TW200927727A - 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 compound represented by the formula (1) below with a polyorganosiloxane having an epoxy group. (In the formula (1), R1, R2 and R3 independently represent a hydrogen atom or a monovalent organic group, provided that when R3 is not a hydrogen atom, at least one of R1 and R2 is a carboxyl group or an organic group having a carboxyl group; and R1 and R2 may combine together to form a ring.)

Description

200927727 IX. Description of the Invention [Technical Field] The present invention relates to a liquid crystal alignment agent, a method of forming a liquid crystal alignment film, and a liquid crystal display element. [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, the long axis of the liquid crystal molecules is continuously twisted between the substrates. A liquid crystal display element having a liquid crystal cell such as a TN (Twisted Nematic) type, an STN (Super Twi sted Nematic) type, or an IPS (In Plane Switching type) formed by 0 to 360° (refer to Japanese Patent Laid-Open No. 56- Japanese Patent Publication No. 91277 and 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, a liquid crystal alignment film must be disposed on the surface of the substrate; the liquid crystal alignment film 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 ash is adhered to the surface of the alignment film, which causes a display failure, and particularly has a TFT (Thin Film). When the substrate of the component is used, there is a problem that the circuit of the TFT element is broken due to the static electricity generated, which causes a decrease in yield. Further, in the liquid crystal display element which is more refined in the future, as the density of the pixel is increased, irregularities are inevitably generated on the surface of the substrate, and it becomes difficult to uniformly perform the rubbing alignment treatment on the -5 - 200927727.

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. According to this method, a uniform alignment of the liquid crystal can be achieved without causing static electricity or dust (refer to Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2000-281, No. 2000-281, pp. Japanese Patent Publication No. 297313, JP-A-2003-307736, JP-A-2004-136646, and JP-A-2002-250924. However, in a liquid crystal cell such as a TN (Twisted Nematic) type or a STN (Super Twisted Nematic) type, the liquid crystal alignment film must have a pretilt characteristic for tilting the liquid crystal molecules at a predetermined angle with respect to the substrate surface, by photoalignment method. When the liquid crystal alignment film is formed, the pretilt angle characteristic is usually imparted by irradiation of radiation inclined from the substrate normal to the incident direction of the substrate surface by Q. 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 operation mode, when a voltage is applied between the substrates to tilt the liquid crystal molecules in a direction parallel to the substrate, it is necessary to tilt the liquid crystal molecules from the normal direction of the substrate toward a direction in the plane of the substrate. As such a means, for example, a method of providing a protrusion on a surface of a substrate, a method of providing a strip shape on a transparent electrode, and a method of causing liquid crystal molecules from a normal direction of a substrate toward a surface of a substrate by using a rubbing alignment -6-200927727 The method of slightly tilting the direction (making it pretilt) and the like.

The above optical alignment 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 regulation property and a pretilt angle expression by a photo-alignment method. The film can uniformly control the tilt direction of the liquid crystal molecules when the voltage is applied (refer to Japanese Laid-Open Patent Publication No. 2003-307736, JP-A-2004-1 63646, JP-A-2004-83810, and JP-A No. 9-2 1 1468). Bulletin and Special Publication 2003-1 1 4437). 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 irradiation is required in order to obtain a large pretilt angle. problem. For example, when a film containing an azobenzene derivative imparts 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 J/m 2 or more from the substrate normal. The report of the oblique radiation irradiation (refer to Japanese Laid-Open Patent Publication No. 2002-250924 and JP-A-2004-83810 and J. of the SID 11/3, 2003, p579). Therefore, it is necessary to provide an excellent liquid crystal alignment energy and pretilt angle expression for the obtained liquid crystal alignment film even when the amount of radiation is small, and a liquid crystal alignment agent having a polymer having a side chain derived from cinnamic acid. Kaiping No. 6-287453). This technique relates to a polymer synthesized by using a cinnamic acid derivative having an alkoxy group, but the coating film of the liquid crystal alignment agent has absorption in a long wavelength region of 3 65 nm or more, for example, in a visible light region, so that in order to form The photo-alignment step of the liquid crystal alignment film is not limited to 200927727. For example, the ultraviolet curing step of the blocking agent in the production of the liquid crystal panel or even the backlight may cause a photoreaction, and there may be a problem that the liquid crystal alignment property or the reliability of the panel is not good.

Further, it is considered that the cinnamic acid derivative having an ester group by using a substituted alkoxy group shifts the absorption spectrum to the short-wavelength side, thereby solving the above-mentioned non-conformity. By this technique, the possibility of causing thermal decomposition of the side chain of the cinnamic acid derivative during post-baking in the liquid crystal panel manufacturing step is not absolutely absent, and there is a fear that the substrate or the panel manufacturing line is inferior. As described above, the photo-alignment method with a small amount of radiation irradiation can form a liquid crystal alignment film having excellent liquid crystal alignment energy, excellent electrical characteristics, and high heat resistance, and does not cause a problem of thermal decomposition at the time of post-baking or because A liquid crystal alignment agent which causes a problem of photolysis due to backlighting during use of a panel has not been known so far. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide excellent storage stability, and it is excellent in formation of a small amount of exposure by radiation irradiation by polarized or non-polarized light without performing rubbing alignment treatment. a liquid crystal alignment film which does not absorb light in a long-wavelength region, and a liquid crystal alignment film which is excellent in electrical properties and heat resistance of the liquid crystal alignment agent; and display characteristics and reliability Properties such as sex - excellent liquid crystal display elements. According to the present invention, in the above object of the present invention, the first aspect is obtained by containing the following formula (1) -8 - 200927727

(In the formula (1), R^R2 and R3 are each independently a hydrogen atom or a monovalent organic group, and when R3 is not a hydrogen atom, at least one of R1 and R2 is a carboxyl group or an organic group having a carboxyl group, and R1 is R2 may be bonded to each other to form a ring.) The compound represented, and having the following formula (S-1)

-Si-〇-- Y1 J (S-ι) (In the formula (Si), X1 is a monovalent organic group having an epoxy group; Y1 is a fluorenylhydroxy group, an alkoxy group having a carbon number of 1 to 10, carbon An alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.) At least one reaction selected from the group consisting of a polyorganosiloxane of a repeating unit, a hydrolyzate thereof, and a condensate of a hydrolyzate It is achieved by obtaining a liquid crystal alignment agent of a sensitive radiation linear polyorganosiloxane. The above object of the present invention 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-aligned liquid crystal alignment film. -9-200927727 The above object of the present invention is achieved by the liquid crystal display device comprising the liquid crystal alignment film formed of the above liquid crystal alignment agent. [Best Mode for Carrying Out the Invention] The liquid crystal alignment agent of the present invention contains the compound represented by the above formula (1) (hereinafter referred to as "cinnamic acid derivative (1)"), and 0 has the above formula ( At least one selected from the group consisting of a polyorganosiloxane of a repeating unit represented by S-I), a hydrolyzate thereof, and a condensate of a hydrolyzate (hereinafter, referred to as "polyorganosiloxane having an epoxy group" Alkane") a sensitive radiation linear polyorganosiloxane obtained by the reaction. <Cinnamic acid derivative (1) > The cinnamic acid derivative (1) used in the present invention is a compound represented by the above formula (1). In the above formula (1), R1 and R2, each of which is not bonded to each other by Q, are each a hydrogen atom or may be an oxygen atom, a sulfur atom or a divalent group -NR- (only R is a hydrogen atom or a carbon number) The alkyl group having 1 to 20 carbon atoms is preferably an aliphatic group having 1 to 40 carbon atoms or an alicyclic group having 3 to 40 carbon atoms, and these aliphatic groups or alicyclic groups may be substituted by fluorine atoms. In the above formula (1), when R3 is not a hydrogen atom, at least one of R1 and R2 is a carboxyl group, or a part of a hydrogen atom of an aliphatic group or an alicyclic group (preferably one) is substituted by a carboxyl group. Organic base. In the above formula (1), a ring in which R1 and R2 may be bonded to each other to form a ring, for example, may be a monocyclic ring having 3 to 8 carbon atoms, a condensed ring having 4 to 40 carbon atoms, and a carbon number of -10 to 200927727 4~ The crosslinked ring of 40 or the crosslinked condensation of carbon number 5 to 40: the total carbon number is preferably 6 to 40. R3 is a monocyclic ring, a condensed ring, a crosslinked ring or a crosslinked link of a hydrogen group. When a ring, a crosslinked ring or a crosslinked condensed ring is used, the alicyclic ring may be a condensed ring of an alicyclic ring and an alicyclic ring or When the alicyclic ring and the ring are a condensed ring of an alicyclic ring and an aromatic ring, it is preferred that the anthracene ring is an alicyclic ring. 0 R3 in the above formula (1) is preferably a hydrogen atom

CbH2b+1, -(CH2)e-CdF2d + 1 (except that a is an integer of 4 to 20, c is an integer of 0^8, and d is a nonenyl or a cholesteryl group. The ring is preferably a condensed ring; the ring is a single ring; the ring is a condensed ring of a condensed ring aroma ring; the imine ring condenses one - ( CH2) a-C00H '- an integer of -ίο, b is an integer from 1 to 18), biliary, (2)

(In the formula (2), R4 and R5 are each independently a hydrogen group', and at least one of R4 and R5 is a group having a number of 1 to 20 alkyl groups or a carbon group which may be substituted by a fluorine atom, R4 and R5 It may be bonded to each other to form a ring.) The compound represented by the formula or the following formula (3) atom or a monovalent organic group substituted with a fluorine atom is a 3 to 40 alicyclic group of the carbon-11 - 200927727

(In the formula (3), r6 is a single bond or a divalent organic group, R7 is a hydrogen atom or a monovalent organic group, R6 and R7 may be bonded to each other to form a ring; and R8 is a carbon which may be substituted by a fluorine atom. A compound represented by an alkyl group having 1 to 20 or an alicyclic group having a carbon number of 3 to 40 which may be substituted by a fluorine atom. The preferred compound represented by the above formula (2), wherein R4 and R5 are not bonded to each other, for example, a compound represented by the following formula (2-1); and R4 and R5 are bonded to each other to form a single Examples of the ring compound include a compound represented by the following formulas (2-2) and (2-3); and R4 and R5 are bonded to each other to form a condensed ring, and examples thereof include the following formula (2). -4) The compound represented by the formula (2-5) to (2-10), and the compound represented by the following formula (2-5) - (2-10), and the R5 and R5 are mutually bonded to each other to form a cross-linking ring. -12- 200927727

CH=CH—COOH (2-1)

-13- 200927727 R15-

R15- o

R15- 〇

CH=CH-COOH (2-8)

CH=CH-COOH 0 (the fat taken by the upper sub-coo < 2-9) wherein R9, R11, R13 and R15 are each independently an alkyl group which may be 1 to 20 carbon atoms which may be a fluorine atom or may be fluorine The atom-substituted carbon number is 3 to 40 ring groups; R101 is a single bond, an oxygen atom, a sulfur atom or a divalent group-, -OCO- or -NR- (only, R is a hydrogen atom or a carbon number of 1 to 20) Alkyl-14- 200927727 base; R12 is a 2-valent group -COO-, -OCO-, -COS-, -SCO-, -CONR- or -NRCO- (only, R is a hydrogen atom or a carbon number of 1-20) Alkyl); R14 is a single bond, an oxygen atom or a divalent group _〇-CH2-, -CH2-0-, -. COO- or -OCO-; R16 is a single bond, an oxygen atom, a sulfur atom or 2 The valence group -COO-, -OCO-, -COS- or -SCO- 〇) In the above formula (2-1), 'as R9, a linear alkyl group having 4 to 20 carbon atoms is preferred; as R1 ( It is preferred to use a single bond, an oxygen atom or a sulfur atom. In the above formula (2-2), each of R11 is a linear alkyl group having 4 to 20 carbon atoms, a cholesteryl group, a cholesteryl group, an adamantyl group or a 4-pentyl group which may be substituted by a fluorine atom. Preferably, a cyclohexyl group or a 4-butylcyclohexyl group; and as Ri2, a divalent group -COO- or -OCO- is preferred. In the above formula (2-3), 'as R13', a linear alkyl group having 4 to 20 carbon atoms which may be substituted by a fluorine atom, a cholesteryl group, a cholesteryl group, an adamantyl group of 4-pentyl ring Hexyl or 4-butylcyclohexyl is preferred. In the above formulae (2-4) to (2-9), as R15, a linear alkyl group having 4 to 20 carbon atoms which may be substituted by a gas is preferable, and a single bond is preferred. Preferred examples of the compound represented by the above formula (2): the compound represented by the above formula (2-1), for example, a compound represented by each of the following formulas (2·.K1) to (HS) The compound represented by the above formula (2-2), for example, a compound represented by the following formula (2-2-1). 200927727

CH=CH a COOH (2-1-2)

(In the above formula, each of 'R9 and R11 is synonymous with the above formula (2U) or (2_2).) The compound 'expressed by the above formula (2)' can be synthesized by an organic chemical method. For example, the compound represented by the above formula (2-1) can be, for example, a method of refluxing a derivative of a succinic anhydride having a group of R9-R1G- with a 4-aminocinnamic acid in acetic acid, or a toluene or xylene It is synthesized by refluxing in the presence of a suitable catalyst such as sulfuric acid or triethylamine. Alternatively, 4-iodophenylamine and maleic anhydride can be synthesized by the same method as described above, and then the radical R9_RlQ_ can be introduced by Michael addition, and then by -16-200927727

The compound represented by the above formula (2-1) is obtained by Heck reaction.

In the compound represented by the above formula (2-2), for example, a divalent group R 1 2 is a compound of 'OCO- (only a bond with "*" is bonded to R11), for example, hydrogenated trimellitic anhydride a product obtained by reacting sulfite with ruthenium chloride to form an acid chloride, and then reacting it with a compound rH-oh, for example, in the presence of a suitable base such as triethylamine to form an ester bond, by recombining with 4 - Amino cinnamic acid is obtained by reaction. In this case, the reaction of the esterified compound with 4-aminocinnamic acid can be carried out under the same conditions as those of the compound represented by the above formula (2-1). The compound represented by the above formula (2-3), for example, a compound obtained by heating maleic anhydride and a styrene derivative by using N-nitrosophenylhydroxylamine aluminum salt and hydroquinone as a catalyst It is obtained by reacting 4-amino cinnamic acid in the same manner as in the synthesis of the compound represented by the above formula (2-1). Among the compounds represented by the above formula (2-4), for example, a ruthenium compound in which R16 is a single bond can be reacted, for example, by a Diels-Alder reaction at a 5-position substituted cyclopentadiene having a radical R15- at the 5-position with maleic anhydride. After the addition, the adduct is reacted with 4-aminocinnamic acid by the same method as in the synthesis of the compound represented by the above formula (2-1). Wherein the 5-position has a radical R15-substituted 5-cyclopentadiene, and an excess amount of the compound R15-X (except that X is a halogen atom) relative to the cyclopentadienyl anion is _20~ 30 ° C anti-quot; should, and get priority. In the compound represented by the above formula (2-5), for example, the compound in which R16 is a single bond', in addition to the substitution of the 5-substituted cyclopentadiene, is substituted with a pentyl group having a -17-200927727-based R15- In addition to the diene, it can be synthesized by the same method as in the synthesis of the compound represented by the above formula (2.3). Wherein the 1-position substituted cyclopentadiene at the 1-position of the group R15- can be used in an amount of 0.8 to 1.2 equivalents of the compound R15-X with respect to 1 equivalent of the cyclopentadienyl anion (only, X is a _ atom ) is reacted at -78 to 20 ° C and is preferably obtained. In the preferred compound represented by the above formula (3), R6 and R7 are not bonded to each other, and examples thereof include a compound represented by the following formula (3-1).

R6 and R7 are bonded to each other to form a single ring, and examples thereof include a compound represented by the following formula (3-2); and R6 and R7 are bonded to each other to form a condensed ring, and may be exemplified by the following formula: (3-3) The compound or the like represented. HOCO—R17—R18 0 ❹

COOH

CH=CH-COOR8 0-3) -18- 200927727 (In the above formula, R8 is synonymous with the above formula (3); R17 is a methyl group or a C 2~10 alkyl group; R18 is an oxygen atom, sulfur Atom or a divalent group - COO-, -OCO- or -NR- (except that R is a hydrogen atom or an alkyl group having a carbon number of 1 to 20). A more specific example of the compound represented by the above formula (3), the compound represented by the above formula (3-2), for example, a compound represented by the following formula (3-2-1).

〇 (In the above formula, each of R8 has the same meaning as in the above formula (3-2); a is an integer of 1 to 10.) In the above formula (3 - 1), for example, a compound wherein the group R18 is a sulfur atom, for example, The 4-iodophenylmaleic anhydride imide amine Michael addition compound HOOC-R17-SH is synthesized by addition of a product to the compound CH2 = CH-COOR8 by Heck reaction. In the compound represented by the above formula (3-2), the compound represented by (3_2-1) may, for example, be 4-nitrocinnamic acid in the presence of potassium carbonate and an alkyl halide having an alkyl group corresponding to R1. The base reacts to form an ester, and the nitro group is reduced to, for example, tin chloride to form an amine group, thereby obtaining a 4-aminocinnamate, and the product is formed by a 1,2,4-tricarboxycyclohexyl ring. It is obtained by reacting hexane anhydride. The latter reaction can be carried out, for example, by refluxing the starting compound in acetic acid or by refluxing in toluene 200927727 or xylene in the presence of a suitable base catalyst such as triethylamine. Further, the compound represented by the above formula (3-3), for example, can be used to heat maleic anhydride and 4-vinylbenzoic acid with N-nitrosophenylhydroxylamine aluminum salt and hydroquinone as a catalyst. The 4-aminocinnamate prepared by the same method as the synthesis of the compound represented by the above formula (3-2-1) by the compound obtained by the reaction, by the above formula (2 - 丨) The same method is obtained by reacting it. 〇<Polyorganooxane having an epoxy group> The polyorganosiloxane having an epoxy group used in the present invention is a polyorganoquinone having a repeating unit represented by the above formula (S-1) At least one selected from the group consisting of oxane, a hydrolyzate thereof, and a condensate of a hydrolyzate. X1 in the above polyorganosiloxane having an epoxy group is represented by the following formula (X1-!) or (X^2)

〇

The indicated base is preferred. Examples of the oxy group having 1 to 10 carbon atoms of Y include a methoxy group and an ethoxy group; and examples of the alkyl group having 1 to 20 carbon atoms include methyl group and ethyl group -20- fluorene.

