CN102893209A - Liquid crystal alignment agent containing polyamic acid ester, and liquid crystal alignment film - Google Patents

Liquid crystal alignment agent containing polyamic acid ester, and liquid crystal alignment film Download PDF

Info

Publication number
CN102893209A
CN102893209A CN2011800240584A CN201180024058A CN102893209A CN 102893209 A CN102893209 A CN 102893209A CN 2011800240584 A CN2011800240584 A CN 2011800240584A CN 201180024058 A CN201180024058 A CN 201180024058A CN 102893209 A CN102893209 A CN 102893209A
Authority
CN
China
Prior art keywords
liquid crystal
formula
acid ester
polyamic acid
aligning agent
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.)
Granted
Application number
CN2011800240584A
Other languages
Chinese (zh)
Other versions
CN102893209B (en
Inventor
作本直树
饭沼洋介
长尾将人
野口勇步
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 CN102893209A publication Critical patent/CN102893209A/en
Application granted granted Critical
Publication of CN102893209B publication Critical patent/CN102893209B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Nonlinear Science (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mathematical Physics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Liquid Crystal (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed is a liquid crystal alignment agent characterised by containing component (A) and component (B). Component (A): a polyamic acid ester which has a repeating group represented by general formula (1), and which fulfils the condition below. Component (B): a polyamic acid which has a repeating group represented by general formula (4). (Condition): In general formula (1), at least one among X1, Y1, A1, A2 has a substituent of at least one structure selected from a group comprising general formula (2) and general formula (3). (In general formula (1), X1 represents a tetravalent organic group, Y1 represents a divalent organic group, R1 represents a C1-5 alkyl group, A1 and A2 independently represent a hydrogen atom or an optionally substituted C1-20 alkyl group or alkenyl group.) (In general formulae (2, 3), D1 and D2 independently represent a protective group which is replaced by hydrogen by heat. B1 represents a single bond or a divalent organic group. In general formula (3), the ester group is bound to a carbon atom.) (In general formula (4), X2 represents a tetravalent organic group, Y2 represents a divalent organic group, and A1 and A2 have the same definition as in general formula (1).

Description

The aligning agent for liquid crystal and the liquid crystal orientation film that contain poly amic acid ester
Technical field
The present invention relates to contain poly amic acid ester and the aligning agent for liquid crystal of polyamic acid and the liquid crystal orientation film that is obtained by this aligning agent for liquid crystal with hot detachment protecting group.
Background technology
The liquid crystal display cells that is used for LCD TV, liquid crystal display etc. is provided for controlling the liquid crystal orientation film of the state of orientation of liquid crystal usually in element.All the time, mainly use the polyimide liquid crystal orientation film that to coat glass substrate etc. and to burn till as the aligning agent for liquid crystal of principal ingredient with the solution of the polyimide precursors such as polyamic acid (polyamic acid) or soluble polyimide as liquid crystal orientation film.
Be accompanied by the high-precision refinement of liquid crystal display cells, require to consider from inhibition that the contrast of liquid crystal display cells is reduced or the reduction of ghost phenomena etc., following characteristic becomes important gradually in the liquid crystal orientation film: namely except embodying excellent liquid crystal aligning and stable tilt angle, also comprise high voltage holding ratio, to by exchanging the inhibition that drives the ghost that causes, less residual charge when applying DC voltage and/or the characteristics such as quick release of the residual charge put aside because of DC voltage.
To the polyimide liquid crystal orientation film, in order to adapt to above-mentioned requirements various schemes have been proposed.For example, as the required short liquid crystal orientation film of time of the ghost disappearance that is caused by DC voltage, proposed to use except polyamic acid and contain the tertiary amine that also contains ad hoc structure the polyamic acid of imide aligning agent for liquid crystal liquid crystal orientation film (for example, refer to Patent Document 1) and use and to contain the specific diamine compound that will have a pyridine skeleton etc. as the liquid crystal orientation film (for example, referring to Patent Document 2) of the aligning agent for liquid crystal of the soluble polyimide of raw material etc.In addition, high and by the ghost that DC voltage the causes short liquid crystal orientation film of required time that disappears as voltage retention, proposed to use the liquid crystal orientation film (for example, referring to Patent Document 3) of aligning agent for liquid crystal of the compound of the compound that has a tertiary amine groups in the compound that has an acid anhydride in the compound that except polyamic acid or its imide amination polymer etc., also contains being selected from of minute quantity and have a carboxylic acid group in the molecule, the molecule and the molecule.
