CN103180294A - Diamine, polyimide precursor, polyimide, liquid-crystal alignment material, liquid-crystal alignment film, and liquid-crystal display element - Google Patents

Diamine, polyimide precursor, polyimide, liquid-crystal alignment material, liquid-crystal alignment film, and liquid-crystal display element Download PDF

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CN103180294A
CN103180294A CN2011800513257A CN201180051325A CN103180294A CN 103180294 A CN103180294 A CN 103180294A CN 2011800513257 A CN2011800513257 A CN 2011800513257A CN 201180051325 A CN201180051325 A CN 201180051325A CN 103180294 A CN103180294 A CN 103180294A
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liquid crystal
acid
diamines
polyimide
amino
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CN103180294B (en
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野田尚宏
铁谷尚士
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • 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

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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  • Quinoline Compounds (AREA)
  • Indole Compounds (AREA)

Abstract

A diamine represented by formula [1] is disclosed. (In formula [1], two of R1 to R9 are primary amino groups, and the remainder each is a hydrogen atom or a monovalent organic group other than amino and may be the same or different. Symbol n is 1 or 2. The hydrogen atoms of the saturated hydrocarbon moiety which constitutes a ring each may have been replaced with a halogen atom or a monovalent organic group other than amino.)

Description

Diamines, polyimide precursor, polyimide, liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device
Technical field
The present invention relates to the liquid crystal aligning agent, liquid crystal orientation film and the liquid crystal display device that use in new diamine, polyimide precursor and polyimide, liquid crystal display device.
Background technology
In liquid crystal display device, liquid crystal orientation film is being born the effect that liquid crystal is orientated on certain direction.Now, the main liquid crystal orientation film of industrial use carries out film forming and makes by being coated on substrate as the liquid crystal aligning agent of the polyamic acid of polyimide precursor, poly amic acid ester or the polyimide consisted of the solution of polyimide.In addition, make mesomorphic phase during parallel-oriented or tilted alignment, after film forming, further adopt the surface of friction prolonged treatment for real estate.In addition, also there is the method for the anisotropy photochemical reaction that propose to utilize adopts polarisation uviolizing etc. to be used as substituting of friction treatment, carried out towards industrialized research in recent years.
In order to improve the display characteristic of this liquid crystal display device, by changing the structure of polyamic acid, poly amic acid ester and polyimide, polyamic acid, poly amic acid ester and polyimide that blending rating is different, or add the method for additive etc., carry out improvement, and the control of tilt angle etc. of liquid crystal aligning and electrical characteristic etc.For example, in order to obtain high voltage holding ratio, various technology have been proposed: use the polyimide resin (with reference to patent documentation 1) with specific repeating structure; There is the soluble polyimide of nitrogen-atoms by use, the time (with reference to patent documentation 2) till the cancellation of shortening after image except imide; In addition, by importing 1-Phenylindole structure in the diamines of the raw material as polyamic acid, can when keeping high voltage holding ratio, reduce residual DC (with reference to patent documentation 3) etc.
But, along with the development of province's electrification of the high performance of liquid crystal display device, big area, display unit etc., and wish can use under various environment, the requirement of liquid crystal orientation film desired characteristic is also strictly got up.Particularly also exist when liquid crystal aligning agent is coated to substrate because of productive temp time (Japanese: タ Network ト タ イ system) elongatedly separate out or separate and then cause that printing is bad, reach the problems such as scorification (Japanese: the baked I is paid I) that cause by accumulating electric charge (RDC), by current technology, be difficult to solve this two kinds of problems simultaneously.
The prior art document
Patent documentation
Patent documentation 1: Japanese patent laid-open 2-287324 communique
Patent documentation 2: Japanese patent laid-open 10-104633 communique
Patent documentation 3: Japanese Patent Laid-Open 2010-70537 communique
Summary of the invention
Invent technical problem to be solved
Problem of the present invention is the problem points that solves above-mentioned prior art, provides and can obtain the good liquid crystal aligning agent of printing and can obtain that to accumulate electric charge few and accumulate diamines, polyimide precursor and polyimide, the liquid crystal aligning agent that uses them, liquid crystal orientation film and the liquid crystal display device of the liquid crystal orientation film that the decay of electric charge is fast.
The technical scheme that the technical solution problem adopts
The inventor has carried out conscientiously research, found that, comprise as two amine components used the specific diamines that means with following formula [1] and polyimide precursor or the liquid crystal aligning agent of polyimide very effective to realizing above-mentioned purpose, thereby completed the present invention.In addition, the diamine compound meaned with following formula [1] is the novel cpd that document is not yet put down in writing.
The feature that solves the of the present invention novel diamines of above-mentioned problem is to mean with following formula [1].
[changing 1]
Figure BDA00003096242600021
(in formula [1], R 1～R 9in two be primary amino, all the other be hydrogen atom or amino beyond any monovalent organic radical group, they each other can be identical or different; N is 1 or 2, and the hydrogen atom that forms ring filling hydrocarbon section can be replaced by any monovalent organic radical group beyond halogen atom or amino.)
In addition, above-mentioned diamines is better to mean with following formula [2].
[changing 2]
Figure BDA00003096242600031
(in formula [2], p means 0～3 integer, R 10mean amino any monovalent organic radical group in addition ,-(R 10) pmean p substituent R 10, they each other can be identical or different; Q means 0～4 integer, R 11mean amino any monovalent organic radical group in addition ,-(R 11) qmean q substituent R 11, they each other can be identical or different; N is 1 or 2, and the hydrogen atom that forms ring filling hydrocarbon section can be replaced by the organic group beyond halogen atom or amino.)
Above-mentioned diamines is more preferably with following formula [3] and means.
[changing 3]
Figure BDA00003096242600032
(in formula [3], n be 1 or 2, m be the integer of 0～2 (n+1), R 12mean fluorine atom or amino 1 valency organic group in addition ,-(R 12) mmean m substituent R 12, they each other can be identical or different.)
In addition, described R 12better the alkyl of carbon number 1～6, R 12be more preferably methyl.
And, be better n=1.
In addition, can be also the diamines meaned with following formula [4-a]～[4-d].
[changing 4]
Figure BDA00003096242600041
The feature of polyimide precursor of the present invention is to react and obtain with two amine components that contain above-mentioned diamines by least one that makes to be selected from tetracarboxylic acid and derivative thereof.
In above-mentioned polyimide precursor, when the integral molar quantity of tetracarboxylic acid and derivative thereof is counted to 100 % by mole, above-mentioned diamines is better 5～95 % by mole.
In addition, the feature of polyimide of the present invention is to obtain by above-mentioned polyimide precursor is carried out to imidization.
And the feature of liquid crystal aligning agent of the present invention is to contain at least one that is selected from above-mentioned polyimide precursor and above-mentioned polyimide.
The feature of liquid crystal orientation film of the present invention is to obtain by above-mentioned liquid crystal aligning agent is coated to substrate and burnt till.
The feature of liquid crystal display device of the present invention is to possess above-mentioned liquid crystal orientation film.
The effect of invention
According to the present invention, can provide and can obtain the good liquid crystal aligning agent of printing and can obtain that to accumulate electric charge few and accumulate the novel diamines of the liquid crystal orientation film that the decay of electric charge is fast.And, by using this diamines, can form the good liquid crystal aligning agent of printing.In addition, by using this liquid crystal aligning agent, obtained that to accumulate electric charge few and accumulate the fast liquid crystal orientation film of decay of electric charge, the liquid crystal display device that therefore has this liquid crystal orientation film is difficult for occurring decline and the scorification of contrast gradient, can obtain the effect of display characteristic excellence etc.
Embodiment
Below, the present invention is described in detail.
Diamines of the present invention is the compound meaned with following formula [1].
[changing 5]
Figure BDA00003096242600051
(in formula [1], R 1～R 9in two be primary amino, all the other be hydrogen atom or amino beyond any monovalent organic radical group, they each other can be identical or different; N is 1 or 2, and the hydrogen atom that forms ring filling hydrocarbon section can be replaced by any monovalent organic radical group beyond halogen atom or amino.)
In formula [1], as halogen atom, can exemplify fluorine atom etc.In addition, in formula [1], as any monovalent organic radical group beyond amino, can exemplify alkyl, hydroxyl, carboxyl, hydroxyl, sulfydryl or carboxylic alkyl, the alkyl be formed by connecting by conjugated groups such as ehter bond, ester bond, amido linkages, the alkyl of silicon atoms, halo alkyl etc.In addition, as any monovalent organic radical group beyond amino, also can exemplify amino by the inertia group of the blocking group protection of the amino formate such as tert-butoxycarbonyl etc. etc.
In addition, in formula [1], amino position being not particularly limited, so long as diamines is not particularly limited, considering from the viewpoint of liquid crystal aligning and synthetic easness, is better the position meaned with following formula [2].
[changing 6]
Figure BDA00003096242600052
(in formula [2], p means 0～3 integer, R 10mean amino any monovalent organic radical group in addition ,-(R 10) pmean p substituent R 10, they each other can be identical or different; Q means 0～4 integer, R 11mean amino any monovalent organic radical group in addition ,-(R 11) qmean q substituent R 11, they each other can be identical or different; N is 1 or 2, and the hydrogen atom that forms ring filling hydrocarbon section can be replaced by the organic group beyond halogen atom or amino.)
In addition, as shown in above-mentioned formula [2], the hydrogen atom with amino phenyl ring can be used as the R of amino any monovalent organic radical group in addition 10or R 11replace, can carry out various selections according to the acquisition difficulty of reagent etc.In addition, in formula [2], as the R of the group of any monovalent organic radical beyond amino 10, R 11, can exemplify alkyl, carboxyl, hydroxyl, sulfydryl or there is the alkyl of these groups, the alkyl be formed by connecting by conjugated groups such as ehter bond, ester bond, amido linkages, the alkyl of silicon atoms, halo alkyl etc.In addition, as R 10or R 11, also can exemplify amino by the inertia group of the blocking group protection of the amino formate such as tert-butoxycarbonyl etc. etc.But, on the viewpoint of the acquisition easness of reagent and synthetic easness, be better that the hydrogen atom with amino phenyl ring is not substituted.Structure example means with following formula [3] more specifically.
[changing 7]
Figure BDA00003096242600061
(in formula [3], n be 1 or 2, m be the integer of 0～2 (n+1), R 12mean fluorine atom or amino 1 valency organic group in addition ,-(R 12) mmean m substituent R 12, they each other can be identical or different.)
In formula [1]～[3], during n=1, be the diamines with indoline structure; During n=2, it is the diamines with tetrahydroquinoline structure.Form ring filling hydrocarbon position although all have, the hydrogen atom of the carbon of this stable hydrocarbon section also can by the halogen atom such as fluorine atom or amino beyond 1 valency organic group replace.In addition, in formula [3], the substituting group that replaces the hydrogen atom of stable hydrocarbon section is R 12.The 1 valency organic group as beyond the amino of the hydrogen atom that replaces stable hydrocarbon section, can exemplify alkyl, hydroxyl, carboxyl etc.The alkyl here can be any in straight chain, side chain, ring-type, can be that stable hydrocarbon can be also unsaturated hydrocarbons, and the part of the hydrogen atom of alkyl can, by carboxyl, hydroxyl, sulfydryl or the replacements such as Siliciumatom and halogen atom, also can be connected by conjugated groups such as ehter bond, ester bond, amido linkages.On the other hand, consider R from the viewpoint of the acquisition easness of synthetic easness and reagent 12it is better the alkyl only formed by carbon atom and hydrogen atom.
The substituting group of the hydrogen atom of the carbon of replacement stable hydrocarbon section is better the alkyl of carbon number 1～6.This be because, use diamines of the present invention and the polyimide precursor such as polyamic acid or the solvability of polyimide in solvent high, so printing is good, if the diamines that the hydrogen atom of making stable hydrocarbon section has been replaced by the alkyl of carbon number 1～6, the polyimide precursor such as polyamic acid or the solvability of polyimide in organic solvent further improve, and printing is better.In addition, due to the polyimide precursors such as polyamic acid or the solvability of polyimide in solvent high, so and consistency excellence between other polymkeric substance, even will adopt diamines of the present invention polyimide precursor or polyimide and other mixed with polymers and in situation about using, also be not easy to occur separate or separate out the printing excellence.Object lesson as the alkyl of carbon number 1～6, but exemplified by methyl, ethyl, propyl group, butyl, the tertiary butyl, hexyl, cyclopentyl, cyclohexyl, vinyl, allyl group, 1-propenyl, 2-propenyl, pseudoallyl, 1-methyl-2-propenyl, 1 or 2 or 3-butenyl, hexenyl, phenyl etc., but be not limited to this.
Replace with these substituting groups in the situation of hydrogen atom of stable hydrocarbon sections, the position of substitution and quantity are not particularly limited, can carry out all selections according to the acquisition easiness of synthetic easness and reagent.Particularly preferred structure is the structure that the hydrogen atom of stable hydrocarbon section is formed by methyl substituted.In addition, from the viewpoint of synthetic easness, considering, is better that the hydrogen atom of stable hydrocarbon section is not substituted.The concrete example of preferred diamines of the present invention below is shown, but is not limited thereto.
[changing 8]
Figure BDA00003096242600081
Figure BDA00003096242600091
[changing 10]
Particularly preferred diamines of the present invention is as follows.
[changing 11]
Figure BDA00003096242600101
Adopt and such using diamines of the present invention that above-mentioned formula [1] means as polyimide precursor or the favorable solubility of polyimide in organic solvent such as the polyamic acid of raw material and poly amic acid esters, so when forming liquid crystal orientation film, can not form the membrane thickness unevenness of pore or generation edge part etc., can obtain the good liquid crystal aligning agent of printing.In addition, if use this liquid crystal aligning agent, can obtain the fast liquid crystal orientation film of the elimination of accumulating and accumulating electric charge that is not easy to occur electric charge, so there is contrast gradient be difficult for to occur the liquid crystal display device of this liquid crystal orientation film decline and scorification, can obtain the effect of display characteristic excellence etc.In addition, can also suppress the increase of the ion density that causes because of life-time service.Also have, liquid crystal aligning is also good.
Can infer that the reason that obtains this effect is, diamines of the present invention comprises pentanoic structure and the stable hydrocarbon section with the position played a role as steric barrier, so can under the state of the electrical property that keeps pentanoic, realize deliquescent raising and with the raising of the consistency of polymkeric substance, and can show characteristic as above.On the other hand, the diamines of patent documentation 3 is to have two keys and do not have the structure of stable hydrocarbon section in the position of the stable hydrocarbon section of diamines of the present invention, if use the diamines of this patent documentation 3, as described later shown in comparative example, can't obtain in the situation that use diamines of the present invention to obtain to accumulate electric charge few and accumulate the fast liquid crystal orientation film of decay of electric charge, in addition, liquid crystal aligning is variation also, and obtains the also result of variation of the solvability of polyimide in organic solvent and consistency.Can infer that its reason is, the diamines of patent documentation 3 is rich in planarity, has in addition the Phenylindole skeleton that can obtain the electronic state different from pentanoic.