200927727 base, η-propyl, η-butyl, η-pentyl, η-hexyl, η-fluorenyl, η-fluorenyl, η- eleven-yard, η-dodecyl, η-fourteen Examples of the aryl group of the alkyl group, the η-pentadecyl group, the η-hexadecene group, the η-octadecyl group, the η-nonadecyl group, and the η-eicosane 6 to 20 include a phenyl group and the like. The polyorganosiloxane having an epoxy group, preferably having a polystyrene-converted weight of 100,000 as measured by coagulation GPC), preferably 1,000 to 1,000,000, 1,000 such a polyorganoquinone having an epoxy group a mixture of an oxane, an epoxy group-containing decane compound, or an epoxy group-containing decane compound, preferably synthesized as a decane having an epoxy group by hydrolysis or hydrolysis/condensation in the presence of a suitable vehicle. Compound, oxypropoxypropyltrimethoxydecane, 3-glycidoxypropane, 3-glycidoxypropylmethyldimethoxypropylmethyldiethoxydecane, 3-ring Oxypropoxy decane, 3-glycidoxy propyl dimethyl ethoxy 3 epoxy cyclohexyl) ethyl trimethoxy decane, 2-(3 ethyl triethoxy decane, etc. as the other Examples of the decane compound include methoxy decane, tetraethoxy decane, tetra-n-propoxy oxalate, tetra-n-butoxy fluorene, tetra-sec-butane, trimethoxy decane, Triethoxy decane, tris-i-propoxy decane, tri-n-butoxydecane, tri-n-heptyl, η-octyl.alkyl, Η-tridecanefluorenyl, η-seventeenth base, etc.; as a carbon number gel permeation chromatography (with a molecular weight of 500~ 〜5,0 0 is better. It is preferred to have an f-alkyl compound and Other solvent, water and contact agents may, for example, be 3-cyclopropyltriethoxyoctane, 3-glycidoxypropyldimethylmethoxyg-decane, 2-(3,4-,4) -Epoxycyclohexyl) 1 such as tetrachlorodecane, tetradecane, tetra-i-propoxydecane, trichloro-η-propoxydecane, -sec-butoxydecane-21 - 200927727

, fluorotrichlorodecane, fluorotrimethoxydecane, fluorotriethoxydecane, fluorotri-n-propoxydecane, fluorotri-i-propoxydecane, fluorotri-n-butoxydecane, fluorine Tris-sec-butoxydecane, methyltrichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltri-i-propoxy Decane, methyltri-n-butoxydecane, methyltris-sec-butoxydecane, 2-(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl)ethyltrimethoxy Baseline, 2-(trifluoromethyl)ethyltriethoxydecane, 2-(trifluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl)ethyltri- I-propoxydecane, 2-(trifluoromethyl)ethyltri-n-butoxydecane, 2-(trifluoromethyl)ethyltris-butoxybutane, 2-(perfluoro -η-hexyl)ethyltrichlorodecane, 2-(perfluoro-η-hexyl)ethyltrimethoxydecane, 2-(perfluoro-η-hexyl)ethyltriethoxydecane, 2-(all Fluoro-η-hexyl)ethyltri-n-propoxydecane, 2-(perfluoro-η-hexyl)ethyltri-1-propoxydecane, 2-(perfluoro-η-hexyl)ethyl Three-n- Oxydecane, 2-(perfluoro-η-hexyl)ethyltris-sec-butoxydecane, 2-(perfluoro-η-octyl)ethyltrichlorodecane, 2-(perfluoro-η- Octyl)ethyltrimethoxydecane, 2-(perfluoro-η-octyl)ethyltriethoxydecane, 2-(perfluoro-η-octyl)ethyltri-n-propoxydecane , 2-(perfluoro-η-octyl)ethyltri-1-propoxydecane, 2-(perfluoro-η-octyl)ethyltri-n-butoxydecane, 2-(perfluoro -η-octyl)ethyltris-sec-butoxydecane, hydroxymethyltrichlorodecane, hydroxymethyltrimethoxydecane, hydroxyethyltrimethoxydecane, hydroxymethyltri-n-propoxy Decane, hydroxymethyltri-i-propoxydecane, hydroxymethyltri-n-butoxydecane, hydroxymethyltris-butoxybutane, 3-(methyl)propenyloxypropyl Trichlorodecane, 3-(methyl)propene-22- 200927727 methoxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyltriethoxydecane, 3-(methyl)propene醯oxypropyl tri-n-propoxydecane-, 3-(methyl)propenyloxypropyltri-i-propoxydecane, 3-(methyl,)propenyloxypropyl Tri-n-butoxydecane, 3-(methyl)propenyloxypropyltris-sec-butoxydecane, 3-mercaptopropyltrichlorodecane, 3-mercaptopropyltrimethoxydecane , 3-mercaptopropyltriethoxydecane, 3-mercaptopropyltri-n-propoxydecane ' 3-mercaptopropyltri-i-propoxydecane, 3-mercapto 0 propyl tri-- Η-butoxydecane, 3-mercaptopropyltris-sec-butoxydecane, mercaptomethyltrimethoxydecane, mercaptomethyltriethoxydecane, vinyltrichlorodecane, vinyl trimethyl Oxydecane, vinyl triethoxydecane, vinyl tri-n-propoxydecane, vinyl tri-i-propoxydecane, vinyl tri-n-butoxydecane, vinyl tri-sec -butoxydecane, allyltrichloromethane, allyltrimethoxydecane,allyltriethoxydecane,allyltri-n-propoxydecane,allyltri-i-propyl Oxydecane, allyl tri-n-butoxydecane, allyl tri-sec-butoxydecane, phenyl trichloro Q decane, phenyl trimethoxy decane, phenyl triethoxy decane, Phenyl tri-n-propoxydecane, phenyl tri-i-propoxydecane, benzene Tri-n-butoxydecane, phenyl tri-sec-butoxydecane, methyldichlorodecane, methyldimethoxydecane, methyldiethoxydecane,methyldi-n-propoxy Base decane, methyl 'di-i-propoxy decane, methyl di-η-butoxy decane, methyl di-sec-butyl oxy decane, dimethyl dichloro decane, dimethyl dimethyl Oxydecane, dimethyldiethoxydecane, dimethyldi-n-propoxydecane, dimethyldi-i-propoxydecane, dimethyldi-n-butoxydecane, Dimethyldi-sec-butoxydecane, (methyl)[2-(perfluoro-η-octyl)ethyl]dichlorodecane, -23- 200927727

(methyl)[2-(perfluoro-η-octyl)ethyl]dimethoxydecane, (methyl)[2-(perfluoro-η-octyl)ethyl]diethoxydecane, (methyl)[2-(perfluoro-η-octyl)ethyl]di-η-propoxydecane, (methyl)[2-(perfluoro-η-octyl)ethyl]di-i -propoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-η-butoxydecane, (methyl)[2_(perfluoro-η-octyl) Bis-sec-butoxydecane, (methyl)(3-mercaptopropyl)dichlorodecane, (methyl)(3-mercaptopropyl)dimethoxydecane, (methyl) ( 3-mercaptopropyl)diethoxydecane, (methyl)(3-mercaptopropyl)di-η-propoxydecane, (methyl)(3-mercaptopropyl)di-i- Propoxy decane, (meth)(3-mercaptopropyl)di-η-butoxydecane, (methyl)(3-mercaptopropyl)di-sec-butoxydecane, (methyl) (vinyl) dichlorodecane, (methyl) (vinyl) dimethoxy decane, (methyl) (vinyl) diethoxy decane, (methyl) (vinyl) di-n-propoxy Baseline, (meth) (vinyl) Di-i-propoxydecane, (meth)(vinyl)di-η-butoxydecane, (meth)(vinyl)bis-sec-butoxydecane, divinyldichlorodecane, Divinyldimethoxydecane, divinyldiethoxydecane, divinyldi-n-propoxydecane, divinyldi-i-propoxydecane, divinyldi-n-butyl Oxydecane, divinyldi-sec-butoxydecane, diphenyldichlorodecane, diphenyldimethoxydecane, diphenyldiethoxydecane, diphenyldi-n-propoxy Pyridin, diphenyldi-i-propoxydecane, diphenylbis-n-butoxy fluorene, monophenyldi-sec-butoxylate, chlorodimethyl sand, methoxy Dimethyl decane, ethoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, iodine trimethyl decane, methoxy trimethyl decane, ethoxy trimethyl-24- 200927727 decane , η-propoxy trimethyl decane, i-propoxy trimethyl decane, η • butoxy trimethyl decane, sec-butoxy trimethyl decane, t-butoxy trimethyl decane (chloro)(vinyl) dimethyl Alkane, (methoxy) (vinyl) dimethyl decane, (ethoxy) (vinyl) dimethyl decane, (chloro) (methyl) diphenyl decane, (methoxy) (methyl) a decane compound having one ruthenium atom such as diphenyl decane or (ethoxy) (methyl) diphenyl decane, Ο

In terms of trade names, for example, 〇-89, 〖(:-893, again -21-3153, again -21-5841, X-21-5842, X-21-5843, X-21-5844, X- 21-5845, X-21-5846 'X-2 1 -5847, X-2 1 -5848, X-22-1 60AS, X-22-1 70B, X-22-1 70BX, X-22-1 70D, X-22-1 70DX, X-22-176B, X-22-1 76D, X-22- 1 76DX, X-22-176F, X-40-2308, X-40-2651, X-40 -2655A, X-40-2671, X-40-2672, X-40-9220 'X-40-9225, X-40-9227 ' X-40-9246, X-40-9247, X-40-9250 , X-40-9323, X-41-1053, X-41-1056 'X-41-1 805, X-4 Bu 1810, KF600 1, KF6002, KF6003, KR212, KR-213, KR-217, KR220L , KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230 'KR5235' KR9218, KR97 06 (above, Shin-Etsu Chemical Co., Ltd.); Glass Resin (Showa Electric Co., Ltd.); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, Toray Dow Corning (share) system); FZ371 1, FZ3722 (above, day UN ICAR (share) system; DMS-S12, DMS-S15, DMS--25- 200927727 S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS- S42, DMS-S45, DMS-S51, DMS-

227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (above, Chisso (manufactured by the company)); methyl phthalate MS51, methyl phthalate MS56 (above, Mitsubishi Chemical Co., Ltd.) : ethyl phthalate 28, ethyl phthalate 40, ethyl phthalate 48 (above, COLCOAT (manufactured by COLCOAT); GR100, GR650, GR908, GR950 (above, Showa Denko (manufactured by the company)) Partial condensate. Among these other decane compounds, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, 3-(methyl) propylene methoxy propyl trimethoxy Base decane, 3-(meth) propylene methoxy propyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, allyl trimethoxy decane, allyl triethoxy Baseline, phenyltrimethoxydecane, phenyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, mercaptomethyltrimethoxydecane, fluorenyl Methyltriethoxydecane, dimethyldimethoxydecane or dimethyldiethoxydecane is preferred. The polyorganosiloxane having an epoxy group used in the present invention has an epoxy equivalent of 100 to 10,000 g/mol, more preferably 150 to 1,000 g/mole. Therefore, when synthesizing a polyorganosiloxane having an epoxy group, the ratio of use of the decane compound having an epoxy group to other decane compounds is set in the above-mentioned range in which the epoxy equivalent of the obtained polyorganosiloxane is adjusted. Preferably. The organic solvent which can be used when synthesizing the polyorganosiloxane having an epoxy group is, for example, a hydrocarbon, a ketone, an ester, an ether, an alcohol or the like. -26-200927727 Examples of the hydrocarbon include toluene and xylene; and examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl η-pentyl hydrazine, diethyl ketone, and a ring. Examples of the ester include ethyl acetate, η-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate. Wait;

Examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, and dioxane. Examples of the alcohol include 1-hexanol and 4-methyl-2-pentane. Alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-η-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Ether, propylene glycol mono-η-propyl ether, and the like. Among these, those which are not water-soluble are preferred. These organic solvents may be used singly or in combination of two or more kinds of organic solvents, preferably from 10 to 10,000 parts by weight, more preferably from 50 to 1,000 parts by weight based on 100 parts by weight of the total decane compound. Parts by weight. The amount of water used in the production of the polyorganosiloxane having an epoxy group is preferably from 0.5 to 100 moles, more preferably from 1 to 30 moles per mole of the total decane compound. As the catalyst, for example, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound or the like can be used. The above-mentioned alkali metal compound may, for example, be sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide or potassium ethoxide. The organic base may, for example, be an amine of 1 to 2 such as ethylamine, diethylamine, piperazine-27-200927727, piperidine, pyrrolidine or pyrrole; for example, triethylamine or tri-n-propyl An amine, a tri-n-butylamine, a pyridine, a 4-di-methylaminopyridine, a diazabicycloundecene, an organic amine, a metal amine such as tetramethylammonium hydroxide Wait. In such an organic base, an organic amine such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine or 4-dimethylaminopyridine; The ammonium 4-grade organic amine is preferred. As the catalyst for producing a polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferred. By using an alkali metal compound or an organic base as a catalyst, since the side reaction such as ring opening of an epoxy group does not occur, the desired polyorganosiloxane can be obtained at a high hydrolysis/condensation rate, and the production stability is excellent. good. Further, the liquid crystal alignment agent of the present invention containing a reaction product of an epoxy group-containing polyorganosiloxane and an cinnamic acid derivative (1) synthesized using an alkali metal compound or an organic base as a catalyst, because of the preservation stability Excellent, so it is more suitable. The reason is as indicated by Chemical Reviews, 95 Q, P1 409 (1995), and it is speculated that it is because of the use of an alkali metal compound or an organic base as a catalyst in hydrolysis or condensation reaction, and the random structure and ladder structure. Alternatively, a cage-type structure is formed to obtain a polyorganosiloxane having a small content of a stanol group. It is presumed that this is because the content of the alkanol group is small, and the condensation reaction between the stanol groups is suppressed. When the liquid crystal alignment agent of the present invention contains other polymers described later, the condensation of the stanol group with other polymers is considered. When the reaction is suppressed, the storage stability is excellent. As the catalyst, it is particularly preferred to use a base. The amount of the organic base to be used varies depending on the type of the organic base, the reaction conditions, and the like, and should be appropriately set. However, for example, it is preferably 0.01 to 3 times by mole relative to the total decane compound. Jia Wei. 〇 5~1 times Mo. The hydrolysis or hydrolysis/condensation reaction in the production of a polyorganosiloxane having an epoxy group is carried out by dissolving a decane compound having an epoxy group and other decane compounds as necessary in an organic solvent, and the solution and the organic base and The water mixing is preferably carried out, for example, by heating in an oil bath or the like. 0 In the hydrolysis/condensation reaction, the heating temperature is preferably preferably 130 ° C or less, more preferably 40 0 to 100 ° C, preferably 0.5 to 12 hours, more preferably 1 to 8 hours. . While heating, the mixture may be stirred or placed under reflux. After the reaction is completed, the organic solvent layer taken out from the reaction liquid is preferably washed with water. In the case of the washing, it is preferred to wash the water by a water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 2% by weight. After the washing is performed until the water layer after washing becomes neutral, Q, and then the organic solvent layer is dried with an appropriate desiccant such as anhydrous calcium sulfate or molecular sieve, and then the solvent is removed to obtain the object. A polyorganosiloxane having an epoxy group. In the present invention, a commercially available product can be used as the polyorganoanthracene having an epoxy group. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (above, Chisso (share) system, etc. <Sensitizing Radiation Linear Polyorganooxane> The radiation sensitive linear polyorganosiloxane used in the present invention can be obtained by using -29-200927727 as described above for the polyorganic oxide chamber having an epoxy group and cinnamic acid. The derivative (I) is preferably synthesized by reacting in the presence of a catalyst. Here, the cinnamic acid derivative (1) 'is preferably used in an amount of 0.001 to 1.5 mol, more preferably 〇.〇1~, relative to the polyoxyalkylene oxide having an epoxy group of 1 mol. 1 mole, and even more preferably 0.05 to 0.9 moles. As the above-mentioned catalyst, as a so-called hardening accelerator for promoting the reaction of an organic base or an epoxy compound with an acid anhydride, a conventional compound can be used. 0 as the above organic base, for example, ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, pyrrole 1 to 2 organic amine; such as triethylamine, tri-n-propylamine, three An organic amine of -n_butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, or an organic amine such as tetramethylammonium hydroxide. In such an organic base, an organic amine such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine or 4-dimethylaminopyridine; such as tetramethyl hydroxide; The ammonium 4-grade organic amine is preferred. 〇 As the hardening accelerator, for example, benzyl dimethylamine, 2,4,6-gin(dimethylaminomethyl)phenol, cyclohexyldimethylamine, triethanolamine, a tertiary amine; Imidazole, 2_n-heptyl imidazole, 2_n_+ monoalkylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, benzyl-2-methylimidazole, benzyl-2-phenylimidazole 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, '1-(2-cyanoethyl)-2-methylimidazole, 1-(2-cyanoethyl)-2 -n-decaine-imidazole, 1-(2-cyanoethyl)-2-phenylimidazole, cyanoethyl)-2-ethyl-4-methylimidazole, 2-phenylene-4-a Base_5_hydroxymethylimene-30- 200927727

Oxazole, 2-phenyl-4,5-di(hydroxymethyl)imidazole, 1-(2-cyanoethyl)-2-phenyl-4,5-bis[(2'-cyanoethoxy) )methylimidazole, 1-(2-cyanoethyl)-2-η-undecylimidazole, trimellitate, 1-(2-cyanoethyl)-2-phenylimidazole Trimellitic acid ester, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole key trimellitate, 2,4-diamino-6-[2'-methyl Imidazolyl-(1')]ethyl-3-triazine, 2,4-diamino-6-(2'-11-undecylimidazolyl)ethyl-s-triazine, 2,4 - a trimeric isocyanate adduct of diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s-triazine or 2-methylimidazole, Trimeric isocyanate adduct of 2-phenylimidazole, trimerization of 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine An imidazole compound of a cyanic acid adduct; an organophosphorus compound such as diphenylphosphine, triphenylphosphine or triphenylphosphonium phosphate; such as benzyltriphenyl iron chloride, tetra-n-butyl bromide, Methyl triphenyl sulphate bromide, ethyl triphenyl rust bromide, η-butyl triphenyl sulphate bromide, tetraphenyl iron bromide, ethyl triphenyl iron , ethyltriphenylhydrazine-hydroxyacetate, tetra-n-butyl-diethyldithiophosphate, tetra-n-butyl benzotriazolate, tetra-η- a quaternary phosphonium salt of butyl phosphonium tetrafluoroborate, tetra-n-butyl phosphonium tetraphenyl borate, tetraphenyl platinic tetraphenyl borate; such as 1,8-diazabicyclo[5.4 .0] an undecylene olefin of eleven carbon-7 or an organic acid salt thereof; an organometallic compound such as zinc octoate, tin octylate, and aluminum acetonitrile complex; such as tetraethylammonium bromide, four - η butyl ammonium bromide, tetraethyl ammonium chloride 31 - 200927727 compound, tetra-ammonium salt of tetra-n-butyl ammonium chloride; boron compound such as boron trifluoride or triphenyl vinegar; a high melting point dispersion type latent hardening accelerator such as a metal halide compound of zinc or tin chloride; an amine addition forming accelerator such as dicyandiamide or an adduct of an amine and an epoxy resin;

微 A microcapsule latent curing accelerator coated with a polymer of a surface of a hardening accelerator such as an imidazole compound, an organophosphorus compound or a quaternary phosphonium salt; an amine salt type latent hardener accelerator; a Lewis acid salt; A latent hardening accelerator such as a high temperature dissociative thermal cationic polymerization type latent curing accelerator such as a Bronsted acid salt. Among these, a 4-grade ammonium salt such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride or tetra-n-butylammonium chloride is preferred. The catalyst is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, even more preferably 0.1 to 1 part by weight based on 1 part by weight of the polyorganosiloxane having an epoxy group. 2 parts by weight. The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C; and the reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours. The synthesis reaction of the sensitive radiation linear polyorganosiloxane can be carried out in the presence of an organic solvent if necessary. Examples of the organic solvent include, for example, a hydrocarbon compound, an ether compound, a vinegar compound, a ketone compound, a guanamine compound, an alcohol compound, etc., among which an ether compound, an ester compound, and a ketone compound are dissolved by a raw material and a product. It is preferable from the viewpoint of the ease of purification of the product and the product. The solvent solid content concentration (the ratio of the total weight of the components other than the solvent - 32 to 200927727 in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, more preferably 5 to 5 times. The amount of 0% by weight is used. The radiation sensitive linear polyorganosiloxane of the present invention is a structure derived from a citric acid derivative (1) by ring-opening addition of an epoxy in a polyorganosiloxane having an epoxy group. It is a very suitable method from the viewpoint of being simple and capable of increasing the introduction rate of the structure derived from the cinnamic acid derivative. Further, when the synthesis of the radiation sensitive linear organopolyoxane of the present invention is carried out, it is not detrimental to the present invention. In the range of the effect, a part of the above cinnamic acid derivative is represented by the following formula (4): R19-R20_Z (4) (in the formula (4), R19 is an alkyl group or alkoxy group having a carbon number of 4 to 20 or a monovalent organic group having a carbon number of 3 to 40 in the alicyclic ring group, wherein a part or all of the hydrogen atom of the alkyl group or the alkoxy group may be substituted by a fluorine atom; and R 2 G is a single bond or a phenyl group; When R19 is an alkoxy group, r2() is a phenyl group, Z is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (only, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH = At least one selected from the group consisting of CH2 and -S02C1.) The compound represented by the compound may be used after being substituted. At this time, the synthesis of the sensitive radiation linear polyorganosiloxane can be achieved by mixing a polyorganosiloxane having an epoxy group, a cinnamic acid derivative, and a compound represented by the above formula (4)-33-200927727 The reaction is carried out. In the above formula (4), as R19, 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 1 is preferable; as R2Q, a single bond or Preferably, 1,4-phenylene is preferred; as Z, a carboxyl group is preferred. Specific examples of the compound represented by the above formula (4) can be exemplified by the following formulas (4-1) to (4-4).