In addition, excellent as liquid crystal aligning, voltage retention is high, ghost is few, reliability is excellent and show the liquid crystal orientation film of high tilt angle, the known liquid crystal orientation film that has used the aligning agent for liquid crystal that contains polyamic acid or its imide amination polymer, described polyamic acid makes (for example, referring to Patent Document 4) by tetracarboxylic dianhydride and the specific diamine compound of the tetracarboxylic dianhydride with ad hoc structure and cyclo-butane.In addition, as occur in the liquid crystal display cells that suppresses the transverse electric field drive pattern by exchanging the method that drives the ghost that causes, proposed to use liquid crystal aligning good and with the method (referring to Patent Document 5) of the large specific liquid crystal orientation film of the interaction of liquid crystal molecule.
But the LCD TV of giant-screen and fine becomes main body in recent years, and is more and more stricter to the requirement of ghost, and requires to have the characteristic that can tolerate long-term use under the environment for use of harshness.Simultaneously, it is higher to require gradually employed liquid crystal orientation film and liquid crystal orientation film in the past to compare reliability, many characteristics for liquid crystal orientation film also are not only to require initial characteristic good, even also can keep good characteristic after also requiring for example to be exposed to for a long time under the high temperature.
On the other hand, there is report to claim, as the component of polymer that consists of the polyimide aligning agent for liquid crystal, because poly amic acid ester can the heat treated because of with its imidizate the time cause the reduction of molecular weight, so the orientation stability of liquid crystal and reliability excellent (referring to Patent Document 6).But poly amic acid ester has the problems such as specific insulation height, the residual charge when applying DC voltage are many usually, but not yet knows the method for the characteristic of the aligning agent for liquid crystal that improves the polyimide that contains described poly amic acid ester.
The prior art document
Patent documentation
Patent documentation 1: Japanese patent laid-open 9-316200 communique
Patent documentation 2: Japanese patent laid-open 10-104633 communique
Patent documentation 3: Japanese patent laid-open 8-76128 communique
Patent documentation 4: Japanese patent laid-open 9-138414 communique
Patent documentation 5: Japanese patent laid-open 11-38415 communique
Patent documentation 6: Japanese Patent Laid-Open 2003-26918 communique
Summary of the invention
As the method for the characteristic of improving the above-mentioned aligning agent for liquid crystal that contains poly amic acid ester, the present invention's be conceived to mix aligning agent for liquid crystal of polyamic acid of poly amic acid ester and electrical characteristics aspect excellence.But the described liquid crystal orientation film that is made by the aligning agent for liquid crystal of mixed poly amic acid ester and polyamic acid is all can't be satisfactory aspect liquid crystal aligning and the electrical characteristics.
Namely, the liquid crystal orientation film that is made by the aligning agent for liquid crystal that contains poly amic acid ester and polyamic acid except causing the gonorrhoea phenomenon, the generation of the ghost that voltage retention reduces, caused by accumulating of DC voltage when also occuring at high temperature to use film and unusual by exchanging the generation that drives the ghost that causes etc.
The object of the present invention is to provide a kind of aligning agent for liquid crystal that contains poly amic acid ester and polyamic acid, it is all good and do not have a liquid crystal orientation film with transparency of gonorrhoea that it can make liquid crystal aligning and electrical characteristics.
According to the inventor's research, the liquid crystal orientation film that is formed by the aligning agent for liquid crystal that contains poly amic acid ester and polyamic acid is analyzed, results verification to the film Surface Creation trickle concavo-convex.But, the inventor finds, the poly amic acid ester that has ad hoc structure with the functional group that under the effect of heat, is replaced by hydrogen atom as described below by use, the micro concavo-convex that can significantly suppress the film Surface Creation, the inventor also finds, when reducing the micro concavo-convex of described film Surface Creation, contain the above-mentioned shortcoming that the aligning agent for liquid crystal of poly amic acid ester and polyamic acid has and be eliminated.
