1)

COOH (5-4)

(In the above formula, h is an integer of 1 to 3, i is an integer of 3 to 18,] is an integer of 5 to 2 ,, k is an integer of 1 to 3, m is an integer of 〇~18, and η is 1~ An integer of 18), wherein a compound represented by any one of the following formulae (5-3-1) to (5-3-3) is preferred. -31- 201035037

CF3 C3H6—ο

COOH (5-3-2 ) C2F5—C3H6—Ο—^ y—COOH (5-3-3 )

The compound represented by the above formula (5) is a compound which reacts with the above-mentioned compound (b) by reacting a polyorganosiloxane having an epoxy group with the above compound (b), and is a site which imparts a pretilt angle developability to the obtained liquid crystal alignment film. In the present specification, the compound represented by the above formula (5) is hereinafter referred to as "other pretilt appearance compound". In the present invention, 'when the above compound (b) is used together with other pretilt-developing compounds, 'total ratio of use of compound (b) and other pretilt-developing compounds' is relative to 1 mol of polyorgano having an epoxy group. The epoxy group (a) has an epoxy group, preferably from 0.001 to 1.5 moles, more preferably from 0.01 to 1 moles, still more preferably from 0.05 to 0.9 moles. In this case, the other pretilt angle developing Ο compound is preferably used in a range of 50 mol% or less, more preferably 25 mol% or less, based on the total amount of the compound (b). If the ratio of use of other pretilt-developing compounds exceeds 50% by mole, the liquid crystal display element is expressed as 〇N, which may cause an abnormal region to occur. As the above catalyst, an organic base or a compound known as a so-called hardening accelerator for promoting the reaction between an epoxy compound and an acid anhydride can be used. As the above organic test, for example, a 1 to 2 organic amine such as ethylamine, diethylamine, -32-201035037 pipe trap, piperidine, pyrrolidine or pyrrole; like triethylamine or tri-n-propylamine a tertiary organic amine such as tri-n-butylamine, pyridine, 4-dimethylaminopyridine or diazetidine; a 4-grade organic amine such as tetramethylammonium hydroxide. Among these organic bases, 'preferably a tertiary organic amine such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine or 4-dimethylaminopyridine; such as tetramethylammonium hydroxide Grade 4 organic amine. The hardening accelerator may, for example, be a tertiary amine such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol or cyclohexyldimethylamine 'triethanolamine. ; like 2-methylimidazole, 2-n-heptyl imidazole, 2-n-indole-alkylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methyl Imidazole, i-(2-cyanoethyl)-2-n-indole-alkylimidazole, 1-(2-cyanoethyl)_2-phenylimidazole, 1-(2-cyanoethyl)- 2-ethylindole-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-(2 -cyanoethyl)-2-phenyl-4,5-bis[(2,-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecane Imidazolium benzoate, 1-(2-cyanoethyl)_2-phenylimidazolium phthalate, 1-(2-cyanoethyl)-2-ethyl-4-methyl Imidazolium phthalate, 2,4-diamino-6-[2'-methylimidazolyl-(1,)]ethyl-s_three tillage, 2,4- Diamino-6-(2,-n-undecylimidazolyl)ethyl-s-triazine, 2,4-diamino-6-[2,-ethyl-4'-methylimidazolyl- (1')]ethyl-s-tripper, isocyanuric acid addition of 2-methylimidazole-33-201035037, isocyanuric acid addition of 2-phenylimidazole, 2,4-diamine - an imidazole compound such as 6-[2,-methylimidazolyl-(1')]ethyl-s-three-pilled isocyanuric acid adduct; like diphenylphosphine, triphenylphosphine, phosphorous acid An organophosphorus compound such as phenyl ester; such as benzyltriphenyl chlorinated chloride, tetra-n-butyl bromide, brominated methyltriphenyl rust, ethyltriphenyl bromide, n-butyl bromide Triphenyl scale, tetraphenyl bromide, ethyl triphenyl iron iodide, ethyl triphenyl phenol acetate, tetra-n-butyl fluorene, bismuth-diethylphosphonium dithiosulfate, a 4-grade iron salt such as tetra-n-butyl benzobenzotriazole salt, tetra-n-butyl iron tetrafluoroborate, tetra-n-butyl rust tetraphenyl borate, tetraphenyl quaternary tetraphenyl borate; a diazobicycloalkene such as 1,8-diazobicyclo[5.4.0]undecene-7 and its organic acid salt; like zinc octoate, octyl Organometallic compound such as tin, acetonitrile, aluminium complex; 4 grades such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride An ammonium salt; a boron compound such as boron trifluoride or triphenyl borate; a metal halide such as zinc chloride or tin chloride; an addition product of dicyanodiamine and an amine and an epoxy resin, etc. a high-melting point-dispersion latent hardening accelerator such as an amine addition accelerator; a microcapsule-type latent accelerator which is formed by coating a surface of a hardening accelerator such as an imidazole compound, an organophosphorus compound, or a quaternary phosphonium salt Amine salt type latent hardening accelerator; -34- 201035037 A latent hardening accelerator such as a pyrolysis type thermal cationic polymerization type latent hardening accelerator such as a Lewis acid or a Bronsted acid salt. Among them, a 4-grade ammonium salt such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride or tetra-n-butylammonium chloride is preferred. The catalyst is preferably used in an amount of preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight, per 100 parts by weight of the polyorganooxane U) having an epoxy group. The reaction temperature is preferably from 0 to 200 ° C, more preferably from 50 to 15 (TC. The reaction time is preferably from 0.1 to 50 hours, more preferably from 0.5 to 20 hours. The radiation-sensitive polyorganosiloxane The synthesis reaction of the alkane can be carried out in the presence of an organic solvent, if necessary. Examples of the organic solvent include a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, a guanamine compound, an alcohol compound, etc. Among them, an ether compound The ester compound and the ketone compound are preferred from the viewpoints of the solubility of the raw material and the product and the ease of purification of the product. The solvent is a solid component concentration (the ratio of the weight of the component other than the solvent in the reaction solution to the total weight of the solution). It is preferably used in an amount of more than 5% by weight, more preferably from 5 to 5% by weight. The radiation-sensitive polyorganosiloxane of the present invention is subjected to ring-opening addition of an epoxy group to an epoxy group. The polyorganosiloxane (a) introduces a structure derived from the compound (b). The production method is simple, and the introduction rate of the structure derived from the compound (b) can be improved, which is an extremely suitable method in this respect. Other components> -35- 201035037 The liquid crystal alignment agent of the present invention contains the above-mentioned radiation-sensitive polyorganosiloxane. The liquid crystal alignment agent of the present invention does not impair the present invention except for the above-mentioned radiation-sensitive polyorganosiloxane. The effect of the invention 'may also contain other components. Examples of such other components include polymers other than radiation-sensitive polyorganosiloxane (hereinafter referred to as "other polymers"), hardeners, and hardening catalysts. a curing accelerator, a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound"), a functional decane compound, a surfactant, etc. [Other polymers] The above other polymers can be used for further The solution properties of the liquid crystal alignment agent of the present invention and the electrical properties of the obtained liquid crystal alignment film are improved. The other polymer may, for example, be at least one selected from the group consisting of polylysine and polyamicimide. a polymer, a polyorganosiloxane such as the above-mentioned radiation-sensitive polyorganosiloxane (hereinafter referred to as "other polyorganisms" , polyglycolate, polyester, polyamine, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimine) derivative, poly(methyl Acrylate, etc. {Polyproline} The above polylysine can be obtained by reacting tetradecanoic dianhydride with a diamine compound. As a tetracarboxylic dianhydride which can be used for the synthesis of polyglycine, it can be exemplified For example, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, butane tetracarboxylic dianhydride, -36-201035037 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride , 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl) -naphtho[1,2-c]-furan-1,3-dione, 1,3,3&,4,5,9-hexahydro-5-(tetrahydro-2,5-dioxo- 3-furyl)-8-methyl-naphtho[l,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3 -cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, the following formula (T-1)~ Tetracarboxylic dianhydride square aliphatic T-14) represent a tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride;

-37- 201035037

(T-l) (T-2)

(Τ-3) OCF,

(Τ-4)

(Τ-9) (Τ-5)

(Τ-10) (Τ-11) (Τ-12) (Τ-8) (Τ-6) (Τ-13)

Pyromellitic dianhydride, 3,3',4,4'-biphenyl fluorene tetracarboxylic dianhydride naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ',4,4' ' 1,4,5,8- -biphenyl ether-38- 201035037 tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic acid Dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-di(3,4-di Carboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyl Phenoxy)diphenylpropanehydride, 3,3',4,4'-perfluoroisopropylidenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid Anhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, meta-phenyl- bis(triphenylphthalic acid) Dihydride, bis(triphenylphthalic acid)-4,4'-fluorene diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, An aromatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride represented by the following formulas (T-15) to (T-18). 〇 -39- 201035037

-40- 201035037 Among them, as a preferred tetracarboxylic dianhydride, 1,3,3&,4,5,91?-hexahydro-5-(tetrahydro-2,5-dioxo) 3--3-furyl)-naphtho[l,2-c]-furan-1,3-dione, 1,3,33,4,5,91)-hexahydro-5-(tetrahydro-2 ,5-dioxo-3-furanyl)-8-methyl-naphtho[l,2-c]-furan-1,3-dione, 2,3,5-tricarboxycyclopentyl acetic acid Anhydride, butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, Pyromellitic dianhydride, 3,3',4,4'-biphenyl maple tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene Carboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic acid dicarboxylic anhydride and the above formulas (Tl), (T-2) and (T-15) to (T-18) respectively The tetracarboxylic dianhydride represented. These tetracarboxylic dianhydrides can be used individually or in combination of 2 or more types. As the diamine which can be used for the synthesis of poly-proline, for example, p-phenylenediamine, meta-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-di Aminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl maple, 3,3'-dimethyl-4,4'-di Aminobiphenyl, 4,4'-di-Q-aminobenzidine, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3-dimethyl- 4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4 amine Phenyl)-1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 2,2-bis(4-aminophenoxy)propane, 2,2- Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-di(4) _Aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1 ,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, -41 - 201035037

