CN101925634A - Diamine compound, liquid crystal aligning agent, and liquid crystal display device using the same - Google Patents

Diamine compound, liquid crystal aligning agent, and liquid crystal display device using the same Download PDF

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CN101925634A
CN101925634A CN2009801031894A CN200980103189A CN101925634A CN 101925634 A CN101925634 A CN 101925634A CN 2009801031894 A CN2009801031894 A CN 2009801031894A CN 200980103189 A CN200980103189 A CN 200980103189A CN 101925634 A CN101925634 A CN 101925634A
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CN101925634B (en
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南悟志
后藤耕平
须贺贵裕
北浩
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Nissan Chemical Corp
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/40—Acylated substituent nitrogen atom
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07D213/80—Acids; Esters in position 3
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    • C07D—HETEROCYCLIC COMPOUNDS
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
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    • 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

Abstract

Disclosed is a liquid crystal aligning agent which enables formation of a liquid crystal alignment film having high voltage holding ratio, in which film relaxation of residual charges accumulated by a DC voltage is fast even after long-time exposure to high temperatures. Also disclosed are a polyamide acid and/or a polyimide (hereinafter also referred to as a polymer) contained in the liquid crystal aligning agent, a diamine compound which can be used as a raw material for the polyamide acid and/or the polyimide, and a highly reliable liquid crystal display device having the liquid crystal alignment film, which device can endure long-time use in severe environments. Specifically disclosed is a diamine compound represented by Formula [1]. [1] (In Formula [1], X1 represents at least one divalent organic group selected from the group consisting of -O-, -NQ1-, -CONQ1-, -NQ1CO-, -CH2O- and -OCO-; Q1 represents a hydrogen atom or an alkyl group having 1-3 carbon atoms; X2 represents a single bond or at least one divalent organic group selected from the group consisting of aliphatic hydrocarbon groups having 1-20 carbon atoms, non-aromatic cyclic hydrocarbon groups and aromatic cyclic hydrocarbon groups; X3 represents a single bond or at least one divalent organic group selected from the group consisting of -O-, -NQ2-, -CONQ2-, -NQ2CO-, -COO-, -OCO- and -O(CH2)m- (wherein m represents an integer of 1-5); Q2 represents a hydrogen atom or an alkyl group having 1-3 carbon atoms; X4 represents a nitrogen-containing aromatic heterocyclic ring; and n represents an integer of 1-4.

Description

Diamine compound, aligning agent for liquid crystal and used the liquid crystal display device of this treatment agent
Technical field
The present invention relates to can be used as the diamine compound of the raw material of the polymkeric substance that is used for liquid crystal orientation film, polyamic acid and the polyimide that uses this diamine compound to make, and aligning agent for liquid crystal.Also relate to the liquid crystal display device that possesses the liquid crystal orientation film that obtains by described aligning agent for liquid crystal.
Background technology
At present, liquid crystal orientation film as liquid crystal display device, main use so-called polyimide liquid crystal orientation film, this polyimide liquid crystal orientation film is to burn till behind the aligning agent for liquid crystal (being also referred to as liquid crystal aligning agent) of principal constituent to make with the solution of polyimide precursor such as polyamic acid or soluble polyimide by coating on glass substrate etc.
Liquid crystal orientation film is that purpose is used with the state of orientation of control liquid crystal.But, high resolving powerization along with liquid crystal display device, the angle that control that descends from the contrast gradient of liquid crystal display device or persistence of vision reduce considers, the voltage retention height of used liquid crystal orientation film, the characteristic that the residual charge when having applied volts DS is few and/or the release of the residual charge accumulated because of volts DS is fast such are more and more important.
In the polyimide liquid crystal orientation film, as the short liquid crystal orientation film of time till the after image disappearance that produces because of volts DS, the known liquid crystal orientation film (for example with reference to patent documentation 1) that the liquid crystal aligning agent that has used the tertiary amine that also contains ad hoc structure except that the polyamic acid of polyamic acid or imido-is arranged has perhaps used the liquid crystal orientation film (for example with reference to patent documentation 2) of the liquid crystal aligning agent that contains in the raw material soluble polyimide that adopts the specific diamines with pyridine skeleton etc. etc.In addition, short liquid crystal orientation film of time till high and after image that produce because of volts DS disappears as voltage retention, known have used the liquid crystal orientation film (for example with reference to patent documentation 3) of liquid crystal aligning agent that compound, intramolecularly that intramolecularly contains 1 carboxyl contain the compound of 1 carboxylic acid anhydride group's compound and the compound that intramolecularly contains 1 uncle's amino that is selected from that except that polyamic acid or its imide amination polymer etc., also comprises minute quantity.
But, big in recent years picture and high-resolution LCD TV are widely used, liquid crystal display device in this purposes with present serve as that the main display applications that shows is compared with literal or still frame, its requirement for after image is stricter, and requires to possess the resistance characteristics that can use for a long time under harsh environment for use.Therefore, the reliability of used liquid crystal orientation film must be higher than existing liquid crystal orientation film, for the electrical characteristic of liquid crystal orientation film, not only requires initial characteristic good, also can keep good characteristic after also requiring for example to be exposed under the high temperature for a long time.
Patent documentation 1: Japanese patent laid-open 9-316200 communique
Patent documentation 2: Japanese patent laid-open 10-104633 communique
Patent documentation 3: Japanese patent laid-open 8-76128 communique
The announcement of invention
The purpose of this invention is to provide polyamic acid that the liquid crystal orientation film that is used for following liquid crystal display device, the aligning agent for liquid crystal that is used to form this liquid crystal orientation film, this aligning agent for liquid crystal comprise and/or polyimide (below be also referred to as polymkeric substance), can be used as the diamine compound of the raw material of this polyamic acid and polyimide.
In addition, the purpose of this invention is to provide and can obtain the also aligning agent for liquid crystal of very fast liquid crystal orientation film of the high and release that is exposed to high temperature under afterwards the residual charge of accumulating because of volts DS for a long time of voltage retention, but and possess this liquid crystal orientation film, under harsh environment for use the high liquid crystal display device of long term reliability.
The present inventor has found the new diamine compound that can reach this purpose after conscientiously studying for achieving the above object.The present invention is based on the invention that these achievements in research are finished, and comprises following technology contents.
(1) diamine compound of following formula [1] expression,
Figure BPA00001186317900021
In the formula [1], X 1For be selected from-O-,-NQ 1-,-CONQ 1-,-NQ 1CO-,-CH 2O-and-at least a kind of divalent organic group of OCO-, Q 1Be the alkyl of hydrogen atom or carbon number 1～3, X 2For singly-bound or be selected from least a kind of divalent organic group of aliphatic alkyl, non-aromatic ring type alkyl and the aromatic hydrocarbyl of carbon number 1～20, X 3For singly-bound or be selected from-O-,-NQ 2-,-CONQ 2-,-NQ 2CO-,-COO-,-OCO-and-O (CH 2) m-at least a kind of divalent organic group, m wherein is 1～5 integer, Q 2Be the alkyl of hydrogen atom or carbon number 1～3, X 4Be nitrogenous fragrant heterocycle, n is 1～4 integer.
(2) diamine compound of above-mentioned (1) record, the diamine compound of formula [1] is at least a kind of the compound that is selected from the expression of following formula [1a]～formula [1f],
Figure BPA00001186317900031
In the formula, Q 1Be the alkyl of hydrogen atom or carbon number 1～3, X 2For singly-bound or be selected from least a kind of divalent organic group of aliphatic alkyl, non-aromatic ring type alkyl and the aromatic hydrocarbyl of carbon number 1～20, X 3For singly-bound or be selected from-O-,-NQ 2-,-CONQ 2-,-NQ 2CO-,-COO-,-OCO-and-O (CH 2) m-at least a kind of divalent organic group, m wherein is 1～5 integer, Q 2Be the alkyl of hydrogen atom or carbon number 1～3, X 4Be nitrogenous fragrant heterocycle, n is 1～4 integer.
(3) diamine compound of above-mentioned (2) record, the X in formula [1a]～formula [1f] 2Straight-chain alkyl-sub-or phenyl ring for singly-bound, carbon number 1～3.
(4) diamine compound of above-mentioned (2) or (3) record, the X in formula [1a]～formula [1f] 3For singly-bound ,-OCO-or-OCH 2-.
(5) diamine compound of each record in above-mentioned (2)～(4), the X in formula [1a]～formula [1f] 4Be imidazole ring, pyridine ring or pyrimidine ring.
(6) diamine compound of each record in above-mentioned (2)～(5), the n in formula [1a]～formula [1f] is 1 or 2 integer.
(7) diamine compound of above-mentioned (1) or (2) record, the X in formula [1a]～formula [1f] 2Be at least a kind of the straight or branched alkylidene group, cyclohexane ring, phenyl ring and the naphthalene nucleus that are selected from carbon number 1～10, X 3For be selected from singly-bound ,-O-,-CONH-,-NHCO-,-COO-,-OCO-and-O (CH 2) m-at least a kind, m wherein is 1～5 integer, X 4For being selected from pyrrole ring, imidazole ring, pyrazoles ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzoglyoxaline ring at least a kind, n is 1 or 2 integer.
(8) diamine compound of above-mentioned (1) or (2) record, the X in formula [1a]～formula [1f] 2Be the straight or branched alkylidene group that is selected from singly-bound, carbon number 1～5 and at least a kind of phenyl ring, X 3For be selected from singly-bound ,-O-,-CONH-,-NHCO-,-COO-,-OCO-and-O (CH 2) m-at least a kind, m wherein is 1～5 integer, X 4For being selected from pyrrole ring, imidazole ring, pyrazoles ring, pyridine ring and pyrimidine ring at least a kind, n is 1 or 2 integer.
(9) diamine compound of above-mentioned (1) or (2) record, the X in formula [1a]～formula [1f] 2Be the straight-chain alkyl-sub-that is selected from singly-bound, carbon number 1～3 and at least a kind of phenyl ring, X 3For be selected from singly-bound ,-OCO-and-OCH 2-at least a kind, X 4For being selected from imidazole ring, pyridine ring and pyrimidine ring at least a kind, n is 1 or 2 integer.
(10) polyamic acid or polyimide, in the described polyamic acid above-mentioned by containing (1)～(9) two amine components of the diamine compound of each record and tetracarboxylic dianhydride the reaction and obtain, described polyimide is obtained by this polyamic acid dehydration closed-loop.
(11) polyamic acid or the polyimide of above-mentioned (10) record, the diamine compound of formula [1] expression are 1～80 mole of % in two amine components.
(12) aligning agent for liquid crystal contains polyamic acid of above-mentioned (10) or above-mentioned (11) record and either party at least and the solvent in the polyimide.
(13) aligning agent for liquid crystal of above-mentioned (12) record, 5～80 quality % in the solvent that this aligning agent for liquid crystal comprises are Weak solvent.
(14) liquid crystal orientation film, the aligning agent for liquid crystal of being put down in writing by above-mentioned (12) or above-mentioned (13) forms.
(15) liquid crystal display device possesses the liquid crystal orientation film that above-mentioned (14) are put down in writing.
Diamine compound of the present invention can obtain by easier method, when this diamine compound is used as the raw material of the polymkeric substance that constitutes liquid crystal orientation film, even can obtain the high and at high temperature long-time also very fast liquid crystal orientation film of release that exposes the residual charge of accumulating because of volts DS the back of voltage retention.Therefore, possess the reliability height of the liquid crystal display device of the liquid crystal orientation film that obtains by aligning agent for liquid crystal of the present invention, be applicable to big picture and high-resolution liquid crystal TV set etc.
The best mode that carries out an invention
Below, the present invention is described in detail.
The present invention relates to formula [1] expression diamine compound, with the diamine compound of formula [1] expression be the polymkeric substance that obtains of raw material, the aligning agent for liquid crystal that contains this polymkeric substance, the liquid crystal orientation film that obtains by this aligning agent for liquid crystal and the liquid crystal display device that possesses this liquid crystal orientation film.
Diamine compound of the present invention is that side chain has nitrogenous fragrant heterocyclic diamine compound (below be also referred to as specific diamine compound).This nitrogenous fragrant heterocycle plays a role by the jump of its conjugated structure as electronics, so in the liquid crystal orientation film that is made by the aligning agent for liquid crystal that contains the polymkeric substance that is obtained by specific diamine compound, can promote the transfer of the electric charge in the liquid crystal orientating membrane.
Based on above-mentioned situation, aligning agent for liquid crystal of the present invention can obtain the voltage retention height when forming liquid crystal orientation film, even and the also very fast liquid crystal orientation film of release of the residual charge of accumulating because of volts DS after at high temperature long-time the exposure.
＜specific diamine compound 〉
Specific diamine compound of the present invention is the diamine compound of following formula [1] expression.
In the formula [1], X 1For be selected from-O-,-NQ 1-,-CONQ 1-,-NQ 1CO-,-CH 2O-and-at least a kind of divalent organic group of OCO-, Q 1Be the alkyl of hydrogen atom or carbon number 1～3, X 2For singly-bound or be selected from least a kind of divalent organic group of aliphatic alkyl, non-aromatic ring type alkyl and the aromatic hydrocarbyl of carbon number 1～20, X 3For singly-bound or be selected from-O-,-NQ 2-,-CONQ 2-,-NQ 2CO-,-COO-,-OCO-and-O (CH 2) m-at least a kind of divalent organic group, m wherein is 1～5 integer, Q 2Be the alkyl of hydrogen atom or carbon number 1～3, X 4Be nitrogenous fragrant heterocycle, n is 1～4 integer.