And then, Knowledge Discovery according to the inventor, when the poly amic acid ester of above-mentioned functional group with being replaced by hydrogen atom under the effect of heat is high molecular, dissolubility in organic solvent is also good, also can make the lower aligning agent for liquid crystal of viscosity when in organic solvent, containing the described aligning agent for liquid crystal that contains poly amic acid ester with high concentration, thus, can easily make liquid crystal orientation film by for example ink-jet method, also can easily make the large liquid crystal orientation film of thickness.
Like this, the present invention is based on above-mentioned knowledge and the invention finished, comprises following technology contents.
1. an aligning agent for liquid crystal is characterized in that, contains following (A) composition and (B) composition.
(A) composition: have the poly amic acid ester of the repetitive of following formula (1) expression, and satisfy the poly amic acid ester of each condition in following (i)～(iii).
[changing 1]
Figure BDA00002403104200041
(in the formula, X 14 valency organic groups, Y 1The divalent organic group, R 1The alkyl of carbon number 1～5, A 1And A 2Alkyl, alkenyl, the alkyl that maybe can have independently respectively substituent carbon number 1～20 for hydrogen atom)
(i) X of formula (1) 1, Y 2Or the two has 1 valency or the divalent substituting group that is selected from least a structure in following formula (2) and (3).
The (ii) A of formula (1) 1, A 2Or the two has 1 valency or the divalent substituting group that is selected from least a structure in following formula (2) and (3).
The (iii) X of formula (1) 1, Y 2Or the two has 1 valency or the divalent substituting group that is selected from least a structure in following formula (2) and (3), and A 1, A 2Or the two has 1 valency or the divalent substituting group that is selected from least a structure in following formula (2) and (3).
[changing 2]
Figure BDA00002403104200042
(the D of formula (2) and formula (3) 1And D 2It is respectively the protecting group that under the effect of heat, is replaced by hydrogen atom.B 1Singly-bound or divalent organic group.Wherein, the atom of the ester group institute bonding in the formula (3) is carbon atom)
(B) composition: the polyamic acid with repetitive of following formula (4) expression.
[changing 3]
Figure BDA00002403104200043
(in the formula, X 24 valency organic groups, Y 2The divalent organic group, A 1And A 2With the A in the formula (1) 1And A 2Define identical)
2. as above-mentioned 1 described aligning agent for liquid crystal, it is characterized in that, (A) content of composition and (B) content of composition count 1/9～9/1 with mass ratio A/B.
3. as above-mentioned 1 or 2 described aligning agent for liquid crystal, it is characterized in that, described (A) composition and (B) the total content of composition be 1～10 quality % with respect to organic solvent.
4. such as aligning agent for liquid crystal as described in each in above-mentioned 1～3, it is characterized in that protecting group D 1It is at least a group that is selected from tert-butoxycarbonyl and 9-fluorenyl methoxy carbonyl.
5. such as aligning agent for liquid crystal as described in each in above-mentioned 1～4, it is characterized in that protecting group D 2It is the tert-butyl group.
As above-mentioned 1～5 in each described aligning agent for liquid crystal, it is characterized in that (A) composition is to have the substituent poly amic acid ester that is selected from least a representation in following formula (5) and (6).
[changing 4]
Figure BDA00002403104200051
(in the formula (5), B 2Singly-bound or divalent organic group, R 2, R 3, R 4Be 1 valency organic group of hydrogen atom or carbon number 1～20 independently respectively)
[changing 5]
(in the formula (6), B 3Singly-bound or divalent organic group.Wherein, the atom of the tert-butoxycarbonyl institute bonding expressed of formula (6) is carbon atom)
As above-mentioned 1～6 in each described aligning agent for liquid crystal, it is characterized in that (A) composition is the Y of formula (1) 1The substituent poly amic acid ester that has at least a representation in the formula of being selected from (5) and (6) in the structure.
As above-mentioned 1～7 in each described aligning agent for liquid crystal, it is characterized in that (A) composition is the A of formula (1) 1, A 2Or the two has the substituent poly amic acid ester of at least a representation in the formula of being selected from (5) and (6).
