TW200413441A - Diamine compound, polyamic acid, imide polymer, liquid crystal alignment agent and liquid crystal display - Google Patents

Abstract

This invention provides a liquid crystal alignment agent capable of not only exhibiting excellent alignment characteristics but also forming a liquid crystal alignment layer film with which the time from cancellation of voltage application to afterimage erasure in a liquid crystal display is short; a polymer thereof; and a diamine compound as a monomer thereof. For example, there are provided liquid crystal alignment agents comprising a diamine compound having an alicyclic group, such as methyl lithocholate (3, 5-diaminobenzoate), a polyamic acid being a product of reaction between the same and a tetracarboxylic anhydride and an imidized polymer therefrom, and a polymer thereof. Also, a liquid crystal display comprising the liquid crystal alignment layer film is provided.

Description

说明, Description of the invention: [Technical field to which the invention belongs] The present invention relates to diamine eight compounds, πA and σσ compounds to make amino acids, fluorinated polymers, and compounds containing at least one of these. A liquid crystal alignment agent and a liquid crystal display element including a liquid crystal alignment film formed of such a liquid crystal alignment d. [Prior art] A pseudolayer structure is formed on a substrate with a liquid crystal alignment film and a transparent electrode by using a nematic liquid crystal with positive dielectric anisotropy. The major axis of the pseudocrystal molecules is 90 degrees or more between the substrates. W (Twisted

Nematic) or liquid crystal display elements with STN (Super Twisted n-view type liquid crystal cells) are known. The liquid aa alignment in these liquid crystal display elements is generally formed on the surface of the coating film composed of a polymer. It is controlled by a liquid crystal alignment film formed by performing an alignment treatment such as a rubbing treatment. Here, the polymers constituting the coating film are known as polyamic acid and polyimide. Generally, these polymers are dissolved in a solvent. In addition, a liquid crystal display element different from the above is known as a vertical alignment type liquid crystal cell in which liquid crystal molecules having negative dielectric anisotropy are arranged perpendicular to a substrate, and the liquid crystal display element has the liquid crystal. Grid liquid crystal display elements. Even in such liquid crystal display elements, the alignment control of liquid crystals is generally composed of a liquid crystal alignment film formed by a liquid crystal alignment agent containing a polymer such as β water fezine, polyimide, and the like. However, in a liquid crystal display device including a liquid crystal alignment film formed with a conventional liquid crystal alignment agent, the ionic charge generated during daylight image display (when a voltage is applied) is transferred by the liquid crystal. Adsorption to the film, even after the image erasing day (the voltage applied solution

〇: \ 37 \ .37061.CX) C 200413441, after), it is also difficult to detach from the liquid crystal alignment film, so electricity will remain in the liquid after the emperor dust is released. A 卞 a 3 ,, ^ Due to the residual voltage, the problem that the afterimage of the displayed image after the application of electric power is released will cause an afterimage still exists. Furthermore, the use of the liquid crystal display element between right and right sides may cause white spot-like display defects' to impair the reliability of the liquid crystal display element. Recently, as represented by the use of liquid crystal televisions, it is inevitable to use such a liquid for a long period of time, and it is necessary to further improve the reliability. [Abstract] Disclosure of the Invention A first object of the present invention is to provide a new diamine compound. A second object of the present invention is to provide a novel polyamidic acid as a crystal directing agent. ... A third object of the present invention is to provide a novel polyfluorene imine polymer as a liquid crystal aligning agent. A fourth object of the present invention is to provide a liquid crystal aligning agent, which can _ have good alignment characteristics ′ and can be formed-eliminating the application of voltage to the disappearance of afterimages (hereinafter referred to as "afterimages" in a liquid crystal display). Disappearance time: Very short liquid crystal alignment film. Another object and advantages of the present invention will be apparent from the following description. According to the present invention, the above objects and advantages of the present invention are based on at least one selected from the following formula: (I)

H2N-G1 ~ A1-D1-CO-bi- (£ i) i nh2

OAS7 \ 8706l.DOC 200413441 (Where: D1 is a divalent hydrocarbon group containing 5 to 30 carbon atoms, G1 is a trivalent organic group, A1 is a single bond or a divalent bonding group, B1 is a single bond, … -N (H)-or /

One N \, E1 is a 1-compensated organic group, a is a compound represented by 1 or 2) and the following formula (II) H2N-G2-A2-D2-CO-B2- (E2) b (II) '

I A2-G2-NH2 (wherein D2 is a trivalent hydrocarbon group having 5 to 30 carbon atoms in an alicyclic ring, G2 is a divalent organic group, A2 is a single bond or a divalent bonding group, B2 is a single bond,- 〇-, -N (Η)-or / -N, protected as a monovalent organic group, b is 1 or 2) and a diamine compound (hereinafter, also referred to as a specific two Amine compound "). According to the present invention, the above-mentioned object and advantages of the present invention are that the second system uses at least one specific monoamine compound and the following formula (III)

O: \ 87N3706ij Dooc (III) 200413441 (wherein G4 is a tetravalent organic group) is obtained by using at least one reaction product of tetracarboxylic dianhydride, namely polyamic acid. According to the present invention, the above-mentioned objects and advantages of the present invention are achieved by the third method by the hydrazone imidized polymer obtained by dehydrating and closing the polyaspartic acid. According to the present invention, the above-mentioned objects and advantages of the present invention are achieved by a fourth liquid crystal aligning agent composed of at least a kind of chemical character composed of a polyamic acid and a fluorinated polymer. According to the present invention, the above-mentioned object and advantages of the present invention, the fifth system is to contain at least one selected from the following formulae (XI) to (XIV)

(Among them, A1, A2, b1, B2, D1, D2, E1, E2, G1, G2, G4,

0 :, S7 \ 87〇61.DOC 200413441 The definitions of a and b are the same as above.) The liquid crystals composed of the polymers composed of the repeating units shown respectively are aligned. According to the present invention, the above-mentioned object and advantages of the present invention are achieved by a liquid crystal display element _ having a liquid crystal alignment film formed from the liquid crystal alignment agent described above. [Embodiment Mode] The present invention will be described in detail below. -<-Amine compound> The diamine compound of the present invention is represented by the above formula (I) or (π). Among them, D1 is represented by the above formula (I) and D2 is represented by the above (II), and the hydrocarbon group having 5 to 30 carbon atoms having an alicyclic ring is preferably a hydrocarbon group having 10 to 30 carbon atoms having an alicyclic ring. It is preferably a hydrocarbon group containing a nested skeleton. In this way, specific examples of the divalent hydrocarbon group (D 3) include structures represented by the following formulae (1-1) and (1-2).

The trivalent hydrocarbon group (D2) can be specifically exemplified by structures represented by the following formulae (II-1) and (II-4).

O: \ 8T.S706 LDOC -10- 200413441

Examples of the trivalent organic group represented by G1 include a group in which three hydrogen atoms are removed from a hydrocarbon having a carbon number of 5 to 5 and a formula represented by the following formula (1-3) and the following formula (1-4), respectively. The base. The divalent organic group represented by G2 is, for example, a group obtained by removing two hydrogen atoms from a hydrocarbon having 5 to 5 carbon atoms.

OCH 2 ~ CH-CH2〇

(M) Specific examples of the bonding group other than A and A2 include keto group, ether group, ester group, amido group, carbamate group and urea group. : Carbon number 1 to 30. Examples of the monovalent organic group represented by E1 and E2 include linear or branched chain alkyl groups; steroid groups, steroid groups, phenethyl groups, and tri% amyl groups. , Cyclohexyl, decahydronaphthyl, dicyclohexyl, alcohol alkyl, and the like; alicyclic groups containing phenyl, methylbenzyl, xylyl, naphthyl, benzyl, and the like; containing ^ Southyl, tetrahydroheptanyl, 4-phenyl, tetrahydrocutyl, bilyl, pyridyl, piperidinyl, "piperidinyl, morpholinyl, fluorinyl, isoquinolinyl, 1 -A heterocyclic organic group such as piperidinylmethyl, morpholinylmethyl, etc .;

O: \ S7 \ 8706l.DOC -11-200413441 is represented by the following formula (IV) -Q4-T4- —s4 (where Q4 is a bivalent cyclic organic selected from the group consisting of aromatic ring, alicyclic (IV) heterocyclic ring and its substituents T4 is a divalent alicyclic group which may also be substituted, and s4 is a group represented by a carbon number of ˜30); and, one or two or more of the above-mentioned organic groups are substituted with i element. Radicals derived from hydrogen atoms.

Among these, an alkyl group having a carbon number of 30 and a fluoroalkyl group having a carbon number of 1 to 4 are preferable: Among the groups represented by the above formula (IV), the following formulae (IV-1) to (IV-4).

(IV-1)

c7h15

(IV-3) (IV-2)

In the above formula (1), when B1 is a single bond, -0-, or -N (H)-, a is 1 and B1 is

One N

Phen 'a is 2 Similarly, when B2 is a single bond or -N (H)-in the above formula (II), b is 1 and B2 is /

At N times; b is 2. Specific examples of the specific diamine compound represented by, v 弋 _ (ι) include:

〇: V87 \ 8706 l.DOC -12-200413441 methyl cholic acid (3,5-diaminobenzoate), ethyl lithocholic acid (3,5-diaminobenzoate), stone Cholic acid propyl (3,5-diaminobenzoate), lithocholic acid butyl (3,5-diaminobenzoate), pentyl lithocholic acid (3,5-diamine) Benzoate), hexyl lithocholic acid (3,5-diamino benzoate), cyclohexyl lithocholic acid (3,5-diamino benzoate), cetyl lithocholic acid (3,5-diaminobenzoate), lithocholic acid heptadyl group (3,5-diaminobenzoic acid), octadecyl lithocholic acid (3,5-diamine group) Benzoate), phenyl lithocholic acid (3,5-diaminobenzoate), benzyl lithocholic acid (3,5-diaminobenzoate), trifluoro lithocholic acid Formaldehyde (3,5-diaminobenzoate), lithocholic acid (2,2,2-trifluoroethyl) (3,5-diaminobenzoate), lithocholic acid (1 , 1,2,2,2-pentafluoroethyl) (3,5-diaminobenzoate), lithocholic acid (4-fluorophenyl) (3,5-diaminobenzoate) ), Lithocholic acid (4- (trifluoromethyl) phenyl) (3,5-diaminobenzoate), lithocholic acid 4- (4-pentylcyclohexyl) phenyl) (3,5-diaminobenzoate), lithocholic acid (4- (4-heptylcyclohexyl) phenyl) (3,5-di Aminobenzoate); N-methylcarboxamide (3,5-diaminobenzoate), N-ethylcarboxamine (3,5-diaminobenzoate) , N, N-Dimethylstilbamine (3,5-diaminobenzoate), N, N-Diethylstilbamine (3,5-diaminobenzoate), N-propylcarboxamide (3,5-diaminobenzoate), N-butylcarboxamine (3,5-diaminobenzoate), N-pentylcarboxamine ( 3,5-diaminobenzoate), 1 hexylcholineamine (3,5-diaminobenzoate), 1 ^ cyclohexylcholineamine (3,5-diaminobenzene) Formate), N-hexadecylcarboxamidine (3,5-diaminobenzoate), N-heptadecanylcarboxamide (3,5-diaminobenzoate) , N-octadecylcarboxamidine (3,5-diaminobenzoate), N-phenylcarboxamidine (3 &gt; 5-diaminobenzoate), N-methyl- N-phenylcarboxamidine 〇A87 \ .87061.DOC -13-200413441 (3,5-diaminobenzoate), N-benzyl cholestyramine (3,5-diaminobenzoic acid vinegar), 1 ^ -trimethylol cholestyramine (3,5-diaminobenzoic acid | Purpose), meaning (2 , 2,2-trifluoroethyl) cholestyramine (3,5-diaminobenzylate), N- (l, 1,2,2,2-pentafluoroethyl) cholestyramine (3,5-diaminobenzoate), N- (4- (trifluoromethyl) phenyl) lithochoramine (3,5-diaminobenzoate), N- (4 -(4-pentylcyclohexyl) phenyl) cholestyramine (3,5-diaminobenzoate), N- (4- (4-heptylcyclohexyl) phenyl) lithochoramine (3,5-diaminobenzylformate); '3 (2,4-diaminophenoxy) choline-24-acid methyl ester, 3 (2,4-diaminophenoxy) Cholan-24-acid ethyl ester, 3 (2,4-diaminophenoxy) cholan-24-acid propyl ester, 3 (2,4-diaminophenoxy) cholan-24-acid Butyl ester, 3 (2,4-diaminophenoxy) bile burn -24-pentyl acetate, 3 (2,4-diaminophenoxy) bile burn 24-g acid, 3 ( 2,4-diaminophenoxy) cholan-24-acid cyclohexyl ester, 3 (2,4-diaminophenoxy) cholan-24-acid hexadecyl ester, 3 (2,4 -Diaminophenoxy) choline-24-acyl heptadecanoate, 3 (2,4-diamine Phenylphenoxy) chole-24-octadecanoate, 3 (2,4-diaminophenoxy) choline-24_ acid phenyl ester, 3 (2,4-diaminophenoxy Group) choline-24-acid benzyl ester, 3 (2,4-diaminophenoxy) choline-24-acid trifluoromethyl ester, 3 (2,4-diaminophenoxy ) Cholan-24-acid (2,2,2-trifluoroethyl) ester, 3 (2,4-diaminophenoxy) cholan-24-acid (1,2,2,2-tetra Fluoroethyl) S, 3 (2,4-diaminophenoxy) choline-24-acid (1,1,2,2,2-pentafluoroethyl), 3 (2,4 -Diaminophenoxy) cholan-24-acid (4-fluorophenyl) vinegar, 3 (2,4-diaminophenoxy) cholan-24-acid (4- (trifluoromethyl) ) Phenyl) g, 3 (2,4-diaminophenoxy) choline-24-acid (4- (4-pentylcyclohexyl) phenyl) §, 3 (2,4-di Aminobenzyloxy) cholan-24-acid (4- (4-heptylcyclohexyl) phenyl) ester; O: \ 87v.37061.DOC -14- 200413441 N-fluorenyl-3 (2,4 -Diaminophenoxy) choline-24-amidamine, N-ethyl-3 (2,4-diaminophenoxy) choline-24-amidamine, N, N-dimethyl- 3 (2,4-diaminophenoxy) bile burner-24-¾ &amp; amine, N, N-diethyl-3 (2,4-diaminophenoxy) ) Cholesterol-24-amidamine, N-propyl-3 (2,4-diaminophenoxy) choline-24-amidamine, N-butyl-3 (2,4-diaminobenzene (Oxy) choline-24-amidamine, N-pentyl-3 (2,4-diaminophenoxy) choline-24-amidamine, N-hexyl-3 (2,4-diamine Phenoxy) choline-24-amidamine, N-cyclohexyl-3 (2,4-diaminophenoxy) choline-24-amidamine, N-hexadecyl-3 (2,4 -Diaminophenoxy) choline-24-amidamine, N-heptadecan-3 (2,4-diaminophenoxy) choline-24-amidamine, N-octadecyl -3 (2,4-diaminophenoxy) choline-24-amidamine, N-phenyl-3 (2,4-diaminophenoxy) choline-24-amidamine, N- Benzyl-3 (2,4-diaminobenzyloxy) cholane-24-amidamine, N-trifluoromethyl-3 (2,4-diaminophenoxy) cholane-24- Amidoamine, N- (2,2,2-trifluoroethyl) -3 (2,4-diaminophenoxy) choline-24-amidamine, (N_ (2,2,2-trifluoro Ethyl) -3 (2,4-diaminophenoxy) choline-24-amidamine), 1 (1,1,2,2,2-pentafluoroethyl) -3 (2,4- Diaminophenoxy) choline-24-amidamine, N- (4-fluorophenyl) -3 (2,4-diaminophenoxy) choline-24-amidamine, N- (4 -(Trifluorofluorenyl) phenyl) -3 (2,4- Diaminophenoxy) choline-24-amidamine, N- (4- (4-pentylcyclohexyl) phenyl) -3 (2,4-diaminophenoxy) choline-24- Ammonium amine, N- (4- (4-heptylcyclohexyl) phenyl) -3 (2,4-diaminophenoxy) bile burner-24-fermenting amine. Of these, methyl lithocholic acid (3,5-diaminobenzoate), ethyl lithocholic acid (3,5-diaminobenzoate), and propyl lithocholic acid ( 3,5-diaminobenzoate), butyl lithocholic acid (3,5-diaminobenzoate), pentyl lithocholic acid (3,5-diaminobenzoate), Hexyl lithocholic acid (3,5-diamino benzoate), stone bile O: \ 87 \ 87061.DOC -15-200413441 cyclohexyl acid (3,5-diamino benzoate), stone Hexadecanyl cholic acid (3,5-diaminobenzoate), Heptadecyl lithocholic acid (3,5-diaminobenzoate), Octadecyl lithocholic acid (3 , 5-diaminobenzoate), trifluoromethyl lithocholic acid (3,5-diaminobenzoate), lithocholic acid (2,2,2-trifluoroethyl) (3 , 5-diaminobenzoic acid), lithocholic acid (1,1,2,2,2-pentafluoroethyl) (3,5-diaminobenzoate), lithocholic acid (4- (4-pentylcyclohexyl) phenyl) (3,5-diaminobenzoate), lithocholic acid (4- (4-heptylcyclohexyl) phenyl) (3,5-diamino) Benzoate); 3 (2,4-diaminophenoxy) choline_2 methyl acid, 3 (2,4-di Aminophenoxy_) Choline-24-acid ethyl ester, 3 (2,4-diaminophenoxy) choline-24-acid propyl ester, 3 (2,4-diaminophenoxy ) Choline-24-acid butyl ester, 3 (2,4-diaminophenoxy) Choline-24-acyl pentyl ester, 3 (2,4-diaminophenoxy) choline-24- Hexyl acid ester, 3 (2,4-diaminophenoxy) cholane-24-acid cyclohexyl ester, 3 (2,4-diaminophenoxy) cholane-24-acid hexadecyl ester , 3 (2,4-diaminophenoxy) cholan-24-acid octadecyl ester, 3 (2,4-diaminophenoxy) cholan-24-acid trifluorofluorenyl ester, 3 (2,4-diaminophenoxy) choline-24-acid (2,2,2-trifluoroethyl) S, 3 (2,4-diaminophenoxy) choline- 24-acid (1,2,2,2-tetrafluoroethyl) g, 3 (2,4-diaminophenoxy) cholan-24-acid (1,1,2,2,2- Pentafluoroethyl) §, 3 (2,4-diaminophenoxy) cholan-24-acid (4- (4-pentylcyclohexyl) phenyl) ester, 3 (2,4-di Aminophenoxy) choline-24-acid (4- (4-heptylcyclohexyl) phenyl) i; especially butyllithocholic acid (3,5-diaminobenzoate) , Ammonium lithocholic acid (3,5-diaminophenylbenzoate), hexyl lithocholic acid (3,5-diaminobenzene) Acid esters), cyclohexyl lithocholic acid (3,5-diaminobenzoate), cetyl lithocholic acid (3,5-diaminobenzylate), heptadecyl lithocholic acid (3,5-diaminophenylbenzoate), octadecyl lithocholic acid (3,5-diaminobenzoate), trifluoromethyl lithocholic acid (3,5-diamine Benzoic acid