(in the above formula (4-1), f is an integer of 1 to 1 ,, g is an integer of 〇~5; and in the above formula (4-2), h is an integer of 5 to 20; and in the above (4-3) i is an integer of 1 to 3, and j is an integer of 0 to 18; and k in the above formula (4-4) is an integer of 1 to 18). Preferred examples of the compound represented by the above formula (4) include dodecanoic acid and stearic acid, and the following formula (4-3-1) to (4-3-3)-34-200927727 cf3 —ο

\—COOH (4-3-1 ) cf3—c3h6—o

COOH (4-3-2) 〇2F5—C3H6—°

—COOH (4-3-3)

Compounds and the like represented by each. The compound represented by the above formula (4) is introduced into the polyorganosiloxane having an epoxy group together with the cinnamic acid derivative (1) under the same reaction conditions as the cinnamic acid derivative (1). The photosensitive polyorganosiloxane is a compound which is a site which imparts a pretilt expression property to the obtained liquid crystal alignment film. In the present specification, the compound represented by the above formula (4) is hereinafter referred to as "other pretilt angle expressing compound". The compound represented by the above formula (4) is preferably 50 mol% or less, more preferably 3, based on the total of the cinnamic acid derivative (1) and the compound represented by the above formula (4). 3 moles of the following ratios are used. When the ratio of the use of the compound represented by the above formula (4) exceeds 50 mol%, the obtained liquid crystal display element may have an abnormal region (d〇main) when it is on (voltage-applied state). The situation. <Other Ingredients> -35- 200927727 The liquid crystal alignment agent of the present invention contains the above-mentioned radiation sensitive linear polymer oxime. • The liquid crystal alignment agent of the present invention may contain, in addition to the above-mentioned linear radiation of the sensitive radiation, other than the organic oxane, other components may be contained as long as it does not impair the effects of the present invention. a polymer other than a radiation-linear polyorganosiloxane (hereinafter referred to as "other polymer"), a curing agent, a curing catalyst, a curing accelerator, or a compound having at least one fluorene epoxy group in the molecule (hereinafter referred to as It is an "epoxy compound", a functional decane compound, a surfactant, etc. <Other Polymers> The above other polymers can be used to further improve the solution characteristics of the liquid crystal alignment agent of the present invention and the electrical properties of the obtained liquid crystal alignment film as other related polymers, for example, polylysine And at least one polymer selected from the group consisting of polyimine, and having the following formula (S-2)

X2 -Si-〇-- 2) -Ϋ2 . (In the formula (S-2), X2 is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or carbon. An aryl group of 6 to 20; Υ2 is a hydroxyl group or an alkoxy group having 1 to 1 carbon atoms.) At least a group selected from the group consisting of a polyoxane, a hydrolyzate thereof and a condensate of a hydrolyzate 1 type (hereinafter referred to as "other polyoxane"), poly-36-200927727 proline, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly( Styrene-phenyl maleic anhydride imide) derivatives, poly(meth)acrylates, and the like. [Polyuric acid] The above polylysine ' can be obtained by reacting a tetracarboxylic dianhydride with a diamine. 0. As the tetracarboxylic dianhydride which can be used for the synthesis of polylysine, for example, butane tetracarboxylic dianhydride, hydrazine, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-di Methyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-Uhl cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3 , 4-cyclobutane tetracarboxylic dianhydride, I, 2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-ring Pentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3,4,4, dicyclohexyltetradecanoic acid dianhydride, 2,3,5-three Indole cyclopentyl acetic acid di-hepatic, 3,5 6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetraazafuran tetradecanoic acid di-Q-anhydride, l,3,3a, 4,5,9b-hexahydro-5-(tetraqi-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3-dione, 1, 3,3&,4,5,91>-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-cbufuran ι %二嗣,1,3,33,4,5,91>-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furan'yl)-naphtho[ l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91}_hexaamine_7_methyl•yl-5-(tetrahydro-2,5-di oxygen Benz-3-furanyl)-naphtho[1,2_(;]_咲 __ • 1,3-diketone, 1,3,3&,4,5,9-hexahydro-7-ethyl- 5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3-dione, i,3,3a,4,5, 9b_hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)·naphtho[丨2_-37- 200927727 C]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]- Furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl )-naphtho[1,2-indolyl]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2- Dicarboxylic anhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.l]octane-2,4-dione -6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxo)

Tetrahydro-3-furanyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo[5_3.1.02'6]undecane-3,5,8,10-tetraone, the following formula (丁-1) and (丁-11

(In the formulae (TI) and (T-II), each of R21 and R22 is a divalent organic group having an aromatic ring, and each of R23 and R24 is a hydrogen atom or an alkyl group, and each of R23 and R24 existing in the plural may be the same or different. An aliphatic or alicyclic tetracarboxylic dianhydride of a compound or the like represented by each of them; -38-

200927727 Pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid 2,3',4,4'-biphenyl milling tetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic acid di-2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid 2,3',4,4'- Dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'- decane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4' -3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-ylphenoxy)diphenylphosphonium dianhydride, 4,4'-bis (3 , 4-dicarboxyphenoxydiphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene dicarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid Dihydride, 2,2',3,3'-biphenyltetracarboxylic acid, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(tris) dianhydride, m- Benzene-bis(triphenylphthalic acid) dibis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(trisphthalic acid)-4,4'-diphenyl Methane dianhydride, ethylene glycol-bis(anhydrotriester), propylene glycol-bis (dehydrated trimellitate), 1,4-butane di-bis (dehydrated benzene) Acid ester), 1,6-hexanediol-bis(dehydrated trimellitene), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2,2-bis(4-phenyl)propane - bis (hydrogen trimellitate), the following formula (T-1) T-4) anhydride, anhydride, anhydride, tetraphenyl bis(dicarboxy) dianhydride dianhydride phenyl anhydride, phenyl phenylene glycol -acid hydroxy group ~ ( -39- 200927727

-40-200927727 An aromatic tetracarboxylic dianhydride such as a compound represented by each. These may be used alone or in combination of two or more.

Among these, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3 a, 4,5,9b - hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]furan-1,3-dione, 1,3,3&,4 ,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-(:]furan-1,3- Diketone, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1] ,2-c]furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1 Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)- 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2 : 3,5 : 6-dianhydride, 4,9- Dioxatricyclo[5.3.1.02,6]-[-alkane-3,5,8,10-tetraketone, pyromellitic dianhydride, 3,3',4,4'-benzophenone Tetracarboxylic dianhydride, 3,3',4,4'-biphenyl maple tetracarboxylic dianhydride, 2,2 , 3,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and the following formula (T-5) ~ (in the compound represented by the above formula (TI)) T-7 -41 - 200927727

(Τ-7) 化合物 Each of the compounds represented by the formula and the compound represented by the above formula (Τ-ΙΙ) has the following formula (T-8) 〇 〇

The compound represented by 〇 0 (T-8) is preferable from the viewpoint that it can exhibit excellent liquid crystal alignment properties from -42 to 200927727.

As a particularly preferred one, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b - hexahydro-5-(tetrazol-2,5-dioxo-3-furanyl)-naphtho[1,2-called furan-1,3-dione, 13,33,4,5,913-six Hydrogen-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo [3.2.1] Octane-2'4-dione-6-spiro_3'_ (tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3) Furyl)-3-methyl-3-cyclohexene-I,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5:6-dianhydride, 4,9-Dioxa S ring [5.3.1.02,6]undecane_3,5,8,10-tetraone, pyromellitic dianhydride, and a compound represented by the above formula (T-5). Examples of the diamine used for the synthesis of the above polyamic acid include P'phenylene diamine, m-phenylenediamine, 4,4,-diaminodiphenylmethane, and 4,4'-di. Aminodiphenylethane, 4,4,-diaminodiphenyl sulfide, 4,4,-diaminodiphenylanthracene, 3,3,-dimethyl-4,4,-di Aminobiphenyl, 4,4,-diaminobenzamide, 4,4,-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2,-= Shenji-4 , 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2'2'.di-trifluoromethyl-4,4'-diamino Biphenyl, 3,3'-di-trifluoromethyl-4'4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3,3-tri Methyl indane, 6-amino-1-( 4'-aminophenyl)-1,3,3-trimethylindan, 3'4'-diaminodiphenyl ether, 3,3 '-Diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminobenzene) Phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropyrrol, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-amine-43- 200927727 phenoxy) Grinding, 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-diamino fluorene, 9,9-dimethyl-2,7-. diamino hydrazine, 9, 9-bis(4-aminophenyl)anthracene, 4,4'-methyl-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diamine Biphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diamine Biphenyl, 1,4,4'-(p-phenylisopropylene)diphenylamine, 4,4'-(m-benzoquinone isopropylidene)diphenylamine, 2,2'-double [ 4-(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4 , 4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, the following formula (D-1)~(D-5)

-44- 200927727

COO

/CH3, ch3 (D-2)

(D-5) -45-200927727 (Y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5). Aromatic diamine;

1,1-m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethyldiamine, hexamethylenediamine, heptamethyldiamine, octamethyldiamine, nine-methyl Diamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienyldiamine, hexahydro-4,7-methyleneindane dimethylenediamine (hexahydro-4,7-methanoindanylenedimethylenediamnine), tricyclo[6.2.1.02,7]-undecene dimethyldiamine, 4,4'-methylenebis(cyclohexylamine), 1,3-double Aliphatic or alicyclic diamines such as (aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane; 2,3-diaminopyridine, 2,6-diamine Bismuthidine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2, 4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)piperazine, 2,4- Diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino -6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-3-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2- Dilute-s-triterpene, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3 ,5-Diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridone propionate, 3,8-diamino-6-phenylphenanthridine , 1,4-diaminopiperazine ' 3,6-diamino acridine, bis(4-aminophenyl)phenylamine, 3,6-diaminocarbazole, N-methyl-3 ,6-Diaminocarbazole, N-ethyl-3,6-diaminocarbazole, -46- 200927727 N-phenyl-3,6-diaminocarbazole, N,N,-di 4-aminophenyl)-benzidine, formula (DI) h2n

(DI) (In the formula (D-Ι), R25 is a monovalent organic group having a ring structure containing a nitrogen atom selected from a group consisting of pyridine, pyrimidine, triterpene, sulfonium 11 and piperazine; X3 It is a divalent organic group; R26 is a hospital group having a carbon number of 1 to 4; a1 is an integer of 0 to 3; and R26 is the same or different when it exists in a plural number.) The compound represented by the following formula (D- II)

(R28)a2 (R28)a2

(D-II) (In the formula (D-II), R27 is a divalent organic group having a ring structure containing a nitrogen atom selected from a group consisting of pyridine, pyrimidine, triazine, piperidine and piperazine; Each of X4 is a divalent organic group; each of R28 is an alkyl group having 1 to 4 carbon atoms; each of a2 is an integer of 0 to 4; each of X4 in the plural may be the same or different, and each of R28 may be the same or The compound represented by the compound or the like has two primary amine groups in the molecule and a diamine of a nitrogen atom other than the amino group of the first-47-200927727 amine; the following formula (D-III) (R31) a3 OR29 —R30 (D-III ) “NH2 ^ (In the formula (D-III), R29 is a group of -Ο-, -COO-, -oco-, -NHCO-, -CONH- and -CO- Selected divalent organic group; R3G is a monovalent organic group having a steroid skeleton, a monovalent organic group having a trifluoromethylphenyl group, a trifluoromethoxyphenyl group or a fluorinated phenyl group or a carbon number of 6 An alkyl group of ～30; R31 is an alkyl group having 1 to 4 carbon atoms; a3 is an integer of 0 to 3; and R31 is the same or different in the presence of a complex number.) The monosubstituted phenylene diamine represented by the following formula; (D-IV) 〇

(D-IV) (In the formula (D-IV), each of R 3 2 is a hydrocarbon group having a carbon number of from 1 to 12, and each of R.sup.1 may be the same or different; each of p is an integer of from 1 to 3; q is from 1 to 20 The integer is a compound such as a diamine-based organooxane such as a compound. These diamines may be used singly or in combination of two or more kinds in the range of -48 to 200927727. The benzene ring of the above aromatic diamine may be substituted by one or two or more alkyl groups having 1 to 4 carbon atoms (preferably methyl groups). In the above formulae (D-1), (D·11) and (D-III), each of R26, R28 and R31 is preferably a methyl group, and a1, a2 and a3 are each preferably 0 or 1, and 0 is more preferable.

In the R3G of the above formula (D-III), the organic group having a valence of the steroid skeleton is preferably a carbon number of 17 to 51, and preferably a carbon number of 17 to 30. Specific examples of R3° having a steroid skeleton include, for example, cholest-3-yl, cholest-5-en-3-yl, cholest-24-en-3-yl, cholester-5,24. -Dien-3-yl, lanostan-3-yl and the like. Among these, P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2 , 2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-di-trifluoromethyl-4,4'-diaminobiphenyl, 2,7-diamino fluorene , 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene , 2,2-bis[4-indole (4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p -phenylphenyldiisopropylidene)diphenylamine, 4,4'-(m-phenylene diisopropylidene)diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4' - bis(4-aminophenoxy)biphenyl, 1,4-cyclohexanediamine, 4,4'-methylene bis(cyclohexylamine), 1,3 bis (aminomethyl) ring Hexane, a compound represented by the above formula (D-1) to (D-5), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3, 6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, > ^-Phenyl-3,6-diamino fluorene ,; ^,] ^ '- bis (4-amino-phenyl) - biphenyl -49-200927727 amine, the following formula (D-6) a compound represented by the above formula (D-Ι) of

(D-6

The compound represented by the above formula (D-7) in the compound represented by the above formula (D-11)

(Dh2n C3H6~(Z/n^^3" Compound represented by nH2, dodecyloxy-2,4-diaminobenzene, pentadecane in the compound represented by the above formula (D-III) Oxy-2,4-diaminobenzene,hexadecanyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, 12-indolyloxy-2 , 5-diaminobenzene, fifteen-epoxy 2,5-diaminobenzene, hexadecanthoxy-2,5-diaminobenzene, octadecyloxy-2,5.diamine Base benzene, the following formula (D--8)~(D-1 6 ) h2n flank, nh2

(D-8) -50- 200927727

-51 200927727

The compound represented by each of (D-16) and the 1,3-bis(3-aminopropyl)-tetramethyldioxane represented by the above formula (D-IV) are preferably supplied to the brewed fiber. The ratio of tetradecanoic dianhydride to the synthesis reaction of the amine acid is preferably 1 to 2 equivalents based on the amine group contained in the diamine, and the ratio of the tetracarboxylic anhydride group is 0.2 to 2 equivalents, more preferably in the ratio of f equivalents. . The compound iridane diamine dianhydride acid i 0.3-1-2 -52- 200927727 polyamine acid synthesis reaction is preferably in an organic solvent, preferably -20~15 (TC, better) For the temperature of 〇~l〇〇°C, it is preferably carried out for 1 to 48 hours, more preferably for 2 to 10 hours, wherein as the organic solvent, as long as it is soluble, it can be dissolved. The lysine may be 'unspecially limited, and examples thereof include N-methyl-2-pyrrolidinium, N,N-dimethylacetamide, N,N-dimethylformamide, and hydrazine. , a non-primary polar solvent such as fluorene-dimethylimidazolidinone, dimethyl hydrazine, γ-butyrolactone, tetramethyl urea, hexamethylphosphoric acid triamide; m-cresol, two a phenol solvent such as cresol, phenol or halogenated phenol. The amount of the organic solvent used (a: when the organic solvent is used, the weak solvent described later means the total amount of the two), the tetracarboxylic dianhydride and the second The total amount of the amine (b) is preferably from 0.1 to 30% by weight based on the total amount (a + b ) of the reaction solution. In the above organic solvent, the produced polyamine does not precipitate. In the periphery, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, etc., which are generally considered to be a weak solvent of polylysine, may be used. Specific examples of the related weak solvent may be, for example, methanol, ethanol, or the like. Propyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone , methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, " ethyl ethoxy propionate, diethyl oxalate, C Diethyl diacrylate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-η-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 mono-53- 200927727 methyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloro Ethane, 1,4-dichlorobutane, trichloroethane Alkane, chlorobenzene, hydrazine-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, isopentyl pentyl propionate, isoamyl isobutyrate, diisoamyl ether When a polyacetic acid is produced by using a weak solvent as described above in an organic solvent, the ratio of use may be appropriately set within a range in which the produced polyamine does not precipitate, and it is preferably a total solvent. 50% by weight or less, more preferably 0% by weight or less. As described above, a reaction solution obtained by dissolving polylysine can be obtained, and the reaction solution can be directly supplied to the liquid crystal alignment agent, or can be reacted. The polyamine acid contained in the solution is supplied to the liquid crystal alignment agent after being isolated, or may be purified by isolating the separated polyamine acid and then supplied to the liquid crystal alignment agent. For the isolation of polylysine, a precipitate may be obtained by injecting the above reaction solution into a large amount of a weak solvent, and the precipitate may be dried under reduced pressure, or the reaction solution may be distilled off under reduced pressure using an evaporator. The method is to go. Further, the poly-proline may be purified by dissolving the polylysine in an organic solvent, followed by precipitation with a weak solvent, or by a step of distilling off under reduced pressure with an evaporator. . [Polyimide] The polyimine which is obtained by reacting a tetracarboxylic dianhydride with a diamine can be synthesized by deuteration after dehydration ring closure. The tetracarboxylic dianhydride used for the synthesis of the polyimine may be the same as the tetracarboxylic dianhydride used in the synthesis of the above polyamic acid.

As the tetracarboxylic dianhydride used for the synthesis of the polyimine used in the present invention, tetracarboxylic dianhydride containing an alicyclic tetracarboxylic dianhydride is preferably used as a particularly preferred alicyclic tetracarboxylic acid. Examples of the acid dianhydride include 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3^4,5,915-hexahydro-5-(tetrahydro-2,5-dioxo-3-- Furyl)-naphtho[l,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-A hydrogen-8-methyl-5-(tetrahydro-2, 5-dioxo-3-furanyl)-naphtho[1,2-(:]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione -6-spiro-3,-(tetrahydrofuran-2',5'-dione)' 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene -1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5:6-dianhydride or 4,9-dioxatricyclo[5.3.1. 02'6] undecane-3,5,8,10-tetraketone. In the synthesis of the above polyimine, an alicyclic tetracarboxylic dianhydride and another tetracarboxylic dianhydride may be used. The proportion of the alicyclic tetracarboxylic dianhydride in the total tetracarboxylic dianhydride is preferably 10 mol% or more, more preferably 50 mol% or more. The diamine to be used may be the same as the diamine used for the synthesis of the above polylysine. The diamine used for the synthesis of the polyimine of the present invention contains the above formula (D-). The diamine diamine represented by III) is preferable. As a preferable specific example, the compound represented by the above formula (D-III) may, for example, be a 'dealkyloxy-2,4-diaminobenzene. , pentadecyloxy-2,4-diaminobenzene, cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy Base-2,5--aminobenzene, fifteen-decyloxy-2,5-diaminobenzene, hexamethylene oxy-55-200927727 yl-2,5-diaminobenzene, octadecyloxy -2,5-diaminobenzene and a compound represented by each of the above formulas (D-8) to (D-16). ' When the above polyimine is synthesized, the above formula (D-III) can be used. The diamine and other diamines represented by - are preferred among other diamines, and examples thereof include P-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4,4'-diamine. Diphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-di- Fluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminopurine, 4,4'-0 diaminodiphenyl ether, 2,2-bis[4-(4-amine Phenyloxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropene, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylenediisopropylidene)diphenylamine, 4,4'-(m-phenylene diiso) Propyl) bisaniline, 1,4-cyclohexanediamine, 4,4'-methylene bis(cyclohexylamine), 1,4-bis(4-aminophenoxy)benzene, 4,4' - bis(4-aminophenoxy)biphenyl, a compound represented by the above formula (D-1) to (D-5), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 〇N,N'-bis(4-aminophenyl)-benzidine, N,N,_bis(4-aminobenzene a compound represented by the above formula (D-6) and a compound represented by the above formula (D-II) in the compound represented by the above formula (DI), -N,N'-dimethyl-benzidine. 1,3-double in the compound represented by the above formula (D-7) and the compound represented by the above formula (D-IV) 3-amino-propyl) - tetramethyl siloxane silicon and the like. When the diamine represented by the above formula (D-III) and the other diamine are used, the diamine represented by the above formula (D-111) is preferably used in an amount of more than 5% by weight based on the total diamine. It is better to use 1% by weight or more. -56- 200927727 A dehydration ring-closure reaction for synthesizing polyamidene which can be used in the present invention, by (i) heating polylysine or (ii) dissolving polylysine In an organic solvent, a dehydrating agent and a dehydration ring-closing catalyst are added to the solution, and if necessary, heating is carried out.