Main synthetic method for such diamines of the present invention describes.Note, below the method for explanation is synthesis example, is not limited to this.
Diamines of the present invention can pass through as shown in following reaction formula, dinitro compound is reduced and nitro is changed into to amino obtain.In addition, in following reaction formula, take phenyl ring and stable hydrocarbon section hydrogen atom not by the halogen atom such as fluorine atom or amino beyond the diamines that replaces of any monovalent organic radical group put down in writing as example.
[changing 12]
Figure BDA00003096242600111
To the reduction dinitro compound method there is no particular limitation, can exemplify use palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-aluminum oxide, platinum sulfide carbon etc. as catalyzer, at ethyl acetate, toluene, tetrahydrofuran (THF), two
Figure BDA00003096242600113
in the solvent of alkane, alcohols etc., the method for being reduced with hydrogen, hydrazine, hydrogenchloride etc.Also can use as required autoclave etc. to carry out adding to depress.On the other hand, while in the substituent structure of the hydrogen atom of substituted benzene ring or stable hydrocarbon section, comprising the unsaturated link(age) position, if use palladium carbon or platinum carbon etc., this unsaturated link(age) position likely is reduced and becomes saturated bond, therefore preferably uses the reductive condition of the transition metal such as reduced iron, tin, tin chloride as catalyzer.
In dinitro compound synthetic, by as shown in following reaction formula, commercially available nitro indolin derivatives or nitro tetrahydroquinoline derivative reacted with the oil of mirbane replaced by leavings group X such as halogens, thereby obtain this dinitro compound.As preferred leavings group X, can exemplify fluorine atom, chlorine atom, bromine atoms, iodine atom, tosyloxy (OTs), mesyloxy (OMs) etc.
[changing 13]
Figure BDA00003096242600112
Above-mentioned reaction can be carried out under the existence of alkali.As long as can synthesizing, the alkali used is not particularly limited, can exemplify the mineral alkalis such as salt of wormwood, sodium carbonate, cesium carbonate, sodium alkoxide, potassium alcoholate, sodium hydroxide, potassium hydroxide, sodium hydride, the organic basess such as pyridine, dimethyl aminopyridine, Trimethylamine 99, triethylamine, Tributylamine etc.In addition, according to circumstances, and if with the palladium catalyst such as dibenzalacetone two palladiums or diphenylphosphino ferrocene palladium or copper catalyst etc., can improve yield.From the viewpoint of synthetic easness, consider, be preferably as follows and state shown in reaction formula, by in nitro indolin derivatives or nitro tetrahydroquinoline derivative, exist-hydrogen of NH-removes with alkali such as sodium hydrides, the method that it is reacted with the 4-fluoronitrobenzene, because the method with beyond the method also can be synthesized, so synthetic method is not particularly limited.
[changing 14]
Diamines of the present invention by be selected from tetracarboxylic acid and tetracarboxylic acid derivatives at least one react, can obtain the polyimide precursors such as polyamic acid of the present invention or poly amic acid ester.In order to obtain this polyimide precursor, the reaction ratio of diamines of the present invention and tetracarboxylic acid and derivative thereof is not particularly limited, but preference to be while counting 100 % by mole as the integral molar quantity by tetracarboxylic acid and derivative thereof, diamines of the present invention is 5～95 % by mole.
As tetracarboxylic acid derivatives, can exemplify tetracarboxylic acid two carboxylic acid halides, tetracarboxylic dianhydride, tetracarboxylic acid diester diacid chloride, tetracarboxylic acid diester etc.For example, by making the tetracarboxylic acid or derivatives thereofs such as tetracarboxylic acid two carboxylic acid halides, tetracarboxylic dianhydride, with two amine components that comprise diamines of the present invention, react, can obtain polyamic acid.In addition, by making reacting of tetracarboxylic acid diester diacid chloride and two amine components that comprise diamines of the present invention, perhaps make tetracarboxylic acid diester and two amine components that comprise diamines of the present invention be reacted existing of suitable condensing agent or alkali is inferior, can obtain poly amic acid ester.In addition, in this specification sheets, two amine components refer in order to obtain polyimide precursor or polyimide and at least one diamines reacted that is selected from tetracarboxylic acid and tetracarboxylic acid derivatives, can use separately diamines of the present invention, also can be used together diamines of the present invention and other diamines.
And, by polyimide precursor is carried out to imidization, specifically make the polyamic acid dehydration closed-loop, or at high temperature heat poly amic acid ester to promote dealcoholysis, to make its closed loop, thereby can obtain polyimide of the present invention.
Below, to polyimide precursors such as polyamic acid of the present invention, poly amic acid esters, and polyimide is described in further detail.In at least one of the tetracarboxylic acid by with being selected from above-mentioned tetracarboxylic dianhydride etc. and tetracarboxylic acid derivatives reacted two amine components that obtain the polyimide precursors such as polyamic acid, to diamines of the present invention containing proportional being not particularly limited.Adopt polyimide precursor of the present invention or by its imidization and the liquid crystal orientation film of polyimide gained in, diamines of the present invention shown in above-mentioned containing proportional more, can obtain that to accumulate electric charge few and accumulate the fast liquid crystal orientation film of decay of electric charge.
For the decay of the electric charge accelerating to accumulate, what it is desirable to two amine components is diamines of the present invention more than 1 % by mole.On the other hand, if consider other the characteristic such as liquid crystal aligning, tilt angle characteristic, two amine components of the present invention in two amine components that polymerization is used be preferably 20～90 % by mole, particularly preferably 30～80 % by mole containing proportional.
In above-mentioned two amine components, the diamines meaned with formula [1] is lower than in the situation of 100 % by mole, and other the diamines beyond the used diamines meaned with formula [1] is not particularly limited.If exemplify its object lesson, as follows.
The example of alicyclic diamine class can exemplify: Isosorbide-5-Nitrae-diamino-cyclohexane, 1,3-diamino-cyclohexane, 4,4 '-diamino-dicyclohexyl methane, 4,4 '-diamino-3,3 '-dimethyl dicyclohexylamine, isophorone diamine etc.
The example of aromatic diamines can exemplify: O-Phenylene Diamine, mphenylenediamine, Ursol D, 2,4 di amino toluene, 2,5-diaminotoluene, 3,5-diaminotoluene, Isosorbide-5-Nitrae-diamino-2-anisole, 2,5-diamino p-Xylol, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, Isosorbide-5-Nitrae-diamino-2, the 5-dichlorobenzene, 4,4 '-diaminostilbene, 2-diphenylethane, 4,4 '-diamino-2,2 '-dimethyl bibenzyl, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diamino-3,3 '-dimethyl diphenylmethane, 2,2 '-diamino Stilbene, 4,4 '-diamino Stilbene, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diaminobenzophenone, two (3-amino-benzene oxygen) benzene of 1,3-, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) phenylformic acid of 3,5-, 4,4 '-bis-(4-amino-benzene oxygen) bibenzyl, two [(4-amino-benzene oxygen) methyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two (4-aminophenyl) hexanaphthenes of 1,1-, α, α '-bis-(4-aminophenyl)-Isosorbide-5-Nitrae-diisopropyl benzene, two (4-aminophenyl) fluorenes of 9,9-, two (3-aminophenyl) HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-diamino-diphenyl amine, 2,4-diamino-diphenyl amine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diamino-anthraquinone, 1,3-diamino pyrene, 1,6-diamino pyrene, 1,8-diamino pyrene, 2,7 diamin of luorene, two (4-aminophenyl) tetramethyl disiloxanes of 1,3-, p-diaminodiphenyl, 2,2 '-tolidine, two (4-aminophenyl) ethane of 1,2-, two (4-aminophenyl) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) butane, two (4-aminophenyl) pentanes of 1,5-, two (4-aminophenyl) hexanes of 1,6-, two (4-aminophenyl) heptane of 1,7-, two (4-aminophenyl) octanes of 1,8-, two (4-aminophenyl) nonanes of 1,9-, two (4-aminophenyl) decane of 1,10-, two (4-amino-benzene oxygen) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) butane, two (4-amino-benzene oxygen) pentanes of 1,5-, two (4-amino-benzene oxygen) hexanes of 1,6-, two (4-amino-benzene oxygen) heptane of 1,7-, two (4-amino-benzene oxygen) octanes of 1,8-, two (4-amino-benzene oxygen) nonanes of 1,9-, two (4-amino-benzene oxygen) decane of 1,10-, two (4-aminophenyls) 1, the 3-malonic ester, two (4-aminophenyl) 1, 4-succinic acid ester, two (4-aminophenyls) 1, the 5-glutarate, two (4-aminophenyls) 1, the 6-adipic acid ester, two (4-aminophenyls) 1, the 7-pimelate, two (4-aminophenyls) 1, the 8-suberate, two (4-aminophenyls) 1, the 9-azelate, two (4-aminophenyls) 1, the 10-sebate, two [4-(4-amino-benzene oxygen) phenoxy group] propane of 1,3-, Isosorbide-5-Nitrae-bis-[4-(4-amino-benzene oxygen) phenoxy group] butane, two [4-(4-amino-benzene oxygen) phenoxy group] pentanes of 1,5-, two [4-(4-amino-benzene oxygen) phenoxy group] hexanes of 1,6-, two [4-(4-amino-benzene oxygen) phenoxy group] heptane of 1,7-, two [4-(4-amino-benzene oxygen) phenoxy group] octanes of 1,8-, two [4-(4-amino-benzene oxygen) phenoxy group] nonanes of 1,9-, two [4-(4-amino-benzene oxygen) phenoxy group] decane of 1,10-etc.
The example of aromatic-aliphatic diamines can exemplify: 3-amino-benzene methyl amine, 4-amino-benzene methyl amine, 3-amino-N-methylbenzene methylamine, 4-amino-N-methylbenzene methylamine, 3-amino-benzene ethylamine, 4-amino-benzene ethylamine, 3-amino-N-methylbenzene ethylamine, 4-amino-N-methylbenzene ethylamine, 3-(3-aminopropyl) aniline, 4-(3-aminopropyl) aniline, 3-(3-methylamino propyl group) aniline, 4-(3-methylamino propyl group) aniline, 3-(4-aminobutyl) aniline, 4-(4-aminobutyl) aniline, 3-(4-methylamino butyl) aniline, 4-(4-methylamino butyl) aniline, 3-(the amino amyl group of 5-) aniline, 4-(the amino amyl group of 5-) aniline, 3-(5-methylamino amyl group) aniline, 4-(5-methylamino amyl group) aniline, 2-(the amino naphthyl of 6-) methylamine, 3-(the amino naphthyl of 6-) methylamine, 2-(the amino naphthyl of 6-) ethylamine, 3-(the amino naphthyl of 6-) ethylamine etc.
The example of hetero ring type Diamines can exemplify: DAP, 2,4-diamino-pyridine, 2,4-diamino-1,3,5-triazines, 2,7-diamino diphenylene-oxide, 3,6-diamino carbazole, 2,4-diamino-6-sec.-propyl-1,3,5-triazine, 2, two (the 4-aminophenyls)-1,3 of 5-, 4-
Figure BDA00003096242600141
diazole etc.
The example of aliphatie diamine class can exemplify: 1, the 2-diaminoethanes, 1, the 3-diaminopropanes, 1, the 4-diaminobutane, 1, the 5-1,5-DAP, 1, the 6-diamino hexane, 1, 7-diamino heptane, 1, the 8-diamino-octane, 1, 9-diamino nonane, 1, the 10-diamino decane, 1, 3-diamino-2, the 2-dimethylpropane, 1, 6-diamino-2, the 5-dimethylhexane, 1, 7-diamino-2, the 5-dimethyl heptane, 1, 7-diamino-4, the 4-dimethyl heptane, 1, 7-diamino-3-methylheptane, 1, 9-diamino-5-methylheptane, 1, 12-diamino dodecane, 1, 18-diamino octadecane, 1, 2-two (the amino propoxy-of 3-) ethane etc.
In addition, as other diamines, can exemplify there is alkyl on side chain, containing fluoroalkyl, aromatic nucleus, aliphatics ring, heterocycle, and the diamine compound of the large ring-type substituent that formed by them.Particularly, the diamines can illustration meaned with following formula [DA-1]～formula [DA-30].
[changing 15]
(in formula, R 13mean the alkyl of carbon number 1～22 or contain fluoroalkyl; S 5expression-COO-,-OCO-,-CONH-,-NHCO-,-CH 2-,-O-,-CO-or-NH-.)
[changing 16]
Figure BDA00003096242600152
(in formula, S 6expression-O-,-OCH 2-,-CH 2o-,-COOCH 2-or-CH 2oCO-; R 14mean the alkyl, alkoxyl group of carbon number 1～22, containing fluoroalkyl or fluoroalkoxy.)
[changing 17]
Figure BDA00003096242600153
(in formula, S 7expression-COO-,-OCO-,-CONH-,-NHCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-or-CH 2-; R 15mean the alkyl, alkoxyl group of carbon number 1～22, containing fluoroalkyl or fluoroalkoxy.)
[changing 18]
Figure BDA00003096242600161
(in formula, S 8expression-COO-,-OCO-,-CONH-,-NHCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-,-CH 2-,-O-or-NH-; R 16mean fluorine-based, cyano group, trifluoromethyl, nitro, azo-group, formyl radical, ethanoyl, acetoxyl group or hydroxyl.)
[changing 19]
Figure BDA00003096242600162
(in formula, R 17the alkyl that means carbon number 3～12; The cis-isomerism of Isosorbide-5-Nitrae-cyclohexylidene is respectively trans.)
[changing 20]
In the situation that utilize light to carry out orientation process, by also, with the diamines of above-mentioned formula [1] and the diamines of above-mentioned [DA-1]～[DA-30], can obtain more stable tilt angle.As and the diamines of use, the diamines of preferred formula [DA-10]～[DA-30], the more preferably diamines of formula [DA-10]～[DA-16].Preferred content to these diamines is not particularly limited, but with respect to the total amount of two amine components, is preferably 5～50 % by mole, from the viewpoint of printing, and preferably 5～30 % by mole.
In addition, as other diamines, also can exemplify following diamines.
[changing 21]
Figure BDA00003096242600181
(in formula, i is 0～3 integer; J is 1～5 integer.)
By importing [DA-31] or [DA-32], can improve voltage retention (VHR), in addition, [DA-33]～[DA-38] can make to accumulate electric charge to be reduced.
In addition, also can exemplify diamino siloxanes as meaned with following formula [DA-39] etc.
[changing 22]
(in formula, the integer that k is 1～10.)
This other diamine compound can be when making liquid crystal orientation film liquid crystal aligning, voltage retentivity, accumulate the characteristic such as electric charge, use a kind or two or more is mixed and uses.
For for obtaining the tetracarboxylic dianhydride that the polyimide precursors such as polyamic acid of the present invention react with two amine components, waiting tetracarboxylic acid and derivative thereof to be not particularly limited.Below exemplify its object lesson.
