TW200927793A - Liquid crystal aligning agent, method for forming liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

Disclosed is a liquid crystal aligning agent containing a radiation-sensitive polyorganosiloxane which is obtained by reacting a cinnamic acid derivative having at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R represents a hydrogen atom or an alkyl group having 1-6 carbon atoms), -CH=CH2 and -SO2Cl with a polyorganosiloxane having an oxethane ring.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal alignment agent, a method for producing a liquid crystal alignment film, and a liquid crystal display device. ^ * [Prior Art] In the prior art, it is known that a nematic liquid crystal having a positive dielectric anisotropy is formed into a sandwich structure with a substrate having a transparent electrode having a liquid crystal alignment film, and if necessary, a liquid crystal molecule A liquid crystal display having a crystal cell such as a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, or an IPS (In Plane Switching type) in which the long axis is continuously twisted between the substrates by 〇~3 60°. The device is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei.

In such a liquid crystal cell, in order to align the liquid crystal molecules with respect to the substrate surface in a predetermined direction, it is necessary to provide a liquid crystal alignment film on the surface of the substrate; the liquid φ crystal alignment film system is usually formed by the surface of the organic film formed on the surface of the substrate. It is formed by a method of rubbing a cloth such as a thread in one direction (friction alignment method). However, since the formation of the liquid crystal alignment film is performed by the rubbing alignment treatment, dust or static electricity is likely to occur in the step, so that dust may adhere to the surface of the alignment film, which may cause a display failure, particularly TFT (Thin In the case of a substrate of a component, there is also a problem that the circuit of the TFT element is broken due to static electricity generated, which causes a decrease in yield. Further, in the liquid crystal display element which is more refined in the future, unevenness is generated on the surface of the substrate due to the increase in density of the pixels, and it is difficult to perform the rubbing alignment treatment uniformly on -4 - 200927793. As another means for aligning the liquid crystal in the liquid crystal cell, it is known to irradiate a polarizing film or a non-polarizing light to a photosensitive film such as polyethylene cinnamate, polyiminoimide or azobenzene derivative formed on the surface of the substrate. The radiation, 'the optical alignment method that gives the liquid crystal alignment energy, according to this method, can achieve uniform liquid crystal alignment without static electricity or dust (refer to Japanese Patent Laid-Open No. 6-2 8745 3, Special Kaiping 1 0-25) Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2000-281. Japanese Laid-Open Patent Publication No. Hei 9-297313, JP-A-2003-307736, JP-A-2004-163646, and JP-A-2002-250924. However, in liquid crystal cells such as TN (Twisted Nematic) type and STN (Super Twisted Nematic) type, the liquid crystal alignment film must have a pretilt angle characteristic of tilting the liquid crystal molecules at a predetermined angle with respect to the substrate surface. When the liquid crystal alignment film is formed, the pretilt angle is usually imparted by inclining the incident direction of the radiation irradiated by the erbium toward the substrate surface from the substrate normal. On the other hand, as an operation mode of a liquid crystal display element different from the above, it is known that a liquid crystal molecule having a negative dielectric anisotropy is vertically aligned to a homeotropic alignment mode of a substrate. In this mode of operation, when a voltage is applied between S t and the liquid crystal molecules are tilted in a direction parallel to the substrate, it is necessary to make the liquid crystal molecules from the normal direction of the substrate toward a plane in the plane of the substrate. For example, a method of providing a protrusion on a surface of a substrate is proposed, and a method of providing a strip shape on a transparent electrode, and using a rubbing alignment compound--5-200927793, the liquid crystal molecules are slightly tilted from a normal direction of the substrate toward a direction in the plane of the substrate. (to make it pre-tilt) method, etc. The above-described photoalignment method is known to be suitable as a method of controlling the tilt direction of liquid crystal molecules in a liquid crystal cell of a vertical alignment mode, that is, it is known to impart a vertical alignment with an alignment specification and a pretilt expression by using a photo-alignment method. " To the film', the tilt direction of the liquid crystal molecules when the voltage is applied is uniformly controlled (refer to Japanese Laid-Open Patent Publication No. 2003-307736, JP-A-2004-163646, JP-A-2004-838 No. 9-2 1 1 468 and JP-A-2003 - 1 1 443 7). As described above, the liquid crystal alignment film produced by the photo-alignment method can be effectively applied to various liquid crystal display elements. However, in the prior art photo-alignment film, a large amount of radiation exposure is required in order to obtain a large pretilt angle. The problem. For example, when a film containing an azobenzene derivative is given a liquid crystal alignment energy by a photo-alignment method, in order to obtain a sufficient pretilt angle, it is necessary to irradiate an optical axis of 10,0 0 OJ/m 2 or more from the substrate normal. The report of the slanting radiation illuminating (refer to Japanese Laid-Open Patent Publication No. Hei 02-250924 and JP-A-2004-83810 and J. of the SID 11/3, 2003, p579). SUMMARY OF THE INVENTION The object of the present invention is to provide a liquid crystal alignment of a liquid crystal alignment film which has excellent liquid crystal alignment energy even with a small amount of light exposure by radiation irradiation without polarization or non-polarization treatment. The method of producing the liquid crystal alignment film, and a liquid crystal display element having excellent properties such as display characteristics and signalability. -6- 200927793 Further objects and advantages of the present invention will be apparent from the following description. According to the present invention, in the above object of the present invention, the first aspect is obtained by containing a residue having a residue, a trans group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). -CH = at least one cinnamic acid derivative selected from the group consisting of CH2 and -S02C1, and a radiation-sensitive linear polyorganoindene obtained by reacting with a polyorganosiloxane having an oxetane ring A liquid crystal alignment agent of oxyalkylene is achieved. In the above object of the present invention, the second aspect is achieved by a method of forming a coating film by applying the above-described liquid crystal alignment agent onto a substrate, and irradiating the coating film with a radiation liquid crystal alignment film. In the above object of the present invention, the third aspect is achieved by a liquid crystal display element comprising a liquid crystal alignment film formed of the above liquid crystal alignment agent. ❹ [Best Mode for Carrying Out the Invention] The liquid crystal alignment agent of the present invention contains a group having a carboxyl group, a group of -SH, -NCO, and -MHR (wherein R is a hydrogen atom or a carbon number of 1 to 6). ), -CH = CH2 and - S02C1 are selected from the group consisting of at least one type of cinnamic acid derivative, and a polyorganic aerobics having an oxetane ring (hereinafter referred to as "having oxygen" The sensitized radiation linear polyorganotate obtained by the reaction of the polyorganocaline of the cyclobutane ring. -7- 200927793 [cinnamic acid derivative] The present invention has a carboxyl group, a hydroxyl group, _SH, _NCO, -NHR (only R is a hydrogen atom or an alkyl group having a carbon number of 1-6), _CH = CH2 and -S The at least one cinnamic acid derivative selected from the group formed by Ο2 C1 is preferably the following formula (A-1)

(A-1) (In the formula (A-1), R1 is an alkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms having an alicyclic group, and the hydrogen atom of the above alkyl group Some or all of them may be substituted by fluorine atoms; R2 is a single bond, an oxygen atom, -(:00_ or -OCO-; R3 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic ring a divalent or divalent condensed cyclic group, except that part or all of the above-mentioned divalent aromatic hydroquinone atom may be substituted by a fluorine atom; R4 is a single bond, an oxygen atom, -COO- or -OCO-; R5 is a single bond, a methyl group, a C 2 to 10 alkyl group or a divalent aromatic group; when R 5 is a single bond, R 6 is a hydrogen atom 'R 5 is a methyl group, an alkyl group or a divalent aromatic group. The radical 'R6 is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR, _CH=CH2 or -SO2CI'. However, the above R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and r7 is a fluorine atom, a methyl group or a cyanogen group. Base; a is an integer of 〇~3; b is an integer of 〇~4.) The compound represented or the following formula (A_2) -8 - 200927793 r8—0—rCH=CH_^ (Α·2) 〇) d (in the formula (Α-2), 'R8 is the base of the carbon number 1~4〇 or the test contains an alicyclic group or aroma a monovalent organic group having a carbon number of 3 to 40, wherein a part or all of the hydrogen atom of the above fluorenyl group may be substituted by a fluorine atom; R9 is a single bond, an oxygen atom, -COO- or -OCO-; R10 is a methyl group, an alkylene group having 2 to 1 Å, a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group, except for the above 2 A part or all of the valent aromatic hydrogen atom may be substituted by a fluorine atom; R11 is a single bond, -〇C〇-(CH2;)e-, -COO-(CH2)g- or -〇-(CH2) I-' wherein e, g and i are each an integer of 1 to 1 ;; R12 is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR, -CH=CH2 or -S02Cl, except that the above R is a hydrogen atom or carbon An alkyl group having 1 to 6; R 13 is a fluorine atom, a methyl group or a cyano group; c is an integer of 0 to 3; and d is an integer of 〇 4 to 4). The fluorenyl group having 1 to 40 carbon atoms of R in the above formula (A-1) is preferably a group of, for example, a carbon number of 1 to 2 Å. Only a part or all of the hydrogen atoms of the group may be replaced by fluorine atoms. . Examples of the related alkyl group include, for example, η-pentyl, η-hexyl, η-heptyl, η-octyl, η-fluorenyl, η-fluorenyl, η-lauroyl, η-twelve Courtyard, η_12 yard base, η-fourteen yard base, η - fifteen yard base, η -16 yard base, η -17 yard base, η -18 yard base, η-nonadecane Base, η-icosyl, 4,4,4-trifluorobutyl, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-seven Fluoryl, 3,3,4,4,5,5,5-heptafluoropentyl, -9- 200927793 2,2,2-difluoroethyl ' 2,2,3,3,3 -pentafluoropropene Base, 2-(perfluorobutyl)ethyl, 2-(perfluorooctyl)ethyl, 2-(perfluorodecyl)ethyl, and the like. Examples of the monovalent organic group having 3 to 4 carbon atoms and having an alicyclic group of R1 include a cholesteryl group, a cholesteryl group, and an adamantyl group. 'As a divalent aromatic group of R3, for example, 1,4-phenylene group, 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, q 1,4-extended hexyl group; and the divalent heterocyclic ring of R3; Examples of the group include, for example, a 1,4-pyridylpyridyl group, a 2,5-extended pyridyl group, an anthracene, a tetrahydrofuranyl group, and the like. Examples of the divalent condensed cyclic group of R3 include an anthranyl group. The divalent aromatic group R of R 5 may, for example, be a 1,4-phenylene group or the like. Examples of the compound represented by the above formula (A-1), as the cinnamic acid derivative having a carboxyl group, for example, the following formula (A-1-C1) to (A-!-C24)-10-200927793 1_o^ O^Or CH=CH—COOH (A-1-C1)

R1-COO CH=CH—COOH (A-1-C2) CH=CH—COOH (A-1-C3) COO—^~^—CH=CH—COOH (A-1-C4) ❹

R1-COO

-COO

J〇T CH=CH—COOH (A-1-C5) coo Or-CH—COOH (A-1- C6) COO—^~~^>—CH=CH—COOH (A-1-C7) COO —<^~^-CH—CH—COOH (A-1-C8)

CH=CH—CO COOH (A-1-C9) ❹

R1-COO

CH=CH—CO

Or COOH (A-1-C10)

CH=CH——CO 1-〇- 1_ohO~ coo 〇- CH=CH—CO R1-COO O~ coo 〇- CH=CH—CO JOr

R COOH (A-1-C12) COOH (A-1-C13)

'COO CH=CH—CO Or COOH (A-1-C14) coo 〇- CH=CH—CO o COOH (A-1-C15) -11 - 200927793 R1—CH=CH-COOH (A-1- C16) CH=CH—COOH (A-1-C17) R1COO—CH=CH—COOH (A-1-C18) CH=CH—CQ〇-(CH 2 )-COOH (A-1-C19) 〇1. Fraction CH=CH—C00-(CH2)-C00H (A-1-C20)

R1COO CH=CH—C00-(CH2)—COOH (A-1-C21) f C00-^~^>—CH=CH—CQ0-(CH2)-C00H (A-1-C22) COQ-^~ ~^>—CH=CH—COO-(CH2)-COOH (A-1-C23)

R1COO COO-^ j^CH=CH—CO〇-(CH2)-COOH (A-1-C24) ❹ where R1 is synonymous with the above formula (Al), and f is an integer represented by 1 to 10 The compound or the like; as the cinnamic acid derivative having a hydroxyl group, for example, the following formula (A-1-Ol) - (A-1-013) -12- 200927793 1_οΌ· CH=CH-CO <y

R1-COO

CH=CH—CO JOr OH (A-1-02)

CH=CH——CO OH (A-1-03)

G

Coo JOr CH=CH—CO J〇T OH (A-1-04) R1-COO o coo ~Qr CH=CH—CO 分 - (A-1-05)

-COO

CH=CH—CO OH (A-1-06)