9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7, aminoguanidine, 9 9-base benzene, 4,4,-methylene-bis(2-chlorophenylamine卜,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, , 4, amino- 5,5 (4, amine, tetrachloromethylaminobiphenyl, 4 4, phenyl isopropylidene) diphenylamine, 4,4,-(inter)phenyl isopropylidene , di-p-amine, 2,2-bis[4-(4-amino-2-trifluoromethylphenyloxy)phenyl]hexyl diphenyl, 4,4,-diamino-2,2 '-Bis(trimethylene)biphenyl, ^propanyl bis[(4-yl-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, @aminobenzene), 6_ (4,6-(4-Chalconesyloxy)hexyloxy (2,4-fluoroindolceptone-4-chalconeoxy)hexyloxy (2,4-diamino) Benzene), 8_(4_

Octyloxy (2,4-diaminobenzene), 8-(4'-fluoro-4-chalcethoxyoxy (2,4-diaminobenzene), 1-12 Alkyloxy·2,4·diaminobenzene 1 tetraalkyloxy-2,4-diaminobenzene, 1-pentadecyloxy-2,4-diaminobenzene, 1-ten Hexaalkyloxy-2,4-diaminobenzene, ;- octadecyloxy 2,4 · a 'fee basic, 1-cholesteryloxy-2,4-aminobenzene , 1-cholestene-based oxy-2,4-diaminobenzene, dodecyloxy (3,5-diaminobenzimidyl), tetradecyloxy (3,5-di Aminobenzylidene), pentadecyloxy (3,5-diaminobenzimidyl), hexadecyloxy (3,5-diaminobenzimidyl), 18 Alkyloxy (3,5-diaminobenzimidyl), cholesteryloxy (3,5-diaminobenzimidyl), cholesteryloxy (3,5-diamino) Benzomethane), (2,4-diaminophenoxy) palmitate, (2,4-diaminophenoxy)stearate, (2,4-diaminophenoxy) -4-trifluoromethylbenzoate, an aromatic diamine such as a diamine compound represented by the following formula (Dl) to (D-5); -42- 20103503 7

H2N

NH 2

Coo-^)-oco-^^ CF

(D-l)

(D-2)

(D-3) (1)-4)

An aromatic diamine having a hetero atom such as diaminotetraphenylthiophene; m-xylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6 -Hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-decanediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydro-extension Cyclopentadiene diamine, hexahydro-4,7-extension bridge decyl dimethylene diamine, tricyclo[6.2.1 ·02,7]undecene dimethyldiamine, 4,4 An aliphatic diamine such as '-methylene di(cyclohexylamine) or an alicyclic diamine; -43-201035037 A diamine-based organooxane such as an aminohexamethyldioxane. Among them, preferred diamines include p-phenylenediamine, 4,4 'diaminodiphenylmethane, anthracene, 5-diaminonaphthalene, and 2,7-diamino group.芴, 4,4'·diaminodiphenyl ether, 4,4′-(p-phenylene isopropylidene)diphenylamine, 2′2_[4·(4-aminophenoxy)benzene Hexafluoropropane, 2,2-bis(4-amine base)/, fluoropropane, 2,2_bis[4-(4-amino-2-trifluoromethylphenoxy)benzene Hexafluoropropane, 4,4,-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4,-0-[(4-amino-2-trifluoromethyl) Phenoxy]-octafluorobiphenyl, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1- Cholesteryloxy-2,4-diaminobenzene, 1-cholestyloxy-2,4-diaminobenzene, decyloxy (3,5-diaminobenzimidyl) , octadecyloxy (3,5-diamine basic methyl), cholesteryloxy (3,5-diaminobenzylidene), cholesteryloxy (3,5-diamine) A benzylidene group and a diamine represented by the above formula (D-1) to (D-5). The xa may be used alone or in combination of two or more. The use ratio of the tetracarboxylic dianhydride and the diamine compound used for the synthesis reaction of poly-proline is preferably 0.2 to 2 with respect to the amine group contained in 1 equivalent of the diamine compound. The ratio of the equivalent is more preferably a ratio of 〜.3 to 1.2 equivalents. The synthesis reaction of poly-proline is preferably carried out in an organic solvent, preferably at a temperature of -2 0 to 150 ° C, more preferably 〇 to i 〇〇 t, preferably for 05 to 24 hours. Better to carry out 2~1 〇 hours. In addition, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyaminic acid, and examples thereof include -44-201035037, for example, N-methyl-2-pyrrolidone and N,N-dimethyl group. Acetamide, N,N-dimethylformamide, N,N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethyl urea, hexamethylphosphoric acid triamide, etc. An aprotic polar solvent; a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol. The amount of the organic solvent (a) is the total amount (b) of the tetracarboxylic dianhydride and the diamine compound relative to the total amount of the reaction solution (a + b), preferably 0.1 to 50% by weight, more preferably 5 to 5. 30% by weight. As described above, a reaction solution in which polylysine is dissolved can be obtained. The ruthenium solution can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after separating the polyamic acid contained in the reaction solution, or after purifying the separated polyamic acid, For preparing a liquid crystal alignment agent. When polypyridic acid is dehydrated and closed to form polyimine, the above reaction solution can be directly used for dehydration ring closure reaction, or the polylysine contained in the reaction solution can be separated and used for dehydration ring closure reaction, or will be separated. After the polyamic acid is refined, it is used for the dehydration ring closure reaction. Q Separation of poly-proline can be carried out by injecting the above reaction solution into a large amount of a poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure; or removing the organic solvent in the reaction solution by vacuum evaporation The method is carried out. Alternatively, the polylysine may be redissolved in an organic solvent and then precipitated in a poor solvent; or the polylysine may be dissolved again in an organic solvent to form a solution, and the solution is washed. The polyamine acid was purified by distilling off under reduced pressure in an evaporator and performing the method one or more times. -45- 201035037 {Polyimide] The above polyimine can be produced by dehydrating and ring-closing a glycine structure of polylysine obtained as above. In this case, the proline structure can be completely dehydrated and closed, and the ruthenium can be completely imidized; or a part of the structure of the proline can be dehydrated and closed to form a partial quinone imine with a valerine structure and a quinone ring structure. Compound. The dehydration ring closure of polylysine can be carried out by adding a dehydrating agent and a dehydration ring-closing catalyst to the solution by transferring the poly-proline to an organic solvent by means of a method of heating the polyamic acid or (Π). And the reaction temperature in the method of heating the poly (protonic acid) of the above (i) is preferably 50 to 200 ° C. More preferably 60 to 170 ° C. The reaction temperature is less than 50 ° C. The dehydration ring-closure reaction cannot be sufficiently carried out; if the reaction temperature exceeds 200. (:, the molecular weight of the obtained polyimine may be lowered. The reaction time in the method of heating the poly-proline is preferably 0.5 to 48 hours. More preferably, it is 2 to 20 hours. In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the solution of the above (π) polyproline, as the dehydrating agent, for example, acetic anhydride, propionic anhydride, or the like may be used. An acid anhydride such as trifluoroacetic acid anhydride. The amount of the dehydrating agent is preferably 0.01 to 20 moles per mole of the structural unit of 1 mole of polyamic acid. Further, as the dehydration ring-closing catalyst, for example, pyridine or trimethyl group can be cited. Pyridine, dimethyl a quaternary amine such as pyridine or triethylamine. However, it is not limited thereto. The amount of the dehydration ring-closure catalyst is preferably 0.01 to 10 moles per 1 mole of the dehydrating agent used. The solvent is exemplified by the use of the organic solvent exemplified in the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 15 CTC. Preferably, it is 0.5 to 20 hours, more preferably 1 to 8 hours. The polyimine obtained in the above method (i) can be directly used for preparing a liquid crystal alignment agent, or the obtained polyimine can be purified and used. In the above method (ii), a reaction solution containing polyiminoimine can be obtained. The reaction solution can be directly used for preparing a liquid crystal alignment agent; and the dehydrating agent and the dehydration ring can be removed from the reaction solution. After the catalyst, the ruthenium is used for preparing the liquid crystal alignment agent; after the separation of the polyimine, it can be used to prepare a liquid crystal alignment agent; or after the separated polyimine is refined, it is used for preparing a liquid crystal alignment agent. The solution dehydrating agent and the dehydration ring-closure catalyst can be, for example, a method such as solvent replacement. Separation and purification of the polyimine can be carried out by the same operation as the separation and purification of the above polylysine. Other polyorganosiloxanes in the present invention are polyorganic sands other than the above-mentioned radiation-sensitive polyorganic sands. The other polyorganic sands can be selected, for example, from a hospital At least one decane compound (hereinafter also referred to as "raw material compound" in a group consisting of a compound and a halogenated compound is preferably hydrolyzed and condensed in the presence of water and a catalyst in a suitable organic solvent. As a raw material decane compound which can be used here, for example, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy group, tetra-47-201035037 isopropoxy decane, tetra-n-butyl Oxy decane, tetra-butoxy decane, tetra-butoxy decane, tetrachloro decane; methyl trimethoxy decane, methyl hydrazine ethoxy decane, methyl tri-n-propyl Base decane, methyl triisopropoxy decane, methyl tri-n-butoxy decane, methyl tri-tert-butoxy decane, methyl tri-tert-butoxy decane, methyl triphenyloxy decane, Trichlorodecane, ethyltrimethoxydecane, ethyltriethoxydecane, ethyltri-n-propoxydecane, ethyltriisopropoxydecane, ethyltri-n-butoxydecane, ethyltri Second _ butoxy decane, ethyl tri-tert-butoxy decane, ethyl trichloro decane, phenyl decyl decyl decane, phenyl triethoxy decane, phenyl trichloro decane; dimethyl Dimethoxy decane, dimethyl diethoxy decane, dimethyl dichloro decane; trimethyl methoxy decane, trimethyl ethoxy decane, trimethyl chloro decane, and the like. Among them, preferred examples of the decane compound include tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, and benzene. The triethoxy group is more than a Q alkane, dimethyl dimethoxy decane, dimethyl diethoxy decane, trimethyl methoxy decane and trimethyl ethoxy decane. The other polyorganosiloxane of the present invention can be synthesized in the same manner as the above-described synthesis method of the polyorganosiloxane (a) having an epoxy group, in addition to the above-mentioned raw material sane compound. For other polyorganosiloxanes, the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography is preferably from 100 to 100,000, more preferably from 500 to 20, 〇〇〇〇-48 to 201035037 {other polymers Ratio of use of the liquid crystal alignment agent of the present invention, when the radiation-sensitive polyorganosiloxane and the other polymer are contained, the content of the other polymer is preferably 100 parts by weight with respect to 100 parts by weight of the radiation-sensitive polyorganosiloxane. It is 10,000 parts by weight or less. The preferred content of other polymers varies depending on the type of other polymer. When the liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of a radiation-sensitive polyorganosiloxane and a polyphthalamide and a polyimine, the ratio of use of the two is better than that of 100 parts by weight of the radiation-sensitive polyorganosiloxane, poly-proline and polyimine are 100 to 5,000 parts by weight in total, and more preferably 200 to 2,000 parts by weight. On the other hand, when the liquid crystal alignment agent of the present invention contains a radiation-sensitive polyorganosiloxane and other polyorganosiloxanes, a ratio of use of the two is better than 100 parts by weight of the radiation-sensitive polyorganosiloxane. The amount of the other polyorganosiloxane is 100 to 2,000 parts by weight. The liquid crystal alignment agent of the present invention, when containing a radiation-sensitive polyorganosiloxane and other polymers, is preferably selected from the group consisting of poly-proline and polyimine. At least one polymer, or other polyorganosiloxane. [Hardifying Agent and Curing Catalyst] The above-mentioned curing agent and curing catalyst are contained in the liquid crystal alignment agent of the present invention for the purpose of making the crosslinking reaction of the radiation-sensitive polyorganosiloxane more robust. 'The above curing accelerator can be based on promoting hardening. The curing reaction undertaken by the agent is contained in the liquid crystal alignment agent of the present invention for the purpose of -49-201035037. As the curing agent, a curing agent which is often used for curing of a curable composition containing a curable compound having an epoxy group or a compound having an epoxy group can be used, and examples thereof include a polyamine, a polycarboxylic acid anhydride, and a polycarboxylic acid. The polyvalent carboxylic acid anhydride may, for example, be an acid anhydride of cyclohexanetricarboxylic acid or another polyvalent carboxylic acid anhydride. Specific examples of the cyclohexane tricarboxylic anhydride include, for example, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid- 3,5-anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride, etc., as other polycarboxylic acid anhydride, for example, 4-methyltetrahydrophthalic anhydride, A Basenorbornene dianhydride, dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, compound represented by the following formula (7)