Tetracarboxylic dianhydride with ester ring type structure or aliphatic structure can exemplify 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, 2, 3, 4-tetramethyl--1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 1, 2, 3, 4-pentamethylene tetracarboxylic dianhydride, 2, 3, 4, 5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 1, 2, 4, 5-hexanaphthene tetracarboxylic dianhydride, 3, 4-dicarboxyl-1-cyclohexyl succsinic acid dianhydride, 3, 4-dicarboxyl-1, 2, 3, 4-tetrahydrochysene-1-naphthalene succinic dianhydride, 1, 2, 3, 4-butane tetracarboxylic acid dianhydride, two rings [3, 3, 0] octane-2, 4, 6, the 8-tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-dicyclohexyl tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic basic ring amyl group acetic acid dianhydride, cis-3, 7-dibutyl ring hot-1, 5-diene-1, 2, 5, the 6-tetracarboxylic dianhydride, three ring [4.2.1.0 2,5] nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dianhydride, six ring [6.6.0.1 2,7.0 3,6.1 9,14.0 10,13] n-Hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dianhydride, 4-(2,5-dioxo tetrahydrofuran (THF)-3-yl)-1,2,3,4-tetralin-1,2-dicarboxylic anhydride etc.
Also have, if also use aromatic tetracarboxylic acid's dianhydride outside the above-mentioned tetracarboxylic dianhydride with alicyclic structure or aliphatic structure, can improve liquid crystal aligning, and can reduce the electric charge of accumulating of liquid crystal structure cell, therefore preferably.As aromatic tetracarboxylic acid's dianhydride, can exemplify pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride etc.
For also being not particularly limited for obtaining the tetracarboxylic acid dialkyl that poly amic acid ester of the present invention reacts with two amine components.Below exemplify its object lesson.
The object lesson of aliphatics tetracarboxylic acid diester can exemplify 1, 2, 3, 4-tetramethylene tetracarboxylic acid dialkyl, 1, 2-dimethyl-1, 2, 3, 4-tetramethylene tetracarboxylic acid dialkyl, 1, 3-dimethyl-1, 2, 3, 4-tetramethylene tetracarboxylic acid dialkyl, 1, 2, 3, 4-tetramethyl--1, 2, 3, 4-tetramethylene tetracarboxylic acid dialkyl, 1, 2, 3, 4-pentamethylene tetracarboxylic acid dialkyl, 2, 3, 4, 5-tetrahydrofuran (THF) tetracarboxylic acid dialkyl, 1, 2, 4, 5-hexanaphthene tetracarboxylic acid dialkyl, 3, 4-dicarboxyl-1-cyclohexyl dialkyl succinate, 3, 4-dicarboxyl-1, 2, 3, 4-tetrahydrochysene-1-naphthalene succinic dialkyl, 1, 2, 3, 4-butane tetracarboxylic acid dialkyl ester, two rings [3, 3, 0] octane-2, 4, 6, 8-tetracarboxylic acid dialkyl, 3, 3 ', 4, 4 ' dicyclohexyl tetracarboxylic acid dialkyl, 2, 3, 5-tricarboxylic basic ring amyl group acetic acid dialkyl, cis-3, 7-dibutyl ring hot-1, 5-diene-1, 2, 5, 6-tetracarboxylic acid dialkyl, three ring [4.2.1.0 2,5] nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dialkyl, six ring [6.6.0.1 2,7.0 3,6.1 9,14.0 10,13] n-Hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dialkyl, 4-(2,5-dioxo tetrahydrofuran (THF)-3-yl)-1,2,3,4-tetralin-1,2-dicarboxylic acid dialkyl esters etc.
As aromatic tetracarboxylic acid's dialkyl, can exemplify Pyromellitic Acid dialkyl, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dialkyl, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid dialkyl, 2,3,3 ', 4-biphenyltetracarboxyacid acid dialkyl, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dialkyl, 2,3,3 ', 4-benzophenone tetracarboxylic acid dialkyl, two (3,4-dicarboxyl phenyl) ether dialkyl, two (3,4-dicarboxyl phenyl) sulfone dialkyl, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl etc.
In addition, by making two amine components such as diamines of the present invention, with dicarboxylic acid, react, can also synthesizing polyamides.For being not particularly limited with the dicarboxylic acid that two amine components react for obtaining polymeric amide.Below exemplify its object lesson.
Object lesson as the aliphatic dicarboxylic acid of dicarboxylic acid or derivatives thereof, can exemplify propanedioic acid, oxalic acid, dimethyl malonic acid, succsinic acid, fumaric acid, pentanedioic acid, hexanodioic acid, muconic acid, 2-methyl hexanodioic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylated pentanedioic acid, 3, the dicarboxylic acid such as 3-diethyl succsinic acid, nonane diacid, sebacic acid and suberic acid.
Dicarboxylic acid as the alicyclic ring same clan, can exemplify 1, the 1-cyclopropane dicarboxylic acid, 1, the 2-cyclopropane dicarboxylic acid, 1, the 1-cyclobutane dicarboxylic acid, 1, the 2-cyclobutane dicarboxylic acid, 1, the 3-cyclobutane dicarboxylic acid, 3, 4-phenylbenzene-1, the 2-cyclobutane dicarboxylic acid, 2, 4-phenylbenzene-1, the 3-cyclobutane dicarboxylic acid, 1-cyclobutene-1, the 2-dicarboxylic acid, 1-cyclobutene-3, the 4-dicarboxylic acid, 1, 1-pentamethylene dicarboxylic acid, 1, 2-pentamethylene dicarboxylic acid, 1, 3-pentamethylene dicarboxylic acid, 1, the 1-cyclohexane dicarboxylic acid, 1, the 2-cyclohexane dicarboxylic acid, 1, the 3-cyclohexane dicarboxylic acid, 1, the 4-cyclohexane dicarboxylic acid, 1, 4-(2-norbornylene) dicarboxylic acid, norbornylene-2, the 3-dicarboxylic acid, two ring [2.2.2] octanes-1, the 4-dicarboxylic acid, two ring [2.2.2] octanes-2, the 3-dicarboxylic acid, 2, 5-dioxo-1, 4-bis-ring [2.2.2] octane dicarboxylic acid, 1, 3-diamantane dicarboxylic acid, 4, 8-dioxo-1, 3-diamantane dicarboxylic acid, 2, 6-spiroheptane dicarboxylic acid, 1, 3-diamantane oxalic acid, dextrocamphoric acid etc.
As aromatic dicarboxylic acid, can exemplify phthalic acid, m-phthalic acid, terephthalic acid, the oreinol dioctyl phthalate, the 5-tert-butyl isophthalic acid, the amino m-phthalic acid of 5-, the 5-Hydroxy M Phthalic Acid, 2,5-dimethyl terephthalic acid, the tetramethyl-terephthalic acid, Isosorbide-5-Nitrae-naphthalene dicarboxylic acids, 2,5-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, 2,7-naphthalene dicarboxylic acids, Isosorbide-5-Nitrae-anthracene dicarboxylic acid, Isosorbide-5-Nitrae-anthraquinone dicarboxylic acid, 2,5-diphenyl dicarboxylic acid, 4,4 '-diphenyl dicarboxylic acid, 1,5-diphenylene dicarboxylic acid, 4,4 " terphenyl dicarboxylic acid, 4,4 '-ditan dicarboxylic acid, 4,4 '-diphenylethane dicarboxylic acid, 4,4 '-diphenyl propane dicarboxylic acid, 4,4 '-phenylbenzene HFC-236fa dicarboxylic acid, 4,4 '-diphenyl ether dicarboxylic acid, 4,4 '-dibenzyl dicarboxylic acid, 4,4 '-stilbene dicarboxylic acid, 4,4 '-ethynylene dibenzoic acid, 4,4 '-carbonyl diurethane phenylformic acid, 4,4 '-alkylsulfonyl dibenzoic acid, 4,4 '-dithiodibenzoic acid, to the phenylene oxalic acid, 3,3 '-to the phenylene dipropionic acid, the 4-o-carboxy cinnamic acid, to the phenylene diacrylate, 3,3 '-[4,4 '-(two pairs of phenylenes of methylene radical)] dipropionic acid, 4,4 '-[4,4 '-(two pairs of phenylenes of oxo)] dipropionic acid, 4,4 '-[4,4 '-(two pairs of phenylenes of oxo)] two butyric acid, (two pairs of phenylene dioxies of isopropylidene) two butyric acid, two (to carboxyl phenyl) dimethylsilane etc.
Dicarboxylic acid as containing heterocycle, can exemplify 1,5-(9-oxo fluorenes) dicarboxylic acid, 3,4-furans dicarboxylic acid, 4,5-thiazole dicarboxylic acid, 2-phenyl-4,5-thiazole dicarboxylic acid, 1,2,5-thiadiazoles-3,4-dicarboxylic acid, 1,2,5-
Figure BDA00003096242600211
diazole-3,4-dicarboxylic acid, 2,3-pyridine dicarboxylic acid, 2,4-pyridine dicarboxylic acid, 2,5-Pyridinedicarboxylic acid, 2, dipicolimic acid 2,3,4-pyridine dicarboxylic acid, 3,5-pyridine dicarboxylic acid etc.
Above-mentioned various dicarboxylic acid can be also the structures of sour two carboxylic acid halides or acid anhydrides.In these omega-dicarboxylic acids, in order to keep the orientation of liquid crystal molecule, preferably can provide the omega-dicarboxylic acids of the polymeric amide of linear structure.Wherein, preferably terephthalic acid, m-phthalic acid (Japanese: the acid of イ ソ テ レ Off タ Le), Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-ditan dicarboxylic acid, 4,4 '-diphenylethane dicarboxylic acid, 4,4 '-diphenyl propane dicarboxylic acid, 4,4 '-phenylbenzene HFC-236fa dicarboxylic acid, 2,2-bis-(phenyl) propane dicarboxylic acid, 4,4-terphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acids, 2,5-Pyridinedicarboxylic acid or their acid two carboxylic acid halides etc.Sometimes also having isomer in these compounds, can be also the mixture that comprises isomer.In addition, the compound that also two or more kinds may be used.In addition, the omega-dicarboxylic acids used in the present invention is not limited to above-mentioned exemplary compounds.
Above-mentioned tetracarboxylic dianhydride waits liquid crystal aligning, voltage retentivity that tetracarboxylic acid and derivative thereof can be when making liquid crystal orientation film, accumulate the characteristic such as electric charge, uses a kind of or and with two or more.
As make two amine components be selected from tetracarboxylic acid and tetracarboxylic acid derivatives at least one react to obtain the method for the polyimide precursors such as polyamic acid, can adopt known synthetic method.
For example, obtain the method for polyamic acid of the present invention as the reaction by tetracarboxylic dianhydride and two amine components, can exemplify the method that tetracarboxylic dianhydride and two amine components are reacted in organic solvent.The reaction of tetracarboxylic dianhydride and diamines is carried out than being easier in organic solvent, and do not generate by product aspect be favourable.
As the organic solvent of the reaction for tetracarboxylic dianhydride and diamines, so long as the soluble solvent of polyamic acid generated is not particularly limited.As concrete example, can exemplify DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, the N-ethyl-2-pyrrolidone, the N-methyl caprolactam, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, the pregnancy sulfoxide, gamma-butyrolactone, Virahol, the methoxymethyl amylalcohol, limonene, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methylcyclohexane, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monobutyl ether, ethyl carbitol, ethylene glycol, ethylene glycol acetate, the glycol monomethyl isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, the propylene glycol monoacetate, propylene glycol monomethyl ether, the glycol tertiary butyl ether, DPGME, Diethylene Glycol, the Diethylene Glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethyl ether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxyl group butylacetic acid ester, the tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, the ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, tetrahydrotoluene, propyl ether, two hexyl ethers, two
Figure BDA00003096242600221
alkane, normal hexane, normal heptane, octane, diethyl ether, pimelinketone, ethylene carbonate, Texacar PC, methyl lactate, the lactic acid ethyl, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid propylene glycol ester list ethyl ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, the 3-methoxy methyl propionate, 3-ethoxy-propionic acid methyl ethyl ester, 3-methoxy propyl acetoacetic ester, the 3-ethoxy-propionic acid, the 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diglyme, the 4-hydroxy-4-methyl-2-pentanone, 3-methoxyl group-N, N-dimethyl propylene acid amides, 3-oxyethyl group-N, N-dimethyl propylene acid amides, 3-butoxy-N, N-dimethyl propylene acid amides etc.These solvents can be used alone, but also also mix together.Also have, even the solvent of insoluble solution polyamic acid, so long as, in the scope that can not separate out at the polyamic acid generated, also can use with above-mentioned solvent.In addition, the moisture in organic solvent hinders polyreaction, and can make the polyamic acid hydrolysis generated, so organic solvent is preferably used the organic solvent through farthest dehydrating.
When being reacted in organic solvent, tetracarboxylic dianhydride and two amine components can exemplify following method: stir the solution that makes two amine components be dispersed or dissolved in organic solvent and obtain, then directly add the tetracarboxylic dianhydride or make the tetracarboxylic dianhydride be dispersed or dissolved in the method for adding again after organic solvent; Add the method for two amine components in the solution obtained the tetracarboxylic dianhydride is dispersed or dissolved in to organic solvent on the contrary; Alternately add the method for tetracarboxylic dianhydride and two amine components etc., can use any method wherein.In addition, when tetracarboxylic dianhydride or two amine components consist of multiple compounds, can under the state be pre-mixed, make its reaction, also can make its respectively reaction successively, then make to react respectively and lower molecular weight body hybrid reaction and obtain the high molecular body.
Condensation temperature now can be selected the arbitrary temp of-20 ℃～150 ℃, preferably the scope of-5 ℃～100 ℃.In addition, polycondensation can be carried out with concentration arbitrarily, if be difficult to obtain the polymkeric substance of high molecular but concentration is too low, if excessive concentration the viscosity of reaction solution become too high and are difficult to stir uniformly, therefore tetracarboxylic dianhydride and the total concn of two amine components in reaction soln are preferably 1～50 quality %, more preferably 5～30 quality %.Can be that initial reaction stage is carried out under high density, append afterwards organic solvent.
In the polyreaction of polyamic acid, the ratio of the total mole number of tetracarboxylic dianhydride's total mole number and two amine components (total mole numbers of tetracarboxylic dianhydride's total mole number/bis-amine components) is better 0.8～1.2.Identical with common polycondensation, this mol ratio is more close to 1.0, and the molecular weight of the polyamic acid of generation is larger.
In addition, poly amic acid ester can reacting or making the tetracarboxylic acid diester be reacted to obtain under the existence of suitable condensing agent, alkali with two amine components by above-mentioned tetracarboxylic acid diester diacid chloride and two amine components.Perhaps, also can pass through with the pre-synthesis polyamic acid of above-mentioned method, the recycling high molecular weight reactive carries out esterification to the carboxylic acid in amido acid and obtains.
