CN101633621A - Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element using liquid crystal orientation agent - Google Patents

Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element using liquid crystal orientation agent Download PDF

Info

Publication number
CN101633621A
CN101633621A CN200910165995A CN200910165995A CN101633621A CN 101633621 A CN101633621 A CN 101633621A CN 200910165995 A CN200910165995 A CN 200910165995A CN 200910165995 A CN200910165995 A CN 200910165995A CN 101633621 A CN101633621 A CN 101633621A
Authority
CN
China
Prior art keywords
liquid crystal
polyamic acid
mole
molecular weight
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN200910165995A
Other languages
Chinese (zh)
Inventor
筒井皇晶
后藤耕平
志田启文
石津谷正英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Publication of CN101633621A publication Critical patent/CN101633621A/en
Pending legal-status Critical Current

Links

Abstract

The invention provides a liquid crystal orientation agent which can form good liquid crystal orientation film with good electric performance and has perfect preservation stability and manufacturing. The liquid crystal orientation agent includes at least a component selected from polyamide acid which is obtained through the polymerization of diamine component and tetracarboxylic dianhydride component, and polyimide obtained through dewatering and loop-closing of polyamide acids; and is characterized in that the diamine component is 6-aminonaphthalene methylamine or 2-(6-aminonaphthalene)ethylamine.

