CN102171604A - Liquid crystal aligning agent and liquid crystal display element using same - Google Patents

Liquid crystal aligning agent and liquid crystal display element using same Download PDF

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CN102171604A
CN102171604A CN200980140403.3A CN200980140403A CN102171604A CN 102171604 A CN102171604 A CN 102171604A CN 200980140403 A CN200980140403 A CN 200980140403A CN 102171604 A CN102171604 A CN 102171604A
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liquid crystal
aligning agent
polyamic acid
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polyimide
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CN102171604B (en
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野田尚宏
小田拓郎
筒井皇晶
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Abstract

A liquid crystal aligning agent capable of providing a liquid crystal alignment film which is not susceptible to film separation or chipping during rubbing, has high voltage holding ratio, and does not easily accumulate electrical charges at the initial stage even when a direct current voltage is applied to the liquid crystal cell. The liquid crystal aligning agent contains at least one kind of polymer selected from polyamic acids, each of which is obtained by reacting a diamine component containing a diamine represented by formula [1] with a tetracarboxylic acid dianhydride component, and polyimides obtained by imidizing the polyamic acids. (In the formula, X represents a single bond, an alkylene having 1-3 carbon atoms, -OCH2-, -CH2OCO-, -NHCO-, -CONH- or -COOCH2-; Y represents an oxygen atom or a sulfur atom; and any hydrogen atom in the five-membered ring can be substituted by an alkyl group having 1-5 carbon atoms).

Description

The liquid crystal display cells of aligning agent for liquid crystal and this aligning agent for liquid crystal of use
Technical field
The present invention relates to the used aligning agent for liquid crystal of liquid crystal display cells, liquid crystal orientation film and liquid crystal display cells.
Background technology
Now, as the liquid crystal orientation film of liquid crystal display cells, mainly using and burning till polyimide that get, so-called as the aligning agent for liquid crystal of major component through coating with polyimide precursor such as polyamic acid or soluble polyamide imide liquor is liquid crystal orientation film.
Liquid crystal orientation film is not only controlled the state of orientation of liquid crystal, and is also influential to the characteristic of liquid crystal display cells.Especially, be accompanied by the high resolving powerization of liquid crystal display cells, the contrast reduction of inhibition liquid crystal display cells or the characteristic of minimizing afterimage phenomena are increasingly important.
Polyimide is in the liquid crystal orientation film, known have a kind of short liquid crystal orientation film of image retention die-out time that is produced by DC voltage, and the aligning agent for liquid crystal that this liquid crystal orientation film uses also contains ad hoc structure tertiary amine (for example referring to patent documentation 1) except polyamic acid or containing the polyamic acid of imino group; Also have a kind of liquid crystal aligning to handle film, the aligning agent for liquid crystal of its use contains the soluble polyimide (for example referring to patent documentation 2) that uses the specific diamines with pyridine skeleton etc. in the raw material.
In addition, polyimide is in the liquid crystal orientation film, the short liquid crystal orientation film of image retention die-out time that also has a kind of voltage retention height and produce by DC voltage, the aligning agent for liquid crystal that this liquid crystal orientation film uses also very little contains the compound (for example referring to patent documentation 3) that the compound that is selected from molecule and contains 1 carboxylic acid group, compound that molecule contains 1 acid anhydride and molecule contain the compound of 1 uncle's amino except polyamic acid or its imide amination polymer etc.
Patent documentation 1: Japanese patent laid-open 9-316200 communique
Patent documentation 2: Japanese patent laid-open 10-104633 communique
Patent documentation 3: Japanese patent laid-open 8-76128 number public Reported
Though the facture to the liquid crystal display afterimage phenomena up to now can shorten the image retention die-out time, not talkative only this is exactly sufficient.
Summary of the invention
The present invention In view of the foregoing, its objective is provides a kind of aligning agent for liquid crystal, and this aligning agent for liquid crystal agent can access following liquid crystal orientation film: film is peeled off or cutting, voltage retention height and liquid crystal cell applied the savings that DC voltage also is difficult for causing the initial stage electric charge even be difficult for during friction taking place.
The inventor furthers investigate for achieving the above object, and the result has finished the present invention.That is, the present invention has following main points.
(1) aligning agent for liquid crystal, it contains at least a polymkeric substance of the polyimide that is selected from polyamic acid and is got by this polyamic acid imidizate, described polyamic acid gets by two amine components and the reaction of tetracarboxylic dianhydride's composition that makes the diamines that contains following formula [1] expression
Figure BPA00001347360900021
In the formula, X represent singly-bound, carbon number 1～3 alkylidene ,-OCH 2-,-CH 2OCO-,-NHCO-,-CONH-or-COOCH 2-, Y represents oxygen atom or sulphur atom, pentacyclic any hydrogen atom can be replaced by the alkyl of carbon number 1～5.
(2) as (1) described aligning agent for liquid crystal, wherein, the Y of formula [1] is an oxygen atom.
(3) as (1) described aligning agent for liquid crystal, wherein, the Y of formula [1] is a sulphur atom.
(4) as each described aligning agent for liquid crystal in (1)～(3), wherein, the X of formula [1] is-CH 2OCO-,-NHCO-or-COOCH 2-.
(5) as (1) described aligning agent for liquid crystal, wherein, the X of formula [1] is-CH 2OCO-,-NHCO-or-COOCH 2-, Y is an oxygen atom.
(6) as each described aligning agent for liquid crystal in (1)～(5), wherein, pentacyclic any hydrogen atom of formula [1] is by methyl substituted.
(7) liquid crystal orientation film, each described aligning agent for liquid crystal gets in (1)～(6) by using.
(8) liquid crystal display cells, it possesses (7) described liquid crystal orientation film.
(9) diamines of following formula [2] expression:
Figure BPA00001347360900031
In the formula, any hydrogen atom of furan nucleus can be replaced by the alkyl of carbon number 1～5.
(10) as (9) described diamines, wherein, any hydrogen atom of furan nucleus can be by methyl substituted.
(11) polyamic acid or by this polyamic acid imidizate polyimide, described polyamic acid contains (9) or (10) described diamines by making two amine components react with tetracarboxylic dianhydride's composition and get.
Aligning agent for liquid crystal of the present invention can access following liquid crystal orientation film: film is peeled off or cutting, voltage retention height and liquid crystal cell applied the savings that DC voltage also is difficult for causing the initial stage electric charge even be difficult for during friction taking place.By using this liquid crystal orientation film, can make the good liquid crystal display of characteristic.
Embodiment
Aligning agent for liquid crystal of the present invention contains that two amine components that are selected from by making the diamines that contains following formula [1] expression and tetracarboxylic dianhydride's composition react the polyamic acid that gets and at least a polymkeric substance of the polyimide that got by this polyamic acid imidizate.By using this diamines, even in liquid crystal aligning is handled in the necessary friction treatment, the film that also can alleviate when friction is peeled off or is cut, and the voltage retention height of gained liquid crystal orientation film is even and apply the savings that DC voltage also is difficult for causing the initial stage electric charge to liquid crystal cell.
The diamines of＜formula [1] 〉
There is no particular limitation for the synthetic method of the diamines of formula [1] expression, for example can synthesize by making it convert amino method to conventional method reduction nitro behind the dinitro compound of synthetic following formula [S1] expression.
Figure BPA00001347360900032
X in following formula [1] and the formula [S1] represent singly-bound, carbon number 1～3 alkylidene ,-OCH 2-,-CH 2OCO-,-NHCO-,-CONH-or-COOCH 2-.
In addition, the Y in following formula [1] and the formula [S1] represents oxygen atom or sulphur atom.
In addition, Y is that any hydrogen atom of the five-membered ring (below be also referred to as furan nucleus) of oxygen atom or the five-membered ring that Y is sulphur atom (below be also referred to as thiphene ring) can be replaced by the alkyl of carbon number 1～5.The replacement radix of furan nucleus or thiphene ring is preferably 0～2, is more preferably the nothing replacement.Thus, can obtain the patience that better rubs.
In following formula [1] and the formula [S1], the position that X is incorporated into furan nucleus or thiphene ring is not particularly limited, but preferably in two or three-digit.
Use X to be-CH 2OCO-or-the voltage retention of liquid crystal orientation film when forming liquid crystal display that the diamines of NHCO-obtains uprise.Moreover, if use X to be-CH 2The diamines of OCO-then can obtain liquid crystal aligning excellence, the difficult liquid crystal display of putting aside of electric charge, thereby better.
In the diamines of formula [1] expression, there is no particular limitation in each substituent position on the phenyl ring.The angle of the liquid crystal aligning from as liquid crystal orientation film the time is considered, position or contraposition between the position relation of 2 amino is preferably, and from the polyamic acid or the polyimide that improve polymerisation reactivity or gained the deliquescent angle of organic solvent is considered, more preferably between the position.Position between the position of 2 amino is closed and is, be 1, during 3-diaminobenzene structure, the optimum seeking site of X is at 4 or 5, particularly from effect that can improve amino nucleophilicity or the angle that is easy to synthesize, more preferably 5.
In the diamines of formula [1] expression, X is incorporated into the position of cis-diene ring (below be also referred to as furan nucleus or thiphene ring), and there is no particular limitation, considers from the complexity that obtains raw material, reactive equal angles, suitably selects described combination according to purpose.
The concrete example of (when being furan nucleus) was as follows when Y was oxygen atom, but was not limited thereto.
Figure BPA00001347360900041
(in the following formula, X represent singly-bound, carbon number 1～3 alkylidene ,-OCH 2-,-CH 2OCO-,-NHCO-,-CONH-or-COOCH 2-, R represents the alkyl of carbon number 1～5, n represents 0～3 integer).
In following formula [T1]～formula [T6], X is preferably-CH 2OCO-or-NHCO-, R is preferably the alkyl of carbon number 1～3, n is preferably 0 or 1 integer.In addition, in the following formula, from the solvent solubility of polyamic acid or polyimide, liquid crystal aligning, friction patience, savings electric charge (below be also referred to as RDC), the structure of preferred formula [T2] or formula [T5].
Especially preferred is that structure, the X with formula [T2] or formula [T5] is-CH 2OCO-or-NHCO-, R are that alkyl, the n of carbon number 1～3 is 0 or 1 integer.Use linking group X to be-CH 2OCO-or-the words voltage retention of the diamines of NHCO-uprises, and particularly uses linking group X to be-CH 2The words liquid crystal aligning of the diamines of OCO-is good especially, is preferred therefore.