For 2 amino (NH in the formula [1] 2) binding site be not particularly limited.Specifically, when n is integer 1, with respect to the linking group (X of side chain 1), can exemplify prosposition on the phenyl ring, 2,4,2,5,2,6,3,4,3,5.When n is integer 2, can exemplify following position.Linking group (X with respect to side chain 1), 2 linking group (X that have side chain on the phenyl ring 1) time, the binding site of 2 amino can exemplify 3,4,3,5,3,6,4,5.In addition, with respect to the linking group (X of side chain 1), 3 linking group (X that have side chain on the phenyl ring 1) time, the binding site of 2 amino can exemplify 2,4,2,5,4,5,4,6.In addition, with respect to the linking group (X of side chain 1), 4 linking group (X that have side chain on the phenyl ring 1) time, the binding site of 2 amino can exemplify prosposition, 2,5,2,6,3,5.When n is integer 3, can exemplify following position.Linking group (X with respect to side chain 1), there is the linking group (X of side chain in the prosposition on the phenyl ring 1) time, the binding site of 2 amino can exemplify 4,5,4,6.In addition, with respect to the linking group (X of side chain 1), 2,4 linking group (X that have side chain on the phenyl ring 1) time, the binding site of 2 amino can exemplify 3,5,3,6,5,6.Linking group (X with respect to side chain 1), 3,5 linking group (X that have side chain on the phenyl ring 1) time, the binding site of 2 amino can exemplify 2,4.When n is integer 4, can exemplify following position.Linking group (X with respect to side chain 1), 2,3 on the phenyl ring, 4 linking group (X that have side chain 1) time, the binding site of 2 amino can exemplify 5,6.In addition, with respect to the linking group (X of side chain 1), 2,4 on the phenyl ring, 5 linking group (X that have side chain 1) time, the binding site of 2 amino can exemplify 3,6.Linking group (X with respect to side chain 1), 2,4 on the phenyl ring, 6 linking group (X that have side chain 1) time, the binding site of 2 amino can exemplify 3,5.Wherein, the angle of the difficulty or ease during from reactive angle in synthesizing polyamides when acid and synthetic diamine compound considers, special good is when n is integer 1, the binding site of 2 amino is 2,4,2,5,3,5, the linking group (X of the side chain when perhaps being integer 2 with respect to n 1), 3 linking group (X that have side chain on the phenyl ring 1) situation under, the binding site of 2 amino is 4,6.
In the formula [1], X 1For be selected from-O-,-NQ 1-,-CONQ 1-,-NQ 1CO-,-CH 2O-and-at least a kind of divalent organic group of OCO-.Wherein, be preferably-O-,-NQ 1-,-CONQ 1-,-NQ 1CO-.Q 1Definition and formula [1] in identical.
X 1Structure more specifically can exemplify following formula [1a]～formula [1f].
Wherein, preferred formula [1a], formula [1b], formula [1c] and formula [1d].Q 1Definition and formula [1] in identical.
In the formula [1], X 2For singly-bound or be selected from least a kind of divalent organic group of aliphatic alkyl, non-aromatic ring type alkyl or the aromatic hydrocarbyl of carbon number 1～20.
The aliphatic alkyl of carbon number 1～20 can also can branch for the straight chain shape.In addition, can contain unsaturated link(age).Be preferably the aliphatic alkyl of carbon number 1～10.
As the concrete example of non-aromatic ring type alkyl, can exemplify cyclopropane ring, tetramethylene ring, pentamethylene ring, cyclohexane ring, suberane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring undecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring, ring n-Hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring eicosane ring, three ring eicosane rings, three ring docosane rings, bicycloheptane ring, decahydro naphthalene nucleus, norbornylene ring, diamantane ring etc.
As the concrete example of aromatic hydrocarbyl, can exemplify phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, Azulene ring, indenes ring, fluorenes ring, anthracene nucleus, phenanthrene ring, 1,8-perinaphthene ring etc.
As the preferred X in the formula [1] 2Can exemplify singly-bound, the straight or branched alkylidene group of carbon number 1～10, the unsaturated alkylene of carbon number 1～10, cyclopropane ring, the tetramethylene ring, the pentamethylene ring, cyclohexane ring, the suberane ring, the norbornylene ring, the diamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, the fluorenes ring, anthracene nucleus, be more preferably singly-bound, the straight or branched alkylidene group of carbon number 1～10, the unsaturated alkylene of carbon number 1～10, cyclohexane ring, the norbornylene ring, the diamantane ring, phenyl ring, naphthalene nucleus, the fluorenes ring, anthracene nucleus, further be more preferably singly-bound, the straight or branched alkylidene group of carbon number 1～10, cyclohexane ring, phenyl ring, naphthalene nucleus, special good is singly-bound, the straight or branched alkylidene group of carbon number 1～5, phenyl ring.Best is the straight-chain alkyl-sub-or the phenyl ring of singly-bound, carbon number 1～3.
In the formula [1], X 3For singly-bound or be selected from-O-,-NQ 2-,-CONQ 2-,-NQ 2CO-,-COO-,-OCO-and-O (CH 2) m-at least a kind of divalent organic group, m wherein is 1～5 integer, be preferably singly-bound ,-O-,-CONQ 2-,-NQ 2CO-,-COO-,-OCO-and-O (CH 2) m-, m wherein is 1～5 integer.Best is singly-bound ,-OCO-or-OCH 2-.Q 2Definition and formula [1] identical.
In the formula [1], X 4Be nitrogenous fragrant heterocycle, be the nitrogenous fragrant heterocycle of at least 1 structure containing the following formula [2a] that is selected from, formula [2b] and formula [2c].
In the formula [2c], Y 1Straight or branched alkyl for carbon number 1～5.
As the preferred X in the formula [1] 4, can exemplify pyrrole ring, imidazole ring,
Figure BPA00001186317900072
Azoles ring, thiazole ring, pyrazoles ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline 99.9 ring, carbazole ring, purine skeleton, thiadiazoles ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzoglyoxaline ring, cinnolines ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, thiodiphenylamine ring,
Figure BPA00001186317900073
Diazole ring, acridine ring, be more preferably pyrrole ring, imidazole ring, pyrazoles ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzoglyoxaline ring, further be more preferably pyrrole ring, imidazole ring, pyrazoles ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzoglyoxaline ring, special good is pyrrole ring, imidazole ring, pyrazoles ring, pyridine ring, pyrimidine ring, and best is imidazole ring, pyridine ring or pyrimidine ring.
In addition, X 3Preferably with discord X 4The formula that is comprised [2a], formula [2b] and the adjacent substituting group combination of formula [2c].
In the formula [1], n is 1～4 integer, from considering that with reactive angle of tetracarboxylic dianhydride n is preferably 1～3 integer.N is preferably 1 or 2 integer.
Preferred X in the formula [1] 1, X 2, X 3, X 4And the combination of n is X 1For be selected from-O-,-NQ 1-,-CONQ 1-,-NQ 1CO-,-CH 2O-and-at least a kind of OCO-, X 2Be unsaturated alkylene, cyclopropane ring, tetramethylene ring, pentamethylene ring, cyclohexane ring, suberane ring, norbornylene ring, diamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, fluorenes ring and the anthracene nucleus of the straight or branched alkylidene group that is selected from carbon number 1～10, carbon number 1～10 at least a kind, X 3For be selected from singly-bound ,-O-,-NQ 2-,-CONQ 2-,-NQ 2CO-,-COO-,-OCO-and-O (CH 2) m-at least a kind, m wherein is 1～5 integer, X 4For be selected from pyrrole ring, imidazole ring,
Figure BPA00001186317900081
Azoles ring, thiazole ring, pyrazoles ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline 99.9 ring, carbazole ring, purine skeleton, thiadiazoles ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzoglyoxaline ring, cinnolines ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, thiodiphenylamine ring,
Figure BPA00001186317900082
Diazole ring and acridine ring at least a kind, n is 1 or 2 integer.
X in the better formula [1] 1, X 2, X 3, X 4And the combination of n is X 1For be selected from-O-,-NQ 1-,-CONQ 1-,-NQ 1CO-reaches-CH 2At least a kind of O-, X 2Be unsaturated alkylene, cyclohexane ring, norbornylene ring, diamantane ring, phenyl ring, naphthalene nucleus, fluorenes ring and the anthracene nucleus of the straight or branched alkylidene group that is selected from carbon number 1～10, carbon number 1～10 at least a kind, X 3For be selected from singly-bound ,-O-,-NQ 2-,-CONQ 2-,-NQ 2CO-,-COO-,-OCO-and-O (CH 2) m-at least a kind, m wherein is 1～5 integer, X 4For being selected from pyrrole ring, imidazole ring, pyrazoles ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzoglyoxaline ring at least a kind, n is 1 or 2 integer.
X in the further better formula [1] 1, X 2, X 3, X 4And the combination of n is X 1For be selected from-O-,-NQ 1-,-CONQ 1-,-NQ 1CO-,-CH 2O-and-at least a kind of OCO-, X 2Be at least a kind of the straight or branched alkylidene group, cyclohexane ring, phenyl ring and the naphthalene nucleus that are selected from carbon number 1～10, X 3For be selected from singly-bound ,-O-,-CONQ 2-,-NQ 2CO-,-COO-,-OCO-and-O (CH 2) m-at least a kind, m wherein is 1～5 integer, X 4For being selected from pyrrole ring, imidazole ring, pyrazoles ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring and benzoglyoxaline ring at least a kind, n is 1 or 2 integer.
X in the special good formula [1] 1, X 2, X 3, X 4And the combination of n is X 1For be selected from-O-,-NQ 1-,-CONQ 1-,-NQ 1CO-reaches-CH 2At least a kind of O-, X 2Be the straight or branched alkylidene group that is selected from singly-bound, carbon number 1～5 and at least a kind of phenyl ring, X 3For be selected from singly-bound ,-O-,-CONQ 2-,-NQ 2CO-,-COO-,-OCO-and-O (CH 2) m-at least a kind, m wherein is 1～5 integer, X 4For being selected from pyrrole ring, imidazole ring, pyrazoles ring, pyridine ring and pyrimidine ring at least a kind, n is 1 or 2 integer.
X in the best formula [1] 1, X 2, X 3, X 4And the combination of n is X 1For be selected from-O-,-NQ 1-,-CONQ 1-and-NQ 1At least a kind of CO-, X 2Be the straight-chain alkyl-sub-that is selected from singly-bound, carbon number 1～3 and at least a kind of phenyl ring, X 3For be selected from singly-bound ,-OCO-and-OCH 2-at least a kind, X 4For being selected from imidazole ring, pyridine ring and pyrimidine ring at least a kind, n is 1 or 2 integer.
X in the special good formula [1] 1, X 2, X 3, X 4And the combination of n is shown in following table 1～table 3.Q 1And Q 2Definition identical with formula [1].
[table 1]
X 1 X 2 X 3 X 4
A-1 -O- Singly-bound Singly-bound Imidazole ring
A-2 -O- Singly-bound Singly-bound Pyridine ring
A-3 -O- Singly-bound Singly-bound Pyrimidine ring
A-4 -NQ 1- Singly-bound Singly-bound Imidazole ring
A-5 -NQ 1- Singly-bound Singly-bound Pyridine ring
A-6 -NQ 1- Singly-bound Singly-bound Pyrimidine ring
A-7 -CONQ 1- Singly-bound Singly-bound Imidazole ring
A-8 -CONQ 1- Singly-bound Singly-bound Pyridine ring
A-9 -CONQ 1- Singly-bound Singly-bound Pyrimidine ring
A-10 -NQ 1CO- Singly-bound Singly-bound Imidazole ring
A-11 -NQ 1CO- Singly-bound Singly-bound Pyridine ring
A-12 -NQ 1CO- Singly-bound Singly-bound Pyrimidine ring
A-13 -O- The straight-chain alkyl-sub-of carbon number 1～3 Singly-bound Imidazole ring
A-14 -O- The straight-chain alkyl-sub-of carbon number 1～3 Singly-bound Pyridine ring
A-15 -O- The straight-chain alkyl-sub-of carbon number 1～3 Singly-bound Pyrimidine ring
A-16 -O- The straight-chain alkyl-sub-of carbon number 1～3 -OCO- Imidazole ring
A-17 -O- The straight-chain alkyl-sub-of carbon number 1～3 -OCO- Pyridine ring
A-18 -O- The straight-chain alkyl-sub-of carbon number 1～3 -OCO- Pyrimidine ring
A-19 -O- The straight-chain alkyl-sub-of carbon number 1～3 -OCH 2- Imidazole ring
A-20 -O- The straight-chain alkyl-sub-of carbon number 1～3 -OCH 2- Pyridine ring
A-21 -O- The straight-chain alkyl-sub-of carbon number 1～3 -OCH 2- Pyrimidine ring
A-22 -NQ 1- The straight-chain alkyl-sub-of carbon number 1～3 Singly-bound Imidazole ring
A-23 -NQ 1- The straight-chain alkyl-sub-of carbon number 1～3 Singly-bound Pyridine ring
A-24 -NQ 1- The straight-chain alkyl-sub-of carbon number 1～3 Singly-bound Pyrimidine ring
A-25 -NQ 1- The straight-chain alkyl-sub-of carbon number 1～3 -OCO- Imidazole ring
A-26 -NQ 1- The straight-chain alkyl-sub-of carbon number 1～3 -OCO- Pyridine ring
A-27 -NQ 1- The straight-chain alkyl-sub-of carbon number 1～3 -OCO- Pyrimidine ring
A-28 -NQ 1- The straight-chain alkyl-sub-of carbon number 1～3 -OCH 2- Imidazole ring
A-29 -NQ 1- The straight-chain alkyl-sub-of carbon number 1～3 -OCH 2- Pyridine ring
A-30 -NQ 1- The straight-chain alkyl-sub-of carbon number 1～3 -OCH 2- Pyrimidine ring
A-31 -CONQ 1- The straight-chain alkyl-sub-of carbon number 1～3 Singly-bound Imidazole ring
[table 2]
X 1 X 2 X 3 X 4
A-32 -CONQ 1- The straight-chain alkyl-sub-of carbon number 1～3 Singly-bound Pyridine ring
A-33 -CONQ 1- The straight-chain alkyl-sub-of carbon number 1～3 Singly-bound Pyrimidine ring
A-34 -CONQ 1- The straight-chain alkyl-sub-of carbon number 1～3 -OCO- Imidazole ring
A-35 -CONQ 1- The straight-chain alkyl-sub-of carbon number 1～3 -OCO- Pyridine ring
A-36 -CONQ 1- The straight-chain alkyl-sub-of carbon number 1～3 -OCO- Pyrimidine ring
A-37 -CONQ 1- The straight-chain alkyl-sub-of carbon number 1～3 -OCH 2- Imidazole ring
A-38 -CONQ 1- The straight-chain alkyl-sub-of carbon number 1～3 -OCH 2- Pyridine ring
A-39 -CONQ 1- The straight-chain alkyl-sub-of carbon number 1～3 -OCH 2- Pyrimidine ring
A-40 -NQ 1CO- The straight-chain alkyl-sub-of carbon number 1～3 Singly-bound Imidazole ring
A-41 -NQ 1CO- The straight-chain alkyl-sub-of carbon number 1～3 Singly-bound Pyridine ring
A-42 -NQ 1CO- The straight-chain alkyl-sub-of carbon number 1～3 Singly-bound Pyrimidine ring
A-43 -NQ 1CO- The straight-chain alkyl-sub-of carbon number 1～3 -OCO- Imidazole ring
A-44 -NQ 1CO- The straight-chain alkyl-sub-of carbon number 1～3 -OCO- Pyridine ring
A-45 -NQ 1CO- The straight-chain alkyl-sub-of carbon number 1～3 -OCO- Pyrimidine ring
A-46 -NQ 1CO- The straight-chain alkyl-sub-of carbon number 1～3 -OCH 2- Imidazole ring
A-47 -NQ 1CO- The straight-chain alkyl-sub-of carbon number 1～3 -OCH 2- Pyridine ring
A-48 -NQ 1CO- The straight-chain alkyl-sub-of carbon number 1～3 -OCH 2- Pyrimidine ring
A-49 -O- Phenyl ring Singly-bound Imidazole ring
A-50 -O- Phenyl ring Singly-bound Pyridine ring
A-51 -O- Phenyl ring Singly-bound Pyrimidine ring
A-52 -O- Phenyl ring -OCO- Imidazole ring
A-53 -O- Phenyl ring -OCO- Pyridine ring
A-54 -O- Phenyl ring -OCO- Pyrimidine ring
A-55 -O- Phenyl ring -OCH 2- Imidazole ring
A-56 -O- Phenyl ring -OCH 2- Pyridine ring
A-57 -O- Phenyl ring -OCH 2- Pyrimidine ring
A-58 -NQ 1- Phenyl ring Singly-bound Imidazole ring
A-59 -NQ 1- Phenyl ring Singly-bound Pyridine ring
A-60 -NQ 1- Phenyl ring Singly-bound Pyrimidine ring
A-61 -NQ 1- Phenyl ring -OCO- Imidazole ring
A-62 -NQ 1- Phenyl ring -OCO- Pyridine ring
[table 3]
X 1 X 2 X 3 X 4
A-63 -NQ 1- Phenyl ring -OCO- Pyrimidine ring
A-64 -NQ 1- Phenyl ring -OCH 2- Imidazole ring
A-65 -NQ 1- Phenyl ring -OCH 2- Pyridine ring
A-66 -NQ 1- Phenyl ring -OCH 2- Pyrimidine ring
A-67 -CONQ 1- Phenyl ring Singly-bound Imidazole ring
A-68 -CONQ 1- Phenyl ring Singly-bound Pyridine ring
A-69 -CONQ 1- Phenyl ring Singly-bound Pyrimidine ring
A-70 -CONQ 1- Phenyl ring -OCO- Imidazole ring
A-71 -CONQ 1- Phenyl ring -OCO- Pyridine ring
A-72 -CONQ 1- Phenyl ring -OCO- Pyrimidine ring
A-73 -CONQ 1- Phenyl ring -OCH 2- Imidazole ring
A-74 -CONQ 1- Phenyl ring -OCH 2- Pyridine ring
A-75 -CONQ 1- Phenyl ring -OCH 2- Pyrimidine ring
A-76 -NQ 1CO- Phenyl ring Singly-bound Imidazole ring
A-77 -NQ 1CO- Phenyl ring Singly-bound Pyridine ring
A-78 -NQ 1CO- Phenyl ring Singly-bound Pyrimidine ring
A-79 -NQ 1CO- Phenyl ring -OCO- Imidazole ring
A-80 -NQ 1CO- Phenyl ring -OCO- Pyridine ring
A-81 -NQ 1CO- Phenyl ring -OCO- Pyrimidine ring
A-82 -NQ 1CO- Phenyl ring -OCH 2- Imidazole ring
A-83 -NQ 1CO- Phenyl ring -OCH 2- Pyridine ring
A-84 -NQ 1CO- Phenyl ring -OCH 2- Pyrimidine ring
A-85 -CONQ 1- Phenyl ring Singly-bound Imidazole ring
A-86 -CONQ 1- Phenyl ring Singly-bound Pyridine ring
A-87 -CONQ 1- Phenyl ring Singly-bound Pyrimidine ring
A-88 -CONQ 1- Phenyl ring -OCO- Imidazole ring
A-89 -CONQ 1- Phenyl ring -OCO- Pyridine ring
A-90 -CONQ 1- Phenyl ring -OCO- Pyrimidine ring
A-91 -CONQ 1- Phenyl ring -OCH 2- Imidazole ring
A-92 -CONQ 1- Phenyl ring -OCH 2- Pyridine ring
A-93 -CONQ 1- Phenyl ring -OCH 2- Pyrimidine ring
The synthetic method of＜specific diamine compound 〉
Manufacture method to the specific diamine compound of formula of the present invention [1] expression is not particularly limited, and as preferred method, can exemplify following method.
