CN102067024A - Liquid-crystal alignment material, liquid-crystal display element employing same, and novel diamine - Google Patents

Liquid-crystal alignment material, liquid-crystal display element employing same, and novel diamine Download PDF

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CN102067024A
CN102067024A CN200980123423.XA CN200980123423A CN102067024A CN 102067024 A CN102067024 A CN 102067024A CN 200980123423 A CN200980123423 A CN 200980123423A CN 102067024 A CN102067024 A CN 102067024A
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liquid crystal
polyamic acid
diamines
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polyimide
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CN102067024B (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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/32—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and esterified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • 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

Provided are a novel diamine, a polyamic acid, and a polyimide which are useful for obtaining a liquid-crystal alignment material giving a liquid-crystal alignment film which has a high voltage retentivity and is less apt to suffer initial charge accumulation therein even when a direct-current voltage is applied to the liquid-crystal cell. Also provided is a liquid-crystal alignment material. The liquid-crystal alignment material contains at least one of: a polyamic acid obtained by reacting a diamine ingredient comprising a diamine of formula [1] with a tetracarboxylic dianhydride ingredient; and a polyimide obtained by imidizing the polyamic acid. (In formula [1], R represents a C1-25 saturated hydrocarbon group).

Description

Aligning agent for liquid crystal and used the liquid crystal display cells of this treating agent and new diamines
Technical field
The present invention relates to be used for aligning agent for liquid crystal, the liquid crystal orientation film of liquid crystal display cells, also relate to the new diamines of the raw material that can be used as polyamic acid that this aligning agent for liquid crystal uses or polyimide.
Background technology
At present, liquid crystal orientation film as liquid crystal display cells, main use so-called polyimide liquid crystal orientation film, this polyimide liquid crystal orientation film is to burn till behind the aligning agent for liquid crystal (being also referred to as aligning agent for liquid crystal) of major component to make with the solution of polyimide precursor such as polyamic acid or soluble polyimide by coating.
Liquid crystal orientation film is that purpose is used with the state of orientation of control liquid crystal.But, high resolving powerization along with liquid crystal display cells, the angle that control that descends from the contrast of liquid crystal display cells or persistence of vision reduce considers, the fast such characteristic of the release of the voltage retention height of used liquid crystal orientation film, the electric charge of accumulating less or accumulating because of DC voltage of accumulating electric charge (RDC) when having applied DC voltage is more and more important.
In the polyimide liquid crystal orientation film, as the short liquid crystal orientation film of time till the after image disappearance that produces because of DC voltage, the known liquid crystal orientation film that the aligning agent for liquid crystal that has used the tertiary amine that also contains ad hoc structure except that the polyamic acid of polyamic acid or imido-is arranged (for example with reference to patent documentation 1) has perhaps used the liquid crystal orientation film (for example with reference to patent documentation 2) of the aligning agent for liquid crystal that contains in the raw material soluble polyimide that adopts the specific diamines with pyridine skeleton etc. etc.
In addition, in the polyimide liquid crystal orientation film, short liquid crystal orientation film of time till high and after image that produce because of DC voltage disappears as voltage retention, known having have used the liquid crystal orientation film (for example with reference to patent documentation 3) of aligning agent for liquid crystal that compound, molecule that molecule contains 1 carboxyl contain the compound of 1 carboxylic acid anhydride group's compound and the compound that molecule contains 1 uncle's amino that is selected from that also comprises minute quantity except that polyamic acid or its imide amination polymer etc.
But the time conduct of only shortening till after image disappears is not enough at the countermeasure of persistence of vision.
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 communique
The announcement of invention
The present invention is the invention of finishing in view of above situation, even its objective is provides that can to obtain voltage retention high and the liquid crystal structure cell applied the aligning agent for liquid crystal of liquid crystal orientation film that DC voltage also is difficult to the electric charge accumulation at the initial stage of causing, and the diamines, polyamic acid and the polyimide that can be used for obtaining this aligning agent for liquid crystal.
The present inventor has finished the present invention after conscientiously studying for achieving the above object.That is, the present invention includes following technology contents.
1. aligning agent for liquid crystal, comprise polyamic acid maybe with this polyamic acid imidizate and at least one side of polyimide, described polyamic acid is by two amine components and the reaction of tetracarboxylic dianhydride's composition of the diamines that contains following formula [1] and get,
Figure BPA00001278712000021
In the formula, R represents the saturated hydrocarbyl of carbon number 1～25.
2. the aligning agent for liquid crystal of above-mentioned 1 record, the diamines of formula [1] expression occupy 20～100 moles of % of synthetic whole two amine components of polyamic acid.
3. the aligning agent for liquid crystal of above-mentioned 1 or 2 records, the diamines of formula [1] expression are in a position or bit position are had the diamines of 2 amino.
4. the aligning agent for liquid crystal of above-mentioned 1 record, with the diamines that comprises following formula [2] expression in two amine components of tetracarboxylic dianhydride's composition reaction,
Figure BPA00001278712000022
In the formula, Ar represents phenyl ring or naphthalene nucleus, R 1Be the alkylidene of carbon number 1～5, R 2Be hydrogen atom or methyl.
5. the aligning agent for liquid crystal of each record in above-mentioned 1～4, tetracarboxylic dianhydride's composition are the tetracarboxylic dianhydride's composition that comprises the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure.
6. liquid crystal orientation film is obtained by the aligning agent for liquid crystal of each record in above-mentioned 1～5.
7. liquid crystal display cells possesses above-mentioned 6 liquid crystal orientation films of putting down in writing.
8. the diamines of following formula [1-1],
Figure BPA00001278712000031
In the formula, R 3Straight chain shape alkyl for carbon number 1～5.
9. the diamines of following formula [1-2],
Figure BPA00001278712000032
In the formula, R 4Saturated hydrocarbyl for the carbon number 3～8 that comprises at least 1 ring structure.
10. polyamic acid is by two amine components and the reaction of tetracarboxylic dianhydride's composition of the diamines that contain above-mentioned 8 or 9 records and get.
11. polyimide gets the above-mentioned 10 polyamic acid imidizates of putting down in writing.
Even aligning agent for liquid crystal of the present invention can obtain the voltage retention height and the liquid crystal structure cell is applied the liquid crystal orientation film that DC voltage also is difficult to cause electric charge accumulation, use this liquid crystal orientation film can make the good liquid crystal panel of characteristic.In addition, even the liquid crystal orientation film that is obtained by aligning agent for liquid crystal of the present invention also is difficult for taking place grinding and unfavorable condition such as impaired through friction treatment.
New diamines, polyamic acid or the polyimide of the application of the invention can easily obtain described good aligning agent for liquid crystal.
In addition, new diamines of the present invention easily synthetic by its raw material as polyamic acid, polyimide etc. is used, can be improved gained polyamic acid or the polyimide dissolubility in solvent.Therefore polyamic acid of the present invention or the polyimide favorable solubility in solvent can obtain filming of homogeneous.
The best mode that carries out an invention
The feature of aligning agent for liquid crystal of the present invention is, contain the reaction of two amine components and tetracarboxylic dianhydride's composition and polyamic acid maybe with this polyamic acid imidizate and polyimide, contain the diamines of formula [1] expression in this two amine component.By using this diamines, the voltage retention height of gained liquid crystal orientation film is even and apply the DC voltage electric charge to the liquid crystal structure cell and also be difficult for accumulating.
The diamines of＜formula [1] 〉
In the diamines of formula [1] expression, be not particularly limited for each the substituent position on the phenyl ring.The angle of the orientation of the liquid crystal when forming liquid crystal orientation film is considered, position or contraposition between the position relation of 2 amino is preferred in addition, are considered from the angle of the solvent solubility that improves polyamic acid or polyimide, more preferably between the position.During the position, that is, be 1 between the position of 2 amino is closed and is, during the structure of 3-diaminobenzene, the position of methylene ester is preferably 4 or 5, considers more preferably 5 from effect that improves amino nucleophilicity and the angle that is easy to synthesize.
R is the saturated hydrocarbyl of carbon number 1～25 in the diamines of formula [1] expression.This saturated hydrocarbyl can be the alkyl of straight chain shape or branch-like, can contain ring structure.As the concrete example of this saturated hydrocarbyl, but exemplified by methyl, ethyl, n-pro-pyl～carbon numbers such as pentacosane base are 25 with interior straight chain shape alkyl; Isopropyl, sec-butyl, the tert-butyl group, isobutyl, 1-ethyl propyl, 1,1-dimethyl propyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1,1-dimethylbutyl, 3, carbon numbers such as 3-dimethylbutyl are 25 with interior and at any branch-like alkyl of place branch; With cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl etc. is the naphthenic base of representative; The group that alkyl such as cyclopropyl methyl, cyclobutylmethyl, cyclopentyl-methyl, cyclohexyl methyl, 2-cyclopropyl ethyl, 2-cyclobutyl ethyl, 2-cyclopentyl ethyl, 2-cyclohexyl ethyl, 2-methyl cyclopropyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 4-tert-butylcyclohexyl, dicyclohexyl and naphthenic base or the naphthenic base more than 2 combine; Two ring (2,2,1) heptane-2-bases, diamantane-1-base, diamantane-1-base-methyl etc. have the group of condensed ring etc.