The concrete example of (when being thiphene ring) was as follows when Y was sulphur atom, but was not limited thereto.
(in the following formula, X represent singly-bound, carbon number 1～3 alkylidene ,-OCH 2-,-CH 2OCO-,-NHCO-,-CONH-or-COOCH 2-, R represents the alkyl of carbon number 1～5, n represents 0～3 integer).
In following formula [U1]～formula [U6], X is preferably-CH 2OCO-or-NHCO-, R is preferably the alkyl of carbon number 1～3, n is preferably 0 or 1 integer.
In addition, in the following formula, from the solvent solubility of polyamic acid or polyimide, liquid crystal aligning, friction patience, savings electric charge (below be also referred to as RDC), the structure of preferred formula [U2] or formula [U5].
Especially preferred is that structure, the X with formula [U2] or formula [U5] is-CH 2OCO-or-NHCO-, R are that alkyl, the n of carbon number 1～3 is 0 or 1 integer.Use linking group X to be-CH 2OCO-or-the words voltage retention of the diamines of NHCO-uprises, and particularly uses linking group X to be-CH 2The words liquid crystal aligning of the diamines of OCO-is good especially, is preferred therefore.
Synthesizing of＜diamines 〉
Specific diamine compound of the present invention by the dinitro matrix of synthesis type [S1] expression after the reduction nitro make its convert to amino come synthetic.There is no particular limitation for the method for reduction dinitro compound, can exemplify use palladium-carbon, platinum oxide, draws Buddhist nun's nickel, platinum black, rhodium-aluminium oxide, platinum sulfide carbon etc. are as catalyzer, at ethyl acetate, toluene, tetrahydrofuran, two
Figure BPA00001347360900061
Alkane, alcohol are in the equal solvent, the method for reducing with hydrogen, hydrazine, hydrogen chloride etc.X in the following formula [S1] represent singly-bound, carbon number 1～3 alkylidene ,-OCH 2-,-CH 2OCO-,-NHCO-,-CONH-or-COOCH 2-, Y represents oxygen atom or sulphur atom, pentacyclic any hydrogen atom can be replaced by the alkyl of carbon number 1～5.
Figure BPA00001347360900062
The synthetic method of dinitro matrix is according to linking group and difference.
At X be-CH 2During OCO-, for example the condensation reaction by dinitro benzylalcohol and furancarboxylic acid or thiophene carboxylic acid can obtain the dinitro matrix.There is no particular limitation for method of condensing, can obtain dinitro matrix [S4] by dinitro benzylalcohol [S2] and carboxyl acyl chloride [S3] are reacted in the presence of alkali.Also can exemplify and in the presence of other dehydrating condensation agent, use alcohol and the method for carboxylic acid reaction etc.
Figure BPA00001347360900063
At X be-during NHCO-, for example the condensation reaction by dinitroaniline and furancarboxylic acid or thiophene carboxylic acid can obtain the dinitro matrix.There is no particular limitation for method of condensing, can obtain dinitro matrix [S7] by dinitroaniline [S5] and carboxyl acyl chloride [S6] are reacted in the presence of alkali.Also can exemplify method that in the presence of other dehydrating condensation agent, makes amine and carboxylic acid reaction etc.
At X be-COOCH 2In-time, for example the condensation reaction by dinitrobenzoic acid and furancarbinol or thenyl alcohol can obtain the dinitro matrix.There is no particular limitation for method of condensing, can obtain dinitro matrix [S10] by dinitrobenzoyl chloride [S8] and alcohol [S9] are reacted in the presence of alkali.Also can exemplify and in the presence of other dehydrating condensation agent, make alcohol and the method for carboxylic acid reaction etc.
By using the reagent or the good alkyl of addition in advance of addition alkyl on furan nucleus or thiphene ring, can obtain the furan nucleus (or thiphene ring) of attached side chain.
＜two amine components 〉
The diamines of following formula [1] expression and tetracarboxylic dianhydride's reaction can obtain polyamic acid, make this polyamic acid imidizate can obtain polyimide.Among the present invention, two used amine components can use the diamines of formula [1] expression separately during synthesizing polyamides acid, also can be used in combination and be selected from more than a kind or 2 kinds of other diamines.
As two amine components, the diamines that contains formula [1] expression can improve the polyamic acid of gained and make this polyamic acid imidizate and polyimide to the dissolubility of organic solvent.What is more, even the friction patience excellence of the liquid crystal orientation film that obtains by the aligning agent for liquid crystal that contains this polyamic acid or polyimide, voltage retention height and apply the savings that DC voltage also is difficult for generation initial stage electric charge to liquid crystal cell.For obtaining such characteristic, the diamines of formula [1] expression is preferably 10～100mol% of the synthetic middle two amine component total amounts of using of polyamic acid, and more preferably 20～100mol% is preferably 30～100mol% especially.
In above-mentioned two amine components, the diamines that is used in combination with the diamines of formula [1] expression is not particularly limited.The object lesson of these diamines is as follows.
As the example of ester ring type diamines, can exemplify 1,4-diamino-cyclohexane, 1,3-diamino-cyclohexane, 4,4 '-diamino-dicyclohexyl methane, 4,4 '-diamido-3,3 '-dimethyl dicyclohexyl amine, isophorone diamine etc.
Example as aromatic diamine, can exemplify o-phenylenediamine, m-phenylene diamine, p-phenylenediamine (PPD), 2, the 4-diaminotoluene, 2, the 5-diaminotoluene, 3, the 5-diaminotoluene, 3, the 5-diamino-N, N-diaryl aniline, 2, the 4-diamino-N, N '-diaryl aniline, 1,4-diamido-2-methoxybenzene, 2,5-diamido-P-xylene, 1,3-diamido-4-chlorobenzene, 3, the 5-diaminobenzoic acid, 1,4-diamido-2, the 5-dichloro-benzenes, 4,4 '-diaminostilbene, 2-diphenylethane, 4,4 '-diamido-2,2 '-dimethyl bibenzyl, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diamido-3,3 '-dimethyl diphenylmethane, 2,2 '-diamido Stilbene, 4,4 '-diamido Stilbene, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino-diphenyl sulfone, 3,3 '-diamino-diphenyl sulfone, 4,4 '-diaminobenzophenone, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 3, two (4-amino-benzene oxygen) benzoic acid of 5-, 4,4 '-two (4-amino-benzene oxygen) bibenzyl, 2, 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-, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1, two (4-aminophenyl) cyclohexanes of 1-, α, α '-two (4-4 aminophenyl)-1, the 4-diisopropylbenzene (DIPB), 9, two (4-aminophenyl) fluorenes of 9-, 2, two (3-aminophenyl) HFC-236fa of 2-, 2,2 '-two (4-aminophenyl) HFC-236fa, 4,4 '-diamino-diphenylamine, 2, the 4-diamino-diphenylamine, 1, the 8-diaminonaphthalene, 1, the 5-diaminonaphthalene, 1, the 5-diaminoanthraquinone-, 1,3-diamido pyrene, 1,6-diamido pyrene, 1,8-diamido pyrene, 2, the 7-diamino-fluorene, 1, two (4-aminophenyl) tetramethyl disiloxanes of 3-, biphenylamine, 2,2 '-dimethylbenzidine, 1, two (4-aminophenyl) ethane of 2-, 1, two (4-aminophenyl) propane of 3-, 1, two (4-aminophenyl) butane of 4-, 1, two (4-aminophenyl) pentanes of 5-, 1, two (4-aminophenyl) hexanes of 6-, 1, two (4-aminophenyl) heptane of 7-, 1, two (4-aminophenyl) octanes of 8-, 1, two (4-aminophenyl) nonanes of 9-, 1, two (4-aminophenyl) decane of 10-, 1, two (4-amino-benzene oxygen) propane of 3-, 1, two (4-amino-benzene oxygen) butane of 4-, 1, two (4-amino-benzene oxygen) pentanes of 5-, 1, two (4-amino-benzene oxygen) hexanes of 6-, 1, two (4-amino-benzene oxygen) heptane of 7-, 1, two (4-amino-benzene oxygen) octanes of 8-, 1, two (4-amino-benzene oxygen) nonanes of 9-, 1, two (4-amino-benzene oxygen) decane of 10-, two (4-aminophenyls) the third-1,3-two acid esters (Japanese: プ ロ パ Application-1,3-ジ オ エ one ト), two (4-aminophenyl) fourth-1,4-two acid esters, two (4-aminophenyls) penta-1,5-two acid esters, two (4-aminophenyls) own-1,6-two acid esters, two (4-aminophenyl) heptan-1,7-two acid esters, two (4-aminophenyls) suffering-1,8-two acid esters, two (4-aminophenyl) ninth of the ten Heavenly Stems-1,9-two acid esters, two (4-aminophenyl) last of the ten Heavenly stems-1,10-two acid esters, 1, two [4-(4-amino-benzene oxygen) phenoxy group] propane of 3-, 1, two [4-(4-amino-benzene oxygen) phenoxy group] butane of 4-, 1, two [4-(4-amino-benzene oxygen) phenoxy group] pentanes of 5-, 1, two [4-(4-amino-benzene oxygen) phenoxy group] hexanes of 6-, 1, two [4-(4-amino-benzene oxygen) phenoxy group] heptane of 7-, 1, two [4-(4-amino-benzene oxygen) phenoxy group] octanes of 8-, 1, two [4-(4-amino-benzene oxygen) phenoxy group] nonanes of 9-, 1, two [4-(4-amino-benzene oxygen) phenoxy group] decane of 10-etc.
As the example of hetero ring type diamines, can exemplify 2,6-diamino-pyridine, 2,4-diamino-pyridine, 2,4-diaminostilbene, 3,5-triazine, 2,7-diamido dibenzofurans, 3,6-diamido carbazole, 2,4-diamido-6-isopropyl-1,3,5-triazine, 2, two (the 4-aminophenyls)-1,3 of 5-, 4-
Figure BPA00001347360900091
Diazole etc.
