CN1564840A - Diamine compound, polyamic acid, imide polymer, liquid crystal alignment agent and liquid crystal display - Google Patents

Diamine compound, polyamic acid, imide polymer, liquid crystal alignment agent and liquid crystal display Download PDF

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CN1564840A
CN1564840A CN 03801167 CN03801167A CN1564840A CN 1564840 A CN1564840 A CN 1564840A CN 03801167 CN03801167 CN 03801167 CN 03801167 A CN03801167 A CN 03801167A CN 1564840 A CN1564840 A CN 1564840A
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acid
ester
aminobenzoate
liquid crystal
bis
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CN1266192C (en
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中田正一
六鹿泰显
河野美沙
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JSR Corp
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J41/00—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Abstract

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 therefor; and a diamine compound as a monomer therefor. 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

Diamine compound, polyamic acid, imide amination polymer, liquid crystal aligning agent and liquid crystal display device
Technical field
The invention relates to diamine compound, polyamic acid, imide amination polymer, contain in these at least one liquid crystal aligning agent and possess the liquid crystal display device of the liquid crystal orientation film that forms by such liquid crystal aligning agent.
Background technology
Liquid crystal display device with TN (Twisted Nematic-twisted-nematic) type or STN (SuperTwisted Nematic-supertwist is to row) type liquid crystal cell is known, this TN type or STN type liquid crystal cell, be will have the positive electricity anisotropic nematic liquid crystal that is situated between with the substrate of band transparency electrode with liquid crystal orientation film to form sandwich structure, the major axis of liquid crystal molecule will be twisted into 90 degree or above and constitute continuously between substrate in the past.Usually the liquid crystal orientation film that forms by the orientation process of implementing friction treatment etc. on the surface of the overlay film that is made of polymkeric substance is controlled the liquid crystal aligning in these liquid crystal display device.At this, as the polymkeric substance that constitutes above-mentioned overlay film, known have polyamic acid and a polyimide, generally uses the liquid crystal aligning agent that dissolves these polymkeric substance and constitute in solvent.
In addition, as with above-mentioned different liquid crystal display device, liquid crystal display device with vertical orientated (VerticalAlignment) type liquid crystal cell is known, and this vertical orientated liquid crystal cell makes that to have a negative electricity anisotropic liquid crystal molecule that is situated between vertical orientated and constitute on substrate.Even in such liquid crystal display device, the control of the orientation of liquid crystal is finished by the liquid crystal orientation film that is formed by the liquid crystal aligning agent that contains polymkeric substance such as polyamic acid, polyimide usually.
But, in the liquid crystal display device that possesses the liquid crystal orientation film that forms by in the past liquid crystal aligning agent, the ionic electric charge that (during impressed voltage) produces when pictorial display is adsorbed by liquid crystal orientation film, even (after removing impressed voltage) after the fade down, also be not easy from the liquid crystal aligning membrane desorption, therefore the also residual voltage of accumulating on the liquid crystal orientation film after voltage is removed results from this retained voltage, has the problem that produces afterimage on the display image after impressed voltage is removed.
And, if use this liquid crystal display device for a long time, the display defect of the stain shape of white often takes place, because this display defect, and have the reliability problems of infringement as liquid crystal display device.Recently, as being representative with the LCD TV purposes, the such liquid crystal display device of long-time continuously use has become inevitable, and the necessity that further improves reliability increases.
Summary of the invention
The 1st purpose of the present invention is to provide the diamine compound of novelty.
The 2nd purpose of the present invention is to provide as the useful novel polyamic acid of liquid crystal aligning agent.
The 3rd purpose of the present invention is to provide as the useful novel imide fluidized polymer of liquid crystal aligning agent.
The 4th purpose of the present invention is to provide liquid crystal aligning agent, it is when can showing good orientation characteristic, can be formed on the liquid crystal display device and to remove behind the impressed voltage to time that afterimage disappears (below, be called " afterimage extinction time ") short liquid crystal orientation film.
Other purpose and advantage of the present invention just can be clear from effective explanation.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 1st, utilize to be selected from following formula (I)
The expression compound and with following formula (II)
At least a diamine compound in the compound of expression (below, also be called " specific diamine compound ") reach,
In formula (I), D 1Be the divalent alkyl that contains the carbonatoms 5～30 of alicyclic ring, G 1Be 3 valency organic radicals, A 1Be the combination base of singly-bound or divalent, B 1Be singly-bound ,-O-,-N (H)-or
E 1Be 1 valency organic radical, a is 1 or 2; In formula (II), D 2Be the 3 valency alkyl that contain the carbonatoms 5～30 of alicyclic ring, G 2Be the divalent organic radical, A 2Be the combination base of singly-bound or divalent, B 2Be singly-bound ,-O-,-N (H)-or E 2Be 1 valency organic radical, b is 1 or 2.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 2nd, be utilized as at least a of specific diamine compound and with following formula (III)
The polyamic acid of the tetracarboxylic dianhydride's of expression at least a resultant of reaction reaches, in formula, and G 4Be 4 valency organic radicals.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 3rd, utilize the imide amination polymer that makes above-mentioned polyamic acid dehydration closed-loop and obtain to reach.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 4th, utilize to contain to be selected from the liquid crystal aligning agent that at least a compound in above-mentioned polyamic acid and the polyimide fluidized polymer forms and to reach.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 5th, utilize the liquid crystal aligning agent contain polymkeric substance to reach, described polymkeric substance contains and is selected from respectively with following formula (XI)～(XIV)
Figure A0380116700074
Figure A0380116700081
The expression repeating unit at least a,
In above-mentioned formula, A 1, A 2, B 1, B 2, D 1, D 2, E 1, E 2, G 1, G 2, G 4, a and b definition same as described above.
In addition, according to the present invention, above-mentioned purpose of the present invention and advantage, the 6th, utilize the liquid crystal display device that possesses the liquid crystal orientation film that forms by above-mentioned liquid crystal aligning agent to reach.
Embodiment
Below, explain the present invention.
＜diamine compound 〉
Diamine compound of the present invention be with above-mentioned formula (I) or (II) expression compound.
At this, in above-mentioned formula (I) with D 1The expression and in above-mentioned formula (II) with D 2The alkyl of the carbonatoms that contains alicyclic ring 5～30 of expression serve as preferably with the alkyl of the carbonatoms 10～30 that contains alicyclic ring, is more preferably the alkyl that contains the steroid skeleton.As such divalent alkyl (D 1), concrete enumerating respectively with the following formula (I-1) and (I-2) structure of expression.
In addition, as 3 valency alkyl (D 2), the concrete structure of enumerating respectively with following formula (II-1)～(II-4) expression.
As with G 13 valency organic radicals of expression for example can be enumerated the base of removing 3 hydrogen atoms from the alkyl of carbonatoms 1～15, and the base of representing with following formula (I-3) and following formula (I-4) respectively.In addition, as with G 2The divalent organic radical of expression for example can be enumerated the base of removing 2 hydrogen atoms from the alkyl of carbonatoms 1～15.
As with A 1And A 2The combination base of expression, the concrete ketone group enumerated, ehter bond, ester bond, amido linkage, amino-formate bond and urea bond.
In addition, as with E 1And E 21 valency organic radical of expression, the straight chained alkyl of the concrete carbonatoms enumerated 1～30 or branched-chain alkyl; Ester ring type bases such as cyclopentyl, cyclohexyl, naphthane base, dicyclohexyl, cholestane base, cholesteryl; The base that contains aromatic nucleus such as phenyl, tolyl, xylyl, naphthyl, benzyl, styroyl, trityl; Contain heterocyclic organic radicals such as furyl, tetrahydrofuran base, thienyl, tetrahydro-thienyl, pyrryl, pyridyl, piperidyl, piperidino-(1-position only), morpholino base, quinolyl, isoquinolyl, the sub-methyl of piperidines, morpholino methyl; With following formula (IV)
-Q 4-T 4-S 4??????????????????????????????(IV)
The base of expression, and replace 1 in the above-mentioned organic radical or be equal to or greater than 2 hydrogen atoms and the base that obtains with halogen, in the formula (IV), Q 4Be the divalent ring-type organic radical that is selected from aromatic nucleus, alicyclic ring, heterocycle and substitution compound thereof, T 4Be commutable divalent ester ring type base, S 4It is the alkyl of carbonatoms 1～30.
Among these bases, preferentially select the alkyl of carbonatoms 1～30, the fluoroalkyl of carbonatoms 1～30 and the base of in the base of above-mentioned formula (IV) expression, representing with following formula (IV-1)～(IV-4) respectively.
In addition, in above-mentioned formula (I), at B 1Be singly-bound ,-O-or-N (H)-time, a is 1, at B 1Be
The time, a is 2.Equally, in above-mentioned formula (II), at B 2Be singly-bound ,-O-or-N (H)-time, b is 1, at B 2Be
Figure A0380116700103
The time, b is 2.
Object lesson as the specific diamine compound of representing with above-mentioned formula (I), can enumerate Methyl lithocholate (3,5-diaminobenzoic acid ester), lithocholic acid ethyl ester (3,5-diaminobenzoic acid ester), lithocholic acid propyl ester (3,5-diaminobenzoic acid ester), lithocholic acid butyl ester (3,5-diaminobenzoic acid ester), lithocholic acid pentyl ester (3,5-diaminobenzoic acid ester), the own ester (3 of lithocholic acid, 5-diaminobenzoic acid ester), lithocholic acid cyclohexyl (3,5-diaminobenzoic acid ester), lithocholic acid n-Hexadecane ester (3,5-diaminobenzoic acid ester), lithocholic acid heptadecane ester (3,5-diaminobenzoic acid ester), lithocholic acid octadecane ester (3,5-diaminobenzoic acid ester), lithocholic acid phenyl ester (3,5-diaminobenzoic acid ester), lithocholic acid benzyl ester (3,5-diaminobenzoic acid ester), lithocholic acid trifluoro methyl esters (3,5-diaminobenzoic acid ester), lithocholic acid (2,2, the 2-trifluoroethyl) ester (3,5-diaminobenzoic acid ester), lithocholic acid (1,1,2,2, the 2-pentafluoroethyl group) ester (3,5-diaminobenzoic acid ester), lithocholic acid (4-fluorophenyl) ester (3,5-diaminobenzoic acid ester), lithocholic acid (4-(trifluoromethyl) phenyl) ester (3,5-diaminobenzoic acid ester), lithocholic acid (4-(4-amyl group cyclohexyl) phenyl) ester (3,5-diaminobenzoic acid ester), lithocholic acid (4-(4-heptyl cyclohexyl) phenyl) ester (3,5-diaminobenzoic acid ester); N-methyl lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-ethyl lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N, N-dimethyl lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N, N-diethyl lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-propyl group lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-butyl lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-amyl group lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-hexyl lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-cyclohexyl lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-hexadecyl lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-heptadecyl lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-octadecyl lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-phenyl lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-methyl-N-phenyl lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-benzyl lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-trifluoromethyl lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-(2,2, the 2-trifluoroethyl) lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-(1,1,2,2, the 2-pentafluoroethyl group) lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-(4-(trifluoromethyl) phenyl) lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-(4-(4-amyl group cyclohexyl) phenyl) lithocholic acid acid amides (3,5-diaminobenzoic acid ester), N-(4-(4-heptyl cyclohexyl) phenyl) lithocholic acid acid amides (3,5-diaminobenzoic acid ester); 3 (2, the 4-diamino phenoxy) cholane-24-acid methyl esters, 3 (2, the 4-diamino phenoxy) cholane-24-acetoacetic ester, 3 (2, the 4-diamino phenoxy) cholane-24-propyl propionate, 3 (2, the 4-diamino phenoxy) cholane-24-acid butyl ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid pentyl ester, 3 (2, the 4-diamino phenoxy) cholane-own ester of 24-acid, 3 (2, the 4-diamino phenoxy) cholane-24-acid cyclohexyl, 3 (2, the 4-diamino phenoxy) cholane-24-acid n-Hexadecane ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid heptadecane ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid octadecane ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid phenenyl ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid benzyl ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid trifluoro methyl esters, 3 (2, the 4-diamino phenoxy) cholane-24-acid (2,2, the 2-trifluoroethyl) ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid (1,2,2,2-tetrafluoro ethyl) ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid (1,1,2,2, the 2-pentafluoroethyl group) ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid (4-fluorophenyl) ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid (4-(trifluoromethyl) phenyl) ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid (4-(4-amyl group cyclohexyl) phenyl) ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid (4-(4-heptyl cyclohexyl) phenyl ester); N-methyl-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-ethyl-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N, N-dimethyl-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N, N-diethyl-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-propyl group-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-butyl-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-amyl group-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-hexyl-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-cyclohexyl-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-hexadecyl-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-heptadecyl-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-octadecyl-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-phenyl-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-benzyl-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-trifluoromethyl-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-(2,2, the 2-trifluoroethyl)-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-(2,2, the 2-trifluoroethyl)-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-(1,1,2,2, the 2-pentafluoroethyl group)-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-(4-fluorophenyl)-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-(4-(trifluoromethyl) phenyl)-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-(4-(4-amyl group cyclohexyl) phenyl)-3 (2, the 4-diamino phenoxy) cholane-24-acid amides, N-(4-(4-heptyl cyclohexyl) phenyl)-3 (2, the 4-diamino phenoxy) cholane-24-acid amides.