From the angle of the property accumulated of accumulating electric charge (RDC) of formed liquid crystal orientation film, in the diamines of formula [1] expression, the less diamines of carbon number of preferred R.For example, the carbon number of R is preferably 1～17, and more preferably 1～8.In addition, from the angle of liquid crystal aligning and rub resistance, the R straight chain shape alkyl that preferably molecular weight is littler.Therefore, in the diamines of formula [1] expression, weigh the concrete example of preferred R from liquid crystal aligning and rub resistance, the aspects such as the property accumulated of accumulating electric charge (RDC), can exemplify the less alkyl of molecular weight that is selected from methyl, ethyl, propyl group, butyl and amyl group.
On the other hand, when R has ring structures such as naphthenic base, possesses the higher effect of solvent solubility of polyamic acid and polyimide.Therefore, in the diamines of formula [1] expression, weigh the concrete example of preferred R from the aspects such as the property accumulated of accumulating electric charge (RDC) of the solvent solubility of polyamic acid and polyimide, formed liquid crystal orientation film, can exemplify cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl methyl, cyclobutylmethyl, cyclopentyl-methyl, cyclohexyl methyl, 2-cyclopropyl ethyl, 2-cyclobutyl ethyl, 2-cyclopentyl ethyl, 2-cyclohexyl ethyl, 2-methyl cyclopropyl, 1-methylcyclohexyl, 2-methylcyclohexyl etc.
There is no particular limitation for the synthetic method of the diamines of formula [1] expression, for example, can synthesize by with conventional method nitroreduction being transformed into amino method again behind the dinitro compound of synthetic following formula [3] expression.
Figure BPA00001278712000051
R in the following formula is identical with R in the formula [1].
The dinitro compound of formula [3] expression can be by shown in the following reaction equation, in the presence of alkali such as pyridine or triethylamine, make with the corresponding dinitro benzene methyl alcohol in the substituent position of targeted diamine with corresponding carboxyl acyl chloride of the R of targeted diamine or acid dianhydride reaction and synthesize.
R in the following formula is identical with R in the formula [1].
Have 2,4-dinitro benzene methyl alcohol, 3,5-dinitro benzene methyl alcohol, 2,5-dinitro benzene methyl alcohol etc. with the corresponding dinitro benzene methyl alcohol in position of the preferred substituted of the diamines of above-mentioned formula [1].
In the diamines of expression, the diamines of the diamines of following formula [1-1] or following formula [1-2] is to the useful especially new diamines of aligning agent for liquid crystal of the present invention in the formula [1].
Figure BPA00001278712000061
In the formula, R 3Straight chain shape alkyl for carbon number 1～5.
Figure BPA00001278712000062
In the formula, R 4Saturated hydrocarbyl for the carbon number 3～8 that contains at least 1 ring structure.
The diamines of the diamines of following formula [1-1] or [1-2] and other formula [1] expression is same, can be synthetic by preceding method.
In the diamines of following formula [1-1] or [1-2], better be the position of 2 amino close be between position or contraposition, in addition, from the angle of the solvent solubility that can improve polyamic acid or polyimide, position between being more preferably.
Below exemplify the preferred concrete example of the diamines of formula [1-1] expression, but the present invention is not limited to this.
Figure BPA00001278712000071
The diamines of following formula [4]～[18] can be divided into the form of following [a], [b] and [c] according to the substituent position on the phenyl ring, and as previously mentioned, the spy is well the form of [b], and the spy is well the diamines of formula [5], formula [8], formula [11], formula [14] or formula [17] specifically.
Figure BPA00001278712000081
R among following formula [a]～[c] is identical with the R of formula [1].
Below, exemplify concrete example, but the present invention is not limited to this as the form of above-mentioned [b] of particularly preferred diamines in the diamines of formula [1-2] expression.
Figure BPA00001278712000082
＜two amine components 〉
The diamines of above-mentioned formula [1] expression and tetracarboxylic dianhydride's reaction can obtain polyamic acid, and this polyamic acid imidizate can be obtained polyimide.
In the present invention, two amine components that use during synthesizing polyamides acid can only be the diamines of formula [1] expression, also can make itself and the combination more than a kind or 2 kinds that is selected from other diamines.
As two amine components, by containing the diamines of formula [1] expression, can improve the solvent solubility of polyamic acid that is obtained and the polyimide that gets by this polyamic acid imidizate.By the aligning agent for liquid crystal that contains this polyamic acid or polyimide the voltage retention height of liquid crystal orientation film, even and DC voltage be added on liquid crystal structure cell electric charge outward also be difficult for accumulating.In order to obtain such characteristic, the diamines of formula [1] expression better occupies 20～100mol% of synthetic whole two amine components of polyamic acid, is more preferably 40～100mol%, and the spy is 50～100mol% well.
In above-mentioned two amine components, there is no particular limitation with diamines that the diamines of formula [1] expression is used in combination.The concrete example of this diamines is as follows.
The example of ester ring type diamines can exemplify: 1, and 4-diamino-cyclohexane, 1,3-diamino-cyclohexane, 4,4 '-diamino-dicyclohexyl methane, 4,4 '-diamido-3,3 '-dimethyl dicyclohexyl amine, isophorone diamine etc.
The example of aromatic diamine can exemplify: o-phenylenediamine, m-phenylene diamine, p-phenylenediamine (PPD), 2, the 4-diaminotoluene, 2, the 5-diaminotoluene, 3, the 5-diaminotoluene, 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-diphenyl-ethane, 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 '-diamino-diphenyl thioether, 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-, 2,2-pair [4-(4-amino-benzene oxygen) phenyl)] HFC-236fa, 2,2-pair [4-(4-amino-benzene oxygen) phenyl)] propane, 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-aminophenyl)-1, the 4-diisopropyl benzene, 9, two (4-aminophenyl) fluorenes of 9-, 2, two (3-aminophenyl) HFC-236fa of 2-, 2, two (4-aminophenyl) HFC-236fa of 2-, 4,4 '-diamino-diphenyl amine, 2,4-diamino-diphenyl amine, 1, the 8-diaminonaphthalene, 1, the 5-diaminonaphthalene, 1, the 5-diamino-anthraquinone, 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) 1, the 3-malonate, two (4-aminophenyls) 1, the 4-succinate, two (4-aminophenyls) 1, the 5-glutarate, two (4-aminophenyls) 1, the 6-adipate, two (4-aminophenyls) 1, the 7-pimelate, two (4-aminophenyls) 1, the 8-suberate, two (4-aminophenyls) 1, the 9-azelate, two (4-aminophenyls) 1, the 10-sebacate, 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.
The example of hetero ring type diamines can exemplify: 2, and 6-diamino-pyridine, 2,4-diamino-pyridine, 2,4-diamino-1,3,5-triazines, 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-oxadiazole etc.
The example of aliphatic diamine can exemplify: 1, and 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.
The example of aromatic-aliphatic diamines can exemplify the diamines of following formula [2] expression.
Figure BPA00001278712000101
Ar in this formula represents phenyl ring or naphthalene nucleus, R 1Be the alkylidene of carbon number 1～5, R 2Be hydrogen atom or methyl.
In the diamines of formula [2] expression, preferred Ar is a phenyl ring, R 2Be hydrogen atom.
The concrete example of the diamines of formula [2] expression can exemplify 3-aminobenzene methyl amine, 4-aminobenzene methyl amine, 3-amino-N-methylbenzene methyl amine, 4-amino-N-methylbenzene methyl amine, 3-aminobenzene ethylamine, 4-aminobenzene ethylamine, 3-amino-N-methylbenzene ethylamine, 4-amino-N-methylbenzene ethylamine, 3-(3-aminopropyl) aniline, 4-(3-aminopropyl) aniline, 3-(3-methylamino propyl group) aniline, 4-(3-methylamino propyl group) aniline, 3-(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-) methyl amine, 3-(the amino naphthyl of 6-) methyl amine, 2-(the amino naphthyl of 6-) ethylamine, 3-(the amino naphthyl of 6-) ethylamine etc., but be not limited to this.