As the example of aliphatic diamine, can exemplify 1, the 2-diaminoethanes, 1, the 3-diaminopropanes, 1, the 4-diaminobutane, 1,5-diamido pentane, 1, the 6-diamino hexane, 1,7-diamido heptane, 1,8-diamido octane, 1,9-diamido nonane, 1, the 10-diamino decane, 1,3-diamido-2, the 2-dimethylpropane, 1,6-diamido-2, the 5-dimethylhexane, 1,7-diamido-2, the 5-dimethyl heptane, 1,7-diamido-4, the 4-dimethyl heptane, 1,7-diamido-3-methylheptane, 1,9-diamido-5-methylheptane, 1,12-diamido dodecane, 1,18-diamido octadecane, 1,2-two (the amino propoxyl group of 3-) ethane etc.
As the example of aromatic-aliphatic diamines, can exemplify the diamines of formula [11] expression.
H 2N-Ar-R 1-NH-R 2 [11]
In the formula, Ar is phenylene or naphthylene, R 1Be the alkylidene of carbon number 1～5, R 2Be hydrogen atom or methyl.
Object lesson as the diamines of formula [11] expression can exemplify the 3-amino-benzylamine, the 4-amino-benzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminobenzene ethamine, 4-aminobenzene ethamine, 3-amino-N-Methylphenethylamine, 4-amino-N-Methylphenethylamine, 3-(3-aminopropyl) aniline, 4-(3-aminopropyl) aniline, 3-(3-methylamino propyl group) aniline, 4-(3-methylamino propyl group) aniline, 3-(the amino butyl of 4-) aniline, 4-(the amino butyl of 4-) aniline, 3-(4-methylamino butyl) aniline, 4-(4-methylamino butyl) aniline, 3-(the amino amyl group of 5-) aniline, 4-(the amino amyl group of 5-) aniline, 3-(5-methylamino amyl group) aniline, 4-(5-methylamino amyl group) aniline, 2-(the amino naphthyl of 6-) methylamine, 3-(the amino naphthyl of 6-) methylamine, 2-(the amino naphthyl of 6-) ethamine, 3-(the amino naphthyl of 6-) ethamine etc.
When the diamines of the diamines of formula [11] expression and formula [1] expression share, gained polyamic acid or polyimide (is polymkeric substance to call them in the following text) further improve the dissolubility of organic solvent, and the liquid crystal aligning excellence when using as liquid crystal orientation film, be preferred therefore.What is more, when share, can give play to the effect of the tilt angle of further increase liquid crystal with the diamines of increase liquid crystal pretilt angle described later (below be also referred to as the inclination diamines).Therefore, in the time will obtaining the tilt angle of identical size, even the consumption of inclination diamines also can obtain big tilt angle less.In addition, also be expected to improve the printing of aligning agent for liquid crystal.
The preferred content of the diamines of formula [11] expression is 10～80mol% of two amine component total amounts, more preferably 20～70mol%.
As the diamines (inclination diamines) of the tilt angle that can increase liquid crystal, can exemplify have chain alkyl, the diamines of substituting group that perfluoroalkyl, aromatic series ring-type base, aliphatics cyclic group or they combine, steroid class skeleton group etc.These diamines can share with the diamines of formula [1] expression.
Below exemplified object lesson, but the present invention is not limited thereto with described substituent diamines.In addition, below in illustrative formula [13]～formula [38], j represents 5～20 integer, k represents 1～20 integer.
Figure BPA00001347360900101
Figure BPA00001347360900121
Figure BPA00001347360900131
Figure BPA00001347360900141
In the above-mentioned diamines, the diamines of formula [12] is excellent preferred because of its liquid crystal aligning.The diamines of formula [19]～formula [26] can be very high because of manifesting of its tilt angle, so can be used for OCB (optical compensation curved) liquid crystal alignment films (hereinafter referred to as the OCB alignment films), vertically-oriented type liquid crystal alignment films (hereinafter referred to as the VA alignment films) suitably.
For example, the TN liquid crystal is with in the alignment films (tilt angle is 3～5 °), and the content of the diamines of formula [12] is preferably 10～30mol% of two amine component total amounts; With in the alignment films (tilt angle is 10～90 °), the content of the diamines of formula [19]～formula [26] is preferably 5～40mol% of two amine component total amounts to OCB, but is not limited thereto with alignment films or VA.
If consider the balance of each characteristic such as dissolubility, liquid crystal aligning, pitch angle, voltage retention, savings electric charge of the polyamic acid that uses in the aligning agent for liquid crystal of the present invention or polyimide, then for example when the diamines of use formula [1], formula [11] and formula [12] expression carries out polymerization, the preferred ratio of each two amine component is 10～50% (formula [1])/20～80% (formula [11])/10～30% (formula [12]) with molar ratio computing, be more preferably 20～40%/30～50%/10～30%, but be not limited thereto.
＜tetracarboxylic dianhydride composition 〉
In the polyamic acid or polyimide that aligning agent for liquid crystal of the present invention is essential, there is no particular limitation with tetracarboxylic dianhydride's composition of above-mentioned two amine components reaction.That is to say, not only can use a kind of tetracarboxylic dianhydride, also can the tetracarboxylic dianhydride more than 2 kinds share.
In the aligning agent for liquid crystal of the present invention, wait from the voltage retention of further raising liquid crystal cell, as with the tetracarboxylic dianhydride of aforementioned two amine components reaction, preferably use tetracarboxylic dianhydride with ester ring type structure or aliphatic structure.
As tetracarboxylic dianhydride, can exemplify 1,2,3 with ester ring type structure or aliphatic structure, 4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,2,3,4-cyclohexane tetracarboxylic dianhydride, 3,4-dicarboxyl-1-cyclohexyl succinic acid dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, [4-(2,5-dioxo tetrahydrofuran-3-yl)-1,2,3,4-naphthane-1, the 2-dicarboxylic anhydride], 1,2,3,4-butane tetracarboxylic acid dianhydride, dicyclo [3,3,0] octane-2,4,6, the 8-tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, suitable-3,7-dibutyl ring suffering-1,5-diene-1,2,5, the 6-tetracarboxylic dianhydride, three ring [4.2.1.02,5] nonane-3,4,7,8-tetrabasic carboxylic acid-3,4:7,8-dianhydride, six ring [6.6.0.12,7.03,6.19,14.010,13] hexadecane-4,5,11,12-tetrabasic carboxylic acid-4,5:11,12-dianhydride etc.Wherein, use 1,2,3, can obtain the alignment films of liquid crystal aligning excellence during 4-cyclo-butane tetracarboxylic dianhydride, thereby be preferred.
What is more, when share with aromatic tetracarboxylic acid's dianhydride, liquid crystal aligning raising and can accelerate the minimizing of the savings electric charge of liquid crystal structure cell.As aromatic tetracarboxylic acid's dianhydride, can exemplify pyromellitic acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride etc.Wherein, pyromellitic acid dianhydride is preferred especially.
Consider from the balance of each characteristic such as the dissolubility of the polyamic acid of gained or polyimide, liquid crystal aligning, voltage retention, savings electric charge, usage rate with the tetracarboxylic dianhydride of ester ring type structure or aliphatic structure and aromatic tetracarboxylic acid's dianhydride with the former/latter's molar ratio computing is preferably 90/10～50/50, more preferably 80/20～60/40.
＜polyreaction 〉
Among the present invention, there is no particular limitation for the polymerisation process of tetracarboxylic dianhydride's composition and two amine components.Generally can obtain polyamic acid to carry out polyreaction, obtain polyimide by making this polyamic acid dehydration closed-loop by in organic solvent, mixing.
As the method that tetracarboxylic dianhydride's composition and two amine components are mixed in organic solvent, following method is arranged: two amine components are dispersed or dissolved in the solution that organic solvent forms stir, the method for tetracarboxylic dianhydride's composition directly being added or after being dispersed or dissolved in organic solvent, adding; Be dispersed or dissolved in the method for adding two amine components in the solution that organic solvent forms at tetracarboxylic dianhydride's composition conversely; The method that tetracarboxylic dianhydride's composition and two amine components alternately add etc.In addition, when tetracarboxylic dianhydride's composition or two amine components were made of multiple compound, the state that described multiple composition can be pre-mixed carried out polyreaction, also can carry out polyreaction respectively successively.
Temperature when tetracarboxylic dianhydride's composition and two amine components carry out polyreaction in organic solvent is generally 0～150 ℃, is preferably 5～100 ℃, more preferably 10～80 ℃.Temperature height then polyreaction is early finished, but temperature is too high, can not obtain high molecular weight polymers sometimes.
In addition, polyreaction concentration is arbitrarily carried out, the words that the total concentration of tetracarboxylic dianhydride's composition and two amine components is too low can be difficult to obtain high molecular weight polymers, and the viscosity of the words reactant liquor of excessive concentration can become too high, be difficult to stir equably, therefore total concentration is preferably 1～50 quality %, more preferably 5～30 quality %.Append organic solvent again after also can carrying out with high concentration at the polyreaction initial stage.
As long as used organic solvent during above-mentioned polyreaction is the polyamic acid that dissolving generates, and there is no particular limitation.Can exemplify N as object lesson, dinethylformamide, N, N-dimethyl acetamide, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 1,3-dimethyl-imidazolinone etc.These solvents can use separately, also can mix use.Moreover, even can not make the solvent of polyamic acid dissolving, as long as in the scope that the polyamic acid that generates is not separated out, also can be mixed in the above-mentioned solvent and use.In addition, the moisture in the organic solvent can hinder polyreaction and then make the polyamic acid hydrolysis of generation, so organic solvent dehydrates the back as far as possible and uses to well.
In the polyreaction of polyamic acid the ratio of used tetracarboxylic dianhydride's composition and two amine components with molar ratio computing be preferably 1: 0.8～1: 1.2, this mol ratio is more near 1: 1, the molecular weight of the polyamic acid of gained is big more.Control the molecular weight of this polyamic acid, the molecular weight of the polyimide of gained behind the scalable imidizate.
There is no particular limitation for the molecular weight of polyamic acid of the present invention or polyimide, but when being contained in aligning agent for liquid crystal, the intensity of filming from gained and consider as the angle of the processing convenience of aligning agent for liquid crystal, weight-average molecular weight is preferably 2000～200000, and more preferably 5000～50000.
Synthesizing of＜polyimide 〉
Used polyimide is the polyimide that is got by above-mentioned polyamic acid imidizate in the aligning agent for liquid crystal of the present invention.The imidizate of polyamic acid can carry out by stirring in organic solvent, in the presence of base catalyst and acid anhydrides in 1～100 hour.