Among these, the preferential Methyl lithocholate (3 of selecting, 5-diaminobenzoic acid ester), lithocholic acid ethyl ester (3,5-diaminobenzoic acid ester), lithocholic acid propyl ester (3,5-diaminobenzoic acid ester), lithocholic acid butyl ester (3,5-diaminobenzoic acid ester), lithocholic acid pentyl ester (3,5-diaminobenzoic acid ester), the own ester (3 of lithocholic acid, 5-diaminobenzoic acid ester), lithocholic acid cyclohexyl (3,5-diaminobenzoic acid ester), lithocholic acid n-Hexadecane ester (3,5-diaminobenzoic acid ester), lithocholic acid heptadecane ester (3,5-diaminobenzoic acid ester), lithocholic acid octadecane ester (3,5-diaminobenzoic acid ester), lithocholic acid trifluoro methyl esters (3,5-diaminobenzoic acid ester), lithocholic acid (2,2, the 2-trifluoroethyl) ester (3,5-diaminobenzoic acid ester), lithocholic acid (1,1,2,2, the 2-pentafluoroethyl group) ester (3,5-diaminobenzoic acid ester), lithocholic acid (4-(4-amyl group cyclohexyl) phenyl) ester (3,5-diaminobenzoic acid ester), lithocholic acid (4-(4-heptyl cyclohexyl) phenyl) ester (3,5-diaminobenzoic acid ester); 3 (2, the 4-diamino phenoxy) cholane-24-acid methyl esters, 3 (2, the 4-diamino phenoxy) cholane-24-acetoacetic ester, 3 (2, the 4-diamino phenoxy) cholane-24-propyl propionate, 3 (2, the 4-diamino phenoxy) cholane-24-acid butyl ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid pentyl ester, 3 (2, the 4-diamino phenoxy) cholane-own ester of 24-acid, 3 (2, the 4-diamino phenoxy) cholane-24-acid cyclohexyl, 3 (2, the 4-diamino phenoxy) cholane-24-acid n-Hexadecane ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid octadecane ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid trifluoro methyl esters, 3 (2, the 4-diamino phenoxy) cholane-24-acid (2,2, the 2-trifluoroethyl) ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid (1,2,2,2-tetrafluoro ethyl) ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid (1,1,2,2, the 2-pentafluoroethyl group) ester, 3 (2, the 4-diamino phenoxy) cholane-24-acid (4-(4-amyl group cyclohexyl) phenyl) ester; 3 (2, the 4-diamino phenoxy) cholane-24-acid (4-(4-heptyl cyclohexyl) phenyl) ester, especially preferentially select lithocholic acid butyl ester (3,5-diaminobenzoic acid ester), lithocholic acid pentyl ester (3,5-diaminobenzoic acid ester), the own ester (3 of lithocholic acid, 5-diaminobenzoic acid ester), lithocholic acid n-Hexadecane ester (3,5-diaminobenzoic acid ester), lithocholic acid heptadecane ester (3,5-diaminobenzoic acid ester), lithocholic acid octadecane ester (3,5-diaminobenzoic acid ester), lithocholic acid trifluoro methyl esters (3,5-diaminobenzoic acid ester), lithocholic acid (2,2, the 2-trifluoroethyl) ester (3,5-diaminobenzoic acid ester), lithocholic acid (1,1,2,2, the 2-pentafluoroethyl group) ester (3,5-diaminobenzoic acid ester), lithocholic acid (4-(4-amyl group cyclohexyl) phenyl) ester (3,5-diaminobenzoic acid ester), lithocholic acid (4-(4-heptyl cyclohexyl) phenyl) ester (3,5-diaminobenzoic acid ester).
In addition, object lesson as the specific diamine compound of representing with above-mentioned formula (II), can enumerate Septochol methyl esters (two (4-Aminobenzoate)), Septochol ethyl ester (two (4-Aminobenzoate)), Septochol propyl ester (two (4-Aminobenzoate)), Septochol butyl ester (two (4-Aminobenzoate)), Septochol pentyl ester (two (4-Aminobenzoate)), the own ester of Septochol (two (4-Aminobenzoate)), Septochol cyclohexyl (two (4-Aminobenzoate)), Septochol n-Hexadecane ester (two (4-Aminobenzoate)), Septochol heptadecane ester (two (4-Aminobenzoate)), Septochol octadecane ester (two (4-Aminobenzoate)), Septochol phenyl ester (two (4-Aminobenzoate)), Septochol benzyl ester (two (4-Aminobenzoate)), Septochol trifluoro methyl esters (two (4-Aminobenzoate)), Septochol (2,2, the 2-trifluoroethyl) ester (two (4-Aminobenzoate)), Septochol (1,1,2,2, the 2-pentafluoroethyl group) ester (two (4-Aminobenzoate)), Septochol (4-fluorophenyl) ester (two (4-Aminobenzoate)), Septochol (4-(trifluoromethyl) phenyl) ester (two (4-Aminobenzoate)), Septochol (4-(4-amyl group cyclohexyl) phenyl) ester (two (4-Aminobenzoate)), Septochol (4-(4-heptyl cyclohexyl) phenyl) ester (two (4-Aminobenzoate)); N-methyl Septochol acid amides (two (4-Aminobenzoate)), N-ethyl Septochol acid amides (two (4-Aminobenzoate)), N, N-dimethyl Septochol acid amides (two (4-Aminobenzoate)), N, N-diethyl Septochol acid amides (two (4-Aminobenzoate)), N-propyl group Septochol acid amides (two (4-Aminobenzoate)), N-butyl Septochol acid amides (two (4-Aminobenzoate)), N-amyl group Septochol acid amides (two (4-Aminobenzoate)), N-hexyl Septochol acid amides (two (4-Aminobenzoate)), N-cyclohexyl Septochol acid amides (two (4-Aminobenzoate)), N-hexadecyl Septochol acid amides (two (4-Aminobenzoate)), N-heptadecyl Septochol acid amides (two (4-Aminobenzoate)), N-octadecyl Septochol acid amides (two (4-Aminobenzoate)), N-phenyl Septochol acid amides (two (4-Aminobenzoate)), N-methyl-N-phenyl Septochol acid amides (two (4-Aminobenzoate)), N-benzyl Septochol acid amides (two (4-Aminobenzoate)), N-trifluoromethyl Septochol acid amides (two (4-Aminobenzoate)), N-(2,2, the 2-trifluoroethyl) Septochol acid amides (two (4-Aminobenzoate)), N-(1,1,2,2, the 2-pentafluoroethyl group) Septochol acid amides (two (4-Aminobenzoate)), N-(4-fluorophenyl) Septochol acid amides (two (4-Aminobenzoate)), N-(4-(trifluoromethyl) phenyl) Septochol acid amides (two (4-Aminobenzoate)), N-(4-(4-amyl group cyclohexyl) phenyl) Septochol acid amides (two (4-Aminobenzoate)), N-(4-(4-heptyl cyclohexyl) phenyl) Septochol acid amides (two (4-Aminobenzoate)); Septochol methyl esters (two (3-Aminobenzoate)), Septochol ethyl ester (two (3-Aminobenzoate)), Septochol propyl ester (two (3-Aminobenzoate)), Septochol butyl ester (two (3-Aminobenzoate)), Septochol pentyl ester (two (3-Aminobenzoate)), the own ester of Septochol (two (3-Aminobenzoate)), Septochol cyclohexyl (two (3-Aminobenzoate)), Septochol n-Hexadecane ester (two (3-Aminobenzoate)), Septochol heptadecane ester (two (3-Aminobenzoate)), Septochol octadecane ester (two (3-Aminobenzoate)), Septochol phenyl ester (two (3-Aminobenzoate)), Septochol benzyl ester (two (3-Aminobenzoate)), Septochol trifluoro methyl esters (two (3-Aminobenzoate)), Septochol (2,2, the 2-trifluoroethyl) ester two (3-Aminobenzoate)), Septochol (1,1,2,2, the 2-pentafluoroethyl group) ester two (3-Aminobenzoate)), Septochol (4-fluorophenyl) ester two (3-Aminobenzoate)), Septochol (4-(trifluoromethyl) phenyl) ester (two (3-Aminobenzoate)); N-methyl Septochol acid amides (two (3-Aminobenzoate)), N-ethyl Septochol acid amides (two (3-Aminobenzoate)), N, N-dimethyl Septochol acid amides (two (3-Aminobenzoate)), N, N-diethyl Septochol acid amides (two (3-Aminobenzoate)), N-propyl group Septochol acid amides (two (3-Aminobenzoate)), N-butyl Septochol acid amides (two (3-Aminobenzoate)), N-amyl group Septochol acid amides (two (3-Aminobenzoate)), N-hexyl Septochol acid amides (two (3-Aminobenzoate)), N-cyclohexyl Septochol acid amides (two (3-Aminobenzoate)), N-hexadecyl Septochol acid amides (two (3-Aminobenzoate)), N-heptadecyl Septochol acid amides (two (3-Aminobenzoate)), N-octadecyl Septochol acid amides (two (3-Aminobenzoate)), N-phenyl Septochol acid amides (two (3-Aminobenzoate)), N-methyl-N-phenyl Septochol acid amides (two (3-Aminobenzoate)), N-benzyl Septochol acid amides (two (3-Aminobenzoate)), N-trifluoromethyl Septochol acid amides (two (3-Aminobenzoate)), N-(2,2, the 2-trifluoroethyl) Septochol acid amides (two (3-Aminobenzoate)), N-(1,1,2,2, the 2-pentafluoroethyl group) Septochol acid amides (two (3-Aminobenzoate)), N-(4-fluorophenyl) Septochol acid amides (two (3-Aminobenzoate)), N-(4-(trifluoromethyl) phenyl) Septochol acid amides (two (3-Aminobenzoate)), N-(4-(4-amyl group cyclohexyl) phenyl) Septochol acid amides (two (3-Aminobenzoate)), N-(4-(4-heptyl cyclohexyl) phenyl) Septochol acid amides (two (3-Aminobenzoate)); Gallodesoxycholic acid methyl esters (two (4-Aminobenzoate)), gallodesoxycholic acid ethyl ester (two (4-Aminobenzoate)), gallodesoxycholic acid propyl ester (two (4-Aminobenzoate)), gallodesoxycholic acid butyl ester (two (4-Aminobenzoate)), gallodesoxycholic acid pentyl ester (two (4-Aminobenzoate)), the own ester of gallodesoxycholic acid (two (4-Aminobenzoate)), gallodesoxycholic acid cyclohexyl (two (4-Aminobenzoate)), gallodesoxycholic acid n-Hexadecane ester (two (4-Aminobenzoate)), gallodesoxycholic acid heptadecane ester (two (4-Aminobenzoate)), gallodesoxycholic acid octadecane ester (two (4-Aminobenzoate)), gallodesoxycholic acid phenyl ester (two (4-Aminobenzoate)), gallodesoxycholic acid benzyl ester (two (4-Aminobenzoate)), gallodesoxycholic acid trifluoro methyl esters (two (4-Aminobenzoate)), gallodesoxycholic acid (2,2, the 2-trifluoroethyl) ester (two (4-Aminobenzoate)), gallodesoxycholic acid (1,1,2,2, the 2-pentafluoroethyl group) ester (two (4-Aminobenzoate)), gallodesoxycholic acid (4-fluorophenyl) ester (two (4-Aminobenzoate)), gallodesoxycholic acid (4-(trifluoromethyl) phenyl) ester (two (4-Aminobenzoate)), gallodesoxycholic acid (4-(4-amyl group cyclohexyl) phenyl) ester (two (4-Aminobenzoate)), gallodesoxycholic acid (4-(4-heptyl cyclohexyl) phenyl) ester (two (4-Aminobenzoate)); N-methyl gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-ethyl gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N, N-dimethyl gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N, N-diethyl gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-propyl group gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-butyl gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-amyl group gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-hexyl gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-cyclohexyl gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-hexadecyl gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-heptadecyl gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-octadecyl gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-phenyl gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-methyl-N-phenyl gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-benzyl gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-trifluoromethyl gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-(2,2, the 2-trifluoroethyl) gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-(1,1,2,2, the 2-pentafluoroethyl group) gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-(4-fluorophenyl) gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-(4-(trifluoromethyl) phenyl) gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-(4-(4-amyl group cyclohexyl) phenyl) gallodesoxycholic acid acid amides (two (4-Aminobenzoate)), N-(4-(4-heptyl cyclohexyl) phenyl) gallodesoxycholic acid acid amides (two (4-Aminobenzoate)); Gallodesoxycholic acid methyl esters (two (3-Aminobenzoate)), gallodesoxycholic acid ethyl ester (two (3-Aminobenzoate)), gallodesoxycholic acid propyl ester (two (3-Aminobenzoate)), gallodesoxycholic acid butyl ester (two (3-Aminobenzoate)), gallodesoxycholic acid pentyl ester (two (3-Aminobenzoate)), the own ester of gallodesoxycholic acid (two (3-Aminobenzoate)), gallodesoxycholic acid cyclohexyl (two (3-Aminobenzoate)), gallodesoxycholic acid n-Hexadecane ester (two (3-Aminobenzoate)), gallodesoxycholic acid heptadecane ester (two (3-Aminobenzoate)), gallodesoxycholic acid octadecane ester (two (3-Aminobenzoate)), gallodesoxycholic acid phenyl ester (two (3-Aminobenzoate)), gallodesoxycholic acid benzyl ester (two (3-Aminobenzoate)), gallodesoxycholic acid trifluoro methyl esters (two (3-Aminobenzoate));