Ο :, '8 · Λ87061.DOC -16- 200413441 酉)' gallstone g ^ (2,2,2-diratethyl) (3,5-diaminophenylbenzoic acid g), stone gall Acid (1,1,2,2,2-pentafluoroethyl) (3,5-diaminobenzoate), lithocholic acid (4-('pentylcyclohexyl) phenyl) (3, 5-diaminobenzoate), lithocholic acid (4- (4-heptylcyclohexyl) phenyl) (3,5-diaminobenzate). Specific examples of the specific diamine compound represented by the above (II) include deoxycholic acid methyl (bis (4-aminobenzoate)) and ethyl deoxycholate (Bis (4-aminobenzoate)), propyldeoxycholate (bis (4-aminobenzoate)), butyldeoxycholate (bis (4-aminobenzoate) Ester)), amyl deoxycholate (bis (4-aminobenzoate)), hexyl deoxycholate (bis (4-aminobenzoate)), cyclohexyl deoxycholate ( Bis (4-aminobenzoate)), cetyl deoxycholate (bis (4-aminobenzoate)), heptadecyl deoxycholate (4-amino Benzoate)), octadecyl deoxycholate (bis (4-aminobenzoate)), phenyl deoxycholate (bis (4-aminobenzoate)), Benzyloxycholate (bis (4-aminobenzoate)), trifluoromethyl deoxycholate (bis (4-aminobenzoate)), deoxycholate (2,2 , 2-trifluoroethyl) (bis (4-aminophenylbenzoate)), deoxycholic acid (1,1,2,2,2-pentafluoroethyl) (bis (4-aminobenzene) Phosphonate)) , Deoxycholic acid (4-fluorophenyl) (bis (4-aminophenylbenzoate)), Deoxycholic acid (4- (trifluoromethyl) phenyl) (bis (4-aminophenyl) Formate)), deoxycholic acid (4- (4-pentylcyclohexyl) phenyl) (bis (4-aminobenzoate)), deoxycholic acid (4- (4-heptyl) Cyclohexyl) phenyl) (bis (4-aminobenzoate)); N-methyldeoxycholamine (bis (4-aminobenzoate)), N-ethyldeoxycholate Amidoamine (bis (4-aminobenzoate)), N, N-dimethyldeoxycholamine (bis (4-aminobenzoate)), N, N-diethyl Oxycholamine (bis (4-aminobenzoate)), N-propyldeoxycholamine (bis (4-aminobenzoate)), N-butyldeoxybenzidine 200413441 Amine (bis (4-aminobenzoate)), N-pentyldeoxycholic acid amine (bis (4-aminobenzoic acid)), N-hexyldeoxycholic acid amine (bis (4 (4) _Aminobenzoic acid esters)), N-cyclohexyldeoxycholic acid amine (bis (4-aminobenzyl acetic acid vinegar)), hexadecyldeoxycholic acid amine (bis (4-aminophenylbenzene) Formic acid vinegar)), N-seven burned deoxycholate (Bis (4-aminobenzoate)), N-octadecyldeoxycholamide (bis (4-aminobenzoate)), N-phenyldeoxycholamine (bis (4-Aminobenzoic acid)), N-fluorenyl-N-phenyldeoxycholic acid amine (bis (4-aminophenylbenzoic acid g)), N-benzyldeoxycholic acid Amine (bis (4-aminobenzoate)), N-trifluoromethyldeoxycholamine (bis (4-aminobenzoate)), N- (2,2,2-tris Fluoroethyl) Deoxycholamide (bis (4-aminophenylbenzoate)), N- (l, 1,2,2,2-pentafluoroethyl) deoxycholamine (bis (4 -Aminobenzoate)), N- (4-fluorophenyl) deoxycholamine (bis (4-aminobenzoate)), N- (4- (trifluorofluorenyl) benzene Group) deoxycholamide (bis (4-aminobenzoate)), N- (4- (4-pentylcyclohexyl) phenyl) deoxycholamide (bis (4-aminophenylphenyl) Acid ester)), N_ (4- (4-heptylcyclohexyl) phenyl) deoxycholamine (bis (4-aminophenylbenzoate); deoxycholate (bis (3-amino) Benzoate)), ethyl deoxycholate (bis (3-aminobenzoate)), propyl deoxycholate (bis 3-aminobenzoate)), butyldeoxycholate (bis (3-aminobenzyl)), amyl deoxycholate (bis (3-aminobenzoate)) , Hexyl deoxycholate (bis (3-aminobenzoate)), cyclohexyl deoxycholate (bis (3-aminobenzoate)), cetyl deoxycholate (bis (3-Aminobenzoate)), Heptadecyl Deoxycholate (Crystalline Benzoate)), Octadecyl Deoxycholate (bis (3-Aminobenzoate) )), Deoxycholate Phenyl (bis (3-aminobenzoate)), Deoxycholate Phenyl (bis (3-aminobenzoate)), Deoxycholate trifluoro Methyl (bis (3-aminobenzoate)), deoxygenation 0: -87 ^ 87061.000 -18-200413441 Cholic acid (2,2,2-trifluoroethyl) (bis (3-aminobenzene) Formic acid vinegar)), deoxycholic acid (1,1,2,2,2-pentafluoroethyl) (bis (3-aminobenzoate)), deoxycholic acid (4, fluorophenyl) (Bis (3-aminobenzoate)), deoxycholic acid (4- (trifluoromethyl) benzyl) (bis (3-aminobenzoate)); N-methyldeoxy Choline (bis (3-amino Phenylacetate)), N-ethyldeoxycholestyramine (bis (3-aminophenylbenzoate)), N, N-Difluorenyldeoxycholamine (bis (3-aminophenylbenzene) Formate)), N, N-diethyldeoxycholamide (bis (3-aminophenylbenzoate)), N-propyldeoxycholamine (bis (3-aminobenzyl) Esters)), N-butyldeoxycholestyramine (bis (3-aminobenzoate)), N-pentyldeoxycholestyramine (bis (3-aminobenzoate)), N-hexyldeoxycholamine (bis (3-aminobenzoate)), N-cyclohexyldeoxycholamine (bis (3-aminobenzoate)), N-hexadecane Deoxycholestyramine (bis (3-aminophenylbenzoate)), N-heptadecane decholcholamine (bis (3-aminobenzoate)), N-octadecane Deoxycholestyramine (bis (3-aminophenylbenzoate)), N-phenyldeoxycholamine (bis (3-aminobenzoate)), N-methyl-N- Phenyldeoxycholamine (bis (3-aminophenylbenzoate)), N-benzylmethyldeoxycholamine (bis (3-aminophenylbenzoate)), N-trifluorofluorene Deoxycholinamine (bis (3-aminobenzoate)), N- (2,2,2-trifluoroethyl) deoxycholamide (bis (3-aminobenzoate)), N- (l, 1,2,2,2-pentafluoroethyl ) Deoxycholamide (bis (3-aminophenylbenzoate)), N- (4-fluorophenyl) deoxycholamine (bisaminobenzoate)), N- (4- (Trifluoromethyl) phenyl) deoxycholamide (bis (3-aminobenzoate)), N- (4- (4-pentylcyclohexyl) phenyl) deoxycholamine (bis (3-aminophenylbenzoate)), N- (4- (4-heptylcyclohexyl) phenyl) deoxycholamine (bis (3-aminobenzoate)); chenodeoxy Cholic acid-methyl (bis (4-aminobenzoate)), ethyl chenodeoxycholate (bis0: '. 87 \ 87061.DOC -19- 200413441 (4-aminobenzoate )), Chenodeoxypropyl (bis (4-aminobenzoic acid 3)), Chenodeoxybutyl (bis (4-aminobenzoate)), Chenodeoxycholic acid Amyl (bis (4-aminobenzoate)), hexyl chenodeoxycholate (bis (4-aminobenzyl ester)), cyclohexyl chenodeoxycholate (bisaminobenzoic acid) Esters)), cetyl chenodeoxycholate (bis (4-aminobenzoate) , Hepadeoxycholic acid heptadecyl (cream (4-aminobenzoate)), Chenodeoxycholic acid octadecyl (bis (4-aminobenzoate)), chenodeoxy Phenylcholine (bis (4-aminobenzoate)), benzyl chenodeoxycholate (bis (4-aminobenzoate)), trifluoromethyl cheodeoxycholate ( Bis (4-aminobenzoate)), chenodeoxycholic acid (2,2,2-trifluoroethyl) (bis ('aminophenylbenzoate)), chenodeoxycholic acid (丨丄 ^ Pentafluoroethyl) (bis (4-aminobenzoate)), chenodeoxycholic acid (4-fluorophenyl) (bis ('aminophenylbenzoate)), trioxane Cholic acid (4- (trifluorofluorenyl) phenyl) (bis (4-aminobenzoate)), chenodeoxycholic acid (4- (4-pentylcyclohexyl) phenyl) (bis ( 4-aminobenzoic acid §)), chenodeoxycholic acid (4- (4-heptylcyclohexyl) phenyl) (bis (4-aminobenzoate)); N-methyl chelate Oxycholamine (bis (4-aminobenzoate)), N-ethyl chenodeoxycholamine (bis (4-aminobenzoate)), N, N-dimethyl goose Deoxycholamide (bis (4-amino Formate N, N-diethylchoridoxamine (bis (cardioaminophenylbenzyl ester)), N-propyl chenodeoxycholamine (bis (4-aminobenzylate) )), N-Butyldeoxycholestamine (bis (4-aminophenylbenzoate)), Amylchoodeoxycholamine (bis (4-aminophenylbenzoate)), N- Hexyl chenodeoxycholamine (bis (4-aminobenzoate)), N-cyclohexyl chenodeoxycholamine (bis (4-aminophenylbenzoate)), N-hexadecane Chenodeoxycholamine (bis (4-aminophenylbenzoate)), N-heptadecanyldeoxycholcholamine (bis (4-aminobenzoate), N- + octadecyl Alkyl 0 '·' S ^ S7〇6 id〇c -20- 200413441 Chenodeoxycholamine (bis (4-aminophenylbenzoate)), phenylchoodeamine (bis (4 (4) -Aminobenzoate)), N-methylphenyl chenodeoxycholamine (bis (cardioaminobenzoate)), N-benzyl chenodeoxycholamine (diamine) Benzoic acid)), N-difluoromethyl hedeoxycholic acid amine (bis (4-aminobenzylformate)), N- (2,2,2-difluoroethyl) chenodeoxy Cholestyramine (bis (4-aminobenzoate)), N- ( l, 1,2,2,2-pentafluoroethyl) hedeoxycholamine (bis (4-aminobenzoate)), N- (4-fluorophenyl) chenodeoxycholamine (Bisaminobenzoate, N- (4- (trifluoromethyl) phenyl) chenodeoxycholamine (bisamidobenzoate)), N- (4- (4-pentyl Cyclohexyl) phenyl) chenodeoxycholamine (bis (4-aminophenylphenylacetate)), N- (4- (4-heptylcyclohexyl) phenyl) chenodeoxycholamine (bis (4-Aminobenzoate)); Cysteoxycholate (bis (3-aminobenzoate)), Chenodeoxycholic acid ethyl (bis (3-aminobenzoate) )), Chenodeoxypropyl (diaminobenzoic acid)), Chenodeoxybutyl (bis (3-aminobenzoate)), Amyl chenodeoxycholate (Bis (3-aminobenzoate)), hexylcholate (diaminobenzyl)), cyclohexyl chelate (bis (3-aminobenzoate)) ), Hexadeoxycholic acid cetyl (bis (3-aminobenzoic acid § intent)), hepoxycholic acid heptadecyl (cream (3-aminobenzoate)), goose Octadecyl deoxycholate (bis (3-Aminobenzoate)), phenyl chenodeoxycholate (bis (3-aminobenzoate)), benzyl cheodeoxycholate (bis (3-aminobenzoate) Acid ester)), chenodeoxycholic acid trifluorofluorenyl (bis (3-aminobenzoate)), cheldeoxycholic acid (2,2,2-trifluoroethyl) (bis (3 · Amino stearic acid ester)), chenodeoxycholic acid (1,1,2,2,2-pentafluoroethyl) (bis (3-aminobenzoate)), chenodeoxycholic acid ( 4-fluorophenyl) (bis (3-aminobenzoate)), chenodeoxycholic acid (4- (trifluoromethyl) phenyl) (bis (3-aminobenzoic acid O: \ 87 \ 8706I.DOC -21-200413441)), chenodeoxycholic acid (4- (4-pentylcyclohexyl) phenyl) (bis (3-aminobenzylcarboxylic acid _)) hedeoxycholic acid ( 4- (4-heptylcyclohexyl) phenyl) (bis (3-aminophenylbenzoate)); N-methyl chenodeoxycholamine (bis (3-aminobenzoate)) , N-ethyl chenodeoxycholamine (bis (3-aminophenylbenzoate)), N, N-dimethyl chenodeoxycholamine (bis (3-aminobenzylate)) ), N, N-diethyl chenodeoxycholamine (bis (3-amine Formate)), N-propyl chenodeoxycholamine (bis (3-aminobenzoate)), N-butyl chenodeoxycholamine (bis (3-aminobenzoate) Ester)), N-pentyl chenodeoxyamine bis (3- (aminoaminobenzoate)), N-hexyl chenodeoxycholamine (bis (3-aminobenzoate)) ), N-cyclohexyl chenodeoxycholamine (bis (3-aminobenzoic acid S)), N-hexadecyl chenodeoxycholamine (bis (3-aminophenylbenzoate) ), N-Heptadecanylcholinecholamine (bis (3-aminophenylbenzoate)), N-octadecylcholineamine (bis (3-aminophenylbenzoate) (Ester)), N-phenyl chenodeoxycholamine (bis (3-aminobenzoate)), N-fluorenyl-N-phenyl chenodeoxycholamine (bis (3-amino) Benzoate)), N-benzylmethyl chenodeoxycholamine (bis (3-aminobenzoate)), N-trifluoromethyl chenodeoxycholamine (bis (3-amine Phenylbenzoate vinegar)), N- (2,2,2-trifluoroethyl) chenodeoxycholamine (bis (3-aminobenzoate)), N- (l, l, 2 , 2,2-pentafluoroethyl) chenodeoxycholamine (bis (3-aminobenzoate) N- (4-fluorophenyl) chenodeoxycholamine (bis (3-aminobenzoate)), N- (4- (trifluoromethyl) phenyl) chenodeoxycholamine (Bis (3-aminobenzoate)), N- (4- (4-pentylcyclohexyl) phenyl) chenodeoxycholamine (bis (3-aminobenzoate)), N- (4- (4-heptylcyclohexyl) phenyl) chenodeoxycholamine (bis (3-aminobenzoate)); deoxy (desoxyO cholic acid methyl (bis (4-amino) Benzoate)), ethyl deoxycholate O: \ 87 \ 87061.DOC -22- 200413441 (bis (4-aminobenzoate)), propyl deoxycholate (bis (4-amino Benzoic acid)), butyl deoxycholate (bis (4-aminobenzoic acid g)), pentyl deoxycholate (bis (4-aminobenzoate)), hexyl deoxycholate ( Bis (4-aminobenzoate)), cyclohexyl deoxycholate (bis (4-aminobenzoate)), cetyl deoxycholate (bis (4-aminobenzoate) )), Heptadecyl deoxycholate (cream (4-aminobenzoate)), Octadecyl deoxycholate (bis (4-aminobenzoate), Phenyl deoxycholate ( (4-aminobenzoate)), benzyl deoxycholate (bis (4-aminobenzoate)), trifluoroamido deoxycholate (bis (4-aminobenzoate) )), Deoxycholic acid (2,2,2-trifluoroethyl) (bis (4-aminobenzoate)), deoxycholic acid (1,1,2,2,2-pentafluoroethyl) ) (Bis (4-aminobenzoate)), deoxycholic acid (4-fluorobenzyl) (bis (4-aminobenzoate)), deoxycholic acid (4- (trifluorofluorenyl) ) Phenyl) (bis (4-aminobenzyl ester)), deoxycholic acid (4- (4-pentylcyclohexyl) phenyl) (bis (4-aminobenzyl ester)), deoxy Cholic acid (4- (4-heptylcyclohexyl) phenyl) (bis (4-aminophenylbenzoate)); N-fluorenyldeoxycholamine (bis (4-aminobenzoate)) ), N-ethyldeoxycholamine (bis (4-aminobenzylate)), N, N-diamidodeoxycholamine (bis (4-aminophenylbenzoate S))), N, N -diethyldeoxycholic acid amine (bis (4-aminobenzoate)), N-propyldeoxycholic acid amine (bis (4-aminophenylbenzoate)), N-butyl Deoxycholamidamine (bis (4-amino Formate)), N-pentyldeoxycholic acid amine (bis (4-aminophenylbenzoate)), N-hexyldeoxycholic acid amine (bis (cardioaminobenzoate)), N- Cyclohexyl deoxycholamine (bis (4-aminophenylbenzoate)), N-hexadecyldeoxycholamine (bis (4-aminophenylbenzoate)), N-heptadecan deoxy Cholesterol (Bis (4-Aminophenylbenzoate)), N-octadecyldeoxycholic acid (bis (4-Aminophenylbenzoate · ester)), N-phenyldeoxycholic acid Amine (bis (cardioaminobenzyl acid Λ 87N8706 丨 .DOC -23-200413441 ester)), N-methyl-N-phenyldeoxycholamine (bis (4-aminobenzoate)), N -Benzyldeoxycholamine (bis (4-aminobenzoate)), N-trifluoromethyldeoxycholamine (bis (4-aminobenzoate)), N- (2 , 2,2-trifluoroethyl) deoxycholamine (bis (4-aminobenzoate)), N- (l, 1,2,2,2-pentafluoroethyl) deoxycholamine (Bis (4-aminobenzoate)), N- (4-fluorophenyl) deoxycholamine (bis (4-aminophenylbenzoate)), N- (4- (trifluoromethyl) ) Phenyl) deoxycholamide ( (4-aminobenzoate)), N- (4- (4-pentylcyclohexyl) phenyl) deoxycholamine (bis (4-aminobenzoate)), N- (4 -(4-heptylcyclohexyl) phenyl) deoxycholamine (bis (4-aminobenzoate)); methyl deoxycholate (bis (3-aminobenzoate)), deoxy Ethyl cholic acid (bis (3-aminobenzoate)), propyl deoxycholate (bis (3-aminobenzoate)), butyl deoxycholate (bis (3-aminobenzoate) Formate)), amyl deoxycholate (bis (3-aminophenylbenzoate)), hexyl deoxycholate (bis (3-aminophenylbenzoate)), cyclohexyl deoxycholate (bis (3-aminobenzoate)), cetyl deoxycholate (bis (3-aminobenzoate)), heptadecyl deoxycholate (cream (3-aminobenzoic acid) Ester)), deoxycholic acid stearyl (bis (3-aminobenzoate)), deoxycholic acid phenyl (bis (3-aminobenzoate)), deoxycholic acid phenylfluorenyl (Bis (3-aminobenzoate)), trifluoromethyl deoxycholate (bis (3-aminobenzoate)), deoxycholic acid (2,2,2-trifluoro (Bis (3-aminobenzoate)), deoxycholic acid (1,1,2,2,2-pentafluoroethyl) (bis (3-aminobenzoic acid g)), deoxy Cholic acid (4-fluorophenyl) (bis (3-aminobenzoate)), deoxycholic acid (4- (trifluorofluorenyl) phenyl) (bis (3-aminobenzoate) ), Deoxycholic acid (4- (4-pentylcyclohexyl) phenyl) (bis (3-aminobenzoate)), deoxycholic acid (4- (4-heptylcyclohexyl) phenyl) (Bis (3-aminophenylbenzoate)); 0. ^ 8787061.DOC -24-200413441 N-methyldeoxycholamine (bis (3-aminobenzoate)), N-ethyl Deoxycholate (bis (3-aminobenzoate)), N, N-dimethyldeoxycholamine (bis (3-aminobenzoate)), N, N-diethyl Deoxycholamide (bis (3-aminobenzoate)), N-propyldeoxycholamine (bis (3-aminobenzoate)), N-butyldeoxycholamine (bis (3-Aminobenzoate)), N-pentyldeoxycholamine (bis (3-aminobenzoate)), N-hexyldeoxycholamine (bis (3-aminobenzoate) Acid ester)), N-cyclohexyl Oxycholamine (bis (3-aminobenzoate)), N-hexadecyldeoxycholamine (bis (3-aminobenzoate)), N-heptadecan deoxycholate Amidoamine (bis (3-aminobenzoate)), N-octadecyldeoxycholamine (bis (3-aminobenzoate)), N-phenyldeoxycholamine (bis (3-Aminobenzoate)), N-methyl-N-phenyldeoxycholamine (bis (3-aminobenzoate)), N-benzyldeoxycholamine (bis (3-Aminophenylbenzoate)), N-trifluoromethyldeoxycholamine (bis (3-aminobenzoate)), N- (2,2,2-trifluoroethyl) Deoxycholamine (bis (3-aminobenzoate)), &gt; ^ (1,1,2,2,2-pentafluoroethyl) deoxycholamine (bis (3-aminobenzyl) Acid esters)), N- (4-fluorobenzyl) deoxycholamine (bis (3-aminophenylphenyl)), N- (4- (trifluoromethyl) phenyl) deoxycholamine (Bis (3-aminobenzoate)), N- (4- (4-pentylcyclohexyl) phenyl) deoxycholamine (bis (3-aminophenylbenzoate)), N- (4- (4-heptylcyclohexyl) phenyl) deoxycholamine (bis (3-aminophenylbenzoic acid) Esters)); cysoxycholate (bis (4-aminophenylbenzoate)), ethyl chlooxycholate (bis (4-aminophenylbenzoate)), cholestyrylcholine Propyl (bis (4-aminobenzyl ester)), butyldeoxycholate (bis (4-aminobenzoate)), pentylcholodeoxycholate (bis (4- Aminobenzoate)), Hexylchododeoxycholate (diaminobenzylformate)), Cyclohexyl hyodeoxycholate (bis (4-aminobenzylformate)) 'Iguano : \ 87 \ 8706l.DOC -25, 200413441 Hexadecyl oxycholate (bis (4-aminobenzoate, hepoxydeoxycholate heptadecyl (cream) (4-aminobenzoate )), Hogodeoxycholic acid stearyl (bis ('aminobenzoate)), Hogodeoxycholic acid phenyl (bis (4-aminobenzoate, phenyldeoxycholate) Methyl (bis (4-aminobenzoate)), trifluoromethyl chodooxycholate (bis (4-aminobenzoate)), hyodeoxycholic acid (2,2, 孓Trifluoroethyl) (bis (cardioaminobenzoate)), hyodeoxycholic acid (1, 丨, 2,2,2-pentafluoroethyl) (bis (4-aminobenzoate) )) Hododeoxycholic acid (4-fluorophenyl) (bis (4-aminobenzoic acid)), Hododeoxycholic acid (4- (trifluoromethyl) phenyl) (bis (4-amino) Benzoic acid vinegar)), hyodeoxycholic acid (4- (4-pentylcyclohexyl) phenyl) (bis (4-aminobenzoate)), hyodeoxycholic acid (4- (4- Heptylcyclohexyl) phenyl) (bis (4-aminobenzoate)); N-fluorenylchododeoxycholamine (bis (4-aminobenzoate)), N-ethyl Hododeoxycholamine (bis (4-aminobenzoic acid ester)), N, N-difluorenyl choridoamine (bis (4-aminobenzoic acid ester)), N, N -Diethylchodrocholamine (bis (4-aminobenzoate)), N-propylchodrocholamine (bis (4-aminobenzoate)), N- Butyl myodeoxycholamine (bis (4-aminophenylbenzoate)), N-pentylchoodeoxyamine (bis (4-aminobenzoate)), N-hexyl pig Deoxycholestyramine (bis (4-aminobenzylate)), N-cyclohexylchondrioxamine (bis (4-aminophenylbenzoate)), N-hexadecyl pig Deoxycholamine (bis (4-aminophenyl benzoate) ), N-heptadecanylcholinecholamine (bis (4-aminobenzoate)), N-octadecylcholoxycholamine (bis (4-aminophenylbenzoate) (Ester)), N-benzylchododeoxycholamine (bis (4-aminophenylbenzoate)), N-fluorenyl-N-phenylchododeoxycholamine (bis (4-amino) Benzamate)), N-benzylchododeoxycholamine (bis (4-aminophenylbenzoate)), N-triaminomethyl-cholestyramine (bis (4-amine Phenylbenzoate)), O: \-87 \ 8706l.DOC -26- 200413441 N- (2,2,2-difluoroethyl) myodeoxycholamine (bis (4-aminobenzyl) Acid ester)), N- (l, 1,2,2,2-pentafluoroethyl) myodeoxycholamine (bis (cardioaminobenzoic acid S)), N- (4-fluorophenyl ) Hododeoxycholamine (Bis (4-Aminobenzoate)), N- (4- (difluorofyl) phenyl) Hododeoxycholamine (Bis (4-Aminobenzoate) Acid ester)), N- (4- (4-pentylcyclohexyl) phenyl) myodeoxycholamide (diaminobenzoate)), N- (4- (4-heptylcyclohexyl) Phenyl) chododeoxycholamine (bis (4-aminobenzoate)); Methyldeoxycholate (bis (3-amine Benzoate)), ethyl hyodeoxycholate (3-aminobenzoate)), propyl hyodeoxycholate (bis (3-aminobenzoate)), hyodeoxycholate Acid butyl (bis (3-aminobenzoate), amyl hyodeoxycholate (bis (3-aminobenzoate), hexyl hyodeoxycholate (bis (3-aminobenzoic acid) Vinegar)), cyclohexyl hyodeoxycholate (bis (3-aminobenzoate)), cetyl hyodeoxycholate (bis (3-aminobenzoate)), and Heptadecyl oxycholate (box (3-amine basic formic acid g)), Octadecyl hyodeoxycholate (bisamino benzoate)), Phenyl hyodeoxycholate (bis ( 3-Aminobenzylate)), benzylcholodeoxycholate (bis (3-aminobenzoate)), Trifluoromethylchodeoxycholate (bis (3-aminobenzyl) Formate)), Hododeoxycholic acid (2,2,2_trifluoroethyl) (Bis (3 · Aminobenzylformate)), Hododeoxycholic acid (1,1,2,2 , 2-pentafluoroethyl) (bis (3-aminobenzoate)), hyodeoxycholic acid (4-fluorophenyl) (bis (3-aminobenzoate)), pork Oxycholic acid 4- (trifluoromethyl) phenyl) (bis (3-aminobenzoic acid)), hyodeoxycholic acid (4- (4-pentylcyclohexyl) phenyl) (bis (3-amine Benzoate)), hyodeoxycholic acid (4- (4-heptylcyclohexyl) phenyl) (bis (3-aminobenzoate)); N-methyl pig deoxycholate Amine (bis (3-aminobenzoic acid g)), N-ethyl pig deoxy O: \ S7 \ 8706l.DOC -27- 200413441 Choline (bis (3-aminobenzoate)) , N, N-Dimethylchododeoxycholamine (bis (3-aminobenzylformate)), N, N-Diethylchodeoxycholamine (bis (3-aminobenzyl) Acid esters)), N-propyl hododeoxycholamine (bis (3-aminobenzoate)), N-butyl hododeoxycholamine (bis (3-aminobenzoate) )), N-pentylchododeoxycholamine (bis (3-aminobenzoate)), N-hexylchododeoxycholamine (bis (3-aminobenzoate)), N-cyclohexylchododeoxycholamine (bis (3-aminobenzoate)), N-hexadecylcholodeoxycholamine (bis (3-aminobenzoate)), N-heptadecane cholinecholamine (bis (3-amine (Formate)), N-octadecyl-l-choletamine (bis (3-aminobenzoate)), N-phenyl-choletamine (bis (3-aminobenzene) Formate)), N-methyl-N-phenylchododeoxycholamine (bis (3-aminophenylbenzoate)), N-benzylchododeoxycholamine (bis (3 -Aminobenzoic acid)), N-trifluoromethylchododeoxycholamine (bis (3-aminobenzoate)), N- (2,2,2-trifluoroethyl) pig Deoxycholestyramine (bis (3-aminobenzoate)), N- (U, 2,2,2-pentafluoroethyl) Hododeoxycholamine (bis (3-aminobenzoate) Vinegar)), N- (4-fluorophenyl) hyodeoxycholamine (bis (3-aminobenzyl ester)), N- (4- (trifluoromethyl) phenyl) hyodeoxy Choline (bis (3-aminobenzoate)), N- (4- (4-pentylcyclohexyl) phenyl) myodeoxycholamine (bis (3-aminophenylbenzoate) )), N- (4- (4-heptylcyclohexyl) phenyl) hyodeoxycholamine (bis (3-aminophenylbenzoate; 3,6-bis (4-aminophenoxy) ) Bile burning-methyl 24-acid, 3,6-bis (4-aminophenoxy) cholan-24-acid ethyl ester, 3,6-bis (4-aminobenzene Based) choline-24-acid propionate, 3,6-bis (4-aminophenoxy) choline-24-acid butyl ester, 3,6-bis (4-aminobenzyloxy) -24-Pentyl acid, 3,6-bis (4-aminophenoxy) bile burn-24-Acid hexadecyl, 3,6-bis (4-aminophenoxy) chole-24- Cyclohexyl acid, 3,6-bis (4- 〇 :, .. 87 \ 87061-DOC -28-200413441 Aminophenoxy) choline-24-acyl hexadecyl, 3,6- Bis (4-aminophenoxy) choline-24-acid heptadecanoate, 3,6-bis (4-aminophenoxy) cholan-24-acid stearyl, 3,6- Bis (4-aminophenoxy) choline-24-acid phenyl ester, 3,6-bis (4-aminophenoxy) choline-24-acid phenylmethyl ester, 3,6-bis (4-Aminophenoxy) cholan-24-acid trifluoromethyl ester, 3,6-bis (4-aminophenoxy) cholan-24-acid (2,2,2-trifluoro Ethyl), (3,6-bis (4-aminophenoxy) choline-24-acid (2,2,2-tetrafluoroethyl) vinegar), 3,6-bis (4- Aminophenoxy) choline-24-acid (1,1,2,2,2-pentafluoroethyl) S, 3,6-bis (4-aminophenoxy) choline-24- Acid (4-fluorophenyl) S, 3,6-bis (4-aminophenoxy) choline-24-acid (4- (tri Methyl) benzyl) S, 3,6-bis (4-aminophenoxy) cholan-24-acid (4- (4-pentylcyclohexyl) phenyl) ester, 3,6-bis (4-Aminophenoxy) cholan-24-acid (4- (4-heptylcyclohexyl) phenyl) ester; fluorenyl-3,6-bis (4-aminophenoxy) bile Alkane-24-fluorenamine, &gt; Ethyl-3,6-bis (4-aminophenoxy) choline-24-fluorenamine, N, N-dimethyl-3,6-bis (4 -Aminophenoxy) choline-24-amidamine, N, N-diethyl-3,6-bis (4-aminophenoxy) bile burning-24-donkey amine, N-propyl- 3,6-bis (4-aminophenoxy) bile burner-24-osmamine, N-butyl-3,6-bis (4-aminophenoxy) bile burner- 24-feamine, N-fluorenyl-3,6-bis (4-aminobenzyloxy) cholera -24-S amine, N-hexyl-3,6-bis (4-aminebasic oxy) cholera-24- Acid amine, N-hexyl-3,6-bis (4-aminophenyllactyl) cholan-24-amidamine, N-hexadecyl-3,6-bis (4-aminophenoxy) ) Choline-24-fluorenamine, N-heptadecyl-3,6-bis (4-aminophenoxy) cholan-24-fluorenamine, N-octadecyl-3,6- Bis (4-aminophenoxy) choline-24-amidamine, N-phenyl-3,6-bis (4- Phenylphenoxy) choline-24-fluorenamine, N-benzyl-3,6-bis (4-aminophenoxy) choline-24, fluorenamine, N-trifluorofluorenyl-3, 6-bis (4-aminophenoxy) cholane O: \ 87 \ 8706l.DOC -29-200413441 -24-iiamine, N- (2,2,2-trifluoroethyl) -3,6 -Bis (4-aminophenoxy) bile burner-24-amidamine, (N- (2,2,2-tetrafluoroethyl) -3,6-bis (4-aminophenoxy) bile Alk-24-amidine) ,! ^ (1,1,2,2,2-pentafluoroethyl) -3,6-bis (4-aminophenoxy) bile burning-24-donylamine, N- (4-fluorophenyl)- 3,6-bis (4-aminophenoxy) bile burn_24_ Brewing amine, N- (4- (trifluoromethyl) phenyl) -3,6-bis (4-aminophenoxy) Cholesterol_24_ Amidine, N- (4- (4-pentylcyclohexyl) phenyl) -3,6-bis (4-aminophenoxy) choline-24-amidine, N- (4 -(4-heptylcyclohexyl) phenyl) -3,6-bis (4-aminophenoxy) cholamine-2 4-acidamine, 3.6-bis (3-aminophenoxy) cholane -24-acid methyl ester, 3,6-bis (3-aminophenoxy) cholan-24-acid ethyl ester, 3,6-bis (3-aminophenoxy) cholan-24-acid Propyl ester, 3,6-bis (3-aminophenoxy) cholan-24-acid butyl ester, 3,6-bis (3-aminophenoxy) cholan-24-acid pentyl ester, 3 , 6-Bis (3-aminophenoxy) cholan-24-acid hexyl ester, 3,6-bis (3-aminophenoxy) cholan-24-acid cyclohexyl ester, 3,6- Bis (3-aminophenoxy) cholan-24-acid hexadecyl ester, 3,6-bis (3-aminophenoxy) cholan-24-acid hexadecyl ester, 3,6- Bis (3-Aminophenoxy) choline-24-acid stearyl, 3,6-bis (3-aminophenoxy) choline-24-acid Ester, 3,6-bis (3-aminophenoxy) choline-24-acid benzyl ester, 3,6-bis (3-aminophenoxy) choline-24-acid trifluoro Fluorenyl ester, 3,6-bis (3-aminophenoxy) choline-24-acid (2,2,2-difluoroethyl) S, (3,6-bis (3-amino Phenoxy) bile burner-24-acid (2,2,2-tetrafluoroethyl) ester), 3,6-bis (3-aminophenoxy) cholan-24-acid (1,1, 2,2,2-pentafluoroethyl) vinegar, 3,6-bis (3-aminophenoxy) cholane-24-acid (4-fluorophenyl) g, 3.6-bis (3-amine (4- (trifluoromethyl) benzyl) ester, 3,6-bis (3-aminophenoxy) cholan-24-acid (4- (4 -Pentylcyclohexyl) phenyl) vinegar, 3,6-bis (3-aminophenoxy) choline-24-acid (4- (4-heptylcyclohexyl) benzene O: \ 87.8706 i.iX ) C -30- 200413441) ester); N-methyl-3,6-bis (3-aminophenoxy) choline-24-amidamine, N-ethyl-3,6-bis (3- Aminophenoxy) choline-24-amidamine, N, N-dimethyl-3,6-bis (3-amine basic oxy) bile burner-24-amine, N, N-diethyl -3,6 -bis (3-aminophenoxy) choline-24-amidamine, N-propyl-3,6- Bis (3-aminophenoxy) choline-24-amidamine, N-butyl-3,6-bis (3-aminophenoxy) choline-24-amidamine, N-pentyl- 3,6-bis (3-aminophenoxy) choline-24-amidamine, N-hexyl-3,6-bis (3-aminophenoxy) choline-24-amidamine, N- Cyclohexyl-3,6-bis (3-aminophenoxy) cholamine-24-Bromoamine, N-hexadecyl-3,6-bis (3-aminophenoxy) cholane-24 -Fluorenamine, N-heptadecanyl_3,6-bis (3-aminophenoxy) choline-24-fluorenamine, N-octadecyl-3,6-bis (3-amino Phenoxy) choline-24-fluorenamine, N-phenyl-3,6-bis (3-aminophenoxy) choline-24-fluorenamine, N-phenylfluorenyl-3,6-bis (3-Aminophenoxy) choline-24-amidamine, N-trifluoromethyl-3,6-bis (3-aminophenoxy) choline-24-amidamine, N- (2 , 2,2-trifluoroethyl) -3,6-bis (3-aminophenoxy) choline-24-amidamine, (N- (2,2,2-tetrafluoroethyl) -3 , 6-bis (3-aminophenoxy) choline-24-fluorenamine), hydrazone (1,1,2,2,2-pentafluoroethyl) _3,6-bis (3-aminobenzene (Oxy)) choline-24-amidamine, N- (4-fluorophenyl) -3,6-bis (3-aminophenoxy) choline-24-amidamine, N- (4- (tri Fluorenyl) benzyl -3,6-bis (3-aminophenoxy) choline_24_ pinamine, N- (4- (4-pentylcyclohexyl) phenyl) _3,6_bis (3-aminophenoxy Group) choline-24-amidamine, N '(4- (4-heptylcyclohexyl) phenyl) &gt; 3,6-bis (3-aminophenoxy) choline-24-acidamine. Among them, chenodeoxycholate (bis (4-aminobenzoate)), ethyl cheodeoxycholate (bis (4-aminobenzylate)), chenodeoxycholic acid Propyl (bis ('aminobenzoic acid)), butyl chenodeoxycholate (bis (4-aminobenzoate)), goose

0: '. 8 7 \ 8706l.DOC -31-200413441 Pentyl deoxycholate (bis (4-aminobenzoate)), hexyl chenodeoxycholate (bis (4-aminobenzoate) Ester)), cyclohexyl chenodeoxycholate (bis (4-aminoaminobenzoic acid S)), cetyl chenodeoxycholate (bis (4-aminophenylbenzoate)), chelate Heptadecyl oxycholate (cream (4-aminobenzoate)), octadecyl cheodeoxycholate (bis (4-aminobenzoate)), triodes Fluoromethyl (bis (4-aminobenzoate)), chenodeoxycholic acid (2,2,2-trifluoroethyl) (bis (4-aminobenzoate)), chenodeoxy Cholic acid (1,1,2,2,2-pentafluoroethyl) (bis (4-aminobenzoic acid)), chenodeoxycholic acid (4- (4-pentylcyclohexyl) phenyl ) (Bis (4-aminophenylbenzoate)), chenodeoxycholic acid (4- (4-heptylcyclohexyl) phenyl) (bis (4-aminobenzoate)); chelation Methyloxycholate (bis (3-aminobenzoate)), ethyl chenodeoxycholate (bis (3-aminobenzoate)), propyl chenodeoxycholate (bis ( 3-aminobenzoate)), goose Oxycholic acid butyl (bis (3-aminobenzoate)), Chenodeoxycholic acid amyl (bis (3-aminobenzoate)), Chenodeoxycholic acid hexyl (bisamino) Benzoate)), hexadecylcholate (bis (3-aminobenzoate)), heptadecylcholate (3-aminobenzoate) )), Octadecyl chenodeoxycholate (bis (3-aminobenzoate)), trifluoromethyl chenodeoxycholate (bis (3-aminophenylbenzoate)), goose Deoxycholic acid (2,2,2-trifluoroethyl) (bis (3-aminobenzoate)), chenodeoxycholic acid (1,1,2,2,2-pentafluoroethyl) ) (Bis (3-aminobenzoate)), chenodeoxycholic acid (4- (4-pentylcyclohexyl) phenyl) (bis (3-aminobenzoate)), chelation Oxycholic acid (4- (4-heptylcyclohexyl) phenyl) (bis (3-aminobenzoate)); 3,6-bis (4-aminophenoxy) choline-2 ' Methyl ester, 3,6-bis (4-aminophenoxy) choline-24 · -acid ethyl ester, 3,6-bis (4-aminophenoxy) choline-24-acid propionate O : \ 87 \ S706I.DOC -32-200413441 ester, 3,6-bis (4-aminophenoxy) Alkane-24-acid butyl ester, 3,6-bis (4-aminophenoxy) choline-24-acid amyl ester, 3,6-bis (4-aminophenoxy) choline-24- Hexyl acid ester, 3,6-bis (4-aminophenoxy) bile burner-hexadecanoate 24-acid, 3,6-bis (4-aminophenoxy) chole-24-acid ten Heptadecyl ester, 3,6-bis (4-aminophenoxy) cholan-24-acid stearyl, 3,6-bis (4-aminophenoxy) cholan-24-acid Fluoromethyl ester, 3,6-bis (4-aminophenoxy) cholan-24-acid (2,2,2-trifluoroethyl) ester, 3,6-bis (4-aminobenzene) (Oxy) choline-24-acid (1,2,2,2-tetrafluoroethyl) ester, 3,6-bis (4-aminophenoxy) choline-24-acid (1,1, 2,2,2-pentafluoroethyl ') ester, 3,6-bis (4-aminophenoxy) cholane-24-acid (4- (4-pentylcyclohexyl) phenyl) ester, 3,6-bis (4-aminophenoxy) choline-24-acid (4- (4-heptylcyclohexyl) benzyl) δ purpose; 3,6-bis (3-aminophenoxy ) Bile Burn-24-Acid, 3,6-bis (3-aminophenoxy) cholane-24-acid ethyl ester, 3,6-bis (3-aminophenoxy) cholane- 24-acid propyl ester, 3,6-bis (3-aminobenzyloxy) cholane-24-acid butyl ester, 3,6-bis (3 -Amino-benzyloxy) cholera-24-pentyl acid, 3,6-bis (3-aminophenoxy) cholera-24-acid hexyl ester, 3,6-bis (3-amine Phenoxy) choline-24-acid hexadecyl '3,6-bis (3-aminobenzyloxy) cholan-24-acid heptadecyl, 3,6-bis (3-amino Stupidoxy) cholan-24-acid octadecyl ester, 3,6-bis (3-aminophenoxy) cholan-24-acid tridecyl ester, 3,6-bis (3-amine Phenylphenoxy) cholan-24-acid (2,2,2-trifluoroethyl) ester, 3,6-bis (3-aminophenoxy) cholan-24-acid (1,2, 2,2-tetrafluoroethyl) ester, 3,6-bis (3-aminophenoxy) cholane-24-acid (1,1,2,2,2-penta-1ethyl) ester, 3 , 6-Bis (3-aminophenoxy) choline-24-acid (4- (4-pentylcyclohexyl) phenyl) S, 3,6-bis (3-aminobenzyloxy) Cholesterol-24-acid (4- (4-heptylcyclohexyl) phenyl) S;. O: \ STx8706I.CXDC -33-200413441 Especially preferred is chenodeoxycholic acid butyl (bis (4-amine Phenyl phenyl yinate)), amyl chenodeoxycholate (bis (4-aminobenzoate)), hexyl chenodeoxycholate (bis (4-aminobenzoate)), goose Cetyl deoxycholate (bis (4-amine Phenylbenzene fate)), chenodeoxycholic acid heptadecyl (cream (4-aminophenyl γ ester)), chenodeoxycholic acid octadecyl (bis (4-aminobenzene f acid) Ester, chenodeoxycholic acid trifluoro f group (bis ('amine basic methyl S)), I | deoxycholic acid (2,2,2-trifluoroethyl) (diaminobenzoic acid S )), Chenodeoxycholic acid (1,1,2,2,2-pentafluoroethyl) (bis (4-aminobenzoic acid)), chenodeoxycholic acid (4- (4- Amylcyclohexyl) phenyl) (bis (4-aminobenzyl ester)), chenodeoxycholic acid (4- (4-heptylcyclohexyl) phenyl) (bis (4-aminobenzyl) Acid ester)). The specific monoamine compound can be synthesized, for example, from a bile acid derivative having one or two hydroxyl groups. For example, using an esterification reaction of an alcohol with a carboxylic acid or an esterification reaction of a halogenated alkyl group with a carboxylate, a dehydrating agent such as an acid catalyst or a base catalyst, dicyclohexylcarbodiimide, etc. The precursor is a dinitro compound, and the desired diamine can be obtained by reducing this. Specifically, for example, fluorescein lithocholic acid (3,5-diaminobenzylformate) can be synthesized from lithocholic acid (丨) according to the following reaction formula.

O: \ 87 \ 8706l.DOC '34-200413441

The diamine compound provided in the synthesis reaction of polyamic acid can be used in combination with a diamine compound other than the specific diamine compound within a range that does not impair the effect of the present invention. Here, the proportion of the specific diamine compound occupied by the diamine compound provided in the synthesis reaction is preferably Mohr%, and the ratio is particularly preferable. In the TN-type and STN-type liquid crystal display elements, it is 0.05 to 30 Moll%. 'In a vertical alignment type liquid crystal display element, it is 10 to 1 mol%. Examples of diamine compounds that can be used in combination include: p-phenylenediamine, m-phenylenediamine, 4,4-monoamino-benzylmethan ', diaminodiphenylethyl, 4,4, and diamine Monophenyl sulfide, 4,4'-diaminodiphenylphosphonium, 3,3, -dimethyl-4,4, diaminobiphenyl, 4,4'-diamine, N-benzyl Aniline, 4,4, -diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4, -diaminobiphenyl, 5-monthly female 1- (4-amine basic group) -1,3,3-trimethylindane, 3,4, -diamino-dibenzyl, 3,3'-diaminodibenzyl Fluorenone, 3,4, -diaminodibenzone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane , 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-Aminophenoxy) phenyl], 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, ι, 3-bis ( 3-aminobenzyloxy) benzyl, 9,9-bis (4-aminobenzyl) -10-hydroanthracene, 2,7-diaminophosphonium, 9,9-bis (4-aminobenzyl) Sulfonium) hydrazone, 4,4'-fluorenylene-bis (2-aniline) 2,2,, 5,5, -tetrachloro O: \ S7 \ S706l.DOC -35- 200413441 -4,4 -monoaminodidimethoxybenzene, 2,2, digas-4,4, -Diamino-5,5, dimethoxybiphenyl, 3,3'-dimethoxy-4,4, -diaminobiphenyl, ι, 4,4,-(p-phenylene diisoprene Propyl) bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 2,2, bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] Hexafluoropropane, 4,4, diamino-2,2'-bis [trifluoromethyl] biphenyl, 4,4, bis [(4-aminotrifluoromethyl) phenoxy] -octafluoro Aromatic diamines such as biphenyl; 1,1-m-diphenylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, hepta Methylene diamine, octamethylene diamine, unamethylene monoamine, 4,4-diamino heptamethylene diamine, ι, 4-diamino cyclohexane, isophorone di Amine, tetrahydrodicyclopentadienyldiamine, hexahydro-4,7-methanolindanyl dimethylene diamine, tricyclo [6.21.02,7] -undecene dimethyl Aliphatic and alicyclic diamines such as diamine, 4,4'-amidinobis (cyclohexylamine), etc .; 2,3--fe group p ratio σ, 2,6 -Diamino p ratio. Stilbene, 3,4-diaminosigma, stilbene, 2,4-diaminopyridine, 5,6-diamino-2,3-diamino-exopyridine, 5,6-diamino- 2,4-dihydroxypyridine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) Piperidine, 2,4-diamino-6-isopropyloxy-1,3,5-triamidine, 2,4-diamino-6-fluorenyloxy-1,3,5-triamine, 2,4 · diamino-6-phenyl-1,3,5-triamidine, 2,4-diamino-6-methyldihydrogen, 2,4-monoethynyl-1,3, 5-triazine '4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-di Amino-1,3-diamidinouracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyaridine lactate, 3,8-diamino-6-benzylphenanthridine, 1,4-diamino piperidine, 3,6-diamino aridine, bis (4-aminophenyl) phenylamine and the following Any one of the formulas (V) and (VI): O: \ 87 \ 8706l.DOC -36- 413441 Grade amine group and the compound shown by the grade amine, etc., have two nitrogen atoms other than one radical in the molecule Diamine

(In the formula, 'R5 represents a monovalent organic group having a ring structure, and the ring structure contains k autopyridine (when. Hydrazone, triazine, piperidine, and piperazine nitrogen atoms; X represents a divalent organic group) H2O ^ Sc-0-NH2 (VI) (In the formula, R6 represents a divalent organic group having a ring structure, and the ring structure contains a telepyridine. Pyridine, acetidine, triazine, piperidine, and piperazine nitrogen atoms ; X represents a bivalent organic group, X may be the same or different.) Mono-substituted diamines are not replaced by the following formula (VII); Diamines are represented by the following formula (VIII) Organosiloxane; F ^ ~ R8 H2N NH2 (VII) (wherein 'R7 represents selected from -0-, -C0〇_, 〇c〇 ...- NHC〇 -... C〇NH- and -CO- Divalent organic group, R8 represents a monovalent organic group selected from a nested skeleton, a trifluoromethyl group and a fluoro group, or an alkyl group having 6 to 30 carbon atoms.) O: \ 87 \ 8706l.DOC -37 -200413441

(In the formula, 'R9 represents a hydrocarbon group having 1 to 12 carbons, and the plural R9 systems may be the same or different, and ^ is an integer. The integer is.) For example, the following formulae (2) to (6) ) And the like. These diamine compounds can be used alone or in combination of two or more kinds.

(In the formula, y is an integer from 2 to 12, and z is an integer from 1 to 5.) Among these, _ is preferably p-monoamine, 4, 4, diaminodiphenylmethane, 4, 4 • 38-0: ^ 8706, ^ 200413441 --- aminodibenzyl sulfur bond, 1,5-diaminonaphthalene, 2,7-»monoamino group, 4,4-&gt; monoaminodiphenyl group Methyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) go, 2,2-bis [4- (4 -Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4'-methylene (cyclohexylamine), 1,4-bis (aminobenzene) Oxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, compounds represented by the above formulae (2) to (6), 2,6-diaminopyridine, 3, Among the compounds represented by the following formula (V), 4-diaminopyridine, 2,4-diaminopyridine, 3,6-diaminopyridine, a compound represented by the following formula (7), Among the compounds represented by the formula (VI), a compound represented by the following formula (8) and a compound represented by the above formula (V Among the compounds represented by II), the compounds represented by the following formulae (9) to (18) and the compounds represented by the formula (VIII) are represented by the following formula (19). yo-CH2CH2— (ch2) 3—

Ο: \ 3 · Λ8706 丨 DOC -39- 200413441

&lt; Tetraweilic acid diif &gt; Examples of the tetracarboxylic dianhydride used in the synthesis of the polyphosphonic acid of the present invention include aliphatic tetraweilic acid dianhydride, alicyclic tetraweilic acid needle and aromatic tetrawei Acid dianhydride. Specific examples of these compounds include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo Butanetetracarboxylic dianhydride, 1,3-diamidino-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro_1,2,3,4-cyclobutane Alkanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid Dianhydride, 3,3,, 4,4, -dicyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentaneacetic dianhydride, 3,5,6-tricarboxy ) -2 -Diacetic acid di Sf, 2,3,4,5, tetrahydrocoanthonic acid dianhydride, 1,3,3 &amp;, 4,5,91) -hexahydro-5 (tetrahydro-2 , 5-dioxo-3-furanyl) -naphtho [1,2-(:]-octane-1,3-dione, 1,3,3 &amp;, 4,5,913-hexahydro-5-methyl -5 (tetrahydro-2,5-dioxo-3- ^ 7 °° southern group) -neo [丨, 2-.]-Octane- 丨, 3-dione, 1,3,3 &amp; , 4,5,913-hexahydro-5-ethyl gastric 5 (tetrahydro-2,5-dioxo-3-octyl) -naphtho [l, 2-c] -Ha · an-1,3- Dione, l, 3,3a, 4,5,9b-hexahydro-7-methyl-5 (tetrahydro O: \ 87 \ 87061.DOC -40- 200413441 -2,5, dioxo-3-furan ) -Naphtho [1,2,7 ^ _c], furan-1,3-dione, 1,3,3 &amp;, 4,5,91 &gt; -hexahydro-7-ethyl-5 (tetrahydro, 2 &lt; ^^^^^ 3-furanyl) -naphtho [l, 2-c] -furan-1,3-dione, 1,3,3a54,5 qk ^^, 9b, hexahydro-8-fluorenyl-5 (tetrahydro -2,5-dioxo-3-furyl) -naphtho [1,2,7 ^ + occ ", furan-1,3-dione, and n, 2-C] -bite. South-1, 3-Second Steel, Yamashimbetsu-hexahydro-"-dimethyl-5 (tetrahydro-2,5-dioxo-3-branyl) -naphtho" 19 L squeeze 1,3- Dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl 1 ^, T-roll, 3, cyclohexene- 丨, 2-dicarboxylic dianhydride, bicyclo [2,2 , 2] -octino-7-ene-2,3,5 6 m △ 'tetrakidic acid dianhydride, and the compound shown by the following formula (IX) and (X), etc.> π January Fatty and fat-type tartaric acid dianhydride; 0 〇

(IX)

(X)

(Wherein R1 and R3 represent a divalent organic group having an aromatic ring, R2 &amp; R4 represents a hydrogen atom or an alkyl group, and the plural r2 and R4 systems may be the same or different, respectively) pyromellitic dianhydride, 3,3 '54, 4, benzophenone tetracarboxylic dianhydride, 3,3,, 4,4, _diphenylfluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, _3,3 ', 4,4'-bibenzyltetraweitraic acid-if, 3,3', 4,4, -diphenyl-41-

0 · 87 \ S7061.DOC 200413441 Methane tetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4, -tetra Phenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4, bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) diphenylphosphonium dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ' , 4,4'-Perfluoroisopropylidene diphthalic dianhydride, 3,3 ', 4,4, -biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenyl phosphorus oxide di Anhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4, 4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (non-hydrogen trimellitate), propylene glycol- Bis (hydrogen-free trimellitate), 1,4-butanediol-bis (hydrogen-free trimellitate), 1,6-hexanediol-bis (hydrogen-free trimellitate), 1 , 8-octanediol-bis (hydrogen-free trimellitate), 2,2-bis (4-hydrooxyphenyl) propane-bis (non-hydrogen trimellitate), 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6-bis (3, 4-Dicarboxyphenyl) is tetrapyric acid dianhydride such as pyridine and compounds represented by the following formulae (20) to (23). These can be used singly or in combination of two or more kinds.

O: \ 8T-8706l.DOC 200413441

Among these, from the viewpoint of showing good liquid crystal alignment, butanedioic tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,3-dimethyl- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5 -(2,5-dioxotetrahydrofuranmethylidene) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 1,3,3 &amp;, 4,5,91) -hexa Hydrogen-5- (tetrahydro-2,5-dioxo-3-creanyl) -naphtho [1,2-〇] crean-1,3-dione, 1,3,3 &amp;, 4, 5,91) -Hexahydro-8-methyl-5 (tetrahydro-2,5-dioxy-3-creanyl) -naphtho [l, 2-c] bran — 嗣, 1, 3, 3 冱, 4,5,913-hexaaza-5,8-difluorenyl-5- (tetrahydro-2,5-dioxy-3-creanyl) -naphtho [l, 2_c] crean-1, 3-diketone, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetrakidic acid dianhydride, pyromellitic dianhydride, 3,3,, 4,4,- Dibenzyl ketone tetracarboxylic dianhydride, 3,3,, 4,4, -diphenyl stone wind tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetraweilic acid dianhydride, according to the above formula () Among the compounds represented by X), the compounds represented by the following formulae (2 sentences to (26) and the compounds represented by the above formula (X) are Among the compounds, compounds represented by the following formula (27) are particularly preferred. Examples include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 3-dimethyl-1,2,3. 〆 · cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 丨, 3,3 ^ 4,5,9 ^ hexahydro-5- (tetrahydro_2,5 -Dioxyfuryl) · naphtho [l, 2_c] furan_1,3-dione, 1,3,3a, 4,5,9 hexahydromethyl'5 (tetrahydro-2,5-di Oxygen · 3-furanyl) -naphtho [l, 2-c] pyran-1,3-dione, 1,3,3 a, 4,5,9b · hexahydro-8-methyl-5 (IV-43,

〇: '87 \ .87061.DOC 200413441 Hydrogen-2,5--oxyfuryl) -naphtho [12 ^] anan ^, 3-dione, pyromellitic dianhydride and the following formula (24) Shown compound.

&lt; Synthesis of polyamic acid> The proportion of tetracarboxylic dianhydride and diamine compound provided in the polyamino acid synthesis reaction of the present invention is 1 equivalent to the amine group contained in the diamine compound, preferably four The ratio of the acid anhydride group of the carboxylic dianhydride is 0.2 to 2 equivalents, and more preferably 0.3 to 12 equivalents. Synthetic reaction of polyamic acid

In the case of 3 cuttings / captures, it is preferable to beat at -20 ~ 150 C, and more preferably at a temperature of 0 ~ 100 C. Here, the organic solvent meter is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone and N Ν_-two * -methyl ethyl can be exemplified. Ammonium amine, N, N-dimethylformamide, dimethylphosphine, γ-butyrobutane, tetramethyl urea, hexamethyl 〇: '. 8T · 37061.DOC -44-200413441 Aprotic polar solvents; m-cresol, xylenol, phenol, halogenated solvents. The amount of the organic solvent used is preferably the total amount of the diisocyanate and the diamine compound relative to the total amount of the reaction solution (: an amount of 0.1 to 30% by weight.丨, the weak solvent of the polyamic acid can be used in combination with alcohols, alkalene and alkene, etc. in the area where the generated polyamic acid does not precipitate. The specific examples of such weak solvents can be Examples: Methanol, ethanol isopropanol, cyclohexanol, ethylene glycol, propylene glycol, chlorobutanediol, triethylene glycol: ethylene glycol monomethyl ester, ethyl lactate, butyl lactate, acetone, methyl ethyl _, Methyl isobutanone, cyclohexanone, methyl acetate_, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, diethyl oxalate, malonic acid Diethyl ether, diethyl ether, ethylene glycol methyl ether, ethylene glycol ^ -n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene diethyl ether Acetate, Diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, Diethylene glycol monomethyl glycol monoethyl ether, Diethylene glycol monomethyl acetate, Diethylene glycol monoethyl ether Acetate, tetrahydrofuran, dichloromethane, 1 'digas ethane, 1,4-dichlorobutane, trigas ethane, chlorobenzene, o-dichlorobenzyl, hexane, heptane, octane, benzyl, Benzene, dimethylbenzyl, etc. As described above, a reaction solution obtained by dissolving polyamic acid can be obtained. Then, the reaction solution is poured into a large amount of a weak solvent to obtain a precipitate, which is dried under reduced pressure. A polyamic acid can be obtained from this precipitate. The polyamino acid is dissolved in an organic solvent, and then the step of precipitating in a weak solution is performed once or several times to refine the polyamino acid. -Poly donkey acid is a diamine compound represented by the formula ⑴ and

O: \ 87 \ 8706I.DOC -45- 200413441 The reaction of the tetracarboxylic dianhydride represented by the aforementioned formula (III) includes a repeating unit represented by the following formula (XI) and a reaction unit represented by the aforementioned formula (II): The reaction of the diamine compound shown with the tetracarboxylic dianhydride represented by the said Formula (III) has a repeating unit represented by a following formula (XII).

••• (XI) In the above formula, the definitions of G4, A1, D1, B1, E1, a, and G1 are as described above.

COOH

Γ H-G2-A: 0-βΜΕ2) ϋ 2-In the above formula, the definitions of G4, G2, A2, D2, B2, E2, and b are as described above. &lt; Pyrimidinated polymer> The piridimidized polymer of the present invention can be prepared by dehydrating and closing the polyphosphonic acid as described above. The dehydration ring closure of polyamic acid is as follows; (1) the method of heating polyamic acid; or (II) the polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring-closing catalyst are added to the solution , The method of heating as needed. The reaction temperature in the method of heating the polyphosphonic acid of the foregoing arsenic is preferably 50 to 200 ° C, and more preferably 60 to 170 ° C. When the reaction temperature is below 50 ° C, the dehydration ring-closure reaction cannot proceed sufficiently, and if the reaction temperature exceeds 200 ° C, the molecular weight of the obtained fluorene imine polymer will decrease. O: \ 37 \ 8706 l.EX) C -46- 200413441 w In addition, in the method of adding a dehydrating agent and a dehydration closing catalyst to the polyamine solution of (π) above, the acetic anhydride can be used as the dehydrating agent. , Propionic anhydride, sulphur, etc.). The amount of the dehydrating agent used is preferably 0.01 to 20 moles relative to the repetition of polyamino acid. Examples of the dehydration ring-closing catalyst include tertiary amines such as pyridine, methylpyridine, dimethylpyridine, and triethylamine. But limited to this special. The amount of dehydrated closed-loop catalyst used should be from 0.01 to 10 moles relative to the dehydrated J 1 used. The organic solvent used in the dehydration ring-closing reaction can be exemplified as an organic solvent used for the synthesis of polyamic acid. Furthermore, the reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180, and more preferably 10 to 150. (:. With respect to the reaction solution thus obtained, by performing the same operation as the method for purifying polyamic acid, the amidine polymer can be refined. The obtained polyimide polymers are each represented by the aforementioned formula. (XI) and the polyamidoacid repeating unit represented by the aforementioned formula (XII) are imidized with fluorene, for example, the fluorenimidated units represented by the following formulae (XIII) and (XIV), respectively. &Lt;; &gt; &lt; 〇

A1—D1—-CO-eME1) ^ (XIII) In the above formula, the definitions of G, G1, A1, D1, B1, E1, and a are the same as described above.

Y Ν—G ~ A 'CO—Β ^ A A2 -... (XIV) -47-200413441 In the above formula, G4, G2, A2, D2, B2, and the definitions are the same as the foregoing. The preferable fluorinated imidization ratio of the fluorinated imidization polymer of the present invention when constituting the liquid crystal aligning agent of the present invention is 10 to 100%, more preferably 30 to 98%. Here, the "fluorene imidization ratio" refers to the ratio of the number of repeating units formed by forming a fluorene imine ring to the total number of repeating units in the polymer in%. At this time, a part of the fluorene imine ring may be an isofluorene ring. The rate of imidization can be controlled by the reaction conditions of the above-mentioned dehydration ring-closing reaction in the 5th week. &Lt; Terminal-modified polymer> The polyamidic acid and amidine imidized polymer of the present invention may also be terminal-modified type whose molecular weight is adjusted. By using this terminal-modified polymer, the effect of the present invention is not impaired, and the coating characteristics of the liquid crystal aligning agent can be improved. Such a terminal-modified type can be synthesized by adding an acid anhydride, a monoamine compound, a monoisocyanate compound, or the like to the reaction system when synthesizing a polyamic acid. Here, the acid anhydride may be, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-deca Hexyl succinic anhydride and the like. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecaneamine, and n-deca Dialkylamine, n-tridecylamine, n-tetradecanylamine, n-pentadecanylamine, n-hexadecylamine, n-hexadecylamine, n-octadecylamine, n-eicosylamine, etc. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. &lt; Logarithmic Viscosity of Polymers> The logarithmic viscosity of Poly-Donamic Acid and Donkey Aminated Polymers of Benming Ming in) 0: .37 ^ 87061.DOC -48-200413441 The value is generally 0.05 ~ 10dl / g, preferably 0.1 to 5 dl / g. The value of the logarithmic viscosity ㈡1 n) of the present invention is the use of N_methyl-2_P than pyrrolidone as the solvent, and the solution with a concentration of 0.5 g / ml is measured at 3 (rc, viscosity, below). Those who described the formula and obtained it.

In = 1 η (time when the solution flows / time when the solvent flows down) 71 (weight concentration of polymer) (i) &lt; Liquid crystal aligning agent> The liquid crystal aligning agent of the present invention is suitable for the polyamic acid and / or donkey of the present invention. The imidized polymer is constituted by being dissolved in an organic solvent. That is, the liquid crystal aligning agent of the present invention contains a polymer, and the polymer has at least one group consisting of repeating units respectively represented by the above formulae (XI) to (XIV). In addition, the liquid crystal aligning agent of the present invention may further contain a polyfluorinated acid and / or a fluorinated polymer (hereinafter, also referred to as a polyimide) which does not have a repeating unit represented by the formulae (XI) to (XIV), respectively. "Other polymers"). Other polymers include polyamidic acid obtained by reacting a diamine compound other than the above-mentioned specific diamine compound with tetracarboxylic dianhydride, and polyimide polymer obtained by dehydrating and closing the polyamidic acid. Pick at least one. Examples of the combination of preferable polymers include a polymer having a repeating unit represented by the above formula (xm) and / or a repeating unit represented by () (acidimidized polymer of the present invention), A combination of a repeating unit of polyamic acid represented by any one of the above formulae (XI) to (xiv). A liquid crystal aligning agent containing such a polymer can obtain a liquid crystal with excellent long-term reliability and a particularly short afterimage disappearance time. 5 Polymer content ratio in the liquid crystal aligning agent

O: \ S7 \ S706LDOC -49- 200413441 1 ~ 99 The ratio ^ is relative to the total amount of the polymer. The awakened imidized polymer of the present invention is% by weight, preferably 2 to 50%. It is particularly preferably 10 to 30% by weight. The temperature when preparing the liquid crystal aligning agent of the present invention is preferably 0. 〇 ~ 2㈧. c 'is more preferably 20 ° C to 6CTC. The organic solvent constituting the liquid crystal aligning agent of the present invention can be exemplified as a solvent for a synthetic reaction of polyamic acid. X can also be appropriately selected and used as an example to be used as a solvent in the synthesis reaction of polyamic acid. The solid content concentration in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, etc., but it is preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is coated on the substrate surface and forms a coating film that becomes a liquid crystal alignment film, but when the solid content concentration is 1% by weight or less, the film thickness of the coating film is too small to obtain a good liquid crystal. Orientation film. In addition, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coating characteristics deteriorate. The liquid crystal aligning agent of the present invention may contain a functional silane-containing compound or an epoxy group-containing compound from the viewpoint of improving the adhesion to the substrate surface. Examples of compounds containing such functional silanes include 3-aminopropyldimethoxylithium, 3-aminopropyltriethoxy silicon, 2-aminopropyltrimethoxylithium, 2 -Aminopropyltriethoxylite, aminoamino) -3_aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylfluorenyldimethyl Oxysilane, 3-ureidopropyltrimethoxysilane,% ureidopropyltriethoxylithium, N-ethoxycarbonyl-3-aminopropyltrioxane Silane, N-ethoxycarbonyl-3-aminopropyltriethoxylate, O: \ 87 \ 8706l.DOC -50- 200413441 triethoxysilylpropyltrivinyltriamine , N-trimethoxysilylpropyltrivinyltriamine, 10-trimethoxysilyl 4,4,7-triazadecane, 10-triethoxysilyl-, 1, 4,7_triazadecane, trimethoxymethoxanyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diaza Nonylacetate, N-benzylaminopropyltrimethoxysilane, N-benzylaminopropyltriethoxysilane, N-phenyl-3-amine Propyldimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, bis (oxyvinyl) -3-aminopropyltrimethoxysilane, tris (bis (oxyethylene) ) -3 —aminopropyltriethoxysilane and so on. Examples of the epoxy-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl. Glyceryl ether, neopentyl glycol diglycidyl ether, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-Tetraglycidyl ether-2, cardiohexanediol, n, n, n ,, n, tetraglycidyl ether-m-xylylenediamine, -bis (N, N-di Glycidylaminomethyl) cyclohexane, \, 1 ^ 3, -tetraglycidyl-4,4, diaminodiphenylmethane and the like. The compounding ratio of the compound containing these functional silanes or the compound containing epoxy groups is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the polymer. &lt; Liquid crystal display element &gt; The liquid crystal display element of the present invention can be produced, for example, by the following method.涂布 The liquid crystal alignment of the present invention is applied on the side of a substrate provided with a patterned transparent conductive film by, for example, a roll coating method, a spin coating method, or a brush method.

O: \ 87 \ S7061.DOC 200413441 j ′,, 丨 cross, and the coating surface is formed by heating. Here, the substrate can be made of glass such as limestone glass, soda glass, etc .; plastics made of polyethylene terephthalate, polybutylene terephthalate, polystone, polycarbonate, etc. Composition of transparent glass. The transparent conductive film provided on one side of the substrate can make a NESA film composed of tin oxide (SnO2) (a registrar of American ppg company M, an indium tin oxide emulsified (In2〇3_Sn〇2)) Etc. The patterning of these permeable membranes can use photolithography or a method using a mask in advance. In the application of the liquid crystal aligning agent, in order to further adhere the substrate surface and the transparent conductive film to the coating film, Good performance 'The surface of the substrate can also be coated with a compound containing a functional Shixiyuan, a compound containing a functional titanium, etc. The heating temperature after the application of the liquid crystal aligning agent should be 80 ~. C, more preferably It is 12 ~ 25 ° C. In addition, the liquid crystal aligning agent of the present invention containing polyamino acid forms a coating film which becomes an alignment film by removing the organic solvent after coating, but further dehydrates and closes the ring by heating. It is also possible to form a coating film that is more imidized. The film thickness of the coating film to be formed should preferably be Η㈣, more preferably 5 to Q5 ㈣. (2) The surface of the formed coating film should be made of, for example, Nalon. __ Abrasive rubbing in a certain direction made of a cloth made of fibers such as snails, snails, and cotton The liquid crystal alignment ability formed by the liquid crystal aligning agent of the present invention can be imparted to the coating film. For example, as shown in, for example, Japanese Patent Application Laid-Open No. 222366 or Japanese Patent Application Laid-Open Newspaper: Normally, partly irradiated with ultraviolet rays, such as changing the front elevation angle or wrongly, as shown in Japanese Patent Application Laid-Open No. 5_107544, a photoresist film is partially formed on the surface of the liquid crystal alignment film where the polishing is performed, and the previous polishing is performed. The processing is different. After the polishing process is performed, the photoresist film is removed and changed.

〇: '87 \ 370ό 1.DOC -52-200413441 The treatment of the liquid crystal alignment energy of the liquid crystal film can improve the visual characteristics of the liquid crystal display element. In addition, depending on the case, the coating film may be irradiated with polarized or unpolarized ultraviolet rays, or an ion beam without using polishing, and the liquid crystal alignment ability may be imparted. In addition, when manufacturing a liquid crystal display element of a vertical alignment type, it is not necessary to perform a polishing process', and the above-mentioned coating film can be directly used as a liquid crystal alignment film. (3) Two substrates for forming a liquid crystal alignment film are prepared as described above, and the polishing directions of the liquid crystal alignment film are set at specific angles respectively, and the two substrates are disposed opposite to each other through a gap (cell space), and a sealing agent is used. The peripheral parts of the two substrates are bonded together, and liquid crystal is injected into the substrate surface and the space between the cells separated by the sealant, and the liquid crystal cells are formed by sealing the injection holes. Then, the polarized light is bonded to the outer surface of the liquid crystal cell, that is, the other surface side of each substrate constituting the liquid crystal cell, so that the direction of polishing of the liquid crystal alignment film whose polarization direction is formed on one side of the substrate is consistent or orthogonal. Plate to obtain a liquid crystal display element. Here, as the sealant, for example, an epoxy resin containing an oxidized chain ball as a hardener and a spacer can be used. Examples of the liquid crystal include a nematic liquid crystal and a nematic liquid crystal. Among them, two rows of soil fluids are preferred. For example, Schiff base liquid crystals and azo oxide-based liquids can be mentioned: biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, i-based liquid crystals, Tri-triphenyl-based liquid crystals, biphenyl-cyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane% hexane, bi-octane-based liquid crystals, Cuban-based liquid crystals, and the like. In addition, as an asymmetric agent such as gasified steroids, steroids "c-1 :)", "CB_15" (Merck), and the like can also be used for sale. further,

87 \ 87061.DOC -53-200413441 It is also possible to use strong dielectric liquid crystals such as p-desyloxybenzylidene-p-amino-2-methylbutyl meat laurate. Also, a polarizing plate attached to the outer surface of a liquid crystal cell can be exemplified by a polarizing film extending the alignment of polyvinyl alcohol and holding a polarizing film called a holmium film capable of absorbing iodine with a protective film of cellulose acetate. A polarizing plate composed of the H film itself. Examples Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. X. In the following examples and comparative examples, the evaluation method of the polymer fluid sun-repellent agent and the liquid crystal display element is as follows. &lt; Voltage retention of the liquid crystal display element> After applying a voltage of 5 V to the liquid crystal display element at an application time of 60 milliseconds and a span of 167 milliseconds, the voltage retention after 167 milliseconds was measured from the release. The radon measuring device uses Vhr-1 manufactured by Dongyang Technology. &lt; Residual image erasing time &gt; 0) After applying a DC voltage of 10V to the liquid crystal display element for one hour, the voltage was released, and the daytime surface was displayed by visual observation. After the voltage was released, the residual voltage on the screen was measured. Shadow disappearance time (Examples 5 to 5 and Comparative Examples 6 to 8). After applying the DC voltage to the liquid crystal display element at an ambient temperature of 100 ° C for 20 hours, the voltage is released from the application of the voltage. After 15 minutes, the flicker disappears in the liquid crystal cell. Find the residual voltage. The less the residual DC voltage, the shorter the disappearance time of the afterimage. Liquid crystal display elements: Examples 22 to 26 and Comparative Examples 11 to 12). &lt; Elevation angle before liquid crystal display element &gt;

Scheffer, et al., J. Appl. Phys., Νιι 19, O: \ 87 \ 8706I.DOC -54. 200413441 2013 (1980), measurement by He-Ne laser light crystal rotation method . <Reliability test of liquid crystal display element> The liquid crystal display element was placed in a 70 ° C thermostatic bath to drive the waveform generator "Function / arbitrary waveform generator" (manufactured by Hewlett Packard) for 24 hours. Uneven light and dark contrast, showing the presence or absence of defects. Examples of synthesis of specific diamine compounds. Synthesis Example 1 (1) Synthesis of methyl lithocholic acid 56. 5 g (0.15 mol) of lithocholic acid and 3 mi of concentrated sulfuric acid were added to 0.5 liter of methanol, and heated under reflux for 6 hours. The obtained solution was concentrated to 1/2 volume flow on a rotary evaporator, and the product was precipitated by adding 1 liter of pure water, and further recovered by suction filtration. This crude product was washed with a saturated aqueous solution of NaHC03 to neutralize the attached H2SO4, and at the same time dissolved and removed unreacted lithocholic acid. After further washing with water and vacuum drying, recrystallization was performed from ethanol to obtain 44 g of methyl lithocholic acid. The analysis results are shown below. W-NMRPMSDA j ppm): 0.621 (34H, m), 3 6 (3H, s). (2) Synthesis of methyl lithocholic acid (3,5-dinitrobenzoate) 1 9.6 g of methyl lithocholic acid (〇 alfalfa: s :,,.. 〇g and 0.1 5 liters of digas methane were dissolved at room temperature. —S / ϋ V * Dissolve this solution and slowly add 3,3-dinitrobenzyl chloride (5. 5 mol) as a solid directly, and stir at room temperature. This mixed solution was evaporated to dryness on a rotary evaporator, the generated H] ⑮h was washed with water, and then dried under vacuum to obtain a crude product. A further 0 ^, 8737061.000 -55- 200413441 was used to recrystallize it in one step to obtain 25.5 g of methyl lithocholic acid (3,5-dinitrophenylarsinate). The analysis results are shown below. lH-NMR (CDC135 5 ppm): 0.6-2.1 (34H, m) 5 3.6 (3H5 s) 5 9.1-9 · 2 (3H, d + t). (3) Synthesis of gadolinium lithocholic acid (3,5-monoaminobenzoic acid g) 9.6 g of methyl lithocholic acid (3,5-dinitrobenzoate) and 0.1 palladium activated carbon g is added to 100 ml of ethanol and heated under reflux. 4 ml of hydrazine monohydrate was slowly dripped into the mixture, and the mixture was further heated under reflux for 2 hours. When hot, the reaction solution was filtered to remove sharp activated carbon, and 1 liter of water was added to precipitate the product. This precipitate was filtered, washed with water, and dried under vacuum, and then recrystallized from ethanol to obtain 6.7 g of methyl lithocholic acid (3,5-diaminobenzoate). The analysis results are shown below. 1H-NMR (DMSO-D6, 5 ppm): 0.6-2.1 (34H? M), 3.6 (3H? S), 4.9 (4H, s), 6.0 (1H, t), 6.4 (2H, d) . Synthesis Example 2 (4) Synthesis of butyl lithocholic acid 56.5 g (0.15 mol) of lithocholic acid and 0.3 ml of concentrated sulfuric acid were added to a solution of 44 g of 1-butanol and 100 ml of chloroform, and heated under reflux for 6 hours. The resulting solution was concentrated on a rotary evaporator to a 1/2 flow, and added to 1 liter of chloroform and 1 L of pure water and stirred. The gas imitation layer was separated and washed with a saturated aqueous solution of NaHC03 to neutralize the attached H2SO4, and at the same time dissolved and removed the unreacted lithocholic acid. It was further washed with water, dried over anhydrous magnesium sulfate, filtered to remove magnesium sulfate, and the solution was concentrated to obtain 52 g of butyl lithocholic acid. (5) Synthesis of butyl lithocholic acid (3,5 · dinitrobenzoate) 8706 l.DOC -56- 200413441 Except the use of butyl lithocholic acid 21.4g (0.05 mole), pyridine 3 9§ And 0.1 m of methylene chloride and 4 g (0.05 mol) of 3,3-dinitrobenzyl chloride, the rest are the same as in (2) to obtain butyl lithochorate (3,5-dinitrate Benzoic acid _) 26g 〇 (6) Synthesis of butyl lithocholic acid g (3,5 · diaminobenzoic acid g) In addition to the use of butyl lithocholic acid (3,5-dinitrobenzoate) ) Except for 9.6 g, the rest are the same as (3), and butyl lithochorate (3,5-diaminobenzoate) is obtained. The analysis results are shown below. , W-NMR (DMSO-D6,5 ppm): 0.6-2.1 (44H, m), 4.0 (2H, t), 4.8 (1H, m), 4.9 (4H, s), 6.0 (1H, s , 6.4 (2H, s) Synthesis Example 3 (7) The synthesis of ammonium lithocholic acid is the same as (4) except that 39 g of 1-pentanol is used, and 54 g of pentamidine lithocholic acid is obtained. (8 ) Synthesis of ammonium lithocholic acid (3,5-dinitrobenzoate), except for using 22 g of ammonium lithocholic acid, the rest is the same as (2), and pentyl lithocholic acid is obtained (3, 5- Dinitrobenzoic acid vinegar) 26 g. (9) Synthesis of ammonium lithocholic acid (3,5-diaminobenzoate) In addition to the use of ammonium lithocholic acid (3,5-distone Except for 9.6 g, the rest is the same as (3), and 6.9 g of ammonium lithochlate (3,5-diaminophenylbenzoate) is obtained. The analysis results are shown below. JH-NMR (DMSO- D6j (5 ppm): 0.6-2.1 (46H, m), 4.0 (2H? T) 5 4.8 (1H, m), 4 · 9 (4H, s), 6.0 (1H, s), 6.4 (2H ， S)。 Synthesis Example-4 O: \ 87.8706l.DOC -57-200413441 (10) The synthesis of heptadecyl lithocholic acid is the same as (4) except that 59 g of 1-heptadecanyl alcohol is used. 92 g of ammonium crude cholic acid was obtained. Purification by column chromatography analysis yielded 8 3 g of heptacholic acid heptaacetate. (11) Synthesis of heptadecyl lithocholic acid (3,5-dinitrobenzoate) Except for 31 g of heptadecyl ester, the rest is the same as (2) to obtain 37 g of heptadecyl lithocholic acid (3,5-dinitrobenzoate). (12) Heptadecyl lithocholic acid (3, Synthesis of 5-diaminobenzoate), except for the use of ammonium lithocholic acid (3,5-bis-stilkybenzoic acid) 9 · 6 g, the rest is the same as (3) to obtain ten lithocholic acid 7.5 g of heptaalkyl (3,5-diaminobenzylformate). The analysis results are shown below. B-NMR (CDC13, 5 ppm): 0.6 · 2 · 4 (70H, m), 3 · 7 (4H, s), 4.0 (2H, t), 4.9 (1H, m), 6.2 (1H, s), 6.8 (2H, s). Synthesis Example 5 (13) Stearyl cholestyrate The ester was synthesized in the same manner as (1) except that 61 g of 1-octadecanol was used to obtain 76 g of octadecyl lithocholic acid.

B) S)) 7.6g ·. The rest is the same as (3) to obtain 7.6 g of lithocholic acid. The analysis results are shown below.

〇: '37'-87061.DOC -58-200413441 ^ H-NMR (CDC13? 5 ppm): 0.6-2.4 (72H5 m) 53.7 (4H? S)? 4.0 (2H, t), 4.9 (1H, m ) 5 6.2 (1H, s), 6.8 (2H, s). Example 1 Synthesis of Polyammonium Acetate Lithium cholestyrate (3,5 · diaminobenzoate) 7.02 g, p-phenylenediamine 13.0 g, and 2,3,5-tricarboxycyclopentane 3.0 g of acetic acid dianhydride was dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at 6 ° C for 6 hours. Then, the reaction solution was poured into a very excessive amount of methanol to precipitate a reaction product. After that, it was washed with methanol and dried under reduced pressure at 4 ° C for 15 hours to obtain a polyamic acid of the present invention having a logarithmic viscosity of 0.93 dl / g (as a "polymer (la)") 48.9 g 〇 Example 2 Synthesis of imidized polymer The polymer (1 a) 25 · 0 g &gt; disintegrated in N-fluorenyl-2-p ratio 450,000 g of each ketone, here &gt; Add 10 ° 6 g and 1 3 6 g of hepatic acetate to the cereal, and heat it at 11 5 ° C for 4 hours to dehydrate and close the ring. Then, inject the reaction solution into a very excess methanol to make The reaction product precipitated. After that, it was washed with methanol and dried under reduced pressure at 40 ° C for 15 hours to obtain the fluorinated imidized polymer of the present invention having a logarithmic viscosity of 0.85 (as " Polymer (lb) ") 21 .2g. Example 3 Synthesis of polyamidic acid except that butyl lithocholic acid (3,5-diaminophenylbenzoate) 7.49g, p-phenylenediamine 12.9g and 2,3,5-trial Gcyclopentyl acetate digf 29.6 g substituted methyl lithocholic acid (3,5-diamino stupid methylformate) 〇2§, p-diamine diamine 13.〇§ and 2,3,5-tricarboxylic acid 0: '8r 37061.DOC 09- 200413441 Except for 3G.Gg of cyclopentylacetic dianhydride, the rest is the same as that in the implementation of ⑴, and the glutamic acid of the present invention having a log viscosity of G.84 dl / g (as a "polymerization" (2a) ") 47.6g 〇 Example 4 Synthesis of imidized polymer except the use of compound (2a) 24.7g instead of polymer (la) 25.〇g, the rest of the same &quot; spiral example 2 To obtain the present invention (i.e., "Polymer (2b)") with a logarithmic viscosity of 0.28. Example 5, Synthesis of Polyphosphonic Acid (3,5-diaminobenzoate) 7.65g, p-phenylenediamine 12.8g, and 2,3,5-dienecyclopentylacetic dianhydride "substituted lithocholic acid methyl acetate (3,5 -Diaminobenzoic acid purpose) 702§, p-phenylenediamine i30g and 2,3,5-trisylcyclopentylacetic dianhydride 3G.Gg Except that, the rest is the same as that of the implementation, and 49.8 g of the polyamidic acid of the present invention (which is referred to as "polymer (3a)") having a log viscosity of 0.88 dl / g is obtained. Example 6 Synthesis of an imidized polymer Using 24.7 g of polymer (3a) instead of 25.0 g of polymer (la), the rest was the same as in Example 2 to obtain the 醯 imidized polymer of the present invention having a log viscosity of 86. (3b) ") 2] L3g. Example 7 Synthesis of Polyamidic Acid Except the use of heptadecanyl hexacholic acid (3,5 · diaminobenzoate) 9.45 g, p.O: 'S7, 87061.DOC -60- 200413441 12.3g and 2,3,5-tricarboxycyclopentylacetic dianhydride 28 3§ Substituted for cholestyryl methyl ester (3,5-diaminophenylbenzoate) 702g, p-phenylenediamine i3. Except 30.0 g of carboxyl cyclopentylacetic dianhydride and 2 g, 5-2 carboxycyclopentanedioic dianhydride, the rest was the same as in Example 丨, and the polyamidic acid of the present invention having a log viscosity of 0.79 dl / g (this was used as a "polymer (4a) ") 49.9g. Example 8 (Synthesis of imidized polymer) Except that 23.5 g of polymer (4a) was used instead of 25.0 g of polymer (la), the rest was the same as in Example 2 to obtain the present invention with a log viscosity of 0.76. 19 3 g of an imidized polymer (as this r polymer (4b) "). Example 9 Synthesis of Polyamidoacid Except for using 9.59 g of octadecyl lithocholic acid (3,5-diaminobenzoate), 12.2 g of p-phenylenediamine and 2,3,5-tricarboxyl ring 28.2 g of amyl acetic dianhydride substituted with ammonium lithocholic acid (3,5-diaminobenzoate) 7.02 g, 13.0 g of p-phenylenediamine and 2,3,5-dikicyclocyclopentyl Except for 30.0 g of acetic dianhydride, the rest was the same as in Example 1 to obtain 49.9 g of the polyamidic acid of the present invention (which is referred to as "polymer (5a)") with a log viscosity of 0.76 dl / g. Example 10 (Synthesis of imidized polymer) Except the use of polymer (5a) 2 3.5 g instead of polymer (ia) 25.0 g, the rest is the same as in Example 2 to obtain the present invention with a log viscosity of 0.73 dl / g. The imidized polymer (referred to as "Polymer (5 b)") 1 9 · 8 g. Comparative Example 1 · 〇: 'S7 \ 87061.DOC -61-200413441 Synthesis of polyamic acid except 4,4-diaminodiphenylmethane 19 8§ and 2,3, tritricyclocyclopentylacetic acid 22.4 g of dianhydride substituted methyl lithocholic acid (3,5-diaminobenzoic acid ester) 7.02 g of paraben and 2,3,5-dicarboxycyclopentylacetic dianhydride other than 〇§, the rest In the same manner as in Example 1, a polyglycolic acid (which is referred to as "polymer (A a)") having a logarithmic viscosity of 0.20 dl / g was obtained, which was 4 · 2 g. Comparative Example 2 Synthesis of imidized polymer. Except using 25.0 g of polymer (Aa) instead of 25.0 g of polymer (ia), 4.5 g and 5.8 g of acetic anhydride were used instead of p ratio 唆 1. .6 g except 3.6 g of acetic anhydride, the rest was the same as in Example 2 to obtain the fluorinated imidized polymer of the present invention having a logarithmic viscosity of 1.20 dl / g (this was referred to as "polymer (Ab)") 3 〇lg. Comparative Example 3 Synthesis of poly (vinylamine), except for the use of 12.80 g of p-phenylenediamine and 25.82 g of pyromellitic dianhydride in place of 7.02 g of lithocholic acid (3,5-diaminophenyl benzoate) and terephthalic acid Except for i.3.0 g of amine and 30.0 g of 2,3,5-dicarboxycyclopentylacetic dianhydride, the rest were the same as in Example 1 to obtain a polyamidic acid having a logarithmic viscosity of 1.1 dl / g (as This is referred to as "Polymer (Ba)") 32.60 g. Comparative Example 4 Synthesis of polyamidic acid except that 5.20 g of diamine shown in the above (10), 1 7.8 g of 4,4-diaminodiphenylsulfonium and 2,3,5-tricarboxy ring were used. 22.4 g of amyl acetic dianhydride 7.02 g of substituted lithocholic acid methyl ester (3,5-diamino benzoate), 13.0 g of p-phenylenediamine and 2,3,5-tricarboxylic acid 200413441 cyclopentyl acetic acid Except for 30.0 g of dihepatitis, the rest are the same as in Example 丨, and a polyamidic acid having a logarithmic viscosity of 0.95 dl / g (this is referred to as "polymer (ca)") 40.6 g. Comparative Example 5 In addition to the synthesis of the polymer, except that the polymer (Ca) 25.0 g was used to replace the polymer (la) 25 () g, 4.5 g of ton bite and 5.8 g of acetic anhydride were used instead of pyridine 10.6§ and acetic anhydride In the same manner as in Example 2, 19.0 g of an acid imidized polymer having a log viscosity of G.96 dl / g (this was referred to as "polymer (Cb)") was obtained. Example 11 (1) Preparation of liquid crystal aligning agent: The polymer (丨 b) obtained in Example 2 was dissolved in γ-butyrolactone to form a 2.5% by weight solid solution, and a filter with a pore size of μηι was used. This solution was filtered to prepare the liquid crystal aligning agent of the present invention. (2) Production of liquid crystal display elements: ③ On the transparent V electric film composed of ITO film provided on one surface of a 1 mm thick glass substrate, use a spin coater to apply the liquid crystal aligning agent of the present invention prepared as described above. And dried at 18 ° C for 1 hour to form a coating film having a dry film thickness of 800 angstroms. ® The coating film formed was ground by using a grinding machine having a roll wound with a roll of Nylon cloth. A liquid crystal alignment film is produced on the surface. Here, the grinding process conditions are the number of rotations of the roller 500 rpm, the moving speed of classification} cm / sec. ◎ As described above, two substrates forming a liquid crystal alignment film are produced, and the edges of each substrate are formed. After applying an indium oxide brush with a diameter of 17 μm, a 0: 'S7 \ 87〇6l.D〇c -63-2UU41J441 series adhesive was applied by the second edition indene brush method, and the orientation direction of each liquid crystal film was polished. Presenting each other: 1. The two substrates are arranged opposite to each other through the gap, and the adhesive is hardened by contacting the outer edge portion. 2. The surface of the main soil plate and the partition separated by the adhesive agent on the outer edge portion are hardened. Nematic liquid crystal "MLC-2GOL" (manufactured by Merck) is filled / filled in the inter-cell space, Then, ^ M is then filled with a manhole to form a liquid crystal cell. Then, on the outer surface of the liquid, the polarization direction of the liquid crystal and the polishing direction of the liquid crystal alignment film are 45 units ^ "" X "and orthogonal to each other Method 'Laminating polarizing plate, making / displaying elements at night and day. CD is made as above and released ~ Night is not visible ... It is applied to the LCD cell and f &amp; guard, no abnormal area can be seen And the alignment of the liquid crystal is good. The rate of 9 to 彳 卩 is 5 degrees. The voltage of the liquid crystal display element is maintained ..., and the afterimage erasing time is extremely short to 0.4 seconds. Example 12 to 15 5, 5 (2b) ~ (5b) instead of the polymer (lb), the rest of the fish ♦ 1_, and the liquid crystal alignment agent is prepared to produce a liquid crystal display element 2: the alignment of the liquid crystal in the liquid crystal display element, Voltage holding rate and disappearance time of Han Ying. Results are shown in Table 1

S7 \ 8706I.DOC -64- Comparative Example 6 Two polyimide (Ab) -substituted polymers obtained in Comparative Example 2 (2): Same as in Example 12, and the alignment of the liquid crystal alignment liquid is not obvious every day . Measure the liquid crystal alignment angle, voltage retention rate, and afterimage disappearance in liquid crystals, clothing, and clothing. Table 2. And bleed ~, 4 meat dumplings. The results are shown in the polymer (Ba) instead of the polymer OB) in Comparative Example 7, and the liquid crystal alignment was adjusted to prepare the liquid crystal alignment and the disappearance time of the afterimage in the liquid crystal display element prepared as a liquid. The results are shown in Table 2. The polymer (i) is used in place of the polymer (i), and a liquid crystal aligning agent is prepared to prepare the liquid crystal alignment in the liquid crystal display element as a liquid and the disappearance time of the afterimage. The results show that this is the same as that of Example 12 except that it was obtained by using Comparative Example 3. The measurement was performed on the manufacturing property, the elevation angle, and the voltage holding ratio. Comparative Example 8 Except that obtained by using Comparative Example 5, the rest were the same as those of Example 12 in the same isotropic display element. Table 2 shows the measured properties, elevation angle, and voltage retention. Table 2

0: 37.87061.DOC -65- 200413441 Example 16 Synthesis of Polyamic Acid will be 112.09g (0.5 mole) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, l, 3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furyl) -naphtho [1,2-C] furan_1, 157.15 g of 3-dione (0.5 mole) and g of lithocholic acid as a monoamine compound (3,5 · diaminophenylbenzoate) 52.47 g (0.1 mole), p-phenylenediamine 97.33 g (0.9 mol) was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. Then, the reaction solution was poured into a very excessive amount of methanol to sink the reaction product. Thereafter, it was washed with methanol and dried under reduced pressure at 4 ° C. for 15 hours to obtain a polyamic acid having a logarithmic viscosity of 0.64 dl / g and an acid imidization rate of 0%. 410 g of amino acid (6a) "). Example 17 Synthesis of fluorinated imidized polymer 30.0 g of polyamino acid (6a) obtained in Example 16 was dissolved in 570 g of N-methylpyrrolidone. 29.2 g of pyridine and 30.2 g of acetic anhydride were added to the solution, and the reaction was dehydrated and closed-looped by heating at no ° C for 4 hours. Then, the reaction> valley was poured into a very excessive amount of methanol to cause the reaction product to settle. After that, it was washed with methanol and dried under reduced pressure at 40 ° C for 15 hours to obtain a brewed imidized polymer having a logarithmic viscosity of 0.24 dl / g and a yield of 96%. 28.8 g as "fluorinated imidized polymer (6b)". Example 18 Synthesis of a saddle polymer In Example 16, except that the diamine compound was butyl lithocholic acid (3,5-di amine

0: ^. 8 ^ 87061.DOC -66-200413441 benzoate) 56.68 g (0.1 mol), p-phenylenediamine 97.33 g (0.9 mol), the rest were the same as in Example 16 to obtain polyfluorene Amino acid (as "Polyamido acid (7a)"), further using this and carrying out the fluorene imidization reaction in the same manner as in Example 丨 7, the log viscosity was 0.27 dl / g, and the fluorene imine ratio was 97% 27.6 g of brewed imidized polymer (this is referred to as "醯 imidized polymer (7b)"). Example 1 9 Synthesis of fluorene imidized polymer In Example 16, except that the diamine compound was ammonium lithocholic acid (3,5-diaminophenyl benzoate) 58.09 g (〇 · ΐ 莫尔). Except for 33 g (0.9 mol) of bendiamine, the rest was the same as in Example 16 to obtain polyamic acid (as "polyamic acid (8a)"). 17 The same fluorene imidization reaction was performed, and a fluorene imidized polymer having a logarithmic viscosity of 0.22 dl / g and a fluorene imidization rate of 95% (as a "fluorene imidized polymer (8b)") 26.9 §. Example 20 Synthesis of fluorinated imidized polymer In Example 16 except that the diamine compound was heptadecyl lithocholic acid (3, amine phenylphosphonic acid s) 74.92 g ((M Mo Ear), p-phenylenediamine 97 except (0.99 moles), the rest is the same as in Example 16 and served as a polyamic acid (as a "polyacrylic acid (9a)"). -Zhou Youtian lL μ This is the same as in Example 17 and the ammonium &amp; imidization reaction is performed to obtain the logarithmic point order. Η ”The brew with a number viscosity of 0.23 dl / g and an imidization rate of 98% Imidized polymer (this was used as "A" 26.3 g of imidized polymer (9b) 〇 Example 2 1 Synthesis of imidized polymer

O: \ srS706I.DOC -67-200413441 In Example 16 of palladium palladium, except that the diamine compound is octadecyl lithocholic acid (3,5_: aminobenzoic acid,) 76_32g (〇) mol), Except for phenylenediamine 97.33 g (0.99 旲), the rest was the same as in Example 16 to obtain polyamino acid (this was used as water I amine hydrazone (10a) "). This was further used in this example. In the same way, the acid imidization reaction was performed in the same way as in Example 7 to obtain a fluorene imidized polymer with a log viscosity of 0.24 and a cyanine imidization rate of 95%. ) ") 28.1g 〇 Comparative Example 9 'Synthesis of imidized polymer In Example 16, except that the diamine compound is a diamine represented by the above formula (4 ^ 6 ^ 0.08 mole), p-phenylenediamine Except for 137 82 g (0 92 moles) of amine, the remainder was the same as in Example 16 to obtain polyamic acid (this was referred to as "polyamic acid (Da)"). Further, this was carried out in the same manner as in Example 17 The amination reaction yielded 27 lg of a brewed imidized polymer with a logarithmic viscosity of 0.26 dl / g and a heart amidation rate of 96% (this is referred to as "醯 imidized polymer (Db)"). Comparative Example 10 Synthesis of fluorinated imidized polymer In Example 16, except that the diamine compound was p-phenylenediamine 108i4g (10 moles), the rest was the same as in Example 16 to obtain polyfluorene. Acid (as "Polyamidoacid (Ea)"), further using this and carrying out the imidization reaction in the same manner as in Example 丨 7, the logarithmic viscosity was 0.41 //, the imidization ratio was 97 % Of fluorene imidized polymer (this is referred to as "fluorene imidized polymer (Eb)") 26.7g.

Reference Synthesis iW -68-200413441 Synthesis of Polyamino Acid In Example 16, except that the tetracarboxylic dianhydride was benzenetetrahydroacid anhydride 9.06g (〇5 mol) and cyclobutane tetracarboxylic dianhydride Except for 98.06 g (0.5 mole) and the diamine being 4,4-diaminodiphenylphosphorane 198 27 g (10 mole), the rest was the same as in Example 16 to obtain a log viscosity of 2.41 dl / g, polydonine amino acid with an imidization rate of 0% (this is referred to as "polyamino acid (Za)"). Example 22 The fluorene imidized polymer (6b) obtained in Example 17 and the polyfluorinated acid (Za) obtained in the above reference synthesis example were used as the fluorinated polymer: polyfluorinated acid = 1 ·· 4 (weight ratio) ratio method, dissolved in ^ 曱 _2-pyrrolidone / butyl soluble fiber / γ-butyrolactone (1/1/8) mixed solvent to form a solid content concentration of 4 reset% The solution was filtered with a filter having a pore size of 1 μm to prepare a liquid crystal aligning agent. The above-mentioned liquid crystal aligning agent was applied on a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film by a spin coater, and dried on a hot plate of 20 ° C for 10 minutes to form a dry average film of 600 °. A coating film of Angstrom. On this coating film, a grinding machine having a roll around which a woven cloth is wound, the rotation speed of the roller is 400 rpm, the moving speed of classification is 3 cm / sec, and the length of the burr is pushed in. _4 mm for polishing treatment. After immersing the above-mentioned oriented film coating base in isopropanol for 1 minute, the substrates of both sides were dried on a hot plate at 10 ° C for 5 minutes. Second, a pair of Each outer edge of the liquid crystal alignment film of the substrate is coated with an epoxy resin adhesive containing alumina balls with a diameter of 5 · 5 spleens, and the liquid crystal alignment film faces are opposite, and overlapped in a state where the grinding direction is twisted by 90 degrees. Pressure-bonding and hardening the adhesive, and then injecting π from the liquid crystal into the substrate and filling the nematic liquid crystal (Merck, MLc⑽2) _ (sgang)

O: \ 8 ^ S7061.DOC -69- 200413441, and then inject the liquid crystal with acrylic light-curing adhesive, and seal the liquid crystal with 0, and attach polarizing plates on the two outer sides of the substrate to make a liquid crystal display element. The residual DC voltage will show a value as low as 400 mV. After the reliability test, uneven brightness and unevenness will not be seen, and defects will be displayed. These results are shown in Table 3. Examples 23 to 26 A liquid crystal display device was produced in the same manner as in Example 22 except that the fluorene imidized polymers obtained in Examples 18 to 21 were used. The results are shown in Table 3.

A liquid crystal display device was produced in the same manner as in Example 22 except that the fluorinated polymer obtained in Comparative Example 9 and 10 was used. The results are shown in Table 4. Table 4 Example Residual DC voltage (mV) of polymer polymer liquid crystals Reliability test (with or without defects) 11 (Db) n- (Za) Good 900 Benefit 12 (Eb) + (Za) Good 900 Benefits are as above In general, according to the present invention, a novel diamine compound can be provided, and the polyamidic acid and the fluorenimide polymer obtained from this and more suitable for use in a liquid crystal aligning agent can be provided. The liquid crystal aligning film formed by the liquid crystal aligning agent according to the present invention is more suitable for 0: -8 ^ 87061.000 -70- 200413441 and is used to form TN type liquid crystal display elements, STN type liquid crystal display elements, and vertical alignment type liquid crystal display elements. And other various liquid crystal display elements. In addition, the preparation of the liquid crystal alignment film of the tongue, the right g-shape &lt;, the night crystal is inconspicuous, is the liquid crystal ^ ... 1-1 1 is also excellent in sin and can be effectively used 〆 、 尽 # 地 用Let Shuang be used in various devices, for example, Machida as a desktop meter, a computer, a computer, a watch, a clock, a counting display, a personal computer, a personal thunderstorm, and a night crystal TV. Display device.

Claims (1)

200413441 The scope of patent application: 1. A diamine compound, at least one of which is selected from the group consisting of: H ^ -G ^ a ^ D ^ CO-B1- (E1) ⑴ I a nh2 (wherein, D1 is a divalent hydrocarbon group containing 5 to 30 carbon atoms, G1 is a trivalent organic group, A1 is a single bond or a divalent bonding group, and B1 is a single bond, -0-, -N (H)- Or / -N \, E1 is a monovalent organic group, a is a compound represented by 1 or 2) and the following formula (Π) H2N-G2-A2 ~ D2-CO-B2- (E2) b (π) I A2-G2-NH2 (where D2 is a trivalent hydrocarbon group containing 5 to 30 carbon atoms, alicyclic, G2 is a divalent organic group, A2 is a single bond or a divalent bonding group, B2 is a single bond,- 〇-, -N (H)-or -N \, E2 is a monovalent organic group, and b is a group of compounds represented by 1). 200413441 2. The diamine compound according to item 1 of the patent application range 1, wherein the group represented by D1 in the above formula (1) or the group represented by D2 in the above formula (11) is a hydrocarbon group containing a steroid skeleton. y 3. A polyamidic acid, which is at least one diamine compound according to item 丨 of the patent application scope, and is represented by the following formula (ΠΙ) (III) (Wherein G4 is a tetravalent organic group) a reaction product obtained by at least one of the tetracarboxylic dianhydrides shown. 4. A kind of fluorene imidized polymer, which is obtained by dehydrating and closing the polyfluorine acid as described in the patent claim No. 3. 5. A liquid crystal aligning agent, which contains at least one selected from the group consisting of polyamic acid such as item 3 of the patent application, and item 4 of patent application ^ 醯 Made of imidized polymers. 6 / liquid crystal aligning agents, which contain at least one kind selected from the group consisting of the following formulae (XI) to (xiv) ... (XI) \ G4 / C〇〇H, C-NH-G- ii 0 ... (XII) 200413441 (Wherein A1, A2, B1, B2, D1, D2, E1, E2, G1, G2, G4, a, and b have the same definitions as described above) and are each a polymer of repeating units shown. 7. The liquid crystal aligning agent according to item 6 of the Shenyan patent, which further contains a polyamic acid and donkey imidization polymerization which do not have a repeating unit represented by any of the above formulae (XI) to (XIV) Thing. 8. The liquid crystal aligning agent according to item 7 of the patent application scope, comprising: a polymer having a repeating unit represented by the above formula (XIII) and / or a repeating unit represented by (χιν); A polydonyl acid of a repeating unit dried by any one of the formulae (XI) to (XIV). 9. A liquid crystal display element comprising a liquid crystal alignment film formed of a liquid crystal alignment agent as set forth in any one of claims 5 to 8. 200413441 Dyeing and designated representative map: (I) The designated representative map in this case is: (none) (II) The component representative symbols of this representative map are simply explained: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: 0 II NH—C, HOOC /; G 4 / COOH, C- II 〇 • NH A1—D1 — CO — -i1-- ... (XI) Ο · Λ3 7 \ 8706l.DOC