(In the formula (7), p is an integer of 1 to 20) and a tetracarboxylic dianhydride which is commonly used in the synthesis of polyproline, and examples thereof include a conjugated double bond such as α-pinene or allo-ocimene. A Die Is-Alder reaction product of an alicyclic compound with maleic anhydride, a hydride thereof, and the like. As the hardening catalyst, for example, a ruthenium hexafluoride compound, a phosphorus hexafluoride compound, aluminum triacetonitrile acetate or the like can be used. These catalysts can be cationically polymerized to catalyze the epoxy group by heating. -50- 201035037 As the above-mentioned hardening accelerator', for example, an imidazole compound; a 4-stage phosphorus compound; a 4-stage amine compound; a 1,8-diazabicyclo[5.4.0]undecene_7 and its organic a diazabicycloalkene such as an acid salt; an organometallic compound such as zinc octoate, tin octylate, and aluminum acetonitrile complex; a boron compound such as boron trifluoride or triphenyl borate; a metal halide such as bismuth zinc or tin chloride; a high melting point dispersion type latent curing accelerator such as an amine addition accelerator such as an addition product of dicyanodiamine, an amine and an epoxy resin; Microcapsule-type latent hardening accelerator formed on the surface of a grade 4 strontium salt; amine salt type latent hardening accelerator; pyrolysis type Q-ion polymerization type such as Lewis acid or Bronsted silicate Potential hardening accelerators, etc. [Epoxy compound] The epoxy compound may be contained in the liquid crystal alignment film from the viewpoint of further improving the adhesion of the formed liquid crystal alignment film to the surface of the substrate. Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl-51- 201035037 oil ether, 2,2-dibromopentyl glycol diglycidyl ether, tetraglycidyl group - 2,4-hexanediol, N,N,N,,N'_tetraglycidyl-m-xylylenediamine, 1,3 -di(N,N-diglycidylaminomethyl)cyclohexane Alkane, N, N, N', N'-tetraglycidyl_4,4,-diaminodiphenylmethane, n,N,-diglycidyl-benzylamine, N,N-bi-dihydrate Glyceryl-aminomethylcyclohexane or the like is preferred. When the liquid crystal alignment agent of the present invention contains an epoxy compound, the content thereof is preferably 100 parts by weight or less, more preferably 40 parts by weight or less, based on the total amount of the radiation-sensitive polyorganosiloxane and the ruthenium other polymer used arbitrarily. Preferably, it is 0.1 to 30 parts by weight. Further, when the liquid crystal alignment agent of the present invention contains an epoxy compound, it can be used together with a basic catalyst such as 1-benzyl-2-methylimidazole for the purpose of efficiently producing the crosslinking reaction. [Functional decane compound] The above functional decane compound can be used for the purpose of further improving the adhesion to the substrate of the liquid crystal alignment film of the obtained Q. The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyl. Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Baseline, 3-guanidinopropyltrimethoxydecane, 3-guanidinopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl - 3-Aminopropyltriethoxydecane, N-triethoxymethyl sulfonylpropyltriazine-52-201035037 s-triamine, N-trimethoxyformamidinylpropyltriethylidene Amine, oxime-trimethoxycarbamido-1,4,7-triazadecane, 10-triethoxycarbamido-1,4,7-triazanonane, 9-trimethoxy Methyl decyl-3,6-diazepine acetate vinegar, 9-triethoxy oxalate-3,6-azaindolyl acetate, N-benzyl-3-amino group Propyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-amino Triethoxy decane, N-bis(oxyethylene)-3-aminopropyltrimethoxydecane, N-di(oxyethyl)-3-aminopropyltriethoxydecane, 3- ❹ glycidoxypropyl trimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, and the like, and the above-mentioned JP-A-63-291922 A reactant of tetracarboxylic dianhydride and a decane compound having an amine group, and the like. When the liquid crystal aligning agent of the present invention contains a functional decane compound, the content thereof is 1 part by weight, preferably 50 parts by weight, based on the total amount of the radiation-sensitive polyorganosiloxane and any other polymer used arbitrarily. More preferably, it is 20 parts by weight or less. [Surfactant] Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, an organic cerium surfactant, and a polyalkylene oxide surface. Active agent, fluorosurfactant, and the like. When the liquid crystal alignment agent of the present invention contains a surfactant, the content thereof is preferably 10 parts by weight to 53 parts by mass to 53350 parts by weight, more preferably 1 part by weight or less based on 100 parts by weight of the entire liquid crystal alignment agent. &lt;Liquid crystal alignment agent&gt; As described above, the liquid crystal alignment agent of the present invention contains a radiation-sensitive polyorganosiloxane as an essential component, and may contain other components as necessary, and it is preferred to dissolve each component in an organic solvent. Formulated as a solution in the form of a solution. As the organic solvent which can be used for formulating the liquid crystal alignment agent of the present invention, it is preferred to dissolve the radiation-sensitive polyorganosiloxane and any other components which are used without any reaction with them.有机 The organic solvent preferably used in the liquid crystal alignment agent of the present invention varies depending on the type of other polymer to be added. The liquid crystal alignment agent of the present invention is a preferred organic solvent when it contains at least one polymer selected from the group consisting of a radiation-sensitive polyorganosiloxane and a group selected from the group consisting of poly-proline and polyimine. The organic solvent exemplified above when used as a polyamic acid synthesis. These organic solvents may be used singly or in combination of two or more. On the other hand, the liquid crystal alignment agent of the present invention is preferred when it contains only a radiation-sensitive polyorganosiloxane as a polymer or a radiation-sensitive polyorganosiloxane and other polyorganosiloxane. The organic solvent may, for example, be 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether or dipropylene glycol. Ethyl ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl solution) Fiber), ethylene glycol monopentyl ether, B-54-201035037 diol monohexyl ether, diethylene glycol, methyl cellosolve acetate, acetic acid acetate, propyl cellosolve acetate, Butyl cellosolve acetate alcohol, ethyl carbitol, propyl carbitol, butyl carbitol, ester, isopropyl acetate, n-butyl acetate, isobutyl acetate , n-amyl acetate, second amyl acetate, oxybutyl ester, methyl amyl acetate, 2-ethyl acetate Butyl 2-ethylhexyl ester, benzyl acetate, n-hexyl acetate, vinegar, octyl acetate, amyl acetate, isoamyl acetate, and the like. Among them, n-propyl acetate, isopropyl acetate, n-butyl acetate, dibutyl acetate acetate, n-pentyl acetate, and second amyl acetate; preferably used in the preparation of the liquid crystal alignment agent of the present invention. The solvent is obtained by using the above-mentioned organic species or two or more types depending on whether or not the other polymer and the type thereof are used. The solvent does not precipitate the components contained in the liquid crystal alignment agent under the preferred solidity described below, and the liquid crystal surface tension is 25~ A range of 40 mN/m. The solid content concentration of the liquid crystal alignment agent of the present invention is preferably in the range of % in consideration of the ratio of the weight of the liquid crystal component to the weight of all the components other than the solvent in the agent. The liquid crystal alignment agent of the present invention is applied to a coating film formed on the surface of the substrate by a crystal alignment film. However, when the solid content concentration is less than, the film thickness of the coating film is too small, and it may be difficult to obtain a good liquid crystal. On the other hand, the solid content concentration exceeds 10 When the weight is too large, it is too large to be applied, and it is difficult to obtain a good liquid crystal alignment film, and the liquid crystal cellosolve, methyl propyl acetate, 3-methyl acetate, cyclohexyl acetate, and preferably isobutyl acrylate. , Wait. The one-component component of the solvent may be a total of I ~ 10 weight of the liquid crystal alignment agent, and the formation liquid is 1% by weight of the alignment film. The film thickness of the film increases to the viscosity of the agent -55-201035037, and the coating property may be insufficient. The range of the particularly preferable solid content concentration varies depending on the method employed when the liquid crystal alignment agent is applied onto the substrate. For example, when it is carried out by a spin coating method, it is particularly preferably in the range of 1.5 to 4.5% by weight. When the printing method is used, the solid content concentration is preferably in the range of 3 to 9 % by weight, whereby the solution viscosity is particularly preferably in the range of 12 to 50 mPa 's. When the ink jet method is used, the solid content concentration is preferably in the range of 1 to 5 % by weight, whereby the solution viscosity is particularly preferably in the range of 3 to 15 mPai. 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 〇 °C to 40 °C. The liquid crystal alignment agent of the present invention obtained as described above is preferably used in the case of forming a liquid crystal alignment film of a liquid crystal display element of a known structure such as TN type, STN type, IPS type or VA type by a photo-alignment method which is exposed by a small amount of light. In the manufacture of new liquid crystal display elements that solve the problem of VA VA panels. Hereinafter, a method of forming a liquid crystal alignment film using the liquid crystal alignment agent of the present invention, a method for producing a liquid crystal display element having the liquid crystal alignment film, and a method for producing a novel liquid crystal display element using the liquid crystal alignment agent of the present invention will be sequentially described. . &lt;Method of Forming Liquid Crystal Alignment Film&gt; The method of forming the liquid crystal alignment film is, for example, a method of forming a coating film of the liquid crystal alignment film of the present invention on a substrate, and then irradiating the coating film with radiation. When the liquid crystal alignment agent of the present invention is used in a TN type, STN type or VA type liquid crystal display element, two base-56-201035037 sheets provided with a pattern-shaped transparent conductive film can be used in pairs. On the other hand, when the liquid crystal alignment agent of the present invention is used in an ips type liquid crystal display device, a substrate provided with a transparent conductive film having a comb-tooth pattern and a substrate having no conductive film are used in pairs. First, on the side of the transparent conductive film of the substrate on which the transparent conductive film is provided or on the side of the substrate without the conductive film, the coating method of the present invention is applied by an appropriate coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method. Liquid crystal alignment agent. Then, the coated surface is formed into a coating film by preheating (prebaking) and then firing (post baking). The prebaking conditions are, for example, 0.1 to 5 ❹ minutes at 40 to 120 ° C; the post-baking conditions are preferably 120 to 300 ° C, more preferably 150 to 250 ° (:, the time is preferably 5 to 2 00 The film thickness of the coating film after post-baking is preferably 0.001 to Ιμπι, more preferably 0.005 to 0.5 μm. The substrate may be, for example, float glass or soda lime glass. Glass; a transparent substrate formed of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether fluorene or polycarbonate. The transparent conductive film may be formed of Sn02. NESA ruthenium film, ITO film formed of In203-Sn02, etc. In order to obtain a pattern-shaped transparent conductive film, a photolithography method, a method of using a mask when forming a transparent conductive film, etc. can be used. The substrate or the transparent conductive film and the coating film are more adhesive, and a functional decane compound, titanate, or the like may be previously coated on the substrate and the transparent conductive film. Next, the coating film is irradiated with linearly polarized or partially polarized radiation or Unpolarized The ray is used to impart alignment energy to the liquid crystal. Here, as the radiation of -57-201035037, ultraviolet rays