'Or COO—(\ /)—CH=CH —CO—/)—OH (A-1-07) CH=CH—CO〇-(CH2)-〇H (A-1-08) CH=CH— C0Q-(CH2)-0H (A-1-09) ❹ R1COO o CH=CH—COO-(CH2)-〇H (A-1-O10) “Or C00-^~~^)—CH=CH— COO-(CH2)-OH (A-1-011) COQ-^~^)—CH=CH—C00-(CH2)-0H (A-1-012) R1COO-C00-(~y~CH=CH -CO〇-(CH2)7〇H (A-1-013) wherein R1 is synonymous with the above formula (Al), and f is a compound represented by the integer-13 to 200927793 of 1 to 10. Wait. The alkyl group having 1 to 4 carbon atoms of R8 in the above formula (A-2) is preferably an alkyl group having 1 to 20 carbon atoms, and only a part or all of the hydrogen atom of the alkyl group may be substituted by a fluorine atom. Examples of the related alkyl group include those exemplified as the alkyl group of R1 in the above formula (A-1). Examples of the monovalent organic group having 3 to 40 carbon atoms of the alicyclic group containing R8 include, for example, φ cholesteryl, cholesteryl, adamantyl, and the like; and the carbon number of the aromatic group as R8 A monovalent organic group of 3 to 40, for example,

(In the above formula, R1 is an alkyl group having 4 to 20 carbon atoms, a fluoroalkane group having 1 to 20 carbon atoms, a cyclohexyl group, an alkylcyclohexyl group having an alkyl group having 1 to 2 carbon atoms or having a carbon number of 1; a group represented by any of fluoroalkylcyclohexyl groups of -20 fluoroalkyl groups. The divalent aromatic group, the divalent alicyclic group, the divalent heterocyclic group or the divalent condensed cyclic group of R1 ^ may, for example, be 2 as r3 in the above formula (A-1). The valent aromatic group, the divalent alicyclic group, the divalent heterocyclic group or the divalent condensed cyclic group are each exemplified. Examples of the compound represented by the above formula (A-2), and examples of the cinnamic acid derivative having a carboxyl group, for example, the following formula (A-2-C1) to (A-2-C6)-14-200927793 R8- 〇C〇-CH=CH—^ J)—QCO—(CH2)a-COOH (A-2-C1) CO—CH=CH ~Qt COOH (A-2-C2) R80~C V-CO—CH =CH —L V-COOH (A-2-C3) R8—CO—CH=CH—^~^-OCQ—(CH2)a-COOH (A-2-C4) R80—CH=CH—^~^ -OCO-(CH2)a-COOH (A-2-C5) ❹ r8oco-ch=ch-oco-^~^-OOC-(CH2)-COOH (A-2-C6) (In the above formula, R8 and In the above formula (A-2), a is a compound of the formula (A), and the like, and a cinnamic acid derivative having a hydroxyl group, and f (A-2-O 1 )~(A- 2-05) ❹

R8-〇C〇—CH=CH OH (A-2-01) R8 -^y~c〇~cH=cH~^y~ OH (A-2-02) r8〇hQ- CO—CH=CH . H (A-2-03) r8oco-ch=ch-^^—oco OH (A-2-04) R80C0-CH=CH—0C0-^~~^)—00C-(CH2)-0H (A -2-05) -15- 200927793 (In the above formula, R8 is a compound represented by the above formula (A-2), and 'h is an integer of 1 to 10. The compound ' represented by the above formula (A-1) or (A-2) can be synthesized by a conventional method having an organic chemistry. - for example, the compound represented by the above formula (A -1 - C 1 ) can be, for example, a hydroxy cinnamic acid and a hydrazinyl group having an alkyl group corresponding to R1, and a suitable base such as potassium@potassium or the like. It is obtained by heating in a suitable aqueous alkali solution such as sodium hydroxide after heating in the presence of the reaction. The compound ' represented by the above formula (A-1-C2) can be, for example, by using a hydroxycinnamic acid and an alkylcarboxylic acid chloride having an alkyl group corresponding to R1 in the presence of a suitable base such as potassium carbonate. It is obtained by reacting at a temperature of from °C to room temperature. The compound represented by the above formula (A - 1 - C 4 ) can be, for example, potassium hydroxybenzoate and a halogenated alkyl group having an alkyl group corresponding to R1 or a toluene-sulfonated alkyl group in potassium carbonate or the like. After reacting at a temperature of from room temperature to 100 ° C in the presence of a suitable base, it is hydrolyzed in an appropriate aqueous alkali solution such as sodium hydroxide, and then, after being converted to acid chloride by thionyl chloride It is obtained by reacting with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate at a temperature of from 〇 ° C to room temperature. The compound represented by the above formula (A-1 - C5 ) can be, for example, a hydroxybenzoic acid and an alkyl carboxylic acid chloride having an alkyl group corresponding to R 1 in the presence of a suitable base such as triethylamine. After reacting at a temperature of 〇°c~room temperature, the sulfhydryl chloride is thiol chloride, and it is in the presence of a suitable base of potassium carbonate, such as -16-27793, with hydroxycinnamic acid as o°c~ It is obtained by reacting at room temperature. The compound represented by the above formula (A-1-C6) can be, for example, present in a suitable base such as potassium carbonate by causing 4-alkyl benzoic acid to be decyl chloride by sulfinium chloride. It is obtained by reacting with hydroxycinnamic acid at a temperature of from 0 ° C to room temperature. The compound represented by the above formula (A-1-C7) can be, for example, sodium methyl 4-hydroxycyclohexylcarboxylate and a halogenated alkyl group having an alkyl group corresponding to R1, such as sodium hydride or sodium metal. After reacting in the presence of a suitable base to form an ether, it is hydrolyzed in an aqueous alkali solution such as sodium hydroxide, and then sulfonium chloride is used as a mercapto chloride, and then, in the presence of a suitable alkali such as potassium carbonate, Hydroxycinnamic acid is obtained by reacting at a temperature of from 0 ° C to room temperature. The compound represented by the above formula (A - 1 - C 8 ) can be, for example, a 4-alkylcyclohexylcarboxylic acid having an alkyl group corresponding to R1 by using thionyl chloride as the mercapto chloride. It is obtained by reacting a hydroxycinnamic acid with a hydroxy cinnamic acid in the presence of a suitable base such as potassium carbonate at a temperature of from room temperature to room temperature.化合物 The compound represented by the above formula (A-1-C9) can be formed by reacting a halogenated alkyl group corresponding to R1 with a hydroxybenzaldehyde in the presence of a base such as potassium carbonate to form an ether bond, and then 4-ethylindole Benzoic acid is obtained by aldol condensation in the presence of sodium hydroxide. The compound represented by the above formula (A-1-C10) to (A-1-C15) can also be obtained by the method according to the method. The compound represented by the above formula (A - 2 - C 1 ) can be reacted, for example, by using palladium and an amine as a catalyst by reacting 4-iodophenol with an alkyl acrylate having an alkyl group corresponding to R1 (generally called After the "Heck reaction", the reaction product is subjected to ring-opening addition of a cyclic -17-200927793 acid anhydride such as succinic anhydride or glutaric anhydride. The compound represented by the above formula (A-2-C2) can be obtained by aldol condensation of 4-alkyl acetophenone corresponding to -R1 with 4-mercaptobenzoic acid in the presence of sodium hydroxide. . The compound represented by the above formula (A-2-C3) can also be obtained by the method according to this. The compound represented by the above formula (A-2-C4) can be obtained by aldol condensation of 4-alkylethyl benzene corresponding to R1 with 4-hydroxybenzaldehyde in the presence of sodium hydroxide. The compound represented by the above formula (A - 2 - C 5 ) can also be obtained by the method according to this. The compound represented by the above formula (A-1-01) can be formed by reacting a halogenated alkyl group having an alkyl group corresponding to R1 with 4-hydroxybenzaldehyde in the presence of a base such as potassium carbonate to form an ether bond. 4-Hydroxyacetamidine is obtained by aldol condensation in the presence of sodium hydroxide. The compound represented by the above formula (A-1-02) to (A-1-◦ 7 ) can also be obtained by the method according to the method. The compound represented by the above formula (A-2-Ol) can be reacted, for example, by using palladium and an amine as a catalyst by reacting 4-φ iodine phenol with an alkyl acrylate having an alkyl group corresponding to R1 (generally referred to as Obtained for "Heck reaction"). The compound represented by the above formula (A-2-02) can be obtained by aldol condensation of 4-alkylethyl benzene benzene corresponding to R1 with 4-hydroxybenzaldehyde in the presence of sodium hydroxide. The compound represented by the above formula (A-2-03) can also be obtained by the method according to this. [Polyorganomethoxyoxane having an oxetane ring] -18- 200927793 The above polyorganosiloxane having an oxetane ring preferably has the following formula (S-1)

Si_Ο-- (S-1) (In the formula (S-1), X is a formula (X-1) ❹ R14 (X-1) (in the formula (X-1), R14 is a carbon number of the alkane The base ''*' indicates a bond bond.) The monovalent organic group of the structure shown; γ1 is a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms. At least one selected from the group consisting of a polyorganism, a hydrolyzate, and a condensate of a hydrolyzate. As the alkyl group of the group R in the group X in the formula (s-i), a methyl group, an ethyl group, an η-propyl group or an η-butyl group is preferred. The base X in the formula (si), preferably for the formula (χ-2) 〇14 p15 β VS) Ο -19- 200927793 (in the formula (X-2), R14 is synonymous with the above formula (Xl); R15 is A methyl group having a carbon number of 2 to 6 which is interrupted by an oxygen atom in the middle or a methyl group; "=) = "" means a bonding bond. The base referred to is more preferably the following formula (X-3)

基 The base represented. Examples of the alkoxy group having 1 to 20 carbon atoms of Y 1 include a methoxy group, an ethoxy 'η-propoxy group, an i-propoxy group, an η-butoxy group, an s-butoxy group, and a butyl group. Examples of the alkyl group having a carbon number of 1 to 10 include, for example, a methyl group, an ethyl group, an η-propyl group, an η-butyl group, an η-pentyl group, an η-hexyl group, an n-heptyl group, and a η-octyl group. Base, η-fluorenyl, η-fluorenyl, and the like. The polyorganic seroconverter with an oxetane ring is a polystyrene-equivalent weight average molecular weight measured by the knee-penetrating color Q-spectrum method (GPC) of 5 〇〇 to 1 〇〇, preferably 〇〇〇 '1, 〇〇〇~1〇, 〇〇〇 better, 1, 〇〇〇~6, 〇〇〇 better. Such a polyorganic electrification chamber having an oxetane ring may preferably be obtained by using a brothel compound having an oxetane ring or a sand compound having an oxetane ring and the like. The mixture of the sand compound is preferably synthesized by hydrolysis or hydrolysis in the presence of a suitable organic solvent, water and a catalyst. The decane compound having an oxetane ring may, for example, be -20-200927793 as shown in the following formula (3 - 1)

