CN103180294B - Diamines, polyimide precursor, polyimide, liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device - Google Patents

Diamines, polyimide precursor, polyimide, liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device Download PDF

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CN103180294B
CN103180294B CN201180051325.7A CN201180051325A CN103180294B CN 103180294 B CN103180294 B CN 103180294B CN 201180051325 A CN201180051325 A CN 201180051325A CN 103180294 B CN103180294 B CN 103180294B
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liquid crystal
acid
polyimide
diamines
polyamic acid
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CN103180294A (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

Abstract

The invention provides the diamines represented with following formula [1].[changing 1] (in formula [1], R 1~ R 9in two be primary amino, all the other are the monovalent organic group beyond hydrogen atom or amino, and they each other can be identical or different; N is 1 or 2, and the hydrogen atom forming ring filling hydrocarbon portion can be replaced by the monovalent organic group beyond halogen atom or 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 carries the effect making liquid crystal orientation on certain direction.Now, the main liquid crystal orientation film of industrial use substrate carries out film forming by being coated on by the liquid crystal aligning agent of the polyimide formed as the polyamic acid of polyimide precursor, poly amic acid ester or the solution by polyimide and obtaining.In addition, make mesomorphic phase for real estate during parallel-oriented or tilted alignment, after film forming, carry out further adopting the surface of friction prolonged treatment.In addition, also have and propose to utilize the method for the anisotropy photochemical reaction of employing polarisation uviolizing etc. to be used as substituting of friction treatment, carried out in recent years towards industrialized research.
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 the improvement of liquid crystal aligning and electrical characteristic etc. and the control etc. of tilt angle.Such as, in order to obtain high voltage holding ratio, propose various technology: use the polyimide resin (with reference to patent documentation 1) with specific repeating structure; By using the soluble polyimide except imide with nitrogen-atoms, shorten the time (with reference to patent documentation 2) till after image cancellation; In addition, by importing 1-Phenylindole structure in the diamines of the raw material as polyamic acid, residual DC (with reference to patent documentation 3) etc. can be reduced while maintenance high voltage holding ratio.
But, along with the development of the power saving etc. of the high performance of liquid crystal display device, big area, display unit, and wish can use under various environment, the requirement of liquid crystal orientation film desired characteristic also strictly got up.Particularly also exist and separate out because the productive temp time (Japanese: タ Network ト タ イ system) is elongated or is separated when liquid crystal aligning agent being coated substrate and then cause printing bad, and the problem such as the scorification (Japanese: baked I pays I) to be caused by accumulated charge (RDC), be difficult to solve this two kinds of problems by current technology simultaneously.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2-287324 publication
Patent documentation 2: Japanese Patent Laid-Open 10-104633 publication
Patent documentation 3: Japanese Patent Laid-Open 2010-70537 publication
Summary of the invention
Invent technical problem to be solved
Problem of the present invention is the problem points solving above-mentioned prior art, provides and can obtain the good liquid crystal aligning agent of printing and can obtain accumulated charge few and the diamines of the liquid crystal orientation film that the decay of accumulated charge is fast, polyimide precursor and polyimide, the liquid crystal aligning agent using them, liquid crystal orientation film and liquid crystal display device.
The technical scheme that technical solution problem adopts
Present inventor has performed and conscientiously study, found that, comprise that to employ the liquid crystal aligning agent of the specific diamines represented with following formula [1] and the polyimide precursor obtained or polyimide as diamine component very effective to realizing above-mentioned purpose, thus complete the present invention.In addition, the diamine compound represented with following formula [1] is the novel cpd that document is not yet recorded.
The feature solving the of the present invention novel diamines of above-mentioned problem represents with following formula [1].
[changing 1]
(in formula [1], R 1~ R 9in two be primary amino, all the other are the monovalent organic group beyond hydrogen atom or amino, and they each other can be identical or different; N is 1 or 2, and the hydrogen atom forming ring filling hydrocarbon portion can be replaced by the monovalent organic group beyond halogen atom or amino.)
In addition, above-mentioned diamines is better represent with following formula [2].
[changing 2]
(in formula [2], p represents the integer of 0 ~ 3, R 10represent the monovalent organic group beyond amino ,-(R 10) prepresent p substituent R 10, they each other can be identical or different; Q represents the integer of 0 ~ 4, R 11represent the monovalent organic group beyond amino ,-(R 11) qrepresent q substituent R 11, they each other can be identical or different; N is 1 or 2, and the hydrogen atom forming ring filling hydrocarbon portion can be replaced by the organic group beyond halogen atom or amino.)
Above-mentioned diamines is more preferably and represents with following formula [3].
[changing 3]
(in formula [3], n be 1 or 2, m be the integer of 0 ~ 2 (n+1), R 12represent 1 valency organic group beyond fluorine atom or amino ,-(R 12) mrepresent 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, also can be the diamines represented with following formula [4-a] ~ [4-d].
[changing 4]
The feature of polyimide precursor of the present invention is, obtains by making at least one being selected from tetracarboxylic acid and derivative thereof react with the diamine component containing above-mentioned diamines.
In above-mentioned polyimide precursor, when the integral molar quantity of tetracarboxylic acid and derivative thereof is counted 100 % by mole, above-mentioned diamines is better 5 ~ 95 % by mole.
In addition, the feature of polyimide of the present invention is, obtains by carrying out imidization to above-mentioned polyimide precursor.
And the feature of liquid crystal aligning agent of the present invention is, containing at least one being selected from above-mentioned polyimide precursor and above-mentioned polyimide.
The feature of liquid crystal orientation film of the present invention is, by above-mentioned liquid crystal aligning agent being coated substrate and carrying out burning till and obtain.
The feature of liquid crystal display device of the present invention is, possesses 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 the few and novel diamines of the liquid crystal orientation film that the decay of accumulated charge is fast of accumulated charge can be obtained.And, by using this diamines, the liquid crystal aligning agent that printing is good can be formed.In addition, by using this liquid crystal aligning agent, obtaining the few and liquid crystal orientation film that the decay of accumulated charge is fast of accumulated charge, not easily there is decline and the scorification of contrast gradient in the liquid crystal display device therefore with this liquid crystal orientation film, can obtain the effect that display characteristic is excellent etc.
Embodiment
Below, the present invention is described in detail.
Diamines of the present invention is the compound represented with following formula [1].
[changing 5]
(in formula [1], R 1~ R 9in two be primary amino, all the other are the monovalent organic group beyond hydrogen atom or amino, and they each other can be identical or different; N is 1 or 2, and the hydrogen atom forming ring filling hydrocarbon portion can be replaced by the monovalent organic group beyond halogen atom or amino.)
In formula [1], as halogen atom, fluorine atom etc. can be exemplified.In addition, in formula [1], as the monovalent organic group beyond amino, the alkyl containing alkyl, hydroxyl, sulfydryl or carboxyl can be exemplified, 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 the monovalent organic group beyond amino, also can exemplify amino by the inertia group etc. of protection such as the blocking group of the amino formate of such as tert-butoxycarbonyl etc.
In addition, in formula [1], being not particularly limited the position of amino, as long as diamines is then not particularly limited, from the viewpoint of the easness of liquid crystal aligning and synthesis, is better the position represented with following formula [2].
[changing 6]
(in formula [2], p represents the integer of 0 ~ 3, R 10represent the monovalent organic group beyond amino ,-(R 10) prepresent p substituent R 10, they each other can be identical or different; Q represents the integer of 0 ~ 4, R 11represent the monovalent organic group beyond amino ,-(R 11) qrepresent q substituent R 11, they each other can be identical or different; N is 1 or 2, and the hydrogen atom forming ring filling hydrocarbon portion 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 by the R as the monovalent organic group beyond amino 10or R 11replace, various selection can be carried out according to the acquisition difficulty etc. of reagent.In addition, in formula [2], as the monovalent organic group R beyond amino 10, R 11, the alkyl with alkyl, carboxyl, hydroxyl, sulfydryl or these groups can be exemplified, 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 etc. of protection such as the blocking group of the amino formate of such as tert-butoxycarbonyl etc.But, in the viewpoint of the acquisition easness of reagent and the easness of synthesis, be better that the hydrogen atom with amino phenyl ring is not substituted.Structure example represents with following formula [3] more specifically.
[changing 7]
(in formula [3], n be 1 or 2, m be the integer of 0 ~ 2 (n+1), R 12represent 1 valency organic group beyond fluorine atom or amino ,-(R 12) mrepresent m substituent R 12, they each other can be identical or different.)
In formula [1] ~ [3], during n=1, it is 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 in this stable hydrocarbon portion also can be replaced by 1 valency organic group beyond the halogen atoms such as fluorine atom or amino.In addition, in formula [3], the substituting group replacing the hydrogen atom in stable hydrocarbon portion is R 12.1 valency organic group beyond the amino of the alternatively hydrogen atom in stable hydrocarbon portion, can exemplify alkyl, hydroxyl, carboxyl etc.Here alkyl can be any one in straight chain, side chain, ring-type, can be stable hydrocarbon also can be unsaturated hydrocarbons, and a part for the hydrogen atom of alkyl by carboxyl, hydroxyl, sulfydryl or the replacement 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, from the viewpoint of synthesis easness and reagent obtain easness, R 12it is better the alkyl be only made up of carbon atom and hydrogen atom.
The substituting group replacing the hydrogen atom of the carbon in stable hydrocarbon portion is better the alkyl of carbon number 1 ~ 6.This is because, use diamines of the present invention and the polyimide precursor such as polyamic acid obtained or polyimide solvability in a solvent high, so printing is good, if the diamines that the hydrogen atom making stable hydrocarbon portion be instead of by the alkyl of carbon number 1 ~ 6, then the polyimide precursor such as polyamic acid or polyimide solvability in organic solvent improve further, and printing is better.In addition, because the polyimide precursors such as polyamic acid or polyimide solvability is in a solvent high, so and excellent compatibility between other polymkeric substance, even if diamines of the present invention will be adopted and the polyimide precursor that obtains or polyimide and other mixed with polymers and use when, also be less likely to occur to be separated or to separate out, printing is excellent.As the object lesson of the alkyl of carbon number 1 ~ 6, can 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 thereto.
When replacing the hydrogen atom in stable hydrocarbon portion with these substituting groups, the position of substitution and quantity are not particularly limited, all selections can be carried out according to the acquisition easiness of the easness of synthesis and reagent.Particularly preferred structure is the structure of hydrogen atom by methyl substituted in stable hydrocarbon portion.In addition, from the viewpoint of the easness of synthesis, be better that the hydrogen atom in stable hydrocarbon portion is not substituted.The concrete example of preferred diamines of the present invention is below shown, but is not limited thereto.
[changing 8]
[changing 10]
Particularly preferred diamines of the present invention is as follows.
[changing 11]
Adopt such diamines of the present invention represented using above-mentioned formula [1] as polyimide precursor or the polyimide favorable solubility in organic solvent such as polyamic acid and poly amic acid ester of raw material, so when forming liquid crystal orientation film, the membrane thickness unevenness of pore or generation edge part etc. can not be formed, the liquid crystal aligning agent that printing is good can be obtained.In addition, if use this liquid crystal aligning agent, then can obtain the accumulation that electric charge is less likely to occur and the fast liquid crystal orientation film of the elimination of accumulated charge, so decline and the scorification of contrast gradient not easily occur the liquid crystal display device with this liquid crystal orientation film, the effect that display characteristic is excellent etc. can be obtained.In addition, the increase of the ion density caused because of life-time service can also be suppressed.Further, liquid crystal aligning is also good.