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. On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the solution of the polyamic acid in the above (ii), as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent to be used is preferably 0.01 to 20 moles per 1 mole of the polyamic acid structural unit. 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 used is preferably 0.01 to 10 mol with respect to the dehydrating agent used. Further, the organic solvent used as the dehydration ring-closure reaction can be exemplified as the synthesis of polyglycine. The organic solvents listed by the user. Then, the reaction temperature of the dehydration ring-closing reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C, and the reaction time is preferably from 5 to 24 hours, more preferably from 1 to 1. 0 hours. The polyimine obtained in the above method (i), which can be directly supplied to the preparation of the liquid crystal alignment agent or can be supplied to the liquid crystal alignment agent after purification of the obtained polyimine, on the other hand A reaction solution containing polyimine can be obtained in the above method (ii). The reaction solution can be supplied to the liquid crystal alignment agent from -57 to 200927727, or can be prepared by removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and can be supplied to the liquid crystal alignment agent, or can be polymerized. After the segregation, the preparation is supplied to the liquid crystal alignment agent, or the selenium imidazole may be purified and supplied to the liquid crystal alignment agent, and the dehydrating agent and the dehydration ring-closing catalyst may be removed from the reaction solution. For example, solvent replacement may be applied. The method. Segregation and purification of the polyimine can be carried out by the same operation as the above-described separation and purification method as polylysine. 0 The polyimine which can be used in the present invention may be a dehydrated structure of the proline structure, or may be a part of the structure of the proline which is dehydrated and closed, and the structure of the quinone ring and the structure of the proline are stored. The imidization rate is low. The polyamidene which can be used in the present invention has a ruthenium iodide ratio of preferably 80% or more and more preferably 85% or more. Here, the "rhodium imidization ratio" is expressed as a percentage based on the ratio of the number of the proline structure in the polymer to the number of the quinone ring in the total number of the quinone ring. In this case, a part of the quinone ring may be an isoindole ring, and the ruthenium imidization ratio may be obtained by dissolving the poly-Q-imine in a suitable heavy hydrogenation solvent (for example, dimethyl hydrazine). The result of iH-NMR measurement at room temperature using tetramethylnonane as a reference substance was calculated by the formula represented by the following formula (i). Ruthenium amination rate (%) = (1 - A 1 / A2 X a) X 1 0 0 ( i ) (In equation (i), A is produced by protons of the nh group visible at i〇ppm The peak area, the peak area produced by other protons in the A2 system, and the ratio of the number of protons in the α-series relative to the protons of the polyimide (poly-proline) in the protons of 1-58-200927727 °) - End-modified polymer - ... The above-mentioned poly-proline and polyimine can be molecularly modified end-modified, such a terminal-modified polymer, in the synthesis of poly-proline It can be synthesized by adding a molecular weight modifier to the reaction system. The above-mentioned molecular weight modifier may, for example, be an acid monoanhydride, a monoamine compound or a monoisomeric cyanate compound. Here, examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, η-mercaptosuccinic anhydride, η-dodecylsuccinic anhydride, η-tetradecyl succinic anhydride, and η- Cetyl succinic anhydride and the like. Further, 'as a monoamine compound' may, for example, be aniline, cyclohexylamine, η-butylamine, η-pentylamine, η-hexylamine, η-heptylamine, η-octylamine, η-fluorenyl Amine, η-decylamine, η-undecylamine, η-dodecylamine, η-tridecylamine, η-tetradecylamine, η-fiute-amine, η-ten Hexamethylamine, η-heptadecaquinolamine, η-octadecylamine, η-icosylamine, and the like. Further, examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. The molecular weight modifier is preferably in the range of 20 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyamic acid. use. -Solid viscosity - The polylysine or polyimine obtained by the above method is a solution having a concentration of 1 〇-59-200927727% by weight, preferably having a solution viscosity of .20 to 800 mPa.s, having 30~ The solution viscosity of 50 〇 mpa.s is better. The solution viscosity (mPa · s ) of the above polymer was a polymer solution having a concentration of 1% by weight with respect to a good solvent using the polymer, and was measured by an E. type rotational viscometer at 25 t. [Other polyoxane] 0 is at least one selected from the group consisting of a polysiloxane having a repeating unit represented by the above formula (S-2), a hydrolyzate thereof, and a hydrolyzate. In the above formula (S-2), X2 is preferably an alkyl group having 1 to 20 carbon atoms or a polyorganosiloxane having an aryl group having 6 to 20 carbon atoms. For example, at least one decane compound (hereinafter referred to as "raw material decane compound") selected from the group consisting of an alkoxy decane compound and a halogenated decane compound is preferably used in the other polyoxyalkylene. In a suitable organic solvent, it is synthesized by hydrolysis or hydrolysis and condensation in the presence of water and a catalyst. As the raw material decane compound which can be used herein, for example, tetramethyl methoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetra-iso-propoxy decane, tetra-n-butoxy Basear, tetra-s-butoxybutane, tetra-tert-butoxydecane, tetrachlorodecane; methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane , methyl triiso-propoxypropane, methyl tri-n-butoxydecane, methyl tri-sec. butoxydecane, methyl tri-tert-butoxydecane, methyltriphenyloxide Base decane, methyl chlorosilane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl tri-n--60-200927727 propoxy decane, ethyl tri-iso-propoxy decane, Ethyl tri-n-butoxydecane, ethyl tri-sec-butoxydecane, ethyl tri-tert-butoxydecane', ethyltrichlorodecane, phenyltrimethoxydecane, phenyl tri Ethoxydecane·-, phenyltrichlorodecane; dimethyldimethoxydecane, dimethyldiethoxy. decane, dimethyldichlorodecane; trimethylmethoxydecane, trimethyl Ethoxy decane, Silane methyl chloride and the like. Among these, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, 0 phenyl trimethoxy decane, phenyl triethoxy decane, and Methyl dimethoxy decane, dimethyl diethoxy decane, trimethyl methoxy decane or trimethyl ethoxy decane is preferred. In the case of synthesizing another polyoxyalkylene oxide, examples of the organic solvent which can be used arbitrarily include an alcohol compound, a ketone compound, a guanamine compound or an ester compound or other aprotic compound. These may be used alone or in combination of two or more.

Examples of the above alcohol compound include methanol, ethanol, η-propanol, i-propanol, η-butanol, i-butanol, sec-butanol, t-butanol, η-pentanol, and i-pentanol. 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, η-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec -heptanol, heptanol-3, η-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethylheptanol-4, η-nonanol, sec- Undecyl alcohol, trimethyl decyl alcohol, sec-tetradecyl alcohol, sec-heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, Monool compound such as benzyl alcohol or diacetone alcohol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, pentanediol-2,4, 2-methyl-61 - 200927727-based pentanediol- 2,4, hexanediol-2,5, heptanediol-2,4,2 1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tri-quot; alkoxide compound; Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene diethylene glycol mono-2-ethyl butyl ether, diethylene glycol single Methyl ether ethyl ether, diethylene Monopropyl ether, diethylene glycol monobutanol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethanol monoethyl ether, dipropylene glycol monopropyl A polyol ether or the like of a group ether or the like. As such an alcohol compound, one type or a combination of hydrazine may be used as the ketone compound, and examples thereof include acetone, methyl-η-propyl ketone, methyl-n-butyl ketone, diethyl ketone ketone, and methyl group. Η-amyl ketone, ethyl-η-butyl ketone, methyl 〇i-butyl ketone, trimethyl fluorenone, cyclohexanone, 2-hexanone, 2,4-pentanedione, acetonyl Acetone, acetophenone, anthrone; acetoacetone, 2,4-hexanedione, 2,4-heptanedioxanone, 2,4-octanedione, 3,5-octanedione , 2,4-oxananedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetra-I-dione, 1,1,1,5,5,5 - β_ of hexafluoro-2,4-heptanedione or the like. These ketone compounds may be used alone or in combination of two or more. The above-described guanamine compound may, for example, be a polyglycol monopropyl ether alcohol monophenyl ether such as methyl acetonate-ethylhexyl glycol-propylene glycol or the like. And two or more kinds of diethylene glycol monoether, diethylenediyl ether, propylene glycol ether, and dipropylene compound use methyl ethyl ketone, methyl-i-butyl 1-hexyl ketone, and two- Methylcyclohexanone, a monoketone compound such as 1,3,5-heptanediedone, and a 3,5-fluorenylmethyl-3,5-heptanedione compound are used. Amine, N-methylmethyl-62- 200927727 decylamine, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, acetamide, N- Methylacetamide, N,N-dimethylacetamide, Ν·B, acetylamine, hydrazine, hydrazine-diethylacetamide, hydrazine-methyl propylamine, Ν-methylpyrrole Ketone, Ν-methyl morpholine, Ν-甲 峨 峨 steep, N-methyl 啦 啦 院 Ν, Ν - acetyl morpholine, Ν - acetyl hydrazine, Ν - 乙Slightly hospital and so on. These guanamine compounds can be used alone or in combination of two or more. Examples of the above ester compound include, for example, diethyl carbonate vinegar, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, and η-propyl acetate. Ester, i-propyl acetate, n-butyl vinegar acetate, i-butyl vinegar acetate, sec-butyl acetate, η-amyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methyl acetate Amyl ester, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, cyclohexyl acetate, η-decyl acetate, methyl acetate, acetonitrile Ethyl ester, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-η- Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, two Ethylene glycol acetate, methoxytriethylene glycol acetate, ethyl propionate, η-butyl propionate, i-pentyl propionate, diethyl oxalate, Acid di-η-butyl ester, methyl lactate, ethyl lactate, η-butyl lactate, η-amyl lactate, diethyl malonate, dimethyl phthalate', diethyl phthalate, etc. . These ester compounds may be used alone or in combination of two or more. Examples of the other aprotic compound include acetonitrile and di-63-.

200927727 Methyl sulfoxide, >^川,>^',:^'-tetraethylsulfonamide, hexamethylphosphoric acid, N-methylmorpholine, N-methylpyrrole, N-ethylpyrrole , N-methyl Illene, N-methyloxime, N-ethylpiperid, N,N-dimethylpiperidinyl imidazole, N-methyl-4-piperidone, N-methyl 2-piperidone, N_. pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl p 1H )-pyrimidinone, and the like. Among these solvents, a polyol compound or a polyol compound ketone ether or ester compound is particularly preferred. As the amount of water used in the synthesis of other polyoxalates, the total amount of the alkoxy group and the halogen atom of the decane compound is preferably from 0.5 to 100 mol, more preferably from 1 to 30 mol. 1 to 1.5 m. The catalyst which can be used in the synthesis of other polyoxyalkylene can be, for example, a metal chelate compound, an organic acid, an inorganic acid, an organic base, an ammonia compound or the like. As the above metal chelate compound, there may be mentioned, for example, a triacetate (acetonitrile) titanium, a tri-n-propoxy group, a mono(acetonitrile) titanium propoxy group, a mono(acetonitrile) titanium, and a third. -η_butoxy•mono(b)titanium, tris-sec-butoxy•mono(acetamidineacetone)titanium, tris-t_7 mono(acetonitrile)titanium, diethoxy•bis(acetamidineacetone) Titanium propoxy bis (acetonitrile) titanium, di-i-propoxy. bis(B) titanium, di-η-butoxy bis(acetonitrile) titanium, two-sec-double ( Ethyl acetonide) Titanium 'di-t-butoxy bis (acetamidine acetonide) ethoxy group ginseng (acetamidine acetonide) titanium, mono-η-propoxy group ginseng (ethylene tridecylamine; -Δ3- Pyridine, hydrazine-methylmethyl-2-hydrogen-2 (part of the original 1 molar is more preferred as an example, alkali gold-based, mono-, di-i-pyruvyloxy, bis-n-indolyl oxyfluoride) Base · Titanium, Monoterpenoids • 64 - 200927727

Titanium, mono-i-propoxy-parameter (acetonitrile) titanium, mono-η-butoxy-parade (acetonitrile) titanium, mono-sec-butoxy-paraben (acetonitrile) titanium , mono-t-butoxy ginseng (acetonitrile) titanium, ruthenium (acetonitrile) titanium, triethoxy methoxy (ethyl acetoacetate) titanium, tri-n-propoxy Mono(ethylacetamidine acetate) titanium, tri-i-propoxy-mono(ethylacetamidine acetate) titanium, tri-n-butoxy-mono(ethylacetamidine acetate) Titanium, tri-sec-butoxy mono(ethylacetate acetate) titanium, tri-t-butoxy mono(ethylacetate acetate) titanium, diethoxy•double (B Acetylacetate) titanium, di-n-propoxy bis(ethylacetamidine acetate) titanium, di-i-propoxy bis(ethyl acetamidine acetate) titanium, two -η-butoxy•bis(ethylacetamidine acetate) titanium, di-sec-butoxy•bis(ethylacetamidine acetate) titanium, di-t-butoxy•double (B Acetyl acetate) titanium, monoethoxy ginseng (ethyl acetoacetate) titanium, mono-η-propoxy ginseng (ethyl acetoacetate) titanium, single-i- Propyloxy• (ethyl acetoacetate) titanium, mono-η-butoxy ginseng (ethyl acetamidine acetate) titanium, mono-sec-butoxy ginseng (ethyl acetoacetate) titanium , mono-t-butoxy ginseng (ethyl acetoacetate) titanium, lanthanum (ethyl acetoacetate) titanium, mono (acetyl acetonide) ginseng (ethyl acetoacetate) titanium a titanium chelate compound such as bis(acetonitrile) bis(ethylacetamidine acetate) titanium, ginseng (acetoxime) mono(ethylacetamidine acetate) titanium; triethoxyl mono( Ethyl acetonide) zirconium, tri-n-propoxy-mono(acetonitrile) zirconium, tri-i-propoxy-mono(acetonitrile) chromium, tris-n-butoxy-single Acetone) zirconium, tris-sec-butoxy mono(acetonitrile) zirconium, tri-t-butoxy mono(acetonitrile) pin, diethoxy bis(acetonitrile) zirconium, -η-propoxy-bis(acetamidineacetone) oxime, di-i-propoxy-65-200927727

Bis(acetylacetone)zirconium, di-n-butoxy•bis(acetoxime)oxime, di-sec-butoxy•bis(acetamidineacetone)chromium, di-t-butoxy•bis ( Ethyl acetonide, zirconium, monoethoxyl, ginseng (acetonitrile) zirconium, mono-η-propoxy oxy-p-(acetonitrile) zirconium, mono-i-propoxy ginseng (acetylacetone) 鍩, mono-η-butoxy ginseng (acetamidine oxime) oxime, mono-sec-butoxy ginseng (acetonitrile) zirconium, mono-t-butoxy ginseng (acetyl acetonide) zirconium, hafnium (acetonitrile) zirconium, triethoxyl-mono(ethylacetamidine acetate) oxime, tri-n-propoxy-mono(ethylacetamidine acetate) pin, tri-i-propoxy Mono-(ethylacetamidine acetate) pin, tri-n-butoxy-mono(ethylacetamidine acetate) zirconium, tris-s-butoxy-mono(ethylacetamidineacetic acid) Ester)zirconium, tris-t-butoxy mono(ethylacetamidine acetate) zirconium, diethoxy bis(ethylacetamidine acetate) cobalt, di-n-propoxy group (ethylethanoacetate) zirconium, di-i-propoxy bis(ethylacetamidine acetate) zirconium, di-η-butoxy•bis(ethylacetamidine) Ester) bismuth, di-sec-butoxy bis(ethylacetamidine acetate) zirconium, di-t-butoxy bis(ethyl acetamidine acetate) oxime, monoethoxylate参(ethylacetamidine acetate) 鍩, mono-η-propoxy ginseng (ethyl acetoacetate) zirconium, mono-i-propoxy ginseng (ethyl acetamidine acetate) Zirconium, mono-η-butoxy• ginseng (ethyl acetamidine acetate) zirconium, mono-sec-butoxy ginseng (ethyl acetamidine acetate) pin, mono-t-butoxy group Sodium (ethyl acetoacetate) chromium, hydrazine (ethyl acetoacetate) pin, mono (acetonitrile) ginseng (ethyl acetoacetate) zirconium, bis (acetamidine) bis ( Zirconium chelate compound such as ethyl acetoacetate) zirconium, ginseng (acetonitrile) mono(ethylacetamidine acetate) zirconium; ginseng (acetonitrile) aluminum, ginseng (ethyl acetoacetic acid) Ester) Aluminum such as aluminum-66 - 200927727 Chelating compounds and the like. 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 , citric 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. 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, and a titanium chelate compound or an organic acid is more preferred. 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 1 part by weight of the raw material decane compound. The water added during the synthesis of the other polyoxyalkylene is intermittently or continuously added to the decane compound of the starting material or dissolved in a solution of the organic solvent. The catalyst may be previously added to the raw material decane compound or the decane compound may be dissolved in a solution of the organic solvent, or dissolved or dispersed in the added water for use.

The reaction temperature at the time of synthesis of the other polyoxyalkylene is preferably 0 to 100 ° C, more preferably 15 to 80 ° C. The reaction time is preferably from 0.5 to 24 hours, more preferably from 1 to 8 hours. [Content ratio of other polymers] The liquid crystal alignment agent of the present invention contains the above-mentioned cinnamic acid containing polysiloxane and other polymers, and the content of the other polymer is linear with respect to the sensitive radiation. 100 parts by weight of oxygen is preferably 10 parts by weight or less. The preferred content of other polymers will vary depending on the type of other polymer. The liquid crystal alignment agent of the present invention is a polymer containing at least one selected from the group consisting of a radiation-sensitive linear polyorganosiloxane and a group of poly-proline and polyimine. A preferred ratio of use is 100 parts by weight relative to the sensitive radiation linear polyorganosiloxane, and the total amount of polyamic acid and polyimine is preferably 100 to 5,000 parts by weight, more preferably 200 to 2,000 parts by weight. On the other hand, when the liquid crystal alignment agent of the present invention is a linear radiation-containing polyorganosiloxane and other polyoxanes, the preferred ratio of use thereof is different from that of the cinnamic acid of the present invention. 100 parts by weight of oxyalkylene, which is -68-200927727, and the amount of polyoxyalkylene is from 100 to 2,000 parts by weight. When the liquid crystal alignment agent of the present invention contains a radiation-sensitive linear polyorganosiloxane and other polymers, as a kind of other polymer, at least one selected from the group consisting of poly-proline and polyimine. Polymers or other polyoxyalkylenes are preferred. <hardener, hardening catalyst and hardening accelerator>

The above-mentioned hardener and hardening catalyst may be contained in the liquid crystal alignment agent of the present invention for the purpose of making the cross-linking reaction of the sensitive radiation linear polyorgano oxane stronger, and the hardening accelerator may be used to promote hardening of the hardening agent. The liquid crystal alignment agent of the present invention may be contained for the purpose of the reaction. As the curing agent, a curing agent which is generally used in the curing of a curable composition containing a curable compound having an epoxy group or a compound having an epoxy group, and examples thereof, for example, a polyamine, a polycarboxylic acid anhydride, and a polyvalent compound can be used. carboxylic acid. Q The above-mentioned polycarboxylic acid anhydride may, for example, be a water-free substance of cyclohexanetricarboxylic acid or another polyvalent carboxylic acid anhydride. Specific examples of the cyclohexane tricarboxylic anhydride include, for example, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3, 5-anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride, etc., and other polycarboxylic acid anhydrides, for example, 4-methyltetrahydrophthalic anhydride, methyl nadic anhydride , ten'-dienyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, the following formula (5) -69- 200927727

(In the formula (5), r is an integer of from 1 to 20.) The compound represented by the synthesis of polyamine and the tetrahydro acid phthalic anhydride generally used, α-terpinene and allo-leene An alicyclic compound having a conjugated double bond, a Diels Alder reaction product of maleic anhydride, a hydrogen additive or the like. Examples of the curing catalyst include a 6-fluorinated ruthenium compound '6 phosphorus fluoride compound, aluminum ginsengacetone, and the like. These catalysts can be cationically polymerized by heating the catalytic epoxy group. The hardening accelerator may, for example, be an imidazole compound; a 4-grade phosphorus compound; a Q 4 amine compound; such as 1,8-diazabicyclo [5.4.0] undecene-7 or an organic acid salt thereof Azabicycloalkenes; organometallic compounds such as zinc octoate, tin octoate, and aluminum acetylacetone complex; boron compounds such as boron trifluoride or triphenyl borate; such as zinc chloride, chlorine a high melting point dispersion type latent hardening accelerator for a metal halide compound of tin, such as dicyandiamide, an amine addition accelerator of an amine and an epoxy resin; -70- 200927727 A microcapsule-type latent hardening accelerator coated with a polymer; an amine salt-type latent hardener accelerator; a thermal cationic polymerization type latent type such as a Lewis acid salt or a Bronsted acid salt Hardening accelerator, etc. <epoxy compound>

The epoxy compound can be used from the viewpoint of improving the adhesion of the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention to the surface of the substrate. Preferred examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl glycol. Ethyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1 ,3,5,6-tetraglycidyl-2,4-hexanediol, hydrazine, hydrazine, Ν', Ν'-tetrahydromethane glyceryl-m-xylenediamine, 1,3-bis(Ν , Ν-diglycidylaminomethyl)cyclohexane, :^,:1^,:^',:^'-tetraglycidyl-4,4'-diaminodiphenylmethane, hydrazine , hydrazine-diglycidyl-benzylamine, hydrazine, hydrazine-diglycidyl-aminomethylcyclohexane, and the like. The ratio of use of these epoxy compounds is 100 parts by weight, preferably 40 parts by weight or less, based on the total of the polymers (referred to as the total of the radiation-sensitive linear polyorganosiloxane and other polymers). More preferably, it is 0.1 to 30 parts by weight. <Functional decane compound> -71 - 200927727