Figure BPA00001186317900121
Specific diamine compound of the present invention is by the dinitro matrix of synthesis type [4] expression, again nitroreduction is converted to amino and obtains.Method for the reduction dinitro compound is not particularly limited, and adopts following method usually: use palladium on carbon, platinum oxide, draw Buddhist nun's nickel, platinum black, rhodium-aluminum oxide, platinum sulfide carbon etc. as catalyzer, at ethyl acetate, toluene, tetrahydrofuran (THF), two Utilize enforcements such as hydrogen, hydrazine, hydrogenchloride in alkane, the alcohols equal solvent.X in the formula [4] 1, X 2, X 3, X 4And n is identical with the definition of formula [1].
The dinitrobenzene style of formula [4] is as obtaining by the following method: be situated between with X 3Make X 2And X 4Be situated between with X in conjunction with the back 1Make dinitrobenzene part bonded method, be situated between with connection portion X 1Make dinitrobenzene part and X 2Be situated between with X in conjunction with the back 3With X 4The bonded method.
X 1For be selected from-O-(ehter bond) ,-NQ 1-(amino key) ,-CONQ 1-(amido linkage) ,-NQ 1CO-(anti-amido linkage) ,-CH 2O-(methylene ether link) and-at least a kind of linking group of OCO-(anti-ester bond), these linking groups can form by methodology of organic synthesis commonly used.The Q of each linking group 1Identical with the definition in the formula [1].
For example, X 1During for ehter bond, methylene ether link, can exemplify corresponding making the halogen derivative that contains dinitrobenzene and contain X 2, X 3And X 4The hydroxy derivatives method of in the presence of alkali, reacting, perhaps make the hydroxy derivatives that contains dinitrobenzene and contain X 2, X 3And X 4The halogen substituted derivative method of in the presence of alkali, reacting.
X 1During for amino key, can exemplify corresponding making the halogen derivative that contains dinitrobenzene and contain X 2, X 3And X 4The amino substitutive derivative method of in the presence of alkali, reacting.
X 1During for anti-ester bond, can exemplify corresponding making the hydroxy derivatives that contains dinitrobenzene and contain X 2, X 3And X 4The acyl chlorides body method of in the presence of alkali, reacting.
X 1During for amido linkage, can exemplify corresponding making the acyl chlorides body that contains dinitrobenzene and contain X 2, X 3And X 4Amino replace the method that body reacts in the presence of alkali.
X 1During for anti-amido linkage, can exemplify corresponding making the amino replacement body that contains dinitrobenzene and contain X 2, X 3And X 4The acyl chlorides body method of in the presence of alkali, reacting.
As the halogen derivative that contains dinitrobenzene and contain the concrete example of dinitrobenzene derivative, can exemplify 3, the 5-dinitrochlorobenzene, 2, the 4-dinitrochlorobenzene, 2, the 4-dinitrofluorobenzene, 3, the 5-dinitrobenzoyl chloride, 3, the 5-dinitrobenzoic acid, 2, the 4-dinitrobenzoyl chloride, 2, the 4-dinitrobenzoic acid, 3,5-dinitrobenzene methyl chloride, 2,4-dinitrobenzene methyl chloride, 3,5-dinitrobenzene methyl alcohol, 2,4-dinitrobenzene methyl alcohol, 2, the 4-dinitraniline, 3, the 5-dinitraniline, 2, the 6-dinitraniline, 2,2, 4-dinitrophenol, 2, the 5-dinitrophenol(DNP), 2, the 6-dinitrophenol(DNP), 2,4-dinitrobenzene guanidine-acetic acid etc.From raw material obtain difficulty or ease, reactive angle is considered, can select wherein a kind or multiple for use.
＜polymkeric substance 〉
Polymkeric substance of the present invention is the polyamic acid that gets of the reaction by two amine components that contain specific diamine compound and tetracarboxylic dianhydride and the polyimide that this polyamic acid dehydration closed-loop is got.Described polyamic acid and polyimide all can be used as the polymkeric substance that obtains liquid crystal orientation film.
The voltage retention that contains proportional many more liquid crystal orientation films that obtained by polymkeric substance of the present invention of the specific diamine compound in described two amine components is high more, even and to be exposed to high temperature under afterwards the release of the residual charge of accumulating because of volts DS for a long time also fast more.
To improve described characteristic is purpose, and 1 mole of % in preferred two amine components is above to be specific diamine compound.5 moles of % that are more preferably in two amine components are above for specific diamine compound, further are more preferably 10 moles more than the %.
100 moles of % that also can be two amine components are specific diamine compound, but the angle of the homogeneous coating during from the coating of liquid crystalline aligning agent considers, specific diamine compound is preferably 80 moles of two amine components below the %, more preferably 40 moles below the %.
Among the present invention, can and with the diamines beyond the specific diamine compound (below be also referred to as other diamine compound).Its concrete example exemplifies as follows.
Ursol D for example; 2,3,5; 6-tetramethyl--Ursol D; 2,5-dimethyl-Ursol D; mphenylenediamine; 2,4-dimethyl-mphenylenediamine; 2; the 5-diaminotoluene; 2, the 6-diaminotoluene; 2, the 5-diaminophenol; 2; the 4-diaminophenol; 3, the 5-diaminophenol; 3,5-diaminobenzene methyl alcohol; 2; 4-diaminobenzene methyl alcohol; 4, the 6-diamino resorcin; 4,4 '-benzidine; 3; 3 '-dimethyl-4,4 '-benzidine; 3,3 '-dimethoxy-4 '; 4 '-benzidine; 3,3 '-dihydroxyl-4,4 '-benzidine; 3; 3 '-two fluoro-4,4 '-biphenyl; 3,3 '-trifluoromethyl-4; 4 '-benzidine; 3,4 '-benzidine; 3,3 '-benzidine; 2; 2 '-benzidine; 2,3 '-benzidine; 4,4 '-diaminodiphenyl-methane; 3; 3 '-diaminodiphenyl-methane; 3,4 '-diaminodiphenyl-methane; 2,2 '-diaminodiphenyl-methane; 2; 3 '-diaminodiphenyl-methane; 4; 4 '-diamino-diphenyl ether; 3,3 '-diamino-diphenyl ether; 3,4 '-diamino-diphenyl ether; 2; 2 '-diamino-diphenyl ether; 2; 3 '-diamino-diphenyl ether; 4,4 '-alkylsulfonyl pentanoic; 3,3 '-alkylsulfonyl pentanoic; two (4-aminophenyl) silane; two (3-aminophenyl) silane; dimethyl-two (4-aminophenyl) silane; dimethyl-two (3-aminophenyl) silane; 4; 4 '-Vermitin; 3; 3 '-Vermitin; 4,4 '-diamino-diphenyl amine; 3,3 '-diamino-diphenyl amine; 3; 4 '-diamino-diphenyl amine; 2; 2 '-diamino-diphenyl amine; 2,3 '-diamino-diphenyl amine; N-methyl (4,4 '-diamino-diphenyl) amine; N-methyl (3; 3 '-diamino-diphenyl) amine; N-methyl (3; 4 '-diamino-diphenyl) amine; N-methyl (2,2 '-diamino-diphenyl) amine; N-methyl (2,3 '-diamino-diphenyl) amine; 4; 4 '-diaminobenzophenone; 3; 3 '-diaminobenzophenone; 3,4 '-diaminobenzophenone; 1, the 4-diaminonaphthalene; 2; 2 '-diaminobenzophenone; 2; 3 '-diaminobenzophenone; 1, the 5-diaminonaphthalene; 1, the 6-diaminonaphthalene; 1; the 7-diaminonaphthalene; 1; the 8-diaminonaphthalene; 2, the 5-diaminonaphthalene; 2, the 6-diaminonaphthalene; 2; the 7-diaminonaphthalene; 2; the 8-diaminonaphthalene; 1, two (4-aminophenyl) ethane of 2-; 1, two (3-aminophenyl) ethane of 2-; 1; two (4-aminophenyl) propane of 3-; 1; two (3-aminophenyl) propane of 3-; 1, two (4-aminophenyl) butane of 4-; 1, two (3-aminophenyl) butane of 4-; two (3; 5-diethyl-4-aminophenyl) methane; 1; two (4-amino-benzene oxygen) benzene of 4-; 1, two (4-amino-benzene oxygen) benzene of 3-; 1, two (4-aminophenyl) benzene of 4-; 1; two (4-aminophenyl) benzene of 3-; 1; two (the 4-amino-benzene methyl) benzene of 4-; 1, two (4-amino-benzene oxygen) benzene of 3-; 4,4 '-[1; 4-phenylene two (methylene radical)] pentanoic; 4; 4 '-[1,3-phenylene two (methylene radical)] pentanoic; 3,4 '-[1; 4-phenylene two (methylene radical)] pentanoic; 3; 4 '-[1,3-phenylene two (methylene radical)] pentanoic; 3,3 '-[1; 4-phenylene two (methylene radical)] pentanoic; 3; 3 '-[1,3-phenylene two (methylene radical)] pentanoic; 1,4-phenylene two [(4-aminophenyl) ketone]; 1; 4-phenylene two [(3-aminophenyl) ketone]; 1; 3-phenylene 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); two (4-aminophenyl) terephthalate; two (3-aminophenyl) terephthalate; two (4-aminophenyl) isophthalic acid ester; two (3-aminophenyl) isophthalic acid ester; N, N '-(1; the 4-phenylene) two (4-aminobenzamide); N; N '-(1, the 3-phenylene) two (4-aminobenzamides); N, N '-(1; the 4-phenylene) two (3-aminobenzamide); N; N '-(1, the 3-phenylene) two (3-aminobenzamides); N, N '-two (4-aminophenyl) terephthalamide; N; N '-two (3-aminophenyl) terephthalamide; N; N '-two (4-aminophenyl) isophthaloyl amine; N, N '-two (3-aminophenyl) isophthaloyl amine; 9, two (4-aminophenyl) anthracenes of 10-; 4; 4 '-two (4-amino-benzene oxygen) sulfobenzide; 2; 2 '-two [4-(4-amino-benzene oxygen) phenyl] propane; 2,2 '-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa; 2,2 '-two (4-aminophenyl) HFC-236fa; 2; 2 '-two (3-aminophenyl) HFC-236fa; 2; 2 '-two (3-amino-4-aminomethyl phenyl) HFC-236fa; 2,2 '-two (4-aminophenyl) propane; 2,2 '-two (3-aminophenyl) propane; 2; 2 '-two (3-amino-4-aminomethyl phenyl) propane; 1; two (4-amino-benzene oxygen) propane of 3-; 1, two (3-amino-benzene oxygen) propane of 3-; 1, two (4-amino-benzene oxygen) butane of 4-; 1; two (3-amino-benzene oxygen) butane of 4-; 1; two (4-amino-benzene oxygen) pentanes of 5-; 1, two (3-amino-benzene oxygen) pentanes of 5-; 1, two (4-amino-benzene oxygen) hexanes of 6-; 1; two (3-amino-benzene oxygen) hexanes of 6-; 1; two (4-amino-benzene oxygen) heptane of 7-; 1, two (3-amino-benzene oxygen) heptane of 7-; 1, two (4-amino-benzene oxygen) octanes of 8-; 1; two (3-amino-benzene oxygen) octanes of 8-; 1; two (4-amino-benzene oxygen) nonanes of 9-; 1, two (3-amino-benzene oxygen) nonanes of 9-; 1,10-(4-amino-benzene oxygen) decane; 1; 10-(3-amino-benzene oxygen) decane; 1; 11-(4-amino-benzene oxygen) undecane; 1,11-(3-amino-benzene oxygen) undecane; 1,12-(4-amino-benzene oxygen) dodecane; 1; 12-(3-amino-benzene oxygen) dodecane; two (4-aminocyclohexyl) methane; two (4-amino-3-methylcyclohexyl) methane; 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; 19-diamino nonane; 1, the 10-diamino decane; 1; 11-diamino undecane; 1,12-diamino dodecane etc.