Can infer that the reason obtaining this effect is, diamines of the present invention comprises the pentanoic structure and stable hydrocarbon portion with the position played a role as steric barrier, so the raising of deliquescent raising and the consistency with polymkeric substance can be realized under the state of electrical property keeping pentanoic, and characteristic as above can be shown.On the other hand, the diamines of patent documentation 3 has double bond in the position in the stable hydrocarbon portion of diamines of the present invention and do not have the structure in stable hydrocarbon portion, if use the diamines of this patent documentation 3, then as shown in comparative example described later, few and the liquid crystal orientation film that the decay of accumulated charge is fast of the accumulated charge that obtains when using diamines of the present invention cannot be obtained, in addition, liquid crystal aligning is also deteriorated, and obtains the result that polyimide solvability in organic solvent and consistency be also deteriorated.Can infer that its reason is, the diamines of patent documentation 3 is rich in planarity, has the Phenylindole skeleton that can obtain the electronic state different from pentanoic in addition.
Main synthetic method for such diamines of the present invention is described.Note, the method below illustrated is synthesis example, is not limited thereto.
Dinitro compound, by such as shown in following reaction formula, reduces and nitro is changed into amino to obtain by diamines of the present invention.In addition, in following reaction formula, do not recorded by the diamines that the monovalent organic group beyond the halogen atoms such as fluorine atom or amino replaces for the hydrogen atom in phenyl ring and stable hydrocarbon portion.
[changing 12]
To reduction dinitro compound method there is no particular limitation, use palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-aluminum oxide, platinum sulfide carbon etc. can be exemplified as catalyzer, at ethyl acetate, toluene, tetrahydrofuran (THF), two in the solvent of alkane, alcohols etc., carry out the method for reducing with hydrogen, hydrazine, hydrogenchloride etc.Also can autoclave etc. be used as required to carry out under elevated pressure.On the other hand, when comprising unsaturated link(age) position in the substituent structure of the hydrogen atom in substituted benzene ring or stable hydrocarbon portion, if use palladium carbon or platinum carbon etc., then this unsaturated link(age) position is likely reduced and becomes saturated bond, therefore preferably uses the transition metal such as reduced iron, tin, tin chloride as the reductive condition of catalyzer.
In the synthesis of dinitro compound, by such as shown in following reaction formula, make commercially available nitro indolin derivatives or nitro tetrahydroquinoline derivative and reacted by the oil of mirbane that the leavings group X such as halogen instead of, thus obtaining this dinitro compound.As preferred leavings group X, fluorine atom, chlorine atom, bromine atoms, atomic iodine, tosyloxy (-OTs), mesyloxy (-OMs) etc. can be exemplified.
[changing 13]
Above-mentioned reaction can be carried out in the presence of base.As long as the alkali used can carry out synthesizing, be not particularly limited, the mineral alkalis such as salt of wormwood, sodium carbonate, cesium carbonate, sodium alkoxide, potassium alcoholate, sodium hydroxide, potassium hydroxide, sodium hydride can be exemplified, the organic basess etc. such as pyridine, dimethyl aminopyridine, Trimethylamine 99, triethylamine, Tributylamine.In addition, according to circumstances, and if with palladium catalyst or the copper catalyst etc. such as dibenzalacetone two palladium or diphenylphosphino ferrocene palladium, then can yield be improved.From the viewpoint of the easness of synthesis, be preferably as follows and state shown in reaction formula, the alkali such as the hydrogen sodium hydride of-NH-existed in nitro indolin derivatives or nitro tetrahydroquinoline derivative are removed, make the method that itself and 4-fluoronitrobenzene react, owing to also can synthesize by the method beyond the method, so be not particularly limited synthetic method.
[changing 14]
Diamines of the present invention, by reacting with at least one being selected from tetracarboxylic acid and tetracarboxylic acid derivatives, 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 as the integral molar quantity of tetracarboxylic acid and derivative thereof is counted 100 % by mole time, diamines of the present invention is 5 ~ 95 % by mole.
As tetracarboxylic acid derivatives, tetracarboxylic acid two carboxylic acid halides, tetracarboxylic dianhydride, tetracarboxylic acid diester diacid chloride, tetracarboxylic acid diester etc. can be exemplified.Such as, by making the tetracarboxylic acid or derivatives thereofs such as tetracarboxylic acid two carboxylic acid halides, tetracarboxylic dianhydride react with the diamine component comprising diamines of the present invention, polyamic acid can be obtained.In addition, by making tetracarboxylic acid diester diacid chloride and the reaction of diamine component comprising diamines of the present invention, or make tetracarboxylic acid diester and the diamine component comprising diamines of the present invention there is inferior reaction at suitable condensing agent or alkali, can poly amic acid ester be obtained.In addition, in this specification sheets, diamine component refers to and carries out with at least one being selected from tetracarboxylic acid and tetracarboxylic acid derivatives the diamines that reacts in order to obtain polyimide precursor or polyimide, can be used alone diamines of the present invention, also can be used together diamines of the present invention and other diamines.
And, by carrying out imidization to polyimide precursor, specifically make polyamic acid dehydration closed-loop, or at high temperature heat poly amic acid ester to promote dealcoholysis, to make its closed loop, thus polyimide of the present invention can be obtained.
Below, to polyimide precursors such as polyamic acid of the present invention, poly amic acid esters, and polyimide is described in further detail.Obtaining in the diamine component of the polyimide precursors such as polyamic acid by reacting with at least one of the tetracarboxylic acid and tetracarboxylic acid derivatives that are selected from above-mentioned tetracarboxylic dianhydride etc., being not particularly limited containing proportional diamines of the present invention.In the liquid crystal orientation film of the polyimide gained adopting polyimide precursor of the present invention or obtained by its imidization, diamines of the present invention shown in above-mentioned containing proportional more, can obtain the few and liquid crystal orientation film that the decay of accumulated charge is fast of accumulated charge.
In order to accelerate the decay of the electric charge accumulated, it is desirable to more than 1 % by mole of diamine component for diamines of the present invention.On the other hand, if consider other the characteristic such as liquid crystal aligning, tilt angle characteristic, then that is polymerized the diamine component of the present invention in the diamine component used is preferably 20 ~ 90 % by mole, particularly preferably 30 ~ 80 % by mole containing proportional.
In above-mentioned diamine component, when the diamines represented with formula [1] is lower than 100 % by mole, other the diamines beyond the used diamines represented with formula [1] is not particularly limited.If exemplify its object lesson, then 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 '-dimethyidicyclohexyl amine, 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-2,5-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 sulfide, 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) hexanaphthene 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 disiloxane 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) pentane of 1,5-, two (4-aminophenyl) hexane of 1,6-, two (4-aminophenyl) heptane of 1,7-, two (4-aminophenyl) octane of 1,8-, two (4-aminophenyl) nonane 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) pentane of 1,5-, two (4-amino-benzene oxygen) hexane of 1,6-, two (4-amino-benzene oxygen) heptane of 1,7-, two (4-amino-benzene oxygen) octane of 1,8-, two (4-amino-benzene oxygen) nonane of 1,9-, two (4-amino-benzene oxygen) decane of 1,10-, two (4-aminophenyl) 1,3-malonic ester, two (4-aminophenyl) 1, 4-succinic acid ester, two (4-aminophenyl) 1,5-glutarate, two (4-aminophenyl) 1,6-adipic acid ester, two (4-aminophenyl) 1,7-pimelate, two (4-aminophenyl) 1,8-suberate, two (4-aminophenyl) 1,9-azelate, two (4-aminophenyl) 1,10-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] pentane of 1,5-, two [4-(4-amino-benzene oxygen) phenoxy group] hexane of 1,6-, two [4-(4-amino-benzene oxygen) phenoxy group] heptane of 1,7-, two [4-(4-amino-benzene oxygen) phenoxy group] octane of 1,8-, two [4-(4-amino-benzene oxygen) phenoxy group] nonane 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 methylamine, 4-amino-benzene methylamine, 3-Amino-N-methyl phenmethyl amine, 4-Amino-N-methyl phenmethyl amine, 3-aminophenethyl amine, 4-aminophenethyl amine, 3-Amino-N-methyl styroyl amine, 4-Amino-N-methyl styroyl amine, 3-(3-aminopropyl) aniline, 4-(3-aminopropyl) aniline, 3-(3-dimethylaminopropyl) aniline, 4-(3-dimethylaminopropyl) aniline, 3-(4-aminobutyl) aniline, 4-(4-aminobutyl) aniline, 3-(4-methylamino butyl) aniline, 4-(4-methylamino butyl) aniline, 3-(5-Aminopentyl) aniline, 4-(5-Aminopentyl) aniline, 3-(5-methylamino-pentyl) aniline, 4-(5-methylamino-pentyl) 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-pyridines, 2,4-diamino-1,3,5-triazines, 2,7-diamino diphenylene-oxide, 3,6-diaminocarbazole, 2,4-diamino-6-sec.-propyls-1,3,5-triazine, 2, two (the 4-aminophenyl)-1,3,4-of 5- diazole etc.
The example of aliphatie diamine class can exemplify: 1, 2-diaminoethanes, 1, 3-diaminopropanes, 1, 4-diaminobutane, 1, 5-1,5-DAP, 1, 6-diamino hexane, 1, 7-diaminoheptane, 1, 8-diamino-octane, 1, 9-diamino nonane, 1, 10-diamino decane, 1, 3-diamino-2, 2-dimethylpropane, 1, 6-diamino-2, 5-dimethylhexane, 1, 7-diamino-2, 5-dimethyl heptane, 1, 7-diamino-4, 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 and there is alkyl on side chain, containing fluoroalkyl, aromatic nucleus, aliphatics ring, heterocycle and the diamine compound of large ring-type substituent that is made up of them.Specifically, the diamines represented with following formula [DA-1] ~ formula [DA-30] can be illustrated.
[changing 15]
(in formula, R 13represent the alkyl of carbon number 1 ~ 22 or contain fluoroalkyl; S 5represent-COO-,-OCO-,-CONH-,-NHCO-,-CH 2-,-O-,-CO-or-NH-.)
[changing 16]
(in formula, S 6represent-O-,-OCH 2-,-CH 2o-,-COOCH 2-or-CH 2oCO-; R 14represent the alkyl of carbon number 1 ~ 22, alkoxyl group, containing fluoroalkyl or fluoroalkoxy.)
[changing 17]
(in formula, S 7represent-COO-,-OCO-,-CONH-,-NHCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-or-CH 2-; R 15represent the alkyl of carbon number 1 ~ 22, alkoxyl group, containing fluoroalkyl or fluoroalkoxy.)
[changing 18]
(in formula, S 8represent-COO-,-OCO-,-CONH-,-NHCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-,-CH 2-,-O-or-NH-; R 16represent fluorine-based, cyano group, trifluoromethyl, nitro, azo-group, formyl radical, ethanoyl, acetoxyl group or hydroxyl.)
[changing 19]
(in formula, R 17represent the alkyl of carbon number 3 ~ 12; The cis-isomerism of Isosorbide-5-Nitrae-cyclohexylidene is respectively trans.)
[changing 20]
When utilizing light to carry out orientation process, by and with the diamines of above-mentioned formula [1] and the diamines of above-mentioned [DA-1] ~ [DA-30], more stable tilt angle can be obtained.As diamines also, the diamines of preferred formula [DA-10] ~ [DA-30], the more preferably diamines of formula [DA-10] ~ [DA-16].The preferred content of these diamines is not particularly limited, but is preferably 5 ~ 50 % by mole relative to the total amount of diamine component, from the viewpoint of printing, preferably 5 ~ 30 % by mole.
In addition, as other diamines, also following diamines can be exemplified.