Chenodeoxycholic acid (2,2,2 - trifluoro-ethyl) ester (bis (3 - aminobenzoate)), Chenodeoxycholic acid (1,1,2,2,2 - pentafluoroethyl) ester (bis (3 - aminobenzoate)), Chenodeoxycholic acid (4 - fluorophenyl) acetate (bis (3 - aminobenzoate)), goose deoxycholate Acid (4 - (trifluoromethyl) phenyl) ester (bis (3 - aminobenzoate)), chenodeoxycholic Acid (4 - (4 - pentyl-cyclohexyl)-phenyl) ester (bis (3 - aminobenzoate)), goose Deoxycholate (4 - (4 - heptyl cyclohexyl)-phenyl) ester (bis (3 - aminobenzoate)); Chenodeoxycholic acid N-methyl amide (bis (3 - aminobenzoate)), N-ethyl-chenodeoxycholic Acid amide (bis (3 - aminobenzoate)), N, N-dimethyl-chenodeoxycholic acid amide (Bis (3 - aminobenzoate)), N, N-diethyl-chenodeoxycholic acid amide (bis (3 - Aminobenzoate)), N-propyl-chenodeoxycholic acid amide (bis (3 - amino acid Ester)), N-butyl-chenodeoxycholic acid amide (bis (3 - aminobenzoate)), N-pentyl Chenodeoxycholic acid amide groups (bis (3 - aminobenzoate)), N-hexyl-chenodeoxycholic Amide (bis (3 - aminobenzoate)), N-cyclohexyl-chenodeoxycholic acid amide (bis (3 - Aminobenzoate)), N-hexadecyl chenodeoxycholic acid amide (bis (3 - aminophenyl Ester)), N-heptadecyl chenodeoxycholic acid amide (bis (3 - aminobenzoate)), N-octadecyl chenodeoxycholic acid amide (bis (3 - aminobenzoate)), N-phenyl-Goose Deoxycholic acid amide (bis (3 - aminobenzoate)), N-methyl-N-phenyl - Goose off Oxygen acid amide (bis (3 - aminobenzoate)), N-benzyl-chenodeoxycholic acid amide (bis (3 - aminobenzoate)), N-trifluoromethyl-chenodeoxycholic acid amide (bis (3 - amino- Benzoate)), N-(2,2,2 - trifluoroethyl) amide chenodeoxycholic acid (bis (3 - amino Benzoate)), N-(1,1,2,2,2 - pentafluoroethyl) chenodeoxycholic acid amide (Bis (3 - aminobenzoate)), N-(4 - fluorophenyl) chenodeoxycholic acid amide (bis (3 - aminobenzoate)), N-(4 - (trifluoromethyl) phenyl) chenodeoxycholic acid Amine (bis (3 - aminobenzoate)), N-(4 - (4 - pentyl-cyclohexyl)-phenyl) Chenodeoxycholic acid amide (bis (3 - aminobenzoate)), N-(4 - (4 - heptyl-ring Hexyl)-phenyl) chenodeoxycholic acid amide (bis (3 - aminobenzoate)); deoxycholic acid Methyl (bis (4 - aminobenzoate)), ethyl deoxycholate (bis (4 - amino-benzoic Ester)), deoxycholic acid ester (bis (4 - aminobenzoate)), deoxycholic acid ester (Bis (4 - aminobenzoate)), deoxycholic acid pentyl ester (bis (4 - aminobenzoate)), Deoxycholic acid hexyl ester (bis (4 - aminobenzoate)), deoxycholic acid cyclohexyl ester (bis (4 - Aminobenzoate)), deoxycholic acid hexadecyl ester (bis (4 - aminobenzoate)), Deoxycholate heptadecyl ester (bis (4 - aminobenzoate)), deoxycholic acid octadecyl ester (bis (4 - aminobenzoate)), deoxycholic acid phenyl ester (bis (4 - aminobenzoate)), Deoxycholic acid benzyl ester (bis (4 - aminobenzoate)), deoxycholic acid trifluoroacetic ester (bis (4 - Aminobenzoate)), deoxycholic acid (2,2,2 - trifluoro-ethyl) ester (bis (4 - Aminobenzoate)), deoxycholic acid (1,1,2,2,2 - pentafluoroethyl) ester (bis (4 - Aminobenzoate)), deoxycholic acid (4 - fluorophenyl) acetate (bis (4 - amino-benzoic Ester)), deoxycholic acid (4 - (trifluoromethyl) phenyl) ester (bis (4 - amino-benzoic Ester)), deoxycholic acid (4 - (4 - pentyl-cyclohexyl)-phenyl) ester (bis (4 - amino- Benzoate)), deoxycholic acid (4 - (4 - heptyl cyclohexyl)-phenyl) ester (bis (4 - Aminobenzoate)); N-methyl-deoxycholic acid amide (bis (4 - aminobenzoate)), Deoxycholic acid N-ethyl amide (bis (4 - aminobenzoate)), N, N-dimethyl-off Oxygen acid amide (bis (4 - aminobenzoate)), N, N-diethyl amide deoxycholate (Bis (4 - aminobenzoate)), N-propyl deoxycholic acid amide (bis (4 - aminophenyl Ester)), N-butyl deoxycholate amide (bis (4 - aminobenzoate)), N- Pentyl deoxycholic acid amide (bis (4 - aminobenzoate)), N-hexyl-deoxycholic acid acyl Amine (bis (4 - aminobenzoate)), N-cyclohexyl-deoxycholic acid amide (bis (4 - amino Benzoate)), N-hexadecyl amide deoxycholate (bis (4 - aminobenzoate)), N-heptadecyl deoxycholic acid amide (bis (4 - aminobenzoate)), N-octadecyl Deoxycholic acid amide (bis (4 - aminobenzoate)), N-phenyl-deoxycholic acid amide (bis (4 - aminobenzoate)), N-methyl-N-phenyl-deoxycholic acid amide (bis (4 - Aminobenzoate)), N-benzyl-deoxycholic acid amide (bis (4 - aminobenzoate)), Deoxycholic acid N-trifluoroacetyl methyl amide (bis (4 - aminobenzoate)), N-(2,2, 2 - trifluoroethyl) deoxycholic acid amide (bis (4 - aminobenzoate)), N-(1,1, 2,2,2 - pentafluoroethyl) deoxycholic acid amide (bis (4 - aminobenzoate)), N- (4 - fluorophenyl) deoxycholic acid amide (bis (4 - aminobenzoate)), N-(4 - (Trifluoromethyl) phenyl) deoxycholic acid amide (bis (4 - aminobenzoate)), N- (4 - (4 - pentylcyclohexyl) phenyl) deoxycholic acid amide (bis (4 - aminobenzoate)), N-(4 - (4 - heptyl cyclohexyl) phenyl) deoxycholic acid amide (bis (4 - amino-benzoic Ester)); methyl deoxycholate (bis (3 - aminobenzoate)), ethyl deoxycholate (Bis (3 - aminobenzoate)), deoxycholic acid ester (bis (3 - aminobenzoate)), Deoxycholic acid ester (bis (3 - aminobenzoate)), deoxycholic acid pentyl ester (bis (3 - Aminobenzoate)), deoxycholic acid hexyl ester (bis (3 - aminobenzoate)), deoxy Acid cyclohexyl ester (bis (3 - aminobenzoate)), deoxycholic acid hexadecyl ester (bis (3 - Aminobenzoate)), deoxycholic acid ester heptadecane (bis (3 - aminobenzoate)), Deoxycholic acid octadecyl ester (bis (3 - aminobenzoate)), deoxycholic acid phenyl ester (bis (3 - Aminobenzoate)), deoxycholic acid benzyl ester (bis (3 - aminobenzoate)), de- Oxygen trifluoroacetic acid methyl ester (bis (3 - aminobenzoate)), deoxycholic acid (2,2,2 - Trifluoroethyl) ester bis (3 - aminobenzoate)), deoxycholic acid (1,1,2,2,2 - Pentafluoroethyl) phosphate bis (3 - aminobenzoate)), deoxycholic acid (4 - fluorophenyl ester) Bis (3 - aminobenzoate)), deoxycholic acid (4 - (trifluoromethyl) phenyl) ester of bis (3 - aminobenzoate)), deoxycholic acid (4 - (4 - pentyl cyclohexyl) phenyl) bis (3 - aminobenzoate)), deoxycholic acid (4 - (4 - heptyl cyclohexyl) phenyl) bis (3 - aminobenzoate)); N-methyl-deoxycholic acid amide (bis (3 - amino acid Ester)), N-ethyl-deoxycholic acid amide (bis (3 - aminobenzoate)), N, N- Deoxycholic acid dimethyl amide (bis (3 - aminobenzoate)), N, N-diethyl-dideoxy Acid amide (bis (3 - aminobenzoate)), N-propyl deoxycholic acid amide (bis (3 - Aminobenzoate)), N-butyl deoxycholate amide (bis (3 - aminobenzoate)), Deoxycholic acid N-pentyl-amide (bis (3 - aminobenzoate)), N-hexyl-deoxycholic acid Amide (bis (3 - aminobenzoate)), N-cyclohexyl-deoxycholic acid amide (bis (3 - Aminobenzoate)), N-hexadecyl amide deoxycholate (bis (3 - amino acid Ester)), N-heptyl-deoxycholic acid amide (bis (3 - aminobenzoate)), N-eighteen Deoxycholic acid alkyl amide (bis (3 - aminobenzoate)), N-phenyl-deoxycholic acid acyl Amine (bis (3 - aminobenzoate)), N-methyl-N-phenyl-deoxycholic acid amide (bis (3 - aminobenzoate)), N-benzyl-deoxycholic acid amide (bis (3 - amino acid Ester)), N-trifluoromethyl-deoxycholic acid amide (bis (3 - aminobenzoate)), N- (2,2,2 - trifluoroethyl) deoxycholic acid amide (bis (3 - aminobenzoate)), N - (1,1,2,2,2 - pentafluoroethyl) deoxycholic acid amide (bis (3 - amino acid Ester)), N-(4 - fluorophenyl) deoxycholic acid amide (bis (3 - aminobenzoate)), N-(4 - (trifluoromethyl) phenyl) deoxycholic acid amide (bis (3 - aminobenzoate)), N-(4 - (4 - pentylcyclohexyl) phenyl) deoxycholic acid amide (bis (3 - amino-benzoic Ester)), N-(4 - (4 - heptyl cyclohexyl) phenyl) deoxycholic acid amide (bis (3 - Aminobenzoate)); pig methyl deoxycholate (bis (4 - aminobenzoate)), Pig deoxycholate ethyl (bis (4 - aminobenzoate)), porcine deoxycholic acid ester (bis (4 - Aminobenzoate)), porcine deoxycholic acid ester (bis (4 - aminobenzoate)), Deoxycholic acid hexyl ester pig (bis (4 - aminobenzoate)), porcine deoxycholic acid cyclohexyl ester (bis (4 - aminobenzoate)), porcine deoxycholic acid hexadecyl ester (bis (4 - amino acid Ester)), porcine deoxycholate heptadecyl ester (bis (4 - aminobenzoate)), porcine deoxycholate Acid octadecyl ester (bis (4 - aminobenzoate)), porcine deoxycholic acid phenyl ester (bis (4 - Aminobenzoate)), porcine deoxycholic acid benzyl ester (bis (4 - aminobenzoate)), porcine Deoxycholic acid trifluoroacetic ester (bis (4 - aminobenzoate)), porcine deoxycholic acid (2,2, 2 - trifluoro-ethyl) ester (bis (4 - aminobenzoate)), porcine deoxycholic acid (1,1,2, 2,2 - pentafluoroethyl) ester (bis (4 - aminobenzoate)), porcine deoxycholate (4 - Fluorophenyl) ester (bis (4 - aminobenzoate)), porcine deoxycholate (4 - (trifluoromethyl Yl)-phenyl) ester (bis (4 - aminobenzoate)), porcine deoxycholate (4 - (4 - E Cyclohexyl)-phenyl) ester (bis (4 - aminobenzoate)), porcine deoxycholate (4 - (4 - heptyl cyclohexyl)-phenyl) ester (bis (4 - aminobenzoate)); N-methyl-pig Deoxycholic acid amide (bis (4 - aminobenzoate)), N-ethyl-pig deoxycholic acid amide (Bis (4 - aminobenzoate)), N, N-dimethyl amide pig deoxycholate (bis (4 - Aminobenzoate)), N, N-diethyl amide pig deoxycholate (bis (4 - aminophenyl Ester)), N-propyl amide pig deoxycholate (bis (4 - aminobenzoate)), N - Butyl deoxycholate pig amide (bis (4 - aminobenzoate)), N-pentyl-pig deoxy Acid amide (bis (4 - aminobenzoate)), N-hexyl amide pig deoxycholate (bis (4 - aminobenzoate)), N-cyclohexyl amide pig deoxycholate (bis (4 - aminophenyl Ester)), N-hexadecyl amide pig deoxycholate (bis (4 - aminobenzoate)), N-heptadecyl deoxycholic acid amide pigs (bis (4 - aminobenzoate)), N-octadecyl Deoxycholic acid amide group pigs (bis (4 - aminobenzoate)), N-phenyl-pig deoxycholate Amide (bis (4 - aminobenzoate)), N-methyl-N-phenyl-pig deoxycholic acid amide (Bis (4 - aminobenzoate)), N-benzyl-pig deoxycholic acid amide (bis (4 - amino- Benzoate)), N-trifluoromethyl-pig deoxycholic acid amide (bis (4 - aminobenzoate)), N-(2,2,2 - trifluoroethyl) amide pig deoxycholic acid (bis (4 - aminobenzoate)), N-(1,1,2,2,2 - pentafluoroethyl) pig deoxycholic acid amide (bis (4 - amino-benzoic Ester)), N-(4 - fluorophenyl) pig deoxycholic acid amide (bis (4 - aminobenzoate)), N-(4 - (trifluoromethyl) phenyl) pig deoxycholic acid amide (bis (4 - aminobenzoate)), N-(4 - (4 - pentylcyclohexyl) phenyl) pig deoxycholic acid amide (bis (4 - aminophenyl Ester)), N-(4 - (4 - heptyl cyclohexyl) phenyl) pig deoxycholic acid amide (bis (4 - aminobenzoate)); pig methyl deoxycholate (bis (3 - aminobenzoate)), Pig deoxycholate ethyl (bis (3 - aminobenzoate)), porcine deoxycholic acid ester (bis (3 - Aminobenzoate)), porcine deoxycholic acid ester (bis (3 - aminobenzoate)), Amyl pig deoxycholate (bis (3 - aminobenzoate)), porcine deoxycholic acid hexyl ester (bis (3 - Aminobenzoate)), porcine deoxycholic acid cyclohexyl ester (bis (3 - aminobenzoate)), Deoxycholic acid hexadecyl ester pig (bis (3 - aminobenzoate)), porcine deoxycholic acid heptadecane Ester (bis (3 - aminobenzoate)), porcine deoxycholic acid octadecyl ester (bis (3 - amino- Benzoate)), porcine deoxycholic acid phenyl ester (bis (3 - aminobenzoate)), pig deoxy Acid benzyl ester (bis (3 - aminobenzoate)), porcine deoxycholic acid trifluoroacetic ester (bis (3 - Aminobenzoate)), porcine deoxycholate (2,2,2 - trifluoro-ethyl) ester (bis (3 - Aminobenzoate)), porcine deoxycholate (1,1,2,2,2 - pentafluoroethyl) ester (bis (3 - aminobenzoate)), porcine deoxycholate (4 - fluorophenyl) acetate (bis (3 - amino- Benzoate)), porcine deoxycholate (4 - (trifluoromethyl) phenyl) ester (bis (3 - amino Benzoate)), porcine deoxycholate (4 - (4 - pentyl-cyclohexyl)-phenyl) ester (bis (3 - aminobenzoate)), porcine deoxycholate (4 - (4 - heptyl cyclohexyl)-phenyl) Ester (bis (3 - aminobenzoate)); N-methyl amide pig deoxycholate (bis (3 - amino Benzoate)), N-ethyl-pig deoxycholic acid amide (bis (3 - aminobenzoate)), N, N-dimethyl amide pig deoxycholate (bis (3 - aminobenzoate)), N, N-two Deoxycholic acid amide ethyl pig (bis (3 - aminobenzoate)), N-propyl pig deoxycholate Acid amide (bis (3 - aminobenzoate)), N-butyl deoxycholate pig amide (bis (3 - Aminobenzoate)), N-pentyl-pig deoxycholate amide (bis (3 - amino acid Ester)), N-hexyl-pig deoxycholic acid amide (bis (3 - aminobenzoate)), N-Ring Pig deoxycholate hexyl amide (bis (3 - aminobenzoate)), N-hexadecyl acellular Oxygen