As base catalyst, can exemplify pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc.Wherein, pyridine has the suitable alkalescence that the reaction of making is carried out, thereby is preferred.
In addition, as acid anhydrides, can exemplify acetic anhydride, trimellitic anhydride, pyromellitic acid acid anhydride etc.Wherein, acetic anhydride owing to be easy to imidizate is finished after carries out making with extra care of gained polyimide, thereby is preferred.
As organic solvent, used solvent in the time of can using aforementioned polyamic acid polyreaction.
The imidizate rate of polyimide can wait and control by adjusting catalytic amount, temperature of reaction, reaction time.The amount of the base catalyst of this moment is 0.2～10 times of mole of acid amides acidic group preferably, is more preferably 0.5～5 times of mole.In addition, the amount of acid anhydrides is 1～30 times of mole of acid amides acidic group preferably, is more preferably 1～10 times of mole.Temperature of reaction preferably-20～250 ℃ is more preferably 0～180 ℃.
There is no particular limitation for the imidizate rate of the polyimide that aligning agent for liquid crystal of the present invention is used, but in order to obtain the more liquid crystal orientation film of high voltage holding ratio, the imidizate rate is preferably more than 40%, more preferably more than 60%, particularly preferably in more than 80%.
The residual catalyzer that interpolation is arranged etc. in De the polyimide solution therefrom, therefore when being used for aligning agent for liquid crystal, polyimide is preferably cleaned the back and is used reclaiming.
Filter after the recovery of polyimide can separate out polyimide by the solution after dropping into imidizate under the stirring of Weak solvent and carry out.Weak solvent as this moment can exemplify methyl alcohol, acetone, hexane, butyl cellosolve, heptane, MEK, methyl isobutyl ketone, ethanol, toluene, benzene etc.The washing of the polyimide that reclaims also can be carried out in this Weak solvent.Reclaiming the polyimide of cleaning thus can be in forming powder behind drying or the heat drying under the normal temperature under normal pressure or decompression.
This operation also can be carried out aforementioned polyamic acid.For example, when not wishing to contain solvent used in the polymerization of polyamic acid in the aligning agent for liquid crystal or when desiring to remove in the reaction solution unreacted monomer component or impurity, can carry out that above-mentioned precipitation reclaims and refining.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention is to contain by the polyamic acid of above-mentioned gained and the coating fluid of at least a polymkeric substance in the polyimide.
If exemplify this Production Example, the reaction solution of then aforementioned polyamic acid or polyimide can directly use, and also can dilute the back and use, and can also use after the material that reclaim be dissolved in organic solvent again precipitating from reactant liquor.In addition, dilution or again in the dissolution process, the appending etc. of additive that can be used to control to the adjustment of the solvent composition of the coating of substrate or be used to improve coating characteristic.Moreover, also can mix or add other resinous principle with the solution that structure is different from the solution of above-mentioned polyimide or polyamic acid.
As above-mentioned dilution or used organic solvent in the dissolution process again, get final product so long as can dissolve the solvent of contained polymkeric substance, there is no particular limitation.As its concrete example, can exemplify N, dinethylformamide, N, N-dimethyl acetamide, N-N-methyl-2-2-pyrrolidone N-, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl pyrrolidone, dimethyl sulfoxide (DMSO), tetramethylurea, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 1,3-dimethyl-imidazolinone etc.Wherein, preferably use N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, 1,3-dimethyl-imidazolinone, gamma-butyrolacton.These solvents can use a kind also can mix use more than 2 kinds.
As being used to control aligning agent for liquid crystal to the coating of substrate and the solvent that adds can exemplify ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, the ethyl carbitol acetic acid esters, ethylene glycol, 1-methoxyl-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, diethylene glycol diethyl ether, single acetate propylene glycol ester, propylene glycol diacetate, DPGME, propylene glycol-1-monomethyl ether-2-acetic acid esters, the single ethylether of propylene glycol-1--2-acetic acid esters, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc.Comprise the solvent that can not make the dissolving of polyamic acid or polyimide separately in these solvents, but as long as in the scope that polymkeric substance is not separated out, these solvents can be mixed in the aligning agent for liquid crystal of the present invention.The solvent that particularly has low surface tension by suitable mixing can improve the homogeneity of filming when coating substrate, so this kind solvent also can be used for aligning agent for liquid crystal of the present invention.Wherein, consider that from the deliquescent angle of polyimide butyl cellosolve, ethyl carbitol, DPGME, diethylene glycol diethyl ether are preferred especially.
As the additive that is used to improve coating characteristic, can exemplify silane coupling agents such as 3-aminopropyl methyldiethoxysilane, 3-phenyl amino propyl trimethoxy silicane, 3-aminopropyltriethoxywerene werene, (aminoethylamino methyl) phenethyl trimethoxy silane.By adding these silane coupling agents, can improve the adaptation of filming to substrate, but addition aggegation easily such as polyamic acid or polyimide when excessive.Therefore, the content of silane coupling agent is preferably 0.5～10 quality %, more preferably 1～5 quality with respect to the gross mass of polyamic acid or polyimide.
The solid component concentration of aligning agent for liquid crystal of the present invention, the setting of the liquid crystal aligning film thickness that can form according to desire is suitably changed, but is preferably 1～10 quality %.Then be difficult to form homogeneous and do not have filming of defective less than 1 quality %, than the 10 quality % storage stability variation of solution sometimes at most.Here said solid constituent is meant from aligning agent for liquid crystal except that the composition after desolvating.In addition, there is no particular limitation for the polyamic acid that aligning agent for liquid crystal of the present invention is used or the concentration of polyimide, but consider from the angle of the characteristic of gained liquid crystal orientation film, preferably more than 1 quality %, more preferably more than 3 quality %, more than 5 quality %.
As above the aligning agent for liquid crystal of gained preferably filtered earlier before coating substrate.
＜liquid crystal display cells 〉
Aligning agent for liquid crystal of the present invention can be coated drying behind the substrate, burn till and form and film.By this coated surface is carried out friction treatment, can be used as friction and use with liquid crystal orientation film.In addition, also can be used as without the VA of friction treatment with (vertical orientated usefulness) liquid crystal orientation film, optical alignment film.
At this moment, as used substrate, so long as the high substrate of the transparency gets final product, there is no particular limitation.Can use plastic bases such as glass plate, acrylic acid substrate or polycarbonate substrate etc., it is preferred being used for the angle that the substrate that is formed with ITO electrode etc. of liquid crystal drive oversimplifies from operation.In addition, for the liquid crystal display cells of reflection-type, also can be only at the opaque materialss such as substrate use silicon wafer of a side, the electrode of this moment also can use catoptrical materials such as aluminium.
As the coating process of aligning agent for liquid crystal, can exemplify spin-coating method, print process, ink-jet method etc., but consider industrial widely-used hectographic printing method from the productivity aspect, this method also is suitable for aligning agent for liquid crystal of the present invention.
Drying process after the coating of liquid crystalline aligning agent is also nonessential, but in the time till burn till after the coating every substrate under all unfixed situation or under the situation of not burning till immediately after the coating, is preferably included drying process.Dry can not make solvent evaporation under the degree because of the distortion such as carrying of substrate in the shape of filming, there is no particular limitation to these drying means.For example, can exemplify on 50～150 ℃, preferred 80～120 ℃ heating plate dry 0.5～30 minute, preferred 1～5 minute method.
Substrate after the aligning agent for liquid crystal coating burn till preferably 100～350 ℃, more preferably 150～300 ℃, preferably under 180～250 ℃ arbitrary temp, carry out again.When having the acid amides acidic group in the aligning agent for liquid crystal, amic acid changes into imido conversion ratio to be changed according to this firing temperature, but aligning agent for liquid crystal of the present invention there is no need 100% imidizate.
About the thickness of filming after burning till, too thickly then consider it is disadvantageous from the power consumption aspect of liquid crystal display cells, too thin then sometimes the reliability of liquid crystal display cells can descend, therefore be preferably 10～200nm, more preferably 50～100nm.
Can be with known rubbing device to the friction treatment that as above is formed at the coated surface on the substrate, the material as the friction cloth of this moment can exemplify cotton, rayon, nylon etc.
Substrate with the liquid crystal orientation film that is obtained by said method can be made the liquid crystal structure cell with known method, forms liquid crystal display cells.As an example of making the liquid crystal structure cell, general adopt following method: will be formed with preferred 1～30 μ m of a pair of substrate clamping of liquid crystal orientation film, the more preferably sept of 2～10 μ m, according to making frictional direction become the setting of requirement at any angle in 0～270 °, fix with sealant on every side, seal behind the injection liquid crystal.As liquid crystal inclosure method, there is no particular limitation, but illustration is injected (ODF) method etc. of dripping that seals behind the vacuum method of liquid crystal, the liquid crystal that drips after with the liquid crystal structure cell inner pressure relief that makes.
De liquid crystal display cells is applicable to TN liquid crystal display cells, stn liquid crystal display element, TFT liquid crystal display cells, OCB liquid crystal display cells therefrom, also has all kinds display elements such as lateral electric-field type (IPS) liquid crystal display cells, VA liquid crystal display cells.
Embodiment
Below exemplify embodiment the present invention is further described in detail, but do not constitute the explanation of limitation of the invention.
(synthesis example 1) 3,5-diamido benzyl furans-2-carboxylate synthetic
In the there-necked flask of 500mL (milliliter), add 1 of 25.0g, the 2 furoyl chloride of 3-dinitro benzylalcohol, 10.5mL and the tetrahydrofuran of 300mL.Drip the again pyridine of 9.0mL stirred 25 hours under room temperature.After reaction finishes, add the 50mL pure water, stirred 1 hour.Add the ethyl acetate extraction organic layer, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.Then, adding anhydrous magnesium sulfate in organic layer dehydrates.After the filtration, remove with rotary evaporator and to desolvate.With tetrahydrofuran/hexane=1/3 (volume ratio, below identical) residue is carried out recrystallization, obtain the Off-white solid (yield 93%) of 27.5g.This Off-white solid 1The H-NMR measurement result is as follows.From this results verification, the solid of gained is the target dinitro compound.In addition, 1H-NMR is meant the NMR (Nuclear Magnetic Resonance) spectrum of hydrogen atom in the molecule.