[changing 21]
(in formula, i is the integer of 0 ~ 3; J is the integer of 1 ~ 5.)
By importing [DA-31] or [DA-32], can improve voltage retention (VHR), in addition, [DA-33] ~ [DA-38] can make accumulated charge reduce.
In addition, the diamino siloxanes etc. as represented with following formula [DA-39] can also be exemplified.
[changing 22]
(in formula, k is the integer of 1 ~ 10.)
Other diamine compound this according to the characteristic such as liquid crystal aligning, voltage retentivity, accumulated charge when making liquid crystal orientation film, can use a kind or two or more is used in combination.
Tetracarboxylic acid and derivative thereof is waited to be not particularly limited for for obtaining the polyimide precursors such as polyamic acid of the present invention with the tetracarboxylic dianhydride that diamine component reacts.Exemplify its object lesson below.
The 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-cyclopentanetetracarboxylic 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, 8-tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-dicyclohexyl tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, cis-3, 7-dibutyl ring pungent-1, 5-diene-1, 2, 5, 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-dioxotetrahydro furans-3-base)-1,2,3,4-tetralin-1,2-dicarboxylic acid dianhydride etc.
Further, if also use aromatic tetracarboxylic acid's dianhydride outward the above-mentioned tetracarboxylic dianhydride with alicyclic structure or aliphatic structure, then can improve liquid crystal aligning, and the accumulated charge of liquid crystal cell can be reduced, therefore preferably.As aromatic tetracarboxylic acid's dianhydride, pyromellitic acid anhydride, 3 can be exemplified, 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-dicarboxyphenyi) ether dianhydride, two (3,4-dicarboxyphenyi) sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydrides etc.
Also be not particularly limited with the tetracarboxylic acid dialkyl that diamine component reacts for for obtaining poly amic acid ester of the present invention.Exemplify its object lesson below.
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-cyclopentanetetracarboxylic 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 cyclopentyl dialkyl acetates, cis-3, 7-dibutyl ring pungent-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-dioxotetrahydro furans-3-base)-1,2,3,4-tetralin-1,2-dicarboxylic acid dialkyl esters etc.
As aromatic tetracarboxylic acid's dialkyl, Pyromellitic Acid dialkyl, 3 can be exemplified, 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-dicarboxyphenyi) ether dialkyl, two (3,4-dicarboxyphenyi) sulfone dialkyl, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl etc.
In addition, by making the diamine component such as diamines of the present invention and dicarboxylic acid react, can also synthesizing polyamides.Be not particularly limited with the dicarboxylic acid that diamine component reacts for for obtaining polymeric amide.Exemplify its object lesson below.
As the object lesson of the aliphatic dicarboxylic acid of dicarboxylic acid or derivatives thereof, 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 can be exemplified, the dicarboxylic acid such as 2-dimethylated pentanedioic acid, 3,3-diethyl succsinic acids, nonane diacid, sebacic acid and suberic acid.
As the dicarboxylic acid of the alicyclic ring same clan, 1,1-cyclopropane dicarboxylic acid can be exemplified, 1,2-cyclopropane dicarboxylic acid, 1,1-cyclobutane dicarboxylic acid, 1,2-cyclobutane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 3,4-phenylbenzene-1,2-cyclobutane dicarboxylic acid, 2,4-phenylbenzene-1,3-cyclobutane dicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,1-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-(2-norbornylene) dicarboxylic acid, norbornylene-2,3-dicarboxylic acid, two rings [2.2.2] octane-Isosorbide-5-Nitrae-dicarboxylic acid, two rings [2.2.2] octane-2,3-dicarboxylic acid, 2,5-dioxo-Isosorbide-5-Nitrae-two ring [2.2.2] octane dicarboxylic acid, 1,3-diamantane dicarboxylic acid, 4,8-dioxo-1,3-diamantane dicarboxylic acid, 2,6-spiral shell [3.3] heptane dicarboxylic acid, 1,3-diamantane oxalic acid, dextrocamphoric acid etc.
As aromatic dicarboxylic acid, phthalic acid can be exemplified, m-phthalic acid, terephthalic acid, oreinol dioctyl phthalate, 5-tert-butyl isophthalic acid, 5-amino isophthalic acid, 5-Hydroxy M Phthalic Acid, 2,5-dimethyl terephthalic acid, 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 acids, 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 '-sulfonyl dibenzoic acid, 4,4 '-dithiodibenzoic acid, to phenylenediacetic acid, 3,3 '-to phenylene dipropionic acid, 4-o-carboxy cinnamic acid, to phenylene diacrylate, 3,3 '-[4,4 '-(methylene radical two pairs of phenylenes)] dipropionic acid, 4,4 '-[4,4 '-(oxo two pairs of phenylenes)] dipropionic acid, 4,4 '-[4,4 '-(oxo two pairs of phenylenes)] two butyric acid, (isopropylidene two pairs of phenylene dioxies) two butyric acid, two (to carboxyl phenyl) dimethylsilane etc.
As the dicarboxylic acid containing heterocycle, 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-can be exemplified diazole-3,4-dicarboxylic acid, 2,3-pyridine dicarboxylic acids, 2,4-pyridine dicarboxylic acids, 2,5-Pyridinedicarboxylic acid, 2, dipicolimic acid 2,3,4-pyridine dicarboxylic acids, 3,5-pyridine dicarboxylic acids etc.
Above-mentioned various dicarboxylic acid also can be 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, preferred terephthalic acid, m-phthalic acid (Japanese: イ ソ テ レ Off タ Le acid), 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 there is isomer in these compounds, also can be the mixture comprising 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.
The tetracarboxylic acids such as above-mentioned tetracarboxylic dianhydride and derivative thereof can according to the characteristics such as liquid crystal aligning, voltage retentivity, accumulated charge when making liquid crystal orientation film, use one or and with two or more.
As making diamine component react to obtain the method for the polyimide precursors such as polyamic acid with at least one being selected from tetracarboxylic acid and tetracarboxylic acid derivatives, known synthetic method can be adopted.
Such as, obtain the method for polyamic acid of the present invention as the reaction by tetracarboxylic dianhydride and diamine component, can exemplify and make tetracarboxylic dianhydride and diamine component carry out the method for reacting 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 in be favourable.
As the organic solvent of the reaction for tetracarboxylic dianhydride and diamines, as long as the soluble solvent of polyamic acid generated is not particularly limited.As concrete example, DMF can be exemplified, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolactone, Virahol, 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, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, DPGME, Diethylene Glycol, 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-methoxybutyl acetic ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, tetrahydrotoluene, propyl ether, two hexyl ethers, two alkane, normal hexane, normal heptane, octane, diethyl ether, pimelinketone, ethylene carbonate, Texacar PC, methyl lactate, lactic acid ethyl, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethyl ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, 3-methoxy methyl propionate, 3-ethoxy-propionic acid methyl ethyl ester, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxyl group-N, N-dimethylpropionamide, 3-oxyethyl group-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide etc.These solvents can be used alone, also can be used in combination.Further, even the solvent of insoluble solution polyamic acid, as long as in the scope that the polyamic acid generated can not be separated out, also can use with above-mentioned solvent.In addition, the moisture in organic solvent hinders polyreaction, and the polyamic acid of generation can be made to be hydrolyzed, and therefore organic solvent preferably uses the organic solvent through farthest dehydrating.
Following method can be exemplified: the solution that stirring makes diamine component be dispersed or dissolved in organic solvent and obtains, the method for then directly adding tetracarboxylic dianhydride or adding again after making tetracarboxylic dianhydride be dispersed or dissolved in organic solvent when tetracarboxylic dianhydride and diamine component are reacted in organic solvent; The method of diamine component is added in the solution obtained tetracarboxylic dianhydride is dispersed or dissolved in organic solvent on the contrary; Alternately add the method etc. of tetracarboxylic dianhydride and diamine component, any one method wherein can be used.In addition, when tetracarboxylic dianhydride or diamine component are made up of multiple compounds, can it be made to react under the state be pre-mixed, it also can be made to react successively respectively, then the low-molecular weight hybrid reaction making to react respectively and obtain and obtain high molecular body.
Condensation temperature now can select the arbitrary temp of-20 DEG C ~ 150 DEG C, preferably the scope of-5 DEG C ~ 100 DEG C.In addition, polycondensation can be carried out with arbitrary concentration, if but concentration is too low, be difficult to the polymkeric substance obtaining high molecular, if excessive concentration, the viscosity of reaction solution becomes too high and is difficult to stir uniformly, therefore tetracarboxylic dianhydride and the diamine component total concn in reaction soln is preferably 1 ~ 50 quality %, more preferably 5 ~ 30 quality %.Can be that initial reaction stage is carried out in higher concentrations, add organic solvent afterwards.
In the polyreaction of polyamic acid, the ratio (total mole number of the total mole number/diamine component of tetracarboxylic dianhydride) of the total mole number of tetracarboxylic dianhydride and the total mole number of diamine component 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 by above-mentioned tetracarboxylic acid diester diacid chloride and diamine component reaction or make tetracarboxylic acid diester and diamine component carry out reacting obtaining under the existence of suitable condensing agent, alkali.Or, also by with the pre-synthesis polyamic acid of above-mentioned method, high molecular weight reactive can be recycled and carries out esterification to obtain to the carboxylic acid in amido acid.
Specifically, can by such as making tetracarboxylic acid diester diacid chloride and diamines under the existence of alkali and organic solvent, and reaction 30 minutes at-20 ~ 150 DEG C, preferably 0 ~ 50 DEG C ~ 24 hours, preferably 1 ~ 4 hour, carry out synthesizing polyamides acid esters.
As alkali, pyridine, triethylamine, 4-dimethylaminopyridine can be used, in order to carry out with making reacting balance, preferred pyridine.Can easily obtain high molecular body from the viewpoint of the amount of easily removing, the addition of alkali is preferably 2 ~ 4 times moles relative to tetracarboxylic acid diester diacid chloride.
In addition, when making to carry out polycondensation under tetracarboxylic acid diester and the existence of diamine component at condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride, N can be used as alkali, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazine methylmorpholine , O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylurea (TMU) Tetrafluoroboric acid ester, O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylurea (TMU) phosphofluoric acid ester, (2,3-dihydroxyl-2-sulfo--3-benzo azoles) phosphonic acid diphenyl ester, 4-(4,6-dimethoxy-1,3,5-triazines-2-base) 4-methoxyl group morpholine hydrochloride n hydrate etc.
In addition, in the method using above-mentioned 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 relative to diamines or tetracarboxylic acid diester.
As the solvent used in above-mentioned reaction, the solvent same with the solvent phase used when the above-mentioned synthesizing polyamides illustrated is sour can be used, consider from monomer and structure adaptability, preferred METHYLPYRROLIDONE, gamma-butyrolactone, can use in them a kind or two or more is used in combination.From the viewpoint of be difficult to occur polymkeric substance precipitation and easily obtain high molecular body, total concn in the reaction soln of the tetracarboxylic acid derivatives such as concentration during synthesis, tetracarboxylic acid diester diacid chloride or tetracarboxylic acid diester and diamine component is better 1 ~ 30 quality %, is more preferably 5 ~ 20 quality %.In addition, in order to prevent tetracarboxylic acid diester diacid chloride to be hydrolyzed, the solvent for the synthesis of poly amic acid ester can be the state of farthest dewatering to the greatest extent, is better prevent being mixed into of foreign gas in nitrogen atmosphere.
Polyimide of the present invention obtains by making above-mentioned polyamic acid dehydration closed-loop.In polyimide of the present invention, the dehydration closed-loop rate (imide rate) of acid amides acidic group does not need one to be decided to be 100%, can adjust arbitrarily according to purposes or object.