In addition, can exemplify have alkyl on two amine side chains, contain fluoroalkyl, the diamines of aromatic ring, aliphatics ring, heterocycle and the big ring-type replacement body that forms by them.But the diamine compound of the concrete following formula of illustration [DA1]～[DA26] expression.
In formula [DA1]～formula [DA5], R 1Be carbon number alkyl below 22 or contain fluoroalkyl more than 1.
In formula [DA6]～formula [DA9], R 2Expression-COO-,-OCO-,-CONH-,-NHCO-,-CH 2-,-O-,-CO-or-NH-, R 3Expression carbon number alkyl below 22 or contain fluoroalkyl more than 1.
Figure BPA00001186317900171
In formula [DA10] and the formula [DA11], R 4Expression-O-,-OCH 2-,-CH 2O-,-COOCH 2-or-CH 2OCO-, R 5Expression the carbon number alkyl below 22, alkoxyl group more than 1, contain fluoroalkyl or fluoroalkoxy.
Figure BPA00001186317900172
In formula [DA12]～formula [DA14], R 6Expression-COO-,-OCO-,-CONH-,-NHCO-,-COOCH 2-,-CH 2OCO-,-CH 2O-,-OCH 2-or-CH 2-, R 7Expression the carbon number alkyl below 22, alkoxyl group more than 1, contain fluoroalkyl or fluoroalkoxy.
Figure BPA00001186317900173
In formula [DA15] and the formula [DA16], R 8Expression-COO-,-OCO-,-CONH-,-NHCO-,-COOCH 2-,-CH 2OCO-,-CH 2O-,-OCH 2-,-CH 2-,-O-or-NH-, R 9Represent fluorine-based, cyano group, fluoroform alkyl, nitro, azo-group, formyl radical, ethanoyl, acetoxyl group or hydroxyl.
Figure BPA00001186317900181
Figure BPA00001186317900191
In addition, also can exemplify the diamino siloxanes etc. of following formula [DA27] expression.
Figure BPA00001186317900192
In the formula [DA27], m is 1～10 integer.
Other diamine compound can be when forming liquid crystal orientation film liquid crystal aligning, voltage preserving property, accumulate characteristic such as electric charge and use separately to mix more than a kind or 2 kinds and use.
To being not particularly limited with the tetracarboxylic dianhydride that two amine components react for obtaining polyamic acid of the present invention.Its concrete example is following to be exemplified.
Can exemplify 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, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) ether, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) sulfone, two (3,4-dicarboxyl phenyl) methane, 2, two (3, the 4-dicarboxyl phenyl) propane of 2-, 1,1,1,3,3,3-hexafluoro-2,2-two (3,4-dicarboxyl phenyl) propane, two (3,4-dicarboxyl phenyl) dimethylsilane, two (3,4-dicarboxyl phenyl) diphenyl silane, 2,3,4,5-pyridine tetracarboxylic dianhydride, 2,6-two (3,4-dicarboxyl phenyl) pyridine, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 3,4,9, the 10-perylenetetracarboxylic dianhydride, 1,3-phenylbenzene-1,2,3,4-tetramethylene tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride (Japanese: オ キ シ ジ Off タ Le テ ト ラ カ Le ボ Application
Figure BPA00001186317900193
Er No water thing), 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 1,2,3,4-tetramethyl--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-suberane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 3,4-dicarboxyl-1-cyclohexyl succsinic acid dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, two ring [3,3,0] octanes-2,4,6, the 8-tetracarboxylic dianhydride, two ring [4,3,0] nonanes-2,4,7, the 9-tetracarboxylic dianhydride, two rings [4,4,0] decane-2,4,7, the 9-tetracarboxylic dianhydride, two rings [4,4,0] decane-2,4,8, the 10-tetracarboxylic dianhydride, three rings [6.3.0.0＜2,6 〉] undecane-3,5,9, the 11-tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, 4-(2,5-dioxo tetrahydrofuran (THF)-3-yl)-1,2,3,4-naphthane-1, the 2-dicarboxylic acid dianhydride, two rings [2,2,2] suffering-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 5-(2, the 5-dioxotetrahydrofuryl)-3-methyl-3-hexanaphthene-1, the 2-dicarboxylic acid dianhydride, Fourth Ring [6,2,1,1,0,2,7] dodecane-4,5,9, the 10-tetracarboxylic dianhydride, 3,5,6-three carboxyl norbornane-2:3,5:6-dicarboxylic acid dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride etc.
Liquid crystal aligning, the voltage preserving property of tetracarboxylic dianhydride when forming liquid crystal orientation film, accumulate characteristic such as electric charge, can use a kind also can more than 2 kinds and use separately.
When the reaction by tetracarboxylic dianhydride and two amine components obtains polyamic acid of the present invention, can adopt known synthetic method.It generally is the method that in organic solvent, makes tetracarboxylic dianhydride and the reaction of two amine components.Being reflected in the organic solvent of tetracarboxylic dianhydride and diamines than being easier to carry out and do not generate by product, therefore preferably.
The organic solvent that uses in the reaction as tetracarboxylic dianhydride and diamines is as long as the polyamic acid that solubilized generates is not particularly limited.Below exemplify its concrete example.
Can exemplify N, dinethylformamide, N,N-dimethylacetamide, the N-N-methyl-2-2-pyrrolidone N-, the N-methyl caprolactam, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, the hexamethyl sulfoxide, gamma-butyrolactone, Virahol, the methoxymethyl amylalcohol, limonene, ethylamino ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methylcyclohexane, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monobutyl ether, ethyl carbitol, ethylene glycol, ethylene glycol acetate, the glycol monomethyl isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, the propylene glycol monoacetate, propylene glycol monomethyl ether, the glycol tertiary butyl ether, dipropylene glycol monomethyl ether, glycol ether, the diglycol monotertiary acetic ester, diglyme, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol list ether, dipropylene glycol monoacetate list ether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxyl group butylacetic acid ester, the tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, Di Iso Propyl Ether, the ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, tetrahydrotoluene, propyl ether, hexyl ether, two Alkane, normal hexane, Skellysolve A, octane, ether, pimelinketone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetate propylene glycol ester list ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, 3-methoxypropionic acid methyl esters, 3-ethoxy-propionic acid methyl ethyl ester, 3-methoxy propyl acetoacetic ester, the 3-ethoxy-propionic acid, the 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diglyme, 4-hydroxy-4-methyl-2 pentanone etc.These solvents can use separately also can mix use.In addition, even the insoluble solvent of separating polyamic acid, as long as in the scope that the polyamic acid that generates is not separated out, can use with above solvent.
In addition, because the moisture in the organic solvent can suppress polyreaction, and makes the polyamic acid hydrolysis of generation, the organic solvent that therefore preferred use dehydrates as much as possible.
When tetracarboxylic dianhydride and two amine components are reacted in organic solvent, can exemplify two amine components are 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 two amine components in the solution that forms the tetracarboxylic dianhydride; Alternately add the method for tetracarboxylic dianhydride and two amine components etc.Can adopt any method wherein.In addition, tetracarboxylic dianhydride or two amine components are during by multiple compound formation, and the state that can be pre-mixed reacts, also can react successively respectively make again react respectively and lower molecular weight body hybrid reaction and form the high molecular body.
The polymeric reaction temperature of this moment can be selected-20 ℃～150 ℃ arbitrary temp, preferred-5 ℃～100 ℃ scope.In addition, though reaction can carried out under the concentration arbitrarily, if but concentration is low excessively, 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 tetracarboxylic dianhydride and the total concentration of two amine components in reaction soln are 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 polyreaction of polyamic acid, the ratio of tetracarboxylic dianhydride's the total mole number and the total mole number of 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.
Polyimide of the present invention be make described polyamic acid dehydration closed-loop and polyimide, can be used as the polymkeric substance that obtains liquid crystal orientation film.
The dehydration closed-loop rate of the acid amides acidic group of polyimide of the present invention (imidization rate) not necessarily wants 100%, can regulate use arbitrarily according to purposes and purpose.
As the method that makes the polyamic acid imidization, can exemplify the hot-imide of the solution of direct heating polyamic acid, in the solution of polyamic acid, add the catalysis imidization of catalyzer.
Temperature when making the polyamic acid hot-imide in solution is 100 ℃～400 ℃, is preferably 120 ℃～250 ℃, is preferably in and implements reaction when the water that imidization reaction is generated is discharged to outside the reactive system.
The catalysis imidization of polyamic acid can by in the solution of polyamic acid, add behind basic catalyst and the acid anhydrides-20～250 ℃, be preferably to 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 reaction of making and carries out required suitable alkalescence, and is therefore preferred.As acid anhydrides, can exemplify diacetyl oxide, trimellitic acid 1,2-anhydride, pyromellitic dianhydride etc., if wherein use diacetyl oxide, 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.
Reaction soln can be dropped into Weak solvent when the reaction soln of polyamic acid or polyimide reclaims the polyamic acid that generates or polyimide makes it form precipitation.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.Drop into Weak solvent and sedimentary polymkeric substance can carry out Air drying or heat drying after the filtered and recycled under normal pressure or decompression.If the polymkeric substance that precipitation is reclaimed repeats 2～10 times being dissolved in organic solvent once more and precipitating the operation of reclaiming once more, then can reduce the impurity in the polymkeric substance.This moment, used Weak solvent can exemplify for example alcohols, ketone, hydrocarbon etc., if use the Weak solvent more than 3 kinds that is selected from wherein, purification efficiency was further improved, and is therefore preferred.
About the contained polyamic acid of aligning agent for liquid crystal of the present invention and the molecular weight of polyimide, from by the intensity of filming of its acquisition and the angle of the operability when forming of filming, the homogeneity of filming consider, the weight-average molecular weight that records with GPC (gel permeation chromatography) method is preferably 5000～1000000, and more preferably 10000～150000.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention is the coating fluid that is used to form liquid crystal orientation film, be the resinous principle that is used to form resin coating be dissolved in organic solvent and solution.Here, described resinous principle is the resinous principle that comprises at least a kind of polymkeric substance that is selected from described polymkeric substance of the present invention.At this moment, the content of resinous principle is preferably 1 quality %～20 quality %, more preferably 3 quality %～15 quality %, particularly preferably 3～10 quality %.
Among the present invention, described resinous principle can all be to be used for multipolymer of the present invention, also can be mixed with polymkeric substance of the present invention other polymkeric substance in addition.At this moment, the content of other polymkeric substance beyond the polymkeric substance of the present invention in the resinous principle is 0.5 quality %～15 quality %, is preferably 1 quality %～10 quality %.
This other polymkeric substance for example can exemplify as and two amine components of tetracarboxylic dianhydride's composition reaction, use the diamine compound beyond the specific diamine compound and the polyamic acid that obtains or polyimide etc.
Be used for the organic solvent of aligning agent for liquid crystal of the present invention so long as resinous principle dissolved organic solvent is got final product, be not particularly limited.Its concrete example exemplifies as follows.
Can exemplify N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrolidone, N-vinyl pyrrolidone, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolactone, 1,3-dimethyl-2-imidazolidinone, ethylamino ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, pimelinketone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2 pentanone etc.These solvents can use separately also can mix use.
Aligning agent for liquid crystal of the present invention can contain described composition in addition.As its example, comprise thickness homogeneity when making the coating of liquid crystalline aligning agent and surface smoothing raising solvent or compound, make compound that the adaptation of liquid crystal orientation film and substrate improves etc.
Make following the exemplifying of concrete example of the solvent (Weak solvent) of thickness homogeneity and surface smoothing raising.
Can exemplify for example Virahol, the methoxymethyl amylalcohol, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monobutyl ether, ethyl carbitol, the ethyl carbitol acetic ester, ethylene glycol, ethylene glycol acetate, the glycol monomethyl isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, the propylene glycol monoacetate, propylene glycol monomethyl ether, the glycol tertiary butyl ether, dipropylene glycol monomethyl ether, glycol ether, the diglycol monotertiary acetic ester, diglyme, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol list ether, dipropylene glycol monoacetate list ether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxyl group butylacetic acid ester, the tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, Di Iso Propyl Ether, the ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, tetrahydrotoluene, propyl ether, hexyl ether, the 1-hexanol, normal hexane, Skellysolve A, octane, ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, the acetate dihydroxypropane single-ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, 3-methoxypropionic acid methyl esters, 3-ethoxy-propionic acid methyl ethyl ester, 3-methoxy propyl acetoacetic ester, the 3-ethoxy-propionic acid, the 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 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, 2-(2-oxyethyl group propoxy-) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactates etc. have the solvent of low surface tension etc.
These Weak solvents can use a kind also can multiple mixing to use.When using described solvent, its amount is preferably 5～80 quality % of all solvents that aligning agent for liquid crystal comprises, more preferably 20～60 quality %.
As the compound that makes thickness homogeneity and surface smoothing raising, can exemplify fluorine class tensio-active agent, silicone based tensio-active agent, nonionic surface active agent etc.