1H?NMR(400MHz，CDCl 3)：δ9.04(t，1H)，8.66-8.63(m，2H)，7.65(dd，1H)，7.32(dd，1H)，6.58(dd，1H)，5.53(s，2H)
Figure BPA00001347360900201
Then, add the methyl alcohol of the dinitro compound of 23.8g, platinum/carbon of 2.4g (mass ratio 1/10, below identical) and 239g in the four-hole boiling flask of 500mL, stirring is 43 hours under nitrogen atmosphere.Reaction is carried out diatomite filtration after finishing, and removes with rotary evaporator and desolvates.With isopropyl alcohol residue is carried out recrystallization, obtain the light orange solid (yield 85%) of 16.1g.
This shallow dark brown solid 1The H-NMR measurement result is as follows.From results verification, the light orange solid of gained is a targeted diamine.
1H?NMR(400MHz，CDCl 3)：δ7.58(dd，1H)，7.21(dd，1H)，6.51(dd，1H)，6.18(dt，2H)，6.00(t，1H)，5.16(s，2H)，3.62(br，4H)
(synthesis example 2) furans-2-ylmethyl 3,5-diaminobenzoic acid ester synthetic
In the four-hole boiling flask of 500mL, add 3 of 25.3g, the furancarbinol of 5-dinitrobenzoyl chloride, 10.0mL and the tetrahydrofuran of 200mL.Drip the again pyridine of 9.7mL stirred 16 hours under room temperature.After reaction finishes, add the 50mL pure water, stirred 1 hour.Add the ethyl acetate extraction organic layer, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.Then, adding anhydrous magnesium sulfate in organic layer dehydrates.After the filtration, remove with rotary evaporator and to desolvate.Residue with silica gel column chromatography (solvent distillation is a hexane: the mixed solvent of ethyl acetate=3: 1) refining, obtain the dinitro compound (yield 95%) of 30.3g.The gained solid 1The H-NMR measurement result is as follows.From this results verification, the solid of gained is the target dinitro compound.
1H?NMR(400MHz，CDCl 3)：δ9.23(t，1H)，9.17(d，2H)，7.49(dd，1H)，6.57(dd，1H)，6.43(dd，1H)，5.44(s，2H)
Figure BPA00001347360900221
The dinitro compound, platinum/carbon of 3.1g and the methyl alcohol of 400mL that in the four-hole boiling flask of 500mL, add 30.3g, under nitrogen atmosphere in stirring at room.Reaction is carried out diatomite filtration after finishing, and removes with rotary evaporator and desolvates.Carry out recrystallization with isopropanol/hexane=1/1 pair residue, obtain the shallow dark brown solid (yield 48%) of 11.6g.
This shallow dark brown solid 1The H-NMR measurement result is as follows.From results verification, the shallow dark brown solid of gained is a targeted diamine.
1H?NMR(400MHz，DMSO-d 6)：δ7.71(dd，1H)，6.57(dd，1H)，6.48(dd，2H)，6.41(d，2H)，6.01(t，1H)，5.20(s，2H)，5.02(br，4H)
Figure BPA00001347360900222
Synthesizing of (synthesis example 3) N-(3, the 5-diamino-phenyl) furans-2-carboxylic acid amides
In the there-necked flask of 500mL, add 3 of 24.1g, the pyridine of 5-dinitroaniline, 11.7mL and the tetrahydrofuran of 300mL.Drip the again 2 furoyl chloride of 13.8mL stirred 18 hours under room temperature.After reaction finishes, add the 50mL pure water, stirred 1 hour.Add the ethyl acetate extraction organic layer, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.Then, adding anhydrous magnesium sulfate in organic layer dehydrates.After the filtration, remove with rotary evaporator and to desolvate.Carry out recrystallization with tetrahydrofuran/hexane=1/3 pair residue, obtain the dinitro compound (yield 85%) of 31.1g.The gained solid 1The H-NMR measurement result is as follows.From this results verification, the solid of gained is the target dinitro compound.
1H?NMR(400MHz，DMSO-d 6)：δ11.1(s，1H)，9.11(d，2H)，8.54(t，1H)，8.05(dd，1H)，7.46(dd，1H)，6.78(dd，1H)
Figure BPA00001347360900231
In the four-hole boiling flask of 1L, add dinitro compound, the 4.2g of 30.9g platinum/carbon, 300g 1,4-two
Figure BPA00001347360900232
The tetrahydrofuran of alkane and 800g, under nitrogen atmosphere in stirring at room.Reaction is carried out diatomite filtration after finishing, and removes with rotary evaporator and desolvates.With isopropyl alcohol residue is carried out recrystallization, obtain the shallow dark brown solid (yield 89%) of 21.4g.
This shallow dark brown solid 1The H-NMR measurement result is as follows.From results verification, the shallow dark brown solid of gained is a targeted diamine.
1H?NMR(400MHz，DMSO-d 6)：δ9.51(s，1H)，7.87(dd，1H)，7.28(dd，1H)，6.65(dd，1H)，6.23(d，2H)，5.60(t，1H)，4.73(br，4H)
Figure BPA00001347360900233
(synthesis example 4) 3,5-diamido benzyl thiophene-2-carboxylic acid ester (DABTh) synthetic
In the there-necked flask of 500mL, add 3 of 21.5g, the 2-thiophene chloride of 5-dinitro benzylalcohol, 12.1mL and the tetrahydrofuran of 200mL.Drip the again pyridine of 9.6mL stirred 48 hours under room temperature.After reaction finishes, add the 50mL pure water, stirred 1 hour.Add the ethyl acetate extraction organic layer, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.Then, adding anhydrous magnesium sulfate in organic layer dehydrates.After the filtration, remove with rotary evaporator and to desolvate.With ethyl acetate and hexane residue is carried out recrystallization, obtain the dinitro compound (yield 82%) of 27.5g.The gained solid 1The H-NMR measurement result is as follows.
1H?NMR(400MHz，CDCl 3)：δ9.03(t，1H)，8.66-8.63(m，2H)，7.90(dd，1H)，7.66(dd，1H)，7.17(dd，1H)，5.52(s，2H)
Figure BPA00001347360900241
In the four-hole boiling flask of 500mL, add dinitro compound, platinum/carbon of 4.3g and the tetrahydrofuran of 200g of 17.5g, under nitrogen atmosphere, stirred 48 hours.Reaction is carried out diatomite filtration after finishing, and removes with rotary evaporator and desolvates.With tetrahydrofuran and isopropyl alcohol residue is carried out recrystallization, obtain the shallow dark brown solid (yield 92%) of 12.9g.
This shallow dark brown solid 1The H-NMR measurement result is as follows.From results verification, the shallow dark brown solid of gained is a targeted diamine.
1H?NMR(400MHz，CDCl 3)：δ7.83(dd，1H)，7.56(dd，1H)，7.10(dd，1H)，6.19-6.17(m，2F)，6.00(t，1H)，5.16(s，2H)，3.61(br，4H)
Figure BPA00001347360900242
(synthesis example 5) 3, the 5-methyl-pyromucic acid that synthesizes adding 8.5g in the four-hole boiling flask of 500mL of 5-diamido benzyl-5-methylfuran-2 carboxylate (MeDABFr) and the methylene chloride of 170mL are cooled to 0 ℃ from room temperature.Then, add the oxalyl dichloro (Japanese: Er salt オ キ ラ リ Le) of 5.9mL and the DMF of 0.5g, under room temperature, stirred 2 hours.After the stirring, add 3 of 13.4g, the pyridine of 5-dinitro benzylalcohol and 6mL stirred 16 hours under room temperature.After reaction finishes, add the 50mL pure water, stirred 1 hour.Afterwards, add the ethyl acetate extraction organic layer, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.In organic layer, add anhydrous magnesium sulfate and dehydrate, behind the diatomite filtration, remove with rotary evaporator and to desolvate.Clean residue with isopropyl alcohol, obtain the dinitro compound (yield 86%) of 17.1g.The gained solid 1The H-NMR measurement result is as follows.
1H?NMR(400MHz，CDCl 3)：δ9.02(t，1H)，8.65-8.62(m，2H)，7.23-7.21(m，1H)，6.20-6.18(m，1H)，5.52-5.50(m，2H)，2.43-2.41(m，3H)
Figure BPA00001347360900251
In the four-hole boiling flask of 500mL, add dinitro compound, platinum/carbon of 1.7g and the tetrahydrofuran of 170g of 16.7g, under nitrogen atmosphere, stirred 21 hours.Reaction is carried out diatomite filtration after finishing, and removes with rotary evaporator and desolvates.With isopropyl alcohol residue is carried out recrystallization, obtain the shallow dark brown solid (yield 68%) of 9.1g.
This shallow dark brown solid 1The H-NMR measurement result is as follows.From results verification, the shallow dark brown solid of gained is a targeted diamine.
1H?NMR(400MHz，CDCl 3)：δ7.15(d，2H)，7.10(d，1H)，6.11-6.09(m，1H)，5.97(t，1H)，5.13(s，2H)，3.57(br，4H)，2.37(s，3H)
Figure BPA00001347360900261
(synthesis example 6) 3,5-diamido benzyl furans-3-carboxylate (3-DABFr) synthetic
In the four-hole boiling flask of 500mL, add the 3-furancarboxylic acid of 8.2g and the methylene chloride of 240mL, be cooled to 0 ℃ from room temperature.Then, add the oxalyl dichloro of 6.4mL and the DMF of 0.5g, under room temperature, stirred 2 hours.After the stirring, add 3 of 15.0g, the pyridine of 5-dinitro benzylalcohol and 9.7mL stirred 47 hours under room temperature.After reaction finishes, add the 50mL pure water, stirred 1 hour.Afterwards, add the ethyl acetate extraction organic layer, clean organic layer with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.In organic layer, add anhydrous magnesium sulfate and dehydrate, after the filtration, remove with rotary evaporator and to desolvate.With ethyl acetate residue is carried out recrystallization, obtain the dinitro compound (yield 78%) of 16.8g.The gained solid 1The H-NMR measurement result is as follows.