As the method making polyamic acid imidization, the hot-imide of the solution of direct heating polyamic acid can be exemplified or in the solution of polyamic acid, add the catalysis imidization of catalyzer.
Temperature when making polyamic acid carry out hot-imide is in the solution 100 ~ 400 DEG C, and preferably 120 ~ 250 DEG C is better carry out imidization while draining into outside system by the water generated by imidization reaction.
The catalysis imidization of polyamic acid by adding basic catalyst and acid anhydrides in polyamic acid solution, at-20 ~ 250 DEG C, preferably can stir and carrying out at 0 ~ 180 DEG C.The amount of basic catalyst is 0.5 ~ 30 mole times of acid amides acidic group, preferably 2 ~ 20 moles times, and the amount of acid anhydrides is 1 ~ 50 mole times of acid amides acidic group, preferably 3 ~ 30 moles times.As basic catalyst, pyridine, triethylamine, Trimethylamine 99, Tributylamine, trioctylamine etc. can be exemplified, wherein pyridine have for make reaction carry out for appropriateness alkalescence, therefore preferably.As acid anhydrides, diacetyl oxide, trimellitic acid 1,2-anhydride, pyromellitic dianhydride etc. can be exemplified, wherein, use during diacetyl oxide and be easy to carry out reacting the purifying after terminating, therefore preferably.Adopt the imide rate of catalysis imidization can be controlled by adjustment catalytic amount and temperature of reaction, reaction times.
In addition, as mentioned above, also by high temperature heating poly amic acid ester to promote dealcoholysis, to make its closed loop, polyimide can be obtained.
In addition, when reclaiming from the reaction soln of the polyimide precursor such as polyamic acid, poly amic acid ester or polyimide polyamic acid, poly amic acid ester, the polyimide generated, reaction soln is poured into poor solvent and make it precipitate.As the poor solvent for precipitating, methyl alcohol, acetone, hexane, ethylene glycol butyl ether, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene, water etc. can be exemplified.Putting in poor solvent the polyimide precursor of precipitation or polyimide can after filtered and recycled, under normal or reduced pressure, at normal temperature or heat and carry out drying.In addition, if the polyimide precursor making precipitation reclaim or polyimide are dissolved in organic solvent and repeat the operation that 2 ~ 10 times redeposition reclaims again, then the impurity in polymkeric substance can be reduced.As poor solvent now, can exemplify such as alcohols, ketone, hydro carbons etc., if use the poor solvent being selected from more than 3 kinds of these solvents, then purification efficiency improves further, therefore preferably.
The polyimide precursor such as polyamic acid, poly amic acid ester contained in liquid crystal aligning agent of the present invention or the molecular weight of polyimide, when the homogeneity of the operability when considering the painting film strength of gained and film is formed, film, the weight average molecular weight utilizing GPC (Gel Permeation Chromatography: gel permeation chromatography) method to measure is better 5000 ~ 1000000, is more preferably 10000 ~ 150000.
The polyimide precursors such as above-mentioned polyamic acid of the present invention, poly amic acid ester and polyimide use together with solvent, can make liquid crystal aligning agent.Liquid crystal aligning agent refers to the solution for the formation of liquid crystal orientation film, is the solution component of polymer for the formation of liquid crystal orientation film being dispersed or dissolved in organic solvent and being formed.In addition, liquid crystal orientation film refers to for making liquid crystal along the film of the direction orientation of regulation.And in the present invention, above-mentioned component of polymer contains at least one of 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 in the polyimide precursors such as above-mentioned polyamic acid of the present invention, poly amic acid ester or polyimide, be mixed with other polymkeric substance.When component of polymer contains other polymkeric substance, the content of other the polymkeric substance in component of polymer total amount is 0.5 quality % ~ 50 quality %, preferably 1 quality % ~ 30 quality %.By adopting the mixture of multiple polymers, the characteristic of liquid crystal aligning agent and liquid crystal orientation film can be improved.
As other such polymkeric substance, such as, can exemplify and use diamines except the above-mentioned diamines represented with formula [1] of the present invention and polyamic acid, poly amic acid ester or the polyimide etc. that obtain as the diamine component reacted with tetracarboxylic dianhydride's composition.
In liquid crystal aligning agent, the at least one being selected from the polyimide precursors such as above-mentioned polyamic acid of the present invention, poly amic acid ester and polyimide and other the polymkeric substance that mixes as required containing proportional, better 1 quality % ~ 20 quality % in component of polymer total amount, be more preferably 3 quality % ~ 15 quality %, spy is well 3 ~ 10 quality %.
As long as the organic solvent of the solvent energy dissolve polymer composition used in liquid crystal aligning agent of the present invention, is not particularly limited.As its concrete example, N can be exemplified, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrolidone, NVP, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolactone, 3-methoxyl group-N, N-dimethylpropionamide, 3-oxyethyl group-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1, 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, also can be used in combination.
Liquid crystal aligning agent of the present invention can comprise composition other than the above.Object lesson has, film uniformity during raising coating of liquid crystalline alignment agent and the compound etc. of the solvent of surface smoothness or the adaptation of compound, raising liquid crystal orientation film and substrate.
As the concrete example improving the homogeneity of thickness and the solvent (poor solvent) of surface smoothness, Virahol can be exemplified, methoxymethyl amylalcohol, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monobutyl ether, ethyl carbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, DPGME, Diethylene Glycol, 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-methoxybutyl acetic ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, tetrahydrotoluene, propyl ether, two hexyl ethers, 1-hexanol, normal hexane, Skellysolve A, octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethyl ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, 3-methoxy methyl propionate, 3-ethoxy-propionic acid methylethyl ester, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 1-methoxy-2-propanol, 1-oxyethyl group-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic ester, propylene glycol-1-single ethyl ether-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 etc. of low surface tension.
These poor solvents can use a kind, or by multiple used in combination.When using solvent as above, be better 5 ~ 80 quality % accounting for solvent total amount contained in liquid crystal aligning agent, be more preferably 20 ~ 60 quality %.
As the compound improving film uniformity and surface smoothness, fluorine class tensio-active agent, siloxane type surfactants, nonionic surfactant etc. can be exemplified.More specifically, such as エ Off ト ッ プ EF301 can be exemplified, EF303, EF352 (illuminating product Co., Ltd. (ト ー ケ system プ ロ ダ クツ society) system), メ ガ Off ァ ッ Network F171, F173, R-30 (Dainippon Ink and Chemicals, Inc (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, relative to resinous principle 100 mass parts contained in liquid crystal aligning agent, is better 0.01 ~ 2 mass parts, is more preferably 0.01 ~ 1 mass parts.
As the concrete example of compound of adaptation improving liquid crystal orientation film and substrate, 3-TSL 8330 can be exemplified, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl Trimethoxy silane, 3-ureidopropyltriethoxysilane, 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)-APTES 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-2,4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-xylene diamine, two (N, the N-diglycidyl amino methyl) hexanaphthene of 1,3-, N, N, N ', the compound containing functional silanes such as N '-four glycidyl group-4,4 '-diaminodiphenyl-methane and the compound etc. containing epoxy group(ing).
Further, except improving the adaptation of substrate and film, in order to prevent degradation under the electrical characteristic that 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]
(in formula, Me represents methyl.)
When using the compound that can improve with the adaptation of substrate, its usage quantity, relative 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 is less than 0.1 mass parts, then cannot expect the effect that adaptation improves, if more than 30 mass parts, then the orientation of liquid crystal is deteriorated sometimes.
In liquid crystal aligning agent of the present invention, in addition to the foregoing, in the scope not damaging effect of the present invention, the dielectric medium for the purpose of the electrical characteristic such as the specific inductivity that is changed liquid crystal orientation film or electroconductibility or conducting material can be added, the cross-linked compound for the purpose of the hardness improving film when forming liquid crystal orientation film or density can also be added.
Liquid crystal aligning agent of the present invention to be coated on substrate and after burning till, can carry out the orientation process such as friction treatment or rayed, or is used as liquid crystal orientation film without orientation process in vertical orientated purposes etc.The polyimide precursor that liquid crystal orientation film of the present invention like this contains use diamines of the present invention and formed or polyimide, so do not form pore or occur thickness uneven of edge part etc., in addition be less likely to occur the accumulation of electric charge, and the electric charge of accumulation is eliminated fast.
As substrate, as long as the high substrate of the transparency is then not particularly limited, the plastic base etc. such as glass substrate or vinylformic acid substrate, polycarbonate substrate can be used.In addition, from the viewpoint of work simplification, preferably use the substrate of the ITO electrode etc. be formed with for liquid crystal drive.And in reflection type liquid crystal display element, if be only limitted to the substrate of side, can use the opaque materials such as silicon wafer, electrode now can use the material of the reflected light such as aluminium.In addition, in the contour performance components of TFT type element, the component for being formed between the electrode of liquid crystal drive and substrate as elements such as transistors is used in.
Be not particularly limited the coating process of liquid crystal aligning agent, the method be coated with is carried out in industrial usual employing 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., these methods can be used according to object.
Liquid crystal aligning agent is coated burning till after on substrate to be carried out at 50 ~ 300 DEG C, preferably 80 ~ 250 DEG C by heating units such as hot-plate, recirculation furnace, infrared heating heating furnaces, solvent is evaporated, thus forms film.If the thickness burning till rear formed film is blocked up, then unfavorable in the power consumption of liquid crystal display device, if excessively thin, then the reliability of liquid crystal display device reduces sometimes, therefore preferably 5 ~ 300nm, more preferably 10 ~ 100nm.When making liquid crystal horizontal alignment or tilted alignment, by friction or polarisation uviolizing etc., the film after burning till is processed.
Liquid crystal display device of the present invention is after being with the substrate of liquid crystal orientation film by aforesaid method by liquid crystal aligning agent acquisition of the present invention, the liquid crystal display device formed by known method manufacture liquid crystal cell.If exemplify an example, then there is following liquid crystal display device: possess the 2 pieces of substrates configured 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, as long as the substrate that the transparency is high, be not particularly limited, on substrate, be normally formed with the substrate of the transparency electrode for driving liquid crystal.As object lesson, the substrate same with the substrate recorded in above-mentioned liquid crystal orientation film can be exemplified.
In addition, liquid crystal orientation film is by carrying out burning till after being coated with liquid crystal aligning agent of the present invention on the substrate and being formed, and detailed content is described above.
The liquid crystal material of the liquid crystal layer forming liquid crystal display device of the present invention is not particularly limited, existing MLC-2003, MLC-6608, MLC-6609 etc. of being made by liquid crystal material, the such as Merck & Co., Inc. (メ ルク society) used with vertical orientation mode can be used.
An example of liquid crystal cell is manufactured if exemplify, following method can be illustrated: a pair substrate preparing to be formed with liquid crystal orientation film, the liquid crystal orientation film of a plate base scatters pearl thing at equal intervals, make liquid crystal aligning face become interior rear flank the laminating of another plate base, decompression injects liquid crystal and the method for sealing; Or drip liquid crystal on the liquid crystal aligning face being scattered with spacer after, baseplate-laminating is carried out the method etc. sealed.Now, the thickness of spacer preferably 1 ~ 30 μm, more preferably 2 ~ 10 μm.
As mentioned above, use the reliability of liquid crystal aligning agent of the present invention and obtained liquid crystal display device good, the LCD TV etc. of large picture and high-resolution can be performed well in.
Embodiment
Below, be described in further detail based on embodiment, but the present invention is not by any restriction of this embodiment.
[synthesis of diamines]
The abbreviation of following use is as follows.