acid amide (bis (3 - aminobenzoate)), N-heptadecyl deoxycholic acid Pig Amine (bis (3 - aminobenzoate)), N-stearyl amide pig deoxycholate (bis (3 - Aminobenzoate)), N-phenyl-pig deoxycholic acid amide (bis (3 - amino acid Ester)), N-methyl-N-phenyl amide pig deoxycholate (bis (3 - aminobenzoate)), N-benzyl amide pig deoxycholate (bis (3 - aminobenzoate)), N-trifluoromethyl-pig Deoxycholic acid amide (bis (3 - aminobenzoate)), N-(2,2,2 - trifluoroethyl) Deoxycholic acid amide pig (bis (3 - aminobenzoate)), N-(1,1,2,2,2 - Pentafluoroethyl) pig deoxycholic acid methyl amide (bis (3 - aminobenzoate)), N- (4 - fluorophenyl) pig deoxycholic acid amide (bis (3 - aminobenzoate)), N-(4 - (Trifluoromethyl) phenyl) pig deoxycholic acid amide (bis (3 - aminobenzoate)), N-(4 - (4 - pentylcyclohexyl) phenyl) pig deoxycholic acid amide (bis (3 - aminophenyl Ester)), N-(4 - (4 - heptyl cyclohexyl) phenyl) pig deoxycholic acid amide (bis (3 - aminobenzoate)); 3,6 - bis (4 - aminophenoxy) cholane-24 - Acid Methyl ester, 3,6 - bis (4 - aminophenoxy) cholane-24 - ethyl 3,6 - bis (4 - Aminophenoxy) cholane-24 - propyl gallate, 3,6 - bis (4 - aminophenoxy) cholane -24 - Butyl, 3,6 - bis (4 - aminophenoxy) cholane-24 - amyl, 3,6 - Bis (4 - aminophenoxy) cholane-24 - acid hexyl ester, 3,6 - bis (4 - aminophenoxy Yl) cholane-24 - cyclohexyl acrylate, 3,6 - bis (4 - aminophenoxy) cholane-24 - Acid Hexadecyl ester, 3,6 - bis (4 - aminophenoxy) cholane-24 - heptadecyl acid ester, 3,6 - Bis (4 - aminophenoxy) cholane-24 - acid octadecyl ester, 3,6 - bis (4 - amino- Phenoxy) cholane-24 - acid phenyl ester, 3,6 - bis (4 - aminophenoxy) cholane-24 - Acid benzyl ester, 3,6 - bis (4 - aminophenoxy) cholane-24 - trifluoroacetic acid methyl ester, 3,6 - Bis (4 - aminophenoxy) cholane-24 - acid (2,2,2 - trifluoroethyl) acrylate, 3,6 - Bis (4 - aminophenoxy) cholane-24 - acid (2,2,2 - trifluoroethyl) ester, 3,6 - bis (4 - aminophenoxy) cholane-24 - Acid (1,1,2,2,2 - pentafluoroethyl) acrylate, 3, 6 - bis (4 - aminophenoxy) cholane-24 - acid (4 - fluorophenyl) ester, 3,6 - bis (4 - Aminophenoxy) cholane-24 - acid (4 - (trifluoromethyl) phenyl) ester, 3,6 - bis (4 - aminophenoxy) cholane-24 - acid (4 - (4 - pentyl-cyclohexyl)-phenyl) ester, 3,6 - bis (4 - aminophenoxy) cholane-24 - acid (4 - (4 - heptyl cyclohexyl) benzene Yl) ester; N-methyl-3, 6 - bis (4 - aminophenoxy) cholane-24 - amide, N - Ethyl 3,6 - bis (4 - aminophenoxy) cholane-24 - amide, N, N-dimethyl- 3,6 - bis (4 - aminophenoxy) cholane-24 - amide, N, N-diethyl-3 ,6 - Bis (4 - aminophenoxy) cholane-24 - acrylamide, N-propyl-3, 6 - bis (4 - amino Phenoxy) cholane-24 - acrylamide, N-butyl-3, 6 - bis (4 - aminophenoxy) Cholane-24 - acrylamide, N-pentyl-3, 6 - bis (4 - aminophenoxy) cholane-24 - Acrylamide, N-hexyl-3, 6 - bis (4 - aminophenoxy) cholane-24 - acrylamide, N-Ring Hexyl-3, 6 - bis (4 - aminophenoxy) cholane-24 - acrylamide, N-hexadecyl -3, 6 - bis (4 - aminophenoxy) cholane-24 - acrylamide, N-heptadecyl-3, 6 - bis (4 - Aminophenoxy) cholane-24 - acrylamide, N-octadecyl-3, 6 - bis (4 - amino- Phenoxy) cholane-24 - acrylamide, N-phenyl-3, 6 - bis (4 - aminophenoxy) bile Alkyl -24 - acrylamide, N-benzyl-3, 6 - bis (4 - aminophenoxy) cholane-24 - acid Amine, N-trifluoromethyl-3, 6 - bis (4 - aminophenoxy) cholane-24 - amide, N - (2,2,2 - trifluoroethyl) -3,6 - bis (4 - aminophenoxy) cholane-24 - Amide, N-(2,2,2 - trifluoroethyl) -3,6 - bis (4 - aminophenoxy) cholane-24 - Amide, N-(1,1,2,2,2 - pentafluoroethyl) -3,6 - bis (4 - aminophenoxy) Cholane-24 - amide, N-(4 - fluorophenyl) -3,6 - bis (4 - aminophenoxy) bile Alkyl -24 - amide, N-(4 - (trifluoromethyl) phenyl) -3,6 - bis (4 - aminophenyl Oxy) cholane-24 - amide, N-(4 - (4 - pentyl-cyclohexyl)-phenyl) -3,6 - Bis (4 - aminophenoxy) cholane-24 - amide, N-(4 - (4 - heptyl cyclohexyl) Phenyl) -3,6 - bis (4 - aminophenoxy) cholane-24 - amide; 3,6 - bis (3 - Aminophenoxy) cholane-24 - methyl ester, 3,6 - bis (3 - aminophenoxy) cholane -24 -, Ethyl 3,6 - bis (3 - aminophenoxy) cholane-24 - propyl gallate, 3,6 - Bis (3 - aminophenoxy) cholane-24 - butyl, 3,6 - bis (3 - aminophenoxy Yl) cholane-24 - acid pentyl ester, 3,6 - bis (3 - aminophenoxy) cholane-24 - hexanoate Ester, 3,6 - bis (3 - aminophenoxy) cholane-24 - cyclohexyl acrylate, 3,6 - bis (3 - Aminophenoxy) cholane-24 - acid hexadecyl ester, 3,6 - bis (3 - aminophenoxy) Cholane-24 - heptadecyl acid ester, 3,6 - bis (3 - aminophenoxy) cholane-24 - Acid ten Eight alkyl ester, 3,6 - bis (3 - aminophenoxy) cholane-24 - acid phenyl ester, 3,6 - bis (3 - Aminophenoxy) cholane-24 - acid benzyl ester, 3,6 - bis (3 - aminophenoxy) cholane -24 - Trifluoroacetic acid methyl ester, 3,6 - bis (3 - aminophenoxy) cholane-24 - acid (2,2, 2 - trifluoro-ethyl) ester, 3,6 - bis (3 - aminophenoxy) cholane-24 - acid (2,2,2 - Trifluoroethyl) ester, 3,6 - bis (3 - aminophenoxy) cholane-24 - acid (1,1,2, 2,2 - pentafluoroethyl) acrylate, 3,6 - bis (3 - aminophenoxy) cholane-24 - acid (4 - Fluorophenyl) ester, 3,6 - bis (3 - aminophenoxy) cholane-24 - acid (4 - ( Trifluoromethyl) phenyl) ester, 3,6 - bis (3 - aminophenoxy) cholane-24 - acid (4 - (4 - pentyl-cyclohexyl)-phenyl) ester, 3,6 - bis (3 - aminophenoxy) cholane-24 - Acid (4 - (4 - heptyl cyclohexyl)-phenyl) ester; N-methyl-3, 6 - bis (3 - amino Phenoxy) cholane-24 - acrylamide, N-ethyl-3, 6 - bis (3 - aminophenoxy) Cholane-24 - amide, N, N-dimethyl-3, 6 - bis (3 - aminophenoxy) cholane - 24 - amide, N, N-diethyl-3, 6 - bis (3 - aminophenoxy) cholane-24 - acid Amine, N-propyl-3, 6 - bis (3 - aminophenoxy) cholane-24 - acrylamide, N-butyl- -3,6 - Bis (3 - aminophenoxy) cholane-24 - acrylamide, N-pentyl-3, 6 - bis (3 - aminophenoxy) cholane-24 - acrylamide, N-hexyl-3, 6 - bis (3 - aminophenyl Oxy) cholane-24 - acrylamide, N-cyclohexyl-3, 6 - bis (3 - aminophenoxy) bile Alkyl -24 - acrylamide, N-hexadecyl-3, 6 - bis (3 - aminophenoxy) cholane-24 - Acrylamide, N-heptadecyl -3,6 - bis (3 - aminophenoxy) cholane-24 - amide, N-octadecyl-3, 6 - bis (3 - aminophenoxy) cholane-24 - acrylamide, N-phenyl- -3,6 - Bis (3 - aminophenoxy) cholane-24 - acrylamide, N-benzyl-3, 6 - bis (3 - aminophenoxy) cholane-24 - acrylamide, N-trifluoromethyl-3, 6 - bis (3 - amino Phenoxy) cholane-24 - amide, N-(2,2,2 - trifluoroethyl) -3,6 - bis (3 - aminophenoxy) cholane-24 - amide, N-(2,2,2 - trifluoroethyl) -3,6 - Bis (3 - aminophenoxy) cholane-24 - amide, N-(1,1,2,2,2 - pentafluoroethyl) -3,6 - Bis (3 - aminophenoxy) cholane-24 - amide, N-(4 - fluorophenyl) - 3,6 - bis (3 - aminophenoxy) cholane-24 - amide, N-(4 - (trifluoromethyl) Phenyl) -3,6 - bis (3 - aminophenoxy) cholane-24 - amide, N-(4 - (4 - Pentyl cyclohexyl) phenyl) -3,6 - bis (3 - aminophenoxy) cholane-24 - amide, N-(4 - (4 - heptyl cyclohexyl) phenyl) -3,6 - bis (3 - aminophenoxy) bile Alkyl -24 - amide. ...
Among these, the preferential gallodesoxycholic acid methyl esters (two (4-Aminobenzoate)) of selecting, gallodesoxycholic acid ethyl ester (two (4-Aminobenzoate)), gallodesoxycholic acid propyl ester (two (4-Aminobenzoate)), gallodesoxycholic acid butyl ester (two (4-Aminobenzoate)), gallodesoxycholic acid pentyl ester (two (4-Aminobenzoate)), the own ester of gallodesoxycholic acid (two (4-Aminobenzoate)), gallodesoxycholic acid n-Hexadecane ester (two (4-Aminobenzoate)), gallodesoxycholic acid heptadecane ester (two (4-Aminobenzoate)), gallodesoxycholic acid octadecane ester (two (4-Aminobenzoate)), gallodesoxycholic acid trifluoro methyl esters (two (4-Aminobenzoate)), gallodesoxycholic acid (2,2, the 2-trifluoroethyl) ester (two (4-Aminobenzoate)), gallodesoxycholic acid (1,1,2,2, the 2-pentafluoroethyl group) ester (two (4-Aminobenzoate)), gallodesoxycholic acid (4-(4-amyl group cyclohexyl) phenyl) ester (two (4-Aminobenzoate)), gallodesoxycholic acid (4-(4-heptyl cyclohexyl) phenyl) ester (two (4-Aminobenzoate)); Gallodesoxycholic acid methyl esters (two (3-Aminobenzoate)), gallodesoxycholic acid ethyl ester (two (3-Aminobenzoate)), gallodesoxycholic acid propyl ester (two (3-Aminobenzoate)), gallodesoxycholic acid butyl ester (two (3-Aminobenzoate)), gallodesoxycholic acid pentyl ester (two (3-Aminobenzoate)), the own ester of gallodesoxycholic acid (two (3-Aminobenzoate)), gallodesoxycholic acid n-Hexadecane ester (two (3-Aminobenzoate)), gallodesoxycholic acid heptadecane ester (two (3-Aminobenzoate)), gallodesoxycholic acid octadecane ester (two (3-Aminobenzoate)), gallodesoxycholic acid benzyl ester (two (3-Aminobenzoate)), gallodesoxycholic acid trifluoro methyl esters (two (3-Aminobenzoate)), gallodesoxycholic acid (2,2, the 2-trifluoroethyl) ester (two (3-Aminobenzoate)), gallodesoxycholic acid (1,1,2,2, the 2-pentafluoroethyl group) ester (two (3-Aminobenzoate)), gallodesoxycholic acid (4-(4-amyl group cyclohexyl) phenyl) ester (two (3-Aminobenzoate)), gallodesoxycholic acid (4-(4-heptyl cyclohexyl) phenyl) ester (two (3-Aminobenzoate)); 3, two (4-amino-benzene oxygen) cholane of 6--24-acid methyl esters, 3, two (4-amino-benzene oxygen) cholane of 6--24-acetoacetic ester, 3, two (4-amino-benzene oxygen) cholane of 6--24-propyl propionate, 3, two (4-amino-benzene oxygen) cholane of 6--24-acid butyl ester, 3, two (4-amino-benzene oxygen) cholane of 6--24-acid pentyl ester, 3, two (4-amino-benzene oxygen) cholane of the 6--own ester of 24-acid, 3, two (4-amino-benzene oxygen) cholane of 6--24-acid n-Hexadecane ester, 3, two (4-amino-benzene oxygen) cholane of 6--24-acid heptadecane ester, 3, two (4-amino-benzene oxygen) cholane of 6--24-acid octadecane ester, 3, two (4-amino-benzene oxygen) cholane of 6--24-acid trifluoro methyl esters, 3, two (4-amino-benzene oxygen) cholane of 6--24-acid (2,2, the 2-trifluoroethyl) ester, 3, two (4-amino-benzene oxygen) cholane of 6--24-acid (1,2,2,2-tetrafluoro ethyl) ester, 3, two (4-amino-benzene oxygen) cholane of 6--24-acid (1,1,2,2, the 2-pentafluoroethyl group) ester, 3, two (4-amino-benzene oxygen) cholane of 6--24-acid (4-(4-amyl group cyclohexyl) phenyl) ester, 3, two (4-amino-benzene oxygen) cholane of 6--24-acid (4-(4-heptyl cyclohexyl) phenyl) ester; 3, two (3-amino-benzene oxygen) cholane of 6--24-acetoacetic ester, 3, two (3-amino-benzene oxygen) cholane of 6--24-propyl propionate, 3, two (3-amino-benzene oxygen) cholane of 6--24-acid butyl ester, 3, two (3-amino-benzene oxygen) cholane of 6--24-acid pentyl ester, 3, two (3-amino-benzene oxygen) cholane of the 6--own ester of 24-acid, 3, two (3-amino-benzene oxygen) cholane of 6--24-acid n-Hexadecane ester, 3, two (3-amino-benzene oxygen) cholane of 6--24-acid heptadecane ester, 3, two (the 3-amino-benzene oxygen trifluoro methyl esters of 6-, 3, two (3-amino-benzene oxygen) cholane of 6--24-acid (2,2, the 2-trifluoroethyl) ester, 3, two (3-amino-benzene oxygen) cholane of 6--24-acid (1,2,2,2-tetrafluoro ethyl) ester, 3, two (3-amino-benzene oxygen) cholane of 6--24-acid (1,1,2,2, the 2-pentafluoroethyl group) ester, 3, two (3-amino-benzene oxygen) cholane of 6--24-acid (4-(4-amyl group cyclohexyl) phenyl) ester, 3, two (3-amino-benzene oxygen) cholane of 6--24-acid (4-(4-heptyl cyclohexyl) phenyl) ester; Especially preferentially select gallodesoxycholic acid butyl ester (two (4-Aminobenzoate)), gallodesoxycholic acid pentyl ester (two (4-Aminobenzoate)), the own ester of gallodesoxycholic acid (two (4-Aminobenzoate)), gallodesoxycholic acid n-Hexadecane ester (two (4-Aminobenzoate)), gallodesoxycholic acid heptadecane ester (two (4-Aminobenzoate)), gallodesoxycholic acid octadecane ester (two (4-Aminobenzoate)), gallodesoxycholic acid trifluoro methyl esters (two (4-Aminobenzoate)), gallodesoxycholic acid (2,2, the 2-trifluoroethyl) ester (two (4-Aminobenzoate)), gallodesoxycholic acid (1,1,2,2, the 2-pentafluoroethyl group) ester (two (4-Aminobenzoate)), gallodesoxycholic acid (4-(4-amyl group cyclohexyl) phenyl) ester (two (4-Aminobenzoate)), gallodesoxycholic acid (4-(4-heptyl cyclohexyl) phenyl) ester (two (4-Aminobenzoate)).