The above-mentioned functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropylpropane. Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyl dimethyl Oxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxyl Carbonyl-3-aminopropyltriethoxydecane, N-triethoxymethylidenepropyltriethylenetriamine, N-trimethoxymethylidenepropyltriethylenetriamine, 10-trimethyl Oxymethalin-1,4,7-triazadecane, 10-triethoxycarbamido-1,4,7-triazadecane, 9-trimethoxycarbamido-3 ,6-diazaindolyl acetate, 9-triethoxyformamidinyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane , N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxy Silane, N- bis (oxy extending ethyl) -3-aminopropyl trimethoxy Silane, N- bis (oxy extending ethyl) -3-aminopropyl triethoxy silane-like. The ratio of use of the functional decane compound is preferably 4 parts by weight or less based on 100 parts by weight of the total of the polymer. <Interacting Agent> Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a polyoxyalkylene surfactant, and a polyepoxide interface. Active agent, fluorine-containing surfactant, and the like. -72-200927727 When the liquid crystal alignment agent of the present invention contains a surfactant, the content thereof is preferably 1 part by weight or less, 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 contains, as described above, a radiation-sensitive linear polyorganosiloxane as an essential component, and if necessary, other components, preferably 0, in which each component is dissolved in an organic solvent. It is prepared by a solution-like composition. As the organic solvent which can be used for preparing the liquid crystal alignment agent of the present invention, the radiation sensitive linear polyorganosiloxane and any other components used are preferably not preferred. The organic solvent which can be preferably 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 a radiation-sensitive linear polyorganosiloxane and at least one polymer selected from the group consisting of polyphthalic acid and polyimine, it is preferably a preferred organic solvent. The solvent exemplified as the synthesis reaction used for polylysine is listed. Among them, a weak solvent which can be used as a synthetic solvent for the synthesis reaction of polylysine can also be appropriately selected. As a particularly preferable organic solvent which can be used at this time, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butylide, N,N-dimethylformamide, hydrazine, Ν-dimethylacetamide, 4-hydroxy-4.methyl-2-pentanone, ethylene glycol 'monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, B Ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-η-propyl ether, ethylene glycol small propyl ether, ethylene glycol-η-butyl ether Butyl-73- 200927727 Cellulite), ethylene glycol dimethyl ether, ethylene glycol ethyl ether glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diethylene glycol Ethyl ether, diethylene glycol monomethyl ether acetate · monoethyl ether acetate, isoamyl propionate, isoamyl iso-pentyl ether, and the like. These may be used alone or in combination. On the other hand, the liquid crystal alignment agent of the present invention contains only polyorganosiloxane as a polymer, or contains a sensitizing siloxane and other polyoxyalkylene. Preferred organic solvents such as 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propane, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene dipropylene glycol ethyl ether, dipropylene glycol propyl ether , dipropylene diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol glycol monobutyl ether (butyl cellosolve), ethylene glycol monopentyl ether, diethylene glycol, A Cellosolve acetate, acid ester, propyl cellosolve acetate, butyl fluorene fiber acetate sterol, ethyl carbitol, propyl carbitol, butyl carbitol, acetic acid i- Propyl ester, n-butyl acetate, i-butyl acetate, ., n-pentyl acetate, sec-pentyl acetate, 3-methoxymethyl acetate, 2-ethylbutyl acetate, acetic acid 2- Ethylhexyl, η-hexyl acetate, cyclohexyl acetate, octyl acetate, ethyl isoamyl ester, and the like. Preferred among these are η-propyl acetate, η-butyl acetate, i-butyl acetate, sec-butyl acetate, sec-amyl acetate, and the like. The solid concentration of the liquid crystal alignment agent of the present invention (liquid acetate, diethanol monomethyl ether, ester, diethylene glycol butyrate, diiso or higher. Sensitive radiation linear linear polyorganoquinone, can be listed Examples of diol monopropyl ether glycol methyl ether, alcohol dimethyl ether, monopropyl ether, ethyl ether, ethylene glycol ethyl cellosolve ethyl ester, methyl carbamide, acetic acid η-propyl acetate Sec-butyl butyl acrylate, acetate, amyl benzyl acetate, i-propyl acetate, η-amyl acetate, acetic acid crystal alignment agent -74- 200927727

The ratio of the total weight of the components other than the solvent to the total weight of the liquid crystal alignment agent is selected in consideration of viscosity, volatility, etc., and a preferable solid content concentration is in the range of 1 to 10% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film of the liquid crystal alignment film. However, when the solid content concentration is less than 1% by weight, it is difficult to obtain an excellent film thickness of the coating film. In the liquid crystal alignment film, when the solid content is more than 10% by weight, if the film thickness of the coating film is too large, it is difficult to obtain an excellent liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent is increased to deteriorate coating properties. 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 12 to 5 OmPa·s; and the solid content concentration is 1 to 5 wt% by the inkjet method. The range is such that 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 0 ° C to 2 0 ° C, more preferably 20 ° C to 60 ° 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 by coating the liquid crystal alignment film of the present invention on a substrate, and then applying a liquid crystal alignment energy to the coating film by a photo-alignment method. -75-200927727 First, the liquid crystal alignment agent of the present invention is applied to the transparent conductive film side of the substrate on which the pattern-shaped transparent conductive film is provided, for example, by a roll coating method, a spin method, a printing method, or an ink jet method. Coating by a suitable coating method such as the method, for example, is carried out by heating at a temperature of 40 to 250 ° C for 0.1 to 120 minutes to form a coating film. The film thickness of the coating film is preferably 0.001 to Ιμπι, 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, soda lime glass, such as polyethylene terephthalate, polybutylene terephthalate, polyether maple, polycarbonate, poly ( An alicyclic olefin) a transparent substrate made of plastic or the like. As the transparent conductive film, a NESA film made of Sn02, an ITO film made of In2〇3-Sn02, or the like can be used. The patterning of these transparent conductive films can be performed by a photo-etching method or a method of using a mask when forming a transparent conductive film. Then, the coating film may be irradiated with linearly polarized or partially polarized ❹ radiation or non-polarized radiation, and if necessary, further 150 to 250. (The temperature of the film is preferably heat-treated for 1 to 120 minutes to impart a liquid crystal alignment energy to the liquid crystal alignment film. In the case of radiation, for example, ultraviolet light and visible light having a wavelength of 150 to 800 nm can be used, and 300% is contained. Ultraviolet light having a wavelength of about 40 nm is preferable, and ultraviolet light having a wavelength of 3 〇 0 nm or more and less than 365 nm is preferable. The liquid crystal alignment agent of the present invention does not have a wavelength of 365 nm or longer. The light in the wavelength region causes photoreaction. Therefore, the liquid crystal panel can be manufactured without any disadvantage in the step, and the light of the backlight in the use of the liquid crystal panel also has the advantage of stability during the period from -76 to 200927727. When the radiation is linearly polarized or partially polarized, the irradiation may be performed in a direction perpendicular to the surface of the substrate, or may be performed in order to impart a pretilt angle from the oblique direction. Further, when the radiation is not polarized, the irradiation is performed. The direction must be the direction of the bevel.

The irradiation amount of the radiation is preferably U/m2 or more and less than 10,000 J/m2, more preferably i〇~3, OOOJ/m2. Further, when the coating film formed of the liquid crystal alignment agent is known to impart liquid crystal alignment energy by a photo-alignment method, it is required to have a radiation exposure amount of 10,000 J/m 2 or more, but the liquid crystal alignment agent of the present invention is used. In the case of the alignment method, the radiation exposure amount is less than 3,000 J/m 2 or less, more preferably 〇〇〇J/m 2 or less, and particularly 800 J/m 2 or less, and excellent liquid crystal alignment property can be imparted to contribute to the liquid crystal display element. The cost of manufacturing is reduced. <Manufacturing Method of Liquid Crystal Display Element> 液晶 A liquid crystal display element formed using the liquid crystal alignment agent of the present invention can be produced, for example, by the following method. Prepare one pair (two pieces) of the substrate on which the liquid crystal alignment film is formed by the above-described method, and the liquid crystal alignment film which is provided thereon is opposed to the polarized light of the linearly polarized light emitted at a predetermined angle, and the substrate The peripheral portion is sealed with a sealant, injected and filled with liquid crystal, and the liquid crystal is injected into the mouth to form 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 room temperature to remove the flow alignment at the time of injection. -77-200927727 Then, the polarizing plate can be bonded to the liquid crystal display element by bonding the polarizing plate in a direction in which the polarizing plate is aligned with the alignment of the liquid crystal alignment film which becomes a substrate. When the liquid crystal alignment film is horizontally aligned, the substrate "on the two substrates in which the liquid crystal alignment film is formed" can be obtained 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 element of type or STN type liquid crystal cell. On the other hand, when the liquid crystal alignment film has a vertical alignment property, the two substrates on which the liquid crystal alignment film is formed are formed in parallel in the direction in which the alignment is easy to form, and the polarizing plate is easily aligned in the polarizing direction and alignment. When the shaft 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, a nematic liquid crystal, a smectic liquid crystal, or the like can be used. When it is a TN type liquid crystal cell or an STN type liquid crystal cell, it is preferable to have a positive dielectric anisotropy for forming a nematic liquid crystal, for example. Use biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, ditriphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cuba Liquid crystal, etc. Further, in the liquid crystal, a cholesteric liquid crystal such as cholesterol chloride, cholesteryl phthalate or cholesteryl carbonate may be further added; a chiral molecular agent sold under the trade names of C-15 and CB-15 (manufactured by MELC) (Chiral agent); a strong dielectric liquid crystal such as p-decyloxybenzylidene-P-amino-2-methylbutyl cinnamate or the like is used later. -78- 200927727 On the other hand, in the case of 'vertical alignment type liquid crystal cell, it is preferable to have negative dielectric anisotropy of crystal, for example, 'crystal, azine-based liquid crystal, Schiff base type liquid crystal, oxidized couple- · Biphenyl liquid crystal, phenylcyclohexane liquid crystal, etc. The polarizing plate used for the outer side of the liquid crystal cell is a polarizing plate or a η film-based polarizing plate which is oriented to extend a polyvinyl alcohol-based polarizing film called a "ruthenium film". Therefore, the liquid crystal display element of the present invention produced is excellent in performance such as long-term reliability. [Embodiment] Hereinafter, the present invention is not limited to the examples described above by way of examples. 〇 In the following examples, the weight average molecular weight is a polystyrene column measured by gel permeation chromatography: Tosoh Co., TSKgelGRCXLII Solvent: Tetrahydrofuran Temperature: 40 ° C Pressure: 68 kgf / Cm2 • Epoxy equivalent, measured according to JIS C2105 “Hydrochloric acid one”. In the following synthesis examples, if necessary, the formation of a nematic liquid dicyanobenzene-based liquid nitrogen-based liquid crystal, and a polarized light-based display characteristic in which an iodine is absorbed by an acetic acid fiber, is repeated. The invention is based on the following conditions. The synthesis was carried out by the methyl ethyl ketone method, and the necessary amount of the product used in the synthesis examples and the examples after the protection was confirmed from -79 to 200927727. <Synthesis of polyorganosiloxane having epoxy group> Synthesis Example 1 2-(3,4-epoxycyclohexyl) was charged in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux tube equipped with a cooling tube. Ethyltrimethoxy chopping lOO.Og, methyl isobutyl ketone 500g, and triethylamine i〇.〇g, mixed at room temperature, 'then', after dropping 100g of deionized water through the dropping funnel for 30 minutes, Continuous mixing under reflux was carried out at 80 ° C for 6 hours. After the reaction was completed, the 'extracted organic layer' was washed with a 0.2% by weight aqueous solution of ammonium nitrate until the washed water became neutral. The polyorganooxy oxane EPS-1 having an epoxy group is obtained by removing the solvent and water by evaporation under reduced pressure to obtain a viscous transparent liquid. The results of 1H-NMR analysis of this polyorganooxynonane EPS-1 confirmed that an epoxy group-based peak having a theoretical strength 〇 was obtained in the vicinity of the chemical shift (δ) = 3.2 ppm, and no epoxy group was caused in the reaction. Side reaction. The viscosity, Mw and epoxy equivalent of this polyorganoboxane EPS-1 are shown in Table 1. Synthesis Examples 2 and 3 In the same manner as in Synthesis Example 1, except that the materials for the mounting were used, the polyorganosiloxanes EPS-2 and 3 having an epoxy group were each obtained in a viscous transparent liquid. The Mw and epoxy equivalents of these polyorganosiloxanes are shown in Table 1. -80-200927727 Synthesis Example 4' In a reaction vessel equipped with a stirrer and a thermometer, 150 g of isopropanol, 5.4 g of a 10% by weight aqueous solution of tetramethylammonium hydroxide (containing tetramethylammonium hydroxide 5.93 mmol) After 270 mmol of water and 12 g of water, 42.5 g (180 mmol) of γ-glycidoxypropyltrimethoxy sand pot was slowly added, and the mixture was further stirred at room temperature for 20 hours to carry out a reaction. After the completion of the reaction, 200 g of toluene was added to the reaction mixture, and isopropanol was removed under reduced pressure. The residue was washed with distilled water using a separating funnel, and washed with distilled water until the aqueous layer of the separating funnel was After the neutralization, the organic layer was taken out, and dried over anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure to obtain a polyorganooxane EPS-4 having an epoxy group. The weight average molecular weight Mw and epoxy equivalent of this polyorganoboxane EPS-4 are shown in Table 1. Further, the abbreviations of the raw material decane compounds in Table 1 are each represented by the following Q. ECETS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane MTMS: methyltrimethoxydecane PTMS: phenyltrimethoxydecane GPTMS: 3_glycidoxypropyltrimethoxy Decane-81 200927727 Table 1 Polyorganosiloxane with epoxy group name Raw material decane compound (g) Mw Epoxy equivalent (g/mole) ECETS MTMS PTMS GPTMS Synthesis Example 1 EPS-1 100 0 0 0 2,200 186 Synthesis Example 2 EPS-2 80 20 0 0 2,500 210 Synthesis Example 3 EPS-3 80 0 20 0 2,000 228 Synthesis Example 4 EPS-4 0 0 0 42.5 3,000 183 <Synthesis of cinnamic acid derivative (1) > Synthesis of the compound represented by the above formula (2-1)] Synthesis Example 2-1 (1) According to the following scheme

CH=CH-COOH acetic acid

Ο 0"21/==\

T N—^ CH=CH-COOH Ο (2-1-1-1), the compound (2 -1 -1 -1 ) was synthesized. In a 200 mL Japanese eggplant type flask equipped with a reflux tube, 12 g of mercapto succinic anhydride, 8.2 g of 4-aminocinnamic acid and 100 mL of acetic acid were charged, and the reaction was carried out under reflux for 2 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate, and the organic layer was washed with water, dried over magnesium sulfate, and then purified, and then purified, and then re-suppleed with a mixed solvent of ethanol and tetrahydrofuran -82-200927727 The white crystal (purity: 98.0%) of the compound (2 -1 -1 -1 ) of 1 〇g was obtained, and the compound obtained here, hereinafter referred to as "compound (2-1-1-1 (1))" ° Synthesis Example 2-1 ( 2 ) Follow the procedure below

H2n

CH=CH-COOH N(Et)3 Ο L N—^ ^-CH=CH-COOH 〇 (2-1-1-1>

The compound (2-1-1-1) was synthesized by another method different from the above Synthesis Example 2-1 (1). In a Japanese eggplant type flask equipped with a reflux tube, a nitrogen introduction tube, and a Dean-Stark tube, 72 g of mercapto succinic anhydride, 49 g of 4-aminocinnamic acid, 70 mL of triethylamine, 500 mL of toluene, and 200 mL of tetrahydrofuran were charged. The reaction was carried out under reflux for 36 hours. After the completion of the reaction, the reaction mixture was washed successively with dilute hydrochloric acid and water, and then the organic layer was dried over magnesium sulfate, concentrated, and recrystallized from a solvent mixture of ethanol and tetrahydrofuran to give 72 g of compound. White crystal of (2-1-1-1) (purity: 99%), the compound obtained here, hereinafter referred to as "compound (2-1-83-200927727 1-1 (2)) Synthesis Example 2-1 (3) follow the process below

Pd(PPh3)4 CH2=CH-COOH

Ci〇H2i

Ο CH=CH-COOH 0 (2-1-1-1), Compound (2 -1 -1 -1 ) was synthesized by the above Synthesis Example 2-1 (1) and 2-. (Synthesis of Compound (2-1-1-1 A)) The reaction was carried out by dissolving 24 mL of Japanese succinic anhydride (24 g), 22 g of 4-iodoaniline and B g in a reflux tube. After the completion of the reaction, the reaction of 1 (2) was carried out in a different type of flask, and only 200 mL of the sulfhydryl group was charged. The mixture was extracted with ethyl acetate for 5 hours, and the organic layer was washed with water and dried over magnesium sulfate. Thereafter, concentration and drying were carried out by recrystallization from ethanol to obtain 3 3 g of a compound (2-1 -1 -1 A ). (Synthesis of Compound (2 -1 -1 -1 ))

Into a three-necked flask equipped with a nitrogen introduction tube and a thermometer, 1 to 4 g of the obtained compound (2-1-1-1A) and 1.38 g of ruthenium triphenylphosphine palladium were placed, and the inside of the flask was replaced with nitrogen. 4.8 mL of dried and deaerated acrylic acid, 25 mL of triethylamine, and 600 mL of N,N-dimethylformamide were added by a syringe, and the mixture was stirred at 90 ° C for 3 hours to carry out a reaction. After the completion of the reaction, the reaction mixture was poured into a dilute aqueous hydrochloric acid solution which was ice-cooled with ice, and then ethyl acetate was added to conduct liquid separation. The organic layer was washed successively with dilute hydrochloric acid, aqueous sodium thiosulfate and water, and then sulfuric acid was used. The magnesium was dried, purified by a ruthenium dioxide column, and recrystallized by using a mixed solvent of ethanol and tetrahydrofuran to obtain 4.2 g of a white crystal of the compound (2-1-1-1) (purity of 9 8.0 %). The compound obtained here is hereinafter referred to as "compound (2-1-1-1 (3))". Synthesis Example 2-1 (4) In the same manner as in Synthesis Example 2-1 (1), except that 18 g of octadecyl succinic anhydride was used in place of the substituted decyl succinic anhydride in the above Synthesis Example 2-1 (1) Implemented to obtain 1 2g of the following formula

CH=CH——COOH (2-1-1-2) -85- 200927727 The white crystal of the compound (2- 1 -1 -2 ) (purity: 98.5 %). [Synthesis of the compound represented by the above formula (2-2)] Synthesis Example 2-2 (1) According to the following scheme

(2-2-1-1A) SOCI2

C2F5C3H6-〇H

ο UC^nhO^' 0 δ-2-Ι-ΙΒ)

Pd(Ph3)4 CH2=CH-COOH

O 〇 2 "5〇3Η6-

I T N —^ CH=CH-COOH O ¢-2-1-1) , the compound (2-2-1-1) was synthesized. -86-200927727 (Synthesis of Compound (2-2-l-lA)) 'In a 500 mL Japanese eggplant type flask equipped with a reflux tube, cyclohexyl-1,2,4-tricarboxylic anhydride 30 g was charged. Further, 33 g of 4-iodoaniline and 200 mL of acetic acid were reacted under reflux for 2 hours. After completion of the reaction, ethyl acetate was added to the reaction mixture, and the organic layer was washed with water, dried over magnesium sulfate, and concentrated, and then recrystallized from ethanol to obtain 31 g of ash Q of compound (2-2-1-1A). Color crystal. (Synthesis of the compound (2-2-1-1B)) The above-obtained compound (2 -2 -1 -1 A ) was placed in a 100 mL Japanese eggplant type flask equipped with a reflux tube and a nitrogen introduction tube. 5 g, 20 mL of sulfinium chloride and 0.1 mL of N,N-dimethylformamide were reacted at 80 ° C for 1 hour. After the completion of the reaction, the thionyl chloride was removed under reduced pressure, and dichloromethane was added to the residue, and the organic layer was washed with water and saturated aqueous sodium hydrogen carbonate. After removing the dichloromethane under reduced pressure, 80 mL of tetrahydrofuran was added. In addition, the above-mentioned three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen introduction tube was charged with 4,4,5,5,5-pentafluoropentanol 6.88, pyridine 6.5 mL, and tetrahydrofuran 20 mL. It was ice-cooled, and a tetrahydrofuran solution containing the reaction product of the above compound (2-2-1-1A) and thionyl chloride was dropped, and the mixture was stirred under ice cooling for 3 hours to carry out a reaction. After the completion of the reaction, the reaction mixture was washed successively with ethyl acetate, dilute hydrochloric acid and water, and the organic layer was dried over magnesium sulfate, and concentrated, and then recrystallized from ethanol to give compound (1 4 g - 87 - 200927727) Gray crystal of 2-2-1-1B) (synthesis of compound (2 -2 -1 -1 )) In the 500 mL three-necked flask equipped with a nitrogen introduction tube and a thermometer, the compound obtained above was loaded (2- 2-1-1B) 14g, 1.8mL of acrylic acid, llmL of triethylamine, 肆triphenylphosphine palladium ruthenium.46g and N,N-dimethylformamide 2 50 m L, after degassing, to 9 The reaction was carried out for 3 hours at 0 °C. After the completion of the reaction, ethyl acetate was added to the reaction mixture, and the mixture was washed successively with dilute hydrochloric acid and water. The organic layer was purified and purified with ruthenium dioxide column, and concentrated by methanol to give a purity of 98%. 9.0 g of the white crystal of the compound (2-2-1-1). Synthesis Example 2-2 ( 2 ) According to the following procedure