If the diamines of formula [2] the expression diamines with formula [1] expression is used in combination, then the dissolubility of the polymkeric substance of gained in organic solvent further improves, and liquid crystal aligning is good when forming liquid crystal orientation film and using, therefore preferably.Also have, this combination can improve the effect of tilt angle of the increase liquid crystal of diamines described later, just can reduce its consumption in the time of will obtaining the tilt angle of identical size like this.There is the poor more tendency of printing of the many more aligning agent for liquid crystal of its consumption in the diamines that can increase the tilt angle of liquid crystal, therefore, if can reduce the consumption of this diamines, just is expected to improve the printing of aligning agent for liquid crystal.
The preferred content of the diamines of formula [2] expression is 10～50mol% of whole two amine components, is more preferably 20～40mol%.When containing the diamines of formula [2] expression, the preferred content of the diamines of formula [1] expression is 20～90mol% of whole two amine components, is more preferably 30～80mol%.
By being contained in synthesizing polyamides two amine components in when acid, when forming liquid crystal orientation film, can increase the known diamines that contains chain alkyl, perfluoroalkyl, aromatic series ring-type base, aliphatics cyclic group and the substituting group that is combined into by them, steroid backbone base etc. of diamines of the tilt angle of liquid crystal.These diamines can be used in combination with the diamines of formula [1] expression in the present invention.Below, exemplify concrete example, but the present invention is not limited to this with this substituent diamines.Also have, in following illustrative structure, j represents 5～20 integer, and k represents 1～20 integer.
Figure BPA00001278712000111
Figure BPA00001278712000121
Figure BPA00001278712000131
Figure BPA00001278712000141
In the above-mentioned diamines, the diamines of formula [19] helps obtaining good liquid crystal aligning.The diamines of formula [26]～[33] therefore is highly suitable for OCB (OpticallyCompensated Bend is optical compensation curved) liquid crystal alignment films (hereinafter referred to as the OCB alignment films), vertical alignment mode liquid crystal alignment films (hereinafter referred to as the VA alignment films) because the presentation capability of tilt angle is very high.
For example, for the TN liquid crystal with alignment films (tilt angle is 3～5 °), the content that can make the diamines of formula [19] is 10～30mol% of whole two amine components, for OCB with alignment films or VA with alignment films (tilt angle is 10～90 °), the content that can make the diamines of formula [26]～[33] is 5～40mol% of whole two amine components, but and in being limited to this.
＜tetracarboxylic dianhydride composition 〉
In polyamic acid of the present invention or the polyimide, there is no particular limitation to the tetracarboxylic dianhydride's composition with above-mentioned two amine components reaction, can be a kind of tetracarboxylic dianhydride, the tetracarboxylic dianhydride that also two or more kinds may be used.
In the aligning agent for liquid crystal of the present invention, from can further improving the angle of the voltage retention of liquid crystal structure cell, as with the tetracarboxylic dianhydride of described two amine components reaction, preferably use tetracarboxylic dianhydride with ester ring type structure or aliphatic structure.Tetracarboxylic dianhydride with ester ring type structure or aliphatic structure can exemplify 1,2,3,4-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, 1,2,4,5-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-1,2-dicarboxylic anhydride], 1,2,3,4-butane tetracarboxylic acid dianhydride, two rings [3,3,0] octane-2,4,6, the 8-tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group 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, especially preferably use 1,2,3,4-cyclo-butane tetracarboxylic dianhydride is because can obtain the good alignment films of liquid crystal aligning by this.
Also have,, then can improve liquid crystal aligning, and can accelerate the release of accumulating electric charge of liquid crystal structure cell if also use aromatic tetracarboxylic acid's dianhydride.Aromatic tetracarboxylic acid's dianhydride can exemplify pyromellitic acid anhydride, 3, and 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, preferred especially pyromellitic acid anhydride.
If consider the orientation, voltage retention of dissolubility, the liquid crystal of the polyamic acid of gained or polyimide, the equilibrium of accumulating each characteristic such as electric charge, usage ratio 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 〉
In the present invention, there is no particular limitation to the polymerisation process of tetracarboxylic dianhydride's composition and two amine components.In general, can carry out polyreaction by mixing in organic solvent and form polyamic acid, again by making this polyamic acid dehydration closed-loop form polyimide.
The method that tetracarboxylic dianhydride's composition and two amine components are mixed in organic solvent can exemplify stir make two amine components be dispersed or dissolved in organic solvent and solution, directly add tetracarboxylic dianhydride's composition therein or tetracarboxylic dianhydride's composition is disperseed or be dissolved in organic solvent after the method for adding again; On the contrary in that tetracarboxylic dianhydride's composition is dispersed or dissolved in organic solvent solution in add two amine components method; Alternately add the method for tetracarboxylic dianhydride's composition and two amine components etc.In addition, when tetracarboxylic dianhydride's composition or two amine components were made up of multiple compound, the state that can in advance these multiple compositions be 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 ℃, better is 5～100 ℃, more preferably 10～80 ℃.The high more polyreaction of temperature is finished more soon, if but too high then can't obtain high molecular weight polymers sometimes.
In addition, polyreaction can be carried out with concentration arbitrarily, but if if the total concentration of tetracarboxylic dianhydride's composition and two amine components is low excessively, then be difficult to obtain high molecular weight polymers, if excessive concentration then the viscosity of reactant liquor is too high, being difficult to stir uniformly, better is 1～50 quality % therefore, is more preferably 5～30 quality %.Can carry out at the polyreaction initial stage, and then append organic solvent with high concentration.
Employed organic solvent during above-mentioned polyreaction is so long as can dissolve the polyamic acid of generation, and then there is no particular limitation.Its concrete example can exemplify N, dinethylformamide, N, N-dimethyl acetamide, N-N-methyl-2-2-pyrrolidone N-, 3-methoxyl-N, N-dimethyl propylene acid amides, N-methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton, 1,3-dimethyl-imidazolinone etc.These solvents can be used alone, but also also mix together.Also have, even the insoluble solvent of separating polyamic acid, so long as in the scope that the polyamic acid that generates can not be separated out, also can use with above-mentioned solvent.In addition, the moisture in the organic solvent hinders polyreaction, and can make the polyamic acid hydrolysis of generation, so organic solvent preferably uses the organic solvent through farthest dehydrating.
Tetracarboxylic dianhydride's composition that the polyreaction of polyamic acid is used and diamines components in proportions with molar ratio computing be preferably 1: 0.8～1: 1.2, this mol ratio molecular weight near 1: 1 resulting polyamic acid more is big more.By controlling the molecular weight of this polyamic acid, can adjust the molecular weight of the polyimide that obtains behind the imidizate.
There is no particular limitation for the molecular weight of polyamic acid of the present invention or polyimide, when being included in the aligning agent for liquid crystal, from the intensity of filming of gained with as the angle of the easy usability of aligning agent for liquid crystal, be preferably 2000～200000 in weight-average molecular weight, more preferably 5000～50000.
Synthesizing of＜polyimide 〉
Polyimide of the present invention is the polyimide that is got by above-mentioned polyamic acid imidizate.The imidizate of polyamic acid can stir in the presence of base catalyst and acid anhydrides and carry out in 1～100 hour by in organic solvent.
Base catalyst can exemplify pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc.Wherein, preferred pyridine makes the alkalescence of reacting the appropriateness of carrying out because it has.In addition, acid anhydrides can exemplify acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc.Wherein preferred acetic anhydride, because after the imidizate end, the polyimide of gained is easily refining.Used solvent when organic solvent can use above-mentioned polyamic acid polyreaction.
The imidizate rate of polyimide can be controlled by regulating catalytic amount and temperature of reaction, reaction time.The amount of base catalyst at this moment better is 0.2～10 times of mole of acid amides acidic group, is more preferably 0.5～5 times of mole.In addition, the amount of acid anhydrides better is 1～30 times of mole of acid amides acidic group, is more preferably 1～10 times of mole.Temperature of reaction better is-20～250 ℃, is more preferably 0～180 ℃.
There is no particular limitation for the imidizate rate of polyimide of the present invention, but from the reason of the liquid crystal orientation film that obtains higher voltage retention, when being contained in aligning agent for liquid crystal, the imidizate rate is preferably more than 40%, be more preferably more than 60%, the spy is more than 80% well.
The remaining catalyzer that interpolation is arranged of the solution of the polyimide that obtains like this etc. when therefore being used for aligning agent for liquid crystal, better are to re-use after polyimide is reclaimed, cleans.
The Weak solvent that the recovery of polyimide can stirred the solution input behind the imidizate filters after polyimide is separated out.At this moment Weak solvent can exemplify methyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene etc.The cleaning of the polyimide after the recovery also can be carried out with this Weak solvent.Carry out normal temperature or heat drying under the polyimide that obtains after reclaiming like this, cleaning can or reduce pressure at normal pressure and form powder.