and visible light including light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays of light having a wavelength of 300 to 400 nm are preferably used. When the radiation is linearly polarized or partially polarized, it can be irradiated from the direction perpendicular to the substrate surface. In order to form the pretilt angle, it is also possible to irradiate from the oblique direction and to combine them. When irradiating the unpolarized radiation, the irradiation direction must be inclined. As the light source used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a heavy hydrogen mercury lamp, a metal halide mercury lamp, an argon resonance lamp, a xenon lamp, or a xenon excimer laser lamp can be used. The above-mentioned preferred wavelength region of ultraviolet light can pass the aforementioned light source. It is obtained by a device used together with, for example, a color filter, a diffraction grating, etc. The irradiation amount of the radiation is preferably U/m2 or more and less than 10,000 J/m2', more preferably 10 to 3,000 J/m2. Liquid crystal alignment energy is imparted to a coating film formed from a conventionally known liquid crystal alignment agent by a photo-alignment method The amount of radiation to be irradiated must be 10,000 J/m2 or more. However, when the liquid crystal alignment agent of the present invention is used, the amount of radiation irradiation in the photoalignment method is 3, 〇〇〇J/m2 or less, and even 1 000 J. When it is at least m2, a good liquid crystal alignment energy can be imparted, which contributes to a reduction in the production cost of the liquid crystal display element. <Method for Producing Liquid Crystal Display Element Having the Liquid Crystal Alignment Film> It is formed using the liquid crystal alignment agent of the present invention. The liquid crystal display element of the liquid crystal alignment film can be produced, for example, as follows: Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and liquid crystal cells are formed by disposing liquid crystal between the two substrates -58-201035037. When manufacturing a liquid crystal cell, the following two methods are mentioned. The first method is a currently known method. First, in order to provide a 'pass gap (cell gap) in the liquid crystal alignment film, the two substrates are placed in the opposite direction, and the peripheral portions of the two substrates are bonded together, and the surface of the substrate and the sealant are separated. After filling the liquid crystal into the interstitial space, the injection hole is sealed to manufacture a liquid crystal cell. The second method is a method called the DropDF (One Drop Fill) method. 〇 Applying, for example, an ultraviolet curable sealing material to a predetermined position on one of the two substrates forming the liquid crystal alignment film, and then dropping the liquid crystal on the liquid crystal alignment film surface, and 'bonding another substrate to make the liquid crystal alignment film pair Then, ultraviolet light is irradiated on the entire surface of the substrate to harden the sealant to produce a liquid crystal cell. In the case of any of the methods, it is then desired to reheat the liquid crystal cell to the temperature at which the liquid crystal used is isotropic, and then slowly cool to room temperature, in addition to the flow alignment at the time of liquid crystal injection. Then, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. In the case where the liquid crystal alignment film is horizontally aligned, the TN type and the STN are obtained by adjusting the angle formed by the polarization direction of the linearly polarized radiation and the angle of each of the substrates and the polarizing plate in two substrates on which the liquid crystal alignment film is formed. A liquid crystal display element of a type or IPS type liquid crystal cell. On the other hand, when the liquid crystal alignment film is vertically aligned, the axis of the two substrates in which the liquid crystal alignment film is formed is aligned in a parallel manner - 59-201035037, and the polarizing plate is attached thereto. By forming the polarization direction and the easy alignment axis at an angle of 45°, a liquid crystal display having a VA type liquid crystal cell can be formed. As the sealant', for example, an epoxy resin containing an alumina sphere as a separator and a curing agent can be used. As the liquid crystal, for example, a nematic liquid crystal, a dish liquid crystal or the like can be used. When it is a TN type liquid crystal cell, an STN type liquid crystal cell or an IPS type liquid crystal cell, Λ preferably has a positive dielectric anisotropy nematic liquid crystal, and for example, a fluorene biphenyl liquid crystal or a phenylcyclohexane type can be used. Liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, di Df alkane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal or the like. Further, in the liquid crystal, a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl phthalate or cholesteryl carbonate may be further added; and sold under the trade names C-1 5, CB·15 (manufactured by Merck). A chiral agent; a ferroelectric liquid crystal such as p-oxyphenylene-p-amino-2-methylbutyl cinnamate or the like. On the other hand, in the case of a VA 〇 type liquid crystal cell, it is preferable to have a negative dielectric anisotropy for forming a nematic liquid crystal, and for example, a dicyanobenzene liquid crystal, a krypton trap liquid crystal, or a Schiff base liquid crystal can be used. An azo-based liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, or the like. The polarizing plate used for bonding to the outer side of the liquid crystal cell may be a polarizing plate formed by stretching a polyvinyl alcohol and sandwiching a polarizing film called absorbing iodine called "H film" with a cellulose acetate protective film. A polarizing plate or the like formed by the film itself. -60-201035037 The liquid crystal display element of the present invention thus produced is excellent in various properties such as display properties and reliability. &lt;Manufacturing Method of Novel Liquid Crystal Display Element&gt; A method of manufacturing a novel liquid crystal display element using the liquid crystal alignment agent of the present invention is characterized in that the liquid crystal of the present invention is applied to the conductive film of a pair of substrates having a conductive film, respectively An alignment agent forms a coating film; and a liquid crystal cell is formed by interposing a liquid crystal molecule layer on the coating film of the pair of substrates on which the coating film is formed, and a liquid crystal cell having a facing arrangement is formed; and the pair of substrates has a conductive film between the substrates a step of irradiating light to the liquid crystal cell in a state where a voltage is applied. Among them, the case of the substrate to be used and the liquid crystal display element having the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention are the same. As the conductive film, a transparent conductive film is preferably used, and for example, a NESA film formed of Sn02, an ITO film formed of In203-Sn02, or the like can be used. Each of the conductive films is preferably a patterned conductive ruthenium film divided into a plurality of regions. When such a conductive film structure is formed, when a voltage is applied between the conductive films (described later), by applying a different voltage to each region, the direction of the pretilt angle of the liquid crystal molecules of each region can be changed, whereby the viewing angle property can be obtained. Further expansion. a method of coating a liquid crystal alignment agent on the conductive film of the substrate, a film thickness of the coating film after pre-baking and post-baking after coating, and a post-baking coating film, and a liquid crystal alignment film having the liquid crystal alignment agent of the present invention as described above The case of the liquid crystal display element is the same. -61&quot; 201035037 The coating film thus formed can be used directly in the production of liquid crystal cells in the following steps, or the coating film surface can be rubbed as needed before the production of the liquid crystal cell. This rubbing treatment is performed by winding a roll of a cloth formed of, for example, a fiber such as nylon, rayon or cotton, and rubbing the surface of the coating film in a certain direction. In the case of performing one rubbing treatment, a resist film is formed on a part of the surface of the coating film, and then in a direction different from the previous rubbing treatment, as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. After the rubbing treatment, the treatment for removing the resist film is performed, and by making the respective regions have different rubbing directions, the viewing angle properties of the obtained liquid crystal display element can be further improved. Then, the liquid crystal layer is opposed to the coating film of the pair of substrates on which the coating film is formed, and the liquid crystal cells in the opposite arrangement are formed. As the nematic liquid crystal which preferably has a negative dielectric anisotropy, the liquid crystal molecules used herein may be, for example, a dicyanobenzene liquid crystal, a helium-well liquid crystal, a Schiff base liquid crystal, or an azo-based liquid crystal. Biphenyl liquid crystal, phenyl ring hospital liquid crystal, and the like. The thickness of the liquid crystal molecule layer is preferably from 1 to 5 μm. The method of forming a liquid crystal cell using the liquid crystal is the same as the case of a liquid crystal display element having a liquid crystal alignment film formed of the above liquid crystal alignment agent of the present invention. Thereafter, light is applied to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates. The voltage applied here may be, for example, a direct current or an alternating current voltage of 5 to 50 V. -62-201035037 As the light to be irradiated, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm, preferably ultraviolet rays having a wavelength of 300 to 400 nm can be used. As the light source of the irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, or an excimer laser lamp can be used. The ultraviolet light of the above preferred wavelength region can be obtained by using the above-mentioned light source and a device such as a color filter, a diffraction grating or the like. The irradiation amount of light is preferably 1,000 J/m2 or more 'less than 〇1 00,00 (H/m2' is more preferably 1,0 00 to 5,0,000 J/m2. Manufacturing of liquid crystals of PSA mode currently known. In the case of a display element, it is necessary to irradiate light such as i00,000 J/m 2 . However, in the method of the present invention, the amount of light irradiation is 50,000 J/m 2 or less, and even when it is 10 000 J/m 2 or less, desired. In addition to contributing to the reduction of the manufacturing cost of the liquid crystal display element, the liquid crystal display element 'can avoid the decrease in electrical properties caused by the irradiation of strong light and the long-term reliability degradation. 〇 Then 'by pasting the outer surface of the liquid crystal cell after the above treatment A liquid crystal display element can be obtained by combining a polarizing plate. The polarizing plate used herein includes a polarizing plate formed by sandwiching a η film with a cellulose acetate protective film, or a polarizing plate formed directly from a ruthenium film. The viewing element has a large viewing angle, and the liquid crystal molecules have an extremely fast response speed, excellent display properties and long-term reliability, and can be manufactured at low cost by reducing manufacturing cost, and are therefore suitable for various uses. 63-201035037 Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited by the examples. In the following examples, the weight average molecular weight is determined by gel permeation chromatography under the following conditions. Polystyrene-converted 値. Column: manufactured by Tosoh ("TSKgelGRCXLII" Solvent: tetrahydrofuran temperature: 4 (TC pressure: 68 kgf/cm2 Epoxy equivalent according to JIS C2 105 "hydrochloric acid-methyl ethyl ketone method". Polymer solution The solution viscosity is enthalpy measured at 25 ° C using an E-type viscometer. Further, in the following examples, the synthesis of the starting compound and the polymer can be repeated as needed by the following synthetic route diagram, ensuring the examples. &lt;Synthesis of Compound (b)&gt; 实施 Example 1 (Synthesis of Compound (3-2-1)) According to the following synthetic route Figure 2, a compound was synthesized (3_2_υ. -64- 201035037