-88 - 200927727

, the compound (2-2-1-2) was synthesized. (Synthesis of Compound (2-2-1-2A)) In a 200 mL Japanese eggplant type flask equipped with a reflux tube, cyclohexane-1,2,4-tricarboxylic anhydride 12 §, thionyl chloride was charged. 3〇1111^ and ]^,>}-dimethylformamide 0.1 mL, and the reaction was carried out by refluxing at 80 ° C for 1 hour. After the completion of the reaction, the thionyl chloride was removed under reduced pressure, and dichloromethane was added to the residue. The organic layer was washed sequentially with saturated aqueous sodium hydrogen carbonate and water, dried over magnesium sulfate, concentrated and dried. Thereafter, tetrahydrofuran was added to make a solution. On the other hand, in a three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen introduction tube, 19 g of β-cholestyl alcohol, pyridine s.OmL, and toluene l〇〇mL were placed, and cooled in an ice bath. The tetrahydrofuran solution containing the above-mentioned reaction product of cyclohexane-1,2,4-tricarboxylic anhydride and thionyl chloride was slowly dropped, and the mixture was further stirred at room temperature for 4 hours to carry out a reaction. After the completion of the reaction, the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, and then recrystallized from ethyl acetate and hexane to give 18 g of compound (2-2-1- 2A). (Synthesis of Compound (2-2-1-2)) -89-200927727 In a 200 mL Japanese front flask equipped with a Dean-Stark tube, the compound (2-2-1-2A) obtained above was charged. 3.3 g of lg, 4-aminocinnamic acid, 0.1 mL of triethylamine and 100 mL of toluene were reacted under reflux for 3 hours. After completion of the reaction, the reaction mixture was washed with water, and the organic layer was dried over magnesium sulfate, and then recrystallized from ethyl acetate and tetrahydrofuran to give 6.1 g of compound (2 - 2 -1 - 2) White crystals (purity 9 9 · 2 %). 〇 [Synthesis of the compound represented by the above formula (3-2)] Synthesis Example 3-2 (1) According to the following scheme

CH=CH—COOH

〇2ν_Ό~ I K2c〇3 I cf3c3h6-i 〇2N_〇~ CH=CH—丨 CH=CH_COOC3H6CF3 (3-2-1-1A)

〇

Ch=ch-cooc3h6cf3 P-2-1-1B)

Ch=ch-cooc3h6cf3 P-2-1-1) -90- 200927727 , Synthesis of compound (3-2-1-1). '(Synthesis of Compound (3-2-1-1A)) · In a 300 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube, 4-nitrocinnamic acid 9.7 §, 4, 4, 4-3 Fluor-1-iodobutane 12 §, 14 g of potassium carbonate and 150 mL of 1-methyl-2-pyrrolidone were stirred at 50 ° C for 1 hour to carry out a reaction. After the completion of the reaction, ethyl acetate was added to the reaction mixture to extract, and the extract was washed with water, dried over magnesium sulfate, and concentrated to dryness to give compound (3 - 2 -1 -1 A ) . (Synthesis of the compound (3-2-1-1B)) In a three-necked flask equipped with a thermometer and a nitrogen introduction tube, the above-obtained compound (3-2-1-1A) 14 g, tin chloride was placed. 53 g of 2 hydrate and 150 mL of ethanol were stirred at 70 ° C for 1 hour to carry out a reaction. After the completion of the reaction, the reaction mixture was poured into ice water, neutralized with a 2M aqueous sodium hydroxide solution, ethyl acetate was added to remove the precipitate, ethyl acetate was added to the filtrate for extraction, and the extract was washed with magnesium sulfate. Drying, by concentration and drying, gave 12 g of the compound (3 - 2 -1 -1 B ). (Synthesis of the compound (3-2-1-1)) In a 200 mL Japanese eggplant type flask equipped with a reflux tube and a nitrogen introduction tube, 12 g of the compound (3-2-1-1B) obtained above was charged. 8.7 g of 1,2,4-cyclohexanetricarboxylic anhydride and 100 mL of acetic acid were reacted under reflux for 1 hour. After the completion of the reaction, the reaction mixture was extracted with ethyl acetate, and washed with water--91-200927727. The extract was dried over magnesium sulfate, concentrated, and dried, using a solvent mixture of ethyl acetate and hexane. Crystallization gave white crystals (purity: 98.3%) of 1 g of the compound (3-2-1-1). <Synthesis of Other Polymer> [Synthesis of Polyamide] Synthesis Example PA-1 〇 will be used as tetracarboxylic dianhydride, pyromellitic dianhydride 109 g (0.50 molar equivalent) and 1,2,3 , 4-cyclobutane tetracarboxylic dianhydride 98 g (0.50 molar equivalent) and 200 g (1.0 molar equivalent) of 4,4-diaminodiphenyl ether as diamine are dissolved in N-methyl-2 - 2,290 g of pyrrolidone, after reacting at 40 ° C for 3 hours, by adding N-methyl-2-pyrrolidone 1, 350 g, to obtain a solution containing 10% by weight of poly-proline (PA-1), about 4,000 g The solution viscosity of the polyamic acid solution was 210 mPa·s. Q Synthesis Example PA-2 will be used as tetracarboxylic dianhydride 1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 § (0.50 mole equivalent) and pyromellitic dianhydride i〇9g (0.50) Mole equivalent) and 198 g (1.0 molar equivalent) of 4,4'-diaminodiphenylmethane as diamine, dissolved in N-methyl-2-pyrrolidone 2,290 g, reacted with 4 (TC 3 After an hour, by adding N-methyl-2-pyrrolidone 1,350g, a solution of about 4,000 of a solution containing 1% by weight of poly-proline (PA-2) is obtained. The viscosity is 135 mPa·s. -92- 200927727 Synthesis Example PA-3 will be used as tetracarboxylic dianhydride 1,2,3,4-cyclobutanetetracarboxylic dianhydride 196§ • (1.0 mole equivalent) and as Diamine 4,4'-diaminodiphenyl ether 200g, (1.0 mole equivalent), dissolved in N-methyl-2-pyrrolidone 2,246g' after reacting at 40 ° C for 4 hours, by 1 and 321 g of N-methyl-2-pyrrolidone were added to obtain a solution containing 10% by weight of poly-proline (PA-3), which was about 3,950 g, and the solution viscosity of the polyaminic acid solution was 220 mPa·s. PA-4 will be used as tetracarboxylic dianhydride 1,2,3,4-cyclobutane tetracarboxylic dianhydride 196§ (1.0 Mo Equivalent) and 212 g (1.0 molar equivalent) of 2,2'-dimethyl-4,4'-diaminobiphenyl as a diamine, dissolved in N-methyl-2-pyrrolidone 4,0 50 g, By reacting at 40 ° C for 3 hours, 3,700 g of a solution containing 10% by weight of polyglycolic acid (PA-4) having a solution viscosity of 170 mPa-s was obtained.

G Synthesis Example PA-5 224 g (1.0 mol equivalent) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 4,4'-diaminodiphenyl as diamine 200 g (1.0 molar equivalent) of the ether, dissolved in 2,404 g of N-methyl-2-pyrrolidone, and reacted at 40 ° C for 4 hours to obtain 15% by weight of polyglycolic acid (PA-5) The solution was about 2,800 g. The polyamic acid solution was taken out in small portions, and N-methyl-2-pyrrolidone was added to prepare a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was -93-200927727 1 90 mPa·s. • [Synthesis of Polyimine] Synthesis Example PI-1 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 112 g (0.50 mol) and hexahydro-8-methyl -5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3-dione 157g (〇0.50 mol) and as a diamine P-phenylenediamine 95g (0.88 mol), 2,2-di-trifluoromethyl-4,4-diaminobiphenyl 32g (0.10 mol), 3,6-double (4 -Aminobenzhydryloxy)cholestane 6.4 g (0.010 mol) and octadecyloxy-2,5-aminobenzene 4.0 g (0.015 mol)' dissolved in N-methyl-2 - 960 g of pyrroleone, reacted at 60 ° C for 9 hours, a small amount of the obtained polyaminic acid solution, and N-methyl-2-pyrrolidone was added to prepare a solution having a polymer concentration of 10% by weight. The measured solution viscosity was 5 8 mPa _ s in the obtained polyaminic acid solution, and 2,740 g of N-methyl-2-pyrrolidone, 396 g of pyridine and 409 g of acetic anhydride were added, and dehydration was carried out at ll ° C for 4 hours. After the ring closure reaction, the dehydration ring closure reaction, by solvent replacement of the solvent in the system with new N-methyl-2-pyrrolidone (by Operation, removing the pyridine and acetic anhydride used in the dehydration ring-closure reaction to the outside of the system, the same as the following) 'To obtain a solution containing 15% by weight of polyfluorene imine (PI-1) having a ruthenium iodide ratio of about 95%. About 2,500g. A small amount of the polyimine solution was taken, and the solvent was removed under reduced pressure, and then dissolved in γ-butyrolactone to prepare a solution having a polymer concentration of 8.0% by weight, and the measured viscosity of the solution of -94-200927727 was 33 mPa·s. Example PI - 2

2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 112g (〇.5〇莫耳) and 1,3,3&,4,5,915-hexahydro-8-methyl -5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[l,2-c]furan-i,3-dione] 57 g (0.50 mol), as a diamine -phenylenediamine 96g (0.89 moles), bisaminopropyltetramethyldioxane 25g (0.10 moles) and 3,6-bis(4-aminobenzylideneoxy)cholestane 13 g (〇.020 mol) and 8.1 g (0.030 mol.) of N-octadecylamine as a monoamine, dissolved in N-methyl-2-pyrrolidone 960 g, at 60 ° C After reacting for 6 hours, a small amount of the obtained polyaminic acid solution was taken out, and N-methyl-2-pyrrolidone was added to prepare a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 60 mPa*s. 2,700 g of N-methyl-2-pyrrolidinone was added to the obtained polyamic acid solution, and 396 g of pyridine and 409 g of acetic anhydride were added to carry out a dehydration ring-closure reaction at 110 ° C for 4 hours, and after dehydration ring closure reaction, The solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain a 15% by weight hydrazine imidization. A solution of about 95% polyethylenimine (PI-2) is about 2,400 g. A small amount of the polyiminoimine solution was taken out, and N-methyl-2-pyrrolidone was added to prepare a solution having a polymer concentration of 6.0% by weight. The viscosity of the solution was measured to be 18 mPa·s s 〇-95-200927727. Example PI-3 will be used as tetracarboxylic dianhydride 2,3,5-tricarboxycyclopentyl acetic acid dianhydride • 224 g (1.0 mol) and p_phenylene diamine as diamine 10 7 g (0.99 mol) And 3,6-bis(4-aminobenzylideneoxy)cholestane 6.43 g (0.010 mole), dissolved in N-methyl-2-pyrrolidone 3,039 g, by 60 ° C After reacting for 6 hours, a solution containing 1% by weight of poly-proline was obtained, and the solution viscosity of the poly-proline was 260 mPa·s. 0 Next, 2,700 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 396 g of pyridine and 306 g of acetic anhydride were added to carry out a dehydration ring-closure reaction at ll ° C for 4 hours, and after dehydration ring closure reaction, The solvent in the system was subjected to solvent replacement with a new N-methyl-2-pyrrolidone to obtain a solution containing 9.0% by weight of polyimine (PI-3) having a ruthenium iodide ratio of about 89%. The polyimine solution was taken out in a small amount of about 3,5 00 g °, and N-methyl-2-pyrrolidone was added to prepare a solution having a polymer concentration of 5.0% by weight, and the measured solution viscosity ❹ was 7 4 mPa·s. Synthesis Example PI-4 4,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 112 g (0.50 mol) and 1,3,3a,4,5,9b-hexahydro- 8-methyl-5(tetrahydro-2,5-dioxo-3-furyl)-naphtho[l,2-c]-furan-l,3-dione 157g (0.50 mol) and as P-phenylenediamine of diamine 89g (〇.82 mole), 2,2'-di-trifluoromethyl-4,4'-diaminobiphenyl 32g (0.10 mole), 1-( 3,5-Diaminobenzylideneoxy)-4-(4-trifluoromethylbenzyloxy)--96- 200927727 Cyclohexane 258 (0-059 mol) and octadecyloxy- 2,5-diaminobenzene 4.0 g (〇.〇mol Mo), dissolved in N-methyl-2-pyrrolidone 2,175 g' by reacting at 60 ° C for 6 hours to obtain a polydecylamine Acid solution. A small amount of the obtained polyamic acid solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a polymer concentration of 10% by weight. The viscosity of the solution measured was 1 10 mPa · s.

3,000 g of N-methyl-2-pyrrolidone was added to 1,5 μg of the obtained polyamidonic acid solution, and 221 g of pyridine and 228 g of acetic anhydride were added to carry out a dehydration ring-closure reaction at 1 1 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new N-methyl-2-pyrrolidone to obtain a polyamidene (PI containing 10% by weight of a ruthenium iodide ratio of about 92%). The solution of -4) is about 4,000 g. The polyimine solution was taken out in small portions, and N-methyl-2-pyrrolidone was added to prepare a solution having a polymer concentration of 4.5% by weight, and the measured solution viscosity was 28 mPa·s.

Synthesis Example PI-5 5,3,5-tricarboxycyclopentylacetic acid dianhydride bjgCo.ow mole as tetracarboxylic dianhydride and 6.8 g (p-phenylene diamine) as diamine 63 mol), 4,4'-diaminodiphenylmethane 3.6 g (〇.〇18 mol) and the compound represented by the above formula (D-10) 4.7 g (〇.〇〇9 mol) 'Dissolved in 140 g of N-methyl-2-pyrrolidone, and the obtained polyamine acid solution was taken out by a small amount of 6 (TC for 4 hours), and N-methyl-2-pyrrolidone was added to prepare a polymerization. A solution having a concentration of 1% by weight, the measured solution -97-200927727 has a viscosity of 1 15 mPa · s. Next, 325 g of N-methyl-2-pyrrolidone is added to the obtained polyamic acid solution, and pyridine is added. 14g and 18g of acetic anhydride were subjected to a dehydration ring-closure reaction at U〇°C for 4 hours, and after dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone to obtain 15.4% by weight. A solution of polyamidolimine (PI-5) having a ruthenium iodide ratio of about 77% is about 220 g. A small amount of the polyimine solution is taken out, and N-methyl-2-pyrrolidone is added to prepare a polymer concentration of 10% by weight. of The measured solution viscosity was 8 4 mPa · s. Synthesis Example PI-6 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 20.9 g (0.093 mol) and as two 9.2 g (0.085 mol) of the amine p-phenylenediamine and 4.9 g (〇0.009 mol) of the compound represented by the above formula (D-10), dissolved in N-methyl-2-pyrrolidone I40 g, The reaction was carried out at 60 ° C for 4 hours to obtain a solution containing poly-proline. The obtained poly-proline solution was taken in small portions, and N-methyl-2-pyrrolidone was added to prepare a polymer concentration of 1 〇. The % by weight solution was measured for the viscosity of the solution to be 126 mPa·s. Next, 325 g of N-methyl-2-diazolone was added to the obtained polyamidonic acid solution, and 7.4 g of lanthanum and acetic anhydride were added. 9.5g is subjected to a 4 hour dehydration ring closure at ii〇°c, and after dehydration ring closure reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone to obtain a content containing ι6 1 weight -98- 200927727 A solution of about 5% iminelamine (PI-6) with an imidization rate of about 54%. A small amount of this polyimine solution is taken and N-methyl-2-pyridyl is added. The alkanone is made into a solution having a polymer concentration of 1% by weight, and the measured solution viscosity is 75 mPa·s. The synthesis example PI-7 0 will be used as the tetracarboxylic dianhydride 2,3,5-tricarboxycyclopentyl acetic acid. 18.8 g (0.084 mol) of dianhydride and 7.4 g (0.068 mol) of p-phenylenediamine as a diamine and 8.9 g (0.017 mol) of the compound represented by the above formula (D-10), dissolved in N 140 g of methyl-2-pyrrolidone was reacted at 60 ° C for 4 hours to obtain a solution containing polylysine. The obtained polyamic acid solution was taken out in small portions, and N-methyl-2-pyrrolidone was added to prepare a solution having a polymer concentration of 10% by weight, and the viscosity of the solution was measured to be 1 2 6 mP a · s. Then, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 6.6 g of pyridine and 8.5 g of acetic anhydride were added thereto, and dehydration ring closure was carried out at 10 ° C for 4 hours, followed by dehydration ring closure reaction. The solvent in the system was subjected to solvent replacement with a new N-methyl-2-pyrrolidone to obtain a solution containing 15.9% by weight of a polyamidimide (PI-7) having a ruthenium iodide ratio of about 55%. 0g ° • Take a small amount of this polyimine solution and add N-methyl-2-pyrrolidone to make a polymer concentration of 1% by weight. The measured solution viscosity is 7 5 mP a · s ° 99- 200927727 Synthesis Example PI-8

19.1 g (0.085 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 7.4 g (0.069 mol) of p-phenylenediamine as diamine and the above formula 8.5 g (0.017 mol) of the compound represented by (D-8), dissolved in 140 g of N-methyl-2-pyrrolidone, and reacted at 6 ° C for 4 hours to obtain a polyglycine-containing compound. Solution. The obtained polyamic acid solution was taken out in small portions, and N-methyl-2-pyrrolidone was added to prepare a solution having a polymer concentration of 10% by weight, and the viscosity of the solution was measured to be 206 mPa·s. Then, the obtained poly group was obtained. 325 g of N-methyl-2-pyrrolidone was added to the proline solution, and 6.7 g of pyridine and 8.7 g of acetic anhydride were added to carry out a dehydration ring-closure reaction at 110 ° C for 4 hours after the dehydration ring-closure reaction, by using a solvent in the system. The N-methyl-2-pyrrolidone was subjected to solvent displacement to obtain about 200 g of a solution containing 15.8% by weight of a polyamidimide (p I - 8 ) having a ruthenium iodide ratio of about 52 %. A small amount of the solution of the polyamidimide solution 'addition of N-methyl-2-pyrrolidone to a polymer concentration of 10% by weight solution' measured by a solution viscosity of 1 05 mPa · s 〇 Synthesis Example PI-9 17.3 g (〇.〇77 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 5.9 g (0.054 mol) of P-phenylenediamine as diamine The compound represented by the above formula (Dl), 4_lg (-100-200927727 0.008 mol) and the compound represented by the above formula (D-8), 7.7 g (0.016 mol), are dissolved in N-methyl-2. Pyrrolidone i 40 g was reacted at 60 ° C for 4 hours. The obtained polyamic acid solution was taken out in small portions, and N-methyl-2-pyrrolidone was added to prepare a solution having a polymer concentration of 10% by weight. The viscosity of the solution was measured and found to be 117 mPa «s. 325 Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyaminic acid solution, and 6.1 g of pyridine and 7.9 g of acetic anhydride were added to carry out dehydration ring closure at 110 ° C for 4 hours, followed by dehydration ring closure reaction. The solvent in the system was subjected to solvent replacement with a new N-methyl-2-pyrrolidone to obtain a solution containing 15.4% by weight of a polyamidimide (PI-9) having a ruthenium iodide ratio of about 55%. 〇g ° A small amount of the polyimine solution was taken out, and N-methyl-2-pyrrolidone was added to prepare a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 1 0 9 mP a · s. 〇 [Synthesis of Other Polyoxane] Synthesis Example PS - 1 In a 200 mL three-necked flask equipped with a cooling tube, 20.8 g of tetraethoxy decane and 28.2 g of 1-ethoxy-2-propanol were charged and heated. The mixture was stirred at 60 ° C, and 0.26 g of maleic anhydride prepared by adding it to another flask having a capacity of 20 mL was dissolved in water of 8 g of an aqueous maleic anhydride solution, and further heated at 6 ° C for 4 hours. The reaction was stirred, the solvent was distilled off from the obtained reaction mixture, 1-ethoxy-2-propanol was added, and the polymer solution containing 10% by weight of polyorganosiloxane was obtained by re-concentration, -101 - 200927727 PS-ι has a weight average molecular weight Mw of 5,100. <Synthesis of Sensitive Radiation Linear Polyorganooxane> Example IE-1