1H?NMR(400MHz，CDCl 3)：δ9.03(t，1H)，8.63-8.61(m，2H)，8.12(dd，1H)，7.41(dd，1H)，6.79(dd，1H)，5.48(d，2H)
Figure BPA00001347360900262
In the four-hole boiling flask of 500mL, add dinitro compound, platinum/carbon of 1.7g and the tetrahydrofuran of 165g of 16.5g, under nitrogen atmosphere, stirred 29 hours.Reaction is carried out diatomite filtration after finishing, and removes with rotary evaporator and desolvates.With tetrahydrofuran and isopropyl alcohol residue is carried out recrystallization, obtain the shallow dark brown solid (yield 57%) of 7.4g.
This shallow dark brown solid 1The H-NMR measurement result is as follows.From results verification, the shallow dark brown solid of gained is a targeted diamine.
1H?NMR(400MHz，CDCl 3)：δ8.04(dd，1H)，7.42(dd，1H)，6.77(dd，1H)，6.14(d，2H)，5.98(t，1H)，5.10(s，2H)，3.57(br，4H)
The abbreviation of the employed compound such as synthetic of polyamic acid and polyimide is as follows:
＜tetracarboxylic dianhydride 〉
CBDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
TDA:3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride
＜diamines 〉
2-DABFr:3,5-diamido benzyl furans-2-carboxylate
FrDAB: furans-2-ylmethyl 3,5-diaminobenzoic acid ester
DAAFr:N-(3, the 5-diamino-phenyl) furans-2-carboxylic acid amides
DABTh:3,5-diamido benzyl thiophene-2-carboxylic acid ester
MeDABFr:3,5-diamido benzyl-5-methylfuran-2 carboxylate
3-DABFr:3,5-diamido benzyl furans-3-carboxylate
Me4APhA:4-amino-N-Methylphenethylamine
P-PDA: p-phenylenediamine
DDM:4,4 '-diaminodiphenyl-methane
C14DAB:4-myristyl oxygen-1, the 3-diaminobenzene
C16DAB:4-cetyl oxygen-1, the 3-diaminobenzene
The 3-ABA:3-amino-benzylamine
＜organic solvent 〉
The NMP:N-N-methyl-2-2-pyrrolidone N-
γ-BL: gamma-butyrolacton
BC: butyl cellosolve
DPM: DPGME
DMF: dimethyl formamide
The mensuration of＜molecular weight 〉
The polyamic acid that is obtained by polyreaction or the molecular weight of polyimide are measured with GPC (normal temperature gel permeation chromatography) device, as the scaled value of polyglycol and polyethylene oxide, calculate number-average molecular weight and weight-average molecular weight.
GPC device: Showa Denko K. K (Shodex society) system (GPC-101)
Pillar: Showa Denko K. K's system (series connection of KD803 and KD803)
Column temperature: 50 ℃
Eluent: N, and dinethylformamide (as adjuvant, the lithium bromide monohydrate (LiBrH of 30mmol/L 2O), the tetrahydrofuran (THF) of the phosphoric acid anhydrous crystal (neighbour-phosphoric acid) of 30mmol/L, 10ml/L)
Sulfuric acid: 1.0ml/ branch
Calibration line is made and is used standard sample: system TSK standard polyethylene oxide (molecular weight about 900 (East ソ one society of TOSOH Co., Ltd), 000,150,000,100,000,30,000) and the polyglycol (molecular weight about 12,000,4 of polymkeric substance laboratory company (Port リ マ one ラ ボ ラ ト リ one society) system, 000,1,000).
The mensuration of＜imidizate rate 〉
Following the calculating of imidizate rate of the polyimide that obtains by chemical imidizate: this polyimide is dissolved in d6-DMSO (in the dimethyl sulfoxide (DMSO)-d6), measures 1H-NMR obtains imidizate not and the ratio of residual acid amides acidic group by the ratio of the integrated value of proton peak, thereby calculates the imidizate rate.
The making of＜liquid crystal structure cell 〉
To make the liquid crystal structure cell as described below by embodiment and the formulated aligning agent for liquid crystal of comparative example.
Aligning agent for liquid crystal is spun on the glass substrate with transparency electrode, after on 70 ℃ the heating plate dry 70 seconds, on 210 ℃ heating plate, carries out 10 minutes burn till, form filming of thickness 100nm.With rayon cloth this coated surface is rubbed under the condition of roller revolution 1000rpm, roller gait of march 50mm/ second, the 0.3mm amount of being pressed into the rubbing device of roller footpath 120mm, obtain having the substrate of liquid crystal orientation film.Prepare 2 substrates, on one liquid crystal aligning face, scatter after the sept of 6 μ m printing and sealing agent thereon with liquid crystal orientation film, then make the liquid crystal aligning face relatively and under the condition of frictional direction quadrature with another piece baseplate-laminating,, make sealant cures, make the negative crystal born of the same parents.In the negative crystal born of the same parents, inject liquid crystal MLC-2003 (Merck ﹠ Co., Inc. (メ Le Network society) system), seal inlet, obtain stable twisted nematic liquid crystal structure cell by the decompression injection method.
The mensuration and the evaluating characteristics of the rerum natura of each liquid crystal structure cell of making are as described below.
In addition, the physical property measurement of the composition of each aligning agent for liquid crystal in embodiment 1～9 and the comparative example 1～3, each liquid crystal orientation film and evaluating characteristics etc. the results are shown in table 2, table 3.
＜friction patience evaluation 〉
Making with above-mentioned＜liquid crystal structure cell〉described in the method manufacturing with the substrate of liquid crystal orientation film.At this moment, the quantitative change that is pressed into of friction condition is 0.5mm.Get the liquid crystal orientation film surface with confocal some laser microscope observation post, carry out following evaluation.
Zero: do not observe that abrasive dust adheres to or the scar that rubs.
△: observe that abrasive dust adheres to or the scar that rubs.
*: observe film and peel off or estimate the friction scar.
＜liquid crystal aligning evaluation 〉
For presenting the quality of liquid crystal aligning, make following liquid crystal structure cell.Aligning agent for liquid crystal is spun on the substrate with transparency electrode, after on 70 ℃ the heating plate dry 70 seconds, on 210 ℃ heating plate, carries out 10 minutes burn till, form filming of thickness 100nm.With rayon cloth this coated surface is rubbed under the condition of roller revolution 1000rpm, roller gait of march 50mm/ second, the 0.3mm amount of being pressed into the rubbing device of roller footpath 120mm, obtain having the substrate of liquid crystal orientation film.Prepare 2 above-mentioned substrates with liquid crystal orientation film, on one liquid crystal aligning face, scatter after the sept of 6 μ m, printing and sealing agent thereon, then make the liquid crystal aligning face relatively and frictional direction be with another piece baseplate-laminating under 180 ° the condition, make sealant cures, make the negative crystal born of the same parents.In the negative crystal born of the same parents, inject liquid crystal MLC-2003 (Merck ﹠ Co., Inc.'s system), seal inlet, obtain antiparallel type liquid crystal structure cell by the decompression injection method.The initial stage orientation of this liquid crystal structure cell of visual observations.The following evaluation.It the results are shown in aftermentioned table 2.
Zero: be orientated well.
*: observe more light leak or orientation bad position.
＜tilt angle is measured 〉
Will be with the making of above-mentioned＜liquid crystal structure cell〉described in the stable twisted nematic liquid crystal structure cell made of method after 2 hours, carry out the mensuration of tilt angle and the mensuration of voltage retention in 105 ℃ of heating.Tilt angle is measured with the Crystal Rotation method.
The mensuration of＜voltage retention 〉
Making with above-mentioned＜liquid crystal structure cell〉described in following the carrying out of mensuration of voltage retention of stable twisted nematic liquid crystal structure cell of method manufacturing: between 60 μ s, applying 4V voltage under 90 ℃ the temperature, voltage behind the mensuration 16.67ms, having calculated voltage can keep what, with this as voltage retention.In addition, the voltage retention determinator of the system VHR-1 mensuration of the voltage retention use Dongyang (East Yang テ of technology Co., Ltd. Network ニ カ society).
The mensuration of＜savings electric charge (RDC) 〉
To making with above-mentioned＜liquid crystal structure cell〉described in the stable twisted nematic liquid crystal structure cell made of method, the interval with 0V～0.1V under 23 ℃ temperature applies DC voltage until 1.0V, measures the flicker amplitude level each voltage under, the making calibration line.After 5 minutes ground connection, apply 3.0V alternating voltage, 5.0V DC voltage 1 hour, only DC voltage just has been to measure the flicker amplitude level behind the 0V immediately afterwards, by estimate RDC (estimating and measuring method of this RDC is with reference to the flicker reference entry) according to the calibration line of making in advance.
Embodiment 1
With the CBDA of 5.00g (0.025mol) as tetracarboxylic dianhydride's composition, with the 2-DABFr of 6.03g (0.026mol) as two amine components, in the NMP of 44.14g, reaction is 16 hours under room temperature, and the concentration that obtains polyamic acid (PAA-1) is the solution of 20 quality %.With polyamic acid (PAA-1) solution of the BC dilution 10.0g of the NMP of 23.3g and 10.0g, obtaining polyamic acid (PAA-1) is the aligning agent for liquid crystal of 4.6 quality %.With the rub evaluation of patience, tilt angle, voltage retention (VHR) and RDC of this aligning agent for liquid crystal.The results are shown in table 2.
Embodiment 2
The NMP that adds 93.33g in polyamic acid (PAA-1) solution (PAA-1 concentration is 20 quality %) of using the 40g that obtains with embodiment 1 identical method dilutes, add the acetic anhydride of 5.77g and the pyridine of 2.39g again, react 3 hours with imidizate in 40 ℃.After about this reaction solution cool to room temperature, drop in the methyl alcohol of 500mL, reclaim the solid of precipitation.With this solid of methanol cleaning 2 times,, obtain the white powder of polyimide (SPI-1) more afterwards in 100 ℃ of drying under reduced pressure.The number-average molecular weight of this polyimide is 13204, and weight-average molecular weight is 30700.In addition, the imidizate rate is 87%.
In the gained polyimide (SPI-1) of 2.00g, add γ-BL of 18.0g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.Add the BC of γ-BL, 6.00g of 8.0g and the DPM of 6.00g again in this solution, stirred 20 hours in 50 ℃, obtaining polyimide (SPI-1) is the aligning agent for liquid crystal of 5 quality %.Carry out the evaluation identical with this aligning agent for liquid crystal with embodiment 1.The results are shown in table 2.