K2C〇3 cf3c3h6h CF3C3H6—o

o

Pd(OAc)2(PPh3)2

Cul

i_Pr2NH

CH III C——COOH CF3C3H6—o

c=c—COOH (3-2-1)

Synthesis Scheme Figure 2 [Synthesis of Compound (3-2-1-1)] In a 1 L section flask, 99 g of 4-deuterated phenol, 124 g of potassium acid, and 585 mL of N,N-dimethylacetamide were added. After stirring at room temperature for 3 hrs, 90 g of 4,4,4-trifluoro-iodide butane was added thereto, and the mixture was stirred at room temperature for 6 hours to carry out a reaction. After completion of the reaction, 1.8 L of hexane was added to the reaction mixture, and the mixture was washed once with water, twice with a sodium hydroxide aqueous solution of a molar concentration, and once with water, then concentrated and dried to give a crude product. Recrystallization from ethanol gave 8 1 g of a pale compound (3-2-1-1). Carbon compartments / L , Brown - 65 - 201035037 [Synthesis of compound (3 - 2 - 1 )] In a 1 L three-necked flask equipped with a nitrogen gas introduction tube and a thermometer, '66 g of the compound obtained above was added (3-2-1) -1), 12.2 mL of propiolic acid, 7 mL of diisopropylamine, 2.8 g of di-triphenylphosphine palladium diacetate, 1.54 g of copper (I) iodide and 200 mL of N,N-di Methylformamide was reacted at room temperature for 1 hour. After completion of the reaction, 1 L of ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed with diluted hydrochloric acid and water, and dried over magnesium sulfate. The obtained solid was purified by a silica gel column using ethyl acetate and hexane as a solvent, and the solvent was distilled off from the purified solvent to obtain a brown powder of the compound (3-2-1). &lt;Synthesis of polyorganosiloxane (a) having an epoxy group&gt; Synthesis Example 1 In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 100. (3,4-Epoxycyclohexyl)ethyltrimethoxydecane, 500 g of methyl isobutyl ketone and 10. g of triethylamine were kneaded at room temperature. Then, 1 〇 〇 g of deionized water was added dropwise from the dropping funnel for 30 minutes, and then reacted at 80 ° C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out, washed with a 2% by weight aqueous solution of ammonium nitrate until the washed water was neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group. EPS-1, a viscous transparent liquid. The iH-NMR analysis of the polyorganooxynonane EPS-1 having an epoxy group was confirmed to have an epoxy group-based peak such as theoretical strength in the vicinity of the chemical shift (δ) = 3.2 ppm. The epoxy group does not produce a secondary-66-201035037 reaction. The polyorganooxynonane EPS-1 having an epoxy group has an Mwj epoxy equivalent of 1 86. &lt;Synthesis of Radiation-Tensible Polyorganooxane&gt; Example 2 In a 200 mL three-necked flask, 6.3 g of the above-prepared polyorganosiloxane having an epoxy group, EPS-1, 60 g of methyl iso 18 g, The compound (3-2-1) obtained in Example 1 and 6 g of bromoammonium bromide were stirred at 80 ° C for 12 hours to carry out a reaction. The reaction mixture was again precipitated, and the precipitate was dissolved in ethyl acetate to obtain a solution. After washing three times, the solvent was distilled off to obtain 1 1 g of sensitized siloxane s oxane S -1 as a brown powder. The weight average molecular weight Mw of the radiation-sensitive polyorganophosphonium was 9,900. Example 3 In a 200 mL three-necked flask, 6.3 g of the above-mentioned poly(polyoxyalkylene oxide EPS-1 having an epoxy group of the above-mentioned synthesis G, 60 g of methyl group 18 g of the compound (3-2-1) obtained in the above Example 1 was added. 2, 〇g stearic acid tetrabutylammonium bromide, stirred at 80 ° C for 12 hours, after the end of the reaction, re-precipitated with hexane, the precipitate was dissolved in ethyl acetate solution, the solution was washed 3 times Thereafter, the solvent was distilled off to obtain a radioactive polyorganosiloxane (S-2) as a brown powder. The radiation-sensitive siloxane oxide S-2 has a weight average molecular weight Mw of 10,200. &lt;Synthesis of Other Polymers&gt; 2,200 &gt; Example 1 gave butyl ketone; After the tetrabutyl hydride was used, the solution polyorganooxyalkylene S-1 was used to obtain butyl ketone, acid and 0.6 g. should. Reaction solution, 12 2g of the radioactive polyorgano-67-201035037 [Synthesis of poly-proline) Synthesis Example PA_1 10 g (〇.50 mol) pyromellitic dianhydride as tetrahydro acid-anhydride And 98g (0.50 mole) 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 200g (1.0 mole) 4,4-diaminodiphenyl ether as diamine are dissolved to 2,29〇 In the N-methyl-2-pyrrolidone of g, after reacting at 40 ° C for 3 hours, adding iwog N-methyl-2-indole ketone ketone to obtain about 4,000 g containing 1 〇 wt% poly 醯 0 A solution of aminic acid (PA·1). The solution viscosity of the polyaminic acid solution was 210 mPa·s. Synthesis Example PA-2 98 g (0.50 mol) of 1,2,3,4-cyclotetracarboxylic dianhydride and 109 g (0.50 mol) pyromellitic dianhydride as diammonic acid dianhydride and as two 198 g (1.0 mol) of amine 4,4'-diaminodiphenylcarbendide was dissolved in 2,290 g of N-methyl-2-pyrrolidone, and after reacting at 40 ° C for 3 hours, U5 0g was added. N-methyl-2-pyrrolidone gave about 4,000 g of a solution containing 1% by weight of polyglycine (PA-2). The solution viscosity of the polyaminic acid solution is i 35 mPa. S ° Synthesis Example PA-3 196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 200 g (1.0 mol) of 4,4'-diaminodiphenyl ether as a diamine was dissolved in 2,246 g of N-methyl-2-pyrrolidone, and after reacting at 40 ° C for 4 hours, 1 was added. 3 2 1 g of N-methyl-2-pyrrolidone gave about 3,9 50 g of a solution containing 10% by weight of polyglycine (PA-3). The polyglycine solution has a solution viscosity of -220-201035037 of 220 mPa-s. Synthesis Example PA-4 196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 212 g (1.0 mol) of 2,2'- as a diamine. Dimethyl-4,4'-diaminobiphenyl was dissolved in 4,050 g of N-methyl-2-pyrrolidone, and after reacting at 40 ° C for 3 hours, 3,700 g of 10% by weight of polylysine was obtained. (PA-4) solution. The solution viscosity of the polyamic acid solution was 170 mPai. ^ Synthesis Example PA-5 224 224 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 200 g (1.0 mol) of 4,4' as a diamine -Diaminodiphenyl ether was dissolved in 2,404 g of N-methyl-2-pyrrolidone, and after reacting at 40 ° C for 4 hours, about 2,800 g was obtained to contain 15 wt% of poly A solution of proline (p A - 5 ). A small amount of the polyamic acid solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 1% by weight, and the solution viscosity was measured to be 190 m P a.s. Synthesis Example PA-6 22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 14.23 g of (0.1 mol) cyclohexane bis(methylamine) were dissolved in 329 3 g of hydrazine. -Methyl-2-D is reacted at 60 ° C for 6 hours. Next, the reaction mixture is poured into a large excess of methanol to cause the reaction product to sink. The sulphate was washed with methanol and dried under reduced pressure at 40 ° C for 15 hours to obtain 32 g of polyamidonic acid PA-6. -69- 201035037 Synthesis Example PA-7 19.61 g (0.1 mol) of cyclobutanetetracarboxylic dianhydride and 21.23 g (0.1 mol) of 4,4'-diamino-2,2'-dimethyl The benzene was dissolved in 3 67.6 g of N-methyl-2-pyrrolidone and allowed to react at room temperature for 6 hours. Then, the reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain 35 g of polyamine acid PA-7. ^ [Synthesis of Polyimine] 〇 Synthesis Example pi_i U2g (0.50 mol) 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 157 § (0.50 mol) as tetracarboxylic dianhydride ,3,3&amp;,4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)·naphtho[i,2-c] -furan-1,3-dione and 95 g (0.88 mol) of p-phenylenediamine as a diamine, 32 g (0.10 mol) of 4,4'-diamino-2,2'-di (three Fluoromethyl)biphenyl, 6.4 g (0.010 mol) of 3,6-bis(4-aminobenzylideneoxy)cholesterane and 4.0 g (0.015 mol) of deca-octadecanyloxy-2, 5-Diaminobenzene dissolved in 960 g of N-methyl-2-pyrrolidone 'reacted at 60 ° C for 9 hours. A small amount of the obtained polylysine solution 'N-methyl-2-pyrrolidone' was added to form a solution having a polymer concentration of 1% by weight, and the measured solution viscosity was 58 mPa·s. 2,740 g of N-methyl-2-pyrrolidone was added to the obtained poly-reactivic acid solution, and 396 g of U was combined with D and 409 g of acetic anhydride, and dehydration was carried out at ii ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone solvent (by this operation, the pyridine and acetic anhydride used in the dehydration-70-201035037 closed-loop reaction are removed to the system. The same), about 2,500 g of a solution containing 15% by weight of polyamidimide (PI-1) having a ruthenium iodide ratio of about 95% was obtained. The polyimine solution was fractionated, and the solvent was removed under reduced pressure, and then dissolved in N-methyl-2-pyrrolidone to form a solution having a polymer concentration of 8.0% by weight, and the measured solution viscosity was 33 mPai. Synthesis Example PI-2 ^ 1 12 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 157 g (0.50 mol) of 1,4,3a,4 as tetracarboxylic dianhydride. 5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3-dione As a diamine, 96 g (0.89 mol) of p-phenylenediamine, 25 g (0.10 mol) of diaminopropyltetramethyldioxane and 13 g (〇.020 mol) 3,6- Bis(4-aminobenzylideneoxy)cholesterane and 8_lg (0.030 mol) N-octadecylamine as a monoamine, dissolved in 960 g of N-methyl-2-pyrrolidone, at 6 (Reaction at TC for 6 hours. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added thereto to form a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 60 mPa's. 2,700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 39.6 g of pyridine and 409 g of acetic anhydride were added, and the mixture was subjected to dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new solvent of N-methyl-2-pyrrolidone to obtain about 2,400 g and 15% by weight. A solution of polyimine (PI 2 ) having an imidization rate of about 95%. A small amount of the polyimine solution is added, and N-methyl-2-pyrrolidone is added, -71 - 201035037 to form a polymer concentration of 6.0. % by weight solution, the measured solution viscosity is 18 m P a · s 〇 Synthesis Example PI-3 will be 224 g (1.0 mol) of tetracarboxylic dianhydride 2,3,5-trimethylcyclopentyl acetic acid The dianhydride and 107 g (0.99 mol) of p-phenylenediamine as a diamine and 6.43 g (0.010 mol) of 3,6-bis(4-aminobenzylideneoxy)cholestane are dissolved to 3, In 0 3 9 g of N-methyl-2-pyrrolidone, a solution containing 1% by weight of polyglycine is obtained when the reaction is 6 hours at 6 ° C. The viscosity of the solution of the polyglycine is 0. It is 260 mPa's. Next, 2,7 g of N-methyl-2-pyrrolidone is added to the obtained polyaminic acid solution, 3 96 g of pyridine and 3 06 g of acetic anhydride are added, and the ring is dehydrated at H0 ° C. The reaction was carried out for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain about 3,500 g of a polyfluorene containing 9.0% by weight of a ruthenium iodide ratio of about 89%. Imine (PI-3) solution少量 A small amount of the polyimine solution is added, N-methyl-2-pyrrolidone is added to form a solution having a polymer concentration of 5.0% by weight, and the measured solution viscosity is 7 4 m P a · s 〇 Synthesis Example PI-4 112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 157 g (0.50 mol) of 1,3,3a,4,5,9b-hexahydro-8 -methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-(:]-furan-1,3-dione and 89 g as diamine ( 0.82 mol) p-phenylenediamine, 32 g (〇.i〇-72- 201035037 mol) 4,4,-diamino-2,2'-bis(trifluoromethyl)biphenyl, 25 g ( 0.059 mol) 1-(3,5-diaminobenzylideneoxy)-4-(4-trifluoromethylbenzyloxy)cyclohexane and 4.0 g (0.011 mol) octadecane The oxy-2,5-diaminobenzene was dissolved in 2,175 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours to obtain a solution containing polylysine. A small amount of the obtained polylysine solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 11 nmPa-s. ^ 3,000 g of N-methyl indole-2-pyrrolidone was added to 1500 g of the obtained polyaminic acid solution, and 221 g of pyridine and 228 g of acetic anhydride were added, and the mixture was subjected to dehydration ring-closure reaction at 1 l ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new solvent of N-methyl-2-pyrrolidone to obtain about 4,000 g of a polyimine (containing 1% by weight of hydrazine imidization ratio of about 92%). I - 4) solution. The polyimine solution was fractionated and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 4.5% by weight, and the solution viscosity was determined to be 28 mP a·s. 〇Synthesis Example PI-5 19.9 g (0.089 mol) of 2,3,5-trimethylcyclopentyl acetic acid monohydride as tetradecanoic dianhydride and 6.8 g (〇.〇63 mol) as diamine a compound represented by the following formula (d_6) for phenyldiamine, 3.6 g (0.018 mol) of 4,4,-diaminodiphenylmethane and 4.7 g (0.009 Torr), dissolved in 14 〇g In N-methyl-2-pyrrolidone, the reaction was carried out at 6 〇π for 4 hours. A small amount of the obtained polyphthalamide solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of % by weight, and the measured solution viscosity was iL5 mPa.s. -73- 201035037