Particularly, can be by for example making tetracarboxylic acid diester diacid chloride and diamines under the existence of alkali and organic solvent, and ,-20～150 ℃, preferably reaction 30 minutes～24 hours, preferably 1～4 hour under 0～50 ℃, carry out the synthesizing polyamides acid esters.
As alkali, can use pyridine, triethylamine, 4-dimethylaminopyridine, in order to make reacting balance ground, carry out, preferably pyridine.From the amount of easily removing and the viewpoint that can easily obtain the high molecular body, consider, the addition of alkali is preferably 2～4 times moles with respect to tetracarboxylic acid diester diacid chloride.
In addition, when making under tetracarboxylic acid diester and the existence of two amine components at condensing agent to carry out polycondensation, can use triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride, N as alkali, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazine methylmorpholine
Figure BDA00003096242600231
, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea (TMU) Tetrafluoroboric acid ester, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea (TMU) phosphofluoric acid ester, (2,3-dihydroxyl-2-sulfo--3-benzo
Figure BDA00003096242600232
azoles) phosphonic acid diphenyl ester, 4-(4,6-dimethoxy-1,3,5-triazines-2-yl) 4-methoxyl group morpholine hydrochloride n hydrate etc.
In addition, state in the use in the method for condensing agent, by adding Lewis acid as additive, reaction can be carried out efficiently.As Lewis acid, the lithium halides such as preferred lithium chloride, lithiumbromide.Lewis acidic addition is better 0.1～1.0 times of molar weight with respect to diamines or tetracarboxylic acid diester.
As the solvent used in above-mentioned reaction, can use the solvent same with the solvent phase used when the above-mentioned synthesizing polyamides illustrated is sour, from the solvability of monomer and polymkeric substance, consider, preferably METHYLPYRROLIDONE, gamma-butyrolactone, can be used a kind in them or two or more is mixed and uses.From being difficult to occur the viewpoint consideration of separating out and easily obtain the high molecular body of polymkeric substance, total concn in the reaction soln of the tetracarboxylic acid derivatives such as concentration, tetracarboxylic acid diester diacid chloride or tetracarboxylic acid diester when synthetic and two amine components is better 1～30 quality %, is more preferably 5～20 quality %.In addition, in order to prevent tetracarboxylic acid diester diacid chloride hydrolysis, for the synthetic solvent of poly amic acid ester, can be the state of dehydration to the greatest extent farthest, be better in nitrogen atmosphere, prevent sneaking into of external gas.
Polyimide of the present invention can obtain by making above-mentioned polyamic acid dehydration closed-loop.In polyimide of the present invention, the dehydration closed-loop rate of acid amides acidic group (imide rate) does not need one to be decided to be 100%, can adjust arbitrarily according to purposes or purpose.
As the method that makes the polyamic acid imidization, can exemplify the direct heating polyamic acid solution hot-imide or add the catalysis imidization of catalyzer in the solution of polyamic acid.
Temperature while making polyamic acid carry out hot-imide in solution is 100～400 ℃, and preferably 120～250 ℃ is better to carry out imidization when the water that will be generated by imidization reaction drains into outside system.
The catalysis imidization of polyamic acid can be by add basic catalyst and acid anhydrides in polyamic acid solution, at-20～250 ℃, preferably under 0～180 ℃, stirs and carry out.The amount of basic catalyst is 0.5～30 mole times of acid amides acidic group, and preferably 2～20 moles times, the amount of acid anhydrides is 1～50 mole times of acid amides acidic group, preferably 3～30 moles times.As basic catalyst, can exemplify pyridine, triethylamine, Trimethylamine 99, Tributylamine, trioctylamine etc., wherein pyridine have for make reaction carry out for appropriate alkalescence, therefore preferably.As acid anhydrides, can exemplify diacetyl oxide, trimellitic acid 1,2-anhydride, pyromellitic dianhydride etc., wherein, be easy to react the purifying after finishing while using diacetyl oxide, therefore preferably.Adopt the imide rate of catalysis imidization to control by adjusting catalytic amount and temperature of reaction, reaction times.
In addition, as mentioned above, also can, by high temperature heating poly amic acid ester to promote dealcoholysis, to make its closed loop, obtain polyimide.
In addition, while from the reaction soln of the polyimide precursor such as polyamic acid, poly amic acid ester or polyimide, reclaiming the polyamic acid that generates, poly amic acid ester, polyimide, pour reaction soln into poor solvent its precipitation is got final product.Poor solvent as for precipitation, can exemplify methyl alcohol, acetone, hexane, ethylene glycol butyl ether, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene, water etc.Put in poor solvent and the polyimide precursor of precipitation or polyimide can be after filtered and recycled, under normal pressure or decompression, under normal temperature or heating, carry out drying.In addition, if the polyimide precursor that precipitation is reclaimed or polyimide are dissolved in organic solvent again and repeat the operation that 2～10 times redeposition reclaims, can reduce the impurity in polymkeric substance.As poor solvent now, can exemplify such as alcohols, ketone, hydro carbons etc., if use the poor solvent more than 3 kinds that is selected from these solvents, purification efficiency further improves, therefore preferably.
The molecular weight of the polyimide precursor such as contained polyamic acid, poly amic acid ester or polyimide in liquid crystal aligning agent of the present invention, in the intensity of filming of considering gained and under the operability while forming of filming, the inhomogeneity situation of filming, (Gel Permeation Chromatography: the weight average molecular weight that gel permeation chromatography) method is measured is better 5000～1000000, is more preferably 10000～150000 to utilize GPC.
The polyimide precursors such as above-mentioned polyamic acid of the present invention, poly amic acid ester and polyimide are used together with solvent, can make liquid crystal aligning agent.Liquid crystal aligning agent refers to the solution that is used to form liquid crystal orientation film, is that the component of polymer that will be used to form liquid crystal orientation film is dispersed or dissolved in organic solvent and the solution that forms.In addition, liquid crystal orientation film refers to for making the film of liquid crystal along the direction orientation of regulation.And, in the present invention, at least one that above-mentioned component of polymer contains polyimide precursors such as being selected from above-mentioned polyamic acid of the present invention, poly amic acid ester and polyimide.
In liquid crystal aligning agent of the present invention, contained component of polymer can be all polyimide precursor or the polyimide such as above-mentioned polyamic acid of the present invention, poly amic acid ester, or is mixed with other polymkeric substance in the polyimide precursors such as above-mentioned polyamic acid of the present invention, poly amic acid ester or polyimide.During polymkeric substance that component of polymer contains other, the content of the polymkeric substance of other in the component of polymer total amount is 0.5 quality %～50 quality %, preferably 1 quality %～30 quality %.By adopting the mixture of multiple polymers, can improve the characteristic of liquid crystal aligning agent and liquid crystal orientation film.
As the polymkeric substance of such other, for example, can exemplify as two amine components that reacts with tetracarboxylic dianhydride's composition use except of the present invention above-mentioned with the diamines the diamines of formula [1] expression must polyamic acid, poly amic acid ester or polyimide etc.
In liquid crystal aligning agent, be selected from least one of the polyimide precursor such as above-mentioned polyamic acid of the present invention, poly amic acid ester and polyimide and mix as required other polymkeric substance containing proportional, in the component of polymer total amount, be better 1 quality %～20 quality %, be more preferably 3 quality %～15 quality %, the spy is well 3～10 quality %.
The solvent used in liquid crystal aligning agent of the present invention, so long as the organic solvent of energy dissolve polymer composition gets final product, is not particularly limited.As its concrete example, can exemplify N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, the N-methyl caprolactam, 2-Pyrrolidone, the N-ethyl pyrrolidone, NVP, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, the pregnancy sulfoxide, gamma-butyrolactone, 3-methoxyl group-N, N-dimethyl propylene acid amides, 3-oxyethyl group-N, N-dimethyl propylene acid amides, 3-butoxy-N, N-dimethyl propylene acid amides, 1, the 3-dimethyl-2-imidazolidinone, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, pimelinketone, ethylene carbonate, Texacar PC, diglyme, 4-hydroxy-4-methyl-2-pentanone etc.These solvents can be used alone, but also also mix together.
Liquid crystal aligning agent of the present invention can comprise above-mentioned composition in addition.Object lesson has, the compound of the adaptation of the film uniformity while improving the coating of liquid crystalline alignment agent and the solvent of surface smoothness or compound, raising liquid crystal orientation film and substrate etc.
Concrete example as the solvent (poor solvent) of the homogeneity that improves thickness and surface smoothness, can exemplify Virahol, the methoxymethyl amylalcohol, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monobutyl ether, ethyl carbitol, the ethyl carbitol acetic ester, ethylene glycol, ethylene glycol acetate, the glycol monomethyl isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, the propylene glycol monoacetate, propylene glycol monomethyl ether, the glycol tertiary butyl ether, DPGME, Diethylene Glycol, the Diethylene Glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethyl ether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxyl group butylacetic acid ester, the tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, the ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, tetrahydrotoluene, propyl ether, two hexyl ethers, the 1-hexanol, normal hexane, Skellysolve A, octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid propylene glycol ester list ethyl ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, the 3-methoxy methyl propionate, 3-ethoxy-propionic acid methylethyl ester, 3-methoxy propyl acetoacetic ester, the 3-ethoxy-propionic acid, the 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, the 1-methoxy-2-propanol, 1-oxyethyl group-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, the propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic ester, the mono-ethyl ether of propylene glycol-1--2-acetic ester, dipropylene glycol, 2-(2-oxyethyl group propoxy-) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate or isoamyl lactate etc. have the solvent of low surface tension etc.
These poor solvents can be used a kind, or multiple mixing is used.While using solvent as above, be better 5～80 quality % that account for solvent total amount contained in liquid crystal aligning agent, be more preferably 20～60 quality %.
Compound as improving film uniformity and surface smoothness, can exemplify fluorine class tensio-active agent, siloxane type surfactants, nonionic surfactant etc.More specifically, can exemplify the system such as エ Off ト ッ プ EF301, EF303, EF352 (the (ト ー ケ of illuminating product Co., Ltd. system プ ロ ダ Network Star society)), メ ガ Off ァ ッ Network F171, F173, R-30 (Dainippon Ink and Chemicals, Inc's (large Japanese イ Application キ society) system), Off ロ ラ ー De FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo ス リ ー エ system society) system), ア サ ヒ ガ ー De AG710, サ ー Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd (Asahi Glass society) system) etc.The usage ratio of these tensio-active agents, with respect to resinous principle contained in liquid crystal aligning agent 100 mass parts, is better 0.01～2 mass parts, is more preferably 0.01～1 mass parts.
Concrete example as the compound of the adaptation that improves liquid crystal orientation film and substrate, can exemplify the 3-TSL 8330, APTES, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (the oxyethylene group)-3-TSL 8330 of N-, two (the oxyethylene group)-APTESs of N-, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 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, two (N, the N-diglycidyl amino methyl) hexanaphthenes of 1,3-, N, N, N ', N ' ,-four glycidyl group-4,4 '-diaminodiphenyl-methanes etc. are containing the compound of functional silanes and containing the compound of epoxy group(ing) etc.
Also have, except the adaptation that improves substrate and film, for degradation under the electrical characteristic that prevent from being caused by backlight, also can import the additive of phenoplast class as follows.The additive of concrete phenoplast class is as follows, but is not limited to these structures.
[changing 23]
Figure BDA00003096242600281
(in formula, Me means methyl.)
Use and to improve and during the compound of the adaptation of substrate, its usage quantity, with respect to 100 mass parts of component of polymer contained in liquid crystal aligning agent, is better 0.1～30 mass parts, is more preferably 1～20 mass parts.If usage quantity less than 0.1 mass parts, can't expect the effect that adaptation improves, if more than 30 mass parts, the orientation variation of liquid crystal sometimes.
In liquid crystal aligning agent of the present invention, except above-mentioned, in the scope of not damaging effect of the present invention, dielectric medium or conducting material that the electrical characteristic such as the specific inductivity of liquid crystal orientation film or electroconductibility are purpose can be added to change, the hardness of the film while forming liquid crystal orientation film or the cross-linked compound that density is purpose can also be added to improve.
Liquid crystal aligning agent of the present invention is being coated on substrate and, after burning till, can carried out the orientation process such as friction treatment or rayed, or in vertical orientated purposes etc. without orientation process and as liquid crystal orientation film.Liquid crystal orientation film of the present invention like this contains polyimide precursor or the polyimide that uses diamines of the present invention and form, so do not form pore or thickness inhomogeneous of edge part etc. occur, be not easy in addition accumulating of electric charge occurs, and the electric charge of accumulating is eliminated fast.
As substrate, so long as the high substrate of the transparency is not particularly limited, can use glass substrate or the plastic bases such as vinylformic acid substrate, polycarbonate substrate etc.In addition, from the viewpoint of work simplification, preferably use the substrate be formed with for the ITO electrode of liquid crystal drive etc.And, in reflection type liquid crystal display element, if only limit to the substrate of a side can use the opaque materials such as silicon wafer, electrode now can be used the catoptrical materials such as aluminium.In addition, in the contour performance components of TFT type element, use and be formed with the member as elements such as transistors between the electrode for liquid crystal drive and substrate.
Coating process to liquid crystal aligning agent is not particularly limited, the method that industrial common employing is coated with by silk screen printing, offset printing, flexographic printing, ink-jet etc.As other coating process, also have dip coating, rolling method, slot coated, spin-coating method etc., can use these methods according to purpose.
After coating on substrate by liquid crystal aligning agent burn till can by the heating units such as hot-plate, recirculation furnace, infrared heating heating furnace 50～300 ℃, preferably carry out under 80～250 ℃, make the solvent evaporation, thereby form, film.If it is blocked up to burn till rear formed thickness of filming, unfavorable aspect the power consumption of liquid crystal display device, if excessively thin, the reliability of liquid crystal display device reduces sometimes, therefore preferably 5～300nm, more preferably 10～100nm.While making liquid crystal horizontal alignment or tilted alignment, by friction or polarisation uviolizing etc., filming after burning till processed.
Liquid crystal display device of the present invention is, after obtaining the substrate with liquid crystal orientation film by aforesaid method by liquid crystal aligning agent of the present invention, by known method, to manufacture the liquid crystal display device that the liquid crystal structure cell forms.If exemplify an example, following liquid crystal display device is arranged: possess 2 substrates of configuration in opposite directions, be arranged on the liquid crystal layer between substrate, and be arranged on the above-mentioned liquid crystal orientation film formed by liquid crystal aligning agent of the present invention between substrate and liquid crystal layer.
As the substrate for liquid crystal display device of the present invention, so long as the high substrate of the transparency gets final product, be not particularly limited, normally on substrate, be formed with the substrate of the transparency electrode for driving liquid crystal.As object lesson, can exemplify with above-mentioned liquid crystal orientation film in the same substrate of the substrate put down in writing.
In addition, liquid crystal orientation film is burnt till after liquid crystal aligning agent of the present invention and is formed by coating on this substrate, and detailed content as mentioned above.