Si(OR16)3(3-1) - (in the formula (3-1), R16 is a methyl group or an ethyl group). 〇 As the above other decane compound, for example, 3-glycidoxypropyldimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3_glycidoxypropylmethyl group can be mentioned. Dimethoxydecane, 3-glycidoxypropylmethyl-ethoxy decane, 3-glycidoxypropyldimethylmethoxydecane, 3-glycidoxypropyl- Methyl ethoxy decane, 2_(3,4•epoxycyclohexyl)ethyldimethoxy sand, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, tetrachlorodecane , tetramethoxy decane 'tetraethoxy decane, tetrapropoxy decane, tetrapropyl propoxy decane, tetra-n-butoxy decane ' U tetra-sec-butoxy decane, trichloro decane, trimethyl Oxydecane, triethoxydecane, di-η-propoxydecane, tris-propoxydecane, tri-n-butoxydecane, di-sec-butoxydecane, fluorotrichlorodecane, fluorine Trimethoxydecane, fluorodiethoxydecane, fluorotridecyloxypropane, fluorotrisethoxypropane, fluorodi-n-butoxydecane, fluorotris-butoxybutane, A Trichlorosilane, methyltrimethoxydecane Methyl triethoxy decane, methyl tri-η-propoxy squalane, methyl trisuccinyl decane, methyl tri-n-butoxy decane, methyl di-sec-butoxy decane , 2_(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl)ethyltrimethoxydecane, 2_(trifluoro-21 - 200927793 methyl)ethyltriethoxydecane, 2- (trifluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl)ethyltri-i-propoxydecane, 2-(trifluoromethyl)ethyltri-η- Butoxy decane, 2-(trifluoromethyl)ethyltris-butoxybutane, 2-(perfluoro-η-hexyl)ethyltrichlorodecane, 2-(all-fluoro-η-hexyl) Ethyltrimethoxydecane, 2-(perfluoro-n-hexyl)ethyl-triethoxydecane, 2-(perfluoro-η-hexyl)ethyltri-n-propoxydecane, 2- (perfluoro-η-hexyl)ethyltri-i-propoxydecane, 2-(perfluoro-φ η-hexyl)ethyltri-n-butoxydecane, 2-(perfluoro-η-hexyl) Ethyl tri-sec-butoxydecane, 2-(perfluoro-η-octyl)ethyltrichlorodecane, 2-(perfluoro-η-octyl)ethyltrimethoxydecane, 2-( Perfluoro-η-octyl) ethyltriethoxy Baseline, 2-(perfluoro-η-octyl)ethyltri-n-propoxydecane, 2-(perfluoro-η-octyl)ethyltri-i-propoxydecane, 2-( Perfluoro-η-octyl)ethyltri-n-butoxydecane, 2-(perfluoro-η-octyl)ethyltris-sec-butoxydecane, hydroxymethyltrichlorodecane, hydroxyl group Trimethoxy decane, hydroxyethyl trimethoxy decane, hydroxymethyl tri-n-propoxy Q decane, hydroxymethyl tri-i-propoxy decane, hydroxymethyl tri-n-butoxy decane , hydroxymethyl tris-sec-butoxydecane, 3-(meth)acryloxypropyltrichlorodecane, 3-(meth)acryloxypropyltrimethoxydecane, 3-(A Acryloxypropyltriethoxydecane, 3-(methyl)propenyloxypropyltris-n-propoxydecane, 3-(methyl)propenyloxypropyltri-i -propoxydecane, 3-(methyl)propenyloxypropyltris-n-butoxydecane, 3-(methyl)propenyloxypropyltris-sec-butoxydecane, 3 - Mercaptopropyltrichloromethane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropyltri-n-propaneoxy矽-22 - 200927793 Alkane, 3-mercaptopropyltri-i-propoxydecane, 3-mercaptopropyltris-n-butoxylate, 3-isylpropyltris-butoxybutoxy Sand yard, sulfhydryl methyltrimethoxy decane, decyl-methyltriethoxy decane, vinyl trichlorodecane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tri-η- Propoxy decane, vinyl tri-i-propoxy decane, vinyl tri-n-butoxy fluorene alkene, vinyl tri- sec-butoxy decane, allyl trichloro decane, allyl Trimethoxy decane, allyl triethoxy decane, allyl tri-n-propoxy φ decane, allyl tri-i-propoxy decane, allyl tri-n-butoxy decane , allyl tris-sec-butoxydecane, phenyl trichlorodecane, phenyltrimethoxydecane, phenyltriethoxydecane, phenyl tri-n-propoxydecane, phenyl tri-i - propoxy decane, phenyl tri-n-butoxy decane, phenyl tris-sec-butoxy decane, methyl dichlorodecane, methyl dimethoxy decane, methyl diethoxy sand, Methyl di-n-propoxy sand, methyl di-i-propyl Baseline, methyl di-η-butoxydecane, methyl di-sec-butoxydecane, dimethyldichlorodecane, dimethyldimethoxydecane, dimethyldiethoxyanthracene Alkane, dimethyldi-η-propoxydecane, dimethyldi-i-propoxydecane, dimethyldi-n-butoxydecane, dimethyldi-sec-butoxylate , (methyl) [2_(perfluoro-η-octyl)ethyl]dichlorodecane, (methyl) [2-(perfluoro-η-octyl)ethyl]dimethoxydecane, (a [2-(perfluoro-η-octyl)ethyl]diethoxydecane, (methyl)[2-(perfluoro-η-octyl)ethyl]di-n-propoxydecane , (methyl) [2-(perfluoro-η-octyl)ethyl]di-i-propoxydecane, (methyl)[2-(perfluoro-η-octyl)ethyl]di- N-butoxydecane '(methyl)[2-(perfluoro-η-octyl)ethyl]di-sec-butoxydecane, (methyl)(3-mercapto-23- 200927793 propyl) Dichlorodecane, (methyl)(3·mercaptopropyl)dimethoxydecane, (methyl)(3-mercaptopropyl)diethoxydecane, (methyl)(3-mercaptopropyl) ― Di-η-propoxydecane, (methyl)(3-mercaptopropyl)di-i-propoxydecane, (methyl)(3-mercaptopropyl)di-η-butoxydecane , (methyl) (3-mercaptopropyl) bis-sec-butoxydecane, (methyl) (vinyl) dichlorodecane, (methyl) (vinyl) dimethoxy decane, (a (vinyl) diethoxy decane, (methyl) (vinyl) di-η-propoxy decane, (methyl) (vinyl) di-i-propoxy decane, (methyl) (vinyl) di-n-butoxydecane, (methyl) (ethinyl)-"-sec-butene-based sandstone, one-ethyl chlorinated sand, divinyldimethoxy Decane, divinyldiethoxydecane, divinyldi-n-propoxydecane, divinyldi-i-propoxydecane, divinyldi-n-butoxydecane, divinyl Di-sec-butoxydecane, diphenyldichlorodecane, diphenyldimethoxydecane, diphenyldiethoxydecane, diphenyldi-n-propoxydecane, diphenyldiene -i-propoxydecane, diphenyldi-n-butoxydecane, diphenyldi- Sec - butoxy decane, chlorodimethyl decane, methoxy dimethyl decane, ethoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, iodine trimethyl decane, methoxy Trimethyl decane, ethoxy trimethyl decane, η-propoxy trimethyl decane, N propoxy trimethyl decane, η - butoxy trimethyl decane, sec - butoxy trimethyl Decane, t-butoxy trimethyl decane, (chloro)(vinyl)dimethyl decane, (methoxy)(vinyl)dimethyl decane, (ethoxy)(vinyl) dimethyl矽, (chloro)(methyl)diphenylnonane, (methoxy)(methyl)diphenylnonane, (ethoxy)(methyl)di-24- 200927793 phenyldecane, etc. In addition to the decane compound of a halogen atom; in the trade name, for example, KC-89' KC-89S, X-21-3153, X-21-5841, X-2 1 -.5 842, X-21-5843, X-21-5844, X-2 1 - 5845, X-2 1 -5846, X-21-5847, X-2 1 -5 848, X-22-160AS, X-22-170B, X-22- 1 70BX, X-22-1 70D, X-22- 1 70DX, X-22-176B, X-22- 1 76D, X-22- 1 76DX , X-22- 1 76F, X-40-2308, X-40-2651, X-40-2655A, X-40-

❹ 2671, X-40-2672, X-40-9220 'X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-93 23, 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, KR 2 2 0 L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR5 00, KR510, KR5206, KR523 0, KR523 5, KR9218, KR9706 (above, Shin-Etsu Chemical Co., Ltd.); Glass Resin (Showa Electric ( Stocks); SH804, SH8 05, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411 'SR2416, SR2420 (above, Toray Dow Corning (share) system); FZ3711, FZ3722 (above, Japan UNICAR) (share) system; DMS-S12 ' DMS-S 1 5 , DMS-S21, DMS-S27, DMS-S3 1, DMS-S32, DMS-S3 3, DMS-S35 ' DMS -S3 8 , DMS- S42 , DMS-S45, DMS-S5 1 , DMS-227 ' PSD-0332 , PDS-1615, PDS-9931, XMS-5025 (above, Chisso); methyl phthalate MS51, methyl decanoic acid Ester MS56 (above, Mitsubishi Chemical Corporation) ): ethyl phthalate 28, ethyl phthalate 40, ethyl phthalate - 25 - 200927793 ester 48 (above, COLCOAT (manufactured by COLCOAT); GR100, GR65 0, GR908, GR950 (above, Showa Electric ( Part of the condensate. - among these, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, 3-(methyl) propylene methoxy propyl trimethoxy decane , 3-(meth)acryloxypropyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, allylmercaptotrimethoxydecane, allyltriethoxy Decane, phenyltrimethoxydecane, phenyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, mercaptomethyltrimethoxydecane, fluorenyl Methyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxy ring Hexyl)ethyltrimethoxydecane or the like is preferred. The polyorganosiloxane having an oxetane ring preferably used in the present invention corresponds to an amount of 1 mole of polyorganooxane of the oxetane ring of 100 to 2,000 g/m. The ear is better, 200~l,000g/mole is better. Therefore, when synthesizing a polyorganosiloxane having an oxetane ring, the use ratio of the decane compound having an oxy-heterocyclobutane ring to other decane compounds is set so that the obtained polyorganosiloxane is obtained. The oxetane ring concentration adjustment is preferably in the above range. When a polyorganosiloxane having an oxetane ring is synthesized as an organic solvent which can be used, for example, an alcohol such as methanol, ethanol or isopropanol; acetone, 2-butanone or methyl isobutyl ketone; In addition to ketones and the like, tetrahydrofuran, toluene, 1,4-dioxane, hexane, petroleum ether and the like. The use of the organic solvent is preferably from 00 parts by weight to 10,000 parts by weight of the total decane compound, more preferably from 50 to 1,000 parts by weight. The amount of the polyorganosiloxane having an oxetane ring is preferably from 0.1 to 1,000 times, preferably from 1.0 to 1 mole, relative to the total decane compound. The catalyst for synthesizing the polyorganosiloxane having an oxetane ring is preferably a basic compound, and examples thereof include ammonia and 4 φ organic amine. As the organic amine, a tertiary amine is preferred; and a 4-grade ammonium salt or a tertiary amine is preferred; as a specific example thereof, for example, triethylamine, tripropylamine, diazabicyclohexadecene carbonization Tetramethylammonium and the like. The amount of the catalyst used is preferably from 1 to 100 parts by weight based on 100 parts by weight of the total. As conditions for synthesizing the polyorganooxane having an oxetane ring, appropriate conditions can be employed, but the total number of the total decane compounds (the total number of hydroxyl groups, halogen atoms, and alkoxy groups) is more than The condensation is preferably 95% or more by condensation to the related polyorganosiloxane, the reaction condition is 10 to 120 ° C, more preferably 0.1 to 30 hours at a reaction temperature of 20 to 80 ° C. More preferably, the reaction time is uo hours. After the completion of the reaction, the organic solvent which has been taken out from the reaction liquid is preferably washed, and when it is washed, it is washed with an aqueous solution of ammonium nitrate containing about 2% by weight of water, which contains a small amount of salt, and is easily washed. In view of the above, it is preferred that the washing is carried out until the water layer after washing. Then, the organic solvent layer is used, if necessary, anhydrous calcium sulfate is used in the range of 10 to 10,000 water, and the ammonium salt is used. The medium, a special example, is less than 90 moles of the reaction hydrolyzable group in the case of a dilute or aminoxycene compound. In order to obtain 3, it is preferred that the agent layer be made of water, for example, by drying it with a suitable desiccant such as a neutral granule, molecular sieve -27-200927793, etc., and then removing the solvent to obtain an oxygen-containing purpose. An organic oxane of a cyclobutane ring. In the present invention, a commercially available product having a oxetane ring, such as a commercially available product, may be exemplified by the trade name "OX-SQ" of East Asia Synthetic Co., Ltd., and the like. . [Mens radiation linear polyorganosiloxane] Φ The radiation-sensitive linear polyorganosiloxane used in the present invention can be obtained by using a cinnamic acid derivative as described above and a polyorganosiloxane having an oxetane ring. Preferably, it is synthesized by reaction in the presence of a catalyst. Wherein the cinnamic acid derivative is preferably 0.001 to 3 moles, more preferably 0.1 to 1 mole, more preferably oxetanealkyl 1 mole, based on the polyorganosiloxane. 0.2 to 0.9 m. In the present invention, a part of the above cinnamic acid derivative may be represented by the following formula (5) ❹ R18-R19-R20 ( 5 ) in the range which does not impair the effects of the present invention (in the formula (5), R18 is carbon a 4 to 20 alkyl group or alkoxy group or a monovalent organic group having an alicyclic group having 3 to 40 carbon atoms, except that a part or all of the hydrogen atom of the above alkyl group or alkoxy group may be substituted by a fluorine atom ; R 9 is a single bond or a phenyl group, but R19 is a phenyl group when R18 is a oxy group; R2Q is a residue, a hydroxy group, -SH, -NCO, -NHR (only 'R is a hydrogen atom or carbon At least one type of -28-200927793 group selected from the group consisting of -1 = 6 alkyl group, -CH = CH2 and -S〇2Cl.) The compound represented is substituted and used. At this time, the synthesis of the sensitized radiation linear polyorganotate is carried out by reacting a mixture of a polyorganosiloxane having an oxetane ring, a cinnamic acid derivative, and a compound represented by the above formula (5). And proceed. • in the above formula (5), R18 is preferably an alkyl group or alkoxy group having a carbon number of 8 to 20 or a fluoroalkyl group or a fluoroalkoxy group having a carbon number of 4 to 2; as R19, a single fluorene bond or 1, 4-phenylene is preferred; as R2G, a carboxyl group is preferred. Preferred examples of the compound represented by the above formula (5) can be exemplified by the following formula (5-1) to (5~4) chF2h+1-CiH2 "COOH (5-1)

(In the above formula, h is an integer of 1 to 3, i is an integer of 3 to 18, j is an integer of 5 to 20, k is an integer of 1 to 3, m is an integer of 〇 18, and η is 1 to 1 Any of the compounds represented by any of 8), wherein, by the following formula (5-3-1)~(5--29 - 200927793 3-3) CF-ϊ—0-

COOH ( 5-3-1 ) cf3—c3h6—〇- -COOH ( 5-3-2 ) c2f5—〇3Η6—〇— -COOH ( 5-3-3 )