This operation also can be carried out above-mentioned polyamic acid.For example, when not wanting to make the used solvent of the polymerization that contains polyamic acid in the aligning agent for liquid crystal, when perhaps wanting to remove unreacted monomer component in the reaction solution and 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 the coating fluid that contains at least a polymkeric substance that is selected from as mentioned above the polyamic acid that obtains and polyimide.
The reaction solution that its Production Example can exemplify above-mentioned polyamic acid or polyimide directly is used as aligning agent for liquid crystal, perhaps can after diluting, be used as aligning agent for liquid crystal, perhaps also can will precipitate from reactant liquor reclaim and product be dissolved in organic solvent once more and come as aligning agent for liquid crystal.In addition, in the operation of dilution and dissolving again, can be used to be controlled at the adjustment of the solvent composition of the coating on the substrate, and be used to improve the appending etc. of additive of the characteristic of filming.Also have, can mix, perhaps can add other resinous principle with structure and the solution of above-mentioned different polyimide or the solution of polyamic acid.
Be used for above-mentioned dilution or again dissolution process organic solvent so long as the polymkeric substance that solubilized contains then there is no particular limitation, its concrete example can exemplify N, dinethylformamide, N, N-dimethyl acetamide, N-N-methyl-2-2-pyrrolidone N-, 3-methoxyl-N, N-dimethyl propylene acid amides, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrolidone, N-vinyl pyrrolidone, dimethyl sulfoxide, tetramethylurea, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton, 1,3-dimethyl-imidazolinone etc.Wherein preferably use N-N-methyl-2-2-pyrrolidone N-, 1,3-dimethyl-imidazolinone, gamma-butyrolacton.These can use to mix more than a kind or 2 kinds and use.
For control aligning agent for liquid crystal on substrate coating 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, diethyl carbitol, propylene-glycol monoacetate, propylene-glycol diacetate, the dipropylene glycol monomethyl ether, propylene glycol-1-monomethyl ether-2-acetic acid esters, propylene glycol-1-one ether-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.These solvents also comprise the solvent that can't dissolve polyamic acid or polyimide separately, if the scope of not separating out at resin can be sneaked in the aligning agent for liquid crystal of the present invention.Particularly knownly mix solvent, when coating substrate, can improve and be coated with film uniformity, also be fit to use for aligning agent for liquid crystal of the present invention with low surface tension by appropriateness.Wherein, particularly from the deliquescent angle of polyimide, the spy is well butyl cellosolve, ethyl carbitol, dipropylene glycol monomethyl ether or diethyl carbitol.
The additive that is used to improve the characteristic of filming can exemplify silane coupling agents such as 3-aminopropyl methyldiethoxysilane, 3-phenyl amino propyl trimethoxy silicane, 3-aminopropyltriethoxywerene werene, (aminoethylamino methyl) phenethyl trimethoxy silane.Interpolation by these silane coupling agents, can improve the adaptation of filming to substrate, if but excessively interpolation then can cause the aggegation of resinous principles such as polyamic acid and polyimide, therefore better be with respect to resinous principles such as polyamic acid or polyimide, the addition of silane coupling agent is 0.5～10 quality %, is more preferably 1～5 quality %.
The solid component concentration of aligning agent for liquid crystal of the present invention can be done appropriate change according to the setting of the thickness of the liquid crystal orientation film that will form, and better is 1～10 quality %.If less than 1 quality % then is difficult to form even and flawless filming, if be higher than 10 quality % then solution storage stability variation sometimes.Also have, there is no particular limitation for the polyamic acid of the present invention in this solid constituent or the concentration of polyimide, from the angle of the characteristic of the liquid crystal orientation film of gained, better is more than the 1 quality %, is more preferably more than the 3 quality %, and the spy is well more than the 5 quality %.
The aligning agent for liquid crystal that obtains as mentioned above preferably filters earlier before coating substrate.
＜liquid crystal display cells 〉
Aligning agent for liquid crystal of the present invention can be by coating substrate, and is dry, burn till the back and form and film, and again by this coated surface is carried out friction treatment, is used as the liquid crystal orientation film of friction usefulness.In addition, also can be used as VA liquid crystal orientation film, the optical alignment film that does not carry out friction treatment.
At this moment, used substrate is not so long as the high substrate of the transparency then has special qualification, can use plastic bases such as glass substrate, acrylic acid substrate or polycarbonate substrate etc., from the angle that production technology is simplified, the preferred substrate that is formed with the ITO electrode that is used for liquid crystal drive etc. that uses.In addition, for the liquid crystal display cells of reflection-type, can be only at the opaque materials such as substrate use silicon wafer of a side, electrode at this moment also can use catoptrical materials such as aluminium.
The coating process of aligning agent for liquid crystal can exemplify spin-coating method, print process, ink-jet method etc., but from the productivity aspect, the flexographic printing method is widely adopted on commercial production, and aligning agent for liquid crystal of the present invention also is fit to adopt this rubbing method.
Though the drying process after the coating of liquid crystalline aligning agent is not essential, but after coating before burn till during this period of time under all unfixed situation of each piece substrate or under the situation of not burning till immediately after the coating, preferably comprise drying process.This drying is so long as make solvent evaporation, reach the shape of filming can be not former because of the transportation of substrate etc. thereby the degree of distortion both can, there is no particular limitation to this drying means.Specifically can exemplify following method, make it, more preferably 1～5 minute at 50～150 ℃, more preferably on 80～120 ℃ the hot plate dry 0.5～30 minute.
The burning till of substrate that has been coated with aligning agent for liquid crystal can be carried out under the arbitrary temp in 100～350 ℃, but better is 150～300 ℃, is more preferably 180 ℃～250 ℃.When in aligning agent for liquid crystal, containing the acid amides acidic group, change with this firing temperature to the conversion ratio that acid imide transforms from amic acid, but aligning agent for liquid crystal of the present invention need not 100% imidizate.
The thickness of filming after burning till is preferably 10～200nm, and 50～100nm more preferably is because if blocked up then undesirable aspect the energy consumption of liquid crystal display cells, if cross thin then the reliability decrease of liquid crystal display cells sometimes.
The friction treatment that is formed at the coated surface on the substrate as mentioned above can be used existing rubbing device.The material of friction cloth at this moment can exemplify cotton, rayon, nylon etc.
The substrate of the band liquid crystal orientation film that the employing said method obtains is made the liquid crystal structure cell by known method, obtains liquid crystal display cells.If for an example of making the liquid crystal structure cell, generally be to adopt following method: will be formed with 1 pair of substrate of liquid crystal orientation film, folder is across being preferably 1～30
μ m, the sept of 2～10 μ m more preferably according to making frictional direction become the setting of requirement at any angle in 0～270 °, are fixed the periphery with sealant, seal after injecting liquid crystal.There is no particular limitation to the method for enclosing liquid crystal, can exemplify the back of reducing pressure and inject the method etc. of dripping that seals behind the vacuum method of liquid crystal, the liquid crystal that drips in to the liquid crystal structure cell that makes.
The liquid crystal display cells of making like this is suitable for various types of display elements such as the liquid crystal display cells, VA liquid crystal display cells of TN liquid crystal display cells, stn liquid crystal display element, TFT liquid crystal display cells, 0CB liquid crystal display cells and lateral electric-field type.
Embodiment
The present invention will be described in more detail below to exemplify embodiment, but the present invention is not limited by this.
Embodiment 1
3,5-diamido benzylacetic acid ester synthetic:
With 20.0g (0.100mol) 3,5-dinitro benzene methyl alcohol is dissolved in the 200ml tetrahydrofuran, adds 30.6g (0.300mol) acetic anhydride, 2.4g (0.030mol) pyridine, refluxes 6 hours under blanket of nitrogen.
Confirm that with TLC (Tin-layer Chromatography thin-layer chromatography) the raw material spot disappears, use ethyl acetate extraction, clean through pure water and remove acetic anhydride and acetate, salt solution is used anhydrous magnesium sulfate drying after cleaning.Use the mixed solvent of ethanol and isopropyl alcohol to carry out recrystallization, obtain milky crystallization (the compound 22g (0.092mol) of formula [ii], yield 92%).
1H-NMR(d-DMSO，δppm)：8.80(1H，t)，8.67(2H，d)，5.33(2H，s)，2.13(3H，s)
1H-NMR is meant the nuclear magnetic resoance spectrum of hydrogen atom in the molecule.
The compound of 20.0g (0.083mol) formula [ii] is dissolved in 200ml1, and the 4-diox fully outgases and the nitrogen displacement, adds the 2.0g platinum oxide, changes nitrogen atmosphere into after fully outgasing once more, at room temperature reacts 24 hours.Reaction is removed platinum oxide with zeyssatite after finishing, and except that after desolvating, uses dissolve with methanol again, carries out charcoal treatment and recrystallization (solvent: ethanol), obtain milky solid (the compound 12g (0.067mmol) of formula [iii], yield 81%).