Liquid crystal material to the liquid crystal layer that forms liquid crystal display device of the present invention is not particularly limited, and can use the existing liquid crystal material be used with vertical orientation mode, such as MLC-2003, the MLC-6608 of Merck & Co., Inc. (メ Le Network society) system, MLC-6609 etc.
If exemplify an example of manufacturing the liquid crystal structure cell, but the following method of illustration: a pair of substrate of preparing to be formed with liquid crystal orientation film, scatter uniformly-spaced thing of pearl on the liquid crystal orientation film of a plate base, make the liquid crystal aligning face become interior rear flank another plate base laminating, the method for liquid crystal sealing is injected in decompression; Or drip liquid crystal on being scattered with the liquid crystal aligning face of spacer after, the method that baseplate-laminating is sealed etc.Now, the thickness of spacer is 1～30 μ m preferably, more preferably 2～10 μ m.
As mentioned above, use liquid crystal aligning agent of the present invention and the reliability of the liquid crystal display device that makes is good, can perform well in the LCD TV of large picture and high-resolution etc.
Embodiment
Below, based on embodiment, be described in further detail, but the present invention is not subject to any restriction of this embodiment.
[synthesizing of diamines]
The abbreviation of following use is as follows.
DMF:N, dinethylformamide
THF: tetrahydrofuran (THF)
RT: room temperature (25 ℃)
Synthesizing of the amino indoline of the 1-that (synthetic example 1) means with following formula (4-aminophenyl)-5-[diamines-1 (Diamine-1)]
[changing 24]
Figure BDA00003096242600301
Synthesizing of (the first operation) 1-(4-nitrophenyl)-5-nitro indoline
[changing 25]
Add 9.30g (213 mmole) sodium hydride (purity 55%), the 100mL DMF that dewaters in two mouthfuls of flasks of 500mL, while stir to be no more than the DMF solution (5-nitro indoline: 35.0g (213 mmole), DMF:100mL) that the condition of 30 ℃ drips 5-nitro indoline under nitrogen atmosphere.After dripping end, at room temperature stir 2 hours.Drip the DMF solution (4-fluoronitrobenzene: 33.0g (234.5 mmole), DMF:100mL) of 4-fluoronitrobenzene in this reaction soln, under nitrogen atmosphere, in stirring at room 6 hours.
After reaction finishes, on one side stirring reaction solution inject at leisure the 100mL pure water on one side, solid is separated out, filter the solid of separating out, it is dissolved in to DMF again, inject the 500mL pure water and make its redeposition, again the filtered and recycled solid.Methyl alcohol, normal hexane for solid to gained disperse to clean, and make its vacuum-drying, thereby obtain orange solid 54.7g (yield 90%).
Synthesizing of (the second operation) diamines-1 (Diamine-1)
[changing 26]
Figure BDA00003096242600311
Take 15.0g (52.6 mmole) by the 1-(4-nitrophenyl) of the first operation gained-5-nitro indoline and 1.50g10 quality % palladium carbon in the four-hole boiling flask of 300mL, add 150mL ethanol, after fully carrying out the nitrogen displacement, be replaced as hydrogen atmosphere, at room temperature carry out vigorous stirring.
After reaction finishes, with glass filter, filter palladium carbon, with rotatory evaporator, filtrate is carried out to removing of solvent.The residue of gained is dissolved in to acetone, add gac and stir a moment, the filter activity charcoal, after removing acetone with rotatory evaporator, carry out recrystallization with the mixing solutions (2:3 mass ratio) of normal hexane and ethyl acetate, obtain the solid 10.5g (yield: 89%) as the lilac of targeted diamine (Diamine-1).The nuclear magnetic resonance spectrum of hydrogen atom in molecule for its structure, 1the H-NMR spectrum is confirmed.Determination data is as follows.
1h NMR (400MHz, [D 6]-DMSO) δ: 6.87-6.23 (aromatics H, 7H), 4.77-4.68 (s-br, 2H), 4.39-4.38 (s-br, 2H), 3.62-3.58 (t, 2H), 2.89-2.87 (t, 2H)
Synthetic (the raceme mixing) of the amino indoline of the 1-that (synthetic example 2) means with following formula (4-aminophenyl)-2-methyl-5-[diamines-2 (Diamine-2)]
[changing 27]
Figure BDA00003096242600321
Synthesizing of (the first operation) 1-(4-nitrophenyl)-2-methyl-5-nitro indoline
[changing 28]
Figure BDA00003096242600322
Add 2.45g (56.1 mmole) sodium hydride (purity 55%), the 100mL DMF that dewaters in two mouthfuls of flasks of 500mL, while stir to be no more than the DMF solution (2-methyl-5-nitro indoline: 10.0g (56.1 mmole), DMF:50mL) that the condition of 30 ℃ drips 2-methyl-5-nitro indoline under nitrogen atmosphere.After dripping end, at room temperature stir 2 hours.Drip the DMF solution (4-fluoronitrobenzene: 8.7g (61.7 mmole), DMF:50mL) of 4-fluoronitrobenzene in this reaction soln, under nitrogen atmosphere, in stirring at room 6 hours.
After reaction finishes, on one side stirring reaction solution inject at leisure the 100mL pure water on one side, solid is separated out, filter the solid of separating out, it is dissolved in to DMF again, inject the 500mL pure water and make its redeposition, again the filtered and recycled solid.Methyl alcohol, normal hexane for solid to gained disperse to clean, and make its vacuum-drying, thereby obtain orange solid 14.4g (yield: 86%).
Synthesizing of (the second operation) diamines-2 (Diamine-2)
[changing 29]
Figure BDA00003096242600323
Take 10.0g (56.1 mmole) by the 1-(4-nitrophenyl) of the first operation gained-2-methyl-5-nitro indoline and 1.00g10 quality % palladium carbon in the four-hole boiling flask of 300mL, add 150mL ethanol, after fully carrying out the nitrogen displacement, be replaced as hydrogen atmosphere, at room temperature carry out vigorous stirring.
After reaction finishes, with glass filter, filter palladium carbon, with rotatory evaporator, filtrate is carried out to removing of solvent.The residue of gained is dissolved in to acetone, add gac and stir a moment, the filter activity charcoal, after removing acetone with rotatory evaporator, carry out recrystallization with the mixing solutions (2:3 mass ratio) of normal hexane and ethyl acetate, obtain the solid 7.03g (yield: 89%) as the lightpink of targeted diamine (Diamine-2).Its structure is used 1the H-NMR spectrum is confirmed.Determination data is as follows.
1h NMR (400MHz, [D 6]-DMSO) δ: 6.86-6.84 (d, 2H), 6.56-6.22 (aromatics H, 7H), 4.77-4.68 (s-br, 2H), 4.39-4.38 (s-br, 2H), 4.83-4.81 (m, 1H), 3.42-3.38 (dd, 1H), 2.89-2.87 (dd, 1H) 1.48-1.47 (s, 3H)
(synthetic example 3) 1-(4-aminophenyl)-2,3, synthetic (the raceme mixing) of the amino indoline of 3-trimethylammonium-5-[diamines-3 (Diamine-3)]
[changing 30]
(the first operation) 1-(4-nitrophenyl)-2,3,3-trimethylammonium-5-nitro indoline synthetic
[changing 31]
Figure BDA00003096242600332
Add 2.16g (48.5 mmole) sodium hydride (purity 55%), the 100mL DMF that dewaters in two mouthfuls of flasks of 500mL, drip 2 while the condition that stirs to be no more than 30 ℃ under nitrogen atmosphere, 3, the DMF solution (2 of 3-trimethylammonium-5-nitro indoline, 3,3-trimethylammonium-5-nitro indoline: 10.0g (48.5 mmole), DMF:50mL).After dripping end, at room temperature stir 2 hours.Drip the DMF solution (4-fluoronitrobenzene: 7.52g (53.3 mmole), DMF:50mL) of 4-fluoronitrobenzene in this reaction soln, under nitrogen atmosphere, in stirring at room 6 hours.
After reaction finishes, on one side stirring reaction solution inject at leisure the 100mL pure water on one side, solid is separated out, filter the solid of separating out, it is dissolved in to DMF again, inject the 500mL pure water and make its redeposition, again the filtered and recycled solid.Methyl alcohol, normal hexane for solid to gained disperse to clean, and make its vacuum-drying, thereby obtain orange solid 13.5g (yield: 85%).
Synthesizing of (the second operation) diamines-3 (Diamine-3)
[changing 32]
Figure BDA00003096242600341
Take the 1-(4-nitrophenyl)-2 of 10.0g (30.5 mmole) by the first operation gained in the four-hole boiling flask of 300mL, 3,3-dimethyl-5-nitro indoline and 1.00g10 quality % palladium carbon, add 150mL ethanol, after fully carrying out the nitrogen displacement, be replaced as hydrogen atmosphere, at room temperature carry out vigorous stirring.
After reaction finishes, with glass filter, filter palladium carbon, with rotatory evaporator, filtrate is carried out to removing of solvent.The residue of gained is dissolved in to acetone, add gac and stir a moment, the filter activity charcoal, after removing acetone with rotatory evaporator, carry out recrystallization with the mixing solutions (2:3 mass ratio) of normal hexane and ethyl acetate, obtain the solid 7.50g (yield: 92%) as the lilac of targeted diamine (Diamine-3).Its structure is used 1the H-NMR spectrum is confirmed.Determination data is as follows.
1h NMR (400MHz, [D 6]-DMSO) δ: 6.86-6.22 (aromatics H, 7H), 4.74-4.66 (s-br, 2H), 4.41-4.39 (s-br, 2H), 4.23-4.21 (m, 1H), 1.48-1.14 (s, 9H)
The 1-that (synthetic example 4) means with following formula (4-aminophenyl)-6-is amino-1,2,3,4-tetrahydroquinoline [diamines-4 (Diamine-4)] synthetic
[changing 33]
Figure BDA00003096242600342
Synthesizing of (the first operation) 6-(tert-butoxycarbonyl) quinolylamine
[changing 34]
Figure BDA00003096242600351
In the four-hole boiling flask of 200mL, make 5.00g (34.7 mmole) 6-quinolylamine be dissolved in 100mLTHF, add 7.57g (34.7 mmole) the two carbonic acid tert-butyl esters, reflux 20 hours under nitrogen atmosphere.
Reaction is removed THF with rotatory evaporator after finishing, and adds ethyl acetate, after water, saturated aqueous common salt clean, uses anhydrous magnesium sulfate drying.After removing by filter anhydrous magnesium sulfate, except desolventizing, residue is carried out to recrystallization with the mixed solvent (1:4 volume ratio) of ethyl acetate and normal hexane with rotatory evaporator, obtain white solid 7.29g (86%).
(the second operation) 6-(tert-butoxycarbonyl) is amino-1,2,3,4-tetrahydroquinoline synthetic
[changing 35]
Figure BDA00003096242600352
Take 6-(tert-butoxycarbonyl) quinolylamine and the 0.50g10 quality % palladium carbon of 5.00g (20.4 mmole) by the first operation gained in two mouthfuls of flasks of 100mL, add 50mL methyl alcohol, after fully carrying out the nitrogen displacement, be replaced as hydrogen atmosphere, carry out vigorous stirring under 60 ℃.
After reaction finishes, with glass filter, filter palladium carbon, with rotatory evaporator, filtrate is carried out to removing of solvent.The residue of gained is dissolved in to acetone, add gac and stir a moment, the filter activity charcoal, after removing acetone with rotatory evaporator, carry out recrystallization with the mixing solutions (2:3 mass ratio) of normal hexane and ethyl acetate, obtain white vitreous solid 3.65g (yield: 72%).
(the 3rd operation) 1-(4-nitrophenyl)-6-is amino-1,2,3,4-tetrahydroquinoline synthetic
[changing 36]
Figure BDA00003096242600361
Add 0.615g (14.1 mmole) sodium hydride (purity 55%), the 20mL DMF that dewaters in two mouthfuls of flasks of 100mL, drip the 6-(tert-butoxycarbonyl) amino-1 by the second operation gained while the condition that stirs to be no more than 30 ℃ under nitrogen atmosphere, 2,3, (6-(tert-butoxycarbonyl) amino-1 for the DMF solution of 4-tetrahydroquinoline, 2,3,4-tetrahydroquinoline: 3.50g (14.1 mmole), DMF:20mL).After dripping end, stir 2 hours.Drip the DMF solution (4-fluoronitrobenzene: 2.19g (15.5 mmole), DMF:20mL) of 4-fluoronitrobenzene in this reaction soln, under nitrogen atmosphere, in stirring at room 20 hours.
After reaction finishes, on one side stirring reaction solution inject at leisure the 30mL pure water on one side, solid is separated out, filter the solid of separating out, it is dissolved in to DMF again, inject the 100mL pure water and make its redeposition, again the filtered and recycled solid.By disperse cleaning with normal hexane, and carry out vacuum-drying, thereby obtain yellow solid.Add 4N hydrochloric acid-ethyl acetate solution for this solid, stir 2 hours under 40 ℃.Add pure water in reaction soln, reclaim water layer, with the sodium bicarbonate neutralization, add ethyl acetate to be extracted, water, saturated aqueous common salt are cleaned, and with anhydrous magnesium sulfate, are dried.After removing by filter anhydrous magnesium sulfate, except desolventizing, column chromatography for residue (the mixed solvent 1:1 volume ratio of ethyl acetate and ethylene dichloride) is carried out to purifying with rotatory evaporator, obtain yellow solid 2.20g (yield: 58%).
(the 4th operation) 1-(4-aminophenyl)-6-is amino-1,2,3,4-tetrahydroquinoline [diamines-4 (Diamine-4)] synthetic
[changing 37]
Figure BDA00003096242600362
Take 10.0 (37.1 mmoles) by the 1-(4-nitrophenyl) of the 3rd operation gained-6-amino-1 in the four-hole boiling flask of 500mL, 2,3,4-tetrahydroquinoline and 1.00g10 quality % palladium carbon, add 300mL ethanol, after fully carrying out the nitrogen displacement, be replaced as hydrogen atmosphere, at room temperature carry out vigorous stirring.
After reaction finishes, with glass filter, filter palladium carbon, with rotatory evaporator, filtrate is carried out to removing of solvent.The residue of gained is dissolved in to acetone, add gac and stir a moment, the filter activity charcoal, after removing acetone with rotatory evaporator, carry out recrystallization with the mixing solutions (5:1 mass ratio) of normal hexane and ethyl acetate, obtain the solid 7.30g (yield: 82%) as the lilac of targeted diamine (Diamine-4).Its structure is used 1the H-NMR spectrum is confirmed.Determination data is as follows.