As above-mentioned 1～8 in each described aligning agent for liquid crystal, it is characterized in that (A) composition is the Y of formula (1) 1Poly amic acid ester for the structure of following formula (7) expression.
[changing 6]
(in the formula, R 5It is the divalent organic group of singly-bound or carbon number 1～20.R 6It is at least a structure that is selected from formula (5) and (6).A is 1～4 integer)
Each described aligning agent for liquid crystal in 10 as above-mentioned 1～9 is characterized in that (A) composition is the Y of formula (1) 1Poly amic acid ester with at least a structure that is selected from the structure that following formula represents.
[changing 7]
Figure BDA00002403104200062
11. as above-mentioned 1～10 in each described aligning agent for liquid crystal, it is characterized in that, in above-mentioned formula (1) and (4), X 1And X 2Structure respectively independently for being selected from least a in the structure that is expressed from the next.
[changing 8]
Figure BDA00002403104200071
12. as above-mentioned 1～11 in each described aligning agent for liquid crystal, it is characterized in that, in the formula (4), Y 2For being selected from least a of structure that following formula represents.
[changing 9]
Figure BDA00002403104200072
13. a liquid crystal orientation film is characterized in that, is coated with in above-mentioned 1～12 each described aligning agent for liquid crystal and burns till and obtain.
14. a liquid crystal orientation film is characterized in that, is coated with each described aligning agent for liquid crystal in above-mentioned 1～12, burn till, and the irradiation polarization ultraviolet ray and obtain.
By the present invention, a kind of surperficial micro concavo-convex of the liquid crystal orientation film that can reduce to make is provided, the liquid crystal of the ghost reduction that the interchange driving causes etc. and the interfacial characteristics of liquid crystal orientation film are enhanced, and residual etc. the electrical characteristics of voltage retention, ion concentration and DC voltage also are enhanced the aligning agent for liquid crystal of Reliability Enhancement.
In addition, viscosity is also lower when containing aligning agent for liquid crystal of the present invention with high concentration in the organic solvent, thus, can easily make liquid crystal orientation film by for example ink-jet method, also can easily make the large liquid crystal orientation film of thickness.
Among the present invention, has poly amic acid ester with the ad hoc structure of the functional group that under the effect of heat, is replaced by hydrogen atom by use, the shortcoming that the fine aligning agent for liquid crystal concavo-convex, that contain poly amic acid ester and polyamic acid that can reduce to generate on the described film surface why has is that assorted meeting is eliminated still and understands, but the inventor thinks following reason.
Namely, be dissolved in the liquid crystal orientation film that forms after the desolventizing the aligning agent for liquid crystal of organic solvent from poly amic acid ester and polyamic acid, although with the lower poly amic acid ester of polyamic acid phase specific surface free energy more multidigit in the surface, but because causing, poly amic acid ester and polyamic acid be separated, form the condensed matter of polyamic acid in mutually or form the condensed matter of poly amic acid ester in mutually at polyamic acid at poly amic acid ester, become thus on the film surface and have in a large number trickle concavo-convex films.
Relative with it, in the aligning agent for liquid crystal of the present invention, by using the above-mentioned poly amic acid ester that has with the ad hoc structure of the functional group that under the effect of heat, is replaced by hydrogen atom, when desolventizing from this aligning agent for liquid crystal, formation liquid crystal orientation film, being separated of poly amic acid ester and polyamic acid promoted, poly amic acid ester does not mix with polyamic acid and exists at the film near surface, and polyamic acid does not mix with poly amic acid ester on the inner and substrate interface at film and exists.
Like this, can not form on the surface of the liquid crystal orientation film that makes by being separated of poly amic acid ester and polyamic acid cause concavo-convex, thereby become level and smooth surface, the gonorrhoea of the film that is caused by concavo-convex generation also reduces.And, think because the poly amic acid ester of orientation stability, reliability excellence is present in the surface, and the polyamic acid of electrical characteristics excellence being present in film inside and electrode interface, the liquid crystal orientation film that therefore possesses the level and smooth surface of no concave-convex has excellent characteristic.