Description

Liquid crystal orientating agent, the liquid crystal orientating membrane that has used this directing agent and liquid crystal display device
The application is that international application no is PCT/JP2005/008055, and international filing date is national applications the dividing an application for the Chinese patent application of " liquid crystal orientating agent, the liquid crystal orientating membrane that has used this directing agent and liquid crystal display device " that number be 200580012719.6 title after the PCT international application on April 27th, 2005 enters China's stage.
Technical field
Used liquid crystal orientating agent, the liquid crystal orientating membrane that has used this directing agent and liquid crystal display device when the present invention relates to form liquid crystal display device.
Background technology
The liquid crystal display device that is used to the indicating meter of mobile telephone, computer or televisor etc. is to have liquid crystal molecule to be formed on structure that the liquid crystal orientating membrane of substrate clamps, to have utilized the effect that relies on liquid crystal orientating membrane to be subjected to voltage with the liquid crystal molecule of certain orientation orientation to make the display element of response.
Because this liquid crystal orientating membrane forms by liquid crystal orientating agent, the directional property of decision liquid crystal molecule and the tilt angle of liquid crystal molecule have a significant impact the electrical characteristic of display element, therefore play very big effect in liquid crystal display device.
At present, the characteristic of developing to improve display element is the liquid crystal orientating membrane of target, for example, disclosed to provide and contained polyamic acid, the polyamic acid of part imidization and the lacquer of polyimide that obtains as diamines and tetracarboxylic dianhydride's condensation of principal constituent with two (amino methyl)-two ring [2.2.1] heptane by using, obtain the technical scheme (for example, with reference to patent documentation 1) of the liquid crystal orientating membrane of voltage retention height, display element that residual electric charge is few.In addition, disclosed and used specific aliphatie diamine and aromatic tetracarboxylic acid's dianhydride, the liquid crystal orientating membrane (for example, with reference to patent documentation 2) that liquid crystal aligning is increased.
But, used under the situation of alicyclic or aliphatie diamine, form corresponding amido acid and salt, when the solvability of this salt was low, reaction sometimes can stop.In addition,, also must continue to stir until formed salt and disappear, compare the reaction needed time with the situation of routine even under the high situation of the solvability of salt.Therefore, having proposed to use the silicomethane acid amides is the manufacture method (for example, with reference to patent documentation 3) of the poly amic acid ester of sillylation reagent and the polyimide that obtained by this poly amic acid ester.
On the other hand, the polymerisation reactivity of aromatic diamine is good, but different because of with the kind of the acid dianhydride of its reaction, the polyamic acid of gained causes heterogeneityization or gelation sometimes in cryopreservation.
Sometimes preparation of these polyamic acids and stability can make a big impact to the preparation and the stability of liquid crystal orientating agent, as liquid crystal orientating agent, wish that it is easy to preparation, storage stability is good, can improve the characteristic (particularly electrical characteristic) of liquid crystal orientating membrane simultaneously.
Patent documentation 1: Japanese patent laid-open 10-7906 communique
Patent documentation 2: Japanese patent laid-open 8-248424 communique
Patent documentation 3: the Japanese Patent spy opens the 2002-322275 communique
The announcement of invention
The present invention is the invention of In view of the foregoing finishing, and its objective is to provide to form the good liquid crystal orientating membrane of electrical characteristic, storage stability and the good liquid crystal orientating agent of preparation property.
The present inventor conscientiously studies the back to achieve these goals and finds, obtain two amine components that polyamic acid maybe carries out this polyamic acid dehydration closed-loop acquisition polyimide as carrying out polyreaction with tetracarboxylic dianhydride's composition, do not use used in the past diamine compound, take this to obtain following liquid crystal orientating agent, thereby finished the present invention with superperformance.Being used in the above-mentioned diamine compound of the present invention several is new diamine compounds.
That is, the present invention includes following technology contents.
1. liquid crystal orientating agent, it is to contain to be selected from that two amine components and tetracarboxylic dianhydride's composition carry out polyreaction and the polyamic acid that obtains and this polyamic acid carried out dehydration closed-loop and at least a kind liquid crystal orientating agent of the polyimide that obtains, this liquid crystal orientating agent is characterised in that, aforementioned two amine components contain at least a kind in the diamines of following formula [1] expression
H 2N-A-R-NH 2[1]
In the formula [1], A is the divalent organic group that phenyl ring or aromatic fused ring form, and one or more hydrogen atoms arbitrarily of this phenyl ring and aromatic fused ring can be replaced by 1 valency organic group beyond the amino, and R is the divalent saturated hydrocarbyl of carbonatoms 1～10.
2. the liquid crystal orientating agent of above-mentioned 1 record, wherein, the A of formula [1] is the divalent aromatic group that is selected from formula [2-1]～formula [2-4],
Figure G2009101659956D00021
Figure G2009101659956D00031
In the above-mentioned formula, one or more hydrogen atoms of phenyl ring and aromatic fused ring can be replaced by 1 valency organic group beyond the amino.
3. the liquid crystal orientating agents of above-mentioned 1 or 2 records, wherein, the R in the formula [1] is by following formula [3] expression,
-(CH 2) n1-(Q) n2-(CH 2) n3-[3]
In the formula [3], Q represents the hydrocarbon ring of carbonatoms 3～7, and n1 and n3 are 0～7 integer, and n2 is 0 or 1, but n1, n2, n3 are not 0 simultaneously.
4. the liquid crystal orientating agent of above-mentioned 3 records, wherein, R is-(CH 2) N1-,-(CH 2) N1-(Q) N2Or-(Q) N2-(CH 2) N3-.
5. the liquid crystal orientating agent of above-mentioned 3 or 4 records, wherein, Q is tetramethylene, pentamethylene or hexanaphthene.
6. the liquid crystal orientating agent of above-mentioned 1 record, wherein, two amine components contain the diamines of formula [4] expression,
In the formula, R 1Be the divalent saturated hydrocarbyl of carbonatoms 1～10, one or more hydrogen atoms arbitrarily of phenyl ring can be replaced by 1 valency organic group beyond the amino.
7. the liquid crystal orientating agent of above-mentioned 1 record, wherein, two amine components contain at least a kind in the diamines of formula [5] expression,
Figure G2009101659956D00033
In the formula, R 2Be the divalent saturated hydrocarbyl of carbonatoms 1～10, one or more hydrogen atoms arbitrarily of naphthalene nucleus can be replaced by 1 valency organic group beyond the amino.
8. the liquid crystal orientating agent of each record in above-mentioned 1～7, wherein, tetracarboxylic dianhydride's composition: the reaction ratio of two amine components is 1: 0.8～1: 1.2 with molar ratio computing.
9. liquid crystal orientating membrane, this liquid crystal orientating membrane is characterised in that, uses the liquid crystal orientating agent of each record in above-mentioned 1～8 to make.
10. liquid crystal display device, this element are characterised in that, have used the liquid crystal orientating membranes of above-mentioned 9 records.
11.6-amino naphthalenes methylamine.
(12.2-6-amino naphthalenes) ethamine.
Can obtain the good liquid crystal orientating membrane of electrical characteristic by liquid crystal orientating agent of the present invention, this liquid crystal orientating membrane is applicable to liquid crystal display device.In addition, the preparation of liquid crystal orientating agent itself and storage stability are good.
The simple declaration of accompanying drawing
Fig. 1 represents the UV absorption spectrum of embodiment 38～40 and comparative example 6.
The best mode that carries out an invention
Below, the present invention is described in detail.
Liquid crystal orientating agent of the present invention is to contain to be selected from the polyamic acid that makes two amine components that use as the monomer component that constitutes polymkeric substance and tetracarboxylic dianhydride's composition carry out polyreaction and obtain, and this polyamic acid carried out dehydration closed-loop and at least a kind liquid crystal orientating agent of the polyimide that obtains, this liquid crystal orientating agent is characterised in that, aforementioned two amine components contain at least a kind in the diamines of following formula [1] expression
H 2N-A-R-NH 2[1]
In the formula [1], A is the divalent organic group that phenyl ring or aromatic fused ring form, and one or more hydrogen atoms arbitrarily of this phenyl ring and aromatic fused ring can be replaced by 1 valency organic group beyond the amino, and R is the divalent saturated hydrocarbyl of carbonatoms 1～10.
The diamines that is used for formula of the present invention [1] expression has that 1 amino directly combines with the aromatic nucleus of A, the saturated hydrocarbyl bonded structure of other 1 amino and carbonatoms 1～10.A in the formula [1] is the divalent organic group that is selected from the organic group of ring (hereinafter referred to as the aromatic fused ring) expression that forms with phenyl ring, a plurality of phenyl ring condensation.
Below, exemplify the concrete example of A, but be not limited thereto.
Figure G2009101659956D00041
Figure G2009101659956D00051
In the formula, one or more hydrogen atoms arbitrarily of aromatic nucleus, condensed ring can be replaced by 1 valency organic group beyond the amino.
Among the present invention, the A of formula [1] is present in the structure of polyamic acid and polyimide, and it is the position of playing the effect that the liquid crystal aligning that makes liquid crystal orientating membrane and stored charge characteristic improve.Though reason is also uncertain, A is pi-conjugated when being aromatic group, and the charge storage characteristic of liquid crystal orientating membrane is better, so more satisfactory.In addition, when being contained in the comparatively small amt of the phenyl ring of A or condensed ring, the condensed ring that perhaps is contained in A be 2～3 phenyl ring condensations form condensed ring the time, can keep the storage stability of liquid crystal orientating agent well, so more satisfactory.
Among the present invention, the divalent organic group of particularly preferably above-mentioned formula of the A in the formula [1] [2-1] or formula [2-2] expression.
When A was formula [2-1], the absorbancy of liquid crystal orientating membrane in visible light-UV scope became lower, and had the effect etc. of high polyamic acid of easy acquisition solvability or polyimide etc., so desirable especially.For example, when A is formula [2-1],, obtain polyimide sometimes by realizing being used in combination of two amine components of insoluble polyamic acid with utilizing imidization reaction.In addition, when A was formula [2-2], the stored charge characteristic was better, so desirable especially.
Below, the R in the formula [1] is described.When general polyamic acid or polyimide skeleton were rigidity, when promptly second-order transition temperature was high, the storage stability of liquid crystal orientating agent is deterioration sometimes.Therefore, in order to address this problem, preferably give polyamic acid or polyimide skeleton with flexibility.Consider the voltage preserving property and the liquid crystal aligning of liquid crystal orientating membrane, R is the divalent saturated hydrocarbyl of carbonatoms 1～10.R is the saturated hydrocarbyl with straight chain shape, a chain or ring texture, does not preferably contain the divalent organic group of aromatic ring.Because R does not contain aromatic group, so have the effect that the absorbancy of liquid crystal orientating membrane in the scope of visible light-ultraviolet ray (UV) becomes lower yet.Consider the saturated hydrocarbyl of the preferred carbonatoms 1～6 of R from the angle of stored charge characteristic.In addition, consider preferred straight catenate saturated hydrocarbyl from the angle of liquid crystal aligning.
Preferred R of the present invention is with following formula [3] expression,
-(CH 2) n1-(Q) n2-(CH 2) n3- [3]
In the formula [3], Q represents the hydrocarbon ring of carbonatoms 3～7, is preferably tetramethylene ring, pentamethylene ring, cyclohexane ring, wherein be more preferably the stable cyclohexane ring of ring structure, n1 and n3 are 0～7 integer, are preferably 0～3 integer, n2 is 0 or 1, but n1, n2 and n3 are not 0 simultaneously.
Below, exemplify the concrete example of the preferred diamines of formula [1] expression, but be not limited to this.
For example, when the A in the formula [1] was a formula [2-1]～formula [2-4], R can exemplify the diamines of formula [6]～formula [9] expression as the diamines with ring structure.
Figure G2009101659956D00061
Figure G2009101659956D00071
In formula [6]～formula [9], Q, n1 and n3 as previously mentioned, the carbonatoms of the hydrocarbon ring of Q, n1 and n3 add up to the integer that is preferably 10 below, in the formula, one or more hydrogen atoms arbitrarily of aromatic ring or hydrocarbon ring can be by the replacement of 1 valency organic group beyond the amino.Concrete example during for the condensed ring in formula [2-5]～formula [2-10] can exemplify the same compound with for formula [2-1]～formula [2-4] time.
The concrete example of formula [6] can exemplify the diamines of formula [10]～formula [16] etc.
Figure G2009101659956D00072
One or more hydrogen atoms arbitrarily of phenyl ring in the diamines of above-mentioned formula [10]～formula [16] can be replaced by 1 valency organic group beyond the amino.In addition, the hydrogen atom arbitrarily in the ring structure of R can be replaced by 1 valency alkyl.Concrete example during for the condensed ring in formula [7]～formula [9] can exemplify with formula [6] in same compound.
As R is diamines when having the saturated hydrocarbyl of branched structure, and the concrete example when promptly the A in the formula [1] is formula [2-1] can exemplify the diamines of formula [17]～formula [26] etc.
Figure G2009101659956D00081
Figure G2009101659956D00091
One or more hydrogen atoms arbitrarily of phenyl ring in the diamines of above-mentioned formula [17]～formula [26] can be replaced by 1 valency organic group beyond the amino.Concrete example when in addition, the A in the formula [1] is the condensed ring of formula [2-2]～formula [2-10] can exemplify the same compound with for formula [2-1] time.
Diamines when being straight catenate saturated hydrocarbyl as R, for example the A in the formula [1] be formula [2-1] and 2～3 such phenyl ring condensations of formula [2-2]～formula [2-4] form ring the time, can exemplify the diamines of formula [27]～formula [31] expression.
Figure G2009101659956D00101
In formula [27]～formula [31], n4 represents 1～10 integer.In the formula, one or more hydrogen atoms arbitrarily of aromatic nucleus, condensed ring can be replaced by 1 valency organic group beyond the amino.
If further exemplify concrete example, can exemplify the diamines of formula [32]～formula [49] etc.
Figure G2009101659956D00111
Figure G2009101659956D00121
Figure G2009101659956D00131
Phenyl ring in the diamines of above-mentioned formula [32]～formula [49] expression, one or more hydrogen atoms arbitrarily of condensed ring can be replaced by 1 valency organic group beyond the amino.Concrete example during in addition, for the condensed ring of formula [2-5]～formula [2-10] can exemplify the same compound with for formula [2-1]～formula [2-4] time.
In the above-mentioned diamines, be preferably the diamines of A by formula [2-1] or formula [2-2] expression.Specifically more preferably formula [6], formula [7], formula [10]～formula [28], formula [32]～formula [43].Be preferably n4 in formula [27], the formula [28] and be the diamines of 1～6 integer.Be more preferably n4 in formula [27], the formula [28] and be the diamines of formula [32]～formula [43] expression of 1～3 integer.
Be used at least a kind of diamines of the two amine components of the present invention above-mentioned formulas of use also capable of being combined [1] expressions and be selected from other more than a kind or 2 kinds of diamines.Below exemplify the example of other diamines, but be not limited in this.
As alicyclic diamine, can exemplify 1,4-diamino-cyclohexane, 1,3-diamino-cyclohexane, 4,4 '-diamino-dicyclohexyl methane, 4,4 '-diamino-3,3 '-dimethyl dicyclohexyl amine and isophorone diamine etc.In addition, example as aromatic diamines, can exemplify the neighbour-, between-, p-phenylenediamine, the diaminotoluene class (for example, 2, the 4-diaminotoluene), 1,4-diamino-2-anisole, 2,5-diamino-p-Xylol, 1,3-diamino-4-chlorobenzene, 3, the 5-diaminobenzoic acid, 1,4-diamino-2, the 5-dichlorobenzene, 4,4 '-diaminostilbene, the 2-diphenylethane, 4,4 '-diamino-2,2 '-dimethyl bibenzyl, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diamino-3,3 '-dimethyl diphenylmethane, 2,2 '-diamino Stilbene, 4,4-diamino Stilbene, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diaminobenzophenone, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 3, two (4-amino-benzene oxygen) phenylformic acid of 5-, 4,4,-two (4-amino-benzene oxygen) bibenzyl, 2, two [(4-amino-benzene oxygen) methyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] the chlordene propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1, two (4-aminophenyl) hexanaphthenes of 1-, α, α '-two (4-aminophenyl)-1, the 4-diisopropyl benzene, 9, two (4-aminophenyl) fluorenes of 9-, 2, two (3-aminophenyl) HFC-236fa of 2-, 2, two (4-aminophenyl) HFC-236fa of 2-, 4,4 '-diamino-diphenyl amine, 2,4-diamino-diphenyl amine, 1, the 8-diaminonaphthalene, 1, the 5-diaminonaphthalene, 1, the 5-diamino-anthraquinone, 1,3-diamino pyrene, 1,6-diamino pyrene, 1,8-diamino pyrene, 2,7 diamin of luorene, 1, two (4-aminophenyl) tetramethyl disiloxanes of 3-, p-diaminodiphenyl, 2,2 '-tolidine, 1, two (4-aminophenyl) ethane of 2-, 1, two (4-aminophenyl) propane of 3-, 1, two (4-aminophenyl) butane of 4-, 1, two (4-aminophenyl) pentanes of 5-, 1, two (4-aminophenyl) hexanes of 6-, 1, two (4-aminophenyl) heptane of 7-, 1, two (4-aminophenyl) octanes of 8-, 1, two (4-aminophenyl) nonanes of 9-, 1, two (4-aminophenyl) decane of 10-, 1, two (4-amino-benzene oxygen) propane of 3-, 1, two (4-amino-benzene oxygen) butane of 4-, 1, two (4-amino-benzene oxygen) pentanes of 5-, 1, two (4-amino-benzene oxygen) hexanes of 6-, 1, two (4-amino-benzene oxygen) heptane of 7-, 1, two (4-amino-benzene oxygen) octanes of 8-, 1, two (4-amino-benzene oxygen) nonanes of 9-, 1, two (4-amino-benzene oxygen) decane of 10-, two (4-aminophenyl) propane-1, the 3-diester, two (4-aminophenyl) butane-1, the 4-diester, two (4-aminophenyl) pentane-1, the 5-diester, two (4-aminophenyl) hexane-1, the 6-diester, two (4-aminophenyl) heptane-1, the 7-diester, two (4-aminophenyl) octane-1, the 8-diester, two (4-aminophenyl) nonane-1, the 9-diester, two (4-aminophenyl) decane-1, the 10-diester, 1, two [4-(4-amino-benzene oxygen) phenoxy group] propane of 3-, 1, two [4-(4-amino-benzene oxygen) phenoxy group] butane of 4-, 1, two [4-(4-amino-benzene oxygen) phenoxy group] pentanes of 5-, 1, two [4-(4-amino-benzene oxygen) phenoxy group] hexanes of 6-, 1, two [4-(4-amino-benzene oxygen) phenoxy group] heptane of 7-, 1, two [4-(4-amino-benzene oxygen) phenoxy group] octanes of 8-, 1, two [4-(4-amino-benzene oxygen) phenoxy group] nonanes of 9-, 1, two [4-(4-amino-benzene oxygen) phenoxy group] decane of 10-etc.
As hetero ring type two amines, can exemplify 2,6-diamino-pyridine, 2,4-diamino-pyridine, 2,4-diaminostilbene, 3,5-triazine, 2,7-diamino diphenylene-oxide, 3,6-diamino carbazole, 2,4-diamino-6-sec.-propyl-1,3,5-triazine, 2, two (the 4-aminophenyls)-1 of 5-, 3,4-oxadiazole etc.
As the example of aliphatie diamine, can exemplify 1,1, the 3-diaminopropanes, 1, the 4-diaminobutane, 1,5-diamino pentane, 1, the 6-diamino hexane, 1,7-diamino heptane, 1,8-diamino octane, 1,9-diamino nonane, 1, the 10-diamino decane, 1,3-diamino-2, the 2-dimethylpropane, 1,6-diamino-2, the 5-dimethylhexane, 1,7-diamino-2, the 5-dimethyl heptane, 1,7-diamino-4, the 4-dimethyl heptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12-diamino dodecane, 1,18-diamino octadecane, 1,2-two (the amino propoxy-of 3-) ethane etc.
In addition, combine chain alkyl, perfluor base by being used in combination, have the substituent organic group of aromatic series ring-type, the diamines of the structure of known organic group with the effect that can improve tilt angle such as the organic group with aliphatics cyclic substituents, steroide skeleton group, can obtain TFT and use liquid crystal orientating agent with liquid crystal cell (6 °～10 ° of tilt angles), VA with liquid crystal cell (90 ° of tilt angles) with liquid crystal cell (4 °～8 ° of tilt angles), OCB with liquid crystal cell (4 °～6 ° of tilt angles), STN.Below exemplify the concrete example of this diamines, but be not limited in this.
J in the formula shown below [50] is 5～20 integer, and the k in the formula shown in formula [51]～formula [60] and formula [63]～formula [66] is 1～20 integer.
Figure G2009101659956D00151
Figure G2009101659956D00161
Figure G2009101659956D00171
Figure G2009101659956D00191
The content of diamines that is preferably formula [1] expression in two amine components that are used to liquid crystal orientating agent of the present invention is at 1 mole more than the %.Be more preferably and contain 10 moles more than the %.Formula [1] is if the ratio of diamines of expression is very few, then the storage stability of liquid crystal orientating agent and electrical characteristic deterioration sometimes.
Be not particularly limited being used for tetracarboxylic dianhydride's composition of the present invention.Can use and be selected from being used in combination more than a kind or 2 kinds of tetracarboxylic dianhydride.Below exemplify concrete example, but be not limited in this.
As tetracarboxylic dianhydride, can exemplify 1,2,3 with alicyclic structure or aliphatic structure, 4-tetramethylene tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 3,4-dicarboxyl-1-cyclohexyl succsinic acid dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, two rings [3,3,0] octane-2,4,6, the 8-tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, suitable-3,7-dibutyl ring suffering-1,5-diene-1,2,5, the 6-tetracarboxylic dianhydride, three ring [4.2.1.0 2,5] nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dianhydride, six ring [6.6.0.1 2,7.0 3,6.1 9,14.0 10,13] n-Hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dianhydride etc.As the aromatic acid dianhydride, can exemplify pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride etc.
10 moles of % of tetracarboxylic dianhydride's composition are above to be that voltage retention increases, so more satisfactory when having the tetracarboxylic dianhydride of alicyclic structure or aliphatic structure.
As the tetracarboxylic dianhydride who preferably has alicyclic structure or aliphatic structure, can exemplify 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, two rings [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride.
If 20 moles of % of tetracarboxylic dianhydride's composition are above to be the aromatic acid dianhydride, then liquid crystal aligning raising, and stored charge reduces.
As preferred aromatic acid dianhydride, can exemplify pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride.
The tetracarboxylic dianhydride's composition that is used to liquid crystal orientating agent of the present invention and the polyreaction of two amine components are not particularly limited.Generally, can carry out polyreaction and form polyamic acid, make this polyamic acid dehydration closed-loop again, can form polyimide by in organic solvent, mixing.
As making tetracarboxylic dianhydride's composition and two amine components blended method in organic solvent, can exemplify and stir the solution that makes two amine components be dispersed or dissolved in organic solvent and form, directly add tetracarboxylic dianhydride's composition then or make tetracarboxylic dianhydride's composition be dispersed or dissolved in the method for adding again behind the organic solvent; Be dispersed or dissolved in organic solvent and the method for adding two amine components in the solution that forms at tetracarboxylic dianhydride's composition on the contrary; Alternately add the method for tetracarboxylic dianhydride's composition and two amine components etc.In addition, when at least one side in tetracarboxylic dianhydride's composition and two amine components was formed by several compounds, the state that can be pre-mixed several compositions carried out polyreaction, also can carry out polyreaction respectively successively.