Specific diamine compound for example can be synthetic by the lithocholic acid derivative with 1 or 2 hydroxyl.For example, use the esterification of alcohol and carboxylic acid or the esterification of halogenated alkyl and carboxylate salt, as required, and with dewatering agents such as acid catalyst or alkaline catalysts, dicyclohexyl carbodiimides, just can access is the dinitro compound of precursor, with its reduction, just can access the diamines of purpose.Specifically, for example, can synthesize Methyl lithocholate (3,5-diaminobenzoic acid ester) according to following reaction by lithocholic acid (1).
Figure A0380116700271
As the diamine compound of the building-up reactions of supplying with polyamic acid, the scope of not damaging effect of the present invention can and with the diamine compound beyond the specific diamine compound.At this, shared ratio in the diamine compound of specific diamine compound in supplying with building-up reactions, with 0.1～100mol% is good, particularly preferred ratio, in TN type and STN type liquid crystal display device, being 0.5～30mol%, in vertical alignment-type liquid crystal display device, is 10～100mol%.
As can and the diamine compound of usefulness, for example can enumerate Ursol D, mphenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-the diamino diphenylethane, 4,4 '-the diamino diphenyl sulfide, 4,4 '-diaminodiphenylsulfone(DDS), 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino N-benzanilide, 4,4 '-diaminodiphenyl oxide, 1, the 5-diaminonaphthalene, 3,3-dimethyl-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (4-aminophenyl) HFC-236fa of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] sulfones of 2-, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 9, two (4-the aminophenyl)-10-hydrogenation anthracenes of 9-, 2, the 7-diamino-fluorene, 9, two (4-aminophenyl) fluorenes of 9-, 4,4 '-methylene radical-two (2-chloroanilines), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 1,4,4 '-(to the phenylene isopropylidene) dianiline, 4,4 '-(metaphenylene isopropylidene) dianiline, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-aromatic diamine such as two [(4-amino-2-trifluoromethyl) phenoxy group)] octafluoro biphenyl; 1,1-m-xylene diamine, 1,3-propylene diamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine, heptamethylene diamines, eight methylene diamine, nine methylene diamine, 4,4-diamino heptamethylene diamines, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene two rings penta 2 alkenylene diamines, six hydrogen-4, indane dimethylene diamines, three ring [6.2.1.0 between 7- 2.7]-undecylene dimethyl diamines, 4,4 '-aliphatic series and ester ring type diamines such as methylene-bis (cyclo-hexylamine); 2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamino-2,3-diamino pyrazine, 5,6-diamino-2, the 4-dihydroxy-pyrimidine, 2,4-diamino-6-dimethylamino-1,3, the 5-triazine, 1, two (3-aminopropyl) piperazines of 4-, 2,4-diamino-6-isopropoxy-1,3, the 5-triazine, 2,4-diamino-6-methoxyl group-1,3, the 5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazines, 2,4-diamino-6-methyl-s-triazine, 2, the 4-diamino-1,3,5-triazines, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenyl thiazole, 2,6-diaminopurine, 5, the 6-diaminostilbene, the 3-FU dimethyl, 3, the 5-diaminostilbene, 2, the 4-triazole, 6,9-diamino-2-oxyethyl group acridine lactate, 3,8-diamino-6-phenylphenanthridineand, 1,4-diamino piperazine, 3, the 6-proflavin, two (4-aminophenyl) phenyl amine and the compound represented with following formula V and (VI) arbitrary formula etc., intramolecularly has the diamines of the nitrogen-atoms beyond 2 primary aminos and this primary amino; Single-substituted two amines with following formula (VII) expression; Diamino organo-siloxane with following formula (VIII) expression; Respectively with the compound of following formula (2)～(6) expressions etc.
Figure A0380116700281
(in the formula V, R 5Expression has 1 valency organic radical of ring structure, and this ring structure contains the nitrogen-atoms that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, and X represents the divalent organic radical.)
Figure A0380116700291
(in the formula (VI), R 6Expression has the divalent organic radical of ring structure, and this ring structure contains the nitrogen-atoms that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, and X represents the divalent organic radical, and the X of several existence can be identical, also can be different.)
(in the formula (VII), R 7Expression is selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic radical of CO-, R 8Expression has the 1 valency organic radical that is selected from steroid skeleton, trifluoromethyl and fluorine-based group or the alkyl of carbonatoms 6～30.)
Figure A0380116700293
(in the formula (VIII), R 9The alkyl of expression carbonatoms 1～12, the R of several existence 9Can be the same or different separately, p is 1～3 integer, and q is 1～20 integer.)
Figure A0380116700294
(in the formula, y is 2～12 integer, and z is 1～5 integer.)
These diamine compounds can use separately or be used in combination more than 2 kinds or 2 kinds.
Among these, the preferential Ursol D of selecting, 4,4 '-diaminodiphenylmethane, 4,4 '-the diamino diphenyl sulfide, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl oxide, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 9, two (4-aminophenyl) fluorenes of 9-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (4-aminophenyl) HFC-236fa of 2-, 4,4 '-(to the phenylene diisopropylidene) dianiline, 4,4 '-(metaphenylene diisopropylidene) dianiline, 1, the 4-cyclohexane diamine, 4,4 '-methylene-bis (cyclo-hexylamine), 1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, respectively with the compound of above-mentioned formula (2)～(6) expressions, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, the compound of in the compound of representing with above-mentioned formula V, representing with following formula (7), the compound of in the compound of above-mentioned formula (VI) expression, representing with following formula (8), in with above-mentioned formula (VII) in the compound of expression respectively with the compound of following formula (9)～(18) expressions and in the compound of above-mentioned formula (VIII) expression with the compound of following formula (19) expression.
＜tetracarboxylic dianhydride 〉
Can enumerate aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic acid dianhydride the tetracarboxylic dianhydride of use in polyamic acid of the present invention synthetic.As these particular compound, for example can enumerate the butane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 3,3 ', 4,4 '-the bicyclohexane tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 3,5,6-three carboxyls norbornane-2-acetate dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, 5-(2,5-dioxo tetrahydrofuran methene base)-and 3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic acid dianhydride, two rings [2,2,2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, respectively with following formula (IX) and (X) aliphatic series such as compound and the ester ring type tetracarboxylic dianhydride of expression;
(in the formula, R 1And R 3Expression has the divalent organic radical of aromatic nucleus, R 2And R 4Expression hydrogen atom or alkyl, the R of several existence 2And R 4Separately can be identical, also can be different.)
Pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenylsulfone acid's dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-biphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-the ditane tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride, 4,4 '-two (3,4-dicarboxyl phenoxy group) diphenyl sulfone dianhydride, 4,4 '-two (3,4-dicarboxyl phenoxy group) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene two O-phthalic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) phenylphosphine oxide dianhydride, to phenylene-two (triphenyl phthalic acid) dianhydride, metaphenylene-two (triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-the phenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-the ditan dianhydride, ethylene glycol-two (dehydration trimellitate), propylene glycol-two (dehydration trimellitate), 1,4-butyleneglycol-two (dehydration trimellitate), 1,6-hexylene glycol-two (dehydration trimellitate), 1,8-ethohexadiol-two (dehydration trimellitate), 2, two (4-hydroxyphenyl) propane-two (dehydration trimellitate) of 2-, 2,3,4,5-pyridine tetracarboxylic dianhydride, 2, two (3, the 4-dicarboxyl phenyl) pyridines of 6-, respectively with the aromatic tetracarboxylic acid dianhydrides such as compound of following formula (20)～(23) expressions.These compounds can use separately more than a kind or 2 kinds or 2 kinds and be used in combination.
Figure A0380116700331
Among these,, preferentially select the butane tetracarboxylic acid dianhydride from showing the viewpoint of good liquid crystal aligning, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 5-(2,5-dioxo tetrahydrofuran methene base)-and 3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic acid dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, two rings [2,2,2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, in with the compound of above-mentioned formula (IX) expression,,, can enumerate 1 as preferential especially compound respectively with the compound of following formula (24)～(26) expression and the compound of in above-mentioned formula (X), representing with following formula (27) in the expression formula compound, 2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3, furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, pyromellitic acid dianhydride and the compound of representing with following formula (24).
Synthesizing of＜polyamic acid 〉
The tetracarboxylic dianhydride who in the building-up reactions of polyamic acid of the present invention, supplies with and the usage ratio of diamine compound, with respect to amino 1 equivalent that contains in the diamine compound, tetracarboxylic dianhydride's anhydride group preferably becomes 0.2～2 normal ratio, and being more preferably becomes 0.3～1.2 normal ratio.
The building-up reactions of polyamic acid, in organic solvent, preferably-20～15 ℃, more preferably under 0～100 ℃ temperature condition, carry out.At this, as organic solvent, if can dissolve the organic solvent of the polyamic acid that is synthesized, just have no particular limits, for example can N-N-methyl-2-2-pyrrolidone N-, N be shown example, dinethylformamide, N, dinethylformamide, methyl-sulphoxide, gamma-butyrolactone, 4-methyl urea, HMPA etc. are non-proton to be polar solvent; Phenol series solvents such as meta-cresol, xylenol, phenol, halogenation phenol.In addition, the usage quantity of organic solvent (a), the total amount of establishing tetracarboxylic dianhydride and diamine compound for the full dose (a+b) of reaction soln, preferably become the amount of 0.1～30 weight % during for (b).
In above-mentioned organic solvent, can be in the scope that the polyamic acid that generates is not separated out also with alcohol, ketone, ester, ether, halon and the hydrocarbon etc. that are the lean solvent of polyamic acid.The object lesson of such lean solvent, for example can enumerate methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, 1, the 4-butyleneglycol, triglycol, methyl glycol, ethyl lactate, n-Butyl lactate, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, methyl acetate, ethyl acetate, butylacetate, methyl methoxy base propionic ester, ethyl ethoxy-c acid esters, oxalic acid diethyl ester, diethyl malonate, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, the ethylene glycol n-butyl ether, glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diglyme, diethyl carbitol, diethylene glycol monomethyl ether, ethyl carbitol, the diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetate, tetrahydrofuran (THF), methylene dichloride, 1, the 2-ethylene dichloride, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, adjacent chlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene etc.
As above, carry out the reaction soln that forms with regard to obtaining dissolving polyamic acid.Then, inject this reaction soln and obtain precipitate in a large amount of lean solvents, this precipitate of drying under reduced pressure just can access polyamic acid.In addition, this polyamic acid is dissolved in the organic solvent again, then the process that will separate out in lean solvent is carried out 1 time or for several times, just can be made with extra care polyamic acid.
Resulting polyamic acid, by having repeating unit, by having repeating unit with following formula (XII) expression with the diamine compound of above-mentioned formula (II) expression with the tetracarboxylic dianhydride's of above-mentioned formula (III) expression reaction with following formula (XI) expression with the diamine compound of above-mentioned formula (I) expression with the tetracarboxylic dianhydride's of above-mentioned formula (III) expression reaction.
In the above-mentioned formula (XI), G 4, A 1, D 1, B 1, E 1, a and G 1Definition as mentioned above.
Figure A0380116700362
In the above-mentioned formula (XII), G 4, G 2, A 2, D 2, B 2, E 2With the definition of b as mentioned above.
＜imide amination polymer 〉
Imide amination polymer of the present invention can prepare by making above-mentioned polyamic acid dehydration closed-loop.The dehydration closed-loop of polyamic acid uses (i) to heat the method for polyamic acid, and perhaps (II) dissolves polyamic acid in organic solvent, adds dewatering agent and dehydration closed-loop catalyzer in this solution, and the method that heats is as required carried out.
Temperature of reaction in the method for the heating polyamic acid of above-mentioned (i) is preferably 50～200 ℃, more preferably 60～170 ℃.50 ℃ of temperature of reaction less thaies then dehydration closed-loop reaction can not fully be carried out, and the molecular weight that temperature of reaction surpasses 200 ℃ of imide amination polymers that then obtain descends sometimes.
On the other hand, in the polyamic acid solution of above-mentioned (II), add in the method for dewatering agent and dehydration closed-loop catalyzer,, for example can use acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride as dewatering agent.The usage quantity of dewatering agent, the repeating unit of polyamic acid is 1 mole relatively, preferably 0.01～20 mole.In addition, as the dehydration closed-loop catalyzer, for example can use tertiary amines such as pyridine, collidine, lutidine, triethylamine.But, be not limited to these.The usage quantity of dehydration closed-loop catalyzer, relative 1 mole of employed dewatering agent, preferably 0.01～10 mole.As the organic solvent that in dehydration closed-loop reaction, uses, can enumerate as the illustrated organic solvent of use in polyamic acid synthetic.And the temperature of reaction of dehydration closed-loop reaction, is more preferably 10～150 ℃ by preferably 0～180 ℃.In addition, to the reaction soln that obtains like this,, just can make with extra care imide amination polymer by carrying out the process for purification identical operations with polyamic acid.