Embodiment 3
With the CBDA of 5.52g (0.028mol) as tetracarboxylic dianhydride's composition, with the C14DAB of the 3-ABA of 2-DABFr, the 1.40g (0.011mol) of 2.00g (0.009mol) and 2.76g (0.009mol) as two amine components, in the NMP of 46.7g, reaction is 16 hours under room temperature, and the concentration that obtains polyamic acid (PAA-2) is the solution of 20 quality %.With polyamic acid (PAA-2) solution of the BC dilution 10.0g of the NMP of 23.3g and 10.0g, obtaining polyamic acid (PAA-2) is the aligning agent for liquid crystal of 4.6 quality %.Carry out the evaluation identical with this aligning agent for liquid crystal with embodiment 1.The results are shown in table 2.
Embodiment 4
The NMP that adds 93.3g in polyamic acid (PAA-2) solution (PAA-2 concentration is 20 quality %) of using the 40.0g that obtains with embodiment 3 identical methods dilutes, add the acetic anhydride of 6.02g and the pyridine of 2.49g again, react 3 hours with imidizate in 60 ℃.After about this reaction solution cool to room temperature, drop in the methyl alcohol of 500mL, reclaim the solid of precipitation.With this solid of methanol cleaning 2 times,, obtain the white dark brown powder of polyimide (SPI-2) more afterwards in 100 ℃ of drying under reduced pressure.The number-average molecular weight of this polyimide is 15850, and weight-average molecular weight is 42234.In addition, the imidizate rate is 92%.
In the gained polyimide (SPI-2) of 2.00g, add γ-BL of 18.0g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.Add the BC of γ-BL, 6.00g of 8.00g and the DPM of 6.00g again in this solution, stirred 20 hours in 50 ℃, obtaining polyimide (SPI-2) is the aligning agent for liquid crystal of 5 quality %.Carry out the evaluation identical with this aligning agent for liquid crystal with embodiment 1.The results are shown in table 2.
Embodiment 5
With the CBDA of 5.57g (0.029mol) as tetracarboxylic dianhydride's composition, with the C14DAB of the 3-ABA of FrDAB, the 1.42g (0.012mol) of 2.02g (0.009mol) and 2.79g (0.009mol) as two amine components, in the NMP of 46.7g, reaction is 16 hours under room temperature, and the concentration that obtains polyamic acid (PAA-3) is the solution of 20 quality %.
With this polyamic acid (PAA-3) solution of the BC dilution 10.0g of the NMP of 23.3g and 10.0g, the polyamic acid (PAA-3) that obtains as aligning agent for liquid crystal of the present invention is the solution of 4.6 quality %.Use its coating fluid to carry out the evaluation identical with embodiment 1.The results are shown in table 2.
Embodiment 6
The NMP that adds 93.3g in polyamic acid (PAA-3) solution (PAA-3 concentration is 20 quality %) of using the 40.0g that obtains with embodiment 5 identical methods dilutes, add the acetic anhydride of 6.06g and the pyridine of 2.53g again, react 3 hours with imidizate in 60 ℃.After about this reaction solution cool to room temperature, drop in the methyl alcohol of 500mL, reclaim the solid of precipitation.With this solid of methanol cleaning 2 times,, obtain the white dark brown powder of polyimide (SPI-3) more afterwards in 100 ℃ of drying under reduced pressure.The number-average molecular weight of this polyimide is 17920, and weight-average molecular weight is 41290.In addition, the imidizate rate is 89%.
In the gained polyimide (SPI-3) of 2.00g, add γ-BL of 18.0g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.Add the BC of γ-BL, 6.00g of 8.00g and the DPM of 6.00g again in this solution, stirred 20 hours in 50 ℃, obtaining polyimide (SPI-3) is the aligning agent for liquid crystal of 5 quality %.Carry out the evaluation identical with this aligning agent for liquid crystal with embodiment 1.The results are shown in table 2.
Embodiment 7
With the CBDA of 5.57g (0.029mol) as tetracarboxylic dianhydride's composition, with the C14DAB of the 3-ABA of DAAFr, the 1.42g (0.012mol) of 1.89g (0.009mol) and 2.79g (0.009mol) as two amine components, in the NMP of 46.7g, reaction is 16 hours under room temperature, and the concentration that obtains polyamic acid (PAA-4) is the solution of 20 quality %.
With polyamic acid (PAA-4) solution of the BC dilution 10.0g of the NMP of 23.3g and 10.0g, the polyamic acid (PAA-4) that obtains as aligning agent for liquid crystal of the present invention is the solution of 4.6 quality %.Use its coating fluid to carry out the evaluation identical with embodiment 1.The results are shown in table 2.
Embodiment 8
The NMP that adds 93.3g in polyamic acid (PAA-4) solution (PAA-4 concentration is 20 quality %) of using the 40.0g that obtains with embodiment 7 identical methods dilutes, add the acetic anhydride of 6.06g and the pyridine of 2.53g again, react 3 hours with imidizate in 60 ℃.After this reaction solution cool to room temperature degree, drop in the methyl alcohol of 500mL, reclaim the solid of precipitation.With this solid of methanol cleaning 2 times,, obtain the white dark brown powder of polyimide (SPI-4) more afterwards in 100 ℃ of drying under reduced pressure.The number-average molecular weight of this polyimide is 15367, and weight-average molecular weight is 39880.In addition, the imidizate rate is 90%.
In the gained polyimide (SPI-4) of 2.00g, add γ-BL of 18.0g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.Add the BC of γ-BL, 6.00g of 8.00g and the DPM of 6.00g again in this solution, stirred 20 hours in 50 ℃, obtaining polyimide (SPI-4) is the aligning agent for liquid crystal of 5 quality %.Carry out the evaluation identical with this aligning agent for liquid crystal with embodiment 1.The results are shown in table 2.
Embodiment 9
With the TDA of 12.0g (0.040mol) as tetracarboxylic dianhydride's composition, with the C16DAB1 of the 2-DABFr of p-PDA, the 2.79g (0.012mol) of 2.59g (0.024mol) and 1.39g (0.004mol) as two amine components, in the NMP of 75.7g, in 50 ℃ of reactions 24 hours, the concentration that obtains polyamic acid was the solution of 20 quality %.
The NMP that adds 187g in this polyamic acid solution of 90.0g dilutes, and adds the acetic anhydride of 39.6g and the pyridine of 18.4g again, reacts 3 hours with imidizate in 40 ℃.
After about this reaction solution cool to room temperature, drop in the methyl alcohol of 1.17L, reclaim the solid of precipitation.With this solid of methanol cleaning 2 times,, obtain the white powder of polyimide (SPI-5) more afterwards in 100 ℃ of drying under reduced pressure.The number-average molecular weight of this polyimide is 15322, and weight-average molecular weight is 28239.In addition, the imidizate rate is 81%.
In the polyimide (SPI-5) of 5.00g, add γ-BL of 62.5g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.γ-the BL that adds 20.8g again in this solution, in 50 ℃ of stirrings 20 hours, making polyimide (SPI-5) was the solution of 5.7 quality %.
On the other hand, in room temperature reaction 5 hours, the concentration of making polyamic acid (PAA-5) was the solution of 15 quality % to the DDM that makes the PMDA of CBDA, 9.60g (0.044mol) of 9.80g (0.050mol) and 19.8g (0.10mol) in the mixed solvent of γ-BL of the NMP of 111g and 111g.The number-average molecular weight of this polyamic acid is 10925, and weight-average molecular weight is 27314.
Add the γ-BL of 225g and the BC of 75.0g in the solution of this polyamic acid (PAA-5) of 200g, stirred 2 hours under room temperature, the concentration that obtains polyamic acid (PAA-5) is the solution of 6 quality %.With 6 quality % solution of the above-mentioned polyimide that obtains (SPI-5) of the 6 quality % solution of this polyamic acid (PAA-5) of 200g and 50.0g after stirring 20 hours under the room temperature, solid constituent (total mass concentration of PAA-5 と SPI-5) reaches 5.9 quality %, obtains aligning agent for liquid crystal of the present invention (BL-1).Carry out the evaluation identical with this aligning agent for liquid crystal with embodiment 1.The results are shown in table 2.
Embodiment 10
With the CBDA of 5.78g (0.029mol) as tetracarboxylic dianhydride's composition, with the C14DAB of the 3-ABA of DABTh, the 1.47g (0.012mol) of 2.24g (0.009mol) and 2.89g (0.009mol) as two amine components, in the NMP of 44.96g, reaction is 16 hours under room temperature, obtains the polyamic acid solution (PAA-6) of 20 quality %.
With polyamic acid (PAA-6) solution of the BC dilution 10.0g of the NMP of 23.3g and 10.0g, the solid constituent that obtains as aligning agent for liquid crystal of the present invention is the solution of 4.6 quality %.Use its coating fluid to carry out the evaluation identical with embodiment 1.The results are shown in table 2.
Embodiment 11
The NMP that adds 93.33g in polyamic acid (PAA-6) solution (PAA-7 concentration is 20 quality %) of using the 40g that obtains with embodiment 10 identical methods dilutes, add the acetic anhydride of 5.61g and the pyridine of 2.32g again, react 3 hours with imidizate in 60 ℃.After about this reaction solution cool to room temperature, drop in the methyl alcohol of 500mL, reclaim the solid of precipitation.With this solid of methanol cleaning 2 times,, obtain the white dark brown powder of polyimide (SPI-6) more afterwards in 100 ℃ of drying under reduced pressure.The number-average molecular weight of this polyimide is 13163, and weight-average molecular weight is 30211.In addition, the imidizate rate is 85%.
In the gained polyimide (SPI-6) of 2.00g, add γ-BL of 18.0g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.Add the BC of γ-BL, 6.00g of 8.0g and the DPM of 6.00g again in this solution, stirred 20 hours in 50 ℃, the solution that obtains polyimide (SPI-6) and be 5 quality % is as aligning agent for liquid crystal of the present invention.Carry out the evaluation identical with its coating fluid with embodiment 1.The results are shown in table 2.
Embodiment 12
With the CBDA of 5.57g (0.029mol) as tetracarboxylic dianhydride's composition, with the C14DAB of the 3-ABA of MeDABFr, the 1.42g (0.012mol) of 2.14g (0.009mol) and 2.79g (0.009mol) as two amine components, in the NMP of 46.7g, reaction is 16 hours under room temperature, and the concentration that obtains polyamic acid (PAA-7) is the solution of 20 quality %.