The compound represented by any of O is preferred. The compound represented by the above formula (5) is a compound which reacts with the above-mentioned cinnamic acid derivative with a polyorganosiloxane having an oxetanyl group to impart a pretilt expression property to the obtained liquid crystal alignment film. In the present specification, the compound represented by the above formula (5) is hereinafter referred to as "another pretilt angle expressive compound". In the present invention, when the above cinnamic acid derivative and other pretilt angle expressing compounds are used together, the total use ratio of the cinnamic acid derivative and other pretilt angle expressing compounds is compared with the oxetane of the polyorganosiloxane. The alkyl 1 Mo' is preferably 0.001 to 1.5 m, more preferably 0.01 to 1 mol, still more preferably 0.05 to 0.5 mol. In this case, the other pretilt performance compound ' is preferably used in a range of 50% by mole or less', more preferably 25% by mole or less, based on the total amount of the cinnamic acid derivative. When the ratio of use of the other pretilt performance compound exceeds 50 mol%, there is a case where the abnormality of the domain occurs when the liquid crystal display element is turned ON. -30- 200927793 As the above catalyst, for example, alumina, titanium tetrabutoxide, titanium isopropoxide, zinc octoate, tin octylate, aluminum acetylacetone complex, hydrazine acetone complex, zirconium acetonide can be used. Complex, benzyldimethylamine, p-sulfonic acid, tetraphenylphosphine bromide, and the like. The amount of the catalyst used is preferably 0.0] by weight, more preferably 0.1 to 20 parts by weight, per 100 parts by weight of the polyorganosiloxane having a heterocyclic butane ring. The reaction temperature is preferably 0 to 300 ° C, more preferably 10 to 2 50 ° C, and the φ time is preferably 〇 1 to 50 hours, more preferably 〇 5 to 2 0 hours. In the synthesis of the sensitive radiation linear polyorganosiloxane, an organic solvent such as a hydrocarbon, an ether, an ester, a ketone, a decylamine or an alcohol may be used as necessary. The ether, the ester, the solubility of the raw material and the product, the ease of purification, and the like are preferable. Specific examples of the particularly preferable organic solvent include toluene toluene, diethylbenzene, rice, and methyl ethyl ketone. Methyl isobutyl ketone, ketone and cyclohexanone. The organic solvent is preferably used in an amount of 5% by weight or more, more preferably 5 to 50% by weight, based on the solid content concentration (the ratio of the weight of the component other than the solvent in the reaction solution to the total weight of the solution). [Other Components] The liquid crystal alignment agent of the present invention contains the above-mentioned radiation sensitive linear oxime. The liquid crystal alignment agent of the present invention, other than the above-mentioned radiation-sensitive linear polyoxane, may not contain other effects as the other components, and may be exemplified by, for example, a radiation-sensitive linear polyorganoalkane. Polymer (hereinafter referred to as "other polymer"), tetra-titanyltoluene aerobic ~1 00 reaction using ketone from a 2-glycol to a polyorganoquinone, Shixi oxygen-31 - 200927793 A crosslinking agent, a functional decane compound, a surfactant, and the like. The above-mentioned other polymer' can be used to further improve the solution characteristics of the liquid crystal alignment agent of the present invention and the electrical characteristics of the obtained liquid crystal alignment film, and examples of the other polymer related thereto include poly-proline and polyimine. At least one polymer selected from the group; having the following formula (S-2) "R17 1 -Si-Ο-- (S-2) © L Y2 (in the formula (S-2), R17 a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; Y2 is a hydroxyl group, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms. At least one selected from the group consisting of a polyorganosiloxane of a repeating unit and a condensate of a hydrolyzate and a hydrolyzate thereof (hereinafter, also referred to as "other polyorganosiloxane"); Proline, polyester, polyamine, cellulose Q derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleic anhydride) derivative, poly(methyl) Acrylate and the like. - Polyproline - The above polyamic acid can be obtained by reacting a tetracarboxylic dianhydride with a diamine compound. Examples of the tetracarboxylic dianhydride which can be used for the synthesis of polylysine include, for example, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, butane tetracarboxylic dianhydride, 1, 2, 3, 4 -cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetra-32- 200927793 carboxylic acid dianhydride, 1,2,3,4-cyclopentane Tetracarboxylic dianhydride, 3,5,6-: flane-2-acetic acid dianhydride, 2,3,4,5·tetrahydrofuran tetracarboxylic acid 1,3,3&,4,5,91?-hexahydro- 5-(tetrahydro-2,5-dioxo-3-indole [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro- 5-dioxo-3-furanyl-8-methyl-naphtho[1,2-c]-furan-1, (2,5-dioxotetrahydrofuranyl)-3-methyl-3- Cyclohexene-anhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic acid dioxime] (T-1)~(T-14) tricarboxyl-norbornic acid Anhydride, yl)-naphtho(tetrahydro-2,5 -3-dione, 5-1,2-dicarboxylic acid:

(Τ-8) (Τ-9) (Τ-10) (Τ-Χ1) 33- 200927793

anhydride;

Pyromellitic dianhydride, 3,3',4,4'-biphenylfluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene Tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3, 3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) Diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl phthalic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy) Phenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(benzene Formic acid) phenylphosphine oxide dianhydride, P-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylbenzene) Dicarboxylic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid) 4,4'-diphenylmethane dianhydride, the following formula (T-15)~(T- 18) -34- 200927793

2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl)-8-methyl-naphtho[l,2-c]-furan-1,3-dione, 2,3,5-tricarboxyl Cyclopentyl acetic acid dianhydride, butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclobutane Alkane tetracarboxylic dianhydride, pyromellitic dianhydride, -35- 200927793 3,3,,4,4,-biphenyl fluorene tetracarboxylic dianhydride, hydrazine, 4,5,8-naphthalenetetracarboxylic acid Anhydride, 2,3,6,7-naphthalene tetradecanoic acid, 1,3,3',4,4'-biphenyl phthalic acid dianhydride and the above formulas (Tl), (T-2) and T-15)~(T-18) each of the four residual acid dianhydrides shown in Table 7^. These tetracarboxylic acid dianthracenes may be used singly or in combination of two or more. * As the diamine compound which can be used for the synthesis of polylysine, for example, P-phenylenediamine, m-phenylenediamine, 4,4,-diaminodiphenylmethane, 〇4,4' -diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'-dimethyl-4,4' -diaminobiphenyl, 4,4'-diaminobenzimidamide, 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, -aminophenyl)-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_bis ( 4-aminophthalic acid 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, 9,9-bis(4-aminophenyl)-10-hydroquinone , 2,7-diaminopurine, 9,9-bis (4- Phenyl, fluorene, 4,4,-methyl-bis(2-chloroaniline), 2,2,5,5,-tetrachloro-4,4'-diaminobiphenyl, 2,2 '-Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4 ,-(p-phenylisopropylene)diphenylamine, 4,4'-(1!1_phenylisopropylene)diphenylamine, 2,2_bis[4-(4-amino-2 · Trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4,-diamino-2,2,-bis-36- 200927793 (trifluoromethyl)biphenyl, 4,4'-double [(4-Amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 6-(4-arylpropenyl aralkyloxy)hexyloxy (2,4-diaminobenzene) , 6-(4'-fluoro_4_aryl propylene fluorene aryloxy) hexyloxy (2,4-diaminobenzene), 8-(4-arylpropene fluorene aryloxy) octane Alkoxy (2,4-diaminobenzene), 8-(4'-fluoro-4-arylacrylofluorene•arylalkyloxy)octyloxy (2,4-diaminobenzene),: 1-dodecyloxy-2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecylφ-alkyloxy-2,4- Diaminobenzene, 1-hexadecyloxy-2,4-diamino Benzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholesteryloxy-2,4-diaminobenzene, choline alkyloxy-2,4-diamine Benzobenzene, dodecyloxy (3,5-diaminobenzimidamide), tetradecyloxy (3,5-diaminobenzimidamide), pentadecyloxy (3, 5-diaminobenzimidamide, hexadecyloxy (3,5-diaminobenzimidamide), octadecyloxy (3,5-diaminobenzimidamide), cholesterol base Oxy (3,5-diaminobenzimidamide), cholesteryloxy (3,5-diaminobenzimidamide), (2,4-diaminophenoxy) palmitate (2,4-diaminophenoxy)stearate, (2,4-diaminophenoxy)-4-trifluoromethylbenzoate, the following formula (Dl) ~( D-5)