Temperature when making tetracarboxylic dianhydride's composition and two amine components carry out polyreaction in organic solvent is generally 0 ℃～150 ℃, is preferably 5 ℃～100 ℃, more preferably 10 ℃～80 ℃.Polyreaction can be finished fast when temperature was high, if but temperature is too high, then can't obtain high molecular weight polymers sometimes.In addition, polyreaction can carried out under the concentration arbitrarily, if but concentration is low excessively, then be difficult to obtain high molecular weight polymers, if concentration is too high, then the viscosity of reaction solution becomes too high, be difficult to carry out the stirring of homogeneous, therefore be preferably 1～50 quality %, more preferably 5～30 quality %.The polyreaction initial stage is carried out under high density, append organic solvent then.
Be used to the organic solvent of above-mentioned reaction so long as the solvent of the polyamic acid that solubilized generates gets final product, be not particularly limited.If exemplify its concrete example, can exemplify N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-methyl caprolactam, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolactone etc.These solvents can use separately also can mix use.In addition, even the insoluble solvent of separating polyamic acid as long as under the prerequisite that the polyamic acid that generates is not separated out, also can use with above-mentioned solvent.In addition, because the moisture in the organic solvent can hinder the carrying out of polyreaction, and can make the polyamic acid hydrolysis of generation, so preferably use the organic solvent through dehydrating as much as possible.
Be used for tetracarboxylic dianhydride's composition of polyreaction of polyamic acid and diamines components in proportions with molar ratio computing be preferably 1: 0.8～1: 1.2, this mol ratio molecular weight near the polyamic acid of 1: 1 gained more is big more.If the molecular weight of polyamic acid is too small, then not high enough sometimes by the intensity of filming of its acquisition, on the contrary, if the molecular weight of polyamic acid is excessive, then can be too high by the viscosity of its liquid crystal orientating agent that makes, film sometimes operation when forming and the homogeneity meeting deterioration of filming.Therefore, the weight-average molecular weight that is used for the polyamic acid of liquid crystal orientating agent of the present invention is preferably 2000～500000, and more preferably 5000～300000.
More than the polyamic acid of Huo Deing can be directly used in liquid crystal orientating agent of the present invention, re-uses after also can making its dehydration closed-loop form polyimide.But, because of the difference of the structure of polyamic acid, sometimes can be insoluble by imidization reaction, be difficult to liquid crystal orientating agent.In this case, can use in the polyamic acid the acid amides acidic group all imidizations, under the deliquescent prerequisite that keeps appropriateness, make the polyamic acid of its imidization.
Make general hot-imide that polyamic acid solution is heated or the imidization that in polyamic acid solution, adds the chemical mode of catalyzer of adopting directly of the imidization reaction of polyamic acid dehydration closed-loop, the molecular weight of the polyimide that obtains by the imidization that carries out the chemical mode of imidization reaction at a lower temperature is difficult for descending, so more satisfactory.
The imidization of chemical mode can be in organic solvent, in the presence of basic catalyst and acid anhydrides polyamic acid is stirred and implement.The temperature of reaction of this moment is-20～250 ℃, is preferably 0～180 ℃, and the reaction times is 1～100 hour.The amount of basic catalyst is 0.5～30 mole a times of amic acid group, is preferably 2～20 moles doubly, and the amount of acid anhydrides is 1～50 mole a times of amic acid group, is preferably 3～30 moles doubly.If the amount of basic catalyst and acid anhydrides is less, then reaction can't fully be carried out, if too much, is difficult to remove fully after then reaction finishes.
Basic catalyst as being used for this moment can exemplify pyridine, triethylamine, Trimethylamine 99, Tributylamine, trioctylamine etc.Wherein, pyridine has the alkalescence that can make the appropriateness that reaction carries out smoothly, so more satisfactory.In addition, as acid anhydrides, can exemplify diacetyl oxide, trimellitic acid 1,2-anhydride, pyromellitic dianhydride etc., wherein, if use diacetyl oxide, so making with extra care easily after then reaction finishes is more satisfactory.As organic solvent, can use the solvent when being used for aforementioned polyamic acid polyreaction.Utilize the imidization rate of the imidization of chemical mode to control by regulating catalytic amount and temperature of reaction, reaction times.
In the polyimide solution of above gained because the remaining catalyzer that interpolation is arranged, so in order to be used for liquid crystal orientating agent of the present invention, preferably precipitation reclaims in the lean solvent that this polyimide solution input is being stirred.The lean solvent that the precipitation that is used for polyimide is reclaimed is not particularly limited, but illustration methyl alcohol, acetone, hexane, ethylene glycol butyl ether, heptane, ethyl methyl ketone, hexone, ethanol, toluene, benzene etc.Lean solvent will be dropped into and after the recovery of sedimentary polyimide filtration washing, under normal pressure or decompression,, powder can be formed with normal temperature or heat drying.Further this powder is dissolved in good solvent, redeposition if this operation is repeated 2～10 times, also can carry out the refining of polyimide.In the time can't removing impurity fully, preferably carry out above-mentioned refining step by precipitation reclaimer operation once.By mix using or use successively the lean solvents more than 3 kinds such as for example alcohols as above-mentioned lean solvent, ketone, hydro carbons, can further improve purification efficiency, so more satisfactory.
In addition, polyamic acid also can same operation precipitate recovery and refining.Desire to make when not containing the polymeric solvent that is useful on polyamic acid in the liquid crystal orientating agent of the present invention, when perhaps having unreacted monomer component or impurity in the reaction soln, also can carry out this precipitation and reclaim and make with extra care.
Liquid crystal orientating agent of the present invention be contain the polyamic acid that is selected from above acquisition or make this polyamic acid dehydration closed-loop and the liquid crystal orientating agent of at least a kind of polymkeric substance of polyimide, use above-mentioned polymkeric substance to be dissolved in organic solvent usually and the solution that forms.Liquid crystal orientating agent can directly use the reaction soln of polyamic acid or polyimide, also can use after the product that reclaim be dissolved in organic solvent again being precipitated by reaction solution.
As this organic solvent,, be not particularly limited so long as the solvent of contained polymer dissolution is got final product.It specifically can exemplify N, dinethylformamide, 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 etc.These solvents can use separately to mix more than a kind or 2 kinds and use.
In addition, even can't make the solvent of polymer dissolution separately, as long as under the prerequisite that polymkeric substance can not be separated out, also can sneak into liquid crystal orientating agent of the present invention.Particularly can make ethyl cellosolve, ethylene glycol butyl ether, ethyl carbitol, butylcarbitol, diethylene glycol monoethyl ether acetate, ethylene glycol, 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, propylene glycol-1-one ether-2-acetic ester, dipropylene glycol, 2-(2-oxyethyl group propoxy-) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactates etc. have the solvent of low surface tension and moderately sneak into.The known homogeneity of filming that can improve like this when coating substrate also is applicable to liquid crystal orientating agent of the present invention.
The solid component concentration of liquid crystal orientating agent of the present invention can be according to the setting of the thickness of liquid crystal orientating membrane to be formed and is suitably changed, and is preferably 1～10 quality %.If less than 1 quality % then be difficult to form the flawless of homogeneous and films, if surpass 10 quality %, the storage stability of solution deterioration sometimes then.
In addition, improve, also can in liquid crystal orientating agent of the present invention, add additives such as silane coupling agent for making the adaptation of filming to substrate.In addition, also can sneak into polymkeric substance of the present invention polyamic acid or polyimide in addition, perhaps add polymkeric substance such as acrylic resin, polyureas, polymeric amide or urethane resinous principle in addition.
Coat substrate after the liquid crystal orientating agent of the present invention of above acquisition filtered, carry out drying again and calcine to form and film,, can form liquid crystal orientating membrane and be used by this coated surface being rubbed or directional process such as illumination.
At this moment, used substrate is not particularly limited so long as the high substrate of transparency gets final product, and can use plastic bases such as glass substrate, vinylformic acid substrate or polycarbonate substrate etc., consider from the angle of the simplification of operation, preferably use the substrate that is formed with the ITO electrode that is used for liquid crystal drive etc.In addition, in the reflection type liquid crystal display element, the substrate of a side can use opaque materials such as silicon chip, and electrode in this case can use light reflecting materials such as aluminium.
As the coating process of liquid crystal orientating agent, can exemplify spin-coating method, print process, ink jet method etc., but consider that from the productivity aspect industrial circle extensively adopts transfer printing, this method is equally applicable to liquid crystal orientating agent of the present invention.
Drying process behind the coating of liquid crystalline directing agent is not necessary, and the coating back time till the calcining preferably comprises drying process when failing to calcine when uncertain or after the coating because of the difference of substrate at once.As long as this drying process makes solvent evaporation to can drying means not being not particularly limited because of cause the filming degree of warpage such as board carrying.Specifically can exemplify 50～150 ℃ of temperature, better be on 80～120 ℃ the hot plate dry 0.5～30 minute, better be 1～5 minute method.
The calcining that has been coated with the substrate of liquid crystal orientating agent can be carried out under 100～350 ℃ arbitrary temp, is preferably 150～300 ℃, more preferably 180～250 ℃.When containing polyamic acid in the liquid crystal orientating agent, change liquid crystal orientating agent of the present invention and indefinite 100% imidization of wanting from the transformation efficiency of polyamic acid to polyimide according to this calcining temperature.But, be preferably under the high temperature more than 10 ℃ of thermal treatment temp of curing than necessary sealing agent in the liquid crystal cell manufacturing processed etc. and calcine.
If filming after the calcining is blocked up, then the current consumption of liquid crystal display device can increase, if thin excessively, then the reliability of liquid crystal display device descends sometimes, and therefore the thickness of filming is preferably 5～300nm, more preferably 10～100nm.
After making the substrate of band liquid crystal orientating membrane by aforesaid method by liquid crystal orientating agent of the present invention, adopt known method to make liquid crystal cell, obtain liquid crystal display device, be liquid crystal display device of the present invention.
Manufacture method to liquid crystal cell is not particularly limited, generally can exemplify with the liquid crystal aligning face of the 1 pair of substrate that is formed with liquid crystal orientating membrane and clamp spacer (spacer), according to the frictional direction that makes liquid crystal orientating membrane is 0～270 ° after requirement is provided with substrate at any angle, use the sealing agent built-in edge, the method that the liquid crystal that reinjects seals.This moment, used spacer was preferably 1～30 μ m, more preferably 2～10 μ m.
The method of enclosing liquid crystal is not particularly limited, for example can exemplifies and to inject the vacuum method of liquid crystal after the liquid crystal cell inner pressure relief that makes, perhaps drip the dripping method of the laggard row sealing of liquid crystal etc.
The liquid crystal display device that adopts liquid crystal orientating agent of the present invention to make has good electrical characteristic, so can form the liquid crystal indicator that is difficult for taking place contrast gradient decline or conditions of streaking, be applicable to TN liquid crystal display device, stn liquid crystal display element, TFT liquid crystal display device, OCB liquid crystal display device, and lateral electric-field type liquid crystal display device, vertical orientation type liquid crystal display device etc. have used the display element of the variety of way of nematic liquid crystal.In addition, by selecting used liquid crystal, can be used for the liquid crystal display device of ferroelectricity or anti-ferroelectricity.
Below, the present invention will be described in more detail to exemplify embodiment, but the present invention is not limited to this.
Embodiment
The explanation of used ellipsis in the present embodiment:
(tetracarboxylic dianhydride)
CBDA:1,2,3,4-tetramethylene tetracarboxylic dianhydride, TDA:3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, PMDA: pyromellitic acid anhydride
(diamines)
3-ABA:3-amino-benzene methylamine (formula [33]), 4-ABA:4-amino-benzene methylamine (formula [32]), 6-ANaMA:6-amino naphthalenes methylamine (formula [38]), 6-DAN:2,6-diaminonaphthalene, 4-APhA:2-(4-aminophenyl) ethamine (formula [34]), 6-ANaEA:2-(6-amino naphthalenes) ethamine (formula [39]), DADOB:1,3-diamino-4-dodecyloxy benzene, DAHOB:1,3-diamino-4-n-Hexadecane oxygen base benzene, DAOOB:1,3-diamino-4-octadecane oxygen base benzene, p-PDA: Ursol D, BAPB:1, two (4-amino-benzene oxygen) benzene of 3-, DDM:4,4 '-diaminodiphenyl-methane, BAPE:1, two (4-aminophenyl) ethane of 2-, DAE:1,2-diaminoethanes, DADPA:4,4 '-diamino-diphenylamine, BAPP:1, two (4-amino-benzene oxygen) pentanes of 5-
(organic solvent)
The NMP:N-N-methyl-2-2-pyrrolidone N-, BCS: ethylene glycol butyl ether, GBL: gamma-butyrolactone, THF: tetrahydrofuran (THF), DMSO: methyl-sulphoxide, DMF:N, dinethylformamide, TFA: trifluoroacetic acid, Et3N: triethylamine, t-BuOH: the trimethyl carbinol
(other)
DPPA: diphenylphosphine acid azide, AcCl: Acetyl Chloride 98Min., Boc: tert-butoxycarbonyl
(synthesis example 1) CBDA/4-ABA
Under the room temperature, 18.83g (0.096 mole) CBDA and 12.22g (0.1 mole) 4-ABA were reacted 5 hours in the NMP of 279g, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, obtains number-average molecular weight and be 12836, weight-average molecular weight is 28165 polyamic acid solution.The mensuration of various molecular-weight average has adopted (strain) セ Application シ ュ ゥ science society system normal temperature gel permeation chromatography (GPC) device (SSC-7200), Shodex corporate system post (KD803,805).In addition, adopt eastern ソ-Co., Ltd.'s system TSK standard polyethylene oxide (molecular weight about 900000,150000,100000,30000) and Port リ マ-ラ ボ ラ ト リ-Co., Ltd.'s system polyoxyethylene glycol (molecular weight about 12000,4000,1000) to make during mensuration and use standard test specimen, calculate number-average molecular weight and weight-average molecular weight as calibration curve.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 2) CBDA/3-ABA
Under the room temperature, 19.22g (0.098 mole) CBDA and 12.22g (0.1 mole) 3-ABA were reacted 5 hours in the NMP of 283g, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 28114, weight-average molecular weight is 45429 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 3) CBDA/4-APhA
Under the room temperature, 19.41g (0.099 mole) CBDA and 13.62g (0.1 mole) 4-APhA were reacted 5 hours in the NMP of 297g, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 7950, weight-average molecular weight is 14498 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 4) CBDA/6-ANaMA
According to the synthetic 6-amino naphthalenes methylamine (6-ANaMA) in the path shown in following (S-1).This 6-amino naphthalenes methylamine is the new compound that document was not put down in writing.
Figure G2009101659956D00261
[operation 1]
Figure G2009101659956D00262
Under the argon gas stream, in 2L glass four-hole boiling flask, add compound (i) (55.0g 220 mmoles), triethylamine (26.6g 260 mmoles) and the trimethyl carbinol (1000mL), stir under the room temperature and make its dissolving.Temperature rise to 50 ℃ in making.Drip diphenylphosphine acid azide (72.3g 260 mmoles)/trimethyl carbinol 100mL therein.With the interior temperature rise to 75 of flask ℃, stirred 4 hours after the dropping.Then, put coldly, the filtrate of thickening filtration gained obtains the 153g concentrated residue.
With column chromatography this concentrated residue is made with extra care (weighting agent: silica dioxide gel, expansion solvent: chloroform), obtain compound (ii) (56.2g, yield: 79.5%).
[operation 2]
Figure G2009101659956D00263
The compound that the aforementioned operation of packing in 1L glass four-hole boiling flask 1 obtains is (56.2g 174 mmoles), dimethyl formamide (220mL) and cupric cyanide (23.4g 261 mmoles) (ii), stirs 1 hour after the interior temperature rise to 85 ℃.Then, in stirring respectively 2 hours and 4 hours under 100 ℃ the temperature and under 145 ℃ the temperature.Then, aforementioned solution is cooled to room temperature, is added in the pure water (1000mL), precipitate is generated.Filter this precipitate, make its drying after the washing.With column chromatography this drying thing is made with extra care (weighting agent: NH silica dioxide gel, expansion solvent: chloroform), obtain (iii) (13.9g yield: 29.8 quality %) of compound.
[operation 3]
Pack in 300mL glass four-hole boiling flask compound (iii) (13.9g 51.8 mmoles) and trifluoroacetic acid (50mL) stir under the room temperature and make its dissolving.Stir below 2 hours postcooling to 5 ℃, add 10% aqueous sodium hydroxide solution (150mL).Then, stirred 1 hour, filter the precipitate that generates, drying.With column chromatography this drying thing is made with extra care (weighting agent: NH silica dioxide gel, launch solvent: normal hexane/chloroform=1/1), again with in the compression leg chromatogram make with extra care (weighting agent: ODS, moving phase: 60% acetonitrile), obtain (iv) (6.0g yield: 69%) of compound.
[operation 4]
Figure G2009101659956D00272
The compound that the aforementioned operation of packing in 300mL teflon system pressurizing vessel 3 obtains is (6.0g 35.7 mmoles), ethanol (100mL), Virahol (100mL) and 28% ammoniacal liquor (16.7mL) and draw Buddhist nun's nickel (1.6g) (iv).Make interior the pressure reach 0.4MPa with hydrogen pressure, the beginning catalytic hydrogenation.Stir 4 hours after-filtration under 40 ℃ temperature, concentrated filtrate obtains the 6.6g crude product.With column chromatography this crude product is made with extra care (weighting agent: MH silica dioxide gel, expansion solvent: chloroform → chloroform/methanol=1/1), obtain 6-ANaMA (3.1g yield: 50%).
With 1H-NMR (400MHz, CDCl 3) gained 6-ANaMA is identified that the result is as follows.
δ7.63-7.55(m，3H)，7.33-7.31(d，1H)，6.69(s，1H)，6.94-6.92(dd，1H)，3.95(s，2H)，3.81(s，2H)，1.63(s，2H)
Then, with above-mentioned same, reaction is 5 hours in the NMP of 6-ANaMA at 25g that makes 1.14g (0.00582 mole) CBDA and 1.03g (0.006 mole) gained under the room temperature, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 18935, weight-average molecular weight is 39763 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 5) CBDA/6-ANaEA
According to path shown below Synthetic 2-(6-amino naphthalenes) ethamine (6-ANaEA).This 2-(6-amino naphthalenes) ethamine is the new compound that document is not put down in writing.
Figure G2009101659956D00281
Under the argon gas stream, in 2L glass eggplant type flask, add aluminum chloride (1.11 moles of 147.6g) and oil of mirbane (1000mL), stir under the room temperature, dissolving.Add Acetyl Chloride 98Min. (1.11 moles of 79.0mL) and oil of mirbane (500mL) therein, stir after 20 minutes ice-cold under the room temperature.This solution is designated as solution P.
Under the argon gas stream, 2-methylnaphthalene of in 3L glass four-hole boiling flask, packing into (1.01 moles of 150g) and oil of mirbane (750mL), ice-cold (3 ℃ of temperature).Drip above synthetic solution P therein, after 1 hour, be added in the frozen water in 3 ℃～5 ℃ stirrings.To the organic layer separatory, and the organic phase that water layer extracts gained is merged with chloroform (300mL * 3), use pure water (500mL), saturated sodium bicarbonate aqueous solution (500mL) and saturated aqueous common salt (500mL) to wash again successively.With concentrating behind the anhydrous sodium sulfate drying, obtain thick resultant (vi) (167g).Should (vi) be directly used in operation 2 by thick resultant.
[operation 2]
Figure G2009101659956D00291
Pack in 1L glass the eggplant type flask 48% caustic soda aqueous solution (302g) and frozen water (430g), dripping bromine (1.19 moles of 190.1g) therein under ice-cold state stirred 30 minutes.This solution is designated as solution Q.
(vi) (55g 299 mmoles) and 1,4-diox (760mL) is heated to 39 ℃ to the thick resultant that the operation of packing in 2L glass four-hole boiling flask 1 obtains, and drips solution Q therein.At this moment, slowly heat release of reaction soln.After dripping end, stirred ice-cold (4 ℃) 20 minutes in 60 ℃.After dripping concentrated hydrochloric acid (285mL) therein, add Sodium Nitrite (74g), with THF (1000mL) extraction organic layer.With merge from the organic phase that water layer extracts gained with THF (500mL), with saturated aqueous common salt (300mL * 6) washing, use anhydrous sodium sulfate drying, concentrated, obtain thick resultant (97g).With chloroform the thick resultant of gained is carried out slurry washing, obtain compound (vii) (31g 167 mmoles).
[operation 3]
Figure G2009101659956D00292
(vii) (0.77 mole of 143g) and ethanol (2000mL) add the vitriol oil (14mL) to the compound that the operation of packing in 3L glass four-hole boiling flask 2 obtains again, are warming up to 70 ℃.In reaction process, divide 2 times again and add vitriol oil 6mL and 20mL, stirred 72 hours.This solution is cooled to after the room temperature concentrates, add ethyl acetate.With saturated aqueous common salt, saturated sodium bicarbonate aqueous solution and saturated aqueous common salt gained solution is washed successively, organic layer concentrates after with anhydrous sodium sulfate drying, obtains thick resultant (viii) (162g 86% purity).This thick resultant is directly used in operation 4.
[operation 4]
Figure G2009101659956D00293
Under the argon gas stream, the thick resultant that obtains in operation 3 in the 2L eggplant type flask (viii) adds 1 in (154g 721 mmoles), 2-ethylene dichloride (770mL), dissolving.Add 5 therein, 5-dimethyl-N, N '-dibromo glycolylurea (108g 377 mmoles) and AIBN (0.6 mole of % of 629mg) post-heating refluxes.Reflux after 1 hour, add 5,5-dimethyl-N, N '-dibromo glycolylurea (10.8g 37.8 mmoles) and AIBN (72.0mg) refluxed 2 hours again.After being cooled to room temperature, add S-WAT (70g), sodium bicarbonate (30g) and pure water, separate water layer and organic layer.Then, will merge,, obtain thick resultant (ix) (231g 78% purity) with concentrating behind the anhydrous sodium sulfate drying with the organic phase and the organic layer of chloroform from water layer extraction gained.This thick resultant is directly used in operation 5.
[operation 5]
Figure G2009101659956D00301
Under the argon gas stream, the ethanol of in the 2L four-hole boiling flask, packing into (800mL), each therein a small amount of sodium Metal 99.5 (20.0g 870 mmoles) that adds, dissolving.After adding diethyl malonate (132mL 869 mmoles) therein, stirred 1 hour in 50 ℃.Behind THF (500mL) solution of the thick resultant (ix) (232g 791 mmoles) that dropping operation 4 obtains in this solution, stirred 1 hour in 70 ℃.Add pure water after this solution is cooled to room temperature, remove ethanol and THF again under reduced pressure.Add chloroform (1500mL) therein and extract,, concentrate, obtain thick resultant (302g) with using anhydrous sodium sulfate drying after the saturated common salt water washing.With column chromatography this thick resultant is made with extra care (weighting agent: silica dioxide gel, expansion solvent: normal hexane/chloroform=1/1), obtain compound (x) (205g 551 mmoles 70%).
[operation 6]
Figure G2009101659956D00302
Compound (x) (205g 551 mmoles) and THF (400mL) that the operation of packing in the 2L four-hole boiling flask 5 obtains add 10% aqueous sodium hydroxide solution (400mL) again, stir 3 hours in 57 ℃.The ice-cold back of this solution is added concentrated hydrochloric acid (150mL) and THF (500mL), extract organic layer behind the separatory.Merge the organic phase from 2 gained of water layer extraction, again this organic phase and above-mentioned organic layer are merged, wash,, obtain thick resultant (xi) (215g) with concentrated behind the anhydrous sodium sulfate drying with saturated aqueous common salt with the THF of the THF of 200mL and 100mL.Should be directly used in operation 7 by thick resultant.
[operation 7]
Figure G2009101659956D00311
The thick resultant (x) that the operation of packing in the 2L eggplant type flask 6 obtains (215g) and DMSO (1000mL), in 100 ℃ of stirrings 1 hour.Behind this solution of concentrating under reduced pressure, carry out slurry washing, obtain compound (xii) (63g 256 mmoles) with chloroform.
Figure G2009101659956D00312
Under the argon gas stream, the compound (xii) (63g 256 mmoles) and the trimethyl carbinol (2000mL) that the operation of packing in the 3L four-hole boiling flask 7 obtains add triethylamine (90mL) again, stir 30 minutes.Adding DPPA (126mL 584 mmoles) back therein refluxed 120 hours.This solution of concentrating under reduced pressure adds ethyl acetate and pure water therein, and organic layer is extracted.With this organic layer and with chloroform the organic phase that water layer extracts gained is merged,, obtain thick resultant (204g) with concentrating behind the anhydrous magnesium sulfate drying.With column chromatography this thick resultant is made with extra care (weighting agent: silica dioxide gel, expansion solvent: chloroform/ethyl acetate=50/1 → 10/1), carry out recrystallization with methyl alcohol again, obtain compound (xiii) (61g 159 mmoles 61%).
[operation 9]
Figure G2009101659956D00313
Behind the compound (xiii) (31g 81 mmoles) that the operation of packing in the 500mL eggplant type flask 8 obtains, while carry out the ice-cold trifluoroacetic acid (150mL) that adds.This solution of concentrating under reduced pressure adds pure water (200mL) again, and is ice-cold.Then, add strong aqua (50mL), filter the solid of separating out.Make the gained solid suspension in ion exchanged water (250mL), add diethylamine (10mL), stir 2 hours after-filtration solids under the room temperature, drying under reduced pressure (60 ℃ of 1mmHg) obtains thick resultant (16.5g).Then, make this thick resultant be suspended in ion exchanged water (200mL), add diethylamine (10mL), stir 2 hours after-filtration solids under the room temperature, drying under reduced pressure (60 ℃ of 1mmHg) obtains 6-ANaEA (13.5g 72 mmoles 89%).
With 1H-NMR (DMSO-d 6) and 13C-NMR (DMSO-d 6) gained 6-ANaEA is identified that the result is as follows.
1H-NMR(DMSO-d 6)δ7.50(d，J＝8.8Hz，1H)，7.41(d，J＝8.8Hz，1H)，7.40(s，1H)，7.13(dd，J＝8.8，2.0Hz，1H)，6.89(dd，J＝8.8，2.0Hz，1H)，6.77(d，J＝8.8，2.0Hz，1H)；
13C-NMR(DMSO-d 6)δ146.0，133.5，132.6，128.0，127.5，126.4，125.1，118.4，105.9，44.0，40.3；
MS(MALDI-TOF)185.8
Then, in the NMP at 26g under the room temperature, make 1.14g (0.00582 mole) CBDA and 1.12g (0.006 mole) synthetic 6-ANaEA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 20885, weight-average molecular weight is 38924 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 6) TDA/6-ANaMA
Under the room temperature, in the NMP of 32g, make 1.78g (0.00594 mole) TDA and 1.03g (0.006 mole) 6-ANaMA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 10432, weight-average molecular weight is 19820 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 7) TDA/6-ANaEA
Under the room temperature, in the NMP of 33g, make 1.78g (0.00594 mole) TDA and 1.12g (0.006 mole) 6-ANaEA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 9441, weight-average molecular weight is 15860 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 8) CBDA/p-PDA, 4-ABA (50)
Under the room temperature, in the NMP of 275g, make 19.02g (0.097 mole) CBDA and 5.41g (0.05 mole) p-PDA and 6.11g (0.05 mole) 4-ABA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 11322, weight-average molecular weight is 21775 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 9) CBDA/p-PDA, 6-ANaMA (50)
Under the room temperature, in the NMP of 30g, make 1.47g (0.00752 mole) CBDA and 0.43g (0.004 mole) p-PDA and 0.69g (0.004 mole) 6-ANaMA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 41427, weight-average molecular weight is 86996 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 10) CBDA/p-PDA, 6-ANaEA (50)
Under the room temperature, in the NMP of 30.7g, make 1.49g (0.0076 mole) CBDA and 0.43g (0.004 mole) p-PDA and 0.75g (0.004 mole) 6-ANaEA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 52727, weight-average molecular weight is 109181 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 11) CBDA/4-ABA, DADOB (20)
Under the room temperature, in the NMP of 197g, make 19.22g (0.098 mole) CBDA and 9.77g (0.08 mole) 4-ABA and 5.85g (0.02 mole) DADOB reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 13557, weight-average molecular weight is 26993 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 12) CBDA/p-PDA, 3-ABA (10)
Under the room temperature, in the NMP of 266g, make 18.63g (0.095 mole) CBDA and 9.73g (0.09 mole) p-PDA and 1.22g (0.01 mole) 3-ABA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 15867, weight-average molecular weight is 34665 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 13) TDA/4-ABA (SPI)
Under the room temperature, in the NMP of 238g, make 29.73g (0.099 mole) TDA and 12.22g (0.1 mole) 4-ABA reaction 24 hours, the modulation polyamic acid solution.With NMP this polyamic acid solution of 50g is diluted to 5 quality %, adds diacetyl oxide 18.1g and pyridine 8.4g again, make their reactions 3 hours, modulation soluble polyimide resin solution in 40 ℃ as imidization catalyst.This solution is dropped in the methyl alcohol of 0.6L, filter the gained throw out, drying obtains white soluble polyimide (SPI) resin.According to measuring the molecular weight of the soluble polyimide of gained with the same method of synthesis example 1, consequently, number-average molecular weight is 8127, weight-average molecular weight is 14284.Make this powder of 1g be dissolved in the NMP of 15g and the BCS of 4g, the modulation soluble polyimide is that 5 quality %, BCS are the soluble polyimide solution of 20 quality %, obtains liquid crystal orientating agent.
(synthesis example 14) TDA/4-APhA (SPI)
Under the room temperature, in the NMP of 247g, make 30.03g (0.1 mole) TDA and 13.62g (0.1 mole) 4-APhA reaction 24 hours, the modulation polyamic acid solution.With NMP this polyamic acid solution of 50g is diluted to 5 quality %, adds diacetyl oxide 17.5g and pyridine 8.2g again, make their reactions 3 hours, modulation soluble polyimide resin solution in 40 ℃ as imidization catalyst.This solution is dropped in the methyl alcohol of 0.6L, filter the gained throw out, drying obtains white soluble polyimide (SPI) resin.According to measuring the molecular weight of the soluble polyimide of gained with the same method of synthesis example 1, consequently, number-average molecular weight is 6255, weight-average molecular weight is 15638.Make this powder of 1g be dissolved in the NMP of 15g and the BCS of 4g, the modulation soluble polyimide is that 5 quality %, BCS are the soluble polyimide solution of 20 quality %, obtains liquid crystal orientating agent.
(synthesis example 15) CBDA, TDA (20)/3-ABA, DADOB (10) is (SPI)
Under the room temperature, in the NMP of 201g, make 15.49g (0.079 mole) CBDA, 6.01g (0.02 mole) TDA, 11.00g (0.09 mole) 3-ABA and 2.92g (0.01 mole) DADOB reaction 24 hours, the modulation polyamic acid solution.With NMP this polyamic acid solution of 50g is diluted to 5 quality %, adds diacetyl oxide 21.5g and pyridine 10.0g again, make their reactions 3 hours, modulation soluble polyimide resin solution in 40 ℃ as imidization catalyst.This solution is dropped in the methyl alcohol of 0.6L, filter the gained throw out, drying obtains white soluble polyimide (SPI) resin.According to measuring the molecular weight of the soluble polyimide of gained with the same method of synthesis example 1, consequently, number-average molecular weight is 5145, weight-average molecular weight is 12297.Make this powder of 1g be dissolved in the NMP of 15g and the BCS of 4g, the modulation soluble polyimide is that 5 quality %, BCS are the soluble polyimide solution of 20 quality %, obtains liquid crystal orientating agent.
(synthesis example 16) PMDA/4-ABA
Under the room temperature, in the NMP of 246g, make 21.37g (0.098 mole) PMDA and 12.22g (0.1 mole) 4-ABA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 11552, weight-average molecular weight is 21936 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 17) PMDA/3-ABA
Under the room temperature, in the NMP of 248g, make 21.59g (0.099 mole) PMDA and 12.22g (0.1 mole) 3-ABA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 11922, weight-average molecular weight is 18111 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 18) PMDA/4-APhA
Under the room temperature, in the NMP of 258g, make 21.59g (0.099 mole) PMDA and 13.62g (0.1 mole) 4-APhA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 9645, weight-average molecular weight is 17114 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 19) PMDA/6-ANaMA
Under the room temperature, in the NMP of 17.7g, make 0.85g (0.00388 mole) PMDA and 0.69g (0.004 mole) 6-ANaMA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 22359, weight-average molecular weight is 40162 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 20) PMDA/6-ANaEA
Under the room temperature, in the NMP of 18.3g, make 0.85g (0.00388 mole) PMDA and 0.75g (0.004 mole) 6-ANaEA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 21059, weight-average molecular weight is 37508 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 21) CBDA, PMDA (50)/4-ABA
Under the room temperature, in the NMP of 184g, make 9.81g (0.05 mole) CBDA, 10.36g (0.0475 mole) PMDA and 12.22g (0.1 mole) 4-ABA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 16335, weight-average molecular weight is 39424 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 22) CBDA, PMDA (80)/4-ABA
Under the room temperature, in the NMP of 187g, make 3.92g (0.02 mole) CBDA, 16.79g (0.077 mole) PMDA and 12.22g (0.1 mole) 4-ABA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 13937, weight-average molecular weight is 25928 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 23) CBDA, PMDA (80)/3-ABA
Under the room temperature, in the NMP of 189g, make 3.92g (0.02 mole) CBDA, 17.23g (0.079 mole) PMDA and 12.22g (0.1 mole) 3-ABA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 17695, weight-average molecular weight is 28721 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 24) CBDA, PMDA (80)/4-APhA
Under the room temperature, in the NMP of 195g, make 3.92g (0.02 mole) CBDA, 16.79g (0.077 mole) PMDA and 13.62g (0.1 mole) 4-APhA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 10268, weight-average molecular weight is 19672 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 25) CBDA, PMDA (80)/6-ANaMA
Under the room temperature, in the NMP of 25.7g, make 0.24g (0.0012 mole) CBDA, 0.97g (0.00468 mole) PMDA and 1.03g (0.006 mole) 6-ANaMA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 22329, weight-average molecular weight is 42648 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 26) CBDA, PMDA (80)/6-ANaEA
Under the room temperature, in the NMP of 26.7g, make 0.24g (0.02 mole) CBDA, 0.97g (0.074 mole) PMDA and 1.12g (0.1 mole) 6-ANaEA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 20124, weight-average molecular weight is 34211 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 27) CBDA, PMDA (80)/DDM, 4-ABA (50)
Under the room temperature, in the NMP of 209g, make 3.92g (0.02 mole) CBDA, 16.90g (0.0775 mole) PMDA and 9.91g (0.05 mole) DDM and 6.11g (0.05 mole) 4-ABA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 15092, weight-average molecular weight is 29672 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 28) CBDA, PMDA (80)/DDM, 4-ABA (10)
Under the room temperature, in the NMP of 227g, make 3.92g (0.02 mole) CBDA, 17.01g (0.078 mole) PMDA and 1.22g (0.01 mole) 4-ABA and 17.84g (0.09 mole) DDM reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 16881, weight-average molecular weight is 36179 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 29) CBDA, PMDA (80)/DDM, 6-ANaMA (10)
Under the room temperature, in the NMP of 28g, make 0.24g (0.0012 mole) CBDA, 1.01g (0.00468 mole) PMDA and 1.07g (0.0054 mole) DDM and 0.10g (0.0006 mole) 6-ANaMA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 22778, weight-average molecular weight is 52389 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 30) CBDA, PMDA (80)/DDM, 6-ANaEA (10)
Under the room temperature, in the NMP of 28.4g, make 0.24g (0.0012 mole) CBDA, 1.02g (0.078 mole) PMDA and 1.07g (0.0054 mole) DDM and 0.11g (0.0006 mole) 6-ANaEA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 25778, weight-average molecular weight is 55165 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 31) CBDA, PMDA (80)/BAPB, 4-ABA (70)
Under the room temperature, in the NMP of 217g, make 3.92g (0.02 mole) CBDA, 17.01g (0.078 mole) PMDA and 8.55g (0.07 mole) 4-ABA and 8.77g (0.03 mole) BAPB reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 10732, weight-average molecular weight is 19902 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 32) PMDA/4-ABA, DAHOB (10)
Under the room temperature, in the NMP of 201g, make 20.94g (0.096 mole) PMDA, 11.00g (0.09 mole) 4-ABA and 3.49g (0.01 mole) DAHOB reaction 10 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 7038, weight-average molecular weight is 12695 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 33) CBDA, PMDA (80)/4-ABA, DADPA (30), BAPP (10)
Under the room temperature, in the NMP of 210g, make 3.92g (0.02 mole) CBDA, 17.01g (0.078 mole) PMDA, 7.33g (0.06 mole) 4-ABA, 5.98g (0.03 mole) DADPA and 2.86g (0.01 mole) BAPP reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 12080, weight-average molecular weight is 29113 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 34) CBDA, PMDA (80)/4-ABA, p-PDA (50)
Under the room temperature, in the NMP of 288g, make 3.92g (0.02 mole) CBDA, 16.58g (0.076 mole) PMDA, 6.11g (0.05 mole) 4-ABA and 5.41g (0.05 mole) p-PDA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 13979, weight-average molecular weight is 30055 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 35) CBDA, PMDA (80)/4-ABA, BAPB (10)
Under the room temperature, in the NMP of 198g, make 3.92g (0.02 mole) CBDA, 17.01g (0.078 mole) PMDA, 11.00g (0.09 mole) 4-ABA and 2.92g (0.01 mole) BAPB reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 11943, weight-average molecular weight is 24961 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(synthesis example 36) PMDA/4-ABA: CBDA/4-ABA=8: 2
Mix the synthesis example 1 synthetic liquid crystal orientating agent of 20 quality % and the synthesis example 16 synthetic liquid crystal orientating agents of 80 quality %, obtain liquid crystal orientating agent.
(synthesis example 37) TDA/p-PDA, DAOOB (10) (SPI)
In 50 ℃, in the NMP of 247g, make 30.03g (0.1 mole) TDA, 9.73g (0.09 mole) p-PDA and 3.77g (0.01 mole) DAOOB reaction 24 hours, the modulation polyamic acid solution.With NMP this polyamic acid solution of 50g is diluted to 5 quality %, adds diacetyl oxide 17.6g and pyridine 8.2g again, make their reactions 3 hours, modulation soluble polyimide resin solution in 40 ℃ as imidization catalyst.This solution is dropped in the methyl alcohol of 0.6L, filter the gained throw out, drying obtains white soluble polyimide (SPI) resin.According to measuring the molecular weight of the soluble polyimide of gained with the same method of synthesis example 1, consequently, number-average molecular weight is 13430, weight-average molecular weight is 26952.Make this powder of 1g be dissolved in the γ-BL of 15g and the BCS of 4g, the modulation soluble polyimide is that 5 quality %, BCS are the soluble polyimide solution of 20 quality %, obtains liquid crystal orientating agent.
(synthesis example 38) TDA/p-PDA, DAOOB (10) be (SPI): CBDA, PMDA (50)/4-ABA=2: 8
Mix the synthesis example 37 synthetic liquid crystal orientating agents of 20 quality % and the synthesis example 21 synthetic liquid crystal orientating agents of 80 quality %, obtain liquid crystal orientating agent.
(relatively synthesis example 1) CBDA/p-PDA
Under the room temperature, in the NMP of 334g, make 18.24g (0.093 mole) CBDA and 10.81g (0.1 mole) p-PDA reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 72383, weight-average molecular weight is 180395 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(relatively synthesis example 2) CBDA/BAPB
Under the room temperature, in the NMP of 271g, make 18.63g (0.095 mole) CBDA and 29.23g (0.1 mole) BAPB reaction 10 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 25 126, weight-average molecular weight is 50853 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(relatively synthesis example 3) CBDA, PMDA (80)/DDM
Under the room temperature, in the NMP of 226g, make 3.92g (0.02 mole) CBDA, 16.14g (0.074 mole) PMDA and 19.83g (0.1 mole) DDM reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 25316, weight-average molecular weight is 54214 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(relatively synthesis example 4) CBDA/6-DAN
Under the room temperature, in the NMP of 31.7g, make 1.49g (0.095 mole) CBDA and 1.27g (0.1 mole) 6-DAN reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 18669, weight-average molecular weight is 35820 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(relatively synthesis example 5) CBDA/DDM
Under the room temperature, in the NMP of 349g, make 19.02g (0.097 mole) CBDA and 19.83g (0.1 mole) DDM reaction 5 hours, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, and according to the method determining molecular weight same with synthesis example 1, the result has obtained that number-average molecular weight is 42439, weight-average molecular weight is 80710 polyamic acid solution.Then, adding lean solvent BCS and NMP modulate in this solution, and making polyamic acid is 5 quality %, and BCS is 20 quality %, obtain liquid crystal orientating agent.
(relatively synthesis example 6) PMDA/BAPE
Under the room temperature, in the NMP of 233g, make 19.87g (0.091 mole) PMDA and 21.21g (0.1 mole) BAPE reaction, the modulation polyamic acid solution.Polyreaction is carried out easily and equably, but solution becomes gets gonorrhoea after 5 hours.
(relatively synthesis example 7) CBDA/p-PDA, DAE (50)
Under the room temperature, in the NMP of 245g, make 18.83g (0.096 mole) CBDA, 5.41g (0.05 mole) p-PDA and 3.0g (0.05 mole) DAE reaction, the modulation polyamic acid solution.But, producing white precipitate in the polyreaction, polymerization is not carried out equably.This precipitate does not disappear after stirring 24 hours yet.
(relatively synthesis example 8) CBDA, TDA (20)/p-PDA, DADOB (20)
Under the room temperature, in the NMP of 189g, make 14.71g (0.075 mole) CBDA, 6.01g (0.02 mole) TDA, 9.73g (0.09 mole) p-PDA and 2.92g (0.01 mole) DADOB reaction 5 hours, the modulation polyamic acid solution.With NMP this polyamic acid solution of 50g is diluted to 5 quality %, adds diacetyl oxide 22.3g and pyridine 10.4g again, make their reactions in 40 ℃, but in reaction process, occur insoluble as imidization catalyst.
(embodiment 1)
The liquid crystal orientating agent that uses synthesis example 1 to obtain carries out the evaluation of voltage preserving property, charge storage characteristic, storage stability.The results are shown in table 1.
The evaluation of＜voltage preserving property〉(voltage retention)
Liquid crystal orientating agent is spun on the glass substrate of being with the ITO electrode, after making its dry 5 minutes on 80 ℃ the hot plate, carries out calcining in 30 minutes, separate out filming of thickness 100nm with 220 ℃ heated air circulation type stoves.Then, the friction gear with roller footpath 120mm utilizes Artificial Fibers cloth, under the condition of roller revolution 700rpm, roller speed of feed 10mm/sec, the amount of being pressed into 0.6mm, this coated surface is rubbed, and obtains the substrate of band liquid crystal orientating membrane.
Prepare the substrate of 2 above-mentioned band liquid crystal orientating membranes, after scattering the spacer of 6 μ m on 1 liquid crystal aligning face therein, printing and sealing agent thereon, go up in addition 1 substrate in the face of fitting according to liquid crystal orientating membrane to the requirement of, frictional direction unanimity after, make sealant cures, make dummy cell.Then, utilize the decompression injection method in this dummy cell, to inject liquid crystal MLC-2003 (Japanese メ Le Network corporate system), seal inlet, obtain twisted nematic liquid crystals (twist nematic liquid crystal) unit.Under polarizing microscope, this unit is observed, found that liquid crystal is directed equably.
Under 23 ℃ temperature, this twisted nematic liquid crystals box is applied the voltage of 4V, last 60 μ s, voltage behind the mensuration 16.67ms, keep degree to calculate voltage and [adopt (strain) Japan テ Network ニ カ system VHR-1 voltage retention determinator as voltage retention, with voltage: ± 4V, the pulse duration: 60 μ s, the setting of (flame period) 16.67ms of flame phase is measured].In addition, under 60 ℃ temperature, carry out same mensuration.
The evaluation of＜charge storage characteristic〉(apply volts DS after retained voltage)
Under 23 ℃ temperature, the twisted nematic liquid crystals box of having measured the voltage retentivity applied 60 minutes stack direct current 3V voltage ± square wave of 3V/30Hz, utilize the optical flicker elimination method to measure to cut off the instant retained voltage that residues in the liquid crystal cell behind the direct current 3V voltage.
The evaluation of＜storage stability 〉
Preserve liquid crystal orientating agent down at 23 ℃ and-20 ℃, confirm to have or not after 3 months and separate out.
(embodiment 2～37)
The liquid crystal orientating agent of the present invention that adopts synthesis example 2～38 to obtain similarly to Example 1, makes liquid crystal cell.Under polarizing microscope, this unit is observed, confirmed that liquid crystal is directed equably.Similarly to Example 1, voltage retention, stored charge characteristic, the storage stability of this liquid crystal cell are estimated.The results are shown in table 1 described later.
(comparative example 1～5)
Adopt the relatively liquid crystal orientating agent of synthesis example 1～5 acquisition, carried out evaluation similarly to Example 1.It the results are shown in table 1 described later.
Liquid crystal orientating agent in the comparative example 1 was separated out after 3 months.The voltage retention of the liquid crystal orientating agent of comparative example 2 is lower, and relatively synthesis example 3 and 4 liquid crystal orientating agents that obtain were separated out after 1 month.The stored charge characteristic of the liquid crystal orientating agent of comparative example 5 is poor.
Table 1
Figure G2009101659956D00421
(embodiment 38)
The liquid crystal orientating agent of the present invention that uses synthesis example 1 to obtain, the UV absorption spectrum of mensuration liquid crystal orientating membrane.The results are shown in Fig. 1.
＜UV absorption spectrometry 〉
Liquid crystal orientating agent is spun on quartz base plate, after making its dry 5 minutes on 80 ℃ the hot plate, carries out 30 minutes calcining, form filming of thickness 100nm with 230 ℃ heated air circulation type stove.Measure the UV absorption spectrum of the substrate of this band liquid crystal orientating membrane with UV-3100PC (SHIMAZU).
(embodiment 39,40)
The liquid crystal orientating agent of the present invention that uses synthesis example 2,3 to obtain carries out the evaluation same with embodiment 38.The results are shown in Fig. 1 described later.
(comparative example 6)
The liquid crystal orientating agent that uses synthesis example 5 relatively to obtain carries out the evaluation same with embodiment 38.Consequently, compare with embodiment 38～embodiment 40, it is big that the absorbancy of 250nm～400nm becomes.
In addition, the UV absorption spectrum is shown in Fig. 1 described later.
The possibility of utilizing on the industry
Manufacturing can be obtained and storage stability is good by liquid crystal orientating agent of the present invention, and electrical characteristics are good Liquid crystal orientating membrane. Therefore, the liquid crystal display cells that adopts liquid crystal orientating agent of the present invention to make can form difficult The liquid crystal indicator of contrast decline and conditions of streaking takes place, and is applicable to TN liquid crystal display cells, STN liquid Crystal display element, TFT liquid crystal display cells, OCB liquid crystal display cells, and lateral electric-field type liquid crystal display unit Part, vertical orientation type liquid crystal display cells etc. have used the display element of the variety of way of nematic crystal. In addition, By selecting used liquid crystal, can be used for the liquid crystal display cells of ferroelectricity or anti-ferroelectricity. In addition, because in the past The absorbance height of liquid crystal orientating membrane in visible light-UV scope, so for a long time the illumination meeting film occurs and decomposes, Cause the liquid crystal display deterioration in characteristics, but liquid crystal orientating agent of the present invention is because the extinction in visible light-UV scope Spend low, so be suitable for strong large-scale tv machine backlight, liquid crystal projector with liquid crystal display cells etc.
Here quoted of the announcement of the full content of Japanese patent application 2005-068290 number specification sheets, claims, accompanying drawing and summary proposing Japanese patent application 2004-132611 number of application on April 28th, 2004 and proposed application on March 11st, 2005 as specification sheets of the present invention.

Claims (2)

1.6-amino naphthalenes methylamine.
(2.2-6-amino naphthalenes) ethamine.
CN200910165995A 2004-04-28 2005-04-27 Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element using liquid crystal orientation agent Pending CN101633621A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2004132611 2004-04-28
JP2004132611 2004-04-28
JP2005068290 2005-03-11

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CNB2005800127196A Division CN100537638C (en) 2004-04-28 2005-04-27 Liquid-crystal aligning agent, liquid-crystal alignment film comprising the same, and liquid-crystal element

Publications (1)

Publication Number Publication Date
CN101633621A true CN101633621A (en) 2010-01-27

Family

ID=38045486

Family Applications (2)

Application Number Title Priority Date Filing Date
CNB2005800127196A Active CN100537638C (en) 2004-04-28 2005-04-27 Liquid-crystal aligning agent, liquid-crystal alignment film comprising the same, and liquid-crystal element
CN200910165995A Pending CN101633621A (en) 2004-04-28 2005-04-27 Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element using liquid crystal orientation agent

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CNB2005800127196A Active CN100537638C (en) 2004-04-28 2005-04-27 Liquid-crystal aligning agent, liquid-crystal alignment film comprising the same, and liquid-crystal element

Country Status (1)

Country Link
CN (2) CN100537638C (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5360376B2 (en) * 2008-03-07 2013-12-04 Ｊｓｒ株式会社 Liquid crystal aligning agent and liquid crystal display element
JP5333454B2 (en) * 2008-11-06 2013-11-06 日産化学工業株式会社 Liquid crystal alignment treatment agent
WO2010074269A1 (en) * 2008-12-26 2010-07-01 日産化学工業株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
WO2011074546A1 (en) * 2009-12-14 2011-06-23 日産化学工業株式会社 Liquid crystal aligning agent and liquid crystal display element using same
CN104169789A (en) * 2012-01-18 2014-11-26 日产化学工业株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
JP2013174860A (en) * 2012-01-24 2013-09-05 Jsr Corp Liquid crystal aligning agent for optical alignment, formation method of liquid crystal alignment film, liquid crystal alignment film and liquid crystal display element
CN104335112A (en) * 2012-03-30 2015-02-04 日产化学工业株式会社 Liquid crystal display element and manufacturing method therefor
TWI527857B (en) * 2014-05-15 2016-04-01 奇美實業股份有限公司 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device
CN106085464B (en) * 2016-06-02 2019-01-15 深圳市华星光电技术有限公司 Alignment film material, the production method of liquid crystal display panel and liquid crystal display panel
WO2018110354A1 (en) * 2016-12-15 2018-06-21 日産化学工業株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using same
KR20200135507A (en) * 2018-03-30 2020-12-02 닛산 가가쿠 가부시키가이샤 Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element
EP3833708A4 (en) * 2018-08-07 2022-05-04 Zymergen Inc. Optically transparent polyimides
CN109266364B (en) * 2018-10-19 2019-07-30 中节能万润股份有限公司 A kind of aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element

Also Published As

Publication number Publication date
CN1946768A (en) 2007-04-11
CN100537638C (en) 2009-09-09

Similar Documents

Publication Publication Date Title
CN100537638C (en) Liquid-crystal aligning agent, liquid-crystal alignment film comprising the same, and liquid-crystal element
JP4840137B2 (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element using the same
CN101589333B (en) Liquid crystal aligning agent, liquid crystal alignment film using the same, and liquid crystal display element
CN101452153B (en) Liquid crystal oriented agent and liquid crystal display element
CN100397159C (en) Liquid crystal orientation agent
CN101836155B (en) Liquid crystal aligning agent, method for forming liquid crystal alignment film and liquid crystal display device
CN102127459B (en) Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device
CN103180294B (en) Diamines, polyimide precursor, polyimide, liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device
CN102031122A (en) Liquid crystal orientation agent, liquid crystal display element, polyamide acids, polyimides, and compound
CN102051186B (en) Liquid crystal aligning agent, liquid crystal display element, polyamide acids, polyimide and compound
CN104220488A (en) Novel diamine, polymer, liquid crystal alignment agent, and liquid crystal alignment film, and liquid crystal display element using same
CN101591544A (en) Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device
CN101671566B (en) Liquid crystal alignment agent and liquid crystal display element
CN102585842B (en) Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device
CN101539687A (en) Liquid crystal alignment agent and liquid crystal display element
CN101634778B (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device
CN101114085A (en) Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device
CN101735824A (en) Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device
CN104380188B (en) Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells
CN101261403A (en) Liquid crystal oriented agent and liquid crystal display element
CN101458427B (en) Liquid crystal oriented agent and liquid crystal display element
CN101458425A (en) Liquid crystal oriented agent and liquid crystal display element
CN101487955B (en) Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element
CN101692144B (en) Liquid crystal aligning agent and liquid crystal display device
CN101256314B (en) Liquid crystal aligning agent and liquid crystal display element

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20100127