Resulting imide amination polymer have respectively with the amido acid repeating unit of above-mentioned formula (XI) and above-mentioned formula (XII) expression by imidization, for example respectively with following formula (XIII) and the imidization unit (XIV) represented.
In the above-mentioned formula (XIII), G 4, G 1, A 1, D 1, B 1, E 1Described as defined above with a.
In the above-mentioned formula (XIV), G 4, G 2, A 2, D 2, B 2, E 2With stating as defined above of b.
Preferred imidization rate when constituting liquid crystal aligning agent of the present invention, in the imide amination polymer of the present invention is 10～100%, is more preferably 30～98%.At this, so-called " imidization rate " is to represent to form number of repeat unit that imide ring the forms ratio with respect to the sum of the repeating unit in the polymkeric substance with %.At this moment, the part of imide ring can be different imide ring.Can control the imidization rate by the condition of regulating above-mentioned dehydration closed-loop reaction.
The polymkeric substance of＜end modified type 〉
Polyamic acid of the present invention and imide amination polymer can be the end modified types that molecular weight is conditioned.Use the polymkeric substance of this end modified type,, can improve the coating characteristics of liquid crystal aligning agent not damaging under the effect of the present invention.When synthesizing polyamides acid,, just can synthesize the polymkeric substance of so end modified type by in reaction system, adding acid anhydrides, monoamine compound, an isocyanate compound etc.At this,, for example can enumerate maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc. as acid anhydrides.In addition, as the monoamine compound, for example can enumerate aniline, hexahydroaniline, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, positive undecylamine, positive amino dodecane, positive tridecyl amine, positive tetradecy lamine, positive pentadecyl amine, positive cetylamine, positive heptadecyl-amine, positive stearylamine, positive 20 amine etc.In addition, as an isocyanate compound, for example can enumerate isocyanic acid phenylester, isocyanic acid naphthyl ester etc.
The logarithm viscosity of＜polymkeric substance 〉
Polyamic acid of the present invention and imide amination polymer, its logarithm viscosity (η 1n) value, normally 0.05～10dl/g, preferably 0.1～5dl/g.
Logarithm viscosity (η among the present invention 1n) value, be to use the N-N-methyl-2-2-pyrrolidone N-as solvent, be that the solution of 0.5g/100ml carries out viscosimetric analysis at 30 ℃ to concentration, obtain according to following formula (i).
＜liquid crystal aligning agent 〉
Liquid crystal aligning agent of the present invention preferentially is chosen in the organic solvent dissolving and contains polyamic acid of the present invention and/or imide amination polymer and form.That is, liquid crystal aligning agent of the present invention contains polymkeric substance and forms, and this polymkeric substance has and is selected from respectively at least a with in the repeating unit of above-mentioned formula (XI)～(XIV) expression.
In addition, liquid crystal aligning agent of the present invention also can contain and not have respectively with the polyamic acid of the repeating unit of above-mentioned formula (XI)～(XIV) expression and/or imide amination polymer (below, also be called " other polymkeric substance ").Other polymkeric substance is to be selected from the diamine compound that makes beyond the above-mentioned specific diamine compound and tetracarboxylic dianhydride's reaction and the polyamic acid that obtains, and make this polyamic acid dehydration closed-loop and imide amination polymer at least a.As the combination of preferred polymkeric substance, can enumerate and have with the repeating unit of above-mentioned formula (XIII) expression and/or with the polymkeric substance (imide amination polymer of the present invention) and the combination that does not have the polyamic acid of the repeating unit of representing with any formula in the above-mentioned formula (XI)～(XIV) of the repeating unit of (XIV) expression.The liquid crystal aligning agent that contains the combination of such polymkeric substance obtains the liquid crystal display device that long-term reliability is good, the afterimage extinction time is short especially, is particularly preferred therefore.Containing of polymkeric substance in this liquid crystal aligning agent is proportional, and with respect to the polymkeric substance full dose, imide amination polymer of the present invention is 1～99 weight %, is more preferably 2～50 weight %, especially preferably 10～30 weight %.
Temperature when preparing liquid crystal aligning agent of the present invention, is more preferably 20 ℃～60 ℃ by preferably 0 ℃～200 ℃.
As the organic solvent that constitutes liquid crystal aligning agent of the present invention, can enumerate as in the building-up reactions of polyamic acid, using illustrated solvent.In addition, in the time of also can being chosen in the building-up reactions of polyamic acid aptly can and with illustrated lean solvent and usefulness.
Solid shape in the liquid crystal aligning agent of the present invention is divided concentration, waits and selects though consider viscosity, volatility, preferably the scope of 1～10 weight %.That is, liquid crystal aligning agent of the present invention is coated on substrate surface, becomes filming of liquid crystal orientation film, but when solid shape was divided concentration less than 1 weight %, this thickness of filming became too small, and can not obtain good liquid crystal orientation film.In addition, when solid shape branch concentration surpassed 10 weight %, the thickness of filming became excessive, can not obtain good liquid crystal orientation film, and the viscosity of liquid crystal orientation film increases, and became the liquid crystal orientation film of coating characteristics deterioration.
In liquid crystal aligning agent of the present invention,, also can contain the compound of functional silanes or contain the compound of epoxy group(ing) from improving viewpoint to the bounding force of substrate surface.As such compound that contains functional silanes, for example can enumerate the 3-aminopropyl trimethoxysilane, the 3-aminopropyl triethoxysilane, the 2-aminopropyl trimethoxysilane, the 2-aminopropyl triethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea propyl trimethoxy silicane, 3-urea propyl-triethoxysilicane, N-ethoxycarbonyl-3-aminopropyl trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three azepine decane, 9-trimethoxysilyl-3,6-three azepine nonyl acetic ester, 9-triethoxysilyl-3,6-three azepine nonyl acetic ester, N-benzyl-3-aminopropyl trimethoxysilane, N-benzyl-3-aminopropyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl triethoxysilane, two (the oxyethylene group)-3-aminopropyl trimethoxysilane of N-, two (the oxyethylene group)-3-aminopropyl triethoxysilanes of N-etc.
In addition, contain epoxy compounds, as preferably for example enumerating ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, the glycerol diglycidylether, 2,2-dibromoneopentyl glycol diglycidylether, 1,3,5,6-four glycidyl group-2, the 4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (N, the N-diglycidyl aminomethyl) hexanaphthenes of 3-, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.The proportioning that these contain the compound of functional silanes or contain epoxy compounds with respect to 100 parts by weight polymer, preferably is equal to or less than 40 weight parts, is more preferably 0.1～30 weight part.
＜liquid crystal display device 〉
Liquid crystal display device of the present invention for example can use following method manufacturing.
(1) in the one side of the substrate that the nesa coating that has formed pattern is set, use methods such as rolling method, method of spin coating, print process to be coated with liquid crystal aligning agent of the present invention, then, by the heating coated face, formation is filmed.At this,, for example can use glass such as float glass, soda glass as substrate; The transparent substrate that plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate constitute.As the nesa coating of the one side that is arranged on substrate, can use by stannic oxide (SnO 2) constitute NESA film (U.S. PPG register of company trade mark), by Indium sesquioxide-stannic oxide (In 2O 3-SnO 2) the ITO film that constitutes etc., in the pattern of these nesa coatings forms, use photolithography or use the method for mask in advance.When carrying out the coating of liquid crystal aligning agent, better for the bounding force that makes substrate surface and nesa coating and film, also can be coated with the compound that contains functional silanes, the compound that contains the functionality titanium etc. in advance on this surface of substrate.Heating temperature after the liquid crystal aligning agent coating, preferably 80～300 ℃, preferably 120～250 ℃.Moreover, contain the liquid crystal aligning agent of the present invention of polyamic acid, after coating, form and become filming of alignment films by removing organic solvent, carry out dehydration closed-loop by heating again, also can be further used as filming of imidization.Formed thickness of filming, preferably 0.001～1 μ m, preferably 0.005～0.5 μ m.
(2) friction treatment of for example using circumvolution to have the roller of the cloth of fibers formations such as nylon, artificial silk, cotton yarn that the coated surface that forms is rubbed in a certain direction.Thus, on filming, give the liquid crystal aligning energy.
In addition, on the liquid crystal orientation film that forms by liquid crystal aligning agent of the present invention, for example open in the flat 6-222366 communique or special opening shown in the flat 6-281937 communique as the spy, by irradiation ultraviolet radiation partly, the processing that pre-tilt angle is changed, perhaps use as the spy opens as shown in the flat 5-107544 communique, form resist film on the liquid crystal orientation film surface portion ground of implementing friction treatment, after the direction different with previous friction treatment carried out friction treatment, remove resist film, processing that the liquid crystal aligning of liquid crystal orientation film can be changed is the visual field characteristic that can improve liquid crystal display device.
In addition, according to circumstances, do not adopt the friction treatment method, ultraviolet ray by irradiation polarized light or non-polarized light on filming or ionic fluid etc. also can be given the liquid crystal aligning energy.
On the other hand, under the situation of the liquid crystal display device of making vertical orientating type, not necessarily must carry out above-mentioned friction treatment, also the above-mentioned former state ground of filming can be used as liquid crystal orientation film.
(3) make 2 substrates that formed liquid crystal orientation film as described above, form the angle of regulation for the frictional direction on the liquid crystal orientation film separately, gap 2 substrates of subtend configuration (gap of box) in clamping, use the periphery of 2 pieces of substrates of sealing agent applying, in substrate surface and gap, inject filling liquid crystal by the box of sealing agent zoning, the sealing filling orifice just constitutes liquid crystal cell.Then,, that is, constitute the another side side of the substrate separately of liquid crystal cell at the outside surface of liquid crystal cell, the consistent or polarization plate of vertically fitting of frictional direction of the liquid crystal orientation film of the one side formation by direction of polarized light and this substrate, and obtain liquid crystal display device.
At this,, for example can use and contain solidifying agent and as Resins, epoxy of the alumina balls of spacer etc. as sealing agent.
As liquid crystal, for example can enumerate nematic liquid crystal and smectic liquid crystal.Especially wherein be best with the nematic liquid crystal, for example can use Schiff's base is that liquid crystal, azoxy are that liquid crystal, biphenyl are that liquid crystal, Santosol 360 are that liquid crystal, ester are that liquid crystal, terphenyl are that liquid crystal, cyclohexyl biphenyl hexane are that liquid crystal, pyrimidine are that liquid crystal, diox is that liquid crystal, bicyclooctane are that liquid crystal, キ ユ バ Application are liquid crystal etc.In addition, in these liquid crystal, also can add chirality agent that cholesteric liquid crystal such as for example cholesterol chlorine, n-nonanoic acid cholesterol ester, carbonic acid cholesterol ester or picture sell as trade(brand)name " C-15 ", " CB-15 " (メ Le Network corporate system) etc. and use.Can also use oxygen base benzylidene-in the last of the ten Heavenly stems amino-forceful electric power Jie property liquid crystal such as 2-first butyl laurate.
In addition, as the polarization plate of fitting, can enumerate polarization plate that polyvinyl alcohol is extended be orientated the polarization film of using the rhodia protective membrane to clamp to be called the H film that absorbs iodine or the polarization plate that itself constitutes by the H film on one side at the outside surface of liquid crystal cell.
Below, according to the present invention of embodiment more specific description, but the present invention is not subjected to the restriction of these embodiment.Have again, as follows in the evaluation method of following embodiment and the polymkeric substance in the Comparative Examples, liquid crystal aligning agent and liquid crystal display device.
The voltage retention of＜liquid crystal display device 〉
After adding the voltage of 5V with time that adds of 60 microseconds, 167 milliseconds pulse on the liquid crystal display device, measure from removing the voltage retention behind the impressed voltage to 167 millisecond.Determinator uses the Dongyang テ Network ニ カ of Co., Ltd. system VHR-1.
＜afterimage extinction time 〉
1. on the liquid crystal display device with the volts DS that added 10V in 1 hour after, remove this impressed voltage, use visual observation display frame, measure to remove behind the impressed voltage time (embodiment 12～15 and Comparative Examples 6～8) that the afterimage to the picture disappears.
2. 100 ℃ envrionment temperature, with the volts DS that added 17V in 20 hours after, remove this impressed voltage, under room temperature environment, relax 15 minutes after, by flashing the voltage that remains in the liquid crystal cell is eliminated, obtain residual DC voltage.Residual DC voltage is few more, the short liquid crystal display device (embodiment 22～26 and Comparative Examples 11～12) of afterimage extinction time.
The pre-tilt angle of＜liquid crystal display device 〉
According to T.J.Scheffer, et.al., J.Appl.Phys., vol.19, the method for 2013 (1980) middle records is measured by the crystal rotation method that uses He-Ne laser.
The reliability test of＜liquid crystal display device 〉
In 70 ℃ thermostatic bath, put into liquid crystal display device, go up continuous drive after 24 hours at drive waveforms generating unit " Function/arbitrary waveform generator " (Hewlett Packard corporate system), confirm to have or not the not even display defect of contrast.
The synthetic embodiment of specific diamine compound
Synthetic embodiment 1
(1) Methyl lithocholate is synthetic
In the methyl alcohol of 0.5L, add 56.5g (0.15mol) lithocholic acid and the 3ml vitriol oil, reflux 6 hours.After using rotatory evaporator with solution concentration to 1/2 amount that obtains, add 1 liter of pure water, make the resultant precipitation, reclaim by suction strainer again.Use NaHCO 3This thick resultant of saturated aqueous solution washing, the H that adheres in neutralization 2SO 4The time, make unreacted lithocholic acid dissolving, and remove.With after its washing, the vacuum-drying, from ethanol, carry out recrystallize again, just obtain the 44g Methyl lithocholate.Analytical results below is shown.
1H-NMR(DMSO-D 6，δppm)：0.6-2.1(34H，m)3.6(3H，s)。
(2) Methyl lithocholate (3,5-dinitrobenzoic acid ester) is synthetic
Mix 19.6g (0.05mol) Methyl lithocholate, 4.0g pyridine and 0.15L methylene dichloride, dissolve in room temperature.Stir on one side this solution, on one side with 11.5g (0.05mol) 3,5-dinitrochlorobenzene formyl slowly adds with intact solid ground, again stirring at room 3 hours.It is solid to use rotatory evaporator that this mixture evaporation is done, wash the solid residue of generation after, carry out vacuum-drying, obtain thick resultant.Make this thick resultant carry out recrystallize with acetone again, just obtain 25.5g Methyl lithocholate (3,5-dinitrobenzoic acid ester).Analytical results below is shown.