Into a 200 mL three-necked flask equipped with a reflux tube, 5.0 g of the polyorganooxane EPS-1 having an epoxy group obtained in the above Synthesis Example 1 and 5.18 g of the above-mentioned cinnamic acid derivative (1) were charged. Example 2-1 (1) The obtained compound (2-1 -1 -1 (1)) (corresponding to 50 mol% with respect to the epoxy group of polyorganooxane) and 0.5 g of tetrabutyl group The ammonium bromide was added with N,N-dimethylacetamide to make the solid content concentration 20% by weight, and the reaction was carried out at 10 ° C for 10 hours. After the reaction was completed, methanol was added to precipitate, and the precipitate was dissolved. After the solution obtained by ethyl acetate was washed with water three times, the solvent was removed by distillation to obtain 7.8 g of a sensitive radiation linear polyorganosiloxane S-IE-1 as a white powder, and a radiation-sensitive linear polyorganosiloxane S-IE. The weight average molecular weight Mw of -1 was 18,100. Examples IE-2 to 8 In the above Example IE-1, the type of the polyorganosiloxane having an epoxy group and the type and amount of the cinnamic acid derivative (1) are as shown in Table 2, respectively. In the same manner as in Example IE-1, each of the synthetic radiation linear polyorganosiloxanes S-IE-2 to S-IE-8, the weight average molecular weight Mw of the linear radiation polyorganosiloxanes Further, in the examples IE-6 and 7, each of the two types of cinnamic acid-102-200927727 organism (1) was used. Also. In Table 2, the "usage amount" of the cinnamic acid derivative (1) means a ratio with respect to the polyorganosiloxane having an epoxy group. Polyorganotoxime type cinnamic acid derivatives having an epoxy group (1) Sensitive radiation linear polyorganooxane mm Usage (mol%) Name Mw Example ffi-1 EPS-1 2-1-1-1 ( 1) 50 S-IE-1 18,100 Example IE-2 EPS-1 2-1-1-1 (1) 75 S-IE-2 21,000 Example IE-3 EPS-2 2-1-1-1 ( 2) 50 S-IE-3 20,500 Example IE-4 EPS-3 2-1-1-1 (3) 50 S-IE-4 17,200 Example IE-5 EPS-1 2-2-1-1 50 S-IE-5 20,800 Example IE-6 EPS-1 2-1-1-1 (2) 30 S-IE-6 21,300 2-1-1-2 20 Example IE-7 EPS-1 2-1 -1-1(2) 40 S-DE-7 21,200 2-2-1-2 10 Example IE-8 EPS-1 3-2-1-1 50 S-IE-8 29,900 <Liquid Crystal Aligning Agent Evaluation of Modulation and Preservation Stability> Example IE-9 100 parts by weight of the radiation-sensitive linear polyorganosiloxane S-IE-1 obtained by blending the above Example IE-1, and the content as another polymer The solution of the polylysine pa-1 obtained in the above Synthesis Example PA-1 is equivalent to 2,000 parts by weight of PA-1, and the solvent composition of 丨_methyl_2_pyrrolidone and butyl cellosolve is added thereto. 1-methyl-2-pyrrolidone: butyl cellosolve = 5 0 : 5 0 (by weight), Content concentration became 3.0 wt% was dissolved -103-200927727, by the agent through the solution A -1Ε -1 1 μιη pore size of the filter. - Store the liquid crystal alignment agent A-IE-1 at -15 °C. Before and after the measurement of the viscosity before and after 25 t by the E-type viscometer, the rate of change before and after the determination is less than 1%. It was judged that the preservation stability "defect" was evaluated as "good" for the storage agent A-IE-1. EXAMPLES IE- ί 〜 32 In the above-described Example IE-9, 'each was carried out in the same manner as Example IE-9 except that the type of the sensitizing alkane and the type and amount of the other polymer were carried. Agent A -1E - 2 ~ A -1E - 2 4. The liquid crystal alignment agent was examined in the same manner, and the evaluation results of the storage stability were shown. Q Examples IE-33 to 36 In the above-described Example IE-9, except for other amounts, each of which is described in Table 3, and used as a table. In addition to the amount of the epoxy compound, 'the same as Example 1E_9' has a concentration of 3 · 0 weight ° /. The solution 'is filtered by the filter, and each modulates the liquid crystal alignment agent A-IE_25~

In addition, in Table 3, the epoxy compound E-1 and the E formula (E-1) or (E-2) were filtered, and the liquid crystal was mixed for 6 months, and the storage viscosity of the stored solution was "good", 10%. As a result, the liquid crystal radioactive polyorgano was self-modulating the liquid crystal alignment as shown in Table 3, and Table IE-9 was carried out in the same manner as in Example IE-9. The type of the polymer, the type and the method described, and the Α-ΙΕ-28 of the solid diameter Ιμιη were prepared. -2 each represents the following -104- 200927727

Example IE - 3 7 A solution containing another polyoxosiloxane PS-1 obtained by the above-mentioned Synthesis Example PS-1 as another polymer was added in an amount equivalent to 500 parts by weight of PS-1, and was added thereto. 100 parts by weight of the radiation-sensitive linear polyorganooxane S-IE-1 obtained in the above Example IE-1, and then 1-ethoxy-indol-2-propanol was added to prepare a solution having a solid concentration of 4.0% by weight. The liquid crystal alignment agent A-IE-29 was prepared by filtering this solution through a filter of pore size Ιμηη. Regarding the liquid crystal alignment agent Α-ΙΕ-29, the evaluation results of the storage stability investigated in the same manner as in the above Example ΙΕ-9 are shown in Table 3. -105- 200927727 Table 3

液晶 Liquid crystal alignment agent name sensitive radiation linear polyorganosiloxane type other polymer epoxy compound preservation stability type usage amount (parts by weight) mm usage volume part) Example ffi-9 A-IE-1 S-IE -1 PA-1 2,000 _ 0 Good example IE-10 A-IE-2 S-IE-1 PA-2 2,000 0 Good example IE-11 A-IE-3 S-IE-1 PA-3 2,000 . 0 Good example IE-12 A-IE-4 S-IE-1 PA-4 2,000 . 0 Good example IE-13 A-IE-5 S-IE-1 PA-5 2,000 _ 0 Good example IE- 14 A-IE-6 S-IE-1 PA-4 500 - 0 Good example IE-15 A-IE-7 S-IE-1 PA-4 1,000 _ 0 Good example IE-16 Α-ΪΕ-8 S-IE-1 PI-1 2,000 _ 0 Good example IE-17 A-IE-9 S-IE-1 PI-2 2,000 _ 0 Good example IE-18 A-IE-10 S-IE-1 PI -3 2,000 _ 0 Good example IE-19 A-IE-11 S-IE-1 PI-4 2,000 0 Good example IE-20 A-IE-12 S-IE-1 PI-5 2,000 - 0 Good - 106- 200927727 Table 3 (Continued) Liquid Crystal Alignment Agent Name Sensitive Radiation Linear Polyorganooxane Type Other Polymer Epoxy Compound Preservation Stability Surface Usage (Parts by Weight) Species Usage (Parts by Weight) Example ffi-21 A -IE-13 S-IE-1 P I-6 2,000 _ 0 Good example IE-22 A-IE-14 S-IE-1 PI-7 2,000 0 Good example IE-23 Α-ΪΕ-15 S-IE-1 PI-8 2,000 _ 0 Good Example IE-24 A-IE-16 S-IE-1 PI-9 2,000 • 0 Good example ffi-25 A-IE-17 S-IE-1 PI-5 1,000 _ 0 Good example IE-26 A -IE-18 S-IE-2 PA-4 2,000 0 Good example IE-27 A-IE-19 S-IE-3 PA-4 2,000 _ 0 Good example IE-28 A-IE-20 S-IE -4 PA-4 2,000 _ 0 Good example IE-29 A-IE-21 S-IE-5 PA-4 2,000 _ 0 Good example IE-30 A-IE-22 S-IE-6 PA-4 2,000 • 0 Good example IE-31 A-IE-23 S-IE-7 PA-4 1,000 0 Good example IE-32 A-IE-24 S-IE-8 PA-4 1,000 _ 0 Good

Table 3 (continued) Liquid crystal alignment agent name sensitive radiation linear polyorganosiloxane type Other polymer epoxy compound storage stability W Usage (parts by weight) Type usage (parts by weight) Example IE-33 A-IE- 25 S-IE-1 PI-5 1,000 E-1 50 Good example ffi-34 A-IE-26 S-IE-1 PI-5 1,000 E-1 200 Good example IE-35 A-IE-27 S -IE-1 PI-7 1,000 E-2 50 Good example IE-36 A-IE-28 S-IE-1 PI-7 1,000 E-2 200 Good example ffi-37 A-IE-29 S-IE -1 PS-1 500 - 0 Good Example IE-38 <Manufacture of Vertical Alignment Type Liquid Crystal Display Element> -107- 200927727 The liquid crystal alignment agent A-IE-1 prepared in the above Example IE-9 was used. A spin coater is applied to a glass substrate with a transparent electrode formed of an ITO film

The surface of the plate was pre-baked on a hot plate at 80 ° C for 1 minute, and then heated in a nitrogen-substituted oven at 200 ° C for 1 hour to form a film thickness of ί. ίμιη. Then, on the surface of the coating film, a polarized ultraviolet ray having a bright line of 3 1 3 nm was irradiated with a gradient of 40° from the substrate normal line using an Hg-Xe lamp and a gran Taylor. A liquid crystal alignment film was formed, and the same operation was repeated to prepare one pair (two sheets) of a substrate having a liquid crystal alignment film. The outer periphery of the surface of the substrate having the liquid crystal alignment film is coated with an epoxy resin adhesive having a diameter of 5.5 μm by screen printing, and the liquid crystal alignment film surface of the pair of substrates is applied. In the opposite direction, the optical axis of the ultraviolet light of each substrate is pressed in the direction parallel to the projection direction of the substrate surface, and the adhesive is thermally cured at 150 ° C for 1 hour, and then the liquid crystal injection port is interposed between the substrates. After filling the negative liquid crystal (MLC-6608 manufactured by MELC Co., Ltd.), the liquid crystal injection port was sealed with an epoxy-based adhesive, and in order to remove the flow alignment during liquid crystal injection, it was heated at 150 ° C for 1 0. After a minute, the temperature is slowly cooled to room temperature. Then, on the outer side surfaces of the substrate, the polarizing plate is 45 in the direction in which the polarizing directions are orthogonal to each other and the optical axis of the ultraviolet ray of the liquid crystal alignment film is 45 toward the substrate surface. The vertical alignment type liquid crystal display element was fabricated by laminating at an angle of °. The evaluation results of these liquid crystal display elements were evaluated by the following methods, and the evaluation results are shown in Table 4. -108-200927727 <Evaluation of Liquid Crystal Display Element> (1) Evaluation of Liquid Crystal Alignment Whether the liquid crystal display element manufactured as described above is changed in brightness and darkness when ON/OFF (additional release) is performed at a voltage of 5 V There is an abnormal area, and it is observed by an optical microscope.

(2) Evaluation of pretilt angle With respect to the liquid crystal display element manufactured as described above, according to the method described in TJ Scheffer et. al. J. Appl. Phys. vo 1. 19, p2013 (1980), by using He-Ne Ray The pre-tilt angle is measured by the crystal rotation method of the light. (3) Evaluation of voltage holding ratio For the liquid crystal display element manufactured above, 6 (TC is applied with an applied time of 60 microseconds, a span of 167 milliseconds, and a voltage of 5 V is applied, and Q is measured, and the measurement is released from external addition to 167 milliseconds. After the voltage holding ratio, the measuring device used (manufactured by TOYO Corporation, VHR-1). (4) Evaluation of afterimage. For the liquid crystal display element manufactured above, a rectangular wave of 30 Hz '3 V with a direct current of 5 V is superimposed on 60. After the ambient temperature of °C is applied for 2 hours, the DC voltage is cut off, the voltage remaining in the liquid crystal cell after the DC voltage is cut off, and the residual DC voltage is obtained by the scintillation erasing method.

200927727 Example IE-39-64 In the above-mentioned Example IE-38, the manufacture of the alignment type liquid crystal display element was carried out in the same manner as in Example IE-3 except that the liquid crystal alignment agent of Table 4 was used, and evaluation was performed. . Example IE-65 <Manufacturing and Evaluation of TN-Aligned Liquid Crystal Display Element> The liquid crystal alignment prepared in the above Example IE-29 was applied to a transparent substrate coated with an ITO film using a spin coater. On the electrode surface, by using 18 (TC heating 1 thick Ο. ίμιη coating film, on the surface of the coating film, using Lan Taylor 稜鏡, so that the bright line containing 313 nm of 1,000 J / m2, from the substrate A liquid crystal alignment film is formed in a direction in which the normal line is inclined by 40°. The same operation as described above is repeated to produce a pair of (a glass substrate having a liquid crystal alignment film on the surface of the conductive film.) The liquid crystal alignment portion is coated with an oxygen resin adhesive having a diameter of 5.5 μm by screen printing, and the polarized ultraviolet light is irradiated in a direction orthogonal to each other, and heated at 150 ° C for 1 hour to form a gap of the adhesive thermosetting plate. Injecting a positive nematic liquid system from the liquid crystal injection port, MLC-622 1 and adding a chiral molecular agent): The oxygen-based adhesive seals the liquid crystal injection port, and, in order to go as listed, perform vertical The results are shown in Qi! I A-IE-2 1, Ming When the glass of the electrode is small, a film Hg-Xe lamp and a polarized ultraviolet light are formed, and the liquid crystal film is applied to the surface of the transparent film to superimpose the substrate under the epoxy of the aluminum film, and then, after the substrate is cooled (MELC) , using a ring to remove the liquid alignment of the liquid crystal injection -110-200927727, heat it at 150 ° C for 10 minutes and then slowly cool to room temperature, then, on the outer two sides of the substrate 'by making the polarizing plate • The polarizing direction is orthogonal to each other, and is bonded in parallel with the polarizing direction of the liquid crystal alignment film to form a TN alignment type liquid crystal display element. Liquid crystal alignment, voltage retention, and residual of the liquid crystal display element The evaluation was carried out in the same manner as in Example IE-3 8. The evaluation results are shown in Table 4. 实施 Example IE-66 In the above Example IE-65, except that the liquid crystal alignment agent prepared in Example IE-32 was used. A-IE-24 was used as a liquid crystal alignment agent in the same manner as in Example IE-65, and a TN alignment type liquid crystal display device was produced and evaluated. The evaluation results are shown in Table 4. 〇-111 - 200927727 Table 4 Liquid crystal Orientation Type of liquid crystal display element operation mode Liquid crystal alignment tilt angle 〇 Voltage holding ratio (%) Afterimage (mV) Example IE-38 A-IE-1 Vertical good 89 98 6 Example IE-39 A-IE-2 Vertical good 89 98 6 Example IE-40 A-IE-3 Vertical good 89 98 6 Example IE-41 A-IE-4 Vertical good 89 98 5 Example IE-42 A-IE-5 Vertical good 89 98 6 Example IE-43 A-IE-6 Vertical good 89 98 5 Example IE-44 A-IE-7 Vertical good 89 99 5 Example IE-45 A-IE-8 Vertical good 89 98 6 Example IE-46 A- IE-9 Vertical good 89 98 6 Example IE-47 A-IE-10 Vertical good 89 98 6 Example IE-48 A-IE-11 Vertical good 89 99 5 Example IE-49 A-IE-12 Vertical good 89 99 6 Example IE-50 A-IE-13 Vertical good 89 99 5 Example IE-51 A-IE-14 Vertical good 89 99 5

-112 200927727 Table 4 (continued) Liquid crystal alignment agent type Liquid crystal display device operation mode Liquid crystal alignment tilt angle 〇 Voltage holding ratio (%) Afterimage (mV) Example IE-52 A-IE-15 Vertical good 89 99 5 Implementation Example IE-53 A-IE-16 Vertical good 89 99 5 Example IE-54 A-IE-17 Vertical good 89 99 5 Example IE-55 A-IE-18 Vertical good 89 98 5 Example E-56 A -IE-19 Vertical good 89 99 5 Example IE-57 A-IE-20 Vertical good 89 99 5 Example IE-58 A-IE-22 Vertical good 89 99 5 Example IE-59 A-IE-23 Vertical Good 89 99 6 Example IE-60 A-IE-25 Vertical good 89 99 5 Example IE-61 A-IE-26 Vertical good 89 98 6 Example IE-62 A-IE-27 Vertical good 89 99 5 Implementation Example IE-63 A-IE-28 Vertical good 89 98 6 Example BE-64 A-IE-29 Vertical good 89 99 3 Example IE-65 A-IE-21 TN good - 99 10 Example IE-66 A - IE-24 TN Good 98 10 ^ <Evaluation of physical properties of coating film> Example IE-67-93 (1) Evaluation of i-line absorption The liquid crystal alignment agents listed in Table 5 were each spin-coated on quartz. 'The substrate' is 80. (Pre-bake on a hot plate for 1 minute, 'heating at 2 ° C for 1 hour to form a coating film having a film thickness'. Using a spectrophotometer (manufactured by Hitachi, Ltd.) The type "υ-2010" measures the UV absorption spectrum in the wavelength range of 250 to 500 nm. The maximum absorbance in this wavelength region is 100. The absorption at 365 nm is -113-200927727. The luminosity is lower than 1 and is judged as "good". In the case of 1 or more, it was judged as "poor", and the evaluation of i-line absorption was performed. - The evaluation results are shown in Table 5. (2) Evaluation of heat resistance in the above-described Example IE-38 < Vertical alignment type liquid crystal display element Manufacturing > In the same manner as in Example IE-28, a vertical alignment type liquid crystal display 7JK element was produced except that the liquid crystal alignment agent listed in Table 5 was used, and the post-zero baking temperature was set to 25 ° C. Regarding the obtained liquid crystal display element, the person who showed excellent vertical alignment (displayed as a uniform black display) was judged as "good", and it was judged that the light leakage was judged as "poor". In Table 5. Examples IE94 and 95 Q ( 1 ) Evaluation of i-line absorption The UV absorption spectrum was measured in the wavelength range of 250 to 500 nm in the same manner as in the above Examples IE-67 to 93 except that the liquid crystal alignment agents listed in Table 5 were used, and the evaluation results are shown in Table 5. (2) Evaluation of heat resistance In the production of <TN alignment type liquid crystal display element of the above Example IE-65, except that each liquid crystal alignment agent listed in Table 5 was used, and the post-baking temperature was set to 2 A -114-200927727 TN alignment type liquid crystal display element was produced in the same manner as in Example IE-65 except for 50 ° C. The obtained liquid crystal display element was shown to exhibit excellent vertical alignment (showing uniformity) The black display is judged as "good" and it is judged that the light leak is judged as "poor". The evaluation results are shown in Table 5. Comparative Example &-1 <Synthesis of Polyglycolic Acid>

22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and the following formula (d-1) ch3 synthesized according to JP-A-2003-5208-8

(d-1) nh2 ο C4H9-0 ch=ch-coo-c6h12—ooc Compound 48.46g (0.1 mol), dissolved in N-methyl-2-pyrrolidone 283.4g, in room The temperature was allowed to react 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. . <Preparation of Liquid Crystal Aligning Agent> The polylysine synthesized 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 prepared, and the liquid-soluble alignment agent RA-IE-1 was prepared by filtering the solution of -115-200927727 with a filter of pore size Ιμηι. <Evaluation of physical properties of coating film> The evaluation of the physical properties of the coating film was carried out in the same manner as in the examples IE-6 7 to 93 except that the liquid crystal alignment agent RA-IE-1 prepared above was used. The evaluation results are shown in Table 5. table 5

Liquid crystal alignment agent type coating film physical property i-line absorption heat resistance Example IE-67 A-IE-1 Good example IE-68 A-IE-2 Good example IE-69 A-IE-3 Good example IE-70 A-IE-4 Liangliang Example IE-71 A-IE-5 Liangliang Example IE-72 A-IE-6 Liangliang Example IE-73 A-IE-7 Liangliang Example ffi- 74 A-IE-8 Liangliang Example IE-75 A-IE-9 Liangliang Example ffi-76 A-IE-10 Liangliang Example ffi-77 A-IE-11 Liangliang Example IE-78 A -IE-12 Liangliang Example IE-79 A-IE-13 Liangliang Example IE-80 A-IE-14 Liangliang Example ffi-81 A-IE-15 Liangliang Example Zheng-82 A-IE -16 良良-116- 200927727 Table 5 (continued) Liquid crystal alignment agent WM Coating physical property i-line absorption heat resistance Example ΙΕ-83 Α-ΙΕ-17 Liangliang example Ε-84 Α-ΙΕ-18 Liangliang implementation Example -85 Α-ΙΕ-19 Liangliang Example ΙΕ-86 Α-ΙΕ-20 Liangliang Example ΙΕ-87 Α-ΙΕ-22 Liangliang Example ΙΕ-88 Α-ΙΕ-23 Liangliang Example -89 Α-ΙΕ-25 良良实施例ΙΕ-90 Α-ΙΕ-26 良良实施例正-91 Α-ΙΕ-27 良良实施例ΙΕ-92 Α- ΙΕ-28 良良实施例ΙΕ-93 Α-ΙΕ-29 Liangliang Example ΙΕ-94 Α-ΙΕ-21 Liangliang Example ΙΕ-95 Α-正-24 Liangliang Comparative ExampleΙΕ-1 RA-IE- 1 bad

<Evaluation of Modulation and Storage Stability of Liquid Crystal Aligning Agent> Examples IE-96 to 107 In the above Example IE-16, except for the type of the sensitive radiation linear polyorganosiloxane and the types and amounts of other polymers As described in Table 6, the same procedure as in Example IE-16 was carried out, and the liquid crystal alignment was modulated to j Α ΙΕ 〇 〇 〇 。 。 ΙΕ ΙΕ 41 41 41. The evaluation results of the storage stability investigated by the same procedure as in Example ι_16 for each liquid crystal alignment agent are shown in Table 6. <Manufacturing and Evaluation of Vertical Alignment Type Liquid Crystal Display Element> Example IΕ -1 0 8~1 1 9 -117- 200927727 In the above-described Example IE-38, except that each of those listed in Table 7 was used as a liquid crystal alignment agent In the same manner as in the example IE-3 8, the production of the vertical alignment type liquid crystal display element was carried out and evaluated, and the evaluation results are shown in Table 7. <Evaluation of physical properties of coating film> Examples IE-120 to 131 In the same manner as in Examples IE-6 7 to 93, the evaluation of i-line absorption and heat resistance were carried out except that each of the liquid crystal alignment agents listed in Table 8 was used. The results of the evaluation and evaluation are shown in Table 8.