1h NMR (400MHz, [D 6]-DMSO) δ: 6.85-6.35 (aromatics H, 7H), 5.00-4.98 (s-br, 2H), 4.59-4.58 (s-br, 2H), 3,94-3,93 (m, 2H), 2.89-2.87 (m, 2H), 2.66-2.64 (m, 2H)
Synthesizing of (synthetic comparative example 1) 1-(4-aminophenyl)-5-amino indole [diamines-5 (Diamine-5)]
[changing 38]
Figure BDA00003096242600371
Synthesizing of (the first operation) 1-(4-nitrophenyl)-5-nitroindoline
[changing 39]
Figure BDA00003096242600372
Add 4.48g (101.8 mmole) sodium hydride (purity 55%), the 50mL DMF that dewaters in two mouthfuls of flasks of 500mL, while stir to be no more than the DMF solution (5-nitroindoline: 15.0g (92.5 mmole), DMF:100mL) that the condition of 30 ℃ drips the 5-nitroindoline under nitrogen atmosphere.After dripping end, at room temperature stir 2 hours.Drip the DMF solution (4-fluoronitrobenzene: 13.1g (92.5 mmole), DMF:100mL) of 4-fluoronitrobenzene in this reaction soln, under nitrogen atmosphere, in stirring at room 6 hours.
After reaction finishes, on one side stirring reaction solution inject at leisure the 100mL pure water on one side, solid is separated out, filter the solid of separating out, it is dissolved in to DMF again, inject the 500mL pure water and make its redeposition, again the filtered and recycled solid.Methyl alcohol, normal hexane for solid to gained disperse to clean, and make its vacuum-drying, thereby obtain yellow solid 25.0g (yield 95%).
Synthesizing of (the second operation) 1-(4-aminophenyl)-5-amino indole [diamines-5 (Diamine-5)]
[changing 40]
Figure BDA00003096242600381
Take 20.0g (70.6 mmole) by the 1-(4-nitrophenyl) of the first operation gained-5-nitroindoline and 2.00g10 quality % palladium carbon in the four-hole boiling flask of 500mL, add 300mL ethanol, after fully carrying out the nitrogen displacement, be replaced as hydrogen atmosphere, reflux 42 hours.
After reaction finishes, with glass filter, filter palladium carbon, with rotatory evaporator, filtrate is carried out to removing of solvent.The residue of gained is dissolved in to acetone, add gac and stir a moment, the filter activity charcoal, after removing acetone with rotatory evaporator, clean residue with normal hexane, thereby obtain the solid 15.0g (yield: 95%) as the lightpink of targeted diamine (Diamine-5).Its structure is used 1the H-NMR spectrum is confirmed.Determination data is as follows.
1h NMR (400MHz, [D 6]-DMSO) δ: 7.25-6.28 (aromatics H, 9H), 5.20 (s-br, 2H), 4.56 (s-br, 2H)
[preparation of the synthetic and liquid crystal aligning agent of polyamic acid and polyimide]
The abbreviation of the compound of following use is as follows.In addition, the composition of the raw material of polymkeric substance synthetic in each embodiment and comparative example and liquid crystal aligning agent is shown in to table 1 and table 2.
<tetracarboxylic dianhydride >
CBDA:1,2,3,4-tetramethylene tetracarboxylic dianhydride
TDA:3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride
CBDE:1,2,3,4-tetramethylene tetracarboxylic acid dimethyl ester
[changing 41]
<diamines >
P-PDA:1, the 4-phenylenediamine
DDM:4, the 4-diaminodiphenyl-methane
C16DAB:4-n-Hexadecane Oxy-1, the 3-diaminobenzene
[changing 42]
Figure BDA00003096242600391
<condensing agent >
DMT-MM:4-(4,6-dimethoxy-1,3,5-triazines-2-yl) 4-methoxyl group morpholine hydrochloride n hydrate
<organic solvent >
The NMP:N-N-methyl-2-2-pyrrolidone N-
γ-BL: gamma-butyrolactone
BC: ethylene glycol butyl ether
DPM: DPGME
The mensuration of<molecular weight >
The molecular weight of the polymkeric substance obtained by polyreaction is measured as follows: measure this polymkeric substance by GPC (normal temperature gel permeation chromatography) device, as polyoxyethylene glycol, polyethylene oxide scaled value, calculate number-average molecular weight and weight-average molecular weight.
GPC device: Shodex company (Showa Denko K. K) system (GPC-101)
Post: Showa Denko K. K's system (series connection of KD803, KD805)
Column temperature: 50 ℃
Elutriant: DMF (as additive, lithiumbromide-hydrate (LiBrH 2o) be that 30 mmoles/L, phosphoric anhydride crystallization (o-phosphoric acid) are that 30 mmoles/L, tetrahydrofuran (THF) (THF) are 10ml/L)
Flow velocity: 1.0ml/ minute
Calibration curve is made and to be used standard test specimen: (East ソ ー society of eastern Cao company) TSK standard polyethylene oxide processed (molecular weight is about 900000,150000,100000,30000) and polymkeric substance laboratory company (Port リ マ ー ラ ボ ラ ト リ ー society) polyoxyethylene glycol processed (molecular weight is about 12000,4000,1000).
The mensuration of<imide rate >
The imide rate of polyimide is measured as follows.The polyimide powder of 20mg is joined to NMR stopple coupon (specification of wasteland's science Co., Ltd. (wasteland's science society) NMR stopple coupon processed), add the deuterate methyl-sulphoxide (DMSO-d6,0.05%TMS mixture) of 0.53ml, by ultrasonic wave, it is dissolved fully.For this solution, measured the proton N MR of 500MHz with the NMR determinator (JNW-ECA500) of NEC Dan Ding Co., Ltd. (Japanese Electricity デ ー タ system society) system.The imide rate is tried to achieve as follows: will come from the proton of unconverted structure before and after imidization and be decided to be the standard proton, and use the peak integrated value of this proton and the proton peak integrated value of the base of the NH from amido acid that occurs is tried to achieve by following formula near 9.5～10.0ppm.In above-mentioned formula, x is the integrated value of proton peak that comes from the NH base of amido acid, and y is the integrated value of standard proton peak, and α is with respect to the number ratio of the standard proton of 1 NH matrix of amido acid during for polyamic acid (the imide rate is 0%).
Imide rate (%)=(1-α x/y) * 100
Synthesizing of the polyamic acid of (embodiment 1) employing CBDA/Diamine-1
In the four-hole boiling flask of 50mL, add 1.50g (6.65 mmole) conduct two amine components by the Diamine-1 of synthetic example 1 gained, the NMP of 15.3g, be cooled to approximately 10 ℃, the CBDA that adds 1.22g (6.20 mmole), return to room temperature, under nitrogen atmosphere, reaction is 6 hours, the solution that the concentration that obtains polyamic acid (PAA-1) is 15 quality %.
Polyamic acid (PAA-1) solution 15.0g is transferred in the Erlenmeyer flask of 50mL, add the NMP of 15.0g, the BC of 7.50g to be diluted, making polyamic acid (PAA-1) is that 6 quality %, NMP are the solution that 74 quality %, BC are 20 quality %, obtains liquid crystal aligning agent of the present invention-1.The number-average molecular weight of this polyamic acid is 12300, and weight-average molecular weight is 33100.
Synthesizing of the polyamic acid of (embodiment 2) employing CBDA/Diamine-2
In the four-hole boiling flask of 50mL, add 1.50g (6.25 mmole) conduct two amine components by the Diamine-2 of synthetic example 2 gained, the NMP of 15.0g, be cooled to approximately 10 ℃, the CBDA that adds 1.14g (5.80 mmole), return to room temperature, under nitrogen atmosphere, reaction is 6 hours, the solution that the concentration that obtains polyamic acid (PAA-2) is 15 quality %.
Polyamic acid (PAA-2) solution 15.0g is transferred in the Erlenmeyer flask of 50mL, add the NMP of 15.0g, the BC of 7.50g to be diluted, making polyamic acid (PAA-2) is that 6 quality %, NMP are the solution that 74 quality %, BC are 20 quality %, obtains liquid crystal aligning agent of the present invention-2.The number-average molecular weight of this polyamic acid is 13700, and weight-average molecular weight is 35600.
Synthesizing of the polyamic acid of (embodiment 3) employing CBDA/Diamine-3
In the four-hole boiling flask of 50mL, add 1.50g (5.80 mmole) conduct two amine components by the Diamine-3 of synthetic example 3 gained, the NMP of 14.3g, be cooled to approximately 10 ℃, the CBDA that adds 1.02g (5.20 mmole), return to room temperature, under nitrogen atmosphere, reaction is 6 hours, the solution that the concentration that obtains polyamic acid (PAA-3) is 15 quality %.
Polyamic acid (PAA-3) solution 15.0g is transferred in the Erlenmeyer flask of 50mL, add the NMP of 15.0g, the BC of 7.50g to be diluted, making polyamic acid (PAA-3) is that 6 quality %, NMP are the solution that 74 quality %, BC are 20 quality %, obtains liquid crystal aligning agent of the present invention-3.The number-average molecular weight of this polyamic acid is 11000, and weight-average molecular weight is 31300.
Synthesizing of the polyamic acid of (embodiment 4) employing CBDA/Diamine-4
In the four-hole boiling flask of 50mL, add 1.50g (6.25 mmole) conduct two amine components by the Diamine-4 of synthetic example 4 gained, the NMP of 15.0g, be cooled to approximately 10 ℃, the CBDA that adds 1.14g (5.80 mmole), return to room temperature, under nitrogen atmosphere, reaction is 6 hours, the solution that the concentration that obtains polyamic acid (PAA-4) is 15 quality %.
Polyamic acid (PAA-4) solution 15.0g is transferred in the Erlenmeyer flask of 50mL, add the NMP of 15.0g, the BC of 7.50g to be diluted, making polyamic acid (PAA-4) is that 6 quality %, NMP are the solution that 74 quality %, BC are 20 quality %, obtains liquid crystal aligning agent of the present invention-4.The number-average molecular weight of this polyamic acid is 14200, and weight-average molecular weight is 36700.
Synthesizing of the polyamic acid of (comparative example 1) employing CBDA/Diamine-5
Diamine-5, the NMP of 15.4g by synthetic comparative example 1 gained that add conduct two amine components of 1.50g (6.75 mmole) in the four-hole boiling flask of 50mL, be cooled to approximately 10 ℃, the CBDA that adds 1.23g (6.25 mmole), return to room temperature, under nitrogen atmosphere, reaction is 6 hours, the solution that the concentration that obtains polyamic acid (PAA-5) is 15 quality %.
The solution 15.0g of this polyamic acid (PAA-5) is transferred in the Erlenmeyer flask of 50mL, add the NMP of 15.0g, the BC of 7.50g to be diluted, making polyamic acid (PAA-5) is that 6 quality %, NMP are the solution that 74 quality %, BC are 20 quality %, obtains the liquid crystal aligning agent of object-5 as a comparison.The number-average molecular weight of this polyamic acid is 12300, and weight-average molecular weight is 32100.
Synthesizing of the soluble polyimide of (embodiment 5) employing CBDA/Diamine-1, C16DAB
C16DAB, the NMP of 27.2g of the Diamine-1 by synthetic example 1 gained, 0.774g (2.22 mmole) that adds conduct two amine components of 2.00g (8.88 mmole) in the four-hole boiling flask of 50mL, be cooled to approximately 10 ℃, the CBDA that adds 1.81g (10.3 mmole), return to room temperature, under nitrogen atmosphere, reaction is 6 hours, the solution that the concentration that obtains polyamic acid (PAA-6) is 15 quality %.
In the solution 20g of polyamic acid (PAA-6), add the NMP of 30.0g to be diluted, then add 2.19g diacetyl oxide and 0.90g pyridine, under 40 ℃, reaction is 3 hours.After this reaction soln is cooled to about room temperature, while stir, slowly pour in the methyl alcohol 180mL that is cooled to approximately 10 ℃, solid is separated out.Reclaim the solid of precipitation, then the dispersion cleaning that amounts to 2 times with methyl alcohol 100mL, carry out drying under reduced pressure under 100 ℃, thereby obtain the lilac powder of polyimide (SPI-1).The number-average molecular weight of this polyimide is 9200, and weight-average molecular weight is 23500.In addition, the imide rate is 81%.
γ-the BL that adds 18.0g in the polyimide (SPI-1) of 2.00g, stir 20 hours in 50 ℃.Stirring polyimide while finishing dissolves fully.Add γ-BL of 8.0g, the BC of 12.0g again in this solution, in 50 ℃ of stirrings 20 hours, obtaining polyimide (SPI-1) was that 5 quality %, γ-BL are the liquid crystal aligning agent-6 that 65 quality %, BC are 30 quality %.
Synthesizing of the soluble polyimide of (embodiment 6) employing CBDA/Diamine-2, C16DAB
C16DAB, the NMP of 6.3g of the Diamine-2 by synthetic example 2 gained, 0.728g (2.09 mmole) that adds conduct two amine components of 2.00g (8.36 mmole) in the four-hole boiling flask of 50mL, be cooled to approximately 10 ℃, the CBDA that adds 1.90g (9.71 mmole), return to room temperature, under nitrogen atmosphere, reaction is 6 hours, the solution that the concentration that obtains polyamic acid (PAA-7) is 15 quality %.
In the solution 20g of polyamic acid (PAA-7), add the NMP of 30.0g to be diluted, then add 2.12g diacetyl oxide and 0.88g pyridine, under 40 ℃, reaction is 3 hours.After this reaction soln is cooled to about room temperature, while stir, slowly pour in the methyl alcohol 160mL that is cooled to approximately 10 ℃, solid is separated out.Reclaim the solid of precipitation, then the dispersion cleaning that amounts to 2 times with methyl alcohol 100mL, carry out drying under reduced pressure under 100 ℃, thereby obtain the lilac powder of polyimide (SPI-2).The number-average molecular weight of this polyimide is 9800, and weight-average molecular weight is 24200.In addition, the imide rate is 80%.
γ-the BL that adds 18.0g in the polyimide (SPI-2) of 2.00g, stir 20 hours in 50 ℃.Stirring polyimide while finishing dissolves fully.Add γ-BL of 8.0g, the BC of 12.0g again in this solution, in 50 ℃ of stirrings 20 hours, obtaining polyimide (SPI-2) was that 5 quality %, γ-BL are the liquid crystal aligning agent-7 that 65 quality %, BC are 30 quality %.
Synthesizing of the soluble polyimide of (embodiment 7) employing CBDA/Diamine-3, C16DAB
C16DAB, the NMP of 24.7g of the Diamine-3 by synthetic example 3 gained, 0.651g (1.87 mmole) that adds conduct two amine components of 2.00g (7.47 mmole) in the four-hole boiling flask of 50mL, be cooled to approximately 10 ℃, the CBDA that adds 1.51g (8.68 mmole), return to room temperature, under nitrogen atmosphere, reaction is 6 hours, the solution that the concentration that obtains polyamic acid (PAA-8) is 15 quality %.