DMF:N, dinethylformamide
THF: tetrahydrofuran (THF)
RT: room temperature (25 DEG C)
The synthesis of the amino indoline [diamines-1 (Diamine-1)] of 1-(4-the aminophenyl)-5-that (synthetic example 1) represents with following formula
[changing 24]
The synthesis of (the first operation) 1-(4-nitrophenyl)-5-nitro indoline
[changing 25]
In two mouthfuls of flasks of 500mL, add 9.30g (213 mmole) sodium hydride (purity 55%), 100mL dewaters DMF, stir the DMF solution (5-nitro indoline: 35.0g (213 mmole), DMF:100mL) dripping 5-nitro indoline with the condition being no more than 30 DEG C under nitrogen atmosphere.After dropping terminates, at room temperature stir 2 hours.The DMF solution (4-fluoronitrobenzene: 33.0g (234.5 mmole), DMF:100mL) of 4-fluoronitrobenzene is dripped, under nitrogen atmosphere, in stirring at room temperature 6 hours in this reaction soln.
After reaction terminates, stirring reaction solution injects 100mL pure water on one side at leisure, and solid is separated out, and filters the solid of separating out, it is dissolved in DMF again, injects 500mL pure water and makes its redeposition, filtered and recycled solid again.Dispersion cleaning is carried out to the solids with methanol of gained, normal hexane, makes its vacuum-drying, thus obtain orange solid 54.7g (yield 90%).
The synthesis of (the second operation) diamines-1 (Diamine-1)
[changing 26]
15.0g (52.6 mmole) is taken by 1-(4-the nitrophenyl)-5-nitro indoline of the first operation gained and 1.50g10 quality % palladium carbon in the four-hole boiling flask of 300mL, add 150mL ethanol, after fully carrying out nitrogen displacement, be replaced as hydrogen atmosphere, at room temperature carry out vigorous stirring.
After reaction terminates, with glass filter palladium carbon, with rotatory evaporator, filtrate is carried out to the removing of solvent.The residue of gained is dissolved in acetone, add gac and stir a moment, filter activity charcoal, after rotatory evaporator removing acetone, carry out recrystallization with the mixing solutions (2:3 mass ratio) of normal hexane and ethyl acetate, obtain the solid 10.5g (yield: 89%) of the lilac as targeted diamine (Diamine-1).The nuclear magnetic resonance spectrum, namely of hydrogen atom in its structure molecule 1h-NMR spectrum confirms.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)
The synthesis (raceme mixing) of the amino indoline [diamines-2 (Diamine-2)] of 1-(4-the aminophenyl)-2-methyl-5-that (synthetic example 2) represents with following formula
[changing 27]
The synthesis of (the first operation) 1-(4-nitrophenyl)-2-methyl-5-nitro indoline
[changing 28]
In two mouthfuls of flasks of 500mL, add 2.45g (56.1 mmole) sodium hydride (purity 55%), 100mL dewaters DMF, stir the DMF solution (2-methyl-5-nitro indoline: 10.0g (56.1 mmole), DMF:50mL) dripping 2-methyl-5-nitro indoline with the condition being no more than 30 DEG C under nitrogen atmosphere.After dropping terminates, at room temperature stir 2 hours.The DMF solution (4-fluoronitrobenzene: 8.7g (61.7 mmole), DMF:50mL) of 4-fluoronitrobenzene is dripped, under nitrogen atmosphere, in stirring at room temperature 6 hours in this reaction soln.
After reaction terminates, stirring reaction solution injects 100mL pure water on one side at leisure, and solid is separated out, and filters the solid of separating out, it is dissolved in DMF again, injects 500mL pure water and makes its redeposition, filtered and recycled solid again.Dispersion cleaning is carried out to the solids with methanol of gained, normal hexane, makes its vacuum-drying, thus obtain orange solid 14.4g (yield: 86%).
The synthesis of (the second operation) diamines-2 (Diamine-2)
[changing 29]
10.0g (56.1 mmole) is taken by 1-(4-the nitrophenyl)-2-methyl-5-nitro indoline of the first operation gained and 1.00g10 quality % palladium carbon in the four-hole boiling flask of 300mL, add 150mL ethanol, after fully carrying out nitrogen displacement, be replaced as hydrogen atmosphere, at room temperature carry out vigorous stirring.
After reaction terminates, with glass filter palladium carbon, with rotatory evaporator, filtrate is carried out to the removing of solvent.The residue of gained is dissolved in acetone, add gac and stir a moment, filter activity charcoal, after rotatory evaporator removing acetone, carry out recrystallization with the mixing solutions (2:3 mass ratio) of normal hexane and ethyl acetate, obtain the solid 7.03g (yield: 89%) of the lightpink as targeted diamine (Diamine-2).Its structure is used 1h-NMR spectrum confirms.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)
The synthesis (raceme mixing) of the amino indoline [diamines-3 (Diamine-3)] of (synthetic example 3) 1-(4-aminophenyl)-2,3,3-trimethylammonium-5-
[changing 30]
The synthesis of (the first operation) 1-(4-nitrophenyl)-2,3,3-trimethylammonium-5-nitro indoline
[changing 31]
In two mouthfuls of flasks of 500mL, add 2.16g (48.5 mmole) sodium hydride (purity 55%), 100mL dewaters DMF, stir while drip 2 with the condition being no more than 30 DEG C 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 dropping terminates, at room temperature stir 2 hours.The DMF solution (4-fluoronitrobenzene: 7.52g (53.3 mmole), DMF:50mL) of 4-fluoronitrobenzene is dripped, under nitrogen atmosphere, in stirring at room temperature 6 hours in this reaction soln.
After reaction terminates, stirring reaction solution injects 100mL pure water on one side at leisure, and solid is separated out, and filters the solid of separating out, it is dissolved in DMF again, injects 500mL pure water and makes its redeposition, filtered and recycled solid again.Dispersion cleaning is carried out to the solids with methanol of gained, normal hexane, makes its vacuum-drying, thus obtain orange solid 13.5g (yield: 85%).
The synthesis of (the second operation) diamines-3 (Diamine-3)
[changing 32]
The 1-(4-nitrophenyl)-2 of 10.0g (30.5 mmole) by the first operation gained is taken 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 nitrogen displacement, be replaced as hydrogen atmosphere, at room temperature carry out vigorous stirring.
After reaction terminates, with glass filter palladium carbon, with rotatory evaporator, filtrate is carried out to the removing of solvent.The residue of gained is dissolved in acetone, add gac and stir a moment, filter activity charcoal, after rotatory evaporator removing acetone, carry out recrystallization with the mixing solutions (2:3 mass ratio) of normal hexane and ethyl acetate, obtain the solid 7.50g (yield: 92%) of the lilac as targeted diamine (Diamine-3).Its structure is used 1h-NMR spectrum confirms.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 synthesis of amino-1,2,3, the 4-tetrahydroquinolines [diamines-4 (Diamine-4)] of 1-(4-the aminophenyl)-6-that (synthetic example 4) represents with following formula
[changing 33]
The synthesis of (the first operation) 6-(tert-butoxycarbonyl) quinolylamine
[changing 34]
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) two t-butyl carbonate, reflux 20 hours under nitrogen atmosphere.
After reaction terminates, remove THF with rotatory evaporator, add ethyl acetate, after water, saturated aqueous common salt cleaning, use anhydrous magnesium sulfate drying.After excessively filtering anhydrous magnesium sulfate, with rotatory evaporator except desolventizing, recrystallization is carried out to the mixed solvent (1:4 volume ratio) of residue with ethyl acetate and normal hexane, obtain the solid 7.29g (86%) of white.
The synthesis of (the second operation) 6-(tert-butoxycarbonyl) amino-1,2,3,4-tetrahydroquinolines
[changing 35]
5.00g (20.4 mmole) is taken by 6-(tert-butoxycarbonyl) quinolylamine of the first operation gained and 0.50g10 quality % palladium carbon in two mouthfuls of flasks of 100mL, add 50mL methyl alcohol, after fully carrying out nitrogen displacement, be replaced as hydrogen atmosphere, at 60 DEG C, carry out vigorous stirring.
After reaction terminates, with glass filter palladium carbon, with rotatory evaporator, filtrate is carried out to the removing of solvent.The residue of gained is dissolved in acetone, add gac and stir a moment, filter activity charcoal, after rotatory evaporator removing acetone, carry out recrystallization with the mixing solutions (2:3 mass ratio) of normal hexane and ethyl acetate, obtain the vitreous solid 3.65g (yield: 72%) of white.
The synthesis of amino-1,2,3, the 4-tetrahydroquinolines of (the 3rd operation) 1-(4-nitrophenyl)-6-
[changing 36]
In two mouthfuls of flasks of 100mL, add 0.615g (14.1 mmole) sodium hydride (purity 55%), 20mL dewaters DMF, stir while drip by the 6-(tert-butoxycarbonyl) of the second operation gained amino-1 with the condition being no more than 30 DEG C under nitrogen atmosphere, 2,3, DMF solution (the 6-(tert-butoxycarbonyl) amino-1 of 4-tetrahydroquinoline, 2,3,4-tetrahydroquinoline: 3.50g (14.1 mmole), DMF:20mL).After dropping terminates, stir 2 hours.The DMF solution (4-fluoronitrobenzene: 2.19g (15.5 mmole), DMF:20mL) of 4-fluoronitrobenzene is dripped, under nitrogen atmosphere, in stirring at room temperature 20 hours in this reaction soln.
After reaction terminates, stirring reaction solution injects 30mL pure water on one side at leisure, and solid is separated out, and filters the solid of separating out, it is dissolved in DMF again, injects 100mL pure water and makes its redeposition, filtered and recycled solid again.By carrying out dispersion cleaning with normal hexane, and carry out vacuum-drying, thus obtain yellow solid.4N hydrochloric acid-ethyl acetate solution is added for this solid, stirs 2 hours at 40 DEG C.In reaction soln, add pure water, reclaim water layer, with sodium bicarbonate neutralization, add ethyl acetate and extract, clean with water, saturated aqueous common salt, be dried with anhydrous magnesium sulfate.After excessively filtering anhydrous magnesium sulfate, with rotatory evaporator except desolventizing, purifying is carried out to residue column chromatography (the mixed solvent 1:1 volume ratio of ethyl acetate and ethylene dichloride), obtains yellow solid 2.20g (yield: 58%).
The synthesis of amino-1,2,3, the 4-tetrahydroquinolines [diamines-4 (Diamine-4)] of (the 4th operation) 1-(4-aminophenyl)-6-
[changing 37]
1-(4-the nitrophenyl)-6-amino-1 of 10.0 (37.1 mmoles) by the 3rd operation gained is taken 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 nitrogen displacement, be replaced as hydrogen atmosphere, at room temperature carry out vigorous stirring.
After reaction terminates, with glass filter palladium carbon, with rotatory evaporator, filtrate is carried out to the removing of solvent.The residue of gained is dissolved in acetone, add gac and stir a moment, filter activity charcoal, after rotatory evaporator removing acetone, carry out recrystallization with the mixing solutions (5:1 mass ratio) of normal hexane and ethyl acetate, obtain the solid 7.30g (yield: 82%) of the lilac as targeted diamine (Diamine-4).Its structure is used 1h-NMR spectrum confirms.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)
The synthesis of (synthesis comparative example 1) 1-(4-aminophenyl)-5-amino indole [diamines-5 (Diamine-5)]
[changing 38]
The synthesis of (the first operation) 1-(4-nitrophenyl)-5-nitroindoline
[changing 39]
In two mouthfuls of flasks of 500mL, add 4.48g (101.8 mmole) sodium hydride (purity 55%), 50mL dewaters DMF, stir the DMF solution (5-nitroindoline: 15.0g (92.5 mmole), DMF:100mL) dripping 5-nitroindoline with the condition being no more than 30 DEG C under nitrogen atmosphere.After dropping terminates, at room temperature stir 2 hours.The DMF solution (4-fluoronitrobenzene: 13.1g (92.5 mmole), DMF:100mL) of 4-fluoronitrobenzene is dripped, under nitrogen atmosphere, in stirring at room temperature 6 hours in this reaction soln.