H2n

Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 14 g of pyridine and 18 g of acetic anhydride were added, and the mixture was dehydrated at 11 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new solvent of N-methyl-2-pyrrolidone to obtain about 22 g of a polyimine (PI) containing about 5.4% by weight of ruthenium iodide of about 77%. -5) solution. A small amount of the polyimine solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 1% by weight, and the measured solution viscosity was 8 4 m P a · s 〇 Synthesis Example PI - 6 20.9 g (0.093 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 9.2 g (0.085 mol) of p-phenylene diamine and 4-9 g as diamine ( The compound represented by the above formula (D-6) was dissolved in 140 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 4 hours to obtain a solution containing polylysine. The obtained polyimine solution was fractionated, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 126 mPa*s. Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 7.4 g of pyridine and 9.5 g of acetic anhydride were added, and the mixture was dehydrated at 110 ° C for 4 hours. After the dehydration ring closure reaction, a solvent of -74-201035037 in the system was replaced with a new solvent of N-methyl-2-pyrrolidone to obtain about 220 g of polyamidiamine containing 16.1% by weight of ruthenium iodide (about 54%). A solution of PI-6). A small amount of the polyimine solution is added, N-methyl-2-pyrrolidone is added to form a solution having a polymer concentration of 1% by weight, and the measured solution viscosity is 7 5 mP a·s. The synthesis example PI-7 will be used as 18.8 g (0.084 mol) of 2,3,5-tricarboxy-cyclopentyl acetic acid dianhydride of tetracarboxylic dianhydride and 7.4 g (0.068 mol) of p-phenylene diamine and 8.9 g as diamine (0.017 mol) The compound represented by the above formula (D-6) was dissolved in 140 g of N-methyl-2-pyrrolidone, and reacted at 6 (TC for 4 hours to obtain a solution containing polylysine. The obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 126 mPa's. Next, the obtained polyglycine solution was added. 3 25 g of N-methyl-2-pyrrolidone, adding 6.6 g of pyridine and 8.5 g of acetic anhydride, dehydrating and blocking at 4 l ° C for 4 hours. After dehydration ring closure reaction, the solvent is used in the system. The N-methyl-2-pyrrolidone solvent was replaced to obtain about 210 g of a solution containing 15.9% by weight of a polyamidimide (PI-7) having a ruthenium iodide ratio of about 55%. The polyimine solution was fractionated, N-methyl-2-pyrrolidinium was added to form a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 7 5 mP a · s 〇 Synthesis Example PI-8 19.1 g (0.085 mol) of 2,3,5-tricarboxy-75-201035037 cyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride and 7.4 g (0.069 mol) of a diphenyl group as a diamine Amine and 8.5 g (0.017 mol) of the compound represented by the following formula (D-7), dissolved in 140 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 4 hours to obtain a polyglycine-containing compound. Solution: A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 206 mPai.

Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 6.7 g of pyridine and 8.7 g of acetic anhydride were added, and the mixture was dehydrated at 110 ° C for a ring closure reaction for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new solvent of N-methyl-2-pyrrolidone to obtain about 200 g of polyimine (PI-8) containing 15.8% by weight of ruthenium iodide of about 52%. )The solution. A small amount of the polyimine solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 1% by weight, and the measured solution viscosity was 10.5 m P a · s ° Synthesis Example PI- 9 17.3 g (0.077 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 5.9 g (0.054 mol) of p-phenylenediamine as a diamine, 4.1 g (0.008 mol) of the compound represented by the above formula (D-6) and 7.7 g (0.016 mol) of the compound represented by the following formula (D-7), dissolved in 140 g of -76-201035037 N-methyl-2- The pyrrolidone was reacted at 60 ° C for 4 hours. A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 17 mPai. Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 6. lg of pyridine and 7.9 g of acetic anhydride were added, and the mixture was dehydrated at U0 °C for a ring closure reaction for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new solvent of N-methyl-2-pyrrolidone to obtain about 21 g of polyimine (PI- containing 15.4% by weight of ruthenium iodide of about 55%). 9) solution. A small amount of the polyimine solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 1% by weight, and the measured solution viscosity was 1 0 9 mP a·s 〇 [other polyoxyl Synthesis of alkane] Synthesis Example PS-1 In a 200 mL three-necked flask equipped with a cooling tube, 20.8 g of tetraethoxydecane and 28.2 g of 1-ethoxy-2-propanol were placed, and the mixture was stirred and heated at 60 °C.马 An aqueous solution of maleic anhydride formulated in another flask having a capacity of 20 mL was added thereto, and the aqueous maleic anhydride solution was obtained by dissolving 26.26 g of maleic anhydride in 10.8 g of water. The reaction was carried out by heating and stirring at 60 ° C for 4 hours. The solvent was distilled off from the obtained reaction mixture, and 1-ethoxy-2-propanol was added thereto, followed by concentration again to obtain a polymer solution containing 10% by weight of polyorganooxane PS-1. The weight average molecular weight Mw of PS-1 was 5,1〇〇. &lt;Preparation of liquid crystal alignment agent&gt; Example 4 -77-201035037 As another polymer, a solution containing the poly-proline acid PA-1 obtained in the above Synthesis Example PA-1 was selected and converted into poly-proline acid PA-1. Equivalent to an amount of 1,000 parts by weight. 100 parts by weight of the radiation-sensitive polyorganosiloxane X-1 obtained in the above Example 2 was added thereto, and N-methyl-2-pyrrolidone and butyl cellosolve were further added to form The solvent composition was N-methyl-2-pyrrolidone: a solution of butyl cellosolve = 50:50 (weight ratio) and a solid concentration of 3.0% by weight. ^ Filter the solution through a filter with a pore size of 1 μηη to prepare a liquid crystal alignment agent