1H-NMR(CDCl 3，δppm)：0.6-2.1(34H，m)，3.6(3H，s)，9.1-9.2(3H，d+t)。
(3) Methyl lithocholate (3,5-diaminobenzoic acid ester) is synthetic
Adding 9.6g Methyl lithocholate (3,5-dinitrobenzoic acid ester) and 0.1g drape over one's shoulders the palladium activated carbon in 100ml ethanol, carry out reflux.To this mixture 4ml hydrazine 1 hydrate that drips at leisure, continued reflux again 2 hours.Filter this reaction soln when hot, remove and drape over one's shoulders the palladium activated carbon, add 1L water again, make the resultant precipitation.Filtration, washing, this post precipitation of vacuum-drying carry out recrystallize from ethanol, obtain 6.7 g Methyl lithocholates (3,5-diaminobenzoic acid ester).Analytical results below is shown.
1H-NMR(DMSO-D 6，δppm)：0.6-2.1(34H，m)，3.6(3H，s)，4.9(4H，s)，6.0(1H，t)，6.4(2H，d)。
Synthetic embodiment 2
(4) the lithocholic acid butyl ester is synthetic
In the solution of 1-butanols 44g and 100ml chloroform, add 56.5g (0.15mol) lithocholic acid and the 0.3ml vitriol oil, reflux 6 hours.After making solution concentration to 1/2 amount that obtains with rotatory evaporator, add 1L chloroform and 1L pure water, stir.With the chloroform layer separatory, use NaHCO 3Saturated aqueous solution washing, the H that adheres in neutralization 2SO 4The time, make unreacted lithocholic acid dissolving, remove.With its washing, use anhydrous magnesium sulfate drying again.Filter sal epsom, solution is concentrated, obtain 52g lithocholic acid butyl ester.
(5) lithocholic acid butyl ester (3,5-dinitrobenzoic acid ester) is synthetic
Except using 21.4g (0.05mol) lithocholic acid butyl ester, 3.9g pyridine, 0.1L methylene dichloride, 11.4g (0.05mol) 3, beyond the 5-dinitrochlorobenzene formyl and (2) similarly make, obtain 26g lithocholic acid butyl ester (3,5-dinitrobenzoic acid ester).
(6) lithocholic acid butyl ester (3,5-diaminobenzoic acid ester) is synthetic
Except use 9.6g lithocholic acid butyl ester (3,5-dinitrobenzoic acid ester) in addition and (3) similarly make, obtain 7.0g lithocholic acid butyl ester (3,5-diaminobenzoic acid ester).Analytical results below is shown.
1H-NMR(DMSO-d 6，δppm)：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)。
Synthetic embodiment 3
(7) the lithocholic acid pentyl ester is synthetic
Except using the 39g1-amylalcohol and (4) similarly make, obtain 54g lithocholic acid amylalcohol.
(8) lithocholic acid pentyl ester (3,5-dinitrobenzoic acid ester) is synthetic
Except using 22g lithocholic acid pentyl ester and (2) similarly make, obtain 26g lithocholic acid pentyl ester (3,5-dinitrobenzoic acid ester).
(9) lithocholic acid pentyl ester (3,5-diaminobenzoic acid ester) is synthetic
Except use 9.6g lithocholic acid pentyl ester (3,5-dinitrobenzoic acid ester) in addition and (3) similarly make, obtain 6.9g lithocholic acid pentyl ester (3,5-diaminobenzoic acid ester).Analytical results below is shown.
1H-NMR(DMSO-d 6，δppm)：0.6-2.1(46H，m)，4.0(2H，t)，4.8(1H，m)，4.9(4H，s)，6.0(1H，s)，6.4(2H，s)。
Synthetic embodiment 4
(10) lithocholic acid heptadecane ester is synthetic
Except using the 59g1-heptadecyl alcohol and (4) similarly makes, obtain 92g rubble cholic acid pentyl ester, by making with extra care, obtain 83g lithocholic acid heptadecane ester with column chromatography.
(11) lithocholic acid heptadecane ester (3,5-dinitrobenzoic acid ester) is synthetic
Except using 31g lithocholic acid heptadecane ester.(2) similarly make, obtain 37g lithocholic acid heptadecane ester (3,5-dinitrobenzoic acid ester).
(12) lithocholic acid heptadecane ester (3,5-diaminobenzoic acid ester) is synthetic
Except use 9.6g lithocholic acid pentyl ester (3,5-dinitrobenzoic acid ester) in addition and (3) similarly make, obtain 7.5g lithocholic acid heptadecane ester (3,5-diaminobenzoic acid ester).Analytical results below is shown.
1H-NMR(CDCl 3，δppm)：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)。
Synthetic embodiment 5
(13) lithocholic acid octadecane ester is synthetic
Except using the 61g1-stearyl alcohol and (10) similarly make, obtain 76g lithocholic acid octadecane ester.
(14) lithocholic acid octadecane ester (3,5-dinitrobenzoic acid ester) is synthetic
Except using 32g lithocholic acid octadecane ester and (2) similarly make, obtain 33g lithocholic acid octadecane ester (3,5-dinitrobenzoic acid ester).
(15) lithocholic acid octadecane ester (3,5-diamino yl benzoic acid ester) is synthetic
Except use 9.6g lithocholic acid octadecane ester (3,5-dinitrobenzoic acid ester) in addition and (3) similarly make, obtain 7.6g lithocholic acid octadecane ester (3,5-diaminobenzoic acid ester).Analytical results below is shown.
1H-NMR(CDCl 3，δppm)：0.6-2.4(72H，m)，3.7(4H，s)，4.0(2H，t)，4.9(1H，m)，6.2(1H，s)，6.8(2H，s)。
Embodiment 1
Synthesizing of polyamic acid
Dissolving 7.02g Methyl lithocholate (3,5-diaminobenzoic acid ester), 13.0g Ursol D and 30.0g2 in the 450gN-N-methyl-2-2-pyrrolidone N-, 3,5-tricarboxylic basic ring amyl group acetate dianhydride carries out reaction in 6 hours at 60 ℃.Then, reaction soln is injected superfluous greatly methyl alcohol, make the resultant of reaction precipitation.Then, use methanol cleaning, under reduced pressure, in 40 ℃ of dryings 15 hours, obtain the polyamic acid of the present invention that 48.9g logarithm viscosity is 0.93dl/g [it being called " polymkeric substance (1a) "].
Embodiment 2
Synthesizing of imide amination polymer
Dissolving 25.0g polymkeric substance (1a) in the 450gN-N-methyl-2-2-pyrrolidone N-adds 10.6g pyridine and 13.6g diacetyl oxide in this solution, by 115 ℃ of heating 4 hours, carry out the dehydration closed-loop reaction.Then, reaction solution is injected superfluous greatly methyl alcohol, make the resultant of reaction precipitation.Then, use methanol cleaning, under reduced pressure, in 40 ℃ of dryings 15 hours, obtain the imide amination polymer of the present invention that 21.2g logarithm viscosity is 0.85dl/g [it being called " polymkeric substance (1b) "].
Embodiment 3
Synthesizing of polyamic acid
Except replacing 7.02g Methyl lithocholate (3,5-diaminobenzoic acid ester), 13.0g Ursol D and 30.0g2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and use 7.49g lithocholic acid butyl ester (3,5-diaminobenzoic acid ester), 12.9g Ursol D and 29.6g2,3, beyond the 5-tricarboxylic basic ring amyl group acetate dianhydride, similarly make with embodiment 1, obtain the polyamic acid of the present invention that 47.6g logarithm viscosity is 0.84dl/g [it being called " polymkeric substance (2a) "].
Embodiment 4
Synthesizing of imide amination polymer
Use the 24.7g polymkeric substance (2a) except replacing 25.0g polymkeric substance (1a) and embodiment 2 similarly makes, obtain the imide amination polymer of the present invention that 21.1g logarithm viscosity is 0.82dl/g [it being called " polymkeric substance (2b) "].
Embodiment 5
Synthesizing of polyamic acid
Except replacing 7.02g Methyl lithocholate (3,5-diaminobenzoic acid ester), 13.0g Ursol D and 30.0g2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and use 7.65g lithocholic acid pentyl ester (3,5-diaminobenzoic acid ester), 12.8g Ursol D and 29.5g2,3, beyond the 5-tricarboxylic basic ring amyl group acetate dianhydride, similarly make with embodiment 1, obtain the polyamic acid of the present invention that 49.8g logarithm viscosity is 0.88dl/g [it being called " polymkeric substance (3a) "].
Embodiment 6
Synthesizing of imide amination polymer
Use the 24.7g polymkeric substance (3a) except replacing 25.0g polymkeric substance (1a) and embodiment 2 similarly makes, obtain the imide amination polymer of the present invention that 21.3g logarithm viscosity is 0.86dl/g [it being called " polymkeric substance (3b) "].
Embodiment 7
Synthesizing of polyamic acid
Except replacing 7.02g Methyl lithocholate (3,5-diaminobenzoic acid ester), 13.0g Ursol D and 30.0g2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and use 9.45g lithocholic acid heptadecane ester (3,5-diaminobenzoic acid ester), 12.3g Ursol D and 28.3g2,3, beyond the 5-tricarboxylic basic ring amyl group acetate dianhydride, similarly make with embodiment 1, obtain the polyamic acid of the present invention that 49.9g logarithm viscosity is 0.79dl/g [it being called " polymkeric substance (4a) "].
Embodiment 8
Synthesizing of imide amination polymer
Use the 23.5g polymkeric substance (4a) except replacing 25.0g polymkeric substance (1a) and embodiment 2 similarly makes, obtain the imide amination polymer of the present invention that 19.3g logarithm viscosity is 0.76dl/g [it being called " polymkeric substance (4b) "].
Embodiment 9
Synthesizing of polyamic acid
Except replacing 7.02g Methyl lithocholate (3,5-diaminobenzoic acid ester), 13.0g Ursol D and 30.0g2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and use 9.59g lithocholic acid octadecane ester (3,5-diaminobenzoic acid ester), 12.2g Ursol D and 28.2g2,3, beyond the 5-tricarboxylic basic ring amyl group acetate dianhydride, similarly make with embodiment 1, obtain the polyamic acid of the present invention that 48.9g logarithm viscosity is 0.76dl/g [it being called " polymkeric substance (5a) "].
Embodiment 10
Synthesizing of imide amination polymer
Use the 23.5g polymkeric substance (5a) except replacing 25.0g polymkeric substance (1a) and embodiment 2 similarly makes, obtain the imide amination polymer of the present invention that 19.8g logarithm viscosity is 0.73dl/g [it being called " polymkeric substance (5b) "].
Comparative Examples 1
Synthesizing of polyamic acid
Except replacing 7.02g Methyl lithocholate (3,5-diaminobenzoic acid ester), 13.0g Ursol D and 30.0g2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and use 19.8g4,4-diaminodiphenylmethane and 22.4g 2,3 are beyond the 5-tricarboxylic basic ring amyl group acetate dianhydride, similarly make with embodiment 1, obtain the polyamic acid that 40.2g logarithm viscosity is 1.20dl/g [it being called " polymkeric substance (Aa) "].
Comparative Examples 2
Synthesizing of imide amination polymer
Use 25.0g polymkeric substance (Aa) except replacing 25.0g polymkeric substance (1a), replace 10.6g pyridine and 13.6g diacetyl oxide and use beyond 4.5g pyridine and the 5.8g diacetyl oxide, similarly make with embodiment 2, obtain the imide amination polymer of the present invention that 30.1g logarithm viscosity is 1.20dl/g [it being called " polymkeric substance (Ab) "].
Comparative Examples 3
Synthesizing of polyamic acid
Except replacing 7.02g Methyl lithocholate (3,5-diaminobenzoic acid ester), 13.0g Ursol D and 30.0g2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and using beyond 12.80g Ursol D and the 25.82g pyromellitic acid dianhydride, similarly make with embodiment 1, obtain the polyamic acid that 32.60g logarithm viscosity is 1.10dl/g [it being called " polymkeric substance (Ba) "].
Comparative Examples 4
Synthesizing of polyamic acid
Except replacing 7.02g Methyl lithocholate (3,5-diaminobenzoic acid ester), 13.0g Ursol D and 30.0g2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and use diamines, the 17.8g4 of 5.20g with above-mentioned formula (10) expression, 4-diaminodiphenylmethane and 22.4g2,3, beyond the 5-tricarboxylic basic ring amyl group acetate dianhydride, similarly make with embodiment 1, obtain the polyamic acid that 40.6g logarithm viscosity is 0.95dl/g [it being called " polymkeric substance (Ca) "].
Comparative Examples 5
Synthesizing of imide amination polymer
Use 25.0g polymkeric substance (Ca) except replacing 25.0g polymkeric substance (1a), replace 10.6g pyridine and 13.6g diacetyl oxide and use beyond 4.5g pyridine and the 5.8g diacetyl oxide, similarly make with embodiment 2, obtain the imide amination polymer that 19.0g logarithm viscosity is 0.96dl/g [it being called " polymkeric substance (Cb) "].
Embodiment 11
(1) preparation of liquid crystal aligning agent
The polymkeric substance (1b) that obtains of dissolving embodiment 2 in gamma-butyrolactone, making solid shape branch concentration is the solution of 2.5 weight %, filters this solution with the strainer of aperture 1 μ m, is prepared into liquid crystal aligning agent of the present invention.
(2) making of liquid crystal display device
1. be provided with on the nesa coating that the ITO film constitutes in the one side by the glass substrate of thick 1mm, the liquid crystal aligning agent of the present invention that uses the spin coater coating to be prepared into as described above 180 ℃ of dryings 1 hour, and forms filming of dry film thickness 800 dusts.
2. use the rubbing machine of roller that established coated surface is carried out friction treatment, make liquid crystal orientation film with circumvolution nylon system cloth.At this, the friction treatment condition: the roller revolution is 500rpm, and the translational speed of step is 1cm/s.
3. make 2 substrates that form liquid crystal orientation film as described above, outer edge at each substrate, after using silk screen print method to be coated with the epoxy resin tackiness agent of the alumina balls that contain diameter 17 μ m, 2 pieces of substrates of the subtend with gap of being situated between configuration become the frictional direction on separately the liquid crystal orientation film and are parallel to each other, the outer edge is contacted with each other and crimping, tackiness agent is solidified.