After reaction terminates, stirring reaction solution injects 100mL pure water on one side at leisure, and solid is separated out, and filters the solid of separating out, it is dissolved in DMF again, injects 500mL pure water and makes its redeposition, filtered and recycled solid again.Dispersion cleaning is carried out to the solids with methanol of gained, normal hexane, makes its vacuum-drying, thus obtain yellow solid 25.0g (yield 95%).
The synthesis of (the second operation) 1-(4-aminophenyl)-5-amino indole [diamines-5 (Diamine-5)]
[changing 40]
20.0g (70.6 mmole) is taken by 1-(4-the nitrophenyl)-5-nitroindoline of the first operation gained and 2.00g10 quality % palladium carbon in the four-hole boiling flask of 500mL, add 300mL ethanol, after fully carrying out nitrogen displacement, be replaced as hydrogen atmosphere, reflux 42 hours.
After reaction terminates, with glass filter palladium carbon, with rotatory evaporator, filtrate is carried out to the removing of solvent.The residue of gained is dissolved in acetone, add gac and stir a moment, filter activity charcoal, after rotatory evaporator removing acetone, clean residue with normal hexane, thus obtain the solid 15.0g (yield: 95%) as the lightpink of targeted diamine (Diamine-5).Its structure is used 1h-NMR spectrum confirms.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)
[synthesis of polyamic acid and polyimide and the preparation of liquid crystal aligning agent]
The abbreviation of the compound of following use is as follows.In addition, the raw material of the polymkeric substance synthesized in each embodiment and comparative example and the composition of liquid crystal aligning agent are shown in 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:1,4-phenylenediamine
DDM:4,4-diaminodiphenyl-methane
C16DAB:4-n-Hexadecane Oxy-1,3-diaminobenzene
[changing 42]
< condensing agent >
DMT-MM:4-(4,6-dimethoxy-1,3,5-triazines-2-base) 4-methoxyl group morpholine hydrochloride n hydrate
< organic solvent >
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 measures as follows: measure this polymkeric substance by GPC (normal temperature gel permeation chromatography) device, calculate number-average molecular weight and weight-average molecular weight as polyoxyethylene glycol, polyethylene oxide scaled value.
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 DEG C
Elutriant: DMF (as additive, lithiumbromide-hydrate (LiBrH 2o) be 30 mmoles/L, phosphoric anhydride crystallization (o-phosphoric acid) is 30 mmoles/L, tetrahydrofuran (THF) (THF) is 10ml/L)
Flow velocity: 1.0ml/ minute
Calibration curve making standard test specimen: Dong Cao company (East ソ ー society) TSK standard polyethylene oxide (molecular weight is about 900000,150000,100000,30000) processed and Polymer 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 measures as follows.The polyimide powder of 20mg is joined NMR stopple coupon (specification of wasteland's science Co., Ltd. (wasteland's science society) NMR stopple coupon processed), add the deuterated dimethylsulfoxide (DMSO-d6,0.05%TMS mixture) of 0.53ml, make it dissolve completely by ultrasonic wave.For this solution, determine the proton N MR of 500MHz with the NMR determinator (JNW-ECA500) that NEC Dan Ding Co., Ltd. (Japanese Electricity デ ー タ system society) makes.Imide rate is tried to achieve as follows: the proton coming from unconverted structure before and after imidization is decided to be standard proton, uses the peak integrated value of this proton and the proton peak integrated value of the NH base from amido acid that occurs near 9.5 ~ 10.0ppm to be tried to achieve by following formula.In above-mentioned formula, x is the integrated value of the proton peak of the NH base coming from amido acid, and y is the integrated value at standard proton peak, and α is the number ratio relative to the standard proton of 1 NH matrix of amido acid time polyamic acid (imide rate is 0%).
Imide rate (%)=(1-α x/y) × 100
(embodiment 1) adopts the synthesis of the polyamic acid of CBDA/Diamine-1
Add in the four-hole boiling flask of 50mL 1.50g (6.65 mmole) as diamine component by the NMP of Diamine-1,15.3g of synthetic example 1 gained, be cooled to about 10 DEG C, add the CBDA of 1.22g (6.20 mmole), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-1) is the solution of 15 quality %.
Polyamic acid (PAA-1) solution 15.0g is transferred in the Erlenmeyer flask of 50mL, the BC adding NMP, 7.50g of 15.0g dilutes, the solution of to make polyamic acid (PAA-1) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains liquid crystal aligning agent-1 of the present invention.The number-average molecular weight of this polyamic acid is 12300, and weight-average molecular weight is 33100.
(embodiment 2) adopts the synthesis of the polyamic acid of CBDA/Diamine-2
Add in the four-hole boiling flask of 50mL 1.50g (6.25 mmole) as diamine component by the NMP of Diamine-2,15.0g of synthetic example 2 gained, be cooled to about 10 DEG C, add the CBDA of 1.14g (5.80 mmole), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-2) is the solution of 15 quality %.
Polyamic acid (PAA-2) solution 15.0g is transferred in the Erlenmeyer flask of 50mL, the BC adding NMP, 7.50g of 15.0g dilutes, the solution of to make polyamic acid (PAA-2) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains liquid crystal aligning agent-2 of the present invention.The number-average molecular weight of this polyamic acid is 13700, and weight-average molecular weight is 35600.
(embodiment 3) adopts the synthesis of the polyamic acid of CBDA/Diamine-3
Add in the four-hole boiling flask of 50mL 1.50g (5.80 mmole) as diamine component by the NMP of Diamine-3,14.3g of synthetic example 3 gained, be cooled to about 10 DEG C, add the CBDA of 1.02g (5.20 mmole), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-3) is the solution of 15 quality %.
Polyamic acid (PAA-3) solution 15.0g is transferred in the Erlenmeyer flask of 50mL, the BC adding NMP, 7.50g of 15.0g dilutes, the solution of to make polyamic acid (PAA-3) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains liquid crystal aligning agent-3 of the present invention.The number-average molecular weight of this polyamic acid is 11000, and weight-average molecular weight is 31300.
(embodiment 4) adopts the synthesis of the polyamic acid of CBDA/Diamine-4
Add in the four-hole boiling flask of 50mL 1.50g (6.25 mmole) as diamine component by the NMP of Diamine-4,15.0g of synthetic example 4 gained, be cooled to about 10 DEG C, add the CBDA of 1.14g (5.80 mmole), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-4) is the solution of 15 quality %.
Polyamic acid (PAA-4) solution 15.0g is transferred in the Erlenmeyer flask of 50mL, the BC adding NMP, 7.50g of 15.0g dilutes, the solution of to make polyamic acid (PAA-4) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains liquid crystal aligning agent-4 of the present invention.The number-average molecular weight of this polyamic acid is 14200, and weight-average molecular weight is 36700.
(comparative example 1) adopts the synthesis of the polyamic acid of CBDA/Diamine-5
Add in the four-hole boiling flask of 50mL 1.50g (6.75 mmole) as diamine component by the NMP of Diamine-5,15.4g of synthesis comparative example 1 gained, be cooled to about 10 DEG C, add the CBDA of 1.23g (6.25 mmole), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-5) is the solution of 15 quality %.
The solution 15.0g of this polyamic acid (PAA-5) is transferred in the Erlenmeyer flask of 50mL, the BC adding NMP, 7.50g of 15.0g dilutes, the solution of to make polyamic acid (PAA-5) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains the liquid crystal aligning agent-5 as comparison other.The number-average molecular weight of this polyamic acid is 12300, and weight-average molecular weight is 32100.
(embodiment 5) adopts the synthesis of the soluble polyimide of CBDA/Diamine-1, C16DAB
Add in the four-hole boiling flask of 50mL 2.00g (8.88 mmole) as diamine component by the NMP of C16DAB, 27.2g of Diamine-1,0.774g (2.22 mmole) of synthetic example 1 gained, be cooled to about 10 DEG C, add the CBDA of 1.81g (10.3 mmole), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-6) is the solution of 15 quality %.
The NMP adding 30.0g in the solution 20g of polyamic acid (PAA-6) dilutes, then adds 2.19g diacetyl oxide and 0.90g pyridine, reacts 3 hours at 40 DEG C.After this reaction soln is cooled to room temperature, stirs in the methyl alcohol 180mL slowly pouring into and be cooled to about 10 DEG C, solid is separated out.Reclaim the solid of precipitation, then carry out with methyl alcohol 100mL the dispersion cleaning amounting to 2 times, at 100 DEG C, carry out drying under reduced pressure, thus 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, imide rate is 81%.
In the polyimide (SPI-1) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.In this solution, add the γ-BL of 8.0g, the BC of 12.0g again, stir 20 hours in 50 DEG C, obtain that polyimide (SPI-1) is 5 quality %, the liquid crystal aligning agent-6 of γ-BL to be 65 quality %, BC be 30 quality %.
(embodiment 6) adopts the synthesis of the soluble polyimide of CBDA/Diamine-2, C16DAB
Add in the four-hole boiling flask of 50mL 2.00g (8.36 mmole) as diamine component by the NMP of C16DAB, 6.3g of Diamine-2,0.728g (2.09 mmole) of synthetic example 2 gained, be cooled to about 10 DEG C, add the CBDA of 1.90g (9.71 mmole), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-7) is the solution of 15 quality %.
The NMP adding 30.0g in the solution 20g of polyamic acid (PAA-7) dilutes, then adds 2.12g diacetyl oxide and 0.88g pyridine, reacts 3 hours at 40 DEG C.After this reaction soln is cooled to room temperature, stirs in the methyl alcohol 160mL slowly pouring into and be cooled to about 10 DEG C, solid is separated out.Reclaim the solid of precipitation, then carry out with methyl alcohol 100mL the dispersion cleaning amounting to 2 times, at 100 DEG C, carry out drying under reduced pressure, thus 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, imide rate is 80%.
In the polyimide (SPI-2) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.In this solution, add the γ-BL of 8.0g, the BC of 12.0g again, stir 20 hours in 50 DEG C, obtain that polyimide (SPI-2) is 5 quality %, the liquid crystal aligning agent-7 of γ-BL to be 65 quality %, BC be 30 quality %.
(embodiment 7) adopts the synthesis of the soluble polyimide of CBDA/Diamine-3, C16DAB
Add in the four-hole boiling flask of 50mL 2.00g (7.47 mmole) as diamine component by the NMP of C16DAB, 24.7g of Diamine-3,0.651g (1.87 mmole) of synthetic example 3 gained, be cooled to about 10 DEG C, add the CBDA of 1.51g (8.68 mmole), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-8) is the solution of 15 quality %.
The NMP adding 30.0g in the solution 20g of polyamic acid (PAA-8) dilutes, then adds 2.00g diacetyl oxide and 0.83g pyridine, reacts 3 hours at 40 DEG C.After this reaction soln is cooled to room temperature, stirs in the methyl alcohol 160mL slowly pouring into and be cooled to about 10 DEG C, solid is separated out.Reclaim the solid of precipitation, then carry out with methyl alcohol 100mL the dispersion cleaning amounting to 2 times, at 100 DEG C, carry out drying under reduced pressure, thus 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, imide rate is 81%.