C Α-1. The liquid crystal alignment agent Α-1 was stored at -15 ° C for 6 months. The viscosity was measured by an E-type viscometer at 25 °C before and after storage. The rate of change before and after storage of the solution viscosity is less than 10%, and the storage stability is evaluated as "good", and the storage stability is "unqualified". The storage stability of the liquid crystal alignment agent A-1 at this time is evaluated. Examples 5 to 8, 10-14, and 17 to 21, in the same manner as in the above-described Example 4, except that the type of the radiation-sensitive polyorganosiloxane and the type and amount of the other polymer are as shown in Table 1. Liquid crystal alignment agents A-2 to A-5, A-7-A-11, and Α-14 to Α-18» were separately prepared. These liquid crystal alignment agents were evaluated for storage stability in the same manner as in Example 4. The evaluation results are shown in the table. 1 shows. Example 9 Dissolving 1 〇 0 parts by weight of the radiation-sensitive poly-78-201035037 organic oxime obtained in the above Example 2 in a mixed solvent composed of Ν-methyl-2-pyrrolidone and butyl cellosolve. Alkyl s-, 1, ruthenium by weight of the other polymer of the above-mentioned synthesis example PA-6 obtained from polyamine phthalic acid PA-6, forming a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 5 0 : 50 (weight ratio), a solution having a solid concentration of 3.0% by weight. Passing through a pore size of 1 μπι The solution was filtered to prepare a liquid crystal alignment agent A-6. The liquid crystal alignment agent was evaluated for storage stability in the same manner as in Example 4. The evaluation results are shown in Table 1. 〇 Example 1 5 and 1 6 Other polymerizations Liquid crystal alignment agents A-1 2 and A-1 3 were prepared in the same manner as in Example 9 except that the types and amounts of the materials were as shown in Table 1. The liquid crystal alignment agent was evaluated for storage stability in the same manner as in Example 4. The evaluation results are shown in Table 1. Example 22 As another polymer, a solution containing the G-polyorganosiloxane (PS-1) obtained in the above Synthesis Example PS-1 was selected, and it was converted into PS-1 equivalent to 2,000. The amount of the parts by weight was added to 1 part by weight of the radiation-sensitive polyorganosiloxane X-1 obtained in the above Example 2, and then 1-ethoxy-2-propanol was added thereto to form a solid concentration of 4.0. The solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent Α-19. The liquid crystal alignment agent was evaluated for storage stability in the same manner as in Example 4. The evaluation results are shown in Table 1. 79- 201035037 &lt;Formation of liquid crystal alignment film and liquid crystal display Manufacture and evaluation of the device&gt; Example 23 The liquid crystal alignment agent A-1 prepared in the above Example 4 was applied on the transparent electrode surface of the glass substrate with the transparent electrode formed of the ITO film using a spin coater, at 8 After prebaking on a hot plate at 0 °C for 1 minute, it was heated in an internal nitrogen-substituted oven at 200 ° C for 1 hour to form a coating film having a film thickness of 1 μm. Next, an Hg-Xe lamp was used. With a GUn-Tayl〇r prism, the surface of the coating film was irradiated with a polarized ultraviolet ray of 200 J/m 2 containing a bright line of 313 nm from a direction in which the substrate was normal by 40° to form a liquid crystal alignment film. The same operation was repeated to manufacture one pair (two pieces) of a substrate having a liquid crystal alignment film. By screen printing, an epoxy resin adhesive having an alumina ball of 5.5 μm in diameter is applied to the outer periphery of one surface of the substrate having the liquid crystal alignment film, and then the liquid crystal alignment film faces of the pair of substrates are opposed. The optical axis of the ultraviolet light of each substrate was pressed against the projection direction of the substrate surface in antiparallel, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, from the liquid crystal injection port, 负 is filled with a negative liquid crystal (MLC-6608, manufactured by Merck, Inc.) in a gap between the substrates, and then an epoxy-based adhesive is used to seal the liquid crystal injection port, and then 'liquid crystal injection is removed. After the flow alignment, it was heated at 150 ° C for 1 minute and then slowly cooled to room temperature. Then, the polarizing plates were bonded to the outer surfaces of the substrate so that the polarizing directions of the polarizing plates were orthogonal to each other, and the optical axis of the ultraviolet ray of the liquid crystal alignment film was formed at an angle of 45° with respect to the projection direction of the substrate surface, thereby producing a liquid crystal display element. The liquid crystal display element was evaluated by the following method. The evaluation results are shown in Table 2 of -80-201035037. (1) Evaluation of liquid crystal alignment property When Ο N _ 0 FF (applied-released) voltage of 5 V was applied to the liquid crystal display element manufactured as described above, the presence or absence of an abnormal region of light and dark change by an optical microscope was observed. Be "good." (2) Evaluation of Pretilt Angle The liquid crystal display element manufactured as described above is described in Non-Patent Document 2 (T. J. 0 Scheffer et. al. J. Appl. Phys. Vol. 19, P20 1 3 (1 980)). The method was carried out by measuring the pretilt angle by a crystal rotation method using He-Ne laser. (3) Evaluation of voltage holding ratio On the liquid crystal display element manufactured above, after applying a voltage of 5 V at an application time of 60 μsec and an interval of 167 msec, the voltage retention after the release of the application for 167 msec was measured. rate. The measuring device used "VHR-1" manufactured by Toyo Technica Co., Ltd. Ο (4) Evaluation of burn-in resistance In the liquid crystal display device manufactured above, a rectangular wave of 30 Hz and 3 V with a DC voltage of 5 V was applied for 2 hours at an ambient temperature of 70 ° C, and the cut was obtained by a flash erase method. The voltage remaining in the liquid crystal cell after the DC voltage is broken, that is, the residual DC voltage. (5) Evaluation of pretilt stability The liquid crystal display element produced above was stored at 23 ° C for 30 days, and then the pretilt angle was measured again. When the amount of change from the initial stage is less than PC, the pre--81-201035037 inclination stability is "good". (Examples 24 to 41) A liquid crystal alignment film was formed in the same manner as in the above Example 2 except that the liquid crystal alignment agent of the type shown in Table 2 was used as the liquid crystal alignment agent, and a liquid crystal display element was produced and evaluated. The results are shown in Table 2.

-82- 201035037 [Table 1]

Liquid crystal alignment agent name Liquid crystal alignment polyorganosiloxane name Other polymer name Other polymer addition amount (parts by weight) Storage stability Example 4 A-1 S-1 PA-1 1,000 Good example 5 A- 2 S-1 PA-2 1,000 Good Example 6 A-3 S-1 PA-3 1,000 Good Example 7 A-4 S-1 PA-4 1,000 Good Example 8 A-5 S-1 PA- 5 1,000 Good Example 9 A-6 S-1 PA-6 1,000 Good Example 10 A-7 S-1 PI-1 1,000 Good Example 11 A-8 S-1 PI-2 1,000 Good Example 12 A- 9 S-1 PI-3 15000 Good Example 13 A-10 S-1 PI-4 1,000 Good Example 14 A-11 S-1 PI-5 15000 Good Example 15 A-12 S-1 PI- 6 1,000 Good example 16 A-13 S-1 PI-7 1,000 Good example 17 A-14 S-1 PI-8 1,000 Good example 18 A-15 S-1 PI-9 1,000 Good example 19 A- 16 S-1 PA-4 500 Good Example 20 A-17 S-1 PA-4 2,000 Good Example 21 A-18 S-2 PA-4 1,000 Good Example 22 A-19 S-1 PS-1 2,000 Good-83- 201035037 [Table 2]