With polyamic acid (PAA-7) solution of the BC dilution 10.0g of the NMP of 23.3g and 10.0g, the polyamic acid (PAA-7) that obtains as aligning agent for liquid crystal of the present invention is the solution of 4.6 quality %.Use its coating fluid to carry out the evaluation identical with embodiment 1.The results are shown in table 2.
Embodiment 13
The NMP that adds 93.3g in polyamic acid (PAA-7) solution (PAA-7 concentration is 20 quality %) of using the 40.0g that obtains with embodiment 12 identical methods dilutes, add the acetic anhydride of 6.06g and the pyridine of 2.53g again, react 3 hours with imidizate in 60 ℃.After about this reaction solution cool to room temperature, drop in the methyl alcohol of 500mL, reclaim the solid of precipitation.With this solid of methanol cleaning 2 times,, obtain the white dark brown powder of polyimide (SPI-7) more afterwards in 100 ℃ of drying under reduced pressure.The number-average molecular weight of this polyimide is 15787, and weight-average molecular weight is 36433.In addition, the imidizate rate is 87%.
In the gained polyimide (SPI-7) of 2.00g, add γ-BL of 18.0g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.Add the BC of γ-BL, 6.00g of 8.00g and the DPM of 6.00g again in this solution, stirred 20 hours in 50 ℃, obtaining polyimide (SPI-7) is the aligning agent for liquid crystal of 5 quality %.Carry out the evaluation identical with this aligning agent for liquid crystal with embodiment 1.The results are shown in table 2.
Embodiment 14
With the CBDA of 5.57g (0.029mol) as tetracarboxylic dianhydride's composition, with the C14DAB of the 3-ABA of 3-DABFr, the 1.42g (0.012mol) of 2.02g (0.009mol) and 2.79g (0.009mol) as two amine components, in the NMP of 46.7g, reaction is 16 hours under room temperature, and the concentration that obtains polyamic acid (PAA-8) is the solution of 20 quality %.
With polyamic acid (PAA-8) solution of the BC dilution 10.0g of the NMP of 23.3g and 10.0g, the polyamic acid (PAA-8) that obtains as aligning agent for liquid crystal of the present invention is the solution of 4.6 quality %.Use its coating fluid to carry out the evaluation identical with embodiment 1.The results are shown in table 2.
Embodiment 15
The NMP that adds 93.3g in polyamic acid (PAA-8) solution (PAA-8 concentration is 20 quality %) of using the 40.0g that obtains with embodiment 14 identical methods dilutes, add the acetic anhydride of 6.06g and the pyridine of 2.53g again, react 3 hours with imidizate in 60 ℃.After about this reaction solution cool to room temperature, drop in the methyl alcohol of 500mL, reclaim the solid of precipitation.With this solid of methanol cleaning 2 times,, obtain the white dark brown powder of polyimide (SPI-8) more afterwards in 100 ℃ of drying under reduced pressure.The number-average molecular weight of this polyimide is 16142, and weight-average molecular weight is 38574.In addition, the imidizate rate is 89%.
In the gained polyimide (SPI-8) of 2.00g, add γ-BL of 18.0g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.Add the BC of γ-BL, 6.00g of 8.00g and the DPM of 6.00g again in this solution, stirred 20 hours in 50 ℃, obtaining polyimide (SPI-8) is the aligning agent for liquid crystal of 5 quality %.Carry out the evaluation identical with this aligning agent for liquid crystal with embodiment 1.The results are shown in table 2.
Embodiment 16
With the CBDA of 5.57g (0.029mol) as tetracarboxylic dianhydride's composition, with the Me4APhA of the 2-DABFr of 2.02g (0.009mol) and 3.05g (0.021mol) as two amine components, in the NMP of 46.7g, reaction is 16 hours under room temperature, and the concentration that obtains polyamic acid (PAA-9) is the solution of 20 quality %.The number-average molecular weight of this polyamic acid is 21329, and weight-average molecular weight is 45294.
With polyamic acid (PAA-9) solution of the BC dilution 10.0g of the NMP of 23.3g and 10.0g, the polyamic acid (PAA-9) that obtains as aligning agent for liquid crystal of the present invention is the solution of 4.6 quality %.Use its coating fluid to carry out the evaluation identical with embodiment 1.The results are shown in table 2.
Comparative example 1
With the CBDA of 12.5g (0.064mol) as tetracarboxylic dianhydride's composition, with the C14DAB of the 3-ABA of 5.56g (0.046mol) and 6.25g (0.020mol) as two amine components, in the NM of 97.20g P, reaction is 16 hours under room temperature, and the concentration that obtains polyamic acid (PAA-10) is the solution of 20 quality %.
With polyamic acid (PAA-10) solution of the BC dilution 10.0g of the NMP of 23.3g and 10.0g, obtaining polyamic acid (PAA-10) is the solution of 4.6 quality %, and this solution is the aligning agent for liquid crystal that is used as comparison other.Use its coating fluid and embodiment 1 similarly to make the liquid crystal structure cell, and carry out the evaluation of the mensuration and the characteristic of rerum natura
Comparative example 2
The NMP that adds 116.67g in polyamic acid (PAA-10) solution (PAA-10 concentration is 20 quality %) of using the 50g that obtains with comparative example 1 identical method dilutes, add the acetic anhydride of 7.39g and the pyridine of 3.15g again, in 70 ℃ the reaction 3 hours with imidizate, but the reaction in gelation takes place.
The NMP that adds 116.67g in polyamic acid (PAA-10) solution (PAA-10 concentration is 20 quality %) of using the 50g that obtains with comparative example 1 identical method dilutes once more, adding the acetic anhydride of 7.39g and the pyridine of 3.15g again, is to carry out imidizate under 50 ℃ the condition in temperature of reaction.
After about this reaction solution cool to room temperature, drop in the methyl alcohol of 250mL, reclaim the solid of precipitation.With this solid of methanol cleaning 2 times,, obtain the white powder of polyimide (SPI-9) more afterwards in 100 ℃ of drying under reduced pressure.The number-average molecular weight of this polyimide is 16338, and weight-average molecular weight is 39865.In addition, the imidizate rate is 80%.
In the polyimide (SPI-9) of 1g, add γ-BL of 9g, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.Add the BC of γ-BL, 3.00g of 4.0g and the DPM of 3.0g again in this solution, stirred 20 hours in 50 ℃, obtaining polyimide (SPI-9) is the solution of 5 quality %, obtains the aligning agent for liquid crystal of object as a comparison.Make the liquid crystal structure cell in the same manner with this aligning agent for liquid crystal and embodiment 1, and carry out physical property measurement, evaluating characteristics.
Comparative example 3
With the CBDA of 5.70g (0.029mol) as tetracarboxylic dianhydride's composition, with the Me4APhA of 4.51g (0.030mol) as two amine components, in the NMP of 46.7g, reaction is 16 hours under room temperature, and the concentration that obtains polyamic acid (PAA-11) is the solution of 20 quality %.The number-average molecular weight of this polyamic acid is 19630, and weight-average molecular weight is 48201.
With polyamic acid (PAA-11) solution of the BC dilution 10.0g of the NMP of 23.3g and 10.0g, obtaining polyamic acid (PAA-11) is the solution of 4.6 quality %, obtains the aligning agent for liquid crystal of object as a comparison.Make the liquid crystal structure cell in the same manner with this aligning agent for liquid crystal and embodiment 1, and carry out physical property measurement, evaluating characteristics.
[table 1]
[table 2]
Figure BPA00001347360900401
The industrial possibility of utilizing
By aligning agent for liquid crystal of the present invention, even be difficult in the time of can obtaining rubbing that film is peeled off or cutting, voltage retention height and liquid crystal cell applied the liquid crystal orientation film that DC voltage also is difficult for causing the savings of initial stage electric charge. Therefore, the liquid crystal display cells made from aligning agent for liquid crystal of the present invention can obtain the high liquid crystal display of reliability, is applicable to various types of display elements such as TN liquid crystal display cells, stn liquid crystal display element, TFT liquid crystal display cells, VA liquid crystal display cells, IPS liquid crystal display cells, OCB liquid crystal display cells.
In addition, quote of the announcement of the full content of Japanese patent application 2008-260486 number instructions, claim scope and summary proposing on October 7th, 2008 here as instructions of the present invention.

Claims (11)

1. aligning agent for liquid crystal, it contains at least a polymkeric substance of the polyimide that is selected from polyamic acid and is got by this polyamic acid imidizate, described polyamic acid gets by two amine components and the reaction of tetracarboxylic dianhydride's composition that makes the diamines that contains following formula [1] expression
Figure FPA00001347360800011
In the formula, X represent singly-bound, carbon number 1～3 alkylidene ,-OCH 2-,-CH 2OCO-,-NHCO-,-CONH-or-COOCH 2-, Y represents oxygen atom or sulphur atom, pentacyclic any hydrogen atom can be replaced by the alkyl of carbon number 1～5.
2. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, the Y of formula [1] is an oxygen atom.
3. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, the Y of formula [1] is a sulphur atom.
4. as each described aligning agent for liquid crystal in the claim 1～3, it is characterized in that the X of formula [1] is-CH 2OCO-,-NHCO-or-COOCH 2-.
5. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, the X of formula [1] is-CH 2OCO-,-NHCO-or-COOCH 2-, Y is an oxygen atom.
6. as each described aligning agent for liquid crystal in the claim 1～5, it is characterized in that pentacyclic any hydrogen atom of formula [1] is by methyl substituted.
7. liquid crystal orientation film gets by each described aligning agent for liquid crystal in the use claim 1～6.
8. liquid crystal display cells, it possesses the described liquid crystal orientation film of claim 7.
9. the diamines of following formula [2] expression:
In the formula, any hydrogen atom of furan nucleus can be replaced by the alkyl of carbon number 1～5.
10. diamines as claimed in claim 9 is characterized in that, any hydrogen atom of furan nucleus can be by methyl substituted.
11. polyamic acid or the polyimide that is got by this polyamic acid imidizate, described polyamic acid gets by making two amine components and the reaction of tetracarboxylic dianhydride's composition that contain claim 9 or 10 described diamines.
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