In the polyimide (SPI-3) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.In this solution, add the γ-BL of 8.0g, the BC of 12.0g again, stir 20 hours in 50 DEG C, obtain that polyimide (SPI-3) is 5 quality %, the liquid crystal aligning agent-8 of γ-BL to be 65 quality %, BC be 30 quality %.
(embodiment 8) adopts the synthesis of the soluble polyimide of CBDA/Diamine-4, C16DAB
Add in the four-hole boiling flask of 50mL 2.00g (8.36 mmole) as diamine component by the NMP of C16DAB, 6.3g of Diamine-4,0.728g (2.09 mmole) of synthetic example 4 gained, be cooled to about 10 DEG C, add the CBDA of 1.90g (9.71 mmole), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-8) is the solution of 15 quality %.
The NMP adding 30.0g in the solution 20g of polyamic acid (PAA-8) dilutes, then adds 2.12g diacetyl oxide and 0.88g pyridine, reacts 3 hours at 40 DEG C.After this reaction soln is cooled to room temperature, stirs in the methyl alcohol 180mL slowly pouring into and be cooled to about 10 DEG C, solid is separated out.Reclaim the solid of precipitation, then carry out with methyl alcohol 100mL the dispersion cleaning amounting to 2 times, at 100 DEG C, carry out drying under reduced pressure, thus 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, imide rate is 82%.
In the polyimide (SPI-4) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.In this solution, add the γ-BL of 8.0g, the BC of 12.0g again, stir 20 hours in 50 DEG C, obtain that polyimide (SPI-4) is 5 quality %, the liquid crystal aligning agent-9 of γ-BL to be 65 quality %, BC be 30 quality %.
(comparative example 2) adopts the synthesis of the soluble polyimide of CBDA/Diamine-5, C16DAB
Add in the four-hole boiling flask of 50mL 2.00g (8.96 mmole) as diamine component by the NMP of C16DAB, 27.3g of Diamine-5,0.781g (2.24 mmole) of synthesis comparative example 1 gained, be cooled to about 10 DEG C, add the CBDA of 2.04g (10.4 mmole), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-9) is the solution of 15 quality %.
The NMP adding 30.0g in the solution 20g of polyamic acid (PAA-9) dilutes, then adds 2.20g diacetyl oxide and 0.91g pyridine, reacts at 40 DEG C, but after being through for some time, starting gelation and cannot stir.Fail to prepare soluble polyimide (SPI-5).Therefore, the liquid crystal aligning agent-10 as comparison other cannot be prepared.
(embodiment 9)
< adopts the synthesis > of the polyamic acid of CBDA/Diamine-1, DDM
Add in the four-hole boiling flask of 50mL 2.50g (11.1 mmole) as diamine component by NMP, 17.9g of DDM, 17.9g of Diamine-1,0.943g (4.77 mmole) of synthetic example 1 gained γ-BL, be cooled to about 10 DEG C, add the CBDA of 2.89g (14.8 mmole), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-10) is the solution of 15 quality %.
This polyamic acid (PAA-10) solution 30.0g is transferred in the Erlenmeyer flask of 100mL, add the γ-BL of NMP, 2.20g of 28.0g, the BC of 15.0g dilutes, to make polyamic acid (PAA-10) be 6 quality %, NMP is 54 quality %, the solution of γ-BL to be 20 quality %, BC be 20 quality %, obtains fusion polyamic acid solution (BL-PAA1).The number-average molecular weight of this polyamic acid is 10400, and weight-average molecular weight is 29100.
< adopts the synthesis > of the soluble polyimide of TDA/p-PDA, C16DAB
The NMP of C16DAB, 35.4g of p-PDA, 0.718g as diamine component (2.06 mmole) of 2.00g (18.5 mmole) is added in the four-hole boiling flask of 50mL, be cooled to about 10 DEG C, add the TDA of 6.12g (20.4 mmole), under nitrogen atmosphere, in 40 DEG C of reactions 20 hours, the concentration obtaining polyamic acid (PAA-15) was the solution of 20 quality %.
The NMP adding 93.3g in the solution 40.0g of polyamic acid (PAA-15) dilutes, then adds the diacetyl oxide of 9.51g and the pyridine of 7.36g, reacts 3 hours at 40 DEG C.After this reaction soln is cooled to room temperature, stirs in the methyl alcohol 500mL slowly pouring into and be cooled to about 10 DEG C, solid is separated out.Reclaim the solid of precipitation, then carry out with methyl alcohol 300mL the dispersion cleaning amounting to 2 times, at 100 DEG C, carry out drying under reduced pressure, thus 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, imide rate is 85%.
In the polyimide (SPI-6) of 7.00g, add the γ-BL of 80.5g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.In this solution, add the γ-BL of 29.2g again, stir 20 hours in 50 DEG C, make the solution that polyimide (SPI-6) is 6 quality %, γ-BL is 94 quality %, obtain fusion polyimide solution (BL-SPI).
The preparation > of < fusion class liquid crystal aligning agent
The obtained fusion polyamic acid solution (BL-PAA1) of 40g is taken in the Erlenmeyer flask of 200mL, add the obtained fusion polyimide solution (BL-SPI) of 10.0g again, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-1.
(embodiment 10)
< adopts the synthesis > of the polyamic acid of CBDA/Diamine-2, DDM
Add in the four-hole boiling flask of 50mL 2.50g (10.4 mmole) as diamine component by NMP, 17.3g of DDM, 17.3g of Diamine-2,0.887g (4.47 mmole) of synthetic example 2 gained γ-BL, be cooled to about 10 DEG C, add the CBDA of 2.72g (13.9 mmole), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-11) is the solution of 15 quality %.
This polyamic acid (PAA-11) solution 30.0g is transferred in the Erlenmeyer flask of 100mL, add the γ-BL of NMP, 2.20g of 28.0g, the BC of 15.0g dilutes, to make polyamic acid (PAA-11) be 6 quality %, NMP is 54 quality %, the solution of γ-BL to be 20 quality %, BC be 20 quality %, obtains fusion polyamic acid solution (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
The obtained fusion polyamic acid solution (BL-PAA2) of 40g is taken respectively in the Erlenmeyer flask of 200mL, add with obtained fusion polyimide solution (BL-SPI) 10.0g of method similarly to Example 9 again, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-2.
(embodiment 11)
< adopts the synthesis > of the polyamic acid of CBDA/Diamine-3, DDM
Add in the four-hole boiling flask of 50mL 2.50g (9.35 mmole) as diamine component by NMP, 16.2g of DDM, 16.2g of Diamine-3,0.794g (4.01 mmole) of synthetic example 3 gained γ-BL, be cooled to about 10 DEG C, add the CBDA of 2.43g (12.4 mmole), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-12) is the solution of 15 quality %.
This polyamic acid (PAA-12) solution 30.0g is transferred in the Erlenmeyer flask of 100mL, add the γ-BL of NMP, 2.20g of 28.0g, the BC of 15.0g dilutes, to make polyamic acid (PAA-12) be 6 quality %, NMP is 54 quality %, the solution of γ-BL to be 20 quality %, BC be 20 quality %, obtains fusion polyamic acid solution (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
The obtained fusion polyamic acid solution (BL-PAA3) of 40g is taken respectively in the Erlenmeyer flask of 200mL, add with obtained fusion polyimide solution (BL-SPI) 10.0g of method similarly to Example 9 again, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-3.
(embodiment 12)
< adopts the synthesis > of the polyamic acid of CBDA/Diamine-4, DDM
Add in the four-hole boiling flask of 50mL 2.50g (10.4 mmole) as diamine component by NMP, 17.3g of DDM, 17.3g of Diamine-4,0.887g (4.47 mmole) of synthetic example 4 gained γ-BL, be cooled to about 10 DEG C, add the CBDA of 2.72g (13.9 mmole), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-13) is the solution of 15 quality %.
This polyamic acid (PAA-13) solution 30.0g is transferred in the Erlenmeyer flask of 100mL, add the γ-BL of NMP, 2.20g of 28.0g, the BC of 15.0g dilutes, to make polyamic acid (PAA-13) be 6 quality %, NMP is 54 quality %, the solution of γ-BL to be 20 quality %, BC be 20 quality %, obtains fusion polyamic acid solution (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
The obtained fusion polyamic acid solution (BL-PAA4) of 40g is taken respectively in the Erlenmeyer flask of 200mL, add with obtained fusion polyimide solution (BL-SPI) 10.0g of method similarly to Example 9 again, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-4.
(comparative example 3)
< adopts the synthesis > of the polyamic acid of CBDA/Diamine-5, DDM
Add in the four-hole boiling flask of 50mL 2.50g (11.2 mmole) as diamine component by NMP, 18.1g of DDM, 18.1g of Diamine-5,0.952g (4.80 mmole) of synthesis comparative example 1 gained γ-BL, be cooled to about 10 DEG C, add the CBDA of 2.92g (14.9 mmole), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-14) is the solution of 15 quality %.
This polyamic acid (PAA-14) solution 30.0g is transferred in the Erlenmeyer flask of 100mL, add the γ-BL of NMP, 2.20g of 28.0g, the BC of 15.0g dilutes, to make polyamic acid (PAA-14) be 6 quality %, NMP is 54 quality %, the solution of γ-BL to be 20 quality %, BC be 20 quality %, obtains fusion polyamic acid solution (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
The obtained fusion polyamic acid solution (BL-PAA4) of 40g is taken respectively in the Erlenmeyer flask of 200mL, add with obtained fusion polyimide solution (BL-SPI) 10.0g of method similarly to Example 9 again, 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 as diamine component (2.57 mmole) of CBDE, 250g (23.1 mmole) of 6.35g (24.4 mmole) is added in the four-hole boiling flask of 100mL, be cooled to about 10 DEG C, add the DMT-MM of 21.3g (77.1 mmole), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining poly amic acid ester (PAE-1) is the solution of 12 quality %.
In the solution of this polyamic acid (PAE-1), add the NMP of 81.2g, stir in the methyl alcohol 1.0L pouring at leisure and be cooled to about 10 DEG C, solid is separated out.Reclaim the solid of precipitation, then carry out with methyl alcohol 500mL the dispersion cleaning amounting to 2 times, at 100 DEG C, carry out drying under reduced pressure, thus 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.
In this poly amic acid ester (PAE-1) 7.00g, add the γ-BL of 80.5g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.In this solution, add the γ-BL of 29.2g again, stir 20 hours in 50 DEG C, make the solution that poly amic acid ester (PAE-1) is 6 quality %, γ-BL is 94 quality %, obtain fusion polyamic acid ester solution (BL-PAE).
The preparation > of < fusion class liquid crystal aligning agent
The fusion polyamic acid solution (BL-PAA1) that the use method similarly to Example 9 of 40g is obtained is taken in the Erlenmeyer flask of 200mL, add the obtained fusion polyamic acid ester solution (BL-PAE) of 10.0g again, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-6.
(embodiment 14)
The fusion polyamic acid solution (BL-PAA2) that the use method similarly to Example 10 of 40g is obtained is taken in the Erlenmeyer flask of 200mL, add the fusion polyamic acid ester solution (BL-PAE) that the use method similarly to Example 13 of 10.0g is obtained again, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-7.
(embodiment 15)
The fusion polyamic acid solution (BL-PAA3) that the use method similarly to Example 11 of 40g is obtained is taken in the Erlenmeyer flask of 200mL, add the fusion polyamic acid ester solution (BL-PAE) that the use method similarly to Example 13 of 10.0g is obtained again, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-8.