In the solution 20g of polyamic acid (PAA-8), add the NMP of 30.0g to be diluted, then add 2.00g diacetyl oxide and 0.83g pyridine, under 40 ℃, reaction is 3 hours.After this reaction soln is cooled to about room temperature, while stir, slowly pour in the methyl alcohol 160mL that is cooled to approximately 10 ℃, solid is separated out.Reclaim the solid of precipitation, then the dispersion cleaning that amounts to 2 times with methyl alcohol 100mL, carry out drying under reduced pressure under 100 ℃, thereby obtain the lilac powder of polyimide (SPI-3).The number-average molecular weight of this polyimide is 9500, and weight-average molecular weight is 22200.In addition, the imide rate is 81%.
γ-the BL that adds 18.0g in the polyimide (SPI-3) of 2.00g, stir 20 hours in 50 ℃.Stirring polyimide while finishing dissolves fully.Add γ-BL of 8.0g, the BC of 12.0g again in this solution, in 50 ℃ of stirrings 20 hours, obtaining polyimide (SPI-3) was that 5 quality %, γ-BL are the liquid crystal aligning agent-8 that 65 quality %, BC are 30 quality %.
Synthesizing of the soluble polyimide of (embodiment 8) employing CBDA/Diamine-4, C16DAB
C16DAB, the NMP of 6.3g of the Diamine-4 by synthetic example 4 gained, 0.728g (2.09 mmole) that adds conduct two amine components of 2.00g (8.36 mmole) in the four-hole boiling flask of 50mL, be cooled to approximately 10 ℃, the CBDA that adds 1.90g (9.71 mmole), return to room temperature, under nitrogen atmosphere, reaction is 6 hours, the solution that the concentration that obtains polyamic acid (PAA-8) is 15 quality %.
In the solution 20g of polyamic acid (PAA-8), add the NMP of 30.0g to be diluted, then add 2.12g diacetyl oxide and 0.88g pyridine, under 40 ℃, reaction is 3 hours.After this reaction soln is cooled to about room temperature, while stir, slowly pour in the methyl alcohol 180mL that is cooled to approximately 10 ℃, solid is separated out.Reclaim the solid of precipitation, then the dispersion cleaning that amounts to 2 times with methyl alcohol 100mL, carry out drying under reduced pressure under 100 ℃, thereby obtain the lilac powder of polyimide (SPI-4).The number-average molecular weight of this polyimide is 10200, and weight-average molecular weight is 28900.In addition, the imide rate is 82%.
γ-the BL that adds 18.0g in the polyimide (SPI-4) of 2.00g, stir 20 hours in 50 ℃.Stirring polyimide while finishing dissolves fully.Add γ-BL of 8.0g, the BC of 12.0g again in this solution, in 50 ℃ of stirrings 20 hours, obtaining polyimide (SPI-4) was that 5 quality %, γ-BL are the liquid crystal aligning agent-9 that 65 quality %, BC are 30 quality %.
Synthesizing of the soluble polyimide of (comparative example 2) employing CBDA/Diamine-5, C16DAB
C16DAB, the NMP of 27.3g by Diamine-5, the 0.781g (2.24 mmole) that synthesize comparative example 1 gained that add conduct two amine components of 2.00g (8.96 mmole) in the four-hole boiling flask of 50mL, be cooled to approximately 10 ℃, the CBDA that adds 2.04g (10.4 mmole), return to room temperature, under nitrogen atmosphere, reaction is 6 hours, the solution that the concentration that obtains polyamic acid (PAA-9) is 15 quality %.
In the solution 20g of polyamic acid (PAA-9), add the NMP of 30.0g to be diluted, then add 2.20g diacetyl oxide and 0.91g pyridine, reacted under 40 ℃, but after after a while, start gelation and can't stir.Fail to prepare soluble polyimide (SPI-5).Therefore, can't prepare the liquid crystal aligning agent of object-10 as a comparison.
(embodiment 9)
Synthesizing of the polyamic acid of<employing CBDA/Diamine-1, DDM >
In the four-hole boiling flask of 50mL, add 2.50g (11.1 mmole) conduct two amine components the Diamine-1 by synthetic example 1 gained, 0.943g (4.77 mmole) DDM, 17.9g NMP, 17.9g γ-BL, be cooled to approximately 10 ℃, the CBDA that adds 2.89g (14.8 mmole), return to room temperature, under nitrogen atmosphere, reaction is 6 hours, the solution that the concentration that obtains polyamic acid (PAA-10) is 15 quality %.
This polyamic acid (PAA-10) solution 30.0g is transferred in the Erlenmeyer flask of 100mL, add γ-BL of NMP, the 2.20g of 28.0g, the BC of 15.0g to be diluted, making polyamic acid (PAA-10) is that 6 quality %, NMP are that 54 quality %, γ-BL are the solution that 20 quality %, BC are 20 quality %, obtains polyamic acid solution for fusion (BL-PAA1).The number-average molecular weight of this polyamic acid is 10400, and weight-average molecular weight is 29100.
Synthesizing of the soluble polyimide of<employing TDA/p-PDA, C16DAB >
C16DAB, the NMP of 35.4g of p-PDA, 0.718g (2.06 mmole) that adds conduct two amine components of 2.00g (18.5 mmole) in the four-hole boiling flask of 50mL, be cooled to approximately 10 ℃, the TDA that adds 6.12g (20.4 mmole), under nitrogen atmosphere, in 40 ℃ of reactions 20 hours, the solution that the concentration that obtains polyamic acid (PAA-15) is 20 quality %.
In the solution 40.0g of polyamic acid (PAA-15), add the NMP of 93.3g to be diluted, then add the diacetyl oxide of 9.51g and the pyridine of 7.36g, under 40 ℃, reaction is 3 hours.After this reaction soln is cooled to about room temperature, while stir, slowly pour in the methyl alcohol 500mL that is cooled to approximately 10 ℃, solid is separated out.Reclaim the solid of precipitation, then the dispersion cleaning that amounts to 2 times with methyl alcohol 300mL, carry out drying under reduced pressure under 100 ℃, thereby obtain the white powder of polyimide (SPI-6).The number-average molecular weight of this polyimide is 9500, and weight-average molecular weight is 20900.In addition, the imide rate is 85%.
γ-the BL that adds 80.5g in the polyimide (SPI-6) of 7.00g, stir 20 hours in 50 ℃.Stirring polyimide while finishing dissolves fully.Again to the γ-BL that adds 29.2g in this solution, stir 20 hours in 50 ℃, making polyimide (SPI-6) is the solution that 6 quality %, γ-BL are 94 quality %, obtains polyimide solution for fusion (BL-SPI).
The preparation of<fusion class liquid crystal aligning agent >
Take the polyamic acid solution for fusion (BL-PAA1) made of 40g in the Erlenmeyer flask of 200mL, the polyimide solution for fusion (BL-SPI) made that adds again 10.0g, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-1.
(embodiment 10)
Synthesizing of the polyamic acid of<employing CBDA/Diamine-2, DDM >
In the four-hole boiling flask of 50mL, add 2.50g (10.4 mmole) conduct two amine components the Diamine-2 by synthetic example 2 gained, 0.887g (4.47 mmole) DDM, 17.3g NMP, 17.3g γ-BL, be cooled to approximately 10 ℃, the CBDA that adds 2.72g (13.9 mmole), return to room temperature, under nitrogen atmosphere, reaction is 6 hours, the solution that the concentration that obtains polyamic acid (PAA-11) is 15 quality %.
This polyamic acid (PAA-11) solution 30.0g is transferred in the Erlenmeyer flask of 100mL, add γ-BL of NMP, the 2.20g of 28.0g, the BC of 15.0g to be diluted, making polyamic acid (PAA-11) is that 6 quality %, NMP are that 54 quality %, γ-BL are the solution that 20 quality %, BC are 20 quality %, obtains polyamic acid solution for fusion (BL-PAA2).The number-average molecular weight of this polyamic acid is 11200, and weight-average molecular weight is 31000.
The preparation of<fusion class liquid crystal aligning agent >
Take respectively the polyamic acid solution for fusion (BL-PAA2) made of 40g in the Erlenmeyer flask of 200mL, add again polyimide solution for fusion (BL-SPI) 10.0g made with method similarly to Example 9, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-2.
(embodiment 11)
Synthesizing of the polyamic acid of<employing CBDA/Diamine-3, DDM >
In the four-hole boiling flask of 50mL, add 2.50g (9.35 mmole) conduct two amine components the Diamine-3 by synthetic example 3 gained, 0.794g (4.01 mmole) DDM, 16.2g NMP, 16.2g γ-BL, be cooled to approximately 10 ℃, the CBDA that adds 2.43g (12.4 mmole), return to room temperature, under nitrogen atmosphere, reaction is 6 hours, the solution that the concentration that obtains polyamic acid (PAA-12) is 15 quality %.
This polyamic acid (PAA-12) solution 30.0g is transferred in the Erlenmeyer flask of 100mL, add γ-BL of NMP, the 2.20g of 28.0g, the BC of 15.0g to be diluted, making polyamic acid (PAA-12) is that 6 quality %, NMP are that 54 quality %, γ-BL are the solution that 20 quality %, BC are 20 quality %, obtains polyamic acid solution for fusion (BL-PAA3).The number-average molecular weight of this polyamic acid is 13600, and weight-average molecular weight is 36000.
The preparation of<fusion class liquid crystal aligning agent >
Take respectively the polyamic acid solution for fusion (BL-PAA3) made of 40g in the Erlenmeyer flask of 200mL, add again polyimide solution for fusion (BL-SPI) 10.0g made with method similarly to Example 9, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-3.
(embodiment 12)
Synthesizing of the polyamic acid of<employing CBDA/Diamine-4, DDM >
In the four-hole boiling flask of 50mL, add 2.50g (10.4 mmole) conduct two amine components the Diamine-4 by synthetic example 4 gained, 0.887g (4.47 mmole) DDM, 17.3g NMP, 17.3g γ-BL, be cooled to approximately 10 ℃, the CBDA that adds 2.72g (13.9 mmole), return to room temperature, under nitrogen atmosphere, reaction is 6 hours, the solution that the concentration that obtains polyamic acid (PAA-13) is 15 quality %.
This polyamic acid (PAA-13) solution 30.0g is transferred in the Erlenmeyer flask of 100mL, add γ-BL of NMP, the 2.20g of 28.0g, the BC of 15.0g to be diluted, making polyamic acid (PAA-13) is that 6 quality %, NMP are that 54 quality %, γ-BL are the solution that 20 quality %, BC are 20 quality %, obtains polyamic acid solution for fusion (BL-PAA4).The number-average molecular weight of this polyamic acid is 12500, and weight-average molecular weight is 30800.
The preparation of<fusion class liquid crystal aligning agent >
Take respectively the polyamic acid solution for fusion (BL-PAA4) made of 40g in the Erlenmeyer flask of 200mL, add again polyimide solution for fusion (BL-SPI) 10.0g made with method similarly to Example 9, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-4.
(comparative example 3)
Synthesizing of the polyamic acid of<employing CBDA/Diamine-5, DDM >
In the four-hole boiling flask of 50mL, add 2.50g (11.2 mmole) conduct two amine components Diamine-5,0.952g (4.80 mmole) by synthetic comparative example 1 gained DDM, 18.1g NMP, 18.1g γ-BL, be cooled to approximately 10 ℃, the CBDA that adds 2.92g (14.9 mmole), return to room temperature, under nitrogen atmosphere, reaction is 6 hours, the solution that the concentration that obtains polyamic acid (PAA-14) is 15 quality %.
This polyamic acid (PAA-14) solution 30.0g is transferred in the Erlenmeyer flask of 100mL, add γ-BL of NMP, the 2.20g of 28.0g, the BC of 15.0g to be diluted, making polyamic acid (PAA-14) is that 6 quality %, NMP are that 54 quality %, γ-BL are the solution that 20 quality %, BC are 20 quality %, obtains polyamic acid solution for fusion (BL-PAA5).The number-average molecular weight of this polyamic acid is 13600, and weight-average molecular weight is 37700.
The preparation of<fusion class liquid crystal aligning agent >
Take respectively the polyamic acid solution for fusion (BL-PAA4) made of 40g in the Erlenmeyer flask of 200mL, add again polyimide solution for fusion (BL-SPI) 10.0g made with method similarly to Example 9, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-5.
(embodiment 13)
<fusion PAE >
The triethylamine of NMP, 0.60g (5.90 mmole) of C16DAB, 71.5g of p-PDA, 0.896g (2.57 mmole) of conduct two amine components that adds CBDE, the 250g (23.1 mmole) of 6.35g (24.4 mmole) in the four-hole boiling flask of 100mL, be cooled to approximately 10 ℃, the DMT-MM that adds 21.3g (77.1 mmole), return to room temperature, under nitrogen atmosphere, reaction is 24 hours, the solution that the concentration that obtains poly amic acid ester (PAE-1) is 12 quality %.
Add the NMP of 81.2g in the solution of this polyamic acid (PAE-1), pour at leisure in the methyl alcohol 1.0L that is cooled to approximately 10 ℃ while stir, solid is separated out.Reclaim the solid of precipitation, then the dispersion cleaning that amounts to 2 times with methyl alcohol 500mL, carry out drying under reduced pressure under 100 ℃, thereby obtain the white powder of poly amic acid ester (PAE-1).The number-average molecular weight of this poly amic acid ester is 12300, and weight-average molecular weight is 27000.
γ-the BL that adds 80.5g in this poly amic acid ester (PAE-1) 7.00g, stir 20 hours in 50 ℃.Stirring polyimide while finishing dissolves fully.Again to the γ-BL that adds 29.2g in this solution, stir 20 hours in 50 ℃, making poly amic acid ester (PAE-1) is the solution that 6 quality %, γ-BL are 94 quality %, obtains polyamic acid ester solution (BL-PAE) for fusion.
The preparation of<fusion class liquid crystal aligning agent >
Take the polyamic acid solution for fusion (BL-PAA1) that the use method similarly to Example 9 of 40g makes in the Erlenmeyer flask of 200mL, the polyamic acid ester solution (BL-PAE) for the fusion made that adds again 10.0g, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-6.
(embodiment 14)
Take the polyamic acid solution for fusion (BL-PAA2) that the use method similarly to Example 10 of 40g makes in the Erlenmeyer flask of 200mL, the polyamic acid ester solution (BL-PAE) for fusion that adds again the use method similarly to Example 13 of 10.0g to make, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-7.
(embodiment 15)
Take the polyamic acid solution for fusion (BL-PAA3) that the use method similarly to Example 11 of 40g makes in the Erlenmeyer flask of 200mL, the polyamic acid ester solution (BL-PAE) for fusion that adds again the use method similarly to Example 13 of 10.0g to make, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-8.
(embodiment 16)
Take the polyamic acid solution for fusion (BL-PAA4) that the use method similarly to Example 12 of 40g makes in the Erlenmeyer flask of 200mL, the polyamic acid ester solution (BL-PAE) for fusion that adds again the use method similarly to Example 13 of 10.0g to make, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-9.
(comparative example 4)
Take the polyamic acid solution for fusion (BL-PAA5) of using the method same with comparative example 3 to make of 40g in the Erlenmeyer flask of 200mL, the polyamic acid ester solution (BL-PAE) for fusion that adds again the use method similarly to Example 13 of 10.0g to make, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-10 (comparative example).