1H-NMR(CDCl 3，δppm)：6.11(2H，d)，5.98(1H，t)，4.92(2H，s)，3.60(4H，Br)，2.13(3H，s)
The contracted notation that contracts of synthetic etc. compound that is used for polyamic acid and polyimide is as follows.
＜tetracarboxylic dianhydride 〉
CBDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
＜diamines 〉
DABAc:3,5-diaminobenzene methyl acetic acid ester
DABBu:3,5-diaminobenzene methylbutyrate
DABCPr:3,5-diaminobenzene methyl cyclopropane carboxylate
DABCPe:3,5-diaminobenzene methyl cyclopentane carboxylate
DABCPP:3,5-diaminobenzene methyl 3-cyclopentanepropanoiacid acid ester
DABCHx:3,5-diaminobenzene methylcyclohexanecarboxylic acid ester
C14DAB:4-tetradecyloxyaniline-1, the 3-diaminobenzene
3-ABA:3-aminobenzene methyl amine
＜organic solvent 〉
The NMP:N-N-methyl-2-2-pyrrolidone N-
γ-BL: gamma-butyrolacton
BC: butyl cellosolve
DPM: dipropylene glycol monomethyl ether
The mensuration of＜molecular weight 〉
The following mensuration of molecular weight of the polyimide that gets by polyreaction: measure this polyimide by GPC (normal temperature gel permeation chromatography) device, calculate number-average molecular weight and weight-average molecular weight as polyglycol, polyethylene oxide scaled value.
GPC device: Shodex (Showa Denko K. K) corporate system (GPC-101)
Post: Shodex corporate system (series connection of KD803, KD805)
Column temperature: 50 ℃
Eluent: N, and dinethylformamide (as adjuvant, lithium bromide monohydrate (LiBrH 2O) be that 30mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) are 10ml/L for 30mmol/L, tetrahydrofuran (THF))
Flow velocity: 1.0ml/ minute
Calibration curve is made of standard sample: East ソ one (eastern Cao) corporate system TSK standard polyethylene oxide (molecular weight about 900,000,150,000,100,000,30,000) and polymkeric substance laboratory (PolymerLaboratory) corporate system polyglycol (molecular weight about 12,000,4,000,1,000)
The mensuration of＜imidizate rate 〉
Following the calculating of imidizate rate of the polyimide that obtains by polyreaction: this polyimide is dissolved in d6-DMSO (dimethyl sulfoxide-d6), measure 1H-NMR, try to achieve imidizate not and the ratio of remaining acid amides acidic group by the ratio of the integrated value of proton peak, thereby calculate the imidizate rate.
The making of＜liquid crystal structure cell 〉
The aligning agent for liquid crystal that the aligning agent for liquid crystal that modulates with embodiment 2～7, the aligning agent for liquid crystal that embodiment 13～24 modulates and comparative example 1～2 modulate, the liquid crystal structure cell is made in operation as follows.
Aligning agent for liquid crystal is coated on the glass substrate of band transparency electrode with spin-coating method, after on 80 ℃ the hot plate dry 5 minutes, on 210 ℃ hot plate, carries out 10 minutes burn till, formed filming of thickness 70nm.Adopt the rubbing device of roller footpath 120mm, use rayon cloth, under the condition of roller rotating speed 1000rpm, roller gait of march 50mm/sec, the amount of being pressed into 0.3mm, this coated surface is rubbed, obtained the substrate of band liquid crystal orientation film.Prepare 2 substrates that should be with liquid crystal orientation film, scatter the sept of 6 μ m therein on the liquid crystal aligning face of a slice, printing and sealing agent thereon then, make the liquid crystal aligning face relatively and after fitting another plate base thereon under the condition of frictional direction quadrature, make sealant cures, made the negative crystal born of the same parents.Adopt the decompression injection method, in this negative crystal born of the same parents, inject liquid crystal MLC-2003 (Merck Japanese firm (メ Le Network ジ ヤ パ Application society) system),, made the twisted nematic liquid crystal structure cell the inlet sealing.
Below recorded and narrated the method for the evaluation of the mensuration of rerum natura of each the liquid crystal structure cell that makes and characteristic.
The mensuration of the composition of each aligning agent for liquid crystal in embodiment 2～7, the comparative example 1～2, the rerum natura of each liquid crystal orientation film and the evaluation of characteristic etc. the results are summarized in table 1, table 2.In addition, the mensuration of the rerum natura of the composition of each aligning agent for liquid crystal among the embodiment 13～24, each liquid crystal orientation film and the evaluation of characteristic etc. the results are summarized in table 3, table 4.
The evaluation of＜rub resistance 〉
The demonstration test of rub resistance is as follows: rub with the condition that will the amount of being pressed into changes 0.5mm into, with confocal some laser capture microdissection sem observation the film surface, estimate following carrying out.
Zero: do not observe that abrasive dust adheres to and the scar that rubs.
△: observe that abrasive dust adheres to and the scar that rubs.
*: the friction scar is peeled off or be observed visually to film.
＜tilt angle is measured 〉
The twisted nematic liquid crystal structure cell that makes is carried out the mensuration of tilt angle and the mensuration of voltage retention in heating under 105 ℃ after 5 minutes.The mensuration of tilt angle adopts crystal rotation method (Crystal rotation method).
The mensuration of＜voltage retention 〉
Following the carrying out of mensuration to the voltage retention of the twisted nematic liquid crystal structure cell that makes: under 90 ℃ temperature, this liquid crystal structure cell is applied the voltage 60 μ s of 4V, measure the voltage behind the 16.67ms, having calculated voltage can keep what, with this as voltage retention.In addition, the VHR-1 voltage retention determinator of the system mensuration of the voltage retention employing (East Yang テ of Toyo Corp. Network ニ カ society).
＜accumulate the assessment of electric charge (RDC) 〉
Under 23 ℃ temperature, the twisted nematic liquid crystal structure cell that makes is applied DC voltage, from 0V to 1.0V, measure the flicker amplitude level under each voltage with the interval of 0.1V, make calibration curve.After 5 minutes ground connection, apply alternating voltage 3.0V, DC voltage 5.0V, measure the flicker amplitude level after 1 hour, estimate RDC by contrasting ready-made calibration curve.
(appraisal procedure of this RDC is called flicker reference entry (Off リ Star カ one reference entry).)
Embodiment 2
Tetracarboxylic dianhydride's composition uses 5.00g (0.025mol) CBDA, and two amine components use 4.69g (0.026mol) DABAc, and in 38.73g NMP, reaction is 16 hours under room temperature, obtains polyamic acid solution (PAA-1).
10.0g polyamic acid solution (PAA-1) is diluted with 23.3g NMP, 10.0g BC, and forming solid constituent is that 6 quality %, NMP are that 64 quality %, BC are the solution of 30 quality %, obtains aligning agent for liquid crystal of the present invention.Make the liquid crystal structure cell with this coating fluid according to above-mentioned steps, carry out the evaluation of the mensuration and the characteristic of aforesaid rerum natura.
Embodiment 3
In 20g polyamic acid solution (PAA-1), add 46.67g NMP and dilute, add 3.29g acetic anhydride and 1.40g pyridine, react 3 hours down with imidizate at 40 ℃.After being cooled to this reaction solution about room temperature, be fed in the 250ml methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the white powder of polyimide (SPI-1).The number-average molecular weight of this polyimide is 12259, and weight-average molecular weight is 35793.The imidizate rate is 80% in addition.
In the polyimide that obtains (SPI-1) 2g, add 18g NMP, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.Add 8.0g NMP, 12.0g BC again in this solution, in 50 ℃ of stirrings 20 hours, forming polyimide was that 5 quality %, NMP are that 65 quality %, BC are the solution of 30 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid, make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Embodiment 4
Tetracarboxylic dianhydride's composition uses 6.09g (0.031mol) CBDA, and two amine components use 4.00g (0.022mol) DABAc, 3.04g (0.01mol) C14DAB, reacts 16 hours under room temperature in 74.5g NMP, obtains polyamic acid solution (PAA-2).
10.0g polyamic acid solution (PAA-2) is diluted with 23.3g NMP, 10.0g BC, and forming solid constituent is that 6 quality %, NMP are that 64 quality %, BC are the solution of 30 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Embodiment 5
In 50g polyamic acid solution (PAA-2), add 116.67g NMP and dilute, add 7.39g acetic anhydride and 3.15g pyridine, react 3 hours down with imidizate at 50 ℃.
After being cooled to this reaction solution about room temperature, be fed in the 1.25L methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the white powder of polyimide (SPI-2).The number-average molecular weight of this polyimide is 16321, and weight-average molecular weight is 39857.The imidizate rate is 85% in addition.
In polyimide (SPI-2) 2g, add 18g γ-BL, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.In this solution, add 8.0g γ-BL, 6.0g BC, 6.0gDPM again, stirred 20 hours in 50 ℃, forming polyimide is that 5 quality %, γ-BL are that 65 quality %, DPM are that 15 quality %, BC are the solution of 15 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Embodiment 6
Tetracarboxylic dianhydride's composition uses 13.53g (0.073mol) CBDA, two amine components use 4.00g (0.022mol) DABAc, 3.67g (0.030mol) 3-ABA, 7.12g (0.022mol) C14DAB, in 116.0g NMP, under room temperature, reacted 16 hours, obtain polyamic acid solution (PAA-3).
10.0g polyamic acid solution (PAA-3) is diluted with 23.3g NMP, 10.0g BC, and forming solid constituent is that 6 quality %, NMP are that 64 quality %, BC are the solution of 30 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Embodiment 7
In 100g polyamic acid solution (PAA-3), add 233.33g NMP and dilute, add 15.66g acetic anhydride and 6.67g pyridine, react 3 hours down with imidizate at 70 ℃.
After being cooled to this reaction solution about room temperature, be fed in the 1.25L methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the Sandy powder of polyimide (SPI-3).The number-average molecular weight of this polyimide is 18649, and weight-average molecular weight is 41774.The imidizate rate is 94% in addition.
In polyimide (SPI-3) 2g, add 18g γ-BL, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.In this solution, add 8.0g γ-BL, 6.0g BC, 6.0gDPM again, stirred 20 hours in 50 ℃, forming polyimide is that 5 quality %, γ-BL are that 65 quality %, DPM are that 15 quality %, BC are the solution of 15 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Comparative example 1
Tetracarboxylic dianhydride's composition uses 12.5g (0.064mol) CBDA, and two amine components use 5.56g (0.046mol) 3-ABA, 6.25g (0.020mol) C14DAB, reacts 16 hours under room temperature in 97.20g NMP, obtains polyamic acid solution (PAA-4).
10.0g polyamic acid solution (PAA-4) is diluted with 23.3g NMP, 10.0g BC, and forming solid constituent is that 6 quality %, NMP are that 64 quality %, BC are the solution of 30 quality %, obtains the aligning agent for liquid crystal of object as a comparison.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Comparative example 2
In 50g polyamic acid solution (PAA-4), add 116.67g NMP and dilute, add 7.39g acetic anhydride and 3.15g pyridine, react 3 hours down with imidizate at 70 ℃, but in the reaction gelation takes place.
In 50g polyamic acid solution (PAA-4), add 116.67g NMP once more and dilute, add 7.39g acetic anhydride and 3.15g pyridine, change the temperature of reaction of imidizate into 50 ℃ and react.
After being cooled to this reaction solution about room temperature, be fed in the 250ml methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the white powder of polyimide (SPI-4).The number-average molecular weight of this polyimide is 16338, and weight-average molecular weight is 39865.The imidizate rate is 80% in addition.
In polyimide (SPI-4) 1g, add 9g γ-BL, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.In this solution, add 4.0g γ-BL, 3.0g BC, 3.0gDPM again, stirred 20 hours in 50 ℃, forming polyimide is that 5 quality %, γ-BL are that 65 quality %, DPM are that 15 quality %, BC are the solution of 15 quality %, obtains the aligning agent for liquid crystal of object as a comparison.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Table 1
Table 2
Example Rub resistance Tilt angle [°] Voltage retention (VHR) [%], 90 ℃ RDC[V]*
Embodiment 2 ○ 1.2 90 0.15
Embodiment 3 ○ 1.0 93 0.15
Embodiment 4 ○ 3.2 90 0.20
Embodiment 5 ○ 2.8 93 0.15
Embodiment 6 ○ 12.5 91 0.20
Embodiment 7 ○ 4.5 95 0.15
Comparative example 1 △ 6.0 85 0.50
Comparative example 2 × 3.5 92 0.45
*: utilize the optical flicker reference entry, the RDC after DC voltage (DC) has just been cut off
Embodiment 8
3,5-diamido benzyl butyric ester synthetic:
Figure BPA00001278712000281
With 20.0g (0.100mol) 3,5-dinitro benzene methyl alcohol, 2.4g (0.030mol) pyridine are dissolved among the 200ml dehydration DMF, add 11.80g (0.110mol) butyl chloride in ice bath, stir 6 hours under room temperature.
Confirm that with TLC the raw material spot disappears, reaction solution is injected the pure water of cooling,, clean with the first alcohol and water with the solid filtering of separating out., with the mixed solvent of ethanol and isopropyl alcohol carry out recrystallization, obtain milky crystallization (the compound 24g (0.082mol) of formula [iv], yield 82%) thereafter.
1H-NMR(d-DMSO，δppm)：8.80(t，1H)，8.67(d，2H)，5.35(s，2H)，2.45(m，2H)，1.65(m，2H)，0.93-0.89(m，3H)
The compound of 24.0g (0.082mol) formula [iv] is dissolved in 200ml 1, and the 4-diox fully outgases and the nitrogen displacement, adds 2.4g platinum/carbon, changes nitrogen atmosphere into after fully outgasing once more, at room temperature reacts 24 hours.After reaction finishes, remove platinum/carbon, carry out again removing after the charcoal treatment and desolvate, obtain dark brown sticking body (the compound 12g (0.058mol) of formula [v], yield 71%) with diatomite filtration.
1H-NMR(CDCl 3，δppm)：6.11(d，2H)，5.99(t，1H)，4.94(s，2H)，3.62(br，4H)，2.30-1.98(m，2H)，1.61-1.50(m，2H)，0.91-0.86(m，3H)
Embodiment 9
3,5-diamido benzyl cyclopropanecarboxylcompound synthetic:
Figure BPA00001278712000282
With 20.0g (0.100mol) 3,5-dinitro benzene methyl alcohol, 15.7ml cyclopropanecarbonyl chloride are dissolved in the 200ml tetrahydrofuran.To the 10.0ml pyridine that wherein drips, at room temperature stirred 24 hours.After reaction finishes, add the 50ml pure water, stirred 1 hour.Add ethyl acetate therein and carry out solvent extraction, the organic layer that extracts is cleaned successively with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.Organic layer after cleaning adds anhydrous magnesium sulfate and dewaters, and after it is filtered, boils off solvent with rotary evaporator from filtrate.Residue isopropyl alcohol recrystallization after steaming desolventized obtains dinitro compound (the compound 24g (0.090mol) of formula [vi], yield 90%).
1H-NMR(CDCl 3，δppm)：8.80(t，1H)，8.67(d，2H)，5.33(s，2H)，1.80-1.73(m，1H)，0.98-0.92(m，4H)
Compound, the 2.0g platinum oxide of 20.0g (0.075mol) formula [vi] are added 250ml1, in the 4-diox, under nitrogen atmosphere, stir in room temperature.Reaction is removed platinum oxide with diatomite filtration after finishing, and steams with rotary evaporator to desolventize again.Residue after steaming desolventized is dissolved in the 200ml methyl alcohol, adds the 2.0g activated charcoal and at room temperature stirs.Remove activated charcoal with diatomite filtration, desolventize with the rotary evaporator steaming again, residue is carried out recrystallization with ethyl acetate/hexane=1/5, obtain Off-white solid (the compound 12.0g (0.582mol) of formula [vii], yield 78%).
1H-NMR(CDCl 3，δppm)：6.11(d，2H)，5.98(t，1H)，4.92(s，2H)，3.60(br，4H)，1.78-1.65(m，1H)，0.98-0.92(m，4H)
Embodiment 10
3,5-diamido benzyl rings pentane carboxylate synthetic:
Figure BPA00001278712000291
With 20.0g (0.100mol) 3,5-dinitro benzene methyl alcohol, 12.9ml cyclopentane formyl chloride are dissolved in the 200ml tetrahydrofuran.To the 9.0ml pyridine that wherein drips, at room temperature stirred 22 hours.After reaction finishes, add the 50ml pure water, stirred 1 hour.Add ethyl acetate therein and carry out solvent extraction, the organic layer that extracts is cleaned successively with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.Organic layer after cleaning adds anhydrous magnesium sulfate and dewaters, and after it is filtered, boils off solvent with rotary evaporator from filtrate.Residue isopropyl alcohol recrystallization after steaming desolventized obtains dinitro compound (the compound 24g (0.082mol) of formula [viii], yield 82%).
1H-NMR(CDCl 3，δppm)：9.01(t，1H)，8.56-8.54(m，2H)，5.30(d，2H)，2.91-2.83(m，1H)，2.03-1.58(m，8H)
Compound, the 2.5g platinum/carbon of 24.0g (0.082mol) formula [viii] are added in the 250ml methyl alcohol, under nitrogen atmosphere, stir in room temperature.Reaction is removed platinum/carbon with diatomite filtration after finishing, and steams with rotary evaporator to desolventize again.Residue after steaming desolventized is dissolved in the 200ml methyl alcohol, adds the 2.0g activated charcoal and at room temperature stirs.Remove activated charcoal with diatomite filtration, desolventize with the rotary evaporator steaming again, carry out drying under the decompression, obtain brown liquid (the compound 19.3g (0.082mol) of formula [ix], yield 96%).
1H-NMR(CDCl 3，δppm)：6.10(d，2H)，5.97(t，1H)，4.92(s，2H)，3.52(br，4H)，2.77(m，1H)，1.95-1.51(m，8H)
Embodiment 11
3,5-diamido benzyl 3-cyclopentanepropanoiacid acid ester synthetic:
Figure BPA00001278712000301
With 23.1g (0.117mol) 3,5-dinitro benzene methyl alcohol, 19.3ml 3-cyclopentyl propionyl chloride are dissolved in the 250ml tetrahydrofuran.To the 10.3ml pyridine that wherein drips, at room temperature stirred 16 hours.After reaction finishes, add the 50ml pure water, stirred 1 hour.Add ethyl acetate therein and carry out solvent extraction, the organic layer that extracts is cleaned successively with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.Organic layer after cleaning adds anhydrous magnesium sulfate and dewaters, and after it is filtered, boils off solvent with rotary evaporator from filtrate.Residue after steaming desolventized obtains dinitro compound (the compound 29.8g (0.092mol) of formula [x], yield 79%) with hexane/ethyl acetate=3/1 recrystallization.
1H-NMR(CDCl 3，δppm)：9.02(t，1H)，8.57-8.54(m，2H)，5.30(s，2H)，2.49-2.43(m，2H)，1.83-1.45(m，9H)，1.18-1.04(m，2H)
Compound, the 3.1g platinum/carbon of 29.8g (0.092mol) formula [x] are added in the 300ml methyl alcohol, under nitrogen atmosphere, stir in room temperature.Reaction is removed platinum/carbon with diatomite filtration after finishing, and steams with rotary evaporator to desolventize again.Residue after steaming desolventized obtains Sandy solid (the compound 21.6g (0.082mol) of formula [xi], yield 89%) with ethyl acetate/hexane=1/6 recrystallization.
1H-NMR(CDCl 3，δppm)：6.11(d，2H)，5.99(t，1H)，4.92(s，2H)，3.60(br，4H)，2.39-2.34(m，2H)，1.81-1.45(m，9H)，1.17-1.20(m，2H)
Embodiment 12
3,5-diamido benzyl cyclohexane carboxylate synthetic:
Figure BPA00001278712000311
With 20.1g (0.101mol) 3,5-dinitro benzene methyl alcohol, 14.5ml 3-cyclohexane formyl chloride are dissolved in the 200ml tetrahydrofuran.To the 9.0ml pyridine that wherein drips, at room temperature stirred 23 hours.After reaction finishes, add the 50ml pure water, stirred 1 hour.Add ethyl acetate therein and carry out solvent extraction, the organic layer that extracts is cleaned successively with 1N hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.Organic layer after cleaning adds anhydrous magnesium sulfate and dewaters, and after it is filtered, boils off solvent with rotary evaporator from filtrate.Residue isopropyl alcohol recrystallization after steaming desolventized obtains dinitro compound (the compound 25.0g (0.081mol) of formula [xii], yield 81%).
1H-NMR(CDCl 3，δppm)：9.01(t，1H)，8.55-8.53(m，2H)，5.30(d，2H)，2.44(tt，1H)，2.02-1.92(m，2H)，1.83-1.64(m，3H)，1.55-1.18(m，5H)
Compound, the 2.5g platinum/carbon of 24.8g (0.081mol) formula [xii] are added in the 250ml methyl alcohol, under nitrogen atmosphere, stir in room temperature.Reaction is removed platinum/carbon with diatomite filtration after finishing, and steams with rotary evaporator to desolventize again.Residue after steaming desolventized is dissolved in the 200ml methyl alcohol, adds the 2.0g activated charcoal and at room temperature stirs.Remove activated charcoal with diatomite filtration, desolventize with the rotary evaporator steaming again, carry out drying under the decompression, obtain brown liquid (the compound 19.3g (0.078mol) of formula [xiii], yield 96%).
1H-NMR(CDCl 3，δppm)：6.10(d，2H)，5.98(t，1H)，4.92(s，2H)，3.61(br，4H)，2.34(tt，1H)，1.98-1.89(m，2H)，1.81-1.14(m，8H)
Embodiment 13
Tetracarboxylic dianhydride's composition uses 7.64g (0.039mol) CBDA, two amine components use 2.50g (0.012mol) DABBu, 1.95g (0.016mol) 3-ABA, 3.84g (0.012mol) C14DAB, in 63.79g NMP, under room temperature, reacted 16 hours, obtain polyamic acid solution (PAA-5).
10.0g polyamic acid solution (PAA-5) is diluted with 23.3g NMP, 10.0g BC, and forming polyamic acid is that 6 quality %, NMP are that 64 quality %, BC are the solution of 30 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Embodiment 14
In 50g polyamic acid solution (PAA-5), add 116.67g NMP and dilute, add 7.83g acetic anhydride and 3.33g pyridine, react 3 hours down with imidizate at 70 ℃.After being cooled to this reaction solution about room temperature, be fed in the 1.25L methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the Sandy powder of polyimide (SPI-5).The number-average molecular weight of this polyimide is 16358, and weight-average molecular weight is 38735.The imidizate rate is 90% in addition.
In polyimide (SPI-5) 2g, add 18g γ-BL, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.In this solution, add 8.0g γ-BL, 6.0g BC, 6.0gDPM again, stirred 20 hours in 50 ℃, forming polyimide is that 5 quality %, γ-BL are that 65 quality %, DPM are that 15 quality %, BC are the solution of 15 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Embodiment 15
Tetracarboxylic dianhydride's composition uses 5.00g (0.025mol) CBDA, and two amine components use 5.32g (0.026mol) DABCPr, reacts 16 hours under room temperature in 41.32g NMP, obtains polyamic acid solution (PAA-6).
10.0g polyamic acid solution (PAA-6) is diluted with 23.3g NMP, 10.0g BC, and forming polyamic acid is that 6 quality %, NMP are that 64 quality %, BC are the solution of 30 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Embodiment 16
In 20g polyamic acid solution (PAA-6), add 46.67g NMP and dilute, add 3.06g acetic anhydride and 1.31g pyridine, react 3 hours down with imidizate at 40 ℃.After being cooled to this reaction solution about room temperature, be fed in the 250ml methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the white powder of polyimide (SPI-6).The number-average molecular weight of this polyimide is 13329, and weight-average molecular weight is 33233.The imidizate rate is 81% in addition.
In polyimide (SPI-6) 2.00g of gained, add 18.0g γ-BL, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.In this solution, add 8.0g γ-BL, 6.00g BC, 6.00g DPM again, stirred 20 hours in 50 ℃, forming polyimide is that 5 quality %, γ-BL are that 65 quality %, DPM are that 15 quality %, BC are the solution of 15 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Embodiment 17
Tetracarboxylic dianhydride's composition uses 5.52g (0.028mol) CBDA, two amine components use 1.79g (0.009mol) DABCPr, 1.42g (0.011mol) 3-ABA, 2.79g (0.009mol) C14DAB, in 46.1gNMP, under room temperature, reacted 16 hours, obtain polyamic acid solution (PAA-7).
10.0g polyamic acid solution (PAA-7) is diluted with 23.3g NMP, 10.0g BC, and forming polyamic acid is that 6 quality %, NMP are that 64 quality %, BC are the solution of 30 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Embodiment 18
In 40.0g polyamic acid solution (PAA-7), add 93.3g NMP and dilute, add 6.02g acetic anhydride and 2.49g pyridine, react 3 hours down with imidizate at 60 ℃.After being cooled to this reaction solution about room temperature, be fed in the 500ml methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the white powder of polyimide (SPI-7).The number-average molecular weight of this polyimide is 17430, and weight-average molecular weight is 48532.The imidizate rate is 90% in addition.
In this polyimide (SPI-7) 2.00g, add 18.0g γ-BL, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.In this solution, add 8.00g γ-BL, 6.00g BC, 6.00g DPM again, stirred 20 hours in 50 ℃, forming polyimide is that 5 quality %, γ-BL are that 65 quality %, DPM are that 15 quality %, BC are the solution of 15 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Embodiment 19
Tetracarboxylic dianhydride's composition uses 5.71g (0.029mol) CBDA, two amine components use 2.11g (0.009mol) DABCPe, 1.47g (0.012mol) 3-ABA, 2.88g (0.009mol) C14DAB, in 48.7g NMP, under room temperature, reacted 16 hours, obtain polyamic acid solution (PAA-8).
10.0g polyamic acid solution (PAA-8) is diluted with 23.3g NMP, 10.0g BC, and forming polyamic acid is that 6 quality %, NMP are that 64 quality %, BC are the solution of 30 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Embodiment 20
In 40.0g polyamic acid solution (PAA-8), add 93.3g NMP and dilute, add 5.98g acetic anhydride and 2.57g pyridine, react 3 hours down with imidizate at 60 ℃.After being cooled to this reaction solution about room temperature, be fed in the 500ml methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the white dark brown powder of polyimide (SPI-8).The number-average molecular weight of this polyimide is 14757, and weight-average molecular weight is 36865.The imidizate rate is 90% in addition.
In this polyimide (SPI-8) 2.00g, add 18.0g γ-BL, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.In this solution, add 8.00g γ-BL, 6.00g BC, 6.00g DPM again, stirred 20 hours in 50 ℃, forming polyimide is that 5 quality %, γ-BL are that 65 quality %, DPM are that 15 quality %, BC are the solution of 15 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Embodiment 21
Tetracarboxylic dianhydride's composition uses 5.71g (0.029mol) CBDA, two amine components use 2.36g (0.009mol) DABCPP, 1.47g (0.012mol) 3-ABA, 2.88g (0.009mol) C14DAB, in 48.7g NMP, under room temperature, reacted 16 hours, obtain polyamic acid solution (PAA-9).
10.0g polyamic acid solution (PAA-9) is diluted with 23.3g NMP, 10.0g BC, and forming polyamic acid is that 6 quality %, NMP are that 64 quality %, BC are the solution of 30 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Embodiment 22
In 40.0g polyamic acid solution (PAA-9), add 93.3g NMP and dilute, add 5.86g acetic anhydride and 2.51g pyridine, react 3 hours down with imidizate at 60 ℃.After being cooled to this reaction solution about room temperature, be fed in the 500ml methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the white dark brown powder of polyimide (SPI-9).The number-average molecular weight of this polyimide is 14900, and weight-average molecular weight is 35161.The imidizate rate is 91% in addition.
In this polyimide (SPI-9) 2.00g, add 18.0g γ-BL, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.In this solution, add 8.00g γ-BL, 6.00g BC, 6.00g DPM again, stirred 20 hours in 50 ℃, forming polyimide is that 5 quality %, γ-BL are that 65 quality %, DPM are that 15 quality %, BC are the solution of 15 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Embodiment 23
Tetracarboxylic dianhydride's composition uses 5.71g (0.029mol) CBDA, two amine components use 2.23g (0.009mol) DABCHx, 1.47g (0.012mol) 3-ABA, 2.88g (0.009mol) C14DAB, in 49.2g NMP, under room temperature, reacted 16 hours, obtain polyamic acid solution (PAA-10).
10.0g polyamic acid solution (PAA-10) is diluted with 23.3g NMP, 10.0g BC, and forming polyamic acid is that 6 quality %, NMP are that 64 quality %, BC are the solution of 30 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Embodiment 24
In 40.0g polyamic acid solution (PAA-10), add 93.3g NMP and dilute, add 5.92g acetic anhydride and 2.54g pyridine, react 3 hours down with imidizate at 60 ℃.After being cooled to this reaction solution about room temperature, be fed in the 500ml methyl alcohol, reclaim the precipitated solid material.Then, with this solid matter with washed with methanol for several times after, at 100 ℃ of following drying under reduced pressure, obtain the white dark brown powder of polyimide (SPI-10).The number-average molecular weight of this polyimide is 15864, and weight-average molecular weight is 41355.The imidizate rate is 88% in addition.
In this polyimide (SPI-10) 2.00g, add 18.0g γ-BL, stirred 20 hours in 50 ℃.Polyimide dissolves fully when stirring end.In this solution, add 8.00g γ-BL, 6.00g BC, 6.00g DPM again, stirred 20 hours in 50 ℃, forming polyimide is that 5 quality %, γ-BL are that 65 quality %, DPM are that 15 quality %, BC are the solution of 15 quality %, obtains aligning agent for liquid crystal of the present invention.Use this coating fluid to make the liquid crystal structure cell similarly to Example 2, carry out the evaluation of the mensuration and the characteristic of rerum natura.
Table 3
Figure BPA00001278712000361
Table 4
Example Rub resistance Tilt angle [°] Voltage retention (VHR) [%], 90 ℃ RDC[V]*
Embodiment 13 ○ 11.7 ?92 0.15
Embodiment 14 ○ 4.7 ?94 0.20
Embodiment 15 ○ 1.1 ?91 0.22
Embodiment 16 ○ 0.8 ?93 0.20
Embodiment 17 ○ 5.0 ?92 0.22
Embodiment 18 ○ 3.8 ?95 0.12
Embodiment 19 ○ 5.4 ?92 0.33
Embodiment 20 ○ 3.7 ?94 0.29
Embodiment 21 ○ 6.2 ?93 0.30
Embodiment 22 ○ 3.7 ?93 0.25
Embodiment 23 ○ 5.5 ?93 0.32
Embodiment 24 ○ 3.7 ?94 0.25
*: utilize the optical flicker reference entry, the RDC after DC voltage (DC) has just been cut off
From embodiment 2,4,6,13,15,17,19,21 and 23 and comparative example 1 more as can be known, for the aligning agent for liquid crystal that contains polyamic acid, the diamines of part or all employing formula [1] expression by making two amine components, the voltage retention of liquid crystal structure cell improves, and the electric charge of accumulating when DC voltage puts on the liquid crystal structure cell reduces, and the rub resistance of liquid crystal orientation film also improves.In addition, from embodiment 3,5,7,14,16,18,20,22 and 24 and comparative example 2 more as can be known, for the aligning agent for liquid crystal that contains polyimide, the diamines by part or all the employing formula [1] that makes two amine components is represented also can obtain same effect.Also have, from embodiment 4 and embodiment 6, and embodiment 5 and embodiment 7 more as can be known, with the diamines of formula [1] and the diamines combination of formula [2], can improve the effect that increases liquid crystal pretilt angle.
Utilizability on the industry
By aligning agent for liquid crystal of the present invention can obtain voltage retention high and apply DC voltage, the few alignment films of the electric charge of accumulating after stopping. Therefore, the liquid crystal display cells that uses aligning agent for liquid crystal of the present invention to make can be used as the high liquid crystal display device of reliability, is suitable for 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.
Here quote of the announcement of the full content of Japanese patent application 2008-158456 number instructions, claims and the summary of filing an application on June 17th, 2008 as instructions of the present invention.

Claims (11)

1. aligning agent for liquid crystal is characterized in that, comprise polyamic acid maybe with this polyamic acid imidizate and at least one side of polyimide, described polyamic acid is by two amine components and the reaction of tetracarboxylic dianhydride's composition of the diamines that contains following formula [1] and get,
Figure FPA00001278711900011
In the formula, R represents the saturated hydrocarbyl of carbon number 1～25.
2. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, the diamines of formula [1] expression occupies 20～100 moles of % of synthetic whole two amine components of polyamic acid.
3. aligning agent for liquid crystal as claimed in claim 1 or 2 is characterized in that, the diamines of formula [1] expression is in a position or bit position is had the diamines of 2 amino.
4. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, with the diamines that comprises following formula [2] expression in two amine components of tetracarboxylic dianhydride's composition reaction,
Figure FPA00001278711900012
In the formula, Ar represents phenyl ring or naphthalene nucleus, R 1Be the alkylidene of carbon number 1～5, R 2Be hydrogen atom or methyl.
5. as each described aligning agent for liquid crystal in the claim 1～4, it is characterized in that tetracarboxylic dianhydride's composition is the tetracarboxylic dianhydride's composition that comprises the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure.
6. liquid crystal orientation film is characterized in that, is obtained by each described aligning agent for liquid crystal in the claim 1～5.
7. liquid crystal display cells is characterized in that, possesses the described liquid crystal orientation film of claim 6.
8. the diamines of following formula [1-1],
In the formula, R 3Straight chain shape alkyl for carbon number 1～5.
9. the diamines of following formula [1-2],
Figure FPA00001278711900022
In the formula, R 4Saturated hydrocarbyl for the carbon number 3～8 that comprises at least 1 ring structure.
10. polyamic acid is characterized in that, by the reaction of two amine components that contain claim 8 or 9 described diamines and tetracarboxylic dianhydride's composition and get.
11. polyimide is characterized in that, the described polyamic acid imidizate of claim 10 is got.
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