Liquid crystal alignment voltage maintained burn-in pre-tilt agent name Orientation pre-tilt angle (.) Rate (°/.) Residual DC voltage (mV) Stability Example 23 A-1 Good 87 99 20 Good example 24 A-2 Good 87 99 18 Good example 25 A-3 Good 87 99 19 Good example 26 A-4 Good 87 99 15 Good example 27 A-5 Good 87 99 20 Good example 28 A-6 Good 87 99 20 Good example 29 A-7 Good 88 99 21 Good Example 30 A-8 Good 88 99 23 Good Example 31 A-9 Good 88 99 22 Good Example 32 A-10 Good 88 99 21 Good Example 33 A-11 Good 88 99 22 Good Example 34 A-12 Good 88 99 22 Good Example 35 A-13 Good 88 99 20 Good Example 36 A-14 Good 88 99 21 Good Example 37 A-15 Good 88 99 23 Good Example 38 A -16 Good 87 99 20 Good Example 39 A-17 Good 87 99 19 Good Example 40 A-18 Good 88 99 良好 Good Example 41 A-19 Good 87 99 20 Good -84- 201035037 Example 42 &lt; Production of Cell&gt; Using Liquid Crystal Alignment Agent A-1 prepared in the above Example 4. The transparent electrode pattern (two types) and the ultraviolet irradiation amount (three references) were changed as follows, and a total of six liquid crystal display elements were produced and evaluated. [Production of liquid crystal cell having a transparent electrode without a picture] The liquid crystal alignment film printing machine (manufactured by Nippon Photo Printing Co., Ltd.) was applied to the transparent electrode surface of a glass substrate having a transparent electrode formed of an ITO film. The prepared liquid crystal alignment agent A-1 was heated on a hot plate at 80 ° C for 1 minute (prebaking), and after removing the solvent, it was heated on a hot plate at 150 ° C for 1 minute (post-baking) to form an average. A coating film having a film thickness of 600A. The coating film was subjected to a rubbing treatment by a friction device having a roller for winding a rayon cloth at a car rotation speed of 400 rpm, a table moving speed of 3 cm/s, and a pile pressing length of 〇.lmm. Thereafter, ultrasonic cleaning was carried out for 1 minute in ultrapure water, and then dried in a 1 ° C cleaning oven for 1 Torr to obtain a substrate having a coating film after rubbing treatment. This operation was repeated to obtain a pair (2 pieces) of a substrate having a coating film subjected to rubbing treatment. Next, 'the epoxy resin of the alumina ball having a diameter of 5·5 μm is applied to the outer edges of the rubbing-treated coating films of the pair of substrates, and then the pressure-sensitive adhesive is superposed and pressed so that the coating film faces. Harden the adhesive. Then, the liquid crystal injection port was filled with a nematic liquid crystal (manufactured by Merck Co., Ltd., MLC-6608) from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell. -85- 201035037 . • Repeat the above procedure to make three liquid cells with a transparent electrode without a picture. One of them is directly used for the pretilt angle evaluation described later. The remaining two liquid crystal cells were used to evaluate the pretilt angle and the voltage holding ratio after light irradiation in a state where a voltage was applied between the conductive films by the following method. Two of the liquid crystal cells obtained above were applied with an alternating current of 60 Hz at a frequency of 1 〇V between the electrodes, and an ultraviolet ray irradiation device was used in a state where the liquid crystal was driven. The device irradiated with ultraviolet rays by using a metal halide lamp as a light source. It is 1 0,000 J/m2 or 1 00,000 J/m2. Further, the amount of irradiation is measured by a light meter which is measured on the basis of a wavelength of 3 6 5 nm. [Evaluation of Pretilt Angle] The pretilt angle was measured for each of the liquid crystal cells produced as described above in the same manner as in Example 23, and as a result, the liquid crystal cell to which the light was not irradiated had a pretilt angle of 89° and the irradiation amount was 10,000 J/m 2 . The pretilt angle of the cell was 88°, and the pretilt angle of the liquid crystal cell having an irradiation amount of 100,000 J/m 2 was 84°. [Evaluation of Voltage Retention Rate] The respective liquid crystal cells produced as described above were measured in the same manner as in the above Example 2, and the voltage holding ratio was measured. As a result, the voltage holding ratio of the liquid crystal cell of the irradiation amount l〇, 〇〇〇J/m2 was measured. The current retention of the liquid crystal cell of 99%, and the irradiation amount l〇〇, 〇〇〇J/m2 was 84°. [Production of Liquid Crystal Cell Having Patterned Transparent Electrode] The slit pattern shown in Fig. 1 is formed, and liquid crystal alignment is used on each electrode surface of glass substrates A and B each having ITO electrodes divided into a plurality of regions. Film printing machine (manufactured by Japan Photo Printing Co., Ltd.), coating the liquid crystal alignment agent A-1 prepared above, heating on a hot plate at 80 ° C for 1 minute (prebaking), -86-201035037, after removing the solvent, The plate was heated on a hot plate at 150 ° C for 10 minutes (post-baking) to form a coating film having an average film thickness of 600 A. The coating film was ultrasonically washed in ultrapure water for 1 minute, and then dried in a 100 ° C cleaning oven for 10 minutes to obtain a substrate having a coating film. This operation was repeated to obtain a pair of (two pieces) substrates having a coating film. Next, an epoxy resin adhesive having an oxide ball of 5.5 μm in diameter was applied to each of the outer edges of the pair of substrates having the coating film, and then the pressure-sensitive adhesive was superposed and pressed so that the surface of the coating film faced each other to harden the adhesive. then. From the liquid crystal injection port, a nematic liquid crystal (MLC-660 8 manufactured by Merck Co., Ltd.) was filled between a pair of substrates, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to produce a liquid crystal cell. The above operation was repeated to fabricate three liquid crystal cells having a patterned transparent electrode. One of them is directly used for the response speed evaluation described later. The remaining two liquid crystal cells are used in the same manner as in the production of the liquid crystal cell having the above-described non-transparent transparent electrode, and the light is irradiated with an irradiation amount of 10,000 J/m 2 or 100,000 J/m 2 in a state where a voltage is applied between the conductive films, and then used. Evaluate the response speed. Further, the electrode pattern used here is the same pattern as the electrode pattern in the PSA mode. [Evaluation of response speed] No voltage was applied to each of the liquid crystal cells manufactured as described above, and the visible light lamp 'passed by the optical multimeter' was used to measure the brightness of the light transmitted through the liquid crystal cell, and the 値 was used as the relative transmittance of 0%. Next, when a 60-V alternating current was applied between the electrodes of the liquid crystal cell for 5 seconds, the transmittance was measured in the same manner as described above, and the enthalpy was used as a relative transmittance of 100%. -87-201035037 When 60 V alternating current was applied to each of the liquid crystal cells at this time, the time at which the relative transmittance was changed from 10% to 90% was measured, and this time was defined as the response speed and evaluated. As a result, the response speed of the liquid crystal cell which is not irradiated with light is 5 2 msec, the response speed of the liquid crystal cell having an irradiation amount of 10,000 J/m 2 is 48 msec, and the response speed of the liquid crystal cell having an irradiation amount of 100,000 J/m 2 is 29 msec. . From the results of Example 42, it is understood that in the method of the present invention, it is assumed that the ultraviolet irradiation amount is l〇〇, 〇〇〇J/m2 (in the PSA mode, usually ^ is used), and the degree of pretilt angle obtained is obtained. Too much, the pretilt angle is appropriate at an irradiation dose of 10,000 J/m2 or less. Further, even if the amount of irradiation is small, a sufficient response speed can be obtained, and the voltage holding ratio is also excellent. Therefore, according to the method of the present invention, since the advantage of the PSA mode can be realized with a small amount of light irradiation, there is no problem that display mottle generation due to high light irradiation amount, low voltage holding property, and long-term reliability are insufficient, and a viewing angle can be manufactured. Wide liquid crystal display elements with fast response, high transmittance, and high contrast. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a pattern of a transparent conductive film produced in Example 42. The pattern is a pattern of a transparent conductive film in a liquid crystal cell having a patterned transparent conductive film. [Main component symbol description] Tear. -88-

Claims (1)

201035037 VII. Applying for a patent. 1. A liquid crystal alignment agent characterized by comprising a radiation-sensitive polyorganosiloxane having a structure represented by the following formula (1), c=c-C 2 . The liquid crystal alignment agent of the first aspect, wherein the above-mentioned radiation-sensitive polyorganotite is (a) a polyorganosiloxane having an epoxy group and (b) having a structure represented by the above formula (1) and a carboxyl group. The reaction product of the compound or a compound having a group represented by the following formula (2) 'C3C-COOH(2). 3. The liquid crystal alignment agent of claim 2, wherein the compound (b) is a compound represented by the following formula (3) or (4). (R1 in the formula (3) is a hydrogen atom, a group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or a carbon atom having an alicyclic group of 3 to 40; a monovalent organic group, R2 is a single bond, an oxygen atom, a sulfur atom, *-COO-, *-COS-, *-SCO- or *-〇CO- (where 'in the above' with "*,, The linkage is linked to R1), and R3 is a divalent aromatic group, an alicyclic group of divalent-89-201035037, a divalent heterocyclic group or a divalent fused ring group, or a heterocyclic ring and a aryl group. A divalent group of a ring-condensed structure or a divalent group 'R4 having a structure in which a heterocyclic ring and an alicyclic ring are condensed are a single bond, an oxygen atom, a sulfur atom, *_c〇〇_, *-COS-, *-SC 〇- or *-〇c〇- (wherein, above, the linkage and r3 are attached) 'R5 is a fluorine atom or a cyano group, a is an integer of 〇~3, and b is an integer of 0 to 4, R·6 in the formula (4) is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having a carbon number of 40, or a carbon atom having an alicyclic group of 〇3 to 40. The monovalent organic group 'R7 is an oxygen atom or a divalent aromatic group, and R8 is an oxygen atom, -COO-* or - OCO-* (wherein, above, a linkage and R9 linkage), R9 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group Or a divalent group having a structure in which a heterocyclic ring and an aromatic ring are condensed or a divalent group having a structure in which a heterocyclic ring and an alicyclic ring are condensed, and R1Q is a single bond, -OCO-(CH2)e-* or -0 -(CH2)f-* (wherein, in the above, a linking bond and a carboxyl group are bonded), wherein e Q and f are each an integer of 1 to 1 Å, R 11 is a fluorine atom or a cyano group, and c is 〇 〜 An integer of 3, d is an integer of 0 to 4. The liquid crystal alignment agent according to any one of claims 1 to 3, further comprising a group selected from the group consisting of polylysine and polyimine The liquid crystal alignment agent of any one of the above claims 1 to 3, further comprising a polyorganoles other than the above-mentioned radiation-sensitive polyorganosiloxane. 90-201035037 A method for forming a liquid crystal alignment film, which is characterized in that a liquid crystal alignment agent as disclosed in any one of claims 1 to 5 is coated on a substrate. A step of forming a coating film to irradiate the coating film with radiation. A liquid crystal display element comprising a liquid crystal alignment film formed by a method for forming a liquid crystal alignment film according to claim 6 of the patent application. A method for producing a liquid crystal display device, comprising: coating a liquid crystal alignment agent according to any one of claims 1 to 5 on the conductive film of a pair of substrates having a conductive film; a coating film is formed, and a liquid crystal molecule layer is formed on the coating film of the pair of substrates on which the coating film is formed, and a liquid crystal cell having a facing arrangement is formed, and a voltage is applied between the conductive films of the pair of substrates. 'The aforementioned liquid crystal cell is irradiated with light. 9. The method of manufacturing a liquid crystal display device of claim 8, wherein the conductive film is a patterned conductive film divided into a plurality of regions. A liquid crystal display element is characterized in that it is manufactured by a method of manufacturing a liquid crystal display element according to the eighth or ninth aspect of the patent application. A radiation-sensitive polyorganosiloxane having a structure represented by the above formula (1). -91 -