Table 6 Liquid Crystal Alignment Agent Name Sensitive Radiation Linear Polyorganooxane View Other Polymer Preservation Stability Type Usage (Parts by Weight) Example IE96 A-IE-30 S-IE-1 PA-1 1,000 Good Practice IE97 A -IE-31 S-IE-1 PA-2 1,000 Good Practice IE98 A-IE-32 S-IE-1 PA-3 1,000 Good Practice IE99 A-IE-33 S-IE-1 PA-5 1,000 Good EXAMPLE IE100 A-IE-34 S-IE-1 PI-1 1,000 Good Practice IE101 A-IE-35 S-IE-1 PI-2 1,000 Good Practice IE102 A-IE-36 S-IE-1 PI -3 1,000 Good Practice IE103 A-IE-37 S-IE-1 PI-4 1,000 Good Practice IE104 A-IE-38 S-IE-1 PI-6 1,000 Good Practice IE105 A-IE-39 S- IE-1 PI-7 1,000 Good Practice IE106 A-IE-40 S-IE-1 PI-8 1,000 Good Practice IE107 A-IE-41 S-IE-1 PI-9 1,000 Good-118- 200927727 Table 7 Liquid crystal alignment agent (name) Liquid crystal display element operation mode Liquid crystal alignment tilt angle (.) Voltage retention rate (%) Afterimage (residual DC voltage) (mV) Example IE-108 A-IE-30 Vertical alignment good 89 98 6 Example IE-109 A-IE-31 Vertical alignment good 89 98 6 Example ffi-ll〇A-IE-32 Vertical alignment good 89 98 6 Real Example IE-111 A-IE-33 Vertical alignment good 89 98 6 Example IE-112 A-IE-34 Vertical alignment good 89 99 6 Example IE-113 A-IE-35 Vertical alignment good 89 99 6 Example IE -114 A-IE-36 Vertical alignment good 89 99 6 Example ffi-115 Α-ΪΕ-37 Vertical alignment good 89 99 6 Example IE-116 A-IE-38 Vertical alignment good 89 99 6 Example IE-117 A-IE-39 Vertical alignment good 89 99 6 Example IE-118 A-IE-40 Vertical alignment good 89 99 6 Example IE-119 A-IE-41 Vertical alignment good 89 99 6

〇-119- 200927727 Table 8 Liquid crystal alignment agent name Coating property i-line absorption heat resistance Example IE-120 A-IE-30 Liangliang Example IE-121 Liangliang Example IE-122 A-IE-32 Liangliang Example IE-123 A-IE-33 Liangliang Example ffi-124 A-IH-34 Liangliang Example ffi-125 A-IE-35 Liangliang Example IE-126 A-IE-36 Liangliang Example IE-127 Embodiment IE-128 -^IE-37__ Liangliang A-IE-38 Liangliang Example IE-129 A-IE-^Q Liangliang Example IE-130 ^ A"IE" 4D Good Practice Ffi-131 - A-IH-41 Synthesis of Liangliang <Sensitive Radiation Linear Polyorganooxane> Example IE-132 In the above Example IE-1, except that 5.0 g of the above Synthesis Example 4 was used EPS-4 replaces EPS" as a polyorganosiloxane having an epoxy group's use as a compound of cinnamic acid derivative (1) (2-2-1-1(2)) relative to EPS- 4 having an epoxy group of 50 mol%, which was carried out in the same manner as in Example IE-1, to obtain a weight average of the radiation-sensitive linear polyorganosiloxane S-IE-9, S-IE-9. The molecular weight Mw is 1,600 ° ° Example IE-133 above In the embodiment IE-1, except that it is used by -120- 相对 relative to E P S -1

200927727 has a compound having an epoxy group of 50 mol% (2-2-1-1 (2) compound (2-2-1-1 (1)), and % ringing molar relative to EPS-1 The weight average of the radiation-sensitive linear polyorganosiloxane S-S-IE-10 was obtained by performing the same procedure as the above-mentioned formula of the other pretilt-exhibiting compound (the mixture of the compounds represented by the same method). The molecular weight Mw was 1,800. Example IE-134-141 In the above Example IE-133, except that the types and amounts of cinnamic acid-derived and other pretilt-representative compounds were respectively shown in the Table, and Examples IE -133 was carried out in the same manner, and each of the desired polyorganosiloxanes S-IE-11 to S-IE-18 was obtained. The weight average molecular weight Mw of the above-mentioned sensitizing radiation machine oxime is shown in Table 9. Further, In Table 9, other pretilt performance compounds (4-3-1), "(4-3-2)" and "(4-3-3)" are described in the formula (4-3-1). , (4-3-2) or (4-3-3), <Evaluation of preparation and storage stability of liquid crystal alignment agent> Examples IE-142 to 171 in the above embodiment IE·9 In addition to the sensitive radiation linear oxygen The type and amount of other polymers were carried out in the same manner as in Example IE-9 except that the type and amount of the other polymers were carried out, and the respective monomers A-IE-42 to A-IE-71 were prepared. The evaluation results of the preservation stability investigated in the same way as the implementation are listed in the table) Substitute: Base is 5 4-3-1) Example IE-1 IE-10, substance (1) 9 Note: Radiation linear clustering The abbreviation ": refers to each of the above compounds. 丨 Organic 矽 10 notes: crystal matching to the case IE - 9 10 ° -121 - 200927727 <Manufacturing and evaluation of vertical alignment type liquid crystal display element> • Example IE-172~201 - Evaluation of the manufacture of each vertical alignment type liquid crystal display element 'in the same manner as in Example 1E_38' except that the liquid crystal alignment agent as shown in Table 1 was used in the above-mentioned Example IE-3 8 The results are shown in Table 11. 〇 <Physical property evaluation of coating film> Examples IE-202 to 23 1 The same procedure as in the above Examples IE-67 to 93 was carried out except that the liquid crystal alignment agents listed in Table 12 were used. , evaluation of i-line absorption and evaluation of heat resistance. The evaluation results are listed in Table 12. 2. ❹ -122 20 0927727 Table 9

聚 Polyorganosiloxane type cinnamic acid derivatives with epoxy groups (1) Other tilting angles Representation compounds Sensitive radiation Linear polyorganosiloxane name usage (mol%) Name usage (mol%) Name Mw implementation Example IE-132 EPS-4 2-1-1-1(2) 50 _ 0 S-IE-9 16,200 Real lung! Jffi-133 EPS-1 2-1-1-1(2) 50 (4-3 -1) 5 S-IE-10 18,400 Example IE-134 EPS-1 2-1-1-1 (2) 50 (4-3-1) 10 S-IE-11 18,800 Example ffi-135 EPS- 1 2-1-1-1(2) 50 (4-3-1) 20 S-IE-12 19,100 Example IE-136 EPS-1 2-1-1-1(2) 50 (4-3- 2) 20 S-IE-13 19,500 Example IE-137 EPS-1 2-1-1-1 (2) 50 (4-3-3) 20 S-IE-14 19,600 Example IE-138 EPS-1 2-1-1-1(2) 50 Dodecanoic acid 20 S-IE-15 19,000 Example IE-139 EPS-1 2-1-1-1 (2) 50 Stearic acid 20 S-IE-16 19,300 Example IE-140 EPS-1 2-1-1-1 (3) 50 Dodecanoic acid 20 S-IE-17 19,100 Example IE-141 EPS-1 2-1-1-1 (3) 50 Stearic acid 20 S-IE-18 19,300 123- 200927727

Table 10 Liquid crystal alignment agent name Sensitive radiation linear polyorganosiloxane species Other polymer storage stability type Usage (parts by weight) Example IE-142 A-IE-42 S-正-9 PA-4 1,000 Good example IE-143 A-IE-43 S-IE-9 PA-4 500 Good Practice IE-144 A-IE-44 S-IE-9 PA-4 1,000 Good Practice IE-145 A-IE-45 S- IE-9 PI-5 1,000 Good Practice IE-146 A-IE-46 S-IE-9 PI-6 1,000 Good Practice IE-147 A-IE-47 S-正-9 PI-7 1,000 Good Practice IE-148 A-IE-48 S-IE-9 PI-8 1,000 Good Practice IE-149 A-IE-49 S-IE-9 PI-9 1,000 Good Practice IE-150 A-IE-50 S- IE-9 PA-4 2,000 Good Practice IE-151 A-IE-51 S-IE-10 PA-4 2,000 Good Practice IE-152 A-IE-52 S-IE-10 PI-5 2,000 Good Practice Positive-153 A-IE-53 S-IE-10 PI-6 2,000 Good example IE-154 A-IE-54 S-IE-10 PI-7 2,000 Good example IE-155 A-IE-55 S- IE-10 PI-8 2,000 Good Practice IE-156 A-IE-56 S-IE-10 PI-9 2,000 Good Practice IE-157 A-IE-57 S-IE-11 PA-4 2,000 Good Practice IE-158 A-IE-58 S-IE-12 PA-4 2,000 Good Practice IE-159 A-IE-59 S-IE-13 PA-4 2,000 Good Example IE-160 A-IE-60 S-IE-14 PA-4 2,000 Good Practice IE-161 A-IE-61 S-IE-15 PA-4 2,000 Good Practice IE-162 A-IE-62 S -IE-16 PA-4 2,000 Good Practice -163 A-IE-63 S-IE-17 PA-4 2,000 Good IE-164 A-IE-64 S-IE-18 PA-4 2,000 Good implementation Example IE-165 A-IE-65 S-IE-18 PA-4 1,000 Good Practice IE-166 A-IE-66 S-IE-18 PA-4 500 Good Practice IE-167 A-IE-67 S -IE-18 PI-5 1,000 Good example IE-168 A-IE-68 S-IE-18 PI-6 1,000 Good example ffi-169 A-IE-69 S-IE-18 PI-7 1,000 Good implementation Example ffi-ΠΟ A-IE-70 S-IE-18 PI-8 1,000 Good Practice IE-171 A-IE-71 S-IE-18 PI-9 1,000 Good-124- 200927727 Table 1 1

Liquid crystal display element liquid crystal alignment agent (name) Alignment liquid crystal tilt angle voltage retention afterimage (residual mode alignment (.) rate (%) DC voltage) (mV) Example IE-172 A-IE-42 Vertical alignment good 89 99 5 Example IE-173 A-IE-43 Vertical alignment good 89 99 5 Example ffi-174 A-IE-44 Vertical alignment good 89 99 5 Example IE-175 A-IE-45 Vertical alignment good 89 99 5 Implementation Example IE-176 A-IE-46 Vertical alignment good 89 99 5 Example ffi-177 A-IE-47 Vertical alignment good 89 99 5 Example IE-178 A-IE-48 Vertical alignment good 89 99 5 Example IE -179 A-IE-49 Vertical alignment good 89 99 5 Example IE-180 A-IE-50 Vertical alignment good 89 98 5 Example IE-181 A-IE-51 Vertical alignment good 89 99 5 Example IE-182 A-IE-52 Vertical alignment good 89 99 5 Example IE-183 A-IE-53 Vertical alignment good 89 99 5 Example IE-184 A-IE-54 Vertical alignment good 89 99 5 Example IE-185 A- IE-55 Vertical alignment good 89 99 5 Example IE-186 A-IE-56 Vertical alignment good 89 99 5 Example IE-187 A-IE-57 Vertical alignment good 89 99 5 Example I IE-188 A-IE -58 Vertical alignment good 89 9 9 5 Example IE-189 A-IE-59 Vertical alignment good 89 99 5 Example IE-190 A-IE-60 Vertical alignment good 89 99 5 Example IE-191 A-IE-61 Vertical alignment good 89 98 5 EXAMPLE IE-192 A-IE-62 Vertical alignment good 89 98 5 Example IE-193 A-IE-63 Vertical alignment good 89 99 5 Example IE-194 A-IE-64 Vertical alignment good 89 99 5 Example IE-195 A-IE-65 Vertical alignment good 89 99 5 Example IE-196 A-IE-66 Vertical alignment good 89 99 5 Example IE-197 A-IE-67 Vertical alignment good 89 99 5 Example IE- 198 A-IE-68 Vertical alignment good 89 99 5 Example IE-199 A-IE-69 Vertical alignment good 89 99 5 Example IE-200 A-IE-70 Vertical alignment good 89 99 5 Example IE-201 A -IE-71 Vertical alignment good 89 99 5 -125- 200927727

Table 12 Liquid crystal alignment agent name Coating property i-line absorption heat resistance Example IE-202 A-IE-42 Liangliang Example IE-203 A-IE-43 Liangliang Example IE-204 A-IE-44 Liangliang EXAMPLE IE-205 A-IE-45 良良实施例 IE-206 A-IE-46 良良实施例 IE-207 A-IE-47 良良实施例 IE-208 A-IE-48 良良实施例IE-209 A-IE-49 Liangliang Example IE-210 A-IE-50 Liangliang Example ffi-211 A-IE-51 Liangliang Example IE-212 A-IE-52 Liangliang Example ffi- 213 A-IE-53 Liangliang Example IE-214 A-IE-54 Liangliang Example ffi-215 A-IE-55 Liangliang Example IE-216 A-IE-56 Liangliang Example IE-217 A -IE-57 Liangliang Example IE-218 A-IE-58 Liangliang Example IE-219 A-IE-59 Liangliang Example IE-220 A-IE-60 Liangliang Example ffi-221 A-IE -61 good example ffi-222 A-IE-62 good example IE-223 A-IE-63 good example ffi-224 A-IE-64 good example IE-225 A-IE-65 Liangliang Example IE-226 A-IE-66 Liangliang Example IE-227 A-IE-67 Liangliang Example IE-228 A-IE-68 Liangliang Example ffi-229 A-IE-69 LiangliangEXAMPLES IE-230 A-IE-70 良良实施例 IE-231 A-IE-71 良良-126- 200927727 The 'liquid crystal alignment agent' of the present invention can be specifically understood from the above examples, as A liquid crystal alignment agent which is excellent in liquid crystal alignment and electrical properties can be formed with a small amount of radiation exposure in comparison with a liquid crystal alignment agent which is known from the prior art. Moreover, since the light reaction is not caused by light of a long wavelength region, for example, a wavelength of 365 nm or more, and the heat resistance of the obtained liquid crystal alignment film is high, the liquid crystal panel can be manufactured without a step of 0. . Further, the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention does not cause photoreaction due to light in a long wavelength region, and the backlight of the liquid crystal panel also has long-term stability. Therefore, when the liquid crystal alignment element is applied to a liquid crystal display element, the liquid crystal display element can be manufactured at a lower cost than the prior art, and the obtained liquid crystal display element is excellent in performance such as display characteristics and reliability. Therefore, these liquid crystal display elements can be effectively applied to various devices, for example, as applicable to desktop computers, watches, desk clocks, counting display boards, word processing, personal computers, liquid crystal televisions, and the like. -127-

Claims (1)

200927727 X. Patent application scope 1 · A liquid crystal alignment agent characterized by containing the following formula (1) In the formula (1), R^R2 and R3 are each independently a hydrogen atom or a monovalent organic group, and when R3 is not a hydrogen atom, at least one of R1 and R2 is a carboxyl group or an organic group having a carboxyl group, R1 And R2 may be bonded to each other to form a ring) a compound represented by the formula (S-1) Γί1 one-Si-O one .Y1 . (In the formula (S-), χΐ is an i-valent organic group having an epoxy group; γ ΐ is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a carbon number of 6 to 20 The aryl group) is a radiation-sensitive linear polyorganosiloxane obtained by reacting at least one selected from the group consisting of a polyorganosiloxane of a repeating unit and a condensate of a hydrolyzate and a hydrolyzate. 2. The liquid crystal alignment agent of claim 1, wherein the compound represented by the above formula (1) is the following formula (2) -128 to 200927727 CH=CH—COOH (In the formula (2), R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group. However, at least one of R 4 and R 5 has a carbon number of 1 to 20 which may be substituted by a fluorine atom. An alkyl group or a group of a 3 to 40 alicyclic group which may be substituted by a fluorine atom, wherein R 4 and R 5 may be bonded to each other to form a ring, or a compound represented by the following formula (3) © (In the formula (3), R6 is a single bond or a divalent organic group; R7 is a hydrogen atom or a monovalent organic group; R6 and R7 may be bonded to each other to form a ring, and R8 may be substituted by a fluorine atom. A compound represented by an alkyl group having 1 to 20 carbon atoms or an alicyclic group having a carbon number of 3 to 40, which may be substituted by a fluorine atom. 3. The liquid crystal alignment agent of claim 1, wherein Χι in the above formula (S-1) is the following formula (χι·ι) or (χΐ_2) -129- 200927727 ο (χ1-ι) The base represented. Ο 4. As claimed in paragraphs 1 to 3 of the patent application, it further contains a polymer of one type consisting of polyproline and polyimine. 5. The liquid crystal alignment agent selected from the group of liquid crystal alignment agents of the following formula (S-2), as in any one of claims 1 to 3 of the patent application. -X2 -Si Ο-- -Y2 . $-2) (In the formula (S-2), X2 is a hydroxyl group, a halogen atom, a carbon number alkoxy group or a carbon number 6 to 20 aryl group number 1 At least one selected from the group consisting of a polyoxane represented by the alkoxy group of 1-10, a hydrolyzate thereof, and a hydrolyzate. In the method of forming a liquid crystal alignment film, it is preferable to apply a coating film as in the first to third aspects of the patent application, and to irradiate the coating film with radiation. An alkyl group having a number of 1 to 20; a group characterized by a hydroxyl group or a carbon condensate is formed on a substrate by a liquid crystal alignment agent -130-200927727 7. A liquid crystal display element characterized by a patent application scope A liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of items 1 to 3. 8. A sensitive radiation linear polyorganosiloxane which is characterized by the compound represented by the above formula (1) and a water organic sand oxide plant having a repeating unit represented by the above formula (s-i) At least one reaction selected from the group consisting of a hydrolyzate and a condensate of a hydrolyzate is obtained. 〇 9·~ The compound represented by the above formula (1). -131 - 200927727 VII. Designated representative map: (1) The representative representative of the case is: None (2), the representative symbol of the representative figure is simple: no 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -4-