(embodiment 16)
The fusion polyamic acid solution (BL-PAA4) that the use method similarly to Example 12 of 40g is obtained is taken in the Erlenmeyer flask of 200mL, add the fusion polyamic acid ester solution (BL-PAE) that the use method similarly to Example 13 of 10.0g is obtained again, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-9.
(comparative example 4)
The fusion polyamic acid solution (BL-PAA5) obtained by the method same with comparative example 3 of 40g is taken in the Erlenmeyer flask of 200mL, add the fusion polyamic acid ester solution (BL-PAE) that the use method similarly to Example 13 of 10.0g is obtained again, stir 20 hours under nitrogen atmosphere, obtain fusion class liquid crystal aligning agent BL-10 (comparative example).
(test example 1) varnish (liquid crystal aligning agent) printing is tested
Utilize flexographic printing process will to be coated on the Cr plate of cleaning by embodiment 1 ~ 16 and the obtained liquid crystal aligning agent of comparative example 1 ~ 4 with alignment films printing press (Nissha Printing Co., Ltd (Japan description printing society) system " オ Application グ ス ト ロ ー マ ー "), thus carry out coating test.Anilox roller (Anilox roll) drips the liquid crystal aligning agent of about 1.0mL, and after implementing 10 idlings, printing press shuts down 10 minutes, makes press plate dry.Then, 1 piece of Cr substrate prints, the substrate after printing is placed on hot-plate upper 5 minute of 70 DEG C, carries out the predrying of film, observe membrane stage.Observation is by visual and observe with 50 times with opticmicroscope (Nikon Corp. (ニ コ Application society) system " ECLIPSE ME600 ").Evaluate as follows: the situation not observing pore is designated as well, the situation observing pore is designated as bad, in addition, the situation that the thickness of edge part is not uneven is designated as well, situation uneven for the thickness of edge part is designated as bad.Result is shown in table 3.
[making of liquid crystal cell]
For the liquid crystal aligning agent obtained by embodiment 1 ~ 16 and comparative example 1 ~ 4, make liquid crystal cell according to method as follows.Be spun on by liquid crystal aligning agent on the glass substrate with transparency electrode, on the hot-plate of 80 DEG C after dry 70 seconds, the hot-plate of 220 DEG C carries out 10 minutes burn till, and forming thickness is the film of 100nm.For the liquid crystal aligning process utilizing friction to carry out orientation, the friction gear being 120mm with roller footpath rubs to this coated surface with artificial silk cloth under the condition that roller rotating speed is 1000rpm, roller gait of march is 50mm/ second, intrusion is 0.3mm, obtains the substrate being with liquid crystal orientation film.
Prepare 2 and carry out the substrate with liquid crystal orientation film of this liquid crystal aligning process, the liquid crystal aligning face of a slice wherein scatters the spacer of 6 μm, then printing and sealing agent thereon, fit another plate base to make liquid crystal aligning face relatively and frictional direction orthogonal (Twisted Nematic liquid crystal structure cell), then sealant cures is made, obtained negative crystal born of the same parents.When for Twisted Nematic liquid crystal structure cell, in this negative crystal born of the same parents, inject liquid crystal MLC-2003 (Merck & Co., Inc. (メ ルク society) system) by decompression injection method, sealing inlet, obtains Twisted Nematic liquid crystal structure cell.
The mensuration of the ion density before and after (test example 2) high-temperature circulation test
For the liquid crystal cell made by the method recorded in above-mentioned [making of liquid crystal cell], measure the ion density of original state, in addition, be carried out at the mensuration of the ion density after 100 DEG C of maintenances 30 hours (high temperature ageing).During ion density measures, determine the ion density during choppy sea to liquid crystal cell applying voltage ± 10V, frequency 0.01Hz.Carry out at mensuration temperature is 80 DEG C.Determinator all uses Toyo Corp. (East Yang テ Network ニ カ society) make 6245 type liquid crystal evaluation of physical property devices.Result is shown in table 3.
Accumulated charge (RDC) before and after (test example 3) high-temperature circulation test measures
At the temperature of 23 DEG C, with the condition of the interval of 0.1V from OV to 1.0V, volts DS is applied to obtained liquid crystal cell, measure the flicker amplitude level under each voltage, make the calibration curve of the volts DS of flicker amplitude level and applying.Ground connection is after 5 minutes, and the condition reaching half with brightness applies voltage of alternating current (V 50) and volts DS 5.0V, measuring the flicker amplitude level after 1 hour, estimating RDC (flicker reference entry) by contrasting ready-made calibration curve.Then, volts DS is set to 0V, use the same method the RDC of estimation after 10 minutes, thus measure the decay of RDC.The RDC recorded thus is shown in the hurdle of " after DCon1 hour (accumulation) and the RDC after DCoff10 minute (decay) " of table 3.In addition, the data of the RDC shown in table 3 are results liquid crystal cell being kept at 100 DEG C the RDC after 30 hours (high temperature ageing).
The evaluation of (test example 4) orientation
By the liquid crystal cell that visual observation is obtained, observe the state of orientation of liquid crystal.Be designated as well by the situation of liquid crystal zero defect ground orientation, be designated as bad by the situation that orientation defect occurs, result is shown in table 3.
Consequently, embodiment 1 ~ 4 and comparative example 1 are the evaluations of the homopolymer (polyamic acid) that have employed diamines and CBDA, but adopt the embodiment 1 ~ 4 of diamine compound of the present invention compared with the comparative example 1 not using diamine compound of the present invention, accumulation (the RDC value after DCon1 hour) and the decay (the RDC value after DCoff10 minute) of RDC are significantly less.In addition, owing to being independent polyamic acid, therefore in printing, do not confirm large difference, but embodiment 1 ~ 4 is compared with comparative example 1, the ion density after original state and high temperature ageing is all little, is value no problem in practical.And, in embodiment 1 ~ 4, liquid crystal zero defect ground orientation, but the liquid crystal in comparative example 1 creates defect, and compared with embodiment 1 ~ 4, orientation is poor.
Embodiment 5 ~ 8 and comparative example 2 are the evaluations adopting soluble polyimide and obtain, adopt in the embodiment 5 ~ 8 of diamines of the present invention, can be made into soluble polyimide, being separated or separating out when printing can not occur, also do not have the uneven of pore and film, printing is good.In addition, in embodiment 5 ~ 8, accumulation and the decay of RDC also significantly reduce.And the ion density after original state and high temperature ageing is all little, is value no problem in practical.On the other hand, in employing as in the comparative example 2 of the Diamine-5 of the diamines of patent documentation 3, soluble polyimide can not made.In addition, in embodiment 5 ~ 8, liquid crystal zero defect ground orientation.
Embodiment 9 ~ 12 and comparative example 3 are soluble polyimides and adopt diamines of the present invention and the evaluation of the fusion class material of polyamic acid that obtains, due to the excellent compatibility of diamines of the present invention and soluble polyimide, therefore in the liquid crystal aligning agent of embodiment 9 ~ 12, there is not being separated or separating out when printing, also do not have the uneven of pore and film, printing is good.On the other hand, in comparative example 3, there is local existenceization and cause being separated in soluble polyimide and polyamic acid, and in this printing test, result is separated, and the printing of edge part is poor.In addition, in embodiment 9 ~ 12, the accumulation of RDC also significantly reduces compared with comparative example 3 with decay.And embodiment 9 ~ 12 is compared with comparative example 3, and the ion density after original state and high temperature ageing is all little, is value no problem in practical.In addition, in any one of embodiment 9 ~ 12, liquid crystal is zero defect ground orientation all.
Embodiment 13 ~ 16 and comparative example 4 are poly amic acid esters and adopt the diamines of the present invention etc. and the evaluation of the fusion class material of polyamic acid that obtains, due to the excellent compatibility of diamines of the present invention and poly amic acid ester, therefore in the liquid crystal aligning agent of embodiment 13 ~ 16, there is not being separated or separating out when printing, also do not have the uneven of pore and film, printing is good.On the other hand, the liquid crystal aligning agent of comparative example 4 is same with comparative example 3, and result is being separated property difference, and separative tendency during printing, the printing of edge part is poor.In addition, in embodiment 13 ~ 16, the accumulation of RDC also significantly reduces compared with comparative example 4 with decay.And embodiment 13 ~ 16 is compared with comparative example 4, and the ion density after original state and high temperature ageing is all little, is value no problem in practical.In addition, in any one of embodiment 13 ~ 16, liquid crystal is zero defect ground orientation all.
According to these results, for adopting diamines of the present invention and the liquid crystal aligning agent that obtain and liquid crystal orientation film, can confirm that printing well and can obtain the few and liquid crystal orientation film that the decay of accumulated charge is fast of accumulated charge.
[table 1]
Mol ratio is represented in ※ bracket.
[table 2]
Mol ratio is represented in ※ bracket.
[table 3]
The possibility that industry utilizes
Adopt diamines of the present invention and the printing of liquid crystal aligning agent that obtains is good and can obtain the few and liquid crystal orientation film that the decay of accumulated charge is fast of accumulated charge.Therefore, the liquid crystal display device using liquid crystal aligning agent of the present invention to obtain can be used as the high liquid crystal display device of reliability, is 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 (9)

1. with the diamines that following formula [1] represents,
[changing 1]
In formula [1], R 1~ R 9in R 2, R 7be primary amino, all the other are hydrogen atoms; N is 1 or 2, and the hydrogen atom forming ring filling hydrocarbon portion can be replaced by the alkyl of carbon number 1 ~ 6.
2. diamines as claimed in claim 1, it is characterized in that, the alkyl of described carbon number 1 ~ 6 is methyl.
3. diamines as claimed in claim 1, is characterized in that, represent with following formula [4-a] ~ [4-d],
[changing 4]
4. a polyimide precursor, is characterized in that, obtains by making at least one being selected from tetracarboxylic acid and derivative thereof react with the diamine component comprising diamines according to claim 1.
5. polyimide precursor as claimed in claim 4, is characterized in that, when the integral molar quantity of tetracarboxylic acid and derivative thereof is counted 100 % by mole, diamines according to claim 1 is 5 ~ 95 % by mole.
6. a polyimide, is characterized in that, obtains by carrying out imidization to polyimide precursor according to claim 4.
7. a liquid crystal aligning agent, is characterized in that, containing at least one being selected from polyimide precursor according to claim 4, polyimide precursor according to claim 5 and polyimide according to claim 6.
8. a liquid crystal orientation film, is characterized in that, by liquid crystal aligning agent according to claim 7 being coated substrate and carrying out burning till and obtain.
9. a liquid crystal display device, is characterized in that, has liquid crystal orientation film according to claim 8.
CN201180051325.7A 2010-08-31 2011-08-30 Diamines, polyimide precursor, polyimide, liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device Active CN103180294B (en)

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Families Citing this family (9)

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Publication number Priority date Publication date Assignee Title
CN104204925A (en) * 2012-03-30 2014-12-10 日产化学工业株式会社 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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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
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
WO2018110354A1 (en) * 2016-12-15 2018-06-21 日産化学工業株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using same
WO2019189637A1 (en) * 2018-03-30 2019-10-03 日産化学株式会社 Novel liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element
CN111732528B (en) * 2020-07-31 2021-01-01 南昌大学 Preparation method of N-aryl indoline derivative
CN111732516B (en) * 2020-07-31 2021-01-05 南昌大学 A kind ofNProcess for preparing (E) -aryl-substituted heterocyclic compounds

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (5)

* 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
JP4088985B2 (en) * 1997-05-09 2008-05-21 コニカミノルタホールディングス株式会社 Organic electroluminescence device using new amino compound
KR101026662B1 (en) * 2002-08-29 2011-04-04 닛산 가가쿠 고교 가부시키 가이샤 Material for liquid crystal alignment 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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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