The test of (test example 1) varnish (liquid crystal aligning agent) printing
Be coated on the Cr plate through cleaning with alignment films printing press (Nissha Printing Co., Ltd (Japan description printing society) system " オ Application グ ス ト ロ ー マ ー ") the liquid crystal aligning agent that utilizes the flexographic printing method to be made by embodiment 1～16 and comparative example 1～4, thereby carry out the coating test.At the upper liquid crystal aligning agent that drips about 1.0mL of anilox roller (Anilox roll), after implementing 10 idlings, printing press shuts down 10 minutes, makes the press plate drying.Then, on 1 Cr substrate, printed, the substrate after printing is placed on to upper 5 minute of hot-plate of 70 ℃, that is filmed is predrying, observes membrane stage.Observation is by visual and observed with 50 times with opticmicroscope (Nikon Corp. (ニ コ Application society) system " ECLIPSE ME600 ").Estimate as follows: the situation that will not observe pore is designated as well, the situation of observing pore is designated as bad, in addition, inhomogeneous situation is not occurred the thickness of edge part to and be designated as well, inhomogeneous situation is occurred the thickness of edge part to and be designated as bad.The results are shown in table 3.
[making of liquid crystal structure cell]
For the liquid crystal aligning agent made by embodiment 1～16 and comparative example 1～4, according to method as follows, make the liquid crystal structure cell.Liquid crystal aligning agent is spun on the glass substrate with transparency electrode, on the hot-plate of 80 ℃ after dry 70 seconds, carries out 10 minutes burn till on the hot-plate of 220 ℃, what to form thickness be 100nm films.For the liquid crystal aligning that utilizes friction to be orientated, process, take friction gear that the roller footpath is 120mm at the roller rotating speed as 1000rpm, roller gait of march as 50mm/ second, with artificial silk cloth, this coated surface is rubbed under the amount of the being pressed into condition that is 0.3mm, obtain the substrate with liquid crystal orientation film.
Prepare 2 and carried out the substrate with liquid crystal orientation film that this liquid crystal aligning is processed, scatter therein the spacer of 6 μ m on the liquid crystal aligning face of a slice, then printing and sealing agent thereon, fit another plate base so that the liquid crystal aligning face is relative and frictional direction quadrature (stable twisted nematic liquid crystal structure cell), then make sealant cures, make the negative crystal born of the same parents.In situation for stable twisted nematic liquid crystal structure cell, in this negative crystal born of the same parents, by the decompression injection method, inject liquid crystal MLC-2003 (Merck & Co., Inc. (メ Le Network society) system), the sealing inlet, obtain stable twisted nematic liquid crystal structure cell.
The mensuration of the ion density before and after (test example 2) high-temperature circulation test
The liquid crystal structure cell of making for method of record in [making of liquid crystal structure cell] of above-mentioned, measure the ion density of original state, in addition, is carried out at 100 ℃ of mensuration that keep the ion density after 30 hours (high temperature ageing).During ion density is measured, measured the ion density when liquid crystal structure cell is applied to the choppy sea of voltage ± 10V, frequency 0.01Hz.Measuring temperature, be to carry out under 80 ℃.Determinator is all used the (East Yang テ of Toyo Corp. Network ニ カ society) make 6245 type liquid crystal evaluation of physical property devices.The results are shown in table 3.
The electric charge (RDC) of accumulating before and after (test example 3) high-temperature circulation test is measured
At the temperature of 23 ℃, from the condition of OV to 1.0V, the liquid crystal structure cell made is applied to volts DS at the interval with 0.1V, measure the flicker amplitude level under each voltage, make the calibration curve of the volts DS that glimmers amplitude level and apply.After ground connection 5 minutes, the condition that reaches half with brightness applies voltage of alternating current (V 50) and volts DS 5.0V, measure the flicker amplitude level after 1 hour, estimate RDC (flicker reference entry) by contrasting ready-made calibration curve.Then, volts DS is made as to 0V, the RDC of estimation after 10 minutes that use the same method, thereby the decay of mensuration RDC.The RDC recorded thus is shown in the hurdle of " (accumulate) after DCon1 hour and RDC (decay) " after DCoff10 minute of table 3.In addition, the data of the RDC shown in table 3 are the results that the liquid crystal structure cell kept under 100 ℃ to the RDC after 30 hours (high temperature ageing).
The evaluation of (test example 4) orientation
The liquid crystal structure cell made by visual observation, the state of orientation of having observed liquid crystal.The situation of liquid crystal zero defect ground orientation is designated as well, the situation that defect occurs to be orientated is designated as bad, the results are shown in table 3.
Consequently, embodiment 1～4 and comparative example 1 are the evaluations of the homopolymer (polyamic acid) that adopted diamines and CBDA, but adopt the embodiment 1～4 of diamine compound of the present invention to compare with the comparative example 1 that does not use diamine compound of the present invention, the accumulating of RDC (the RDC value after DCon1 hour) and decay (the RDC value after DCoff10 minute) are significantly less.In addition, owing to being independent polyamic acid, therefore do not confirm large difference aspect printing, but embodiment 1～4 compares with comparative example 1, the ion density after original state and high temperature ageing is all little, is no problem in practical value.And, in embodiment 1～4, liquid crystal zero defect ground orientation, but the liquid crystal in comparative example 1 has produced defect, with embodiment 1～4, compares, and orientation is poor.
Embodiment 5～8 and comparative example 2 be adopt soluble polyimide and evaluation, adopt in the embodiment 5～8 of diamines of the present invention, can be made into soluble polyimide, being separated or separating out in the time of can not printing, also there is no the inhomogeneous of pore and film, printing is good.In addition, in embodiment 5～8, accumulating and decaying of RDC also significantly reduces.And the ion density after original state and high temperature ageing is all little, it is no problem in practical value.On the other hand, in the comparative example 2 in employing as the Diamine-5 of the diamines of patent documentation 3, can not make soluble polyimide.In addition, in embodiment 5～8, liquid crystal zero defect ground orientation.
The evaluation of the fusion class material of the polyamic acid that embodiment 9～12 and comparative example 3 are soluble polyimides with adopting diamines of the present invention, consistency excellence due to diamines of the present invention and soluble polyimide, being separated or separating out while therefore in the liquid crystal aligning agent of embodiment 9～12, printing not occurring, also there is no the inhomogeneous of pore and film, printing is good.On the other hand, in comparative example 3, local existenceization occurs and causes being separated in soluble polyimide and polyamic acid, and in this printing test, result is to separate, and the printing of edge part is poor.In addition, in embodiment 9～12, accumulating with decay of RDC compared also and significantly reduced with comparative example 3.And embodiment 9～12 compares with comparative example 3, the ion density after original state and high temperature ageing is all little, is no problem in practical value.In addition, in any of embodiment 9～12, liquid crystal is zero defect ground orientation all.
The evaluation of the fusion class material of the polyamic acid that embodiment 13～16 and comparative example 4 are poly amic acid esters with the diamines that adopts the present invention etc., consistency excellence due to diamines of the present invention and poly amic acid ester, being separated or separating out while therefore in the liquid crystal aligning agent of embodiment 13～16, printing not occurring, also there is no the inhomogeneous of pore and film, printing is good.On the other hand, the liquid crystal aligning agent of comparative example 4 and comparative example 3 are same, and result is that being separated property is poor, separative tendency during printing, and the printing of edge part is poor.In addition, in embodiment 13～16, accumulating with decay of RDC compared also and significantly reduced with comparative example 4.And embodiment 13～16 compares with comparative example 4, the ion density after original state and high temperature ageing is all little, is no problem in practical value.In addition, in any of embodiment 13～16, liquid crystal is zero defect ground orientation all.
According to these results, for adopting diamines of the present invention liquid crystal aligning agent and liquid crystal orientation film, can confirm that printing is good and can obtain that to accumulate electric charge few and accumulate the fast liquid crystal orientation film of decay of electric charge.
[table 1]
Mean mol ratio in the ※ bracket.
[table 2]
Figure BDA00003096242600531
Mean mol ratio in the ※ bracket.
[table 3]
Figure BDA00003096242600541
The possibility of utilizing on industry
Adopt diamines of the present invention and the printing of liquid crystal aligning agent good and can obtain that to accumulate electric charge few and accumulate the fast liquid crystal orientation film of decay of electric charge.Therefore, use the liquid crystal display device that liquid crystal aligning agent of the present invention makes can be used as the liquid crystal display device that reliability is high, be suitable for various types of display elements such as TN (twisted nematic) liquid crystal display device, stn liquid crystal display element, TFT liquid crystal display device, VA liquid crystal display device, IPS liquid crystal display device, OCB (optics self compensation double refraction) liquid crystal display device.

Claims (13)

1. the diamines meaned with following formula [1],
[changing 1]
Figure FDA00003096242500011
In formula [1], R 1～R 9in two be primary amino, all the other be hydrogen atom or amino beyond any monovalent organic radical group, they each other can be identical or different; N is 1 or 2, and the hydrogen atom that forms ring filling hydrocarbon section can be replaced by any monovalent organic radical group beyond halogen atom or amino.
2. diamines as claimed in claim 1, is characterized in that, with following formula [2], mean,
[changing 2]
Figure FDA00003096242500012
In formula [2], p means 0～3 integer, R 10mean amino any monovalent organic radical group in addition ,-(R 10) pmean p substituent R 10, they each other can be identical or different; Q means 0～4 integer, R 11mean amino any monovalent organic radical group in addition ,-(R 11) qmean q substituent R 11, they each other can be identical or different; N is 1 or 2, and the hydrogen atom that forms ring filling hydrocarbon section can be replaced by the organic group beyond halogen atom or amino.
3. diamines as claimed in claim 2, is characterized in that, with following formula [3], mean,
[changing 3]
Figure FDA00003096242500021
In formula [3], n be 1 or 2, m be the integer of 0～2 (n+1), R 12mean fluorine atom or amino 1 valency organic group in addition ,-(R 12) mmean m substituent R 12, they each other can be identical or different.
4. diamines as claimed in claim 3, is characterized in that, described R 12it is the alkyl of carbon number 1～6.
5. diamines as claimed in claim 4, is characterized in that, R 12it is methyl.
6. diamines as described as any one in claim 1～5, is characterized in that n=1.
7. diamines as claimed in claim 1, is characterized in that, with following formula [4-a]～[4-d], mean,
[changing 4]
Figure FDA00003096242500022
8. a polyimide precursor, is characterized in that, by make to be selected from tetracarboxylic acid and derivative thereof at least one with comprise claim 1～7 in two amine components of the described diamines of any one react and obtain.
9. polyimide precursor as claimed in claim 8, is characterized in that, when the integral molar quantity of tetracarboxylic acid and derivative thereof is counted to 100 % by mole, in claim 1～7, the described diamines of any one is 5～95 % by mole.
10. a polyimide, is characterized in that, by the described polyimide precursor of claim 8 or 9 is carried out to imidization, obtains.
11. a liquid crystal aligning agent, is characterized in that, contains and be selected from polyimide precursor claimed in claim 8, polyimide precursor claimed in claim 9, and at least one of polyimide claimed in claim 10.
12. a liquid crystal orientation film, is characterized in that, obtains by the described liquid crystal aligning agent of claim 11 is coated to substrate and burnt till.
13. a liquid crystal display device, is characterized in that, has the described liquid crystal orientation film of claim 12.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105446012A (en) * 2014-09-19 2016-03-30 株式会社日本显示器 Liquid crystal display device and material for alignment film
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CN111732528A (en) * 2020-07-31 2020-10-02 南昌大学 A kind ofNProcess for preparing (E) -arylindoline derivatives
CN111732516A (en) * 2020-07-31 2020-10-02 南昌大学 A kind ofNProcess for preparing (E) -aryl-substituted heterocyclic compounds
CN111936923A (en) * 2018-03-30 2020-11-13 日产化学株式会社 Novel liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102058764B1 (en) * 2012-03-30 2019-12-23 닛산 가가쿠 가부시키가이샤 Polyimide-based liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
JP6146077B2 (en) * 2012-06-29 2017-06-14 Jsr株式会社 Method for producing liquid crystal alignment film
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10310574A (en) * 1997-05-09 1998-11-24 Minolta Co Ltd Novel amino compound, its production and use
CN101137345A (en) * 2005-03-11 2008-03-05 宝洁公司 Hair coloring compositions for use in oxidative hair dyeing
CN101490188A (en) * 2006-07-18 2009-07-22 日产化学工业株式会社 Liquid crystal orienting agent and liquid crystal oriented film and liquid crystal display element using the same
CN101636468A (en) * 2007-02-06 2010-01-27 住友化学株式会社 Contain the composition of benzazolyl compounds and use said composition and the luminous element that obtains

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06337424A (en) * 1993-05-28 1994-12-06 Hitachi Chem Co Ltd Composition for liquid crystal oriented film, manufacture of liquid crystal oriented film, liquid crystal oriented film, liquid crystal sandwiching substrate and liquid crystal display element
US7524541B2 (en) * 2002-08-29 2009-04-28 Nissan Chemical Industries, Ltd. Material for liquid crystal aligning and liquid crystal displays made by using the same
WO2005105892A1 (en) * 2004-04-28 2005-11-10 Nissan Chemical Industries, Ltd. Liquid-crystal aligning agent, liquid-crystal alignment film comprising the same, and liquid-crystal element
JP5359643B2 (en) * 2008-08-20 2013-12-04 Ｊｎｃ株式会社 Diamine, liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10310574A (en) * 1997-05-09 1998-11-24 Minolta Co Ltd Novel amino compound, its production and use
CN101137345A (en) * 2005-03-11 2008-03-05 宝洁公司 Hair coloring compositions for use in oxidative hair dyeing
CN101490188A (en) * 2006-07-18 2009-07-22 日产化学工业株式会社 Liquid crystal orienting agent and liquid crystal oriented film and liquid crystal display element using the same
CN101636468A (en) * 2007-02-06 2010-01-27 住友化学株式会社 Contain the composition of benzazolyl compounds and use said composition and the luminous element that obtains

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN107077032B (en) * 2014-10-20 2021-04-16 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same
CN110300921A (en) * 2016-12-15 2019-10-01 日产化学株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal expression element using it
CN110300921B (en) * 2016-12-15 2022-08-09 日产化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same
CN111936923A (en) * 2018-03-30 2020-11-13 日产化学株式会社 Novel liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
CN111936923B (en) * 2018-03-30 2023-12-22 日产化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
CN111732528A (en) * 2020-07-31 2020-10-02 南昌大学 A kind ofNProcess for preparing (E) -arylindoline derivatives
CN111732516A (en) * 2020-07-31 2020-10-02 南昌大学 A kind ofNProcess for preparing (E) -aryl-substituted heterocyclic compounds
CN111732528B (en) * 2020-07-31 2021-01-01 南昌大学 Preparation method of N-aryl indoline derivative

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