On the other hand, the functional group of the above-mentioned ad hoc structure that poly amic acid ester has is replaced by hydrogen atom with burning till the heating in the processing by imidizate subsequently, therefore, there is not above-mentioned functional group in the liquid crystal orientation film that makes, do not exist by the existence of the functional group of these ad hoc structures and the impact that brings yet, can obtain having the liquid crystal orientation film of characteristic same when not having the poly amic acid ester of functional group of ad hoc structure with use.
Embodiment
＜poly amic acid ester and polyamic acid 〉
The poly amic acid ester that uses among the present invention and polyamic acid are for the polyimide precursor that obtains polyimide, for having the polymkeric substance that can carry out the position of following imidization reaction by heating.
[changing 10]
Figure BDA00002403104200091
[changing 11]
Figure BDA00002403104200092
The poly amic acid ester that contains in the aligning agent for liquid crystal of the present invention and polyamic acid have respectively following formula (1) and following formula (4).
[changing 12]
Figure BDA00002403104200093
In the following formula (1), R 1For carbon number 1～5, better be 1～2 alkyl.Along with the increase of the carbon number of alkyl, the temperature of carrying out imidizate uprises in the poly amic acid ester.Therefore, be easy to viewpoint from the imidizate that causes because of heat and consider R 1The spy is methyl well.In formula (1) and formula (4), A 1And A 2Alkyl, alkenyl or the alkynyl that maybe can have independently respectively substituent carbon number 1～20 for hydrogen atom.As the concrete example of abovementioned alkyl, but exemplified by methyl, ethyl, propyl group, butyl, the tert-butyl group, hexyl, octyl group, decyl, cyclopentyl, cyclohexyl, dicyclohexyl etc.As above-mentioned alkenyl, can exemplify an above CH who to be present in the described alkyl 2-CH 2Structure is substituted by the group of CH=CH structure.More specifically, can exemplified by vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl group, 1,3-butadiene base, 2-pentenyl, 2-hexenyl, cyclopropanyl, cyclopentenyl, cyclohexenyl group etc.As above-mentioned alkynyl, can exemplify an above CH who to be present in the described alkyl 2-CH 2Structure is substituted by the group of C ≡ C-structure, more specifically can exemplify ethinyl, 1-propinyl, 2-propynyl etc.
Abovementioned alkyl, alkenyl, alkynyl need only whole carbon number and are 1～20 and also can have substituting group, can also form ring structure by substituting group.Forming ring structure by substituting group represents between the substituting group or a part of bonding of substituting group and main body framework becomes ring structure.
As this substituent example, can exemplify halogen group, hydroxyl, sulfydryl, nitro, aryl, organic oxygen base, organic sulfenyl, organic silica-based, acyl group, ester group, thioester substrate, phosphate-based, amide group, alkyl, alkenyl, alkynyl.
As substituent halogen group, can exemplify fluorine atom, chlorine atom, bromine atoms, iodine atom.
But as substituent aryl exemplified by phenyl.This aryl can further be replaced by other above-mentioned substituting groups.
Can be represented by-structure that O-R-represents as substituent organic oxygen base.This R can be identical or different, can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.Can also further replace among these R above-mentioned substituting group is arranged.As the concrete example of organic oxygen base, can exemplify methoxyl, ethoxy, propoxyl group, butoxy, amoxy, own oxygen base, heptan oxygen base, octyloxy etc.
Can be represented by-structure that S-R represents as substituent organic sulfenyl.As this R, can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.Can also further replace among these R above-mentioned substituting group is arranged.As the concrete example of organic sulfenyl, can exemplify methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl, heptan sulfenyl, hot sulfenyl etc.
Can be by-Si-(R) as substituent organosilicon alkyl 3The structure of expression represents.This R can be identical or different, can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.Can also further replace among these R above-mentioned substituting group is arranged.As the concrete example of organosilicon alkyl, can exemplify TMS, triethyl silyl, tripropyl silylation, tributyl silylation, three amyl group silylation, three hexyl silane bases, amyl group dimethylsilyl, hexyl dimethylsilyl etc.
As substituent acyl group can by-C(O)-structure that R represents represents.As this R, can exemplify above-mentioned alkyl, alkenyl, aryl etc.Can also further replace among these R above-mentioned substituting group is arranged.As the concrete example of acyl group, can exemplify formoxyl, acetyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl, benzoyl etc.
As substituent ester group can by-C(O) O-R or-structure that OC (O)-R represents represents.As this R, can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.Can also further replace among these R above-mentioned substituting group is arranged.
As substituent thioester substrate can by-C(S) O-R or-structure that OC (S)-R represents represents.As this R, can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.Can also further replace among these R above-mentioned substituting group is arranged.
As substituent phosphate-based can by-OP(O)-(OR) 2The structure of expression represents.This R can be identical or different, can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.Can also further replace among these R above-mentioned substituting group is arranged.
Can be by-C (O) NH as substituent amide group 2, or-C (O) NHR ,-NHC (O) R ,-C (O) N (R) 2The structure that ,-NRC (O) R represents represents.This R can be identical or different, can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.Can also further replace among these R above-mentioned substituting group is arranged.
As substituent aryl, can exemplify the group identical with above-mentioned aryl.This aryl can further be replaced by other above-mentioned substituting groups.
As substituent alkyl, can exemplify the group identical with above-mentioned alkyl.This alkyl can further be replaced by other above-mentioned substituting groups.
As substituent alkenyl, can exemplify the group identical with above-mentioned alkenyl.This alkenyl can further be replaced by other above-mentioned substituting groups.
As substituent alkynyl, can exemplify the group identical with above-mentioned alkynyl.This alkynyl can further be replaced by other above-mentioned substituting groups.
Usually, if introduce bulky structure, then have and reduce amino reactivity and the possibility of liquid crystal aligning, therefore as A 1And A 2Be more preferably the alkyl that hydrogen atom maybe can have substituent carbon number 1～5, the spy is well hydrogen atom, methyl or ethyl.
In above-mentioned formula (1) and formula (4), X 1And X 2Be respectively the organic group of 4 valencys independently, Y1 and Y 2Be the organic group of divalent independently respectively.X 1, X 2Be the organic group of 4 valencys, be not particularly limited.In the polyimide precursor, X 1, X 2Can mix has more than 2 kinds.If enumerate X 1, X 2Concrete example, then can exemplify independently respectively X-1～the X-46 of following expression.Wherein, consider X from the complexity that obtains monomer 1, X 2Better be to be independently respectively X-1, X-2, X-3, X-4, X-5, X-6, X-8, X-16, X-19, X-21, X-25, X-26, X-27, X-28 or X-32.
[changing 13]
Figure BDA00002403104200121
[changing 14]
Figure BDA00002403104200122
[changing 15]
Figure BDA00002403104200123
[changing 16]
Figure BDA00002403104200124
In addition, in formula (1) and (4), Y 1, Y 2Be the organic group of divalent independently respectively, be not particularly limited.In the polyimide precursor, Y 1And Y 2Can mix independently respectively has more than 2 kinds.If enumerate Y 1, Y 2Concrete example, then can exemplify following Y-1～Y-103.
Wherein, in order to obtain good liquid crystal aligning, better be that the diamines that linearity is high is incorporated in the poly amic acid ester, as Y 1Be more preferably the diamines of Y-7, Y-10, Y-11, Y-12, Y-13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y-44, Y-45, Y-46, Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75 or Y-98.In addition, when wanting to improve tilt angle, better be that the diamines that will have the structure of chain alkyl, aromatic ring, aliphatics ring, steroid skeleton or their combination on the side chain is incorporated in the poly amic acid ester, as Y 1Be more preferably the diamines of Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, Y-87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96 or Y-97.By adding these diamines of 1～50 % by mole of whole diamines, can embody arbitrarily tilt angle.
By reducing the specific insulation of polyamic acid, can reduce the ghost that the savings by DC voltage causes, therefore better be that the diamines that will have heteroatomic structure, Ppolynuclear aromatic structure or have a biphenyl backbone is incorporated in the polyamic acid, be more preferably Y-19, Y-23, Y-25, Y-26, Y-27, Y-30, Y-31, Y-32, Y-33, Y-34, Y-35, Y-36, Y-40, Y-41, Y-42, Y-44, Y-45, Y-49, