CN101641322A - Diamine compound, polyamic acid, polyimide and liquid crystal aligning agent - Google Patents

Diamine compound, polyamic acid, polyimide and liquid crystal aligning agent Download PDF

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CN101641322A
CN101641322A CN200880009119A CN200880009119A CN101641322A CN 101641322 A CN101641322 A CN 101641322A CN 200880009119 A CN200880009119 A CN 200880009119A CN 200880009119 A CN200880009119 A CN 200880009119A CN 101641322 A CN101641322 A CN 101641322A
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liquid crystal
diamines
polyimide
aligning agent
polyamic acid
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CN101641322B (en
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三木德俊
南悟志
高山祐树
保坂和义
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/76—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and etherified 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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Abstract

Disclosed is a novel diamine which has an effect of increasing the pretilt angle of a liquid crystal when used as a raw material for a liquid crystal aligning agent. This diamine enables to verticallyalign a liquid crystal even when used in a small amount.In addition, this diamine hardly precipitates even when a poor solvent is mixed in a liquid crystal aligning agent solution for improving coatability of the agent. Specifically disclosed is a diamine represented by the following formula (1). (1) (In the formula (1), R1 represents a phenylene; R2 represents a cyclohexylene or a phenylene; R3represents a cyclohexylene; and R4 represents an alkyl group having 3-12 carbon atoms, a fluoroalkyl group having 3-12 carbon atoms, an alkoxy group having 3-12 carbon atoms or a fluoroalkoxy group having 3-12 carbon atoms.

Description

Diamine compound, polyamic acid, polyimide and aligning agent for liquid crystal
Technical field
The present invention relates to can be used as new diamine compound (the present invention also abbreviates diamines as) that the raw material of the polymkeric substance that is used for liquid crystal orientating membrane uses, use this diamines and polyamic acid, polyimide and aligning agent for liquid crystal.
Background technology
At present, the liquid crystal orientating membrane that is used for liquid crystal display device in most cases uses polyimide film, and this polyimide film is by making as the method that the solution coat of the solution of the polyamic acid of polyimide precursor or solvent soluble polyimide is burnt till behind substrate.This polyamic acid or solvent soluble polyimide generally synthesize by the reaction of tetracarboxylic acid derivatives such as tetracarboxylic dianhydride and diamines.
One of desired characteristic of liquid crystal orientating membrane is the control that the directional inclination angle of liquid crystal molecule and substrate surface is remained the so-called liquid crystal pretilt angle of certain value.The big I of known this tilt angle changes by the structure that selection constitutes the polyimide of liquid crystal orientating membrane.
Utilize the structure of polyimide to control in the technology of tilt angle, the method that the diamines that will have a side chain uses as the part of polyimide raw material is owing to can control tilt angle according to the usage ratio of this diamines, therefore than the tilt angle that is easier to obtain to want, can be used as the method that adds big tilt angle.As the side-chain structure of the diamines of the tilt angle that strengthens liquid crystal, known combination (for example with reference to patent documentation 2), the steroid skeleton (for example with reference to patent documentation 3) that chain alkyl or fluoro-alkyl (for example with reference to patent documentation 1), cyclic group or cyclic group and alkyl are arranged.
In addition, carried out improving the structural research of the stability and the operation dependency of tilt angle for the described diamines that is used to strengthen the tilt angle of liquid crystal, as side-chain structure used herein, proposed to comprise the side-chain structure (for example with reference to patent documentation 4,5) of ring structures such as phenyl or cyclohexyl.In addition, the diamines (for example with reference to patent documentation 6) that side chain has 3 or 4 these ring structures has also been proposed.
In recent years, compared with the past along with liquid crystal display device is widely used in the LCD TV and the high-accuracy portable equipment (display part of digital camera or mobile telephone) of big picture, used substrate is tending towards maximizing, and the concavo-convex change of substrate profile is big.Under this situation, consider,, require coating of liquid crystalline oriented film equably for large substrate and substrate profile from the angle of display characteristic.
In the making processes of liquid crystal orientating membrane, when the solution of polyamic acid solution or solvent soluble polyimide was applied to substrate, industrial circle generally waited by flexible printing and implements.The solvent of coating fluid is except the good solvent of dissolving resin such as N-N-methyl-2-2-pyrrolidone N-or gamma-butyrolactone (below be also referred to as good solvent), in order to improve the homogeneity of filming, also sneaked into the low solvent of dissolving resin such as ethylene glycol butyl ether (below be also referred to as Weak solvent).But, the ability of Weak solvent dissolving polyamic acid or polyimide, so can separate out (for example with reference to patent documentation 7) by polymkeric substance during macro-mixing.Particularly this problem more highlights in the solution of solvent soluble polyimide.In addition, the tendency of using the aforementioned polyimide that has the diamines of side chain and get to exist the coating homogeneity of solution to descend, the therefore necessary combined amount that increases Weak solvent, the mixing allowance of this solvent also becomes the key property of polyimide.
Patent documentation 1: Japanese patent laid-open 2-282726 communique
Patent documentation 2: Japanese patent laid-open 3-179323 communique
Patent documentation 3: Japanese patent laid-open 4-281427 communique
Patent documentation 4: Japanese patent laid-open 9-278724 communique
Patent documentation 5; The international text that discloses No. 2004/52962
Patent documentation 6: the Japanese Patent spy opens the 2004-67589 communique
Patent documentation 7: Japanese patent laid-open 2-37324 communique
The announcement of invention
The purpose of this invention is to provide new diamines as the raw material use of polyamic acid and/or polyimide, this diamines has the effect of the tilt angle that strengthens liquid crystal when using as the raw material of the polyamic acid that constitutes liquid crystal orientating membrane and/or polyimide (below be also referred to as polymkeric substance), just can make the liquid crystal vertical orientation with less usage ratio, and polymkeric substance is difficult for also separating out when having sneaked into Weak solvent in the coating fluid of polymkeric substance.
In addition, the purpose of this invention is to provide the polymkeric substance that obtains by described new diamines, contain the aligning agent for liquid crystal of this polymkeric substance, and the liquid crystal display device that possesses the liquid crystal orientating membrane that obtains with this aligning agent for liquid crystal.
The present inventor has finished the present invention that can realize above purpose after conscientiously studying, the present invention possesses following technical characterictic.
1. the diamines of following formula (1) expression,
In the formula (1), R 1Be phenylene, R 2Be cyclohexylidene or phenylene, R 3Be cyclohexylidene, R 4Be in the fluoroalkyl of the alkoxyl group of the fluoro-alkyl of the alkyl of carbon number 3～12, carbon number 3～12, carbon number 3～12 or carbon number 3～12 any.
2. the diamines of above-mentioned 1 record, in the formula (1), R 1Be 1,4-phenylene, R 2Be 1,4-cyclohexylidene or 1,4-phenylene, R 3Be 1, the 4-cyclohexylidene.
3. the diamines of above-mentioned 1 or 2 records, this diamines are by following formula (2-1) expression,
Figure G2008800091198D00032
In the formula (2-1), n is 2～11 integer, 1, and the cis-trans isomerization of 4-cyclohexylidene is respectively trans-isomer(ide).
4. the diamines of above-mentioned 1 or 2 records, this diamines are by following formula (2-2) expression,
Figure G2008800091198D00033
In the formula (2-2), n is 2～11 integer, 1, and the cis-trans isomerization of 4-cyclohexylidene is a trans-isomer(ide).
5. make two amine components of the diamines that contains each record in above-mentioned 1～4 and tetracarboxylic dianhydride reaction and polyamic acid or make this polyamic acid dehydration closed-loop and polyimide.
6. the polyamic acid or the polyimide of above-mentioned 5 records, 10 moles of % in two amine components are above to be the diamines of each record in above-mentioned 1～4.
7. aligning agent for liquid crystal contains above-mentioned 5 or 6 polyamic acid and/or the polyimide of putting down in writing.
8. the aligning agent for liquid crystal of above-mentioned 7 records contains organic solvent, and this organic solvent contains the Weak solvent of 5～60 quality %.
9. liquid crystal orientating membrane adopts the aligning agent for liquid crystal of above-mentioned 7 or 8 records and gets.
10. liquid crystal display device possesses above-mentioned 9 liquid crystal orientating membranes of putting down in writing.
When diamines of the present invention uses as the raw material of the polymkeric substance that constitutes liquid crystal orientating membrane, possesses the effect that strengthens liquid crystal pretilt angle significantly.As described later shown in the table 2, the tilt angle of the liquid crystal orientating membrane that the diamines of being represented by formula (2-1) of the present invention (m-PBCH5DABz) obtains is about 86 °, the tilt angle of the liquid crystal orientating membrane that is obtained by diamines (m-PBCH7DABz) is about 87 °, but the tilt angle of the liquid crystal orientating membrane that is obtained by the existing diamines (PCH7DAB) of the patent documentation 4 with similar structures is about 22 °, unexpectedly about 4 times.
Therefore, can give liquid crystal with big tilt angle with less usage ratio by the aligning agent for liquid crystal that diamines of the present invention obtains, and can make the liquid crystal vertical orientation.
When modulation is used to obtain the coating fluid of liquid crystal orientating membrane, under the situation of improving coating a large amount of use Weak solvents when using good solvent, also be difficult for separating out by polymkeric substance in the aligning agent for liquid crystal of diamines acquisition of the present invention, when coating large substrate, the film of homogeneous can be formed, the good liquid crystal orientating membrane of characteristic can be made.
The best mode that carries out an invention
Below, the present invention is described in detail.
1. diamines
Diamines of the present invention is by conjugated group (CH 2O-) will have-phenylene-cyclohexylidene-or phenylene-cyclohexylidene-R 4The side chain of structure be incorporated into the diamino phenyl ring and compound.That is, the diamino benzene derivant of following formula (1) expression,
Figure G2008800091198D00041
In the formula (1), R 1Be phenylene, R 2Be cyclohexylidene or phenylene, R 3Be cyclohexylidene.Phenylene and cyclohexylidene can possess substituting group as required.R 4Be the alkyl of carbon number 3～12, the fluoro-alkyl of carbon number 3～12, the alkoxyl group of carbon number 3～12 or the fluoroalkyl of carbon number 3～12.Alkyl, fluoro-alkyl, alkoxyl group and fluoroalkyl can be straight chain shape or branch-like, preferred straight chain shape, and can have suitable substituents.
Binding site for the amino in the phenyl ring that constitutes described diamino phenyl ring is not particularly limited.As concrete example, with respect to the conjugated group (CH of side chain 2O-), can exemplify prosposition on the phenyl ring, 2,4,2,5,2,6,3,4,3,5.Reactive angle during wherein, from synthesizing polyamides acid is considered preferred 2,4,2,5,3,5.If also consider diamines synthetic difficulty or ease, then be more preferably 2,5 or 3,5.
Consider from the angle of the tilt angle that more effectively strengthens liquid crystal, in the diamines of described formula (1) expression, be preferably R 1Be 1, the 4-phenylene.In addition, be preferably R 2Be 1,4-phenylene or 1, the 4-cyclohexylidene is more preferably R 2Be 1,4-phenylene or 1,4-is anti--cyclohexylidene, that special good is R 2Be 1,4-is anti--cyclohexylidene.In addition, be preferably R 3Be 1, the 4-cyclohexylidene, that special good is R 3Be 1,4-is anti--cyclohexylidene.
Therefore, R 1, R 2And R 3Combination in, be preferably R 1Be 1,4-phenylene, R 2Be 1,4-cyclohexylidene or 1,4-phenylene, R 3Be 1, the 4-cyclohexylidene.Be more preferably R 1Be 1,4-phenylene, R 2Be 1,4-phenylene or 1,4-is anti--cyclohexylidene, R 3Be 1,4-is anti--cyclohexylidene.
The preferred concrete example of the diamines of following formula of the present invention (1) expression is as follows.N in the following formula is 2～11 integer, is preferably 2～8 integer.In addition, 1 in the formula, the cis-trans isomerization of 4-cyclohexylidene is respectively trans-isomer(ide).
Figure G2008800091198D00061
Method for the diamines of making described formula of the present invention (1) expression is not particularly limited, and can exemplify following method as preferred method.
Figure G2008800091198D00062
The dinitro compound of synthetic following formula (3) is converted into amino by common method reduction nitro, can obtain the diamines of formula of the present invention (1) expression by this.R in the formula (3) 1, R 2, R 3, R 4Definition identical with the definition in the formula (1).
The dinitro compound of formula (3) can pass through reactions such as the compound of hydroxyl of following formula (4) expression and dinitrobenzene benzyl chloride and get.R in the formula (4) 1, R 2, R 3, R 4Definition identical with the definition in the formula (1).
HO-R 1-R 2-R 3-R 4????(4)
The compound of the hydroxyl of following formula (4) expression can make by the method shown in following reaction formula [1] or the reaction formula [2], but the present invention is not limited thereto.
R 1During for cyclohexylidene, can exemplify the synthesis path of reaction formula [1].R in the reaction formula [1] 1, R 2, R 3, R 4Definition identical with the definition in the formula (1).X 1Protecting groups such as expression methyl or phenmethyl, X 2Expression MgBr, MgCl or Li etc.
As the reagent that is used for dehydration reaction, can exemplify inorganic acids such as hydrochloric acid or sulfuric acid, organic acids such as tosic acid, anhydrides such as diacetyl oxide or trifluoroacetic anhydride etc.
As reduction reaction, can exemplify and adopt palladium (Pd) or platinum (Pt) etc. as the hydrogenation of catalyzer or used the catalytic reduction reaction etc. of metals such as iron, tin or zinc.As the reaction of deprotection base, can exemplify and use boron tribromide (BBr 3) the methyl reaction etc. that breaks away from reaction or take off phenmethyl by the hydrogenation of having used Pd catalyzer etc.
Figure G2008800091198D00071
By above reaction formula [1], can make the compound of the hydroxyl of following formula shown below (4) expression.
Figure G2008800091198D00081
R 2During for phenylene, can exemplify the synthesis path of reaction formula [2].R in the reaction formula [2] 1, R 2, R 3, R 4Definition identical with the definition in the formula (1).X 1Protecting groups such as expression methyl or phenmethyl, X 3Expression halogen atom, mesyloxy, phenylsulfonyloxy, trifluoro-methanesulfonyl oxy, B (OH) 2, MgBr, MgCl or Li etc., X 4Expression halogen atom, mesyloxy, phenylsulfonyloxy, trifluoro-methanesulfonyl oxy, B (OH) 2, MgBr, MgCl or Li etc.As the reaction of deprotection base, can exemplify and use BBr 3The methyl reaction etc. that breaks away from reaction or take off phenmethyl by the hydrogenation of having used Pd catalyzer etc.
Figure G2008800091198D00091
By above reaction formula [2], can make the compound of the hydroxyl of following formula shown below (4) expression.
Figure G2008800091198D00092
Diamines of the present invention further makes this polyamic acid dehydration closed-loop can obtain the polyimide that side chain has specific structure by obtaining the polyamic acid that side chain has specific structure with tetracarboxylic acid or derivatives thereof reactions such as tetracarboxylic acid, tetracarboxylic acid two carboxylic acid halides, tetracarboxylic dianhydrides.
2. polyamic acid
Polyamic acid of the present invention is the polyamic acid that gets by two amine components of the diamines that contains formula (1) expression and tetracarboxylic dianhydride's reaction.Polyimide of the present invention be make this polyamic acid dehydration closed-loop and polyimide.This polyamic acid and polyimide all can be used as the polymkeric substance that obtains liquid crystal orientating membrane.
For by to obtain containing of diamines that the formula (1) in two amine components (below be also referred to as two amine components) of polyamic acid represents proportional no specific with described tetracarboxylic dianhydride reaction.Containing of the diamines of formula (1) in described two amine components expression is proportional many more, adopt polyamic acid of the present invention or polyimide and the liquid crystal pretilt angle of liquid crystal orientating membrane big more.
Tilt angle with the increasing liquid crystal is a purpose, is preferably the above diamines for formula (1) expression of 1 mole of % of two amine components.
So that the liquid crystal vertical orientation is a purpose, be preferably the above diamines of 10 moles of % of two amine components for formula (1) expression, be more preferably 15 moles more than the %.
So that the liquid crystal vertical orientation is a purpose, 100 moles of % that can be two amine components are the diamines of formula (1) expression, but the angle of the homogeneous coating during from coating of liquid crystalline aligning agent described later is considered, the diamines of formula (1) expression is preferably 80 moles of two amine components below the %, more preferably 40 moles below the %.
In described two amine components, during 100 moles of % of diamines less than of formula (1) expression, be not particularly limited for the diamines beyond the diamines of used formula (1) expression.Its concrete example is following to be exemplified.
Ursol D, mphenylenediamine, 2, the 4-diaminotoluene, 2, the 5-diaminotoluene, 2, the 6-diaminotoluene, 2,4-dimethyl-1, the 3-diaminobenzene, 2,5-dimethyl-1, the 4-diaminobenzene, 2,3,5,6-tetramethyl--1, the 4-diaminobenzene, 2, the 4-diaminophenol, 2, the 5-diaminophenol, 4, the 6-diamino resorcin, 2, the 5-diaminobenzoic acid, 3, the 5-diaminobenzoic acid, N, N-diallyl-2,4-diamino aniline, N, N-diallyl-2,5-diamino aniline, 4-amino-benzene methylamine, 3-amino-benzene methylamine, 2-(4-aminophenyl) ethamine, 2-(3-aminophenyl) ethamine, 1, the 5-naphthylene diamine, 2, the 7-naphthylene diamine, 4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxyl-4,4 '-benzidine, 3,3 '-dicarboxyl-4,4 '-benzidine, 3,3 '-two fluoro-4,4 '-benzidine, 2,2 '-trifluoromethyl-4,4 '-benzidine, 3,3 '-trifluoromethyl-4,4 '-benzidine, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diamino-diphenyl amine, 3,3 '-diamino-diphenyl amine, 3,4 '-diamino-diphenyl amine, N-methyl (4,4 '-diamino-diphenyl) amine, N-methyl (3,3 '-diamino-diphenyl) amine, N-methyl (3,4 '-diamino-diphenyl) amine, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 4,4 '-diamino-N-benzanilide, 1, two (4-aminophenyl) ethane of 2-, 1, two (3-aminophenyl) ethane of 2-, 4,4 '-diamino tolane, 1, two (4-aminophenyl) propane of 3-, 1, two (3-aminophenyl) propane of 3-, 2, two (4-aminophenyl) propane of 2-, 2, two (3-aminophenyl) propane of 2-, 2, two (3-amino-4-aminomethyl phenyl) propane of 2-, 2, two (4-aminophenyl) HFC-236fa of 2-, 2, two (3-aminophenyl) HFC-236fa of 2-, 2, two (3-amino-4-aminomethyl phenyl) HFC-236fa of 2-, 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-, 1, two (4-amino-benzene oxygen) undecanes of 11-, 1, two (4-amino-benzene oxygen) dodecanes of 12-, two (4-aminophenyl) malonic ester, two (4-aminophenyl) succinate, two (4-aminophenyl) glutarate, two (4-aminophenyl) adipic acid ester, two (4-aminophenyl) pimelate, two (4-aminophenyl) suberate, two (4-aminophenyl) azelate, two (4-aminophenyl) sebate, 1, two (4-aminophenyl) benzene of 4-, 1, two (4-aminophenyl) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (the 4-amino-benzene methyl) benzene of 4-, 1, two (the 4-amino-benzene methyl) benzene of 3-, two (4-aminophenyl) terephthalate, two (3-aminophenyl) terephthalate, two (4-aminophenyl) isophthalic acid ester, two (3-aminophenyl) isophthalic acid ester, 1,4-phenylene two [(4-aminophenyl) ketone], 1,4-phenylene two [(3-aminophenyl) ketone], 1,3 phenylenes two [(4-aminophenyl) ketone], 1,3-phenylene two [(3-aminophenyl) ketone], 1,4-phenylene two (4-Aminobenzoate), 1,4-phenylene two (3-Aminobenzoate), 1,3-phenylene two (4-Aminobenzoate), 1,3-phenylene two (3-Aminobenzoate), N, N '-(1, the 4-phenylene) two (4-aminobenzamides), N, N '-(1, the 3-phenylene) two (4-aminobenzamide), N, N '-(1, the 4-phenylene) two (3-aminobenzamides), N, N '-(1, the 3-phenylene) two (3-aminobenzamide), two (4-aminophenyl) terephthalamide, two (3-aminophenyl) terephthalamide, two (4-aminophenyl) isophthaloyl amine, two (3-aminophenyl) isophthaloyl amine, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 4,4 '-two (4-amino-benzene oxygen) sulfobenzide, 2, the 6-diamino-pyridine, 2, the 4-diamino-pyridine, 2, the 4-diaminostilbene, 3, the 5-triazine, 2,6-diamino diphenylene-oxide, 2,7-diamino diphenylene-oxide, 3,6-diamino diphenylene-oxide, 2,6-diamino carbazole, 2,7-diamino carbazole, 3,6-diamino carbazole, 2,4-diamino-6-sec.-propyl-1,3, the 5-triazine, 2, two (the 4-aminophenyls)-1 of 5-, 3, the 4-oxadiazole, 1, the 3-diaminopropanes, 1, the 4-diaminobutane, 1,5-diamino pentane, 1, the 6-diamino hexane, 1,7-diamino heptane, 1,8-diamino octane, 1,9-diamino nonane, 1, the 10-diamino decane, 1,11-diamino undecane, 1,12-diamino dodecane, 1, the 4-diamino-cyclohexane, 1, the 3-diamino-cyclohexane, two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane.
For being not particularly limited with the tetracarboxylic dianhydride of two amine components reaction in order to obtain polyamic acid of the present invention.Its concrete example exemplifies as follows.
Pyromellitic acid anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,5,6-anthracene tetracarboxylic 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) methane dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, 2,2-two (3,4-dicarboxyl phenyl) propane dianhydride, 2, two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2-, 2,5-dicarboxyl methyl terephthaldehyde acid dianhydride, 4,6-dicarboxyl methyl m-phthalic acid dianhydride, 4-(2,5-dioxo tetrahydrochysene-3-furyl) Tetra hydro Phthalic anhydride, 1,4-two (2,5-dioxo tetrahydrochysene-3-furyl) benzene, 1, two (2, the 6-dioxo tetrahydrochysene-4-pyranyl) benzene of 4-, 1,4-two (2,5-dioxo tetrahydrochysene-3-methyl-3-furyl) benzene, 1, two (2, the 6-dioxo tetrahydrochysene-4-methyl-4-pyranyl) benzene of 4-, 1,2,3,4-butane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 4-(2,5-dioxo tetrahydrochysene-3-furyl)-hexanaphthene-1, the 2-dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, two ring [2.2.2] suffering-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-6-methyl isophthalic acid-naphthalene succinic dianhydride, two ring [3.3.0] octanes-2,4,6, the 8-tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5,6-norbornane tetracarboxylic dianhydride, 3,5,6-three carboxyls norbornane-2-acetate dianhydride, three ring [4.2.1.0 2,5] nonane-3,4,7,8-tetracarboxylic dianhydride, Fourth Ring [4.4.1.0 2,5.0 7,10] undecane-3,4,8,9-tetracarboxylic dianhydride, six ring [6.6.0.1 2,7.0 3,6.1 9,14.0 10,13] n-Hexadecane-4,5,11,12-tetracarboxylic dianhydride, 1, two (2, the 5-dioxo tetrahydrochysene-3-furyl) hexanes, 1 of 4-, two (2, the 6-dioxo tetrahydrochysene-4-pyranyl) hexanes of 4-.
As the method that makes described two amine components and tetracarboxylic dianhydride reaction, easier is in organic solvent hybrid diamine composition and tetracarboxylic dianhydride's method.
As this organic solvent,, be not particularly limited so long as the organic solvent of the polyamic acid that solubilized generates gets final product.Its concrete example can exemplify N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-methyl caprolactam, methyl-sulphoxide, gamma-butyrolactone etc.These solvents can use separately also can mix use.In addition, even use can't make polyamic acid dissolved solvent separately, as long as in the scope that the polyamic acid that generates is not separated out, can also use with above-mentioned solvent.In addition,, also can make the polyamic acid hydrolysis of generation, so organic solvent re-uses after preferably dehydrating as much as possible because the moisture in the organic solvent can hinder the carrying out of polyreaction.
Method as hybrid diamine composition and tetracarboxylic dianhydride in organic solvent, can exemplify diamines is dispersed or dissolved in organic solvent and the solution that forms stirs, directly add the tetracarboxylic dianhydride or make the tetracarboxylic dianhydride be dispersed or dissolved in the method for adding again behind the organic solvent; On the contrary, be dispersed or dissolved in organic solvent and the method for adding diamines in the solution that forms the tetracarboxylic dianhydride; With tetracarboxylic dianhydride and diamines alternately or be added into the method etc. of organic solvent simultaneously.Can adopt any method wherein.
Temperature of reaction during synthetic described polyamic acid can be selected-20 ℃～150 ℃ temperature arbitrarily, preferred-5 ℃～100 ℃ scope.In addition, though reaction can carried out under the concentration arbitrarily, if it is but low excessively as two amine components of raw material and tetracarboxylic dianhydride's concentration, then be difficult to obtain high molecular weight polymers, if excessive concentration, then the viscosity of reaction solution becomes too high, is difficult to carry out the stirring of homogeneous, therefore be preferably 1～50 quality %, more preferably 5～30 quality %.Can implement reaction with high density in initial reaction stage, append organic solvent afterwards again.
In the building-up reactions of polyamic acid, the ratio of the mole number of tetracarboxylic dianhydride's mole number and two amine components is preferably 0.8～1.2.Same with common polycondensation, this mol ratio is more near 1.0, and the molecular weight of the polyamic acid of generation is big more.
Molecular weight for polyamic acid of the present invention is not particularly limited.The intensity that operation, the homogeneity of filming and gained when considering coating of liquid crystalline aligning agent described later filmed, the weight-average molecular weight that records with GPC (gel permeation chromatography) method is preferably 5000～300000, and more preferably 10000～150000.
3. polyimide
Polyimide of the present invention be make described polyamic acid dehydration closed-loop and polyimide, can be used as the polymkeric substance that is used to obtain liquid crystal orientating membrane.
In the polyimide of the present invention, the dehydration closed-loop rate of acid amides acidic group (imidization rate) not necessarily will reach 100%, can at random adjust according to purposes and purpose.
As the method that makes the polyamic acid dehydration closed-loop, can exemplify the hot-imide that does not use catalyzer and polyamic acid is heated, the catalysis imidization that uses catalyzer.
When making the polyamic acid hot-imide, Yi Bian preferably on one side the solution of polyamic acid is heated to 100～400 ℃, be preferably 120～250 ℃ of water that carry out imidization reaction and generate and discharge outside the systems and react.
The catalysis imidization of polyamic acid can add basic catalyst and acid anhydrides in the solution of polyamic acid, in-20～250 ℃, be preferably and stir under 0～180 ℃ the temperature and implement.The amount of basic catalyst is 0.5～30 mole a times of acid amides acidic group, is preferably 2～20 moles doubly, and the amount of acid anhydrides is 1～50 mole a times of acid amides acidic group, is preferably 3～30 moles doubly.
As basic catalyst, can exemplify pyridine, triethylamine, Trimethylamine 99, Tributylamine, trioctylamine etc., wherein pyridine possesses the alkalescence that makes the reaction appropriateness of carrying out, and is therefore preferred.
As acid anhydrides, can exemplify diacetyl oxide, trimellitic acid 1,2-anhydride, pyromellitic dianhydride etc., if use diacetyl oxide wherein, refining the becoming easily after then reaction finishes, therefore preferred.The imidization rate of catalysis imidization can be controlled by regulating catalytic amount and temperature of reaction, reaction times.
Molecular weight to polyimide of the present invention is not particularly limited.The intensity that operation, the homogeneity of filming and gained when considering coating of liquid crystalline aligning agent described later filmed, the weight-average molecular weight that records with the GPC method is preferably 5000～300000, and more preferably 10000～150000.
When from the reaction soln of polyamic acid or polyimide, reclaiming polymkeric substance, reaction soln can be dropped into and make its precipitation in the Weak solvent.As being used for sedimentary Weak solvent, can exemplify methyl alcohol, acetone, hexane, ethylene glycol butyl ether, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene, water etc.To drop into Weak solvent and after the recovery of sedimentary polymer filtration, be preferably in normal pressure or decompression drying under normal temperature or heating condition down.
4. aligning agent for liquid crystal
Aligning agent for liquid crystal of the present invention is the coating fluid that is used to make liquid crystal orientating membrane, and its main component is the composition that contains the resinous principle that is used to form resin coating and make this resinous principle dissolved organic solvent.
Aligning agent for liquid crystal of the present invention is the treatment agent that contains the either party at least (below be also referred to as polymkeric substance of the present invention) of described polyamic acid of the present invention and polyimide as described resinous principle.The content of the polymkeric substance of the present invention in the resinous principle is preferably more than the 5 quality %, more preferably more than the 10 quality %.
Described resinous principle can be a polymkeric substance of the present invention all, also can be mixed with other polymkeric substance in addition in polymkeric substance of the present invention.As the example of this other polymkeric substance, can exemplify as two amine components use beyond the diamines of formulas (1) expression diamines and polyamic acid or polyimide etc.
For resinous principle dissolved organic solvent is not particularly limited.As concrete example, can exemplify N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-methyl caprolactam, methyl-sulphoxide, gamma-butyrolactone etc.These organic solvents are the high good solvents of dissolving resin.
Except described good solvent,, preferably use the low Weak solvent of solvability of polymkeric substance in order to improve the coating homogeneity of aligning agent for liquid crystal.Among the present invention, can exemplify ethyl cellosolve as preferred Weak solvent, ethylene glycol butyl ether, ethyl carbitol, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, the ethyl carbitol acetic ester, ethylene glycol, ethylene glycol ether, 1-methoxyl group-2-propyl alcohol, 1-oxyethyl group-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, the propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic ester, the single ether of propylene glycol-1--2-acetic ester, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol list ether, 4-hydroxy-4-methyl-2 pentanone, 2-(2-oxyethyl group propoxy-) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate.This Weak solvent is the low Weak solvent of dissolving resin.These solvents are preferably 5～60 quality % of the contained organic solvent of aligning agent for liquid crystal, more preferably 10～50 quality %.
The concentration of the resinous principle in the aligning agent for liquid crystal of the present invention can suitably be adjusted according to the thickness of liquid crystal orientating membrane to be formed and the device etc. that is used for the coating of aligning agent for liquid crystal.The general resin concentration of aligning agent for liquid crystal can be illustrated as 1～20 quality %, better is 2～10 quality %.
Can contain described composition in addition in the aligning agent for liquid crystal of the present invention.As its example, compound that contains functional silanes that the adaptation that is used to make liquid crystal orientating membrane and substrate improves or the compound that contains epoxy group(ing) be can exemplify, the fluorine class tensio-active agent of the flatness of filming, silicone based tensio-active agent, nonionic surfactant etc. are used to improve.
When comprising the compound that contains functional silanes or containing the compound of epoxy group(ing), it is measured with respect to 100 mass parts resinous principles, better all is 0.1～30 mass parts, more preferably 1～20 mass parts, particularly preferably 1～10 mass parts.
When containing tensio-active agent, it is measured with respect to resinous principle 100 mass parts, is preferably 0.01～2 mass parts, more preferably 0.01～1 mass parts.
5. liquid crystal orientating membrane and liquid crystal display device
After aligning agent for liquid crystal of the present invention and commercially available polyimide aligning agent for liquid crystal are similarly coated substrate and are burnt till, carry out directional process by friction treatment or photo-irradiation treatment etc. and form liquid crystal orientating membrane, perhaps in the vertical orientation purposes of part, need not to carry out directional process and form liquid crystal orientating membrane.
Coating process for aligning agent for liquid crystal of the present invention is not particularly limited, and generally can wait by silk screen printing, flexible printing, offset printing, ink jet printing and implement.In addition, the method as using coating fluid comprises dip-coating, roller coat, slot coated, spin coating etc., can select described method according to purpose.After coating on the substrate by described method, can solvent evaporation be formed by heater meanses such as hot plates and film.
Being coated with burning till behind the aligning agent for liquid crystal can carry out under 100～300 ℃ arbitrary temp, better is 150 ℃～250 ℃.This burns till and can utilize hot plate, recirculation furnace, infrared heating heating furnace to wait to implement.
Friction treatment can be used enforcements such as artificial silk cloth, nylon cloth, cotton.Because vertical orientation is difficult to obtain by friction treatment the directed state of homogeneous with liquid crystal orientating membrane, when therefore using with aligning agent for liquid crystal as vertical orientation, does not preferably rub and uses.
Liquid crystal cell of the present invention can make by common method, is not particularly limited for its making method.Generally can adopt following method: on the glass substrate that is formed with liquid crystal orientating membrane at least one side's the substrate, be coated with sealing agent, scatter spacer again to keep certain interval, then with 2 baseplate-laminatings, make sealant cures, make sylphon, then, under vacuum, inject liquid crystal, the inlet sealing is made the method for liquid crystal cell from liquid crystal injecting port; Perhaps, after being dispersed with the liquid crystal that drips on the substrate of spacer, 2 baseplate-laminatings are made the method etc. of liquid crystal cell.As liquid crystal, can use the fluoro liquid crystals of the dielectric constant anisotropy possess plus or minus or cyano group class liquid crystal etc. according to purposes.
As mentioned above, can give liquid crystal with bigger tilt angle by the liquid crystal orientating membrane that aligning agent for liquid crystal of the present invention obtains, the liquid crystal orientating membrane that can be used as various uses uses.
Embodiment
Below, exemplifying embodiment the present invention is specifically described, these embodiment do not constitute the limitation of the invention interpretation certainly.
[synthesizing of diamines of the present invention]
＜embodiment 1 〉
Synthesizing of diamines [9]
Figure G2008800091198D00171
Through add in nitrogen metathetical 4 mouthfuls of flasks bromination 4-p-methoxy-phenyl magnesium [1] (the 0.5M-tetrahydrofuran solution, 2.4 liters (L), 1.2mol) and tetrahydrofuran (THF) (200mL).4-(anti--4-n-pentyl cyclohexyl) pimelinketone [2] (300g, tetrahydrofuran (THF) 1.20mol) (280g) solution will be dripped after the reactor cooling to 0 ℃.Slowly be warming up to 25 ℃ after dripping end, stir in 25 ℃ more all night.Reaction is cooled to 0 ℃ with reaction solution after finishing, and slowly drips 10% acetic acid aqueous solution (1.0L) again.Then, remove water layer, add toluene (2.4L), with saturated aqueous common salt (1.0L), saturated sodium bicarbonate aqueous solution (1.0L) and saturated aqueous common salt (1.0L) washing by the separatory operation.Desolventize with steaming under the decompression behind the anhydrous magnesium sulfate drying organic layer.The compound [3] (cis-trans isomer mixture) of gained (430g) is directly used in following reaction.
With TMS (Si (CH 3) 4) be reference material, in deuterochloroform with NMR determinator (400MHz) to the gained compound 1H-NMR measures.The measurement result of compound [3] is as follows, and other compound is like this equally.
Compound [3] (cis-trans isomer mixture):
1H-NMR(400MHz，CDCl 3，δppm)：7.47-7.30(2H，m)，6.98-6.82(2H，m)，3.81-3.79(3H，m)，2.34-0.81(30H，m).
Reflux down, (430g is 1.20mol) with tosic acid monohydrate (13.1g, dehydrated toluene 72.0mmol) (2.5L) mixture reaction 2 hours to make compound [3] (cis-trans isomer mixture) when dewatering.Reaction is adjusted into 80 ℃ with temperature after finishing, with saturated sodium bicarbonate aqueous solution (1.5L) and saturated aqueous common salt (1.5L) washing.Desolventize with steaming under the decompression behind the anhydrous magnesium sulfate drying organic layer.(1: 1v/v) mixed solvent carries out recrystallization to the thick resultant of gained, obtains compound [4] (cis-trans isomer mixture) (receipts amount 379g, yield 89%) with ethyl acetate/ethanol.
Compound [4] (cis-trans isomer mixture):
1H-NMR(400MHz，CDCl 3，δppm)：7.32(2H，d)，6.84(2H，d)，6.02(1H，m)，3.80(3H，s)，2.48-1.75(9H，m)，1.38-0.86(19H，m).
Hydrogen exists down, in 25 ℃ to compound [4] (cis-trans isomer mixture) (379g, 1.10mol), 5% palladium on carbon (moisture, 19.0g, 5wt%), the mixture of ethyl acetate (1.0L) and ethanol (1.0L) stirs.Reaction finishes back diatomite filtration reaction mixture, with toluene (1.0L) washing diatomite.Decompression is concentrated filtrate down, obtains compound [5] (cis-trans isomer mixture) (receipts amount 347g, yield 91%).
Compound [5] (cis-trans isomer mixture):
1H-NMR(400MHz，CDCl 3，δppm)：7.14(2H，m)，6.83(2H，m)，3.78(3H，s)，2.64-2.35(1H，m)，1.88-1.52(8H，m)，1.49-0.74(22H，m).
In the displacement of 0 ℃ of nitrogen down compound [5] (cis-trans isomer mixture) (347g, drip in methylene dichloride 1.00mol) (2.0L) solution boron tribromide (the 1.0M-dichloromethane solution, 1.0L, 1.0mol).Dripping the back stirred 2 hours in 0 ℃.Reaction adds reaction solution in the distilled water after finishing at every turn slightly.With ethyl acetate (2.0L) extraction, extraction liquid is washed 2 times with distilled water (1.0L).Organic layer with dried over mgso after decompression steam down and desolventize.With ethanol the thick resultant of gained is carried out recrystallization, use washing with alcohol again, obtain compound [6] (trans-isomer(ide)) (receipts amount 183g, yield 55%).1 of compound [6], the cis-trans isomerization of 4-cyclohexylidene are trans-isomer(ide).
Compound [6] (trans-isomer(ide)):
1H-NMR(400MHz，CDCl 3，δppm)：7.07(2H，d)，6.75(2H，d)，4.60(1H，s)，2.37(1H，m)，1.90-1.71(8H，m)，1.39-0.84(22H，m).
In 25 ℃, compound [6] (trans-isomer(ide)) (41.66g, 127mmol), 3,5-dinitrobenzene benzyl chloride [7] (27.57g, 127mmol), dropping sodium (5.08g, distilled water 120mmol) (110g) solution in the solution of THF (220g).Heat to 40 ℃, stirred 8 hours.Reaction finishes postcooling to 25 ℃, and this reaction mixture is injected distilled water (2L).Filter the gained crystallization, in acetonitrile, carry out ultrasonic washing 2 times.Then, (1: 1v/v) the mixed solvent recrystallization is 2 times, obtains compound [8] (trans-isomer(ide)) (receipts amount 43.4g, yield 67%) with acetonitrile/ethyl acetate.1 of compound [8], the cis-trans isomerization of 4-cyclohexylidene are trans-isomer(ide).
Compound [8] (trans-isomer(ide)):
1H-NMR(400MHz，CDCl 3，δppm)：9.00(1H，s)，8.65(2H，s)，7.17(2H，d)，6.92(2H，d)，5.23(2H，s)，2.41(1H，t)，1.92-1.60(8H，m)，1.41-0.86(22H，m).
Hydrogen exists down, in 60 ℃ to compound [8] (trans-isomer(ide)) (43.34g, 85.2mmol), (4.3g, 10wt%) the mixture of, diox (260g), toluene (260g) stirred 10 hours platinum oxide (IV).Reaction finishes the back in 80 ℃ of filtrations.In 0 ℃ of stirring and cooling gained filtrate, there is crystallization to separate out.Toluene wash 2 times are used in the crystallization that filtration is separated out, and obtain diamines [9] (trans-isomer(ide)) (receipts amount 24.4g, yield 64%).1 of compound [9], the cis-trans isomerization of 4-cyclohexylidene are trans-isomer(ide).
Diamines [9] (trans-isomer(ide)):
1H-NMR (400MHz, CDCl 3, δ ppm): 7.10 (2H, d), 6.88 (2H, s), 6.18 (2H, s), 5.98 (1H, d), 4.86 (2H, s), 3.59 (4H, wide), 2.38 (1H, t), 1.90-1.71 (8H, m), 1.40-0.86 (22H, m).
＜embodiment 2 〉
Synthesizing of diamines [15]
Figure G2008800091198D00201
With nitrogen to 4-(anti--4-n-pentyl cyclohexyl) bromobenzene [10] (50.0g, 162mmol), 4-anisole ylboronic acid [11] (36.9g, 243mmol), (mixing solutions of yellow soda ash (44.6g, 420mmol)/distilled water 0.6L) outgases for toluene (1.4L), ethanol (0.16L) and aqueous sodium carbonate.In this solution, add Pd (PPh under the nitrogen atmosphere 3) 4(0.934g, 0.808mmol) stirred 6 hours in 90 ℃ the back.Reaction finishes the back branch and gets organic layer, with distilled water (0.5L) washing 2 times.Organic layer with dried over mgso after decompression steam down and desolventize.(1: 1v/v) mixed solvent carries out recrystallization to the thick resultant of gained, with obtaining compound [12] (trans-isomer(ide)) (receipts amount 40.0g, yield 73%) after the hexane wash with ethyl acetate/hexane.1 of compound [12], the cis-trans isomerization of 4-cyclohexylidene are trans-isomer(ide).
Compound [12] (trans-isomer(ide)):
1H-NMR(400MHz，CDCl 3，δppm)：7.51(2H，d)，7.47(2H，d)，7.26(2H，d)，6.96(2H，d)，3.84(3H，s)，2.50(1H，t)，1.90(4H，t)，1.53-1.42(2H，m)，1.36-1.20(9H，m)，1.12-1.01(2H，m)，0.90(3H，t).
In the displacement of 0 ℃ of nitrogen down compound [12] (trans-isomer(ide)) (40.0g, drip in methylene dichloride 119mmol) (0.5L) solution boron tribromide (the 1.0M-dichloromethane solution, 0.120L, 120mmol).Dripping the back stirred 2 hours in 0 ℃.Reaction adds reaction solution in the distilled water (0.5L) after finishing at every turn slightly.With ethyl acetate (0.5L) extraction, extraction liquid is washed 2 times with distilled water (0.3L).Organic layer with dried over mgso after decompression steam down and desolventize.With ethyl acetate-hexane (1: 1) mixed solvent the thick resultant of gained is carried out recrystallization, use hexane wash, obtain compound [13] (trans-isomer(ide)) (receipts amount 29.5g, yield 77%).1 of compound [13], the cis-trans isomerization of 4-cyclohexylidene are trans-isomer(ide).
Compound [13] (trans-isomer(ide)):
1H-NMR(400MHz，CDCl 3，δppm)：7.47-7.45(4H，m)，7.26(2H，d)，6.88(2H，d)，4.82(1H，s)，2.49(1H，t)，1.90(4H，t)，1.55-1.40(2H，m)，1.36-1.21(9H，m)，1.12-1.01(2H，m)，0.90(3H，t).
In 25 ℃ at compound [13] (trans-isomer(ide)) (13.2g, 40.9mmol), 3,5-dinitrobenzene benzyl chloride [7] (10.6g, 49.1mmol), tetrahydrofuran (THF) (160g) and N, dropping sodium in the solution of dinethylformamide (42g) (1.97g, distilled water 49.1mmol) (50g) solution.Drip the back in stirring at room 4 hours.Reaction finishes postcooling to 25 ℃, adds distilled water (0.5L) and carries out ultrasonic washing.Filter the gained crystallization, obtain thick resultant.With acetonitrile/N, (8: 1v/v) mixed solvent carries out recrystallization to this thick resultant to dinethylformamide, obtains compound [14] (trans-isomer(ide)) (receipts amount 15.7g, yield 76%).1 of compound [14], the cis-trans isomerization of 4-cyclohexylidene are trans-isomer(ide).
Compound [14] (trans-isomer(ide)):
1H-NMR(400MHz，CDCl 3，δppm)：9.03(1H，t)，8.68(2H，d)，7.56(2H，d)，7.48(2H，d)，7.27(2H，d)，7.06(2H，d)，5.29(2H，s)，2.51(1H，t)，1.91(4H，t)，1.54-1.40(2H，m)，1.36-1.20(9H，m)，1.13-1.00(2H，m)，0.90(3H，t).
In the nitrogen atmosphere down, in room temperature ℃ to compound [14] (trans-isomer(ide)) (15.7g, 31.2mmol), (1.57g, 10wt%) the mixture of Ji diox (280g) stirs after 16 hours and stirred 3 hours in 80 ℃ platinum oxide (IV).Reaction finishes the back in 80 ℃ of filtrations.Decompression removes the solvent steaming of gained filtrate down, obtains thick resultant.The Yong diox carries out recrystallization to this thick resultant, obtains diamines [15] (trans-isomer(ide)) (receipts amount 9.37g, yield 68%).1 of compound [15], the cis-trans isomerization of 4-cyclohexylidene are trans-isomer(ide).
Diamines [15] (trans-isomer(ide)):
1H-NMR (400MHz, CDCl 3, δ ppm): 7.51-7.45 (4H, m), 7.25 (2H, d), 7.01 (2H, d), 6.21 (2H, d), 5.99 (1H, t), 4.92 (2H, s), 3.61 (4H, wide), 2.49 (1H, t), 1.90 (4H, t), 1.55-1.41 (2H, m), 1.36-1.21 (9H, m), 1.13-1.00 (2H, m), 0.90 (3H, t).
＜embodiment 3 〉
Synthesizing of diamines [21]
Figure G2008800091198D00221
Under the nitrogen atmosphere, with 2,5-methyl-dibromobenzoate [16] (10.0g, diethyl ether solution 34.0mmol) (113mL) are cooled to-50 ℃, with in this solution, dripped in 30 minutes diisobutylaluminium hydride (the 0.94M hexane solution, 86.86mL, 81.65mmol).Stirring was stirred 1.5 hours in 0 ℃ after 1 hour again to reaction soln.Then, adding entry (4.4mL), Sodium Fluoride (4.4g) and sellaite (3.8g) in 0 ℃ in reaction soln stops reaction.Desolventize with steaming under the decompression behind the diatomite filtration, obtain the thick resultant (receipts amount 8.21g) of compound [17].This thick resultant is not made with extra care the reaction of directly using it for thereafter.
Compound [17]:
1H-NMR(400MHz，CDCl 3，δppm)：7.66(1H，d)，7.39(1H，d)，7.28(1H，dd)，4.50(2H，d)，2.01(1H，t).
Under the nitrogen atmosphere, in the dichloromethane solution (0.3L) of the thick resultant (8.21g) of compound [17], add triethylamine (10.8mL, 77.2mmol).Reaction soln is cooled to 0 ℃, and the adding methylsulfonyl chloride (4.78mL, 61.8mmol).Under reflux, stirred 10 hours again after 16 hours in 25 ℃ of stirrings.Add water after reaction soln is cooled to 25 ℃ reaction is stopped, using dichloromethane extraction.Organic layer washes with water, steams down with decompression after the dried over mgso to desolventize again, and obtains thick resultant.Refining with silica gel column chromatography (hexane/ethyl acetate=20/1), obtain compound [18] (receipts amount 8.19g, yield (2 stages) 85%).
Compound [18]:
1H-NMR(400MHz，CDCl 3，δppm)：7.63(1H，d)，7.44(1H，d)，7.33(1H，dd)，4.64(2H，s).
With compound [18] (5.67g, 17.3mmol) and similarly to Example 1 synthetic compound [6] (5.15g 18.1mmol) is dissolved in the mixed solvent of tetrahydrofuran (THF) (50mL) and acetonitrile (9mL), adds sodium iodide (0.259g, 1.73mmol) and salt of wormwood (5.01g, 36.2mmol).Reaction soln is heated to 80 ℃, stirred 48 hours.Remove insolubles by suction strainer after reaction soln is cooled to 25 ℃.Remove the solvent in the filtrate under reduced pressure, obtain thick resultant.With making with extra care with silica gel column chromatography (hexane/ethyl acetate=50/1) behind the thick resultant of hexane wash, obtain compound [19] (receipts amount 6.75g, yield 68%).
Compound [19]:
1H-NMR(400MHz，CDCl 3，δppm)：7.73(1H，d)，7.43(1H，d)，7.31(1H，dd)，7.15(2H，d)，6.91(2H，d)，5.05(2H，s)，2.42-2.33(1H，m)，1.97-1.66(8H，m)，1.47-0.89(22H，m).
Under the nitrogen atmosphere, at compound [19] (7.86g, 13.6mmol), three (dibenzalacetones), two palladiums (0) (62.4mg, 0.0682mmol), (±)-2,2 '-two (diphenylphosphine)-1,1 '-dinaphthalene (BINAP) (0.127g, 0.205mmol), sodium tert-butoxide (t-BuONa) (3.67g, 38.2mmol) toluene (55mL) solution in add benzophenone imine (5.49mL 32.7mmol), be heated to 80 ℃.Reaction soln was stirred 24 hours, reaction soln is injected ethyl acetate (275mL) after being cooled to 25 ℃ reaction is stopped.Remove behind the insolubles solvent in the filtrate steamed by suction strainer and remove, obtain thick resultant.Make with extra care with silica gel column chromatography (hexane/ethyl acetate=10/1), obtain compound [20] (trans-isomer(ide)) (receipts amount 9.72g, yield 92%).1 of compound [20], the cis-trans isomerization of 4-cyclohexylidene are trans-isomer(ide).
Compound [20] trans-isomer(ide):
1H-NMR(400MHz，CDCl 3，δppm)：7.73(2H，d)，7.68(2H，d)，7.46-7.33(6H，m)，7.32-7.20(4H，m)，7.19-7.14(2H，m)，7.08(2H，d)，7.04(2H，d)，6.99(2H，d)，6.89(1H，d)，6.78(2H，d)，6.31(1H，dd)，6.16(1H，d)，4.93(2H，s)，2.42-2.32(1H，m)，1.94-1.66(8H，m)，1.43-0.89(22H，m).
Compound [20] (trans-isomer(ide)) (13.9g, add in methyl alcohol 17.9mmol) (180mL) suspension sodium acetate (7.05g, 86.0mmol) and hydroxylamine hydrochloride (4.48g, 64.5mmol).Stir that the aqueous sodium hydroxide solution with methylene dichloride and 0.1M carries out separatory, the organic layer dried over mgso after 1 hour.Decompression is steamed down and is desolventized, and obtains thick resultant.Make with extra care with silica gel column chromatography (hexane/ethyl acetate=1/1), carry out recrystallization with methylene chloride again, obtain diamines [21] (trans-isomer(ide)) (receipts amount 6.07g, yield 76%).1 of compound [21], the cis-trans isomerization of 4-cyclohexylidene are trans-isomer(ide).
Diamines [21] trans-isomer(ide):
1H-NMR(400MHz，CDCl 3，δppm)：7.13(2H，d)，6.92(2H，d)，6.65-6.56(3H，m)，4.93(s，2H)，3.70-3.30(brord，4H)，2.43-2.33(m，1H)，1.93-1.61(m，8H)，1.44-0.81(m，22H).
＜embodiment 4 〉
Synthesizing of diamines [24]
According to embodiment＜1 same synthetic method, adopt compound [22], obtain diamines [24] (trans-isomer(ide)) through compound [23] (trans-isomer(ide)).
Compound [23] (trans-isomer(ide)):
1H-NMR(400MHz，CDCl 3，δppm)：9.01(t，1H)，8.65(d，2H)，7.17(d，2H)，6.94(d，2H)，5.23(s，2H)，2.46-2.35(m，1H)，1.93-1.70(m，8H)，1.45-1.20(m，12H)，1.20-0.93(m，9H)，0.88(t，3H)，0.91-0.80(m，2H).
Diamines [24] (trans-isomer(ide)):
1H-NMR(400MHz，CDCl 3，δppm)：7.10(d，2H)，6.88(d，2H)，6.18(d，2H)，5.98(t，1H)，4.86(s，2H)，3.59(bs，4H)，2.43-2.32(m，1H)，1.93-1.70(m，8H)，1.43-1.19(m，12H)，1.19-0.92(m，9H)，0.88(t，3H)，0.91-0.78(m，2H).
＜synthesis example 1 〉
Synthesizing of diamines [29]
Figure G2008800091198D00251
Under the room temperature, in through 4 mouthfuls of flasks of nitrogen metathetical, add 4-bromo-4 '-(n-pentyl) biphenyl [25] (25.0g, 82.4mmol) and tetrakis triphenylphosphine palladium (0) (4.76g, 4.12mmol) after add bromination 4-p-methoxy-phenyl magnesium [1] (0.5M-tetrahydrofuran solution again, 280mL, 140mmol), carry out reflux then.After reaction end postcooling to room temperature is separated out solid, will filter in reaction solution impouring ethyl acetate (200g)/1M hydrochloric acid (280mL).Washing gained solid washs after drying with ethyl acetate, obtains white-yellowish solid compound [26] (receipts amount 26.8g, yield 98%).
Compound [26]:
1H-NMR(400MHz，CDCl 3，δppm)：7.66-7.54(8H，m)，7.23(2H，d)，7.0-6.98(2H，m)，3.86(3H，s)，2.65(2H，t)，1.68-1.64(2H，m)，1.40-1.33(4H，m)，0.93-0.89(3H，m).
In the displacement of 0 ℃ of nitrogen down compound [26] (25.00g, drip in dehydration methylene dichloride (300g) solution 75.7mmol) boron tribromide (the 1.0M-dichloromethane solution, 75.7mL, 75.7mmol).Dripping the back made reaction carry out in 2 hours in 0 ℃ of stirring.Reaction adds reaction solution in the distilled water after finishing at every turn slightly.With heating, organic layer is washed 2 times with distilled water 300mL to 60 ℃ ethyl acetate 2.5L extraction.Organic layer concentrates until solvent after with dried over mgso and becomes about 500mL.The solid that filtration is separated out washs after drying with ethyl acetate, obtains orange red solid chemical compound [27] (receipts amount 19.1g, yield 80%).
Compound [27]:
1H-NMR(400MHz，DMSO-d6，δppm)：9.58(1H，s)，7.69-7.64(4H，m)，7.61-7.59(2H，m)，7.55-7.53(2H，m)，7.27(2H，d)，6.88-6.86(2H，m)，2.60(2H，t)，1.64-1.56(2H，m)，1.35-1.28(4H，m)，0.87(3H，t).
Under the room temperature, compound [27] (11.00g, 34.8mmol), 3,5-dinitrobenzene benzyl chloride [1] (7.53g, 34.8mmol), dropping sodium (1.39g, distilled water 30g solution 34.8mmol) in the solution of tetrahydrofuran (THF) (80g).Heat to 40 ℃, stirred 8 hours.Reaction finishes postcooling to room temperature, and this reaction mixture is injected distilled water 400mL.Add acetonitrile (150g) after filtering the gained crystallization, disperse to filter once more after the washing with ultrasonic unit.Then, (400g) carries out recrystallization with acetonitrile, obtains to be loess look solid compound [28] (receipts amount 13.5g, yield 78%).
Compound [28]:
1H-NMR(400MHz，DMSO-d6，δppm)：8.80(1H，t)，8.81(2H，d)，7.71-7.69(6H，m)，7.62-7.60(2H，m)，7.29-7.27(2H，m)，7.20-7.17(2H，m)，5.46(2H，s)，2.61(2H，t)，1.64-1.56(2H，m)，1.35-1.28(4H，m)，0.88(3H，t).
Hydrogen exists down, in 65 ℃ to compound [28] (12.00g, 24.2mmol), (1.2g, 10wt%) the mixture of, diox (180g) stirred 17 hours platinum oxide.Reaction finishes the back replaces with nitrogen, adds tetrahydrofuran (THF) (1L) again, is heated to 80 ℃ solid dissolving back is filtered with diatomite.Filtrate concentrated until quantity of solvent become about 100g, disperse to wash after-filtration with ultrasonic unit, drying obtains the diamines [29] (receipts amount 7.7g, yield 72%) of tea white.
Diamines [29]:
1H-NMR(400MHz，DMSO-d6，δppm)：7.69(4H，s)，7.64-7.60(4H，m)，7.29(2H，d)，7.06-7.04(2H，m)，5.88(2H，d)，5.76(1H，t)，4.86(2H，s)，4.78(4H，s)，2.61(2H，t)，1.64-1.56(2H，m)，1.35-1.28(4H，m)，0.88(3H，t).
[synthesizing of polyamic acid of the present invention or polyimide]
The breviary symbol and the structure of the compound that shown below is uses in embodiment and the comparative example.
(tetracarboxylic dianhydride)
BODA: two ring [3.3.0] octanes-2,4,6,8-tetracarboxylic dianhydride
CBDA:1,2,3,4-tetramethylene tetracarboxylic dianhydride
Figure G2008800091198D00271
(diamines)
P-PDA: Ursol D
DBA:3, the 5-diaminobenzoic acid
M-PBCH5DABz:1,3-diamino-5-{4-[is anti--4-(anti--4-n-pentyl cyclohexyl) cyclohexyl] phenoxymethyl } benzene
P-PBCH5DABz:1,4-diamino-5-{4-[is anti--4-(anti--4-n-pentyl cyclohexyl) cyclohexyl] phenoxymethyl } benzene
M-BPCH5DABz:1,3-diamino-5-{4-[4-(anti--4-n-pentyl cyclohexyl) phenyl] phenoxymethyl } benzene
M-PBCH7DABz:1,3-diamino-5-{4-[is anti--4-(anti--4-n-heptyl cyclohexyl) cyclohexyl] phenoxymethyl } benzene
M-PBCH5DABEs:3, the 5-diamino-and 4-[is anti--and 4-(anti--4-n-pentyl cyclohexyl) cyclohexyl] phenyl } benzoic ether
PCH7DAB:1,3-diamino-4-[4-(anti--4-n-heptyl cyclohexyl) phenoxy group] benzene
PBP5DABz:1,3-diamino-4-[(4-n-pentyl phenyl) phenoxymethyl] benzene
(remarks)
M-PBCH5DABz is the operation synthetic diamines [9] by similarly to Example 1.
M-BPCH5DABz is the operation synthetic diamines [15] by similarly to Example 2.
P-PBCH5DABz is the operation synthetic diamines [21] by similarly to Example 3.
M-PBCH7DABz is the operation synthetic diamines [24] by similarly to Example 4.
M-PBCH5DABEs is the operation synthetic compound [6] that adopts by similarly to Example 1, and the embodiment that opens the 2004-67589 communique according to the Japanese Patent spy is synthetic.
PCH7DAB is synthetic according to the embodiment of Japanese patent laid-open 9-278724 communique.
PBP5DABz is by the operation synthetic diamines [29] same with synthesis example 1.
Figure G2008800091198D00281
Figure G2008800091198D00291
(organic solvent)
The NMP:N-N-methyl-2-2-pyrrolidone N-
BCS: ethylene glycol butyl ether
The measuring method that adopts among the following embodiment is as described below.
[molecular weight]
In the present embodiment, measure the number-average molecular weight (below be also referred to as Mn) of polyimide under the following conditions with Xiao De (Shodex) corporate system normal temperature gel permeation chromatograph (GPC) device (GPC-101) and Xiao De corporate system post (KD-803, KD-805).
Column temperature: 50 ℃
Elutriant: N, and dinethylformamide (as additive, lithiumbromide monohydrate (LiBrH 2O) be 30.0mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) is 30.0mmol/L, and tetrahydrofuran (THF) is 10ml/L)
Flow velocity: 1.0mL/ minute
Working curve is made and is used standard model: eastern Cao (East ソ one) Co., Ltd.'s system TSK standard polyethylene oxide (molecular weight about 900000,150000,100000,30000) and polymkeric substance laboratory (PolymerLaboratories) corporate system polyoxyethylene glycol (molecular weight about 12000,4000,1000)
[imidization rate]
In the present embodiment, the following mensuration of imidization rate of polyimide.
The 20.0mg polyimide powder is packed in the NMR sample tube, add about 0.53ml deuterate methyl-sulphoxide (DMSO-d 6, 0.05%TMS (Si (CH 3) 4) melange), by ultrasonic wave it is dissolved fully.Measure the proton N MR of the 500MHz of this solution with the NMR determinator.
The imidization rate is that the benchmark proton is determined with the proton from unconverted structure before and after the imidization, obtains according to following formula with the peak integrated value of this proton and near occur 10.0ppm the proton peak integrated value from the NH base of amido acid.
Imidization rate (%)=(1-α x/y) * 100
In the following formula, x is the proton peak integrated value from the NH base of amido acid, and y is the peak integrated value of benchmark proton, α be polyamic acid (imidization rate 0%) with respect to 1 number ratio from the benchmark proton of the proton of the NH base of amido acid.
＜embodiment 5 〉
In NMP (22.0g), mix BODA (5.07g, 20.3mmol), p-PDA (2.48g, 22.9mmol), as the m-PBCH5DABz (1.82g of side chain diamines, 4.05mmol), add CBDA (1.12g in 40 ℃ of reactions after 5 hours, 5.71mmol) and NMP (20.0g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
After adding NMP is diluted to 6 quality % in this polyamic acid solution (30.0g), add diacetyl oxide (4.48g), pyridine (3.47g), in 80 ℃ of reactions 3 hours as imidization catalyst.This reaction soln is dropped in the methyl alcohol (427ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (A) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 48%, and number-average molecular weight is 12100, and weight-average molecular weight is 30400.
＜embodiment 6 〉
In NMP (22.0g), mix BODA (4.88g, 19.5mmol), p-PDA (2.39g, 22.1mmol), as the m-BPCH5DABz (1.73g of side chain diamines, 3.91mmol), add CBDA (1.16g in 40 ℃ of reactions after 5 hours, 5.92mmol) and NMP (18.0g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
After adding NMP is diluted to 6 quality % in this polyamic acid solution (30.0g), add diacetyl oxide (3.88g), pyridine (3.01g), in 80 ℃ of reactions 3 hours as imidization catalyst.This reaction soln is dropped in the methyl alcohol (374ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (B) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 41%, and number-average molecular weight is 15400, and weight-average molecular weight is 47000.
＜embodiment 7 〉
In NMP (20.0g), mix BODA (4.69g, 18.7mmol), p-PDA (2.30g, 21.3mmol), as the p-PBCH5DABz (1.63g of side chain diamines, 3.63mmol), add CBDA (1.03g in 40 ℃ of reactions after 5 hours, 5.25mmol) and NMP (16.0g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
After adding NMP is diluted to 6 quality % in this polyamic acid solution (20.0g), add diacetyl oxide (2.59g), pyridine (2.01g), in 80 ℃ of reactions 3 hours as imidization catalyst.This reaction soln is dropped in the methyl alcohol (249ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (C) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 40%, and number-average molecular weight is 12900, and weight-average molecular weight is 35800.
＜embodiment 8 〉
In NMP (19.0g), mix BODA (4.46g, 17.8mmol), p-PDA (2.18g, 20.2mmol), as the m-PBCH7DABz (1.70g of side chain diamines, 3.57mmol), add CBDA (0.98g in 40 ℃ of reactions after 5 hours, 5.00mmol) and NMP (15.5g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
After adding NMP is diluted to 6 quality % in this polyamic acid solution (20.0g), add diacetyl oxide (2.65g), pyridine (2.11g), in 80 ℃ of reactions 3 hours as imidization catalyst.This reaction soln is dropped in the methyl alcohol (280ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (D) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 45%, and number-average molecular weight is 14100, and weight-average molecular weight is 39800.
＜comparative example 1 〉
In NMP (22.0g), mix BODA (5.07g, 20.3mmol), p-PDA (2.48g, 22.9mmol), as the m-PBCH5DABEs (1.87g of side chain diamines, 4.04mmol), add CBDA (1.0g in 40 ℃ of reactions after 5 hours, 5.10mmol) and NMP (20.0g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
After adding NMP is diluted to 6 quality % in this polyamic acid solution (30.0g), add diacetyl oxide (4.28g), pyridine (3.32g), in 80 ℃ of reactions 3 hours as imidization catalyst.This reaction soln is dropped in the methyl alcohol (408ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (E) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 45%, and number-average molecular weight is 14900, and weight-average molecular weight is 38800.
＜comparative example 2 〉
In NMP (19.4g), mix BODA (4.47g, 17.9mmol), p-PDA (2.18g, 20.2mmol) as the PBP5DABz (1.56g of side chain diamines, 3.57mmol), add CBDA (1.07g in 40 ℃ of reactions after 5 hours, 5.46mmol) and NMP (17.5g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
After adding NMP is diluted to 6 quality % in this polyamic acid solution (20.0g), add diacetyl oxide (3.10g), pyridine (2.38g), in 80 ℃ of reactions 3 hours as imidization catalyst.This reaction soln is dropped in the methyl alcohol (275ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (F) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 45%, and number-average molecular weight is 15800, and weight-average molecular weight is 40800.
The dissolubility test of＜polyimide〉(comparison of ethylene glycol butyl ether mixing allowance)
Adopt the polyimide powder that obtains in embodiment 5～8, comparative example 1 and the comparative example 2, carry out the comparison of the mixing allowance of ethylene glycol butyl ether in polyimide solution according to following steps.
In polyimide powder (1.30g), add NMP (8.70g), stirred the polyimide solution of acquisition resin concentration 13 quality % 40 hours in 80 ℃.This polyimide solution (1.00g) branch is taken in the sample tube, adds magnetic stir bar, in the time of stirring at room, drip BCS with transfer pipet.Visual Confirmation BCS drips the time point that muddiness that the back occurs does not at once also disappear after the several seconds, with this as terminal point.At this moment, 1 BCS is about 0.004g.The quality of the sample tube integral body before and after the BCS combined amount of terminal point is mixed by affirmation BCS is obtained.
More than Shi Yan result is, the BCS of the terminal point when having used the polyimide of embodiment 5 is 1.40g, the BCS of the terminal point when having used the polyimide of embodiment 6 is 1.16g, the BCS of the terminal point when having used the polyimide of embodiment 7 is 1.07g, the BCS of the terminal point when having used the polyimide of embodiment 8 is 1.36g, the BCS of the terminal point when having used the polyimide of comparative example 1 is 0.11g, and the BCS of the terminal point when having used the polyimide of comparative example 2 is 0.64g.
Embodiment 5～8, comparative example 1 and comparative example 2 the results are summarized in table 1.
Can confirm from above result, use the mixing allowance of ethylene glycol butyl ether of the polyimide of diamines of the present invention to be far longer than and used the polyimide of relatively using diamines.
[modulation of aligning agent for liquid crystal of the present invention and evaluation]
＜embodiment 9 〉
In NMP (20.0g), mix p-PDA (1.46g, 13.5mmol), as the m-PBCH5DABz of side chain diamines (0.67g, 1.49mmol) after, add CBDA (2.85g, 14.5mmol) and NMP (24.9g), in 25 ℃ of reactions 5 hours, obtain polyamic acid solution.In the polyamic acid solution (40.0g) of gained, add NMP (24.0g) and BCS (16.0g), stirred 1 hour, obtain aligning agent for liquid crystal (1).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
The aligning agent for liquid crystal (1) of above acquisition is spun on the glass substrate of being with the ITO electrode, after making its dry 5 minutes on 80 ℃ the hot plate, carries out 1 hour burning till, make the polyimide film of thick 100nm with 230 ℃ heated air circulation type stoves.
With the friction gear of roller footpath 120mm, with the condition of roller rotating speed 1000rpm, roller gait of march 50mm/sec, the amount of being pressed into 0.3mm this polyimide face is carried out the friction treatment of artificial silk cloth, obtain substrate with liquid crystal orientating membrane.
Prepare 2 substrates that should be with liquid crystal orientating membrane, as the inboard, the spacer of clamping 50 μ m makes up and makes frictional direction become opposite direction with the liquid crystal aligning face, with the bonding peripheral part of sealing agent, makes sylphon.In this sylphon, inject liquid crystal MLC-2003 (Japanese Mai Luke Co., Ltd. (メ Le Network ジ ャ パ Application society) system) by the decompression injection method,, made the nematic liquid crystal box of antiparallel orientation the inlet sealing.
The tilt angle of the liquid crystal cell that more than room temperature measuring, makes with tilt angle determinator (Ai Er stone (ELSICON) corporate system, model PAS-301).Consequently, tilt angle is 85.7 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 87.5 °.
In addition, by the liquid crystal cell that polarized light microscope observing other and above-mentioned same operation except not carrying out friction treatment make, confirm liquid crystal vertical orientation equably.
＜embodiment 10 〉
In NMP (18.5g), mix p-PDA (1.34g, 12.4mmol), as the m-PBCH7DABz of side chain diamines (0.65g, 1.37mmol) after, add CBDA (2.61g, 13.3mmol) and NMP (23.0g), in 25 ℃ of reactions 5 hours, obtain polyamic acid solution.In the polyamic acid solution (35.0g) of gained, add NMP (21.1g) and BCS (14.0g), stirred 1 hour, obtain aligning agent for liquid crystal (2).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
Aligning agent for liquid crystal (2) with above acquisition is operated similarly to Example 9, makes the nematic liquid crystal box of antiparallel orientation and has measured tilt angle.Consequently, tilt angle is 86.5 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 87.3 °.
In addition, by the liquid crystal cell that polarized light microscope observing other and above-mentioned same operation except not carrying out friction treatment make, confirm liquid crystal vertical orientation equably.
＜comparative example 3 〉
In NMP (22.0g), mix p-PDA (1.56g, 14.4mmol), as the PCH7DAB of side chain diamines (0.61g, 1.60mmol) after, add CBDA (3.04g, 15.5mmol) and NMP (24.9g), in 25 ℃ of reactions 5 hours, the acquisition polyamic acid solution.In the polyamic acid solution (40.0g) of gained, add NMP (24.0g) and BCS (16.0g), stirred 1 hour, obtain aligning agent for liquid crystal (3).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
Aligning agent for liquid crystal (3) with above acquisition is operated similarly to Example 9, makes the nematic liquid crystal box of antiparallel orientation and has measured tilt angle.Consequently, tilt angle is 22.2 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 22.8 °.
In addition, by the liquid crystal cell that polarized light microscope observing other and above-mentioned same operation except not carrying out friction treatment make, confirm the liquid crystal aligning heterogeneity, not vertical orientation.
Embodiment 9, embodiment 10 and comparative example 3 the results are summarized in table 2.
Can confirm that from above result the polyamic acid that has used diamines of the present invention is relatively compared with the polyamic acid of diamines with having used, and can show bigger tilt angle with less import volume.
＜embodiment 11 〉
Add NMP (25.7g) at polyimide powder (A) that embodiment 5 obtains in (3.50g),, make its dissolving in 80 ℃ of stirrings 40 hours.In this solution, add NMP (2.83g), BCS (26.3g), stirred 1 hour, obtain aligning agent for liquid crystal (4).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
The aligning agent for liquid crystal (4) of above acquisition is spun on the glass substrate of being with the ITO electrode, after making its dry 5 minutes on 80 ℃ the hot plate, carries out 1 hour burning till, make the polyimide film of thickness 100nm with 210 ℃ heated air circulation type stoves.
With the friction gear of roller footpath 120mm, with the condition of roller rotating speed 300rpm, roller gait of march 20mm/sec, the amount of being pressed into 0.3mm the substrate of this band liquid crystal orientating membrane is carried out the friction treatment of artificial silk cloth, obtain substrate with liquid crystal orientating membrane.
Prepare 2 substrates that should be with liquid crystal orientating membrane, after particle (beads) spacer of 6 μ m being dispersed on the liquid crystal aligning face of 1 substrate, printing and sealing agent thereon, with the liquid crystal aligning face of other 1 substrate as the inboard, with their fit make that frictional direction becomes opposite direction after, make sealant cures, make sylphon.In this sylphon, injects liquid crystal MLC-6608 (Japanese Mai Luke Co., Ltd. system) by the decompression injection method, inlet is sealed, made the nematic liquid crystal box of antiparallel orientation.
The tilt angle of the liquid crystal cell that more than room temperature measuring, makes with tilt angle determinator (Ai Er stone corporate system, model PAS-301).Consequently, tilt angle is 85.7 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 86.6 °.In addition, by the liquid crystal cell under the polarized light microscope observing room temperature and through 1 hour heat treated liquid crystal cell, confirm liquid crystal homogeneous orientation, even also realize the homogeneous orientation through the thermal treatment liquid crystal.
In addition, by the liquid crystal cell that polarized light microscope observing other and above-mentioned same operation except not carrying out friction treatment make, confirm liquid crystal vertical orientation equably.
＜embodiment 12 〉
Add NMP (26.3g) at polyimide powder (B) that embodiment 6 obtains in (4.00g),, make its dissolving in 80 ℃ of stirrings 40 hours.In this solution, add NMP (2.68g), BCS (29.3g), stirred 1 hour, obtain aligning agent for liquid crystal (5).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
Carry out similarly to Example 11 processing with the aligning agent for liquid crystal (5) of above acquisition, make nematic liquid crystal box through the antiparallel orientation of friction treatment.By operation similarly to Example 11, the tilt angle that records this liquid crystal cell in room temperature is 45.5 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 45.7 °.
In addition, other does not operate the liquid crystal cell that makes similarly to Example 11 except carrying out friction treatment by polarized light microscope observing, confirms liquid crystal vertical orientation equably.
＜embodiment 13 〉
Add NMP (23.0g) at polyimide powder (C) that embodiment 7 obtains in (3.40g),, make its dissolving in 80 ℃ of stirrings 40 hours.In this solution, add NMP (4.70g), BCS (25.5g), stirred 1 hour, obtain aligning agent for liquid crystal (6).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
Carry out similarly to Example 11 processing with the aligning agent for liquid crystal (6) of above acquisition, make nematic liquid crystal box through the antiparallel orientation of friction treatment.By operation similarly to Example 11, the tilt angle that records this liquid crystal cell in room temperature is 29.8 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 20.0 °.
In addition, other does not operate the liquid crystal cell that makes similarly to Example 11 except carrying out friction treatment by polarized light microscope observing, confirms liquid crystal vertical orientation equably.
＜embodiment 14 〉
In NMP (22.0g), mix BODA (4.32g, 17.3mmol), p-PDA (1.74g, 16.1mmol), as the m-PBCH5DABz (3.10g of side chain diamines, 6.91mmol), add CBDA (1.02g in 40 ℃ of reactions after 5 hours, 5.20mmol) and NMP (18.0g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
After adding NMP is diluted to 6 quality % in this polyamic acid solution (30.0g), add diacetyl oxide (3.63g), pyridine (2.82g), in 80 ℃ of reactions 3 hours as imidization catalyst.This reaction soln is dropped in the methyl alcohol (387ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (G) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 44%, and number-average molecular weight is 14400, and weight-average molecular weight is 43700.
Add NMP (28.6g) at this polyimide powder (G) in (4.00g), stirred 40 hours in 80 ℃, make its dissolving.In this solution, add NMP (3.76g), BCS (29.6g), stirred 1 hour, obtain aligning agent for liquid crystal (7).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
Carry out similarly to Example 11 processing with the aligning agent for liquid crystal (7) of above acquisition, make nematic liquid crystal box through the antiparallel orientation of friction treatment.By operation similarly to Example 11, the tilt angle that records this liquid crystal cell in room temperature is 89.2 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 89.7 °.In addition, by the liquid crystal cell under the polarized light microscope observing room temperature and through 1 hour heat treated liquid crystal cell, confirm liquid crystal homogeneous orientation, even also realize the homogeneous orientation through the thermal treatment liquid crystal.
In addition, other does not operate the liquid crystal cell that makes similarly to Example 11 except carrying out friction treatment by polarized light microscope observing, confirms liquid crystal vertical orientation equably.
＜embodiment 15 〉
In NMP (23.0g), mix BODA (4.41g, 17.6mmol), DBA (2.86g, 18.8mmol), as the m-PBCH5DABz (2.11g of side chain diamines, 4.70mmol), add CBDA (1.01g in 80 ℃ of reactions after 5 hours, 5.15mmol) and NMP (18.0g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
After adding NMP is diluted to 6 quality % in this polyamic acid solution (30.0g), add diacetyl oxide (3.78g), pyridine (2.93g), in 80 ℃ of reactions 3 hours as imidization catalyst.This reaction soln is dropped in the methyl alcohol (408ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (H) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 40%, and number-average molecular weight is 16500, and weight-average molecular weight is 43800.
Add NMP (26.3g) at this polyimide powder (H) in (4.00g), stirred 40 hours in 80 ℃, make its dissolving.In this solution, add NMP (6.40g), BCS (30.0g), stirred 1 hour, obtain aligning agent for liquid crystal (8).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
Carry out similarly to Example 11 processing with the aligning agent for liquid crystal (8) of above acquisition, make nematic liquid crystal box through the antiparallel orientation of friction treatment.By operation similarly to Example 11, the tilt angle that records this liquid crystal cell in room temperature is 86.7 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 87.8 °.In addition, by the liquid crystal cell under the polarized light microscope observing room temperature and through 1 hour heat treated liquid crystal cell, confirm liquid crystal homogeneous orientation, even also realize the homogeneous orientation through the thermal treatment liquid crystal.
In addition, other does not operate the liquid crystal cell that makes similarly to Example 11 except carrying out friction treatment by polarized light microscope observing, confirms liquid crystal vertical orientation equably.
＜embodiment 16 〉
In NMP (43.0g), mix BODA (8.07g, 32.3mmol), DBA (4.58g, 30.1mmol), as the m-PBCH5DABz (5.79g of side chain diamines, 12.9mmol), add CBDA (2.05g in 80 ℃ of reactions after 5 hours, 10.5mmol) and NMP (38.0g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
After adding NMP is diluted to 6 quality % in this polyamic acid solution (20.0g), add diacetyl oxide (2.15g), pyridine (1.66g), in 80 ℃ of reactions 3 hours as imidization catalyst.This reaction soln is dropped in the methyl alcohol (247ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (I) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 45%, and number-average molecular weight is 22600, and weight-average molecular weight is 59500.
Add NMP (14.7g) at this polyimide powder (I) in (3.00g), stirred 40 hours in 80 ℃, make its dissolving.In this solution, add NMP (7.30g), BCS (25.0g), stirred 1 hour, obtain aligning agent for liquid crystal (9).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
Carry out similarly to Example 11 processing with the aligning agent for liquid crystal (9) of above acquisition, make nematic liquid crystal box through the antiparallel orientation of friction treatment.By operation similarly to Example 11, the tilt angle that records this liquid crystal cell in room temperature is 86.5 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 87.2 °.In addition, by the liquid crystal cell under the polarized light microscope observing room temperature and through 1 hour heat treated liquid crystal cell, confirm liquid crystal homogeneous orientation, even also realize the homogeneous orientation through the thermal treatment liquid crystal.
In addition, other does not operate the liquid crystal cell that makes similarly to Example 11 except carrying out friction treatment by polarized light microscope observing, confirms liquid crystal vertical orientation equably.
＜embodiment 17 〉
After adding NMP is diluted to 6 quality % in the polyamic acid solution (20.0g) that embodiment 16 obtains, add diacetyl oxide (4.29g), pyridine (3.33g), in 90 ℃ of reactions 3.5 hours as imidization catalyst.This reaction soln is dropped in the methyl alcohol (260ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (J) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 80%, and number-average molecular weight is 19600, and weight-average molecular weight is 51900.
Add NMP (14.8g) at this polyimide powder (J) in (3.00g), stirred 40 hours in 80 ℃, make its dissolving.In this solution, add NMP (7.40g), BCS (25.1g), stirred 1 hour, obtain aligning agent for liquid crystal (10).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
Carry out similarly to Example 11 processing with the aligning agent for liquid crystal (10) of above acquisition, make nematic liquid crystal box through the antiparallel orientation of friction treatment.By operation similarly to Example 11, the tilt angle that records this liquid crystal cell in room temperature is 88.9 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 89.6 °.In addition, by the liquid crystal cell under the polarized light microscope observing room temperature and through 1 hour heat treated liquid crystal cell, confirm liquid crystal homogeneous orientation, even also realize the homogeneous orientation through the thermal treatment liquid crystal.
In addition, other does not operate the liquid crystal cell that makes similarly to Example 11 except carrying out friction treatment by polarized light microscope observing, confirms liquid crystal vertical orientation equably.
＜embodiment 18 〉
After adding NMP is diluted to 6 quality % in the polyamic acid solution (20.0g) that embodiment 16 obtains, add diacetyl oxide (4.27g), triethylamine (1.51g), in 100 ℃ of reactions 4 hours as imidization catalyst.In this reaction soln, add and after oxalic acid (1.88g) neutralizes it is dropped in the methyl alcohol (253ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (K) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 98%, and number-average molecular weight is 19200, and weight-average molecular weight is 51000.
Add NMP (16.1g) at this polyimide powder (K) in (3.30g), stirred 40 hours in 80 ℃, make its dissolving.In this solution, add NMP (13.6g), BCS (22.0g), stirred 1 hour, obtain aligning agent for liquid crystal (11).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
Carry out similarly to Example 11 processing with the aligning agent for liquid crystal (11) of above acquisition, make nematic liquid crystal box through the antiparallel orientation of friction treatment.By operation similarly to Example 11, the tilt angle that records this liquid crystal cell in room temperature is 88.4 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 89.2 °.In addition, by the liquid crystal cell under the polarized light microscope observing room temperature and through 1 hour heat treated liquid crystal cell, confirm liquid crystal homogeneous orientation, even also realize the homogeneous orientation through the thermal treatment liquid crystal.
In addition, other does not operate the liquid crystal cell that makes similarly to Example 11 except carrying out friction treatment by polarized light microscope observing, confirms liquid crystal vertical orientation equably.
＜embodiment 19 〉
In NMP (20.0g), mix BODA (4.32g, 17.3mmol), p-PDA (2.11g, 19.5mmol), as the m-PBCH7DABz (1.64g of side chain diamines, 3.44mmol), add CBDA (1.01g in 80 ℃ of reactions after 5 hours, 5.15mmol) and NMP (16.4g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
After adding NMP is diluted to 6 quality % in this polyamic acid solution (20.0g), add diacetyl oxide (2.33g), pyridine (1.81g), in 80 ℃ of reactions 3 hours as imidization catalyst.This reaction soln is dropped in the methyl alcohol (250ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (L) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 50%, and number-average molecular weight is 13900, and weight-average molecular weight is 35800.
Add NMP (13.8g) at this polyimide powder (L) in (2.06g), stirred 40 hours in 80 ℃, make its dissolving.In this solution, add NMP (3.05g), BCS (15.5g), stirred 1 hour, obtain aligning agent for liquid crystal (12).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
Carry out similarly to Example 11 processing with the aligning agent for liquid crystal (12) of above acquisition, make nematic liquid crystal box through the antiparallel orientation of friction treatment.By operation similarly to Example 11, the tilt angle that records this liquid crystal cell in room temperature is 88.0 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 88.3 °.In addition, by the liquid crystal cell under the polarized light microscope observing room temperature and through 1 hour heat treated liquid crystal cell, confirm liquid crystal homogeneous orientation, even also realize the homogeneous orientation through the thermal treatment liquid crystal.
In addition, other does not operate the liquid crystal cell that makes similarly to Example 11 except carrying out friction treatment by polarized light microscope observing, confirms liquid crystal vertical orientation equably.
＜embodiment 20 〉
In NMP (39.5g), mix BODA (7.34g, 29.4mmol), DBA (4.17g, 27.4mmol), as the m-PBCH7DABz (5.60g of side chain diamines, 11.7mmol), add CBDA (2.05g in 80 ℃ of reactions after 5 hours, 10.5mmol) and NMP (34.5g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
After adding NMP is diluted to 6 quality % in this polyamic acid solution (20.0g), add diacetyl oxide (2.14g), pyridine (1.67g), in 80 ℃ of reactions 3 hours as imidization catalyst.This reaction soln is dropped in the methyl alcohol (250ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (M) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 45%, and number-average molecular weight is 21900, and weight-average molecular weight is 58100.
Add NMP (15.0g) at this polyimide powder (M) in (3.00g), stirred 40 hours in 80 ℃, make its dissolving.In this solution, add NMP (7.30g), BCS (25.1g), stirred 1 hour, obtain aligning agent for liquid crystal (13).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
Carry out similarly to Example 11 processing with the aligning agent for liquid crystal (13) of above acquisition, make nematic liquid crystal box through the antiparallel orientation of friction treatment.By operation similarly to Example 11, the tilt angle that records this liquid crystal cell in room temperature is 89.6 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 89.7 °.In addition, by the liquid crystal cell under the polarized light microscope observing room temperature and through 1 hour heat treated liquid crystal cell, confirm liquid crystal homogeneous orientation, even also realize the homogeneous orientation through the thermal treatment liquid crystal.
In addition, other does not operate the liquid crystal cell that makes similarly to Example 11 except carrying out friction treatment by polarized light microscope observing, confirms liquid crystal vertical orientation equably.
＜embodiment 21 〉
After adding NMP is diluted to 6 quality % in the polyimide solution (15.5g) that embodiment 20 obtains, add diacetyl oxide (3.32g), pyridine (2.58g), in 90 ℃ of reactions 3.5 hours as imidization catalyst.This reaction soln is dropped in the methyl alcohol (200ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (N) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 80%, and number-average molecular weight is 18600, and weight-average molecular weight is 50100.
Add NMP (12.6g) at this polyimide powder (N) in (2.50g), stirred 40 hours in 80 ℃, make its dissolving.In this solution, add NMP (6.11g), BCS (21.0g), stirred 1 hour, obtain aligning agent for liquid crystal (14).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
Carry out similarly to Example 11 processing with the aligning agent for liquid crystal (14) of above acquisition, make nematic liquid crystal box through the antiparallel orientation of friction treatment.By operation similarly to Example 11, the tilt angle that records this liquid crystal cell in room temperature is 89.5 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 89.7 °.In addition, by the liquid crystal cell under the polarized light microscope observing room temperature and through 1 hour heat treated liquid crystal cell, confirm liquid crystal homogeneous orientation, even also realize the homogeneous orientation through the thermal treatment liquid crystal.
In addition, other does not operate the liquid crystal cell that makes similarly to Example 11 except carrying out friction treatment by polarized light microscope observing, confirms liquid crystal vertical orientation equably.
＜comparative example 4 〉
Add NMP (21.1g) at polyimide powder (E) that comparative example 1 obtains in (3.15g),, make its dissolving in 80 ℃ of stirrings 40 hours.Add NMP (1.95g), BCS (26.3g) in this solution, stirring had resinous principle to separate out after 1 hour, can't obtain aligning agent for liquid crystal.Therefore, can't make liquid crystal cell.
＜comparative example 5 〉
Add NMP (24.4g) at polyimide powder (E) that comparative example 1 obtains in (3.65g),, make its dissolving in 80 ℃ of stirrings 40 hours.Add NMP (5.35g), BCS (27.4g) in this solution, stirring had resinous principle to separate out after 1 hour, can't obtain aligning agent for liquid crystal.Therefore, can't make liquid crystal cell.
＜comparative example 6 〉
Add NMP (20.7g) at polyimide powder (E) that comparative example 1 obtains in (3.10g),, make its dissolving in 80 ℃ of stirrings 40 hours.In this solution, add NMP (27.0g), BCS (11.2g), stirred 1 hour, obtain aligning agent for liquid crystal (15).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
The aligning agent for liquid crystal (15) of above acquisition is spun on the glass substrate of being with the ITO electrode, after making its dry 5 minutes on 80 ℃ the hot plate, carries out 1 hour burning till, make the polyimide film of thickness 100nm with 210 ℃ heated air circulation type stoves.Observe the visible a large amount of pores of coated surface.Carry out similarly to Example 11 processing with the substrate of this band liquid crystal orientating membrane, make nematic liquid crystal box through the antiparallel orientation of friction treatment.By operation similarly to Example 11, the tilt angle that records this liquid crystal cell in room temperature is 76.4 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 80.1 °.But, visible tilt angle in the liquid crystal cell face than big-difference.In addition, by the liquid crystal cell under the polarized light microscope observing room temperature and through 1 hour heat treated liquid crystal cell, the liquid crystal aligning that visible pore causes is bad.
In addition, other does not operate the liquid crystal cell that makes similarly to Example 11 except carrying out friction treatment by polarized light microscope observing, though confirm the liquid crystal vertical orientation, the local light leak part that visible pore causes.
＜comparative example 7 〉
In NMP (100.1g), mix BODA (16.9g, 67.5mmol), p-PDA (6.80g, 62.9mmol), as the PCH7DAB (10.3g of side chain diamines, 27.1mmol), add CBDA (4.10g in 40 ℃ of reactions after 5 hours, 20.9mmol) and NMP (52.2g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.After adding NMP is diluted to 6 quality % in the polyamic acid solution (130.3g) of gained, add diacetyl oxide (15.6g), pyridine (12.1g), in 80 ℃ of reactions 3 hours as imidization catalyst.This reaction soln is dropped in the methyl alcohol (1600ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (O) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 54%, and number-average molecular weight is 18300, and weight-average molecular weight is 45300.
Add NMP (23.5g) at this polyimide powder (O) in (3.20g), stirred 40 hours in 80 ℃, make its dissolving.In this solution, add NMP (2.63g), BCS (24.0g), stirred 1 hour, obtain aligning agent for liquid crystal (16).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
Carry out similarly to Example 11 processing with the aligning agent for liquid crystal (16) of above acquisition, make nematic liquid crystal box through the antiparallel orientation of friction treatment.By operation similarly to Example 11, the tilt angle that records this liquid crystal cell in room temperature is 78.7 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 81.5 °.In addition, by the liquid crystal cell under the polarized light microscope observing room temperature and through 1 hour heat treated liquid crystal cell, confirm liquid crystal homogeneous orientation, but compare, the light leak that visible liquid crystal tilts to be caused with embodiment 14.
In addition, other does not operate the liquid crystal cell that makes similarly to Example 11 except carrying out friction treatment by polarized light microscope observing, confirms liquid crystal vertical orientation equably.
＜comparative example 8 〉
In NMP (100.3g), mix BODA (15.0g, 60.0mmol), p-PDA (4.30g, 39.8mmol), as the PCH7DAB (15.2g of side chain diamines, 40.0m.mol), add CBDA (3.80g in 40 ℃ of reactions after 5 hours, 19.4mmol) and NMP (53.2g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.After adding NMP is diluted to 6 quality % in the polyamic acid solution (130.3g) of gained, add diacetyl oxide (13.9g), pyridine (10.8g), in 80 ℃ of reactions 3 hours as imidization catalyst.This reaction soln is dropped in the methyl alcohol (1600ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (P) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 55%, and number-average molecular weight is 17500, and weight-average molecular weight is 42700.
Add NMP (23.1g) at this polyimide powder (P) in (3.15g), stirred 40 hours in 80 ℃, make its dissolving.In this solution, add NMP (2.65g), BCS (23.6g), stirred 1 hour, obtain aligning agent for liquid crystal (17).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
The aligning agent for liquid crystal (17) of above acquisition is spun on the glass substrate of being with the ITO electrode, after making its dry 5 minutes on 80 ℃ the hot plate, carries out 1 hour burning till, make the polyimide film of thickness 100nm with 210 ℃ heated air circulation type stoves.Observe the visible pore of coated surface.Carry out similarly to Example 11 processing with the substrate of this band liquid crystal orientating membrane, make nematic liquid crystal box through the antiparallel orientation of friction treatment.By operation similarly to Example 11, the tilt angle that records this liquid crystal cell in room temperature is 87.7 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 88.7 °.But, the difference of visible tilt angle in the liquid crystal cell face.In addition, by the liquid crystal cell under the polarized light microscope observing room temperature and through 1 hour heat treated liquid crystal cell, the liquid crystal aligning that visible pore causes is bad.
In addition, other does not operate the liquid crystal cell that makes similarly to Example 11 except carrying out friction treatment by polarized light microscope observing, though confirm the liquid crystal vertical orientation, the local light leak part that visible pore causes.
＜comparative example 9 〉
Add NMP (23.5g) at polyimide powder (F) that comparative example 2 obtains in (3.51g),, make its dissolving in 80 ℃ of stirrings 40 hours.In this solution, add NMP (2.17g), BCS (29.3g), stirred 1 hour, obtain aligning agent for liquid crystal (18).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
The aligning agent for liquid crystal (18) of above acquisition is spun on the glass substrate of being with the ITO electrode, after making its dry 5 minutes on 80 ℃ the hot plate, carries out 1 hour burning till, make the polyimide film of thickness 100nm with 210 ℃ heated air circulation type stoves.Observe the visible a large amount of pores of coated surface.Carry out similarly to Example 11 processing with the substrate of this band liquid crystal orientating membrane, make nematic liquid crystal box through the antiparallel orientation of friction treatment.By operation similarly to Example 11, the tilt angle that records this liquid crystal cell in room temperature is 23.1 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 13.5 °.But, visible tilt angle in the liquid crystal cell face than big-difference.In addition, by the liquid crystal cell under the polarized light microscope observing room temperature and through 1 hour heat treated liquid crystal cell, the liquid crystal aligning that visible pore causes is bad.
In addition, other does not operate the liquid crystal cell that makes similarly to Example 11 except carrying out friction treatment by polarized light microscope observing, though confirm the liquid crystal vertical orientation, the local light leak part that visible pore causes.
＜comparative example 10 〉
Add NMP (21.6g) at polyimide powder (F) that comparative example 2 obtains in (3.23g),, make its dissolving in 80 ℃ of stirrings 40 hours.In this solution, add NMP (4.73g), BCS (24.2g), stirred 1 hour, obtain aligning agent for liquid crystal (19).Do not see that this aligning agent for liquid crystal has muddiness or separates out etc. unusually, confirms that resinous principle dissolves equably.
The aligning agent for liquid crystal (19) of above acquisition is spun on the glass substrate of being with the ITO electrode, after making its dry 5 minutes on 80 ℃ the hot plate, carries out 1 hour burning till, make the polyimide film of thickness 100nm with 210 ℃ heated air circulation type stoves.Observe the visible a large amount of pores of coated surface.Carry out similarly to Example 11 processing with the substrate of this band liquid crystal orientating membrane, make nematic liquid crystal box through the antiparallel orientation of friction treatment.By operation similarly to Example 11, the tilt angle that records this liquid crystal cell in room temperature is 22.1 °, in 120 ℃ liquid crystal cell carried out 1 hour thermal treatment after tilt angle be 15.6 °.But, visible tilt angle in the liquid crystal cell face than big-difference.In addition, by the liquid crystal cell under the polarized light microscope observing room temperature and through 1 hour heat treated liquid crystal cell, the liquid crystal aligning that visible pore causes is bad.
In addition, other does not operate the liquid crystal cell that makes similarly to Example 11 except carrying out friction treatment by polarized light microscope observing, confirms not vertical orientation of liquid crystal, visible local light leak part.
＜printing test 〉
The aligning agent for liquid crystal that obtains with embodiment 11～21, comparative example 6～10 prints.Use the simple and easy printing press of Nissha Printing Co., Ltd's system (S15 type) as printing press.Being printed on evaporation through washing has on the substrate of chromium and implements, and printing area is 8 * 8cm, and squeegee pressure is 0.2mm, 5 of temporary bases, from the time that is printed onto till the interim drying be 90 seconds, interim drying temperature is 70 ℃, carries out 5 minutes dryings.
Being confirmed to be by carry out visual observation under sodium vapor lamp of pore finished.
Confirm thickness difference and edge line with opticmicroscope.
Embodiment 11～21, comparative example 6～10 the results are summarized in table 3 and table 4.
From the result of embodiment 11～21, comparative example 6～10 as can be known, the polyimide that has used diamines of the present invention is relatively compared with the polyimide of diamines with having used, and can show bigger tilt angle with less import volume.Particularly by embodiment 14 and comparative example 7 more as can be known, comparative example 7 is compared with the embodiment 14 that has used diamines of the present invention, if carry out friction treatment, the light leak that the inclination of then visible liquid crystal causes.That is,, also can show bigger tilt angle even used the polyimide of diamines of the present invention to carry out friction treatment.Used the imidization rate height of the polyimide of diamines of the present invention, even but add the mixing allowance of the ethylene glycol butyl ether of wonderful works Weak solvent, separating out of resin can not appear.Consequently, can confirm to use diamines of the present invention and aligning agent for liquid crystal can form the film of homogeneous by the coating means of routine.
[table 1]
Polyimide powder The side chain diamines Side chain diamines amount (mole %) *1 Imidization rate (%) The solvability of polyimide (g) *2
Embodiment 5 ??(A) ??m-PBCH5DABz ??15 ??48 ??1.40
Embodiment 6 ??(B) ??m-BPCH5DABz ??15 ??41 ??1.16
Embodiment 7 ??(C) ??p-PBCH5DABz ??15 ??40 ??1.07
Embodiment 8 ??(D) ??m-PBCH7DABz ??15 ??45 ??1.36
Comparative example 1 ??(E) ??m-PBCH5DABEs ??15 ??45 ??0.11
Comparative example 2 ??(F) ??PBP5DABz ??15 ??45 ??0.64
*1: the usage ratio of side chain diamines that is used for the whole diamines of synthetic of polymkeric substance.
*The quality of 2:BCS mixing terminal point.
[table 2]
Aligning agent for liquid crystal The side chain diamines Side chain diamines amount (mole %) *3 Tilt angle (°) Vertical orientation (not having friction)
Embodiment 9 ??(1) ??m-PBCH5DABz ??10 ??85.7 ??○
Embodiment 10 ??(2) ??m-PBCH7DABz ??10 ??86.5 ??○
Comparative example 3 ??(3) ??PCH7DAB ??10 ??22.2 ??×
*3: the usage ratio of side chain diamines that is used for the whole diamines of synthetic of polymkeric substance.
[table 3]
Polyimide powder Aligning agent for liquid crystal The side chain diamines Side chain diamines amount (mole %) *4 Imidization rate (%) BCS measures (quality %) *5
Embodiment 11 ??(A) ??(4) ??m-PBCH5DABz ??15 ??48 ??48
Embodiment 12 ??(B) ??(5) ??m-BPCH5DABz ??15 ??41 ??50
Embodiment 13 ??(C) ??(6) ??p-PBCH5DABz ??15 ??40 ??48
Embodiment 14 ??(G) ??(7) ??m-PBCH5DABz ??30 ??44 ??48
Embodiment 15 ??(H) ??(8) ??m-PBCH5DABz ??20 ??40 ??48
Embodiment 16 ??(I) ??(9) ??m-PBCH5DABz ??30 ??45 ??53
Embodiment 17 ??(J) ??(10) ??m-PBCH5DABz ??30 ??80 ??53
Embodiment 18 ??(K) ??(11) ??m-PBCH5DABz ??30 ??98 ??43
Embodiment 19 ??(L) ??(12) ??m-PBCH7DABz ??15 ??50 ??48
Embodiment 20 ??(M) ??(13) ??m-PBCH7DABz ??30 ??45 ??53
Embodiment 21 ??(N) ??(14) ??m-PBCH7DABz ??30 ??80 ??53
Comparative example 4 ??(E) ??m-PBCH5DABEs ??15 ??45 ??53
Comparative example 5 ??(E) ??m-PBCH5DABEs ??15 ??45 ??48
Comparative example 6 ??(E) ??(15) ??m-PBCH5DABEs ??15 ??45 ??19
Comparative example 7 ??(O) ??(16) ??PCH7DAB ??30 ??54 ??48
Comparative example 8 ??(P) ??(17) ??PCH7DAB ??50 ??55 ??48
Comparative example 9 ??(F) ??(18) ??PBP5DABz ??15 ??45 ??53
Comparative example 10 ??(F) ??(19) ??PBP5DABz ??15 ??45 ??48
*4: the usage ratio of side chain diamines that is used for the whole diamines of synthetic of polymkeric substance.
*5: BCS shared usage ratio in the solvent total amount in the aligning agent for liquid crystal.
[table 4]
Figure G2008800091198D00471
*6: can't estimate owing to separating out of resinous principle. *7: have directed bad that pore causes.
*8: have light leakage phenomena.
The possibility of utilizing on the industry
When diamines of the present invention uses as the raw material of the polymer that consists of liquid crystal orientating membrane, effect with the tilt angle that strengthens liquid crystal, just can make the liquid crystal vertical orientation with less usage ratio, even and when having used a large amount of Weak solvents in the polymer solution polymer also be difficult for separating out. Therefore, aligning agent for liquid crystal of the present invention can form by coating process commonly used the film of homogeneous, can make and give liquid crystal with the liquid crystal orientating membrane than big tilt angle, so can be used for TN element, STN element, TFT liquid crystal cell and vertical orientation type liquid crystal display cells etc.
Here quote the announcement of all the elements of Japanese patent application 2007-077865 number specification sheets, claims and the summary of filing an application on March 23rd, 2007 as specification sheets of the present invention.

Claims (10)

1. the diamines of following formula (1) expression,
Figure A2008800091190002C1
In the formula (1), R 1Be phenylene, R 2Be cyclohexylidene or phenylene, R 3Be cyclohexylidene, R 4Be in the fluoroalkyl of the alkoxyl group of the fluoro-alkyl of the alkyl of carbon number 3～12, carbon number 3～12, carbon number 3～12 or carbon number 3～12 any.
2. diamines as claimed in claim 1 is characterized in that, the R of formula (1) 1Be 1,4-phenylene, R 2Be 1,4-cyclohexylidene or 1,4-phenylene, R 3Be 1, the 4-cyclohexylidene.
3. diamines as claimed in claim 1 or 2 is characterized in that, described diamines is by following formula (2-1) expression,
Figure A2008800091190002C2
In the formula (2-1), n is 2～11 integer, 1, and the cis-trans isomerization of 4-cyclohexylidene is respectively trans-isomer(ide).
4. diamines as claimed in claim 1 or 2 is characterized in that, described diamines is by following formula (2-2) expression,
Figure A2008800091190002C3
In the formula (2-2), n is 2～11 integer, 1, and the cis-trans isomerization of 4-cyclohexylidene is a trans-isomer(ide).
5. make two amine components that contain each described diamines in the claim 1～4 and tetracarboxylic dianhydride reaction and polyamic acid or make this polyamic acid dehydration closed-loop and polyimide.
6. polyamic acid as claimed in claim 5 or polyimide is characterized in that, 10 moles of % in two amine components are above to be each described diamines in the claim 1～4.
7. aligning agent for liquid crystal is characterized in that, contains claim 5 or 6 described polyamic acid and/or polyimide.
8. aligning agent for liquid crystal as claimed in claim 7 is characterized in that, contains organic solvent, and this organic solvent contains the Weak solvent of 5～60 quality %.
9. liquid crystal orientating membrane is characterized in that, adopts claim 7 or 8 described aligning agent for liquid crystal and gets.
10. liquid crystal display device is characterized in that, possesses the described liquid crystal orientating membrane of claim 9.
CN2008800091198A 2007-03-23 2008-03-21 Diamine compound, polyamic acid, polyimide and liquid crystal aligning agent Active CN101641322B (en)

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