-37- 200927793 〇 CH·, h2n

,ch3 'ch3 (D-2) h2n^

O~(-〇2Η4-o

yNH2 ❹ (D-4) h2n-

fO -s-

z in the NH 2 (D-5) is 1 to 5 (wherein y is an integer of 2 to 12 in the formula (D-4); an integer of the formula (D-5).) -38-200927793 An aromatic diamine having a hetero atom such as diaminotetraphenylthiophene; m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethyldiamine, Hexamethylenediamine, heptamethyldiamine, octamethyldiamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene Amine, 'hexahydro-4,7-methyleneindanylenediamine (hexahydro-4,7-methanoindanylenedimethylenediamn ine), tricyclic oxime [6·2·1. 〇2'7]- eleven An aliphatic or alicyclic diamine such as an alkylene dimethyl diamine or a 4,4'-methylene bis(cyclohexylamine); a diamine organic oxirane such as a diamino hexamethyldioxane; Alkane, etc. Preferred among these are p-phenylenediamine, 4,4'-diaminodiphenylmethane, ], 5-diaminonaphthalene, 2,7-diaminopurine, and 4 ,4,-Diaminodiphenyl ether, 4,4,-(p-phenylisopropylene)diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl] Hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl] ® Fluoropropane, 4,4,-diamino-2,2,-bis(trifluoromethyl)biphenyl, 4,4,-indolyl-2-difluoromethyl)phenoxy]-octafluoro Benzene, 1_hexadecyloxy 2,4-diaminobenzene, 1 octadecyloxy-2,4-diaminobenzene, 丨·cholesteryloxy-2,4-di Aminobenzene, benzoyloxy 2,4-diaminobenzene, hexadecyloxy (3,5-diaminobenzamide), octadecyloxy (3,5) -diaminobenzimidamide), cholesteryloxy (3,5-diaminobenzimidamide), cholesteryloxy (3,5-diaminobenzimid) and the above formula (D-1) The diamine compound represented by each of ~(D-5). These diamine compounds may be used singly or in combination of two or more. -39- 200927793 The use ratio of the tetracarboxylic dianhydride and the diamine compound to the synthesis reaction of poly-proline is 1 equivalent of the amine group contained in the diamine compound, and the acid anhydride group of the tetracarboxylic dianhydride becomes 〇. The ratio of 2~2 equivalents is better, and more preferably _ is 0.3 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at -20 to 150 ° C, more preferably at a temperature of 〇 1 to 10 ° C, preferably for 0.5 to 24 hours. More preferably for 2 to 10 hours. In addition, the organic solvent-soluble agent is not particularly limited as long as it is a polylysine which can be synthesized, and examples thereof include N-methyl-2-pyrrolidone and N,N-dimethylacetamidine. Amine, hydrazine, hydrazine-dimethylformamide, N,N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butane vinegar, tetramethyl urea, hexamethylphosphorous triamide Or a protic-based polar solvent; a phenol-based solvent such as m-cresol, xylenol, phenol or halogenated phenol. The amount of use of the organic solvent (a: when the organic solvent and the weak solvent described later are used as the total amount of both), the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is relative to The total amount (a + b ) of the reaction solution is preferably from 0.1 to 50% by weight, more preferably from 5 to 30% by weight. In the above organic solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon or the like which is generally considered to be a weak solvent of polyproline is used in a range in which the produced polyamine does not precipitate. Specific examples of the related weak solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, and ethylene glycol monomethyl. Ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate 'methyl methoxypropionic acid-40 - 200927793 Ester, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n• Propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-η-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether , diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Ester, tetrahydrofuran, dichloromethane, I,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, guanidine-dichlorobenzene, hexane, heptane, octane, benzene , toluene, xylene, etc. When polylysine is produced, when a weak solvent such as the above is used in an organic solvent, the use ratio thereof can be appropriately set within a range in which the produced polyamic acid does not precipitate, and it is preferably in a total solvent. 50% by weight or less. As described above, a reaction solution in which polylysine is dissolved can be obtained. The reaction solution can be directly supplied to the liquid crystal alignment agent, and the polyamine acid contained in the reaction solution can be supplied to the liquid crystal alignment agent after isolation. The modulation' may also be prepared by purifying the isolated polylysine and supplying it to the liquid crystal alignment agent. The segregation of polylysine can be carried out by injecting the above reaction solution into a large amount of a weak solvent to obtain a precipitate, and the precipitate is dried under reduced pressure or 'removing the reaction solution under reduced pressure with an evaporator. The method is carried out. Further, the poly-proline may be purified by re-dissolving the poly-proline in an organic solvent, followed by precipitation with a weak solvent or by a step of distilling off under reduced pressure with an evaporator. . - Polyimine - 41 - 200927793 The above polyimine can be produced by dehydration ring closure of the proline structure of polylysine obtained as described above. The entire dehydration ring closure of the structure is completely ruthenium imidized' or a portion of the proline structure can be dehydrated and closed to form a partial ruthenium imide of the proline structure and the quinone imine structure. Dehydration ring closure of polylysine, by (i) heating poly-proline acid, or (Π) dissolving poly-proline in an organic solvent, adding φ to a dehydrating agent and a dehydration ring-closing catalyst. It is carried out by heating if necessary. The reaction temperature in the method for heating poly-proline in the above (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C, and the reaction temperature is lower than 50 ° C, the dehydration ring closure reaction is not sufficiently performed. When the reaction temperature exceeds 200 ° C, the molecular weight of the obtained quinone imidized polymer may be lowered. The reaction time in the method of heating the polyamic acid is preferably from 0.5 to 48 hours, more preferably from 2 to 20 hours. On the other hand, in the method of adding the de-pulping agent and the dehydration ring-closing catalyst to the solution of the poly-proline in the above (ii), as the dehydrating agent, for example, acetic anhydride, propionic anhydride, trifluoroacetic anhydride or the like can be used. Anhydride. The amount of the dehydrating agent used is 'mole relative to 1 mol of the polyamic acid structural unit. 〇 1 to 2 0 mol is preferred. Further, as the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used, but it is not limited thereto; the amount of the dehydration ring-closing catalyst is relatively small The dehydrating agent 1 used is 0 · 0 1 to 1 0 mole; the organic solvent used as the dehydration ring closure reaction is exemplified as the organic solvent exemplified by the user of the synthesis of polyglycolic acid; The reaction temperature of the ring closure reaction is preferably 〇~丨8 〇. (:, -42- 200927793 is more preferably 10 to 150 ° C, and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours. The polyimine obtained in the above method (i), The preparation may be directly supplied to the liquid crystal alignment agent, or the obtained polyimine may be purified and supplied to the liquid crystal alignment agent. On the other hand, the reaction containing the polyimine may be obtained in the above method (ii). The solution, the reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or can be prepared by removing the dehydrating agent and the Q dehydration ring-closing catalyst from the reaction solution, and then supplying the solution to the liquid crystal alignment agent, or the polyimine can be supplied to the liquid crystal alignment agent after being isolated. The preparation of the liquid crystal alignment agent or the preparation of the liquid crystal alignment agent after purification of the isolated polyimine. The dehydration agent and the dehydration ring-closing catalyst are removed from the reaction solution, and for example, a method such as solvent replacement can be applied. The isolation and purification of the amine can be carried out by the same operation as the above-described separation method as the poly-proline acid. - Other polyorganooxane - © Polycondensation having the repeating unit represented by the above formula (S-2) Organic oxime At least one selected from the group consisting of a hydrolyzate and a condensate of a hydrolyzate (other polyorganosiloxane), the polystyrene-equivalent weight average molecular weight measured by GPC is 1 〇〇 1 〇, Preferably, the other polyorganic cerebral oxygen chamber of the related type is, for example, at least one decane compound selected from the group consisting of an alkoxy decane compound and a halogenated cleavage compound (hereinafter referred to as 'also referred to as ' The "raw material decane compound" is preferably synthesized by hydrolysis or hydrolysis/condensation in the presence of water and a catalyst in a suitable organic solvent. -43- 200927793 As the raw material decane compound used herein, for example, Tetramethoxydecane, tetraethoxydecane, tetra-n-propoxy fluorene, tetraisopropoxydecane, tetra-n-butoxydecane, tetras-butoxybutane, tetra- Tert-butoxydecane, tetrachlorodecane; methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltris-propane-propoxy-decane, Methyltri-n-butoxydecane, methyltris-sec-butoxydecane, methyltri-tert- Oxydecane, methyltriphenoxydecane, methyltrichlorooxane, ethyltrimethoxydecane, ethyltriethoxydecane, ethyltri-n-propoxydecane, ethyltri-iso - propoxy decane, ethyl tri-n-butoxy decane, ethyl tri-sec-butoxy decane, ethyl tri-tert-butoxy decane, ethyl trichloro decane, phenyl trimethoxy decane, Phenyltriethoxydecane, phenyltrichlorodecane; dimethyldimethoxydecane 'dimethyldiethoxydecane, dimethyldichlorodecane; trimethylmethoxydecane, trimethyl Ethoxy decane, trimethylchloro decane, etc. Among them, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl hydrazine trimethoxy decane, benzene Preferred are triethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, trimethyl methoxy decane or trimethyl ethoxy sand. In the case of synthesizing another polyorganosiloxane, examples of the organic solvent that can be used arbitrarily include an alcohol compound 'ketone compound, a guanamine compound, an ester compound, and other aprotic compounds, and these may be used alone or in combination. Used above. As the above-mentioned alcohol compound, for example, methanol, ethanol, propanol, i-propanol, η-butanol, i-butanol, sec-butanol, t-butanol' η-pentyl-44 - 200927793 alcohol, I-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, η-hexanol, 2-methylpentanol' sec-hexanol, 2-B Butanol, sec-heptanol, heptanol-3, η-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethylheptanol _4, η - Sterol, sec-~|--alkanol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5- a monool compound such as trimethylcyclohexanol, benzyl alcohol or diacetone alcohol; ❹ ethylene glycol, 1,2-propanediol, 1,3-butanediol, pentanediol-2,4,2-A Pentyl glycol-2,4, hexanediol-2,5, heptanediol-2,4,2-ethylhexanediol-1,3,diethylene glycol, dipropylene glycol, triethylene glycol, Polyol compound such as tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol Monophenyl acid, Glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, two Ethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propanol monopropyl _, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether dipropylene glycol single propane A partial acid or the like of a polyol compound such as a group ether. These alcohol compounds may be used alone or in combination of two or more. As the ketone compound, for example, acetone, methyl ethyl hydrazine, methyl hydrazine propyl ketone, methyl-n butyl ketone, diethyl ketone, methyl butyl hydrazine 'methyl η - pentyl can be exemplified. Ketone, ethyl-η-butyl ketone, methyl-η-hexyl hydrazine, monobutyl ketone, trimethyl fluorenone, cyclohexanone, 2-hexanone, methyl ring-45-200927793 hexanone, a monoketone compound of 2,4-pentene diketone, acetonylacetone, ethyl benzene, ketone, etc.; acetamidine acetone, 2,4-hexanedione, 2,4. heptanedione, 3,5 _heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-decanedione, 3,5-nonanedione, 5-methyl-2,4 a β-diketone compound such as hexanedione or 2,2,6,6-tetramethyl-3,5-heptan-2-diketone. These ketone compounds may be used alone or in combination of two or more. φ As the above guanamine compound, for example, formamide, hydrazine-methylformamide, hydrazine, hydrazine dimethylformamide, hydrazine-ethylformamide, hydrazine, hydrazine-diethylformamidine can be mentioned. Amine, acetamide, hydrazine-methylacetamide, hydrazine, hydrazine-dimethylacetamide, acetamide, hydrazine, hydrazine-diethylacetamide, hydrazine-methyl propylamine, ν -methyl[]pyrrolidone, fluorenyl-mercapto-morpholine, hydrazino-methylhydrazine-piperidine, fluorenyl-mercapto-purine, Ν-ethionylmorpholine, Ν-ethinylpiperidine , Ν - 醯 醯 吡 咯 咯 。. These guanamine compounds can be used alone or in combination of two or more. The ester compound may, for example, be diethyl carbonate, φ ethylene, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone or η-propyl acetate. , i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, η-amyl acetate, sec-pentyl acetate, methoxybutyl acetate, methyl acetate amyl acetate, acetic acid 2-ethylbutyl ester, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl hexyl acetate, η-decyl acetate, methyl acetate, ethyl acetate, acetic acid Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, acetic acid Propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, acetic acid -46- 200927793 propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diacetate Glycol ester, methoxytriethylene glycol acetate, ethyl propionate, η-butyl propionate, i-pentyl propionate, grass Diethyl acid, di-n-butyl oxalate, methyl lactate, ethyl lactate, η-butyl lactate, η-amyl lactate, diethyl malonate, dimethyl phthalate, phthalic acid Diethyl ester and the like. These ester compounds may be used alone or in combination of two or more. φ As the above other aprotic compound, for example, acetonitrile, dimethyl hydrazine, hydrazine, hydrazine, hydrazine, hydrazine, tetraethylsulfonamide, hexamethylphosphoric acid triamide or hydrazine-methyl group can be mentioned. Porphyrin, Ν-methylpyrrole, Ν-ethylpyrrole, Ν-methyl-Δ3-pyrroline, Ν-methylpiperidine, Ν-ethylpiperidine, hydrazine, hydrazine-dimethylpiperazine, hydrazine Methylimidazole, hydrazine-methyl-4-piperidone, hydrazine-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1 , 3-dimethyltetrahydro-2(1Η)-pyrimidinone and the like. Among these solvents, a polyol compound or a partial oxime ether or ester compound of a polyol compound is particularly preferred. As the amount of water used in the synthesis of other polyorganosiloxanes, the total s @ 1 mole of the alkoxy group and the halogen atom of the raw material decane compound is preferably 0.5 to 100 moles, more preferably Good for 1 to 30 moles, and even better for 1 to 1.5 moles. As a catalyst which can be used for the synthesis of other polyorganosiloxanes, for example, metal chelate compounds, organic acids, inorganic acids, organic bases, amino groups, alkali metal compounds, and the like can be exemplified. Examples of the metal chelate compound include triethoxy glucose. Stomach-47-200927793 (acetylacetone) titanium, tri-n-propoxy mono(acetonitrile) titanium, and tri-i-propoxy group. ·Single (acetonitrile) titanium, tri-n-butoxy mono(acetonitrile) titanium, tris-butoxybutyric acid, mono(acetonitrile) titanium, tri-t-butoxy. (acetonitrile) titanium, diethoxy bis(acetonitrile) titanium, di-η-propoxy bis(acetoxime) titanium, di-i-propoxy bis(acetonitrile) Titanium, di-n-butoxy bis(acetonitrile) titanium, di-sec-butoxy bis(acetonitrile) titanium, di-t-butoxy bis(acetonitrile) titanium, Monoethyl Q oxy ginseng (acetonitrile) titanium, mono- η-propoxy ginseng (acetonitrile) titanium, mono-i-propoxy ginseng (acetonitrile) titanium, single-η- Butoxy-xhenyl (acetamidine) titanium, mono-sec-butoxy-glycol (acetonitrile) titanium, mono-t-butoxy-glycol (acetonitrile) titanium, bismuth (acetonitrile) Titanium, triethoxyl mono(ethylacetamidine acetate) titanium, tri-n-propoxy mono(ethylacetamidine acetate) titanium, tri-i- Propoxy mono(ethylacetamidine acetate) titanium, tri-n-butoxy mono(ethylacetamidine acetate) titanium, tris-sec-butoxy mono(ethyl acetamidine) Acetate) Titanium, tri-t-butoxy mono(ethylacetate decyl acetate) titanium, diethoxy bis(ethylacetamidine acetate) titanium, di-n-propoxy Bis(ethylacetamidine acetate) titanium, di-i-propoxy bis(ethylacetamidine acetate) titanium 'di-η-butoxy bis(ethyl acetamidine acetate) Titanium, di-sec-butoxy bis(ethylacetamidine acetate) titanium, di-t-butoxy bis(ethylacetamidine acetate) titanium, monoethoxy ginseng ( Ethylacetamidine acetate) titanium, mono-η-propoxy-sodium (ethyl acetoacetate) titanium, mono-i-propoxy ginseng (ethyl acetoacetate) titanium, Mono-η-butoxy ginseng (ethyl acetamidine acetate) titanium, mono-sec-butoxy ginseng (ethyl acetoacetate) titanium, mono-t-butoxy ginseng ( Ethylacetamidine acetate) titanium, bismuth (ethyl ethyl 4-48-200927793 hydrazine acetate) titanium, mono(acetonitrile) ginseng (ethyl acetoacetate) titanium, bis(acetonitrile) Double (ethyl ethyl Titanium chelating compound of titanium, acetaminophen, mono(ethylacetamidine acetate) titanium, etc.; triethoxyl mono(acetonitrile)zirconium, tri-n-propoxy Zirconium (acetylacetone) zirconium, tri-i-propoxy mono(acetonitrile) zirconium, tri-n-butoxy mono(acetonitrile) zirconium, tris-s-butoxy Mono(acetonitrile)zirconium, tris-t-butoxy-mono(acetamidineacetone)zirconium, diethoxybisbis(acetonitrile)zirconium, di-n-propoxy-bis(acetonitrile) Acetone, bismuth, di-i-propoxy bis(acetonitrile) zirconium, di-n-butoxy bis(acetyl acetonide) zirconium, di-sec-butoxy bis(acetonitrile) chrome , di-t-butoxy bis(acetamidine acetonide) chromium, monoethoxy ginseng (acetamidine acetone) zirconium, mono-η-propoxy ginseng (acetonitrile) zirconium, mono-i- Propyl oxy-p-acetonitrile, mono-η-butoxy ginseng (acetonitrile), mono-sec-butoxy ginseng (acetonitrile) zirconium, mono-t-butoxy Zirconium (acetonitrile) zirconium, cerium (acetonitrile) zirconium, triethoxyl mono(ethylacetamidine acetate) zirconium, tri-n-propoxyl Q · Mono (ethyl acetamidine acetate) zirconium, tri-i-propoxy mono(ethyl acetamidine acetate) zirconium, tri-n-butoxy. mono (ethyl acetamidine acetate) Zirconium, tris-butoxy-mono(ethylacetamidine acetate) zirconium, tri-t-butoxy. mono(ethylacetamidine acetate) zirconium, diethoxy bis ( Ethylacetamidine acetate) zirconium, di-n-propoxy bis(ethylacetamidine acetate) hydrazine, di-i-propoxy bis(ethyl acetamidine acetate) hydrazine, Di-n-butoxy bis(ethylacetamidine acetate) zirconium, di-sec-butoxy bis(ethylacetamidine acetate) zirconium, di-t-butoxy bis ( Ethylacetamidine acetate) zirconium, monoethoxyl oxyhydrazide (ethyl acetoacetate), mono-n-propoxy ginseng (ethyl acetoacetate-49-200927793 ester) zirconium, Mono-i-propoxy ginseng (ethyl acetamidine acetate) chromium, mono-η-butoxy ginseng (ethyl acetoacetate) chromium, mono-sec-butoxy ginseng ( Ethyl acetoacetate) zirconium, mono-t-butoxy-para (ethyl acetoacetate) zirconium, cerium (ethyl acetoacetate) zirconium, mono(acetonitrile) ginseng Ethylacetamidine acetate Zirconium chelate compound of zirconium, bis(acetamidineacetone) bis(ethylacetamidine acetate) zirconium, ginseng (acetamidineacetone) mono(ethylacetamidine acetate) zirconium, etc.; An aluminum chelate compound such as aluminum or ginseng (ethyl acetoacetate) aluminum. Examples of the organic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, and anthracene. Diacid, gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, P- Aminobenzoic acid, P-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, hydrazine Tannic acid, tartaric acid, etc. The inorganic acid may, for example, be hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid or phosphoric acid. Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, and monomethyldiethanolamine. Triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, and the like. -50-200927793 Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide. These catalysts may be used alone or in combination of two or more. Among these catalysts, a metal chelate compound, an organic acid or an inorganic acid is preferred, more preferably a titanium chelate compound or an organic acid. The amount of the catalyst used is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 1 part by weight based on 100 parts by weight of the starting decane compound. Φ Water added during the synthesis of other polyorganosiloxanes may be added intermittently or continuously in the decane compound of the starting material or in a solution in which the decane compound is dissolved in an organic solvent. The catalyst may be previously added to the decane compound of the raw material or the decane compound may be dissolved in a solution of an organic solvent, or may be dissolved or dispersed in the added water. The reaction temperature in the synthesis of the other polyorganosiloxane is preferably from 0 to 100 ° C, more preferably from 15 to 8 (TC, and the reaction time is preferably from 0.5 to 24 hours, more preferably from 1 to 8). When the liquid crystal alignment agent of the present invention contains the above-mentioned radiation-sensitive linear polyorganosiloxane and other polymers, the content of other polymers is 100 parts by weight relative to the radiation sensitive linear polyorganosiloxane, 1 〇 Preferably, the weight is less than the weight, and the more preferable content of the other polymers is different depending on the type of the other polymer. The liquid crystal alignment agent of the present invention contains a sensitive radiation linear polyorganosiloxane and a polyglycolic acid and a poly When at least one polymer selected from the group consisting of ruthenium imine, the preferred ratio of use of the two is relative to the radiation-sensitive linear polyorgano-51 - 200927793 oxime, 100 parts by weight, as poly-proline And the total amount of the polyimine is 100 to 5,000 parts by weight, and preferably 200 is 200 to 2,000 parts by weight. On the other hand, the liquid crystal alignment agent of the present invention contains a sensitive radiation linear polyorganosiloxane and other polyorganic The preferred ratio of use of oxane, For 100 parts by weight of the radiation-sensitive linear polyorganosiloxane, the amount of other polyorganosiloxane is 100 to 2,000 parts by weight. The liquid crystal alignment agent of the present invention contains a sensitive radiation linear polyorgano@ oxane In the case of other polymers, it is preferred to use at least one polymer selected from the group consisting of polylysine and polyimine, or other polyorganosiloxane as the type of other polymer. The crosslinking agent can be used for the stabilization of the pretilt angle and the improvement of the film strength. 'As a heat sensitive crosslinking agent, for example, a polyfunctional epoxy compound is effective'. A bisphenol A type epoxy resin or a phenol novolac type epoxy can be used. Resin, cresol novolac type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester epoxy resin, glycidyl diamine epoxy resin, heterocyclic epoxy resin, epoxy group Examples of such commercially available products include EPOLIGHT 400E, 3002 (manufactured by Kyoeisha Chemical Co., Ltd.), EPIKOTE 828, and 152, and epoxy novolac lacquer 180S (Sakamoto Epoxy Resin Co., Ltd.). System) and so on. When a polyfunctional epoxy compound is used as the thermosensitive crosslinking agent, a base catalyst such as 1-benzyl-2-methylimidazole can be used for the purpose of efficiently causing a crosslinking reaction. When the heat-sensitive crosslinking agent is contained, it is preferably 2 〇 0 parts by weight, based on the total ratio of the above-mentioned radiation-sensitive linear polyorganosiloxane and any other polymer used, preferably - 〇〇 -52- 200927793 parts or less, more preferably 50 parts by weight or less. The above functional decane compound can be used for the purpose of improving the adhesion to the substrate of the obtained liquid crystal alignment film, and is a functional decane compound such as 3-amino group. Propyltrimethoxydecane, 3-aminopropyltriethoxylate, 2-aminopropyldimethoxylate, 2-aminopropyltriethoxysilane, Ν- (2 -aminoethyl)-3-aminopropyltrimethoxydecane, Ν-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyl three U methoxy decane, 3- ureidopropyl triethoxy decane, hydrazine-ethoxycarbonyl 3-aminopropyl trimethoxy decane, hydrazine - Oxycarbonyl-3-aminopropyltriethoxydecane, Ν-triethoxycarbenylpropyltriethylenetriamine, Ν-trimethoxycarbamidopropyltriethylenetriamine, 10 -trimethoxycarbamido-1,4,7-triazadecane, 10-triethoxycarbamimidyl-1,4,7-triazadecane, 9-trimethoxyformamidinyl _3,6-diazepine acetate, 9-triethoxycarbamido-3,6-diazaindolyl acetate, Ν-benzyl-3-aminopropyltrimethoxy Baseline, Ν-benzyl-3-aminopropyltriethoxydecane, Ν_ϋphenyl-3-aminopropyltrimethoxydecane, Ν-phenyl-3-aminopropyltriethoxy Base decane, Ν-bis(oxyethyl)-3-aminopropyltrimethoxydecane, fluorene-bis(oxyethyl)-3-aminopropyltriethoxydecane, 3_epoxy Propyloxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, etc., as described in JP-A-63-1589 A reaction of a tetracarboxylic dianhydride with a decane compound having an amine group. When the liquid crystal alignment agent of the present invention contains a functional decane compound, the content thereof is preferably 100 weight% based on the total of the above-mentioned radiation-sensitive linear polyorganosiloxane and any other polymer used. -53- 200927793 The amount is below the amount, more preferably 20 parts by weight or less. Examples of the above-mentioned surfactant include 'nonionic surfactant-agent' anionic surfactant, cationic surfactant, amphoteric surfactant, polyoxyalkylene surfactant, polyepoxide surfactant, and fluorine-containing interface. Active agent, etc. When the liquid crystal alignment agent of the present invention contains a surfactant, the content thereof is preferably 10 parts by weight or less, and more preferably 1 part by weight or less based on 100 parts by weight of the total of the liquid crystal alignment agent. <Liquid Crystal Aligning Agent> The liquid crystal alignment agent of the present invention has the above-mentioned 'containing the radiation-sensitive linear polyorganosiloxane as an essential component, and further contains other components as necessary, and is preferably a solution in which each component is dissolved in an organic solvent. Modulated by the composition of the form. As the organic solvent which can be used for preparing the liquid crystal alignment agent of the present invention, it is preferred to dissolve the radiation sensitive linear polyorganosiloxane and any other components used without being reacted with them. The preferred organic solvent to be used in the liquid crystal alignment agent of the present invention differs depending on the kind of other polymer to be added. When the liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of a radiation-sensitive linear polyorganosiloxane and a polyimine and a polyimide, the preferred organic solvent is exemplified above. The organic solvent used for the synthesis of polylysine is exemplified, and in this case, it can be used as a weak solvent exemplified by the user of the synthesis of the polyamic acid of the present invention, and these organic solvents can be used alone or Two or more types can be used in combination. -54- 200927793 In another aspect, the liquid crystal alignment agent of the present invention contains only a radiation-sensitive linear polyorganosiloxane as a polymer, or a radiation-sensitive linear polyorganosiloxane and other polyorganosiloxanes. Preferred examples of the organic solvent include 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, and dipropylene glycol methyl ether. 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 cellosolve), ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve B Acid ester, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, η-propyl acetate, i-propyl acetate 'n-butyl acetate , butyrate acetate, sec-butyl acetate, η-amyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methyl acetate Acetate, 2 - ethylbutyl acetate, 2 - ethyl hexyl acetate, benzyl acetate, η- hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate and the like. Preferred examples thereof include η-propyl acetate, i-propyl acetate, η-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-amyl acetate, and the like. The preferred solvent to be used for the preparation of the liquid crystal alignment agent of the present invention is obtained by using one or a combination of two or more of the above organic solvents in accordance with whether or not another polymer or the type thereof is used, and is preferably in the following preferred solid concentration. The components contained in the liquid crystal alignment agent are not precipitated, and the surface tension of the liquid crystal alignment agent is in the range of 25 to 40 mN/m. The solid content concentration of the liquid crystal alignment agent of the present invention, that is, the total weight of all the components other than the solvent in the liquid crystal alignment agent-55 - 200927793, is the ratio of the total weight of the liquid crystal alignment agent, and is selected in consideration of viscosity, volatility, and the like. However, it is preferably in the range of 1 to 10% by weight. The liquid crystal alignment agent of the present invention is applied onto the surface of the substrate to form a coating film which becomes a liquid crystal alignment film. However, when the solid content concentration is less than 1% by weight, it is difficult to obtain an excellent liquid crystal alignment when the film thickness of the coating film is too small. In the case of a film, on the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film is too large, and it is difficult to obtain an excellent liquid crystal alignment film. Further, when the viscosity of the liquid crystal alignment agent is large, coating properties are obtained. Insufficient situation. The range of the particularly preferable solid content concentration differs depending on the method used for coating the liquid crystal alignment agent on the substrate, and is particularly preferably in the range of 1.5 to 4.5% by weight by the spin method; The solid content concentration is in the range of 3 to 9 wt%, whereby the solution viscosity is particularly preferably in the range of 1 2 to 50 m P a · s; when the ink jet method is used, the solid content concentration is 1 ~ A range of 5 wt%, whereby the viscosity of the solution is particularly preferably in the range of 3 to 15 mPa.s. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 〇 〇 ° C to 200 ° C, more preferably 1 〇 ° C to 40 ° C. <Method of Forming Liquid Crystal Alignment Film> The liquid crystal alignment agent of the present invention can be suitably used to form a liquid crystal alignment film by a photo-alignment method. The method of forming the liquid crystal alignment film may, for example, be a method of forming a coating film of the liquid crystal alignment film of the invention on a substrate, and then applying a liquid crystal alignment energy to the coating film by a photo-alignment method. First, the liquid crystal alignment agent of the present invention is applied to the transparent-56-200927793 conductive film side of the substrate on which the pattern-shaped transparent conductive film is provided, for example, by a light emulsion coating method, a spin method, a printing method, or an inkjet method. A suitable coating method such as a method is applied, for example, by heating at a temperature of -40 to 250 ° C for 0.1420 minutes to form a coating film. The film thickness of the coating film is preferably 〇_〇〇1 to Ιμηη, more preferably 0.005 to 0.5 μm, in terms of the thickness after solvent removal. As the substrate, for example, glass of float glass or soda lime glass, such as polyethylene terephthalate, polybutylene terephthalate, 0 polyether mill, polycarbonate, and plastics can be used. A transparent substrate or the like. As the transparent conductive film ′, a NESA film made of Sn02, an ITO film made of In2〇3_Sn〇2, or the like can be used, and the pattern of these transparent conductive films can be formed by light etching or transparent conductive. A mask method or the like is used for the film. When the liquid crystal alignment agent is applied, "the adhesion between the substrate and the transparent conductive film and the coating film is more excellent". A functional decane compound or a titanate compound may be applied to the substrate and the transparent conductive film in advance. G, then, by irradiating the coating film with linearly polarized or partially polarized radiation or non-polarized radiation, if necessary, it is preferably subjected to heat treatment at a temperature of 150 to 250 for 1 to 120 minutes. Give liquid crystal alignment energy. Here, as the radiation, for example, ultraviolet light and visible light having a wavelength of 150 nm to 800 nm can be used, but ultraviolet light having a wavelength of 300 nm to 4 〇〇 nm is preferable. When the radiation to be used is linearly polarized or partially polarized, the irradiation may be performed in a direction perpendicular to the substrate surface, or may be performed from the oblique direction in order to impart a pretilt angle, or may be combined. When irradiating unpolarized radiation, the direction of the illumination must be the slope side -57- 200927793. As the light source to be used, 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, an excimer laser or the like can be used. The ultraviolet light in the preferred wavelength region can be obtained by means of, for example, a furnace or a diffraction grating. The irradiation amount 'as the radiation' is preferably U/m2 or more and less than 10,000 J/m2, more preferably 10 to 3,000 j/m2. Further, it is known in the prior art that when a coating film formed of a liquid crystal alignment agent imparts a liquid crystal alignment energy by a photo-alignment method, it is required to have a radiation exposure amount of 〇〇〇J/m2 or more, but the present invention is used. The liquid crystal alignment agent's radiation irradiation amount is 3,000 J/m2 or less even when the photo-alignment method is used, and even more i, 〇〇〇j/m2 or less, can impart excellent liquid crystal alignment property to contribute to the liquid crystal display element. Reduced manufacturing costs. Further, the "pretilt angle" in the present invention means an angle at which liquid crystal molecules are inclined in a direction parallel to the substrate surface. 〇 <Manufacturing Method of Liquid Crystal Display Element> The liquid crystal display element formed using the liquid crystal alignment agent of the present invention can be produced, for example, by the following method. A pair of (two) substrates in which a liquid crystal alignment film is formed by the above-described method is prepared. The liquid crystal alignment film which is provided in these forms is opposed to each other when the polarization direction of the irradiated linearly polarized radiation is at a predetermined angle. The peripheral portion is sealed with a sealant to inject and fill the liquid crystal, and the liquid crystal injection port is closed to constitute a liquid crystal cell. Next, it is desirable to heat the liquid crystal cell until the liquid crystal used is at an isotropic phase temperature, and then cool to a room temperature of -58 to 200927793 to remove the flow alignment at the time of injection. Then, the polarizing plate is bonded to the alignment direction of the liquid crystal alignment film which becomes the substrate in the polarizing direction on both surfaces thereof at a predetermined angle, thereby forming a liquid crystal display element. When the liquid crystal alignment film is horizontally aligned, the substrate formed on the liquid crystal alignment film can have a TN by adjusting the angle formed by the polarization direction of the linearly polarized radiation and the angle between each substrate and the polarizing plate. Liquid crystal display Q element of type or S TN type liquid crystal cell. On the other hand, when the liquid crystal alignment film has a vertical alignment property, the substrate on which the liquid crystal alignment film is formed is formed in a direction in which the direction of the alignment axis is parallel, and the polarizing plate is easily aligned in the polarization direction and the alignment direction. When it is bonded at an angle of 45°, it can be a liquid crystal display element having a vertical alignment type liquid crystal cell. As the sealant, for example, an epoxy resin containing an alumina ball as a spacer and a curing agent can be used. As the liquid crystal, for example, when a TN type liquid crystal cell or a s TN type liquid crystal cell is used as a TN type liquid crystal cell or a stencil type liquid crystal cell, it is preferable to have a positive dielectric anisotropy for forming a nematic liquid crystal. For example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, or the like can be used. Cubic lanthanide liquid crystal, etc. Further, in the liquid crystal, for example, a cholesteric liquid crystal such as Cholesteryl chloride, cholesteryl phthalate or cholesteryl carbonate may be added; and it is sold under the trade names C-15 and CB-15 (manufactured by MELC). It is used as a chiral agent; a strong dielectric property such as P-decyloxybenzylidene-p-amino-2-methylbutylcinnamate, etc. -59-200927793 liquid crystal. On the other hand, in the case of the vertical alignment 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 pyridazine liquid crystal, or a Schiff base type 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 the outer side of the liquid crystal cell may be a polarizing plate of a polarizing film called a "ruthenium film" which absorbs iodine while extending the cellulose acetate protective film while holding the cellulose acetate protective film, or the film itself. A polarizing plate or the like is formed. Therefore, the liquid crystal display element of the present invention produced is excellent in properties such as display characteristics and signalability. [Embodiment] Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the examples. The weight average molecular weight of the following polyorganosiloxane is based on the polystyrene equivalent enthalpy measured by gel permeation chromatography under the following conditions. The solution viscosity of the polyaminic acid solution was measured using a Ε-type viscosity meter at 25 乞. Pipe column: Tosoh (stock) system, TSKgelGRCXLII Solvent: tetrahydrofuran Temperature: 40 °C Pressure: 68kgf/cm2 -60- 200927793 <Synthesis of cinnamic acid derivative> [Synthesis of compound represented by the above formula (A-1)] Synthesis Example 1 According to the following scheme c3f7c3h6-oh 〇 C3F7C3H6-0 K2C〇3

NaOH/H2〇 CI-0-S-^j>-CH3 0 •CH3 (A-1-C4-1A) COOCH3 ❹ C3F7C3H6-OH^-COOH (A-1-C4-1B) SOCI2 K2C03

HO-(\ />-CH=CH-COOH

C3F7C3H6—O^COO"-^ CH=CH——COOH (A-1-C4-1), a synthetic compound (A-1-C4-1). In a 500 mL Japanese eggplant type flask, 4,4,5,5,6,6,6-seven-61 - 200927793 fluorohexanol 53 g and pyridine were 100 mL, and then ice-cooled, and the mixture was dropped for 30 minutes. 6 g of toluenesulfonic acid chloride was dissolved in a solution of pyridine 1 〇〇m L, and the mixture was stirred at room temperature for 5 hours to carry out a reaction. After the reaction was completed, 120 mL of concentrated hydrochloric acid and 500 g of ice were added to the reaction mixture, and ethyl acetate was added thereto, and then the organic layer was washed with water and a saturated aqueous solution of sodium hydrogencarbonate, and the organic layer was dried over magnesium sulfate. 96 g of the compound (A-1 - C4-1 A ) were obtained. φ Next, 96 g of the above compound (A-1-C4-1A), 55 g of methyl 4-hydroxybenzoate, 124 g of potassium carbonate, and cesium, cesium-dimethyl hydride were placed in a 500 m L three-necked flask equipped with a thermometer. The acetamide 300M1 was reacted at 80° (when stirring for 8 hours). After the reaction was completed, ethyl acetate was added to the reaction mixture, and the organic layer was washed with water, then the organic layer was dried over magnesium sulfate, concentrated and dried. A white powder was obtained, and 60 g of sodium hydroxide, 300 mL of water, and 300 mL of tetrahydrofuran were added to the white powder to carry out a reaction under reflux for 24 hours. After the completion of the reaction, filtration was carried out, followed by neutralization of φ by adding concentrated hydrochloric acid to the filtrate. The precipitate was white, and the precipitate was taken out by filtration, and recrystallized from ethanol to obtain white crystals of 34 g of the compound (A - 1 - C 4 -1 B ). Next, the compound (A-1-C4- 1B) Into 34 g, 100 mL of thionyl chloride and N,N-dimethylformamide oxime. 2 mL' were stirred at 80 ° C for 1 hour to carry out the reaction. Then, the thionyl chloride was distilled off under reduced pressure. Dichloromethane was added and the organic layer was washed with aqueous sodium bicarbonate. The mixture was dried over magnesium sulfate, concentrated, and then added with tetrahydrofuran. On the other hand, in a two-neck flask other than the above, 4 g of -62-200927793 hydroxycinnamic acid, 14 g of potassium carbonate, and tetrabutyl hydrazine were charged. .96g, tetrahydrofuran 80 mL, and water 160 mL, while continuously cooling this solution, slowly dropping a tetrahydrofuran solution containing the above-mentioned compound (A_-1 - CM·1 B) and thionyl chloride as a reaction solution after the completion of the dropwise addition After further stirring for 2 hours, the reaction was carried out. After the reaction was completed, the reaction mixture was neutralized with hydrochloric acid and extracted with ethyl acetate. The extract was dried over magnesium sulfate, concentrated, and then recrystallized from ethanol to give 1 9 g of the compound (A - 1 - C 4 - 1 ) was white ruthenium crystal. [Synthesis of the compound represented by the above formula (A-2)] Synthesis Example 2 According to the following scheme ch2 = ch-coo-c6h13 ❹

Pd(PPh3)4 h〇-〇- ch=ch-coo-c6h13 (A-2-C1-1A) Ο ο HQC0-C2H4-C00—CH=CH—COO-C6H13 (A-2 - C1-1) -63- 200927793 In a 2L three-necked flask equipped with a thermometer and a nitrogen introduction tube, 22 g of 4-iodophenol, hexyl acrylate i6 g, triethylamine MmL, tris(triphenylphosphine) 2.38 and N,N-dimethyl group were charged. The guanamine a was sufficiently dried in the system, and then the mixture was heated to 90 t: and stirred under a nitrogen stream for 2 hours to carry out a reaction. After the completion of the reaction, the mixture was extracted with ethyl acetate, and the organic layer was washed with water. , dry solid' gave 12 g of the compound (A-2-C1-1A). Next, the above-mentioned compound (A-2-C1-1A) was charged in a two-necked flask of a 2 〇〇mi^ equipped with a thermometer, a nitrogen introduction tube, and a reflux tube. I2g' acethanide 5 · 5 g, 4 -Methylaminopyridinium_6 g' was sufficiently dried in the system, and then 5.6 g of triethylamine and 100 mL of tetrahydrofuran were added to the mixture, and the reaction was carried out under reflux for 5 hours. After completion of the reaction, the reaction mixture was diluted with hydrochloric acid and extracted with ethyl acetate. The extract was washed with water and dried over magnesium sulfate <""""""&quot&&&&&&&&&&&&&&&&&&&&& - 1 ). <Preparation of Sensitive Radiation Linear Polyorganooxane> Synthesis Example 3 OX-SQ as a polyorganosiloxane having an oxetane ring in a 20 〇mL three-necked flask (trade name, East Asian synthesis) (manufactured by the company): 〇g, methyl isobutyl ketone 66g, compound (A-1-C4-1) llg and W-20〇_N oxidized by the above synthesis example 1 as a cinnamic acid derivative Ming (trade name, manufactured by ICN Pharmaceuticals, Inc.), reacted at room temperature for - 8 - 2009 - 27,793, 4 hours. After the completion of the reaction, the solution was treated with methanol. The solution was dissolved in ethyl acetate and washed with water for 3 times to remove the solvent to obtain a white powder of 3.6 g of a sensitive radiation linear polyorganic CO-1. The weight average molecular weight of the oxane was 14,500. Synthesis Example 4 ❹ In the above Synthesis Example 3, in place of the substitution compound (A_i_, 8 g of the compound synthesized in the above Synthesis Example 2 (A-external' was carried out in the same manner as in Synthesis Example 3, to obtain 3·0 g of polyorganosiloxane. The white powder of (S-CO-2), the weight average molecular weight of the sensitizing radioxane (S-CO-2) was 14,200 <Synthesis of other polymers> [Synthesis of polyplycosic acid] 〇Synthesis Example 5 1,2,3,4-cyclobutane tetracarboxyg (1.0 mol) as tetracarboxylic dianhydride and 212 g of 2,2'-dimethylsuccine as a diamine compound (1. The ear was dissolved in N-methyl-4,050 g, and reacted at 40 ° C for 3 hours to obtain a solution of the amount of polyglycine (PA-1) 3,700 g. The viscosity of the ruthenium solution is 170 mPa·s. [Synthesis of Other Polyorganooxane] After writing the Shen Dian, the latter will be followed by steaming oxirane (S-(S-CO-1) C4-1) to make 2-C1 -1) Sensitive radiation linear linear polyorgano dianhydride 1 9 6 gg -4,4,-diamine 2-pyrrolidone oxime containing 10 citric acid solution -65- 200927793 Synthesis Example 6 200 m L with cooling tube 'Three-methoxy decane 20.8g in a three-necked flask 2-ethoxy-2-propanol 28.2g' was heated to 6 ° C and stirred, and added to a flask of 20 mL capacity to prepare 0.26 g of maleic anhydride dissolved in water. 8 g of maleic anhydride. The aqueous solution was further heated at 6 ° C for 4 hours, stirred to carry out a reaction, and the solvent was distilled off from the obtained reaction mixture, and ethoxylated 2-propanol was added to obtain a concentration of 1 〇 by weight. Polymer solution of decane (PS-1) The weight average molecular weight Mw of this polyorganosiloxane (PS-1) was 5,100° <Preparation of liquid crystal alignment agent> Example 1 Combination of the above synthesis examples 100 parts by weight of the obtained radiation-sensitive linear polyorganosiloxane (S-CO-1) and a solution containing the poly-proline (PA-1) obtained in the above Synthesis Example 5 are converted into PA-1. 1,000 parts by weight, to which N-methyl-2-pyrrolidone and butyl cellosolve are added, and the solvent composition is N-methyl sylvestre: butyl cellosolve = 50:50 (weight ratio), which becomes a solid concentration A 3.0% by weight solution was prepared by filtering it with a filter having a pore size of 1 μm to modulate the liquid crystal alignment agent A-CO-1. Example 2 In the above Example 1, except for the substitution sensitive radiation linear polyorganosiloxane S-CO-1, using the radiation-sensitive linear polyorganosiloxane S-CO-2 obtained in the above Synthesis Example 4, The liquid crystal 66 - 200927793 alignment agent A-CO-2 was prepared in the same manner as in Example i. Example 3: The amount of the other polyalkylene (PS-1)-containing solution obtained in the above Synthesis Example 6 was converted into a PS-1 equivalent to 5 Å by weight, and the above synthesis was added thereto. 100 parts by weight of the sensible polyorganooxy siloxane S-C 0 -1 obtained in Example 3, and λ i : 2 -propanol was added to form a solution having a solid concentration of 4.0% by weight, and then the solution was used for the pore diameter. Filtration of a filter of 1 μm to prepare a liquid crystal alignment agent <Manufacturing and evaluation of a vertical alignment type liquid crystal display element> Example 4 Coating of a liquid crystal alignment agent A-CO-1 spin coater obtained in the above Example 1 On the transparent electrode surface of the enamel plate with the transparent electrode formed by the ruthenium film, after being heated on a hot plate at 80 ° C for 1 minute, it was heated in an oven substituted for nitrogen for 20 hours. . ίμιη coating film, followed by the surface of the coating film, using a Hg-Xe lamp Taylor prism, the polarization of the bright line containing 313nm I 1,0 0 0 J / m2, tilted from the substrate normal 40. A liquid crystal alignment film is formed by irradiation and a liquid crystal alignment film is repeated. The substrate having the liquid crystal alignment film is repeated in the same operation.With respect to the outer periphery of the surface of the substrate having the pair of liquid crystal alignment films on the surface of the alignment film, the screen printing force is 5 Λ E diameter 5 · machine 矽 oxygen (solid radiation L oxy - by A-CO-, using a glass-based pre-baked film thickness and a Gran I outer line to the liquid crystal film (one liquid crystal 5μιη -67-200927793 alumina ball epoxy resin adhesive, after the ultraviolet light axis to the substrate surface In the projection direction, the substrate was superposed in an antiparallel manner and pressed, and the adhesive was thermally cured at 150 ° C for 1 hour. Then, the liquid crystal was injected into the gap of the substrate to fill the negative liquid crystal (MLC-6 608 manufactured by MELC Corporation). After that, the liquid crystal injection port is sealed with an epoxy-based adhesive, and in order to remove the flow alignment during liquid crystal injection, it is heated to 150 ° C and then slowly cooled to room temperature, and then on the outer side of the substrate. By arranging the polarizing plates in a direction in which the polarizing directions Q are orthogonal to each other and at an angle of 45° to the projection direction of the ultraviolet rays of the liquid crystal alignment film toward the substrate surface, a vertical alignment type liquid crystal display is produced. Component. This liquid crystal display element After that, the results are evaluated in the following manner. The results are shown in Table 1. (1) Evaluation of liquid crystal alignment property The liquid crystal display element produced by the above-described liquid crystal display element was subjected to 明ON·OFF (external release) at a voltage of 5 V. Whether there is an abnormal region during the change, and the case where there is no abnormal region is determined as "good" by observation with an optical microscope. (2) Evaluation of the pretilt angle Regarding the liquid crystal display element manufactured above, according to T. Plant Seheffy et. al·J · Appl· Phys· vol. 19' ρ2013 (1980), the pretilt angle is measured by a crystal rotation method using He-N e laser light. -68- 200927793 (3) Evaluation of voltage holding ratio is as described above The manufactured liquid crystal display is not used, and the voltage retention rate after the release is released to 167 ms after 6 〇C with an application time of 60 microseconds and a span of 167 milliseconds (span) plus a voltage of 5 V. 'Measurement device used by TOYO Corporation, VHR-1 ° (4) afterimage in the above-mentioned liquid crystal display device' will be superimposed DC 5V 30Hz, 3V rectangular wave at 60 ° C ambient temperature plus Cut off the DC voltage after 2 hours, at 15 minutes The DC voltage remaining in the liquid crystal display element after standing at room temperature was obtained by a scintillation elimination method. Example 5 In the above Example 4, except for the substitution of the liquid crystal alignment agent A - C 〇 - 1 ', the above Example 3 was used. The prepared liquid crystal alignment agent A - C 〇 - 3 was evaluated in the same manner as in Example 4, and a vertical alignment type liquid crystal display element was produced, and the evaluation results are shown in Table 1. Comparative Example 1 [Synthesis of polylysine 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 22.48 (〇.1 mol) and the following formula (d·1) -69- 200927793 ch3 synthesized according to JP-A-2003-520878

(d-1) nh2. ο

48.46 g (0.1 mol) of the compound represented by C4H9-O-V-CH=CH-C00-C6H12-OCO , was dissolved in 283.4 g of N-methyl-2-pyrrolidone and allowed to react at room temperature for 6 hours. Next, the reaction mixture was poured into a large excess of methanol to precipitate a reaction product, and the precipitate was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain 67 g of polylysine ( RPA-CO-1). <Preparation of Liquid Crystal Aligning Agent> The polylysine RPA-CO-1 obtained above was dissolved in a mixed solvent of N-methyl-2-pyrrolidone and butyl cellosolve (mixing ratio = 50: 50). (weight ratio)) A solution having a solid concentration of 3.0% by weight was filtered through a filter having a pore size of 1 μm to prepare a comparative liquid crystal alignment agent R - C Ο -1. <Preparation and Evaluation of Vertical Alignment Type Liquid Crystal Display Element> In the above-described Example 4, in addition to the liquid crystal alignment agent A-CO-1, the above-mentioned liquid crystal alignment agent R - C Ο -1 was used, Example 4 In the same manner, a vertical alignment type liquid crystal display element was produced and evaluated, and the evaluation results are shown in Table 1 ° Example 6 <Modulation and evaluation of ΤΝ-alignment type liquid crystal display element> -70-200927793 The prepared liquid crystal alignment agent a-CO-2 was applied onto a transparent electrode surface of a glass substrate to which a transparent electrode made of an ITO film was attached using a spin coater, and was dried on a hot plate at 80 °C. After pre-baking for 1 minute, a film thickness of ί. ίμηι was formed on the surface of the coating film by heating at 200 ° C for 1 hour, using an Hg-Xe lamp and a Glan Taylor prism, which would contain 313 nm. The polarized ultraviolet ray i, the 〇〇〇j/m2 is irradiated from the substrate normal at a direction inclined by 40°, and the liquid crystal alignment energy is imparted to form a liquid crystal alignment film, and the same operation is repeated to produce one pair (two pieces) in transparency. A glass substrate having a liquid crystal alignment film on the surface of the conductive film. Each of the pair of substrates is formed with a peripheral portion of the surface of the liquid crystal alignment film, and an epoxy resin adhesive containing an alumina ball having a diameter of 5 · 5 μm is applied by screen printing, and then the direction of the polarized ultraviolet light is The substrate was superposed on the surface of the substrate and the film was pressed at a temperature of 1 to 5 (the TC was heated for 1 hour to thermally cure the adhesive, and then a positive nematic liquid crystal was injected from the liquid crystal injection port in the gap of the substrate (MLC-622 1 manufactured by MELC Corporation). After the addition of the chiral molecular agent, the liquid crystal injection port is sealed with an epoxy-based adhesive, and in order to remove the flow alignment during liquid crystal injection, it is heated at 150 ° C for 10 minutes and then slowly cooled. The polarizing plate is further applied to the outer surfaces of the substrate, and is parallel to the direction in which the polarizing directions of the polarizing plates are orthogonal to each other and to the projection direction of the optical axis of the ultraviolet ray irradiated to the liquid crystal alignment film toward the substrate surface. The TN alignment type liquid crystal display element was produced by lamination. The liquid crystal display element was evaluated for liquid crystal alignment, voltage holding ratio, and afterimage characteristics (residual voltage) in the same manner as in the above Example 4. The results are shown in Table 1. -71 - 200927793 ο ο Remaining image of the liquid crystal display element (residual voltage) (mV) 〇 〇 〇〇 Voltage holding ratio (%) Os 〇\ 〇\ 00 〇\ Pretilt angle 〇 00 Os 〇〇〇ON 00 1 Alignment π^ mode of operation vertical alignment vertical alignment vertical alignment TN alignment liquid crystal alignment agent type A-CO-1 A-CO-3 R-C0-1 A-C0-2 Example 4 Example 5 Comparative Example 1 Example ό - 72-200927793 <Evaluation of Preservation Stability of Liquid Crystal Aligning Agent> Example 7 On the glass substrate, the liquid crystal alignment agent A-CO prepared in the above Example 1 was formed by a spin coating method with a rotation number as a variable. The coating film of 1 was examined for the film thickness of the coating film after the removal of the solvent, and the number of rotations of the coating film was taken up. Then, a part of the liquid crystal alignment agent A-C0-1 was taken out and stored at -1 5 ° C for 5 weeks, and visually observed. In the liquid crystal alignment agent after storage, when the precipitation of insoluble matter was observed, the storage stability was judged as "poor". When no insoluble matter was observed after 5 weeks of storage, the thickness of the film before storage was changed to l on the glass substrate. , a coating method for forming a coating film by spin coating of the number of rotations of 〇〇〇A, and measuring a solvent When the film thickness after the removal is 10% or more from 1,000 people, the storage stability is judged as "poor", and when the film thickness deviation is less than 10%, the storage stability is judged as "good". The evaluation results are shown in Table 2. Further, the film thickness of the coating film was measured using an etch needle type film thickness meter manufactured by KLA-Tencor Co., Ltd. Examples 8 and 9 were replaced in the above Example 7 except The liquid crystal alignment agent A-CO-1 was evaluated for the storage stability of the liquid crystal alignment agent in the same manner as in Example 7 except that each liquid crystal alignment agent described in Table 2 was used. The evaluation results are shown in Table 2. -73- 200927793 Table 2 Liquid crystal alignment agent type storage stability Example 7 A-CO-1 Good example 8 A-CO-2 Good example 9 A-CO-3 Goodly understood from the above examples, this The liquid crystal alignment agent containing a radiation-sensitive polyorganosiloxane is a light alignment method which exhibits excellent liquid crystal alignment property by a light alignment method without a rubbing alignment treatment. A liquid crystal alignment film having a pretilt angle and excellent electrical characteristics. The liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention is more excellent in the afterimage characteristics than the conventional polyimide having a cinnamic acid derivative on the side lock. Therefore, when the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is applied to a liquid crystal display element, a liquid crystal display element can be produced at a lower cost than the prior art, and it is excellent in display characteristics, signalability, and the like. Therefore, such liquid crystal display elements can be effectively applied to various devices, such as devices for desktop computers, watches, desk clocks, counting display panels, word processing, personal computers, liquid crystal televisions, and the like. -74-

Claims (1)

200927793 X. Patent Application Range 1. A liquid crystal alignment agent characterized by having a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), - CH = CH2 and - S02C1 are selected from the group consisting of at least one cinnamic acid derivative, and a radiation-sensitive linear polyorganosiloxane obtained by reacting with a polyorganosiloxane having an oxetane ring . 2. The liquid crystal alignment agent of claim 1, wherein the cinnamic acid derivative is the following formula (A-1) (In the formula (A-1), R1 is an alkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms having an alicyclic group, and a part or all of the hydrogen atom of the alkyl group may be Substituted by a fluorine atom; R2 is a single bond, an oxygen atom, -COO- or -OCO-; R3 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring a group, except that part or all of the hydrogen atom of the above-mentioned divalent aromatic group may be substituted by a fluorine atom; R4 is a single bond, an oxygen atom, -COO- or -OCO-; R5 is a single bond, a methyl group, a carbon a 2 to 10 alkylene group or a divalent aromatic group, when R5 is a single bond, 'R6 is a hydrogen atom', and R5 is a methyl group, an alkyl group or a divalent aromatic group, and 'R6 is a carboxyl group or a hydroxyl group. , -SH, -NCO, -NHR, -CH = CH2 or -S02C1, except that R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R7 is a fluorine atom, a methyl group or a cyano group; a -75- 200927793 An integer represented by 0 to 3; b is an integer of 〇~4) or a compound of the following formula (A_2) -〇-C——CH=CH-II 〇\4r9~r1V (A-2) (In the formula (A-2), R is a group having a carbon number of 1 to 40 or a monovalent organic group having an alicyclic group or an aromatic group having a carbon number of 3 to 40, except for the foregoing A part or all of the hydrogen atom of the alkyl group may be substituted by a fluorine atom; R9 is a single bond, an oxygen atom, -COO- or -0C0-; Ri〇 is a methyl group having a methyl group and a carbon number of 2 to 1 (). a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group. A part or all of the hydrogen atom of the above-mentioned divalent aromatic group may be a fluorine atom. Substituted; Rii is a single bond, _〇C〇_(CH2)e_, -COO-(CH2)g- or -0-((:Η2)ί-, but e, g, and i are each an integer of 1 to 10 R12 is a carboxyl group, a hydroxyl group, _SH, -NCO, -NHR, -CH=CH2 〇 or -S〇2C1' except that the above-mentioned ruler is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and R13 is a fluorine atom, a methyl group or a cyano group; c is an integer of 〇 〜3; d is an integer represented by 0 to 4). The liquid crystal alignment agent of claim 1 or 2, wherein the polyorganosiloxane has a lower The formula (s_n 'f 1 - Si - Ο - (S-1) -76- 200927793 (in the formula (Sl) X has the following formula (x-l) R (X-1) (In the formula (X-1), R14 is an alkyl group having 1 to 6 carbon atoms, "*" represents a monovalent organic group of a structure represented by a bond; 0 is a hydroxyl group, carbon At least one selected from the group consisting of a polyorganosiloxane having a repeating unit of a repeating unit represented by an alkoxy group having 1 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms; and a condensate of a hydrolyzate; . 4. The liquid crystal alignment agent according to claim 1 or 2, which further comprises at least one polymer selected from the group consisting of polylysine and polyimine. 5. For the liquid crystal alignment agent of claim 1 or 2, the system Q further contains the following formula (S-2) - R17 - Si - Ο - (S-2) (Formula (S- In 2), R17 is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; Y2 is a hydroxyl group; a halogen atom: an alkoxy group having a carbon number of 1 to 2 0 or carbon At least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by an alkyl group having 1 to 6 and a hydrolyzate thereof and a condensate of the hydrolysis-77-200927793. A method of forming a liquid crystal alignment film which is characterized in that a coating film of a liquid crystal alignment agent of claim 1 or 2 is coated on a substrate to irradiate radiation to the coating film. A liquid crystal display element characterized by comprising a liquid crystal alignment film formed by the liquid crystal alignment agent of claim 1 or 2. -78- 200927793 VII. Designated representative 囷: (1) The representative representative of the case is: None (2), the representative symbol of the representative 简单 is a simple description: None 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -3-