More specifically can exemplify for example F Top EF301, EF303, EF352 (Tao Kemu (Tokem Products) corporate system), MEGAFAC F171, F173, R-30 (big Japanese ink chemical company system), Frorard FC430, FC431 (Sumitomo 3M corporate system), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd's system) etc.The usage ratio of these tensio-active agents is to be preferably 0.01～2 mass parts with respect to resinous principle 100 mass parts that aligning agent for liquid crystal comprises, more preferably 0.01～1 mass parts.
The concrete example of the compound that improves as the adaptation that makes liquid crystal orientation film and substrate can exemplify the compound that contains functional silanes shown below or contain the compound etc. of epoxy group(ing).
Can exemplify for example 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-phenmethyl-3-TSL 8330, N-phenmethyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, two (oxygen the ethylidene)-3-TSL 8330 of N-, two (oxygen the ethylidene)-3-aminopropyltriethoxywerene werene of N-, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidylether, 1,3,5,6-four glycidyl group-2, the 4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.
With respect to resinous principle 100 mass parts that aligning agent for liquid crystal comprises, the amount of the compound of the used raising and the adaptation of substrate is preferably 0.1～30 mass parts, more preferably 1～20 mass parts.If less than 0.1 mass parts then can not obtain the effect that adaptation improves, if surpass 30 mass parts, the orientation of liquid crystal variation sometimes then.
In the aligning agent for liquid crystal of the present invention except above composition can add in the scope of external harmless effect of the present invention so that electrical characteristic such as the specific inductivity of liquid crystal orientation film and electroconductibility change is the dielectric medium or the conducting material of purpose, film hardness and the density that also can add when forming liquid crystal orientation film with raising are the cross-linked compound of purpose.
＜liquid crystal orientation film liquid crystal display device 〉
Coat aligning agent for liquid crystal of the present invention on the substrate and after burning till, handle, perhaps in vertical orientated purposes etc., can not carry out orientation process and use as liquid crystal orientation film by implementation orientations such as friction treatment or illumination.At this moment, used substrate is not particularly limited so long as the high substrate of transparency gets final product, and can use glass substrate or plastic bases such as vinylformic acid substrate and polycarbonate substrate etc.In addition, from the angle of work simplification, better be to use the substrate that has formed ITO electrode of being used for liquid crystal drive etc.In addition, for reflection type liquid crystal display element, also can only use opaque materials such as silicon wafer at one-sided substrate, electrode at this moment can use catoptrical materials such as aluminium.
Coating process for aligning agent for liquid crystal is not particularly limited, and generally adopts screen painting, offset printing, flexible printing, ink jet method etc. at industrial circle.As other coating process, can exemplify dip coating, rolling method, slit printing, rotary printing etc., can be used according to various objectives.
With aligning agent for liquid crystal coat behind the substrate burn till can by heater meanses such as hot plate 50～300 ℃, be preferably and under 80～250 ℃ the temperature solvent evaporation formed to film.If filming of burning till that the back forms is blocked up, is being disadvantageous aspect the power consumption of liquid crystal display device then, if thin excessively, then the reliability of liquid crystal display device can descend, so coating thickness better is 5～300nm, is more preferably 10～100nm.When making liquid crystal horizontal alignment or tilted alignment, filming after burning till handled by friction or polarized ultraviolet irradiation etc.
Liquid crystal display device of the present invention is after being obtained having the substrate of liquid crystal orientation film by aligning agent for liquid crystal of the present invention by aforesaid method, to make the liquid crystal structure cell with known method, thereby obtain liquid crystal display device.
If will exemplify the example that the liquid crystal structure cell is made, but illustration prepares to be formed with 1 pair of substrate of liquid crystal orientation film, scatters spacer on the liquid crystal orientation film of 1 substrate, with the liquid crystal aligning face as the inboard, with other 1 baseplate-laminating, the method that seals behind the liquid crystal is injected in decompression; Perhaps after liquid crystal is dripped on the liquid crystal orientation film surface that is scattered with spacer with the method etc. of baseplate-laminating and sealing.The thickness of the spacer of this moment better is 1～30 μ m, is more preferably 2～10 μ m.
As mentioned above, adopt the reliability height of the liquid crystal display device that aligning agent for liquid crystal of the present invention makes, can be used for big picture and high-resolution LCD TV etc.
Embodiment
Below exemplify embodiment and comparative example, the present invention will be described in more detail, but these embodiment carry out determinate explanation to the present invention.
[synthesizing of diamine compound]
＜embodiment 1 〉
Synthesizing of diamine compound (4)
Figure BPA00001186317900261
With compound (2) (29.92g, 277mmol) and triethylamine (28.03g, tetrahydrofuran (THF) 277mmol) (300g) solution is cooled to below 10 ℃, drips compound (1) (60.76g, tetrahydrofuran (THF) 263mmol) (150g) solution under the condition of noting heat release.After dropping finishes temperature of reaction being risen to 23 ℃ reacts again.With HPLC (high performance liquid chromatograph) confirm reaction finish after with in the reaction solution impouring distilled water (2L), filter the solid and the washing back of separating out and disperse washing with ethanol (450g), obtain compound (3) (output: 72.91g, yield: 92%).
1H-NMR (400MHz, DMSO-d 6, δ ppm): 9.79 (1H, t), 9.10-9.09 (2H, m), 9.00-8.96 (1H, m), 8.61 (1H widens), 8.50-8.48 (1H, m), 7.79-7.76 (1H, m), 7.40-7.36 (1H, m), 4.57 (2H, s).
Then, in the presence of hydrogen in 60 ℃ of agitate compounds (3) (72.00g, 238mmol), 5% palladium on carbon (water type, 7.2g, 10wt%) and 1,4-two
Figure BPA00001186317900271
The mixture of alkane (720g).Reaction finishes the back with desolventizing the acquisition crude product with the vaporizer steaming behind the diatomite filtration catalyzer.Crude product with ethanol (360g) dispersion washing gained obtains diamine compound (4) (output: 43.62g, yield: 76%).
1H-NMR(400MHz，DMSO-d 6，δppm)：8.64(1H，t)，8.50(1H，d)，8.44(1H，d)，7.67(1H，d)，7.34(1H，q)，6.23(2H，d)，5.94(1H，s)，4.87(4H，s)，4.39(2H，d).
＜embodiment 2 〉
Synthesizing of diamine compound (7)
Figure BPA00001186317900272
With compound (5) (40.00g, 328mmol) and triethylamine (33.18g, tetrahydrofuran (THF) 328mmol) (400g) solution is cooled to below 10 ℃, drips compound (1) (72.00g, tetrahydrofuran (THF) 312mmol) (176g) solution under the condition of noting heat release.After dropping finishes temperature of reaction being risen to 23 ℃ reacts again.With HPLC confirm reaction finish after with in the reaction solution impouring distilled water (3.5L), filter the solid and the washing back of separating out and disperse washing with methyl alcohol (200g), obtain compound (6) (output: 81.4g, yield: 82%).
1H-NMR(400MHz，DMSO-d 6，δppm)：8.83-8.34(5H，m)，7.83-7.66(1H，m)，7.39-7.33(1H，m)，4.69-4.49(2H，m)，2.91-2.85(3H，m).
Then, in the presence of hydrogen in 23 ℃ of agitate compounds (6) (80.00g, 253mmol), the hydroxide palladium on carbon (water type, 8.0g, 10wt%) and 1,4-two
Figure BPA00001186317900281
The mixture of alkane (1200g).Reaction finishes the back with desolventizing the acquisition crude product with the vaporizer steaming behind the diatomite filtration catalyzer.Make gained crude product homogeneous be dissolved in tetrahydrofuran (THF) (150g), solution is splashed in the hexane (660g), solid is separated out in-20 ℃.Then, filter, use cold hexane wash, obtain diamine compound (7) (output: 74.98g, yield: 98%).
1H-NMR (400MHz, DMSO-d 6, δ ppm): 8.46-8.34 (2H, m), 7.63-7.54 (1H widens), 7.36-7.33 (1H, m), 5.86-5.76 (3H, m), 4.86 (4H, s), 4.57-4.53 (2H widens), 2.80 (3H widens).
＜embodiment 3 〉
Synthesizing of diamine compound (10)
Figure BPA00001186317900282
With compound (8) (16.69g, 137mmol) and triethylamine (13.82g, tetrahydrofuran (THF) 137mmol) (200g) solution is cooled to below 10 ℃, drips compound (1) (30.00g, tetrahydrofuran (THF) 130mmol) (150g) solution under the condition of noting heat release.After dropping finishes temperature of reaction being risen to 23 ℃ reacts again.With HPLC confirm reaction finish after with in the reaction solution impouring distilled water (2.8L), filter the solid and the washing back of separating out and disperse washing with ethanol (200g), obtain compound (9) (output: 34.53g, yield: 84%).
1H-NMR(400MHz，DMSO-d 6，δppm)：9.30(1H，t)，9.01-9.00(2H，m)，8.95-8.93(1H，m)，8.47(1H，d)，8.42(1H，dd)，7.69(2H，d)，7.32(1H，q)，3.64-3.58(2H，m)，2.92(2H，t).
Then, in the presence of hydrogen in 60 ℃ of agitate compounds (9) (32.00g, 101mmol), 5% palladium on carbon (water type, 3.2g, 10wt%) and 1,4-two
Figure BPA00001186317900283
The mixture of alkane (320g).Reaction finishes the back with desolventizing the acquisition crude product with the vaporizer steaming behind the diatomite filtration catalyzer.Disperse washing gained crude product with tetrahydrofuran (THF) (150g), obtain diamine compound (10) (output: 19.21g, yield: 74%).
1H-NMR(400MHz，DMSO-d 6，δppm)：8.43-8.39(2H，m)，8.09(1H，t)，7.63(1H，d)，7.30(1H，dd)，6.16(2H，d)，5.92(1H，d)，4.84(4H，s)，3.44-3.28(3H，m)，2.82(3H，t).
＜embodiment 4 〉
Synthesizing of diamine compound (14)
Figure BPA00001186317900291
Compound (12) (35.00g, 321mmol) and triethylamine (97.39g drips compound (11) (29.84g, tetrahydrofuran (THF) 160mmol) (60g) solution in tetrahydrofuran (THF) 962mmol) (240g) solution.Drip and finish back HPLC following response, confirm that reaction finishes the back and adds methylene dichloride (1L), use distilled water (600mL) washing 3 times again.Organic layer anhydrous magnesium sulfate drying after-filtration, steaming desolventizes, and obtains the crude product of compound (13).With ethyl acetate (500g)/hexane (1L) the gained crude product is carried out recrystallization, obtain compound (13) (output: 38.74g, yield: 88%).
1H-NMR(400MHz，CDCl 3，δppm)：8.79(1H，d)，8.71(1H，d)，8.66(1H，dd)，8.46(1H，dd)，7.88-7.85(1H，m)，7.40(1H，q)，7.30(1H，d)，5.38(2H，s).
Then, in the presence of hydrogen in 40 ℃ of agitate compounds (13) (20.00g, 72.7mmol), platinum oxide (IV) (water type, 2.0g, 10wt%) and the mixture of ethyl acetate/ethanol (200g, 100/50 (v/v%)).Reaction finishes the back with steaming the crude product that desolventizes acquisition compound (14) with vaporizer behind the diatomite filtration catalyzer.With the refining gained crude product of silica gel column chromatography (eluting solvent is hexane/ethyl acetate (100/50v/v%)), obtain diamine compound (14) (output: 15.27g, yield: 98%).
1H-NMR(400MHz，CDCl 3，δppm)：8.66(1H，d)，8.57(1H，dd)，7.77-7.73(1H，m)，7.33-7.29(1H，m)，6.67(1H，d)，5.00(2H，s)，3.37(4H，s).
＜embodiment 5 〉
Synthesizing of diamine compound (16)
Figure BPA00001186317900301
Under 23 ℃, compound (2) (29.98g, 277mmol), sodium bicarbonate (29.12g, 347mmol) and the mixed solution and dripping compound (11) of distilled water (630g) (43.00g, ethanol 231mmol) (830g) solution.Drip the end back and confirm to add methylene dichloride (2L) after reaction finishes, remove water layer with HPLC.Then, organic layer steams after with anhydrous magnesium sulfate drying and desolventizes with saturated aqueous common salt (500mL) washing 3 times, organic layer.With ethyl acetate (500g)/hexane (1L) the gained crude product is carried out recrystallization, obtain compound (15) (output: 55.28g, yield: 87%).
1H-NMR (400MHz, CDCl 3, δ ppm): 9.18 (1H, d), 9.17 (1H widens), 8.66-8.62 (2H, m), 8.29-8.25 (1H, m), 7.69-7.66 (1H, m), 7.37-7.33 (1H, m), 6.90 (1H, d), 4.68 (2H, m).
Then, in the presence of hydrogen in 23 ℃ of agitate compounds (15) (3.0g, 10.9mmol), platinum oxide (IV) (water type, 0.3g, 10wt%) and 1,4-two
Figure BPA00001186317900302
The mixture of alkane (30g).Reaction finishes the back with desolventizing acquisition diamine compound (16) (output: 2.30g, yield: 98%) with the vaporizer steaming behind the diatomite filtration catalyzer.
1H-NMR (400MHz, CDCl 3, δ ppm): 8.63 (1H, d), 8.52 (1H, dd), 7.71-7.66 (1H, m), 7.28-7.24 (1H, m), 6.53 (1H, d), 6.18-6.11 (2H, m), 4.22 (2H, s), 3.70 (1H, s), 3.56-3.34 (4H widens).
＜embodiment 6 〉
Synthesizing of diamine compound (19)
Figure BPA00001186317900311
Under 40 ℃, at compound (17) (50.00g, 170mmol), salt of wormwood (47.01g, 340mmol), cuprous iodide (6.48g, 34.0mmol), sarcosine (6.06g, 68.0mmol) and (1L) mixed solution and dripping compound (2) of DMSO (methyl-sulphoxide) (36.78g, 340mmol).Drip the end back and confirm to add ethyl acetate (4L)/distilled water (5L) after reaction finishes, by removing by filter insolubles with HPLC.Then, extract 2 times handle the water layer of removing by separatory, merge organic layer, use anhydrous magnesium sulfate drying with ethyl acetate (500g).With vaporizer steam desolventize obtain crude product after, carry out recrystallization with ethyl acetate (700mL)/hexane (2L), acquisition compound (18) (output: 23.04g, yield: 49%).
1H-NMR (400MHz, CDCl 3, δ ppm): 8.63 (1H widens), 8.50-8.49 (1H widens), 7.95 (1H, t), 7.80-7.76 (3H, m), 7.67 (1H, t), 7.39 (1H, q), 4.52 (2H, d).
Then, in the presence of hydrogen in 23 ℃ of agitate compounds (18) (1.0g, 3.65mmol), platinum oxide (IV) (water type, 0.1g, 10wt%) and the mixture of methyl alcohol (10g).Reaction finishes the back with desolventizing acquisition diamine compound (19) (output: 0.97g, yield: 97%) with the vaporizer steaming behind the diatomite filtration catalyzer.
1H-NMR(400MHz，DMSO-d 6，δppm)：8.52(1H，d)，8.41(1H，dd)，7.69(1H，d)，7.32(1H，q)，5.60(1H，t)，5.17(2H，s)，4.37-4.14(4H，m).
＜embodiment 7 〉
Synthesizing of diamine compound (23)
Figure BPA00001186317900321
Under the nitrogen atmosphere, with compound (21) (51.43g, tetrahydrofuran (THF) 281mmol) (300g) solution remains on below 10 ℃, under the condition of noting heat release, drip compound (20) (50.00g, 281mmol), triethylamine (170.5g, 1.69mol) and DMAP (4-dimethylaminopyridine) (6.87g, tetrahydrofuran (THF) 56.2mmol) (500g) solution.After dropping finishes temperature of reaction is risen to 23 ℃ of stirrings and carry out reflux again after 1 hour.With HPLC confirm reaction finish after with in the reaction solution impouring distilled water (6.4L), filter, washing obtains crude product.With tetrahydrofuran (THF) (243g)/hexane (1458g) the gained crude product is carried out recrystallization, obtain compound (22) (output: 72.58g, yield: 89%).
1H-NMR(400MHz，DMSO-d 6，δppm)：11.25(1H，s)，9.18(1H，d)，9.09(2H，dd)，8.82(1H，dd)，8.57(1H，t)，8.38-8.35(1H，m)，7.64(1H，q).
Then, in the presence of hydrogen in 90 ℃ of agitate compounds (22) (20.00g, 69.4mmol), 5% palladium on carbon (water type, 2.0g, 10wt%) and 1,4-two The mixture of alkane (400g).Reaction finishes the back with desolventizing the acquisition crude product with the vaporizer steaming behind the diatomite filtration catalyzer.Crude product with ethanol (75g) dispersion washing gained obtains diamine compound (23) (output: 10.14g, yield: 64%).
1H-NMR(400MHz，DMSO-d 6，δppm)：9.87(1H，s)，9.03-9.01(1H，m)，8.72-8.70(1H，m)，8.23-8.19(1H，m)，7.54-7.50(1H，m)，6.27-6.26(2H，m)，5.63-5.61(1H，m)，4.75-4.73(2H，m).
＜embodiment 8 〉
Synthesizing of diamine compound (26)
Figure BPA00001186317900331
Under the nitrogen atmosphere, with compound (21) (20.00g, tetrahydrofuran (THF) 112mmol) (120g) solution is cooled to below 10 ℃, under the condition of noting heat release, drip compound (24) (20.57g, 112mmol), triethylamine (68.18g, 674mmol) and DMAP (2.74g, tetrahydrofuran (THF) 22.5mmol) (200g) solution.After dropping finishes temperature of reaction is risen to 23 ℃ of stirrings and carried out reflux again 17 hours after 1 hour.With HPLC confirm reaction finish after with in the reaction solution impouring distilled water (2.6L), filter, washing obtains crude product.(40g) disperses to wash after-filtration to the gained crude product with ethanol, and drying obtains compound (25) (output: 16.45g, yield: 51%).
1H-NMR(400MHz，DMSO-d 6，δppm)：11.4(1H，s)，9.15-9.14(1H，m)，8.86(1H，d)，8.77(1H，d)，8.64-8.60(1H，m)，8.33(1H，d)，8.06(1H，d)，7.66(1H，q)，2.92(2H，t).
Then, in the presence of hydrogen in 60 ℃ of agitate compounds (25) (15.00g, 52.0mmol), 5% palladium on carbon (water type, 1.5g, 10wt%) and 1,4-two
Figure BPA00001186317900332
The mixture of alkane (150g).Reaction finishes the back with steaming the crude product that desolventizes acquisition compound (26) with vaporizer behind the diatomite filtration catalyzer.With silica gel column chromatography (eluting solvent is hexane/ethyl acetate (100/50v/v%)) the gained crude product is made with extra care, make with extra care by the recrystallization of tetrahydrofuran (THF) (400g)/hexane (600g) again, obtain diamine compound (26) (output: 6.11g, yield: 51%).
1H-NMR(400MHz，DMSO-d 6，δppm)：9.54(1H，s)，9.10(1H，d)，8.72(1H，dd)，8.30-8.27(1H，m)，7.90(1H，s)，7.52(1H，q)，6.75(1H，d)，6.61(1H，d)，5.99(1H，m)，4.65-4.59(4H，m).
＜embodiment 9 〉
Synthesizing of diamine compound (29)
Figure BPA00001186317900341
Under the nitrogen atmosphere, compound (27) (10.00g, 49.0mmol) and triethylamine (59.50g, slowly splash in tetrahydrofuran (THF) 588mmol) (100g) solution compound (12) (21.39g, 196mmol).Reaction adds reaction solution in the distilled water (1L) after finishing, and filters washing, the crude product of acquisition compound (28).With acetonitrile (200g)/ethyl acetate (300g) the gained crude product is carried out recrystallization, obtain compound (28) (output: 11.35g, yield: 61%).
1H-NMR(400MHz，DMSO-d 6，δppm)：8.74-8.73(3H，m)，8.61(2H，dd)，7.93(2H，d)，7.50(2H，q)，7.44(1H，s)，5.56(4H，s).
Then, in the presence of hydrogen in 60 ℃ of agitate compounds (28) (8.00g, 20.1mmol), platinum oxide (IV) (water type, 0.8g, 10wt%) and 1,4-two
Figure BPA00001186317900342
The mixture of alkane (80g).Reaction finishes the back with desolventizing the acquisition crude product with the vaporizer steaming behind the diatomite filtration catalyzer.The gained crude product carries out recrystallization with tetrahydrofuran (THF) (200g)/hexane (600g), obtains diamine compound (29) (output: 4.66g, yield: 72%).
1H-NMR(400MHz，DMSO-d 6，δppm)：8.65(2H，d)，8.52(2H，dd)，7.88-7.85(2H，m)，7.40(2H，q)，6.68(1H，s)，6.07(1H，s)，4.96(4H，s)，4.25(4H，s).
＜embodiment 10 〉
Synthesizing of diamine compound (34)
Figure BPA00001186317900351
Under the nitrogen atmosphere, with compound (31) (81.60g, 74.1mmol), (18.29g 24.7mmol) and after the mixture heating up to 50 of DMSO (375g) ℃, drips compound (30) (50.00g, DMSO 24.7mmol) (125g) solution to calcium hydroxide.Drip and finish after finish with HPLC affirmation reaction the back reaction solution to be injected 5 quality % hydrochloric acid frozen water (4L), cross filter solid, washing, the wet product of acquisition compound (32).Then, carry out recrystallization, obtain compound (32) (output: 49.0g, yield: 72%) with 2-propyl alcohol (205g)/hexane (335g).
1H-NMR(400MHz，DMSO-d 6，δppm)：9.73(1H，s)，8.86(1H，d)，8.42(1H，dd)，7.11-7.05(3H，m)，6.90-6.87(2H，m).
Then, under nitrogen atmosphere, with compound (21) (19.34g, tetrahydrofuran (THF) 109mmol) (180g) solution is cooled to below 10 ℃, under the condition of noting heat release, drip compound (31) (30.0g, 109mmol), triethylamine (33.0g, 324mmol) and DMAP (2.65g, DMSO 21.7mmol) (300g) solution.After dropping finishes temperature of reaction is risen to 23 ℃ of stirrings and carried out reflux again 19 hours after 1 hour.With HPLC confirm reaction finish after with in the reaction solution impouring distilled water (3.9L), filter, washing, methanol wash obtains crude product.Make the gained crude product be dissolved in chloroform after-filtration insolubles.Then, concentrated filtrate is made with extra care with silica gel column chromatography (eluting solvent is 1,2-ethylene dichloride/ethyl acetate (100/40v/v%)), obtains compound (33) (output: 35.8g, yield: 86%).
1H-NMR(400MHz，DMSO-d 6，δppm)：9.29(1H，dd)，8.92-8.91(2H，m)，8.52-8.48(2H，m)，7.69-7.66(1H，m)，7.53-7.51(2H，m)，7.44-7.40(2H，m)，7.24(1H，d).
Then, under nitrogen atmosphere, with compound (33) (30.00g, 78.7mmol) and iron powder (26.36g drips ammonium chloride (12.63g, 10 quality % aqueous solution 236mmol) after toluene 472mmol) (170g) solution is heated to 70 ℃.Reaction finishes back solid diatomite filtration.Then, remove from filtrate that organic layer concentrates with vaporizer behind the water layer, obtain crude product.Then, the gained crude product is dissolved in ethyl acetate (1L), organic layer anhydrous magnesium sulfate drying after usefulness distilled water (500mL) washs 3 times, steaming desolventizes.The crude product of gained compound (34) obtains diamine compound (34) (output: 15.4g, yield: 61%) with methyl alcohol (100g)/2-propyl alcohol (100g) recrystallization.
1H-NMR(400MHz，DMSO-d 6，δppm)：9.20(1H，dd)，8.85(1H，dd)，8.43-8.40(1H，m)，7.62-7.59(1H，m)，7.19-7.16(2H，m)，6.88-6.84(2H，m)，6.53(1H，d)，6.02(1H，d)，5.81(1H，dd)，4.69(2H，s)，4.57(2H，s).
＜embodiment 11 〉
Synthesizing of diamine compound (37)
Figure BPA00001186317900361
Under the nitrogen atmosphere, cool off compound (32) (17.00g with ice bath, 61.6mmol), compound (35) (6.57mL, 67.7mmol) and triphenyl phosphine (20.99g, 80.0mmol) tetrahydrofuran (THF) (340g) solution, slowly drip DEAD (diethyl azodiformate) (40 quality % toluene solutions, 34.84mL, 80.0mmol) solution.React after after drip finishing temperature of reaction slowly being risen to 23 ℃.Confirm that with HPLC reaction finishes the back and desolventizes the acquisition crude product with the vaporizer steaming.Then, carry out recrystallization 2 times, obtain compound (36) (output: 17.77g, yield: 79%) with 2-propyl alcohol (450g).
1H-NMR (400MHz, CDCl 3, δ ppm): 8.84 (1H, d), 8.71 (1H widens), 8.63 (1H, dd), 8.30 (1H, dd), 7.80 (1H, d), 7.36 (1H, q), 7.12-7.08 (4H, m), 7.01 (1H, d), 5.04 (2H, s).
Then, under nitrogen atmosphere, in the presence of hydrogen in 23 ℃ of agitate compounds (36) (15.00g, 40.8mmol), platinum oxide (IV) (water type, 1.5g, 10wt%) and 1,4-two
Figure BPA00001186317900371
The mixture of alkane (230g).Reaction finishes the back with desolventizing the acquisition crude product with the vaporizer steaming behind the diatomite filtration catalyzer.The gained crude product obtains diamine compound (37) (output: 9.66g, yield: 77%) with 2-propyl alcohol (60g) recrystallization.
1H-NMR (400MHz, CDCl 3, δ ppm): 8.66 (1H, d), 8.57 (1H, dd), 7.77 (1H, m), 7.34 (1H, q), 6.87 (4H, s), 6.69 (1H, d), 6.16 (1H, d), 6.07 (1H, dd), 5.02 (2H, s), 3.65-3.48 (4H widens).
＜synthesis example 1 〉
Synthesizing of diamine compound (40)
Figure BPA00001186317900372
With compound (38) (23.45g, 190mmol) and triethylamine (19.23g, tetrahydrofuran (THF) 277mmol) (230g) solution is cooled to below 10 ℃, drips compound (1) (41.68g, tetrahydrofuran (THF) 180mmol) (110g) solution under the condition of noting heat release.After dropping finishes temperature of reaction being risen to 23 ℃ reacts again.With HPLC (high performance liquid chromatography) confirm reaction finish after with in the reaction solution impouring distilled water (1.5L), filter the solid of separating out, washing.Then, solid is disperseed washing, obtain compound (39) (output: 50.82g, yield: 89%) with ethanol (380g).
1H-NMR (400MHz, DMSO-d 6, δ ppm): 9.76 (1H, t), 9.09-9.02 (2H, m), 8.99-8.93 (1H, m), 8.50 (1H widens), 7.64-7.60 (1H, m), 7.36-7.32 (1H, m), 7.20-7.14 (1H, m), 4.57 (2H, s), 3.35 (2H, s).
Then, in the presence of hydrogen in 60 ℃ of agitate compounds (39) (48.00g, 151mmol), 5% palladium on carbon (water type, 4.8g, 10wt%) and 1,4-two
Figure BPA00001186317900373
The mixture of alkane (490g).Reaction finishes the back with desolventizing the acquisition crude product with the vaporizer steaming behind the diatomite filtration catalyzer.The gained crude product disperses washing with ethanol (300g), obtains diamine compound (40) (output: 27.20g, yield: 70%).
1H-NMR(400MHz，DMSO-d 6，δppm)：8.64(1H，t)，8.50(1H，d)，8.44(1H，d)，7.67(1H，d)，7.34(1H，q)，6.23(2H，d)，5.94(1H，s)，4.87(4H，s)，4.39(2H，d).
＜synthesis example 2 〉
Synthesizing of diamine compound (43)
Figure BPA00001186317900381
With compound (41) (15.22g, 142mmol) and triethylamine (15.09g, tetrahydrofuran (THF) 149mmol) (150g) solution is cooled to below 10 ℃, drips compound (1) (31.1g, tetrahydrofuran (THF) 135mmol) (50g) solution under the condition of noting heat release.After dropping finishes temperature of reaction being risen to 23 ℃ reacts again.With HPLC confirm reaction finish after with in the reaction solution impouring distilled water (1L), filter the solid of separating out, washing.Then, solid is disperseed washing, obtain compound (42) (output: 36.92g, yield: 90%) with ethanol (300g).
1H-NMR (400MHz, DMSO-d 6, δ ppm): 9.75 (1H widens), 9.10 (2H, s), 8.97-8.92 (1H, m), 7.40-7.22 (5H, m), 4.59-4.52 (2H, m).
Then, in the presence of hydrogen in 60 ℃ of agitate compounds (42) (36.00g, 119mmol), 5% palladium on carbon (water type, 3.6g, 10wt%) and 1,4-two The mixture of alkane (300g).Reaction finishes the back with desolventizing the acquisition crude product with the vaporizer steaming behind the diatomite filtration catalyzer.The gained crude product obtains diamine compound (43) (output: 21.5g, yield: 72%) with methyl alcohol (200g) recrystallization.
1H-NMR (400MHz, DMSO-d 6, δ ppm): 8.55 (1H widens), 7.34-7.17 (5H, m), 6.28 (2H, s), 6.98-6.94 (1H, m), 4.85-4.74 (4H widens), 4.42-4.35 (2H, m).
[table 4]
Diamine compound X 1 X 2 X 3 X 4 n
Embodiment 1 4 -CONH- Methylene radical Singly-bound Pyridine ring 1
Embodiment 2 7 -CON(CH 3)- Methylene radical Singly-bound Pyridine ring 1
Embodiment 3 10 -CONH- Ethylidene Singly-bound Pyridine ring 1
Embodiment 4 14 -O- Methylene radical Singly-bound Pyridine ring 1
Embodiment 5 16 -NH- Methylene radical Singly-bound Pyridine ring 1
Embodiment 6 19 -NH- Methylene radical Singly-bound Pyridine ring 1
Embodiment 7 23 -NHCO- Singly-bound Singly-bound Pyridine ring 1
Embodiment 8 26 -NHCO- Singly-bound Singly-bound Pyridine ring 1
Embodiment 9 29 -O- Methylene radical Singly-bound Pyridine ring 2
Embodiment 10 34 -O- Phenyl -OCO- Pyridine ring 1
Embodiment 11 37 -O- Phenyl -OCH 2- Pyridine ring 1
Synthesis example 1 40 -COO- Ethylidene Singly-bound Pyridine ring 1
Synthesis example 2 43 -CONH- Methylene radical Singly-bound Phenyl ring 1
[synthesizing of polyamic acid and polyimide]
Shown below is the breviary symbol of the compounds such as tetracarboxylic dianhydride of use.
(tetracarboxylic dianhydride)
CBDA:1,2,3,4-tetramethylene tetracarboxylic dianhydride
BODA: dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
Figure BPA00001186317900391
(diamines)
P-PDA: Ursol D
AP18:1,3-diamino (the positive stearoyl of 4-) benzene
PCH7DAB:1,3-diamino-4-[4-(anti--4-n-heptyl cyclohexyl) phenoxy group] benzene
(organic solvent)
The NMP:N-N-methyl-2-2-pyrrolidone N-
BCS: ethylene glycol butyl ether
The molecular weight determination of＜polyimide 〉
The molecular weight of the polyimide in the synthesis example adopts Showa Denko K. K's system normal temperature gel permeation chromatography (GPC) device (GPC-101), the following mensuration of Japanese nitre moral (Shodex) corporate system post (KD-803, KD-805).
Column temperature: 50 ℃
Elutriant: N, and N '-dimethyl formamide (as additive, lithiumbromide monohydrate (LiBrH 2O) 30mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) 30mmol/L, tetrahydrofuran (THF) (THF) 10ml/L)
Flow velocity: 1.0mL/ minute
Working curve is made and is used standard test specimen: TOSOH Co., Ltd's system TSK standard polyethylene oxide (molecular weight 900000,150000,100000,30000) and polymkeric substance laboratory (Polymer Laboratory) corporate system polyoxyethylene glycol (molecular weight about 12000,4000,1000).
The mensuration of＜imidization rate 〉
The following mensuration of imidization rate of the polyimide in the synthesis example.
With the 20mg polyimide powder NMR test tube (wasteland's science Co., Ltd. system NMR stopple coupon standard φ 5) of packing into, add deuterate methyl-sulphoxide (DMSO-d 6, the 0.05%TMS melange) and 0.53ml, utilize ultrasonic wave that it is dissolved fully.Measure the proton N MR of the 500MHz of this solution with NEC data (デ one タ system) Co., Ltd. system NMR tester (JNW-ECA500).The imidization rate is that the benchmark proton is determined with the proton from unconverted structure before and after the imidization, tries to achieve by following formula with the peak integrated value of this proton and near occur 9.5～10.0ppm 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 a benchmark proton peak integrated value, and α is the number ratio with respect to the benchmark proton of NH matrix of 1 amido acid of polyamic acid (the imidization rate is 0%).
＜embodiment 12 〉
In NMP (15.0g), mix BODA (3.33g, 13.3mmol), p-PDA (0.67g, 6.21mmol), PCH7DAB (3.38g, 8.87mmol) and diamine compound (4) (0.64g, 2.66mmol), in 80 ℃ the reaction 5 hours after, add CBDA (0.87g, 4.44mmol) and NMP (13.1g), in 40 ℃ of reactions 6 hours, obtaining resinous principle content was the polyamic acid solution (A) of 24 quality %.The number-average molecular weight of this polyamic acid is 17900, and weight-average molecular weight is 51800.
＜embodiment 13 〉
Add NMP at polyamic acid solution (A) that embodiment 12 obtains in (20.0g), dilution is diacetyl oxide (2.63g) and the pyridine (2.03g) that adds behind the 6 quality % as imidization catalyst, reacts 2 hours in 80 ℃.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 (B) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 40%, and number-average molecular weight is 16400, and weight-average molecular weight is 44800.
＜embodiment 14 〉
In NMP (8.10g), mix BODA (2.33g, 9.33mmol), p-PDA (0.94g, 8.71mmol), AP18 (0.47g, 1.24mmol) and diamine compound (7) (0.64g, 2.63mmol), in 80 ℃ the reaction 5 hours after, add CBDA (0.61g, 3.11mmol) and NMP (6.51g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
Add NMP in the polyamic acid solution (10.0g) of gained, dilution was diacetyl oxide (1.33g) and the pyridine (1.04g) that adds behind the 6 quality % as imidization catalyst, in 80 ℃ of reactions 2 hours.This reaction soln is dropped in the methyl alcohol (120ml), 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 41%, and number-average molecular weight is 17500, and weight-average molecular weight is 46400.
＜embodiment 15 〉
In NMP (14.7g), mix BODA (3.25g, 13.0mmol), p-PDA (0.66g, 6.07mmol), PCH7DAB (3.30g, 8.67mmol) and diamine compound (10) (0.67g, 2.60mmol), in 80 ℃ the reaction 5 hours after, add CBDA (0.85g, 4.33mmol) and NMP (12.0g), in 40 ℃ of reactions 6 hours, obtaining resinous principle content was the polyamic acid solution (D) of 25 quality %.The number-average molecular weight of this polyamic acid is 18800, and weight-average molecular weight is 51800.
＜embodiment 16 〉
Add NMP at polyamic acid solution (D) that embodiment 15 obtains in (20.0g), dilution is diacetyl oxide (2.61g) and the pyridine (2.07g) that adds behind the 6 quality % as imidization catalyst, reacts 2 hours in 80 ℃.This reaction soln is dropped in the methyl alcohol (220ml), 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 42%, and number-average molecular weight is 17400, and weight-average molecular weight is 45800.
＜embodiment 17 〉
In NMP (8.10g), mix BODA (2.22g, 8.87mmol), p-PDA (0.58g, 5.32mmol), PCH7DAB (1.35g, 3.55mmol) and diamine compound (14) (0.64g, 2.96mmol), in 80 ℃ the reaction 5 hours after, add CBDA (0.58g, 2.96mmol) and NMP (6.30g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
Add NMP in gained polyamic acid solution (10.1g), dilution was diacetyl oxide (1.34g) and the pyridine (1.04g) that adds behind the 6 quality % as imidization catalyst, in 80 ℃ of reactions 2 hours.This reaction soln is dropped in the methyl alcohol (140ml), 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 41%, and number-average molecular weight is 18100, and weight-average molecular weight is 47300.
＜embodiment 18 〉
In NMP (10.0g), mix BODA (2.18g, 8.72mmol), p-PDA (0.69g, 6.392mmol), AP18 (0.66g, 1.74mmol) and diamine compound (16) (0.75g, 3.49mmol), in 80 ℃ the reaction 5 hours after, add CBDA (0.57g, 2.91mmol) and NMP (8.30g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
Add NMP in gained polyamic acid solution (10.1g), dilution was diacetyl oxide (1.35g) and the pyridine (1.07g) that adds behind the 6 quality % as imidization catalyst, in 80 ℃ of reactions 2 hours.This reaction soln is dropped in the methyl alcohol (140ml), 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 40%, and number-average molecular weight is 17500, and weight-average molecular weight is 46000.
＜embodiment 19 〉
In NMP (10.5g), mix BODA (2.30g, 9.18mmol), p-PDA (0.46g, 4.28mmol), PCH7DAB (2.33g, 6.12mmol) and diamine compound (19) (0.39g, 1.84mmol), in 80 ℃ the reaction 5 hours after, add CBDA (0.57g, 2.91mmol) and NMP (8.00g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
Add NMP in gained polyamic acid solution (10.0g), dilution was diacetyl oxide (1.31g) and the pyridine (1.04g) that adds behind the 6 quality % as imidization catalyst, in 80 ℃ of reactions 2 hours.This reaction soln is dropped in the methyl alcohol (140ml), 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 18900, and weight-average molecular weight is 49100.
＜embodiment 20 〉
In NMP (10.50g), mix BODA (2.33g, 9.33mmol), p-PDA (0.47g, 4.35mmol), PCH7DAB (2.37g, 6.22mmol) and diamine compound (23) (0.43g, 1.87mmol), in 80 ℃ the reaction 5 hours after, add CBDA (0.61g, 3.11mmol) and NMP (8.10g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
Add NMP in gained polyamic acid solution (10.2g), dilution was diacetyl oxide (1.37g) and the pyridine (1.04g) that adds behind the 6 quality % as imidization catalyst, in 80 ℃ of reactions 2 hours.This reaction soln is dropped in the methyl alcohol (150ml), 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 42%, and number-average molecular weight is 19900, and weight-average molecular weight is 52100.
＜embodiment 21 〉
In NMP (8.10g), mix BODA (2.26g, 9.03mmol), p-PDA (0.72g, 6.62mmol), AP18 (0.45g, 1.20mmol) and diamine compound (26) (0.96g, 4.21mmol), in 80 ℃ the reaction 5 hours after, add CBDA (0.59g, 3.01mmol) and NMP (6.10g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
Add NMP in gained polyamic acid solution (10.0g), dilution was diacetyl oxide (1.34g) and the pyridine (1.04g) that adds behind the 6 quality % as imidization catalyst, in 80 ℃ of reactions 2 hours.This reaction soln is dropped in the methyl alcohol (150ml), 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 40%, and number-average molecular weight is 17900, and weight-average molecular weight is 45800.
＜embodiment 22 〉
In NMP (7.00g), mix BODA (2.22g, 8.87mmol), p-PDA (1.02g, 9.46mmol), AP18 (0.44g, 1.18mmol) and diamine compound (29) (0.38g, 1.18mmol), in 80 ℃ the reaction 5 hours after, add CBDA (0.58g, 2.96mmol) and NMP (6.50g), in 40 ℃ of reactions 6 hours, obtaining resinous principle content was the polyamic acid solution (K) of 26 quality %.The number-average molecular weight of this polyamic acid is 17500, and weight-average molecular weight is 45100.
＜embodiment 23 〉
In NMP (15.0g), mix BODA (3.25g, 13.0mmol), p-PDA (0.56g, 5.20mmol), PCH7DAB (3.30g, 8.67mmol) and diamine compound (34) (1.11g, 3.47mmol), in 80 ℃ the reaction 5 hours after, add CBDA (0.85g, 4.33mmol) and NMP (12.5g), in 40 ℃ of reactions 6 hours, obtain polyamic acid solution.
Add NMP in gained polyamic acid solution (20.0g), dilution was diacetyl oxide (2.65g) and the pyridine (2.07g) that adds behind the 6 quality % as imidization catalyst, in 80 ℃ of reactions 2 hours.This reaction soln is dropped in the methyl alcohol (310ml), 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 40%, and number-average molecular weight is 20100, and weight-average molecular weight is 53400.
＜embodiment 24 〉
In NMP (14.8g), mix BODA (3.25g, 13.0mmol), p-PDA (0.66g, 6.07mmol), PCH7DAB (3.30g, 8.67mmol) and diamine compound (37) (0.80g, 2.60mmol), in 80 ℃ the reaction 5 hours after, add CBDA (0.85g, 4.33mmol) and NMP (12.0g), in 40 ℃ of reactions 6 hours, obtaining resinous principle content was the polyamic acid solution (M) of 25 quality %.The number-average molecular weight of this polyamic acid is 19400, and weight-average molecular weight is 52800.
＜embodiment 25 〉
Add NMP at polyamic acid solution (M) that embodiment 24 obtains in (20.2g), dilution is diacetyl oxide (2.68g) and the pyridine (2.07g) that adds behind the 6 quality % as imidization catalyst, reacts 2 hours in 80 ℃.This reaction soln is dropped in the methyl alcohol (300ml), 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 41%, and number-average molecular weight is 18100, and weight-average molecular weight is 48100.
＜synthesis example 3 〉
In NMP (15.0g), mix BODA (3.29g, 13.2mmol), p-PDA (0.67g, 6.14mmol), PCH7DAB (3.34g, 8.77mmol) and diamine compound (40) (0.68g, 2.63mmol), in 80 ℃ the reaction 5 hours after, add CBDA (0.86g, 4.39mmol) and NMP (11.5g), in 40 ℃ of reactions 6 hours, obtaining resinous principle content was the polyamic acid solution (O) of 25 quality %.The number-average molecular weight of this polyamic acid is 22600, and weight-average molecular weight is 54900.
＜synthesis example 4 〉
Add NMP at polyamic acid solution (O) that synthesis example 3 obtains in (20.0g), dilution is diacetyl oxide (2.65g) and the pyridine (2.08g) that adds behind the 6 quality % as imidization catalyst, reacts 2 hours in 80 ℃.This reaction soln is dropped in the methyl alcohol (320ml), 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 40%, and number-average molecular weight is 18900, and weight-average molecular weight is 49200.
＜synthesis example 5 〉
In NMP (15.2g), mix BODA (3.22g, 12.9mmol), p-PDA (0.65g, 6.00mmol), PCH7DAB (3.26g, 8.57mmol) and diamine compound (43) (0.62g, 2.57mmol), in 80 ℃ the reaction 5 hours after, add CBDA (0.84g, 4.28mmol) and NMP (11.1g), in 40 ℃ of reactions 6 hours, obtaining resinous principle content was the polyamic acid solution (Q) of 25 quality %.The number-average molecular weight of this polyamic acid is 22100, and weight-average molecular weight is 53200.
＜synthesis example 6 〉
Add NMP at polyamic acid solution (Q) that synthesis example 5 obtains in (20.1g), dilution is diacetyl oxide (2.68g) and the pyridine (2.04g) that adds behind the 6 quality % as imidization catalyst, reacts 2 hours in 80 ℃.This reaction soln is dropped in the methyl alcohol (350ml), leach the gained throw out.With this throw out of methanol wash,, obtain polyimide powder (R) in 100 ℃ of drying under reduced pressure.The imidization rate of this polyimide is 41%, and number-average molecular weight is 18400, and weight-average molecular weight is 49100.
[table 5]
Figure BPA00001186317900461
[table 6]
Figure BPA00001186317900462
[the modulation evaluation of aligning agent for liquid crystal]
＜embodiment 26 〉
At the resinous principle content that embodiment 12 obtains is that the polyamic acid [A] of 24 quality % adds NMP (10.2g) and BCS (20.0g) in (10.0g), in 25 ℃ of stirrings 2 hours, and acquisition aligning agent for liquid crystal [1].This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.
[making of liquid crystal structure cell]
The aligning agent for liquid crystal [1] of above acquisition is spun on the ito surface of substrate of the band ITO electrode of 3cm * 4cm (vertical * horizontal stroke), on hot plate, carry out the back recirculation furnace of 5 minutes burn till and carry out 1 hour burning till, obtain the polyimide coating film of thickness 100nm with 210 ℃ in 80 ℃.
The friction gear of the artificial silk cloth by roller footpath 120mm carries out friction treatment with the condition of rotating speed 300rpm, roller gait of march 20mm/ second, the amount of being pressed into 0.3mm to the substrate of this band liquid crystal orientation film, obtains the substrate with liquid crystal orientation film.
Prepare 2 should the band liquid crystal orientation films substrates, printing and sealing agent thereon behind the granulated glass sphere spacer of 6 μ m is scattered on the surface of 1 liquid crystal orientation film therein.With the liquid crystal aligning face of other 1 substrate as the inboard fit make that frictional direction becomes reverse direction after, make sealant cures make the negative crystal born of the same parents.In this negative crystal born of the same parents, inject the nematic liquid crystal structure cell that liquid crystal MLC-6608 (Japanese Mai Luke (メ Le Network) Co., Ltd.'s system) obtains the antiparallel orientation by the decompression injection method.
[evaluation of voltage retention]
Liquid crystal structure cell to above acquisition under 80 ℃ temperature applies 4V voltage 60 μ s, measures behind the 16.67ms and the voltage behind the 1667ms, can what keep as the voltage retention calculating voltage.The results are shown in table 7 described later.
[evaluation that residual charge discharges]
Applied the 10V volts DS 30 minutes for the liquid crystal structure cell after the voltage retention mensuration, short circuit was measured the current potential that produces in the liquid crystal structure cell in 1800 seconds time after 1 second.Then, measure 50 seconds after and the residual charge after 1000 seconds.Measure and adopt Dongyang technology (テ Network ニ カ) Co., Ltd.'s system 6254 type liquid crystal evaluation of physical property devices.The results are shown in table 8 described later.
[evaluation after high temperature is placed]
Liquid crystal structure cell after residual charge measured is measured voltage retention and residual charge place 7 days in temperature is set at 100 ℃ high temperature groove after.The results are shown in table 7 described later and table 8.
＜embodiment 27 〉
Add NMP (36.3g) at polyimide powder [B] that embodiment 13 obtains in (5.1g), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP (18.1g), BCS (25.6g), stirred acquisition aligning agent for liquid crystal [2] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [2] that obtains.The results are shown in table 7 described later and table 8.
＜embodiment 28 〉
Add NMP (32.8g) at polyimide powder [C] that embodiment 14 obtains in (5.0g), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP (16.4g), BCS (29.2g), stirred acquisition aligning agent for liquid crystal [3] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [3] that obtains.The results are shown in table 7 described later and table 8.
＜embodiment 29 〉
At the resinous principle content that embodiment 15 obtains is that the polyamic acid solution [D] of 25 quality % adds NMP (8.9g), BCS (23.6g) in (10.5g), stirs acquisition aligning agent for liquid crystal [4] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [4] that obtains.The results are shown in table 7 described later and table 8.
＜embodiment 30 〉
Add NMP (34.1g) at polyimide powder [E] that embodiment 16 obtains in (5.2g), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP (17.1g), BCS (30.4g), stirred acquisition aligning agent for liquid crystal [5] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [5] that obtains.The results are shown in table 7 described later and table 8.
＜embodiment 31 〉
Add NMP (35.6g) at polyimide powder [F] that embodiment 17 obtains in (5.0g), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP (17.8g), BCS (25.1g), stirred acquisition aligning agent for liquid crystal [6] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [6] that obtains.The results are shown in table 7 described later and table 8.
＜embodiment 32 〉
Add NMP (30.1g) at polyimide powder [G] that embodiment 18 obtains in (5.0g), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP (15.2g), BCS (33.2g), stirred acquisition aligning agent for liquid crystal [7] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [7] that obtains.The results are shown in table 7 described later and table 8.
＜embodiment 33 〉
Add NMP (42.2g) at polyimide powder [H] that embodiment 19 obtains in (5.5g), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP (20.8g), BCS (22.9g), stirred acquisition aligning agent for liquid crystal [8] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [8] that obtains.The results are shown in table 7 described later and table 8.
＜embodiment 34 〉
Add NMP (30.3g) at polyimide powder [I] that embodiment 20 obtains in (5.0g), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP (14.8g), BCS (33.8g), stirred acquisition aligning agent for liquid crystal [9] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [9] that obtains.The results are shown in table 7 described later and table 8.
＜embodiment 35 〉
Add NMP (33.0g) at polyimide powder [J] that embodiment 21 obtains in (5.1g), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP (17.1g), BCS (29.8g), stirred acquisition aligning agent for liquid crystal [10] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [10] that obtains.The results are shown in table 7 described later and table 8.
＜embodiment 36 〉
At the resinous principle content that embodiment 22 obtains is that the polyamic acid solution [K] of 26 quality % adds NMP (15.6g), BCS (17.1g) in (10.0g), stirs acquisition aligning agent for liquid crystal [11] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [11] that obtains.The results are shown in table 7 described later and table 8.
＜embodiment 37 〉
Add NMP (34.5g) at polyimide powder [L] that embodiment 23 obtains in (5.2g), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP (16.5g), BCS (30.3g), stirred acquisition aligning agent for liquid crystal [12] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [12] that obtains.The results are shown in table 7 described later and table 8.
＜embodiment 38 〉
At the resinous principle content that embodiment 24 obtains is that the polyamic acid solution [M] of 25 quality % adds NMP (9.5g), BCS (17.3g) in (8.5g), stirs acquisition aligning agent for liquid crystal [13] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [13] that obtains.The results are shown in table 7 described later and table 8.
＜embodiment 39 〉
Add NMP (35.5g) at polyimide powder [N] that embodiment 25 obtains in (5.0g), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP (17.8g), BCS (25.1g), stirred acquisition aligning agent for liquid crystal [14] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [14] that obtains.The results are shown in table 7 described later and table 8.
＜comparative example 1 〉
At the resinous principle content that synthesis example 3 obtains is that the polyamic acid solution [O] of 25 quality % adds NMP (17.5g), BCS (15.3g) in (10.4g), stirs acquisition aligning agent for liquid crystal [15] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [15] that obtains.The results are shown in table 7 described later and table 8.
＜comparative example 2 〉
Add NMP (34.5g) at polyimide powder [P] that synthesis example 4 obtains in (4.5g), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP (17.2g), BCS (18.8g), stirred acquisition aligning agent for liquid crystal [16] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [16] that obtains.The results are shown in table 7 described later and table 8.
＜comparative example 3 〉
At the resinous principle content that synthesis example 5 obtains is that the polyamic acid solution [Q] of 25 quality % adds NMP (18.8g), BCS (12.2g) in (10.0g), stirs acquisition aligning agent for liquid crystal [17] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [17] that obtains.The results are shown in table 7 described later and table 8.
＜comparative example 4 〉
Add NMP (38.6g) at polyimide powder [R] that synthesis example 6 obtains in (4.7g), made its dissolving in 40 hours in 70 ℃ of stirrings.In this solution, add NMP (19.4g), BCS (15.8g), stirred acquisition aligning agent for liquid crystal [18] 2 hours in 25 ℃.This aligning agent for liquid crystal is not seen to be had muddiness or abnormal conditions such as separates out, and confirms the dissolving of resinous principle homogeneous.Operate the evaluation that makes the liquid crystal structure cell and carried out voltage retention, the evaluation that residual charge discharges, the evaluation after the high temperature placement similarly to Example 26 with the aligning agent for liquid crystal [18] that obtains.The results are shown in table 7 described later and table 8.
[table 7]
Figure BPA00001186317900521
[table 8]
The possibility of utilizing on the industry
Even aligning agent for liquid crystal of the present invention when forming liquid crystal orientation film, can obtain voltage retention high and be exposed to for a long time under the high temperature after the also very fast liquid crystal orientation film of release of the residual charge accumulated because of DC voltage. In addition, can be provided at the high liquid crystal display cells of reliability that can use for a long time under the harsh environment for use. Consequently, can be used for TN element, STN element, TFT liquid crystal cell, also can be used for vertical orientating type or horizontal alignment type (IPS) liquid crystal display cells etc.
Here quote the announcement of all the elements of Japanese patent application 2008-014965 number specification sheets, claims and the summary of filing an application on January 25th, 2008 as specification sheets of the present invention.

Claims (15)

1. the diamine compound of following formula [1] expression,
Figure FPA00001186317800011
In the formula [1], X 1For be selected from-O-,-NQ 1-,-CONQ 1-,-NQ 1CO-,-CH 2O-and-at least a kind of divalent organic group of OCO-, Q 1Be the alkyl of hydrogen atom or carbon number 1～3, X 2For singly-bound or be selected from least a kind of divalent organic group of aliphatic alkyl, non-aromatic ring type alkyl and the aromatic hydrocarbyl of carbon number 1～20, X 3For singly-bound or be selected from-O-,-NQ 2-,-CONQ 2-,-NQ 2CO-,-COO-,-OCO-and-O (CH 2) m-at least a kind of divalent organic group, m wherein is 1～5 integer, Q 2Be the alkyl of hydrogen atom or carbon number 1～3, X 4Be nitrogenous fragrant heterocycle, n is 1～4 integer.
2. diamine compound as claimed in claim 1 is characterized in that, the diamine compound of formula [1] is at least a kind of the compound that is selected from the expression of following formula [1a]～formula [1f],
Figure FPA00001186317800012
In the formula, Q 1Be the alkyl of hydrogen atom or carbon number 1～3, X 2For singly-bound or be selected from least a kind of divalent organic group of aliphatic alkyl, non-aromatic ring type alkyl and the aromatic hydrocarbyl of carbon number 1～20, X 3For singly-bound or be selected from-O-,-NQ 2-,-CONQ 2-,-NQ 2CO-,-COO-,-OCO-and-O (CH 2) m-at least a kind of divalent organic group, m wherein is 1～5 integer, Q 2Be the alkyl of hydrogen atom or carbon number 1～3, X 4Be nitrogenous fragrant heterocycle, n is 1～4 integer.
3. diamine compound as claimed in claim 2 is characterized in that, the X in formula [1a]～formula [1f] 2Straight-chain alkyl-sub-or phenyl ring for singly-bound, carbon number 1～3.
4. as claim 2 or 3 described diamine compounds, it is characterized in that the X in formula [1a]～formula [1f] 3For singly-bound ,-OCO-or-OCH 2-.
5. as each described diamine compound in the claim 2～4, it is characterized in that the X in formula [1a]～formula [1f] 4Be imidazole ring, pyridine ring or pyrimidine ring.
6. as each described diamine compound in the claim 2～5, it is characterized in that the n in formula [1a]～formula [1f] is 1 or 2 integer.
7. diamine compound as claimed in claim 1 or 2 is characterized in that, the X in formula [1a]～formula [1f] 1For be selected from-O-,-NH-,-CONH-,-NHCO-,-CON (CH 3)-,-CH 2O-and-at least a kind of OCO-, X 2Be at least a kind of the straight or branched alkylidene group, cyclohexane ring, phenyl ring and the naphthalene nucleus that are selected from carbon number 1～10, X 3For be selected from singly-bound ,-O-,-CONH-,-NHCO-,-COO-,-OCO-and-O (CH 2) m-at least a kind, m wherein is 1～5 integer, X 4For being selected from pyrrole ring, imidazole ring, pyrazoles ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzoglyoxaline ring at least a kind, n is 1 or 2 integer.
8. diamine compound as claimed in claim 1 or 2 is characterized in that, the X in the formula [1] 1For be selected from-O-,-NH-,-CONH-,-NHCO-,-CON (CH 3)-and-CH 2At least a kind of O-, X 2Be the straight or branched alkylidene group that is selected from singly-bound, carbon number 1～5 and at least a kind of phenyl ring, X 3For be selected from singly-bound ,-O-,-CONH-,-NHCO-,-COO-,-OCO-and-O (CH 2) m-at least a kind, m wherein is 1～5 integer, X 4For being selected from pyrrole ring, imidazole ring, pyrazoles ring, pyridine ring and pyrimidine ring at least a kind, n is 1 or 2 integer.
9. diamine compound as claimed in claim 1 or 2 is characterized in that, the X in the formula [1] 1For be selected from-O-,-NH-,-CONH-,-NHCO-and-CON (CH 3)-at least a kind, X 2Be the straight-chain alkyl-sub-that is selected from singly-bound, carbon number 1～3 and at least a kind of phenyl ring, X 3For be selected from singly-bound ,-OCO-and-OCH 2-at least a kind, X 4For being selected from imidazole ring, pyridine ring and pyrimidine ring at least a kind, n is 1 or 2 integer.
10. polyamic acid or polyimide, it is characterized in that, described polyamic acid is reacted by two amine components that contain each described diamine compound in the claim 1～9 and tetracarboxylic dianhydride and obtains, and described polyimide is obtained by this polyamic acid dehydration closed-loop.
11. polyamic acid as claimed in claim 10 or polyimide is characterized in that, the diamine compound of formula [1] expression is 1～80 mole of % in two amine components.
12. aligning agent for liquid crystal is characterized in that, contains either party at least and solvent in claim 10 or 11 described polyamic acids and the polyimide.
13. aligning agent for liquid crystal as claimed in claim 12 is characterized in that, 5～80 quality % in the solvent that this aligning agent for liquid crystal comprises are Weak solvent.
14. liquid crystal orientation film is characterized in that, is formed by claim 12 or 13 described aligning agent for liquid crystal.
15. liquid crystal display device is characterized in that, possesses the described liquid crystal orientation film of claim 14.
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