4. in the surface and the box gap by the tackiness agent zoning of outer edge of substrate, injecting and fill nematic liquid crystal " MLC-2001 " (メ Le Network corporate system), then, is the adhesive seal filling orifice with epoxy, constitutes liquid crystal cell.After this, at the outside surface of liquid crystal cell, the frictional direction that forms direction of polarized light and liquid crystal orientation film becomes the angles of 45 degree, and vertical mutually and the applying polarization plate is made liquid crystal display device.
5. the liquid crystal display device of forming as described above when impressed voltage is with the releasing impressed voltage on liquid crystal cell, is not seen abnormal area, and the orientation of liquid crystal is good.In addition, the pre-tilt angle of liquid crystal is 1.5 degree.In addition, the voltage retention of liquid crystal display device is 99%, and the afterimage extinction time is extremely short 0.4 second.
Embodiment 12～15
Use the polymkeric substance (2b)～(5b) except replacing polymkeric substance (1b) and embodiment 11 similarly makes, prepare liquid crystal aligning agent, make liquid crystal display device.Measure orientation, voltage retention and the afterimage extinction time of the liquid crystal in the made liquid crystal display device.The results are shown in table 1.
Table 1
Embodiment Polymkeric substance Liquid crystal aligning Pre-tilt angle (degree) Voltage retention (%) Afterimage extinction time (second)
????11 ????(1b) Well ????1.5 ????99 ????0.4
????12 ????(2b) Well ????1.8 ????99 ????0.7
????13 ????(3b) Well ????1.9 ????99 ????0.6
????14 ????(4b) Well ????3.4 ????99 ????0.7
????15 ????(5b) Well ????4.2 ????99 ????0.8
Comparative Examples 6
Use the polyimide (Ab) that Comparative Examples 2 obtains except replacing polymkeric substance (1b) and embodiment 12 similarly prepares liquid crystal aligning agent, make liquid crystal display device.Measure orientation, voltage retention and the afterimage extinction time of the liquid crystal in the made liquid crystal display device.The results are shown in table 2.
Comparative Examples 7
Use the polyimide (Ba) that Comparative Examples 3 obtains except replacing polymkeric substance (1b) and embodiment 12 similarly prepares liquid crystal aligning agent, make liquid crystal display device.Measure orientation, voltage retention and the afterimage extinction time of the liquid crystal in the made liquid crystal display device.The results are shown in table 2.
Comparative Examples 8
Use the polyimide (Cb) that Comparative Examples 5 obtains except replacing polymkeric substance (1b) and embodiment 12 similarly prepares liquid crystal aligning agent, make liquid crystal display device.Measure orientation, voltage retention and the afterimage extinction time of the liquid crystal in the made liquid crystal display device.The results are shown in table 2.
Table 2
Comparative Examples Polymkeric substance Liquid crystal aligning Pre-tilt angle (degree) Voltage retention (%) Afterimage extinction time (second)
????6 ????(Ab) Well ????1.6 ????98 ????12
????7 ????(Ba) Well ????1.3 ????96 ????4.0
????8 ????(Cb) Well ????4.7 ????98 ????8
Embodiment 16
Synthesizing of polyamic acid
Dissolving is as tetracarboxylic dianhydride's 112.09g (0.5mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 157.15g (0.5mol) 1 in the 4500gN-N-methyl-2-2-pyrrolidone N-, 3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-C] furans-1,3-diketone and as 52.47g (0.1mol) Methyl lithocholate (3 of diamine compound, 5-diaminobenzoic acid ester) and 97.33g (0.9mol) Ursol D, 60 ℃ of reactions 6 hours.Then, this solution is injected superfluous greatly methyl alcohol, make the resultant of reaction precipitation.After this, use methanol cleaning, by under reduced pressure, in 40 ℃ of dryings 15 hours, obtaining 410g logarithm viscosity is that 0.64dl/g, imidization rate are 0% polyamic acids [it being called " polyamic acid (6a) "].
Embodiment 17
Synthesizing of imide amination polymer
The polyamic acid (6a) that dissolving 30.0g embodiment 16 obtains in the 570gN-N-methyl-2-2-pyrrolidone N-adds 29.2g pyridine and 30.2g diacetyl oxide in this solution, 110 ℃ of heating 4 hours, carry out the dehydration closed-loop reaction.Then, resultant of reaction is injected superfluous greatly methyl alcohol, make the resultant of reaction precipitation.After this, use methanol cleaning, by under reduced pressure, in 40 ℃ of dryings 15 hours, obtaining 28.8g logarithm viscosity is that 0.24dl/g, imidization rate are 96% imide amination polymers [it being called " imide amination polymer (6b) "].
Embodiment 18
Synthesizing of imide amination polymer
Except in embodiment 16, with 56.68g (0.1mol) lithocholic acid butyl ester (3,5-diaminobenzoic acid ester), 97.33g (0.9mol) Ursol D is as beyond the diamine compound, similarly make with embodiment 16, obtain polyamic acid [it being called " polyamic acid (7a) "], re-use it and carry out the imidization reaction identical with embodiment 17, obtaining 27.6g logarithm viscosity is that 0.27dl/g, imidization rate are 97% imide amination polymers [it being called " imide amination polymer (7b) "].
Embodiment 19
Synthesizing of imide amination polymer
Except in embodiment 16, with 58.09g (0.1mol) lithocholic acid pentyl ester (3,5-diaminobenzoic acid ester), 97.33g (0.9mol) Ursol D is as beyond the diamine compound, similarly make with embodiment 16, obtain polyamic acid [it being called " polyamic acid (8a) "], re-use it and carry out the imidization reaction identical with embodiment 17, obtaining 26.9g logarithm viscosity is that 0.22dl/g, imidization rate are 95% imide amination polymers [it being called " imide amination polymer (8b) "].
Embodiment 20
Synthesizing of imide amination polymer
Except in embodiment 16, with 74.92g (0.1mol) lithocholic acid heptadecane ester (3,5-diaminobenzoic acid ester), 97.33g (0.9mol) Ursol D is as beyond the diamine compound, similarly make with embodiment 16, obtain polyamic acid [it being called " polyamic acid (9a) "], re-use it and carry out the imidization reaction identical with embodiment 17, obtaining 26.3g logarithm viscosity is that 0.23dl/g, imidization rate are 98% imide amination polymers [it being called " imide amination polymer (9b) "].
Embodiment 21
Synthesizing of imide amination polymer
Except in embodiment 16, with 76.32g (0.1mol) lithocholic acid octadecane ester (3,5-diaminobenzoic acid ester), 97.33g (0.9mol) Ursol D is as beyond the diamine compound, similarly make with embodiment 16, obtain polyamic acid [it being called " polyamic acid (10a) "], re-use it and carry out the imidization reaction identical with embodiment 17, obtaining 28.1g logarithm viscosity is that 0.24dl/g, imidization rate are 95% imide amination polymers [it being called " imide amination polymer (10b) "].
Comparative Examples 9
Synthesizing of imide amination polymer
Except in embodiment 16, with 41.66g (0.08mol) with the diamine compound of above-mentioned formula (10) expression, 137.82g (0.92mol) Ursol D as beyond the diamine compound, similarly make with embodiment 16, obtain polyamic acid [it being called " polyamic acid (Da) "], re-use it and carry out the imidization reaction identical with embodiment 17, obtaining 27.1g logarithm viscosity is that 0.26dl/g, imidization rate are 96% imide amination polymers [it being called " imide amination polymer (Db) "].
Comparative Examples 10
Synthesizing of imide amination polymer
Except in embodiment 16, with 108.14g (1.0mol) Ursol D as beyond the diamine compound, similarly make with embodiment 16, obtain polyamic acid [it being called " polyamic acid (Ea) "], re-use it and carry out the imidization reaction identical with embodiment 17, obtaining 26.7g logarithm viscosity is that 0.41dl/g, imidization rate are 97% imide amination polymers [it being called " imide amination polymer (Eb) "].
With reference to synthesis example
Except in embodiment 16, with 109.06g (0.5mol) pyromellitic acid acid anhydride and 98.06g (0.5mol) tetramethylene tetracarboxylic dianhydride as the tetracarboxylic dianhydride, with 198.27g (1.0mol) 4, the 4-diaminodiphenylmethane is as beyond the diamines, similarly make with embodiment 16, obtaining logarithm viscosity is that 2.41dl/g, imidization rate are 0% polyamic acids [it being called " polyamic acid (Za) "].
Embodiment 22
In N-N-methyl-2-2-pyrrolidone N-/ethylene glycol butyl ether/gamma-butyrolactone (1/1/8) mixed solvent, with imide amination polymer: polyamidation polymkeric substance (6b) that the ratio dissolving embodiment 17 of polyamic acid=1: 4 (weight ratio) obtains and the above-mentioned polyamic acid (Za) that obtains with reference to synthesis example, make the solution of solid shape branch concentration 4 weight %, strainer with aperture 1 μ m filters this solution, is prepared into liquid crystal aligning agent.Use spin coater, the above-mentioned liquid crystal aligning agent of coating on the transparency electrode face of the glass substrate that has the transparency electrode that constitutes by the ITO film, drying is 10 minutes on 200 ℃ hot-plate, forms filming of dry average film thickness 600 dusts.Use has the rubbing machine of the roller of circumvolution artificial silk system cloth, is that the translational speed of 400rpm, step is that the condition that 3cm/s, hair foot are pressed into length 0.4mm is carried out friction treatment on this is filmed with the revolution of roller.Above-mentioned liquid crystal orientation film coating substrate flood 1 minute in Virahol after, on 100 ℃ hot-plate with both sides' substrate drying 5 minutes.Then, in a pair of outer rim separately with liquid crystal orientation film of the substrate that friction treatment crosses, coating makes the liquid crystal aligning face relative after having the epoxy resin binder of alumina balls of diameter 5.5 μ m, and overlap and crimping with the state of 90 ° of distortions of frictional direction, tackiness agent is solidified.Then, after between pair of substrate, filling nematic liquid crystal (メ Le Network corporate system, MLC-6221-000 (S010)) from liquid crystal injecting port, with acrylic acid series Photocurable adhesive encapsulated liquid crystals inlet, Polarizer on fitting on the two sides in the outside of substrate is made liquid crystal display device.Residual DC voltage is low, is shown as the value of 400mV, after the reliability test, does not see irregular, the display defect of contrast.These the results are shown in the table 3.
Embodiment 23-26
Except the imide amination polymer that uses embodiment 18-21 gained, all the other and embodiment 22 make liquid crystal display device in the same manner.The result is as shown in table 3.
Table 3
Embodiment Polymkeric substance Liquid crystal aligning Residual DC voltage (mV) Reliability test (having or not display defect)
????22 ????(6b)+(Za) Well ????400 Do not have
????23 ????(7b)+(Za) Well ????440 Do not have
????24 ????(8b)+(Za) Well ????380 Do not have
????25 ????(9b)+(Za) Well ????340 Do not have
????26 ????(10b)+(Za) Well ????340 Do not have
Comparative Examples 11,12
Except using the imide amination polymer that Comparative Examples 9,10 obtains and embodiment 22 similarly make, make liquid crystal display device.The results are shown in the table 4.
Table 4
Comparative Examples Polymkeric substance Liquid crystal aligning Residual DC voltage (mV) Reliability test (having or not display defect)
????11 ????(Db)+(Za) Well ????900 Do not have
????12 ????(Eb)+(Za) Well ????900 Do not have
As previously discussed, according to the present invention, the polyamic acid that is adapted at using in the liquid crystal aligning agent and the imide amination polymer that novel diamine compound can be provided, obtain by this diamine compound.
In order to constitute various liquid crystal display device such as TN type liquid crystal display device, STN type liquid crystal display device, vertical alignment-type liquid crystal display device, can be fit to use the liquid crystal orientation film that forms by liquid crystal aligning agent of the present invention.In addition, the liquid crystal display device that possesses this liquid crystal orientation film, the orientation of liquid crystal and reliability are all good, can in various devices, use effectively, for example can be suitable as display unit such as desk-top computer, wrist-watch, clock watch, counting display panel, word processor, minicomputer, LCD TV and use.

Claims (9)

1. diamine compound, this diamine compound are selected from the compound of following formula (I) expression and at least a with in the compound of following formula (II) expression,
In formula (I), D 1Be the divalent alkyl that contains the carbonatoms 5～30 of alicyclic ring, G 1Be 3 valency organic radicals, A 1Be the combination base of singly-bound or divalent, B 1Be singly-bound ,-O-,-N (H)-or
E 1Be 1 valency organic radical, a is 1 or 2, in formula (II), and D 2Be the 3 valency alkyl that contain the carbonatoms 5～30 of alicyclic ring, G 2Be the divalent organic radical, A 2Be the combination base of singly-bound or divalent, B 2Be singly-bound ,-O-,-N (H)-or
Figure A038011670002C3
E 2Be 1 valency organic radical, b is 1 or 2.
2. diamine compound according to claim 1, wherein, in above-mentioned formula (I) with D 1The expression the base or in above-mentioned formula (II) with D 2The base of expression is the alkyl that contains the steroid skeleton.
3. polyamic acid, this polyamic acid are at least a of the described diamine compound of claim 1 and with the tetracarboxylic dianhydride's of following formula (III) expression at least a resultant of reaction,
Figure A038011670002C4
In the formula, G 4Be 4 valency organic radicals.
4. imide amination polymer, this imide amination polymer makes the described polyamic acid dehydration closed-loop of claim 3 and obtains.
5. liquid crystal aligning agent, this liquid crystal aligning agent contain and are selected from least a in described polyamic acid of claim 3 and the described imide amination polymer of claim 4.
6. liquid crystal aligning agent, this liquid crystal aligning agent contains polymkeric substance, and this polymkeric substance has and is selected from respectively at least a with in the repeating unit of following formula (XI)～(XIV) expression,
In the formula, A 1, A 2, B 1, B 2, D 1, D 2, E 1, E 2, G 1, G 2, G 4, a and b unit as defined above.
7. liquid crystal aligning agent according to claim 6, this liquid crystal aligning agent also contain polyamic acid and/or the imide amination polymer with repeating unit of representing with the arbitrary formula of above-mentioned formula (XI)～(XIV).
8. according to the liquid crystal aligning agent of claim 7, it contains and has with the repeating unit of above-mentioned formula (XIII) expression and/or with the polymkeric substance of the repeating unit of (XIV) expression and contain the polyamic acid with repeating unit that the arbitrary formula in the above-mentioned formula (XI)～(XIV) represents.
9. the liquid crystal display device that possesses liquid crystal orientation film, this liquid crystal orientation film is formed by the described liquid crystal aligning agent of arbitrary claim in the claim 5～8.
CN 03801167 2002-07-29 2003-07-25 Diamine compound, polyamic acid, imide polymer, liquid crystal alignment agent and liquid crystal display Expired - Fee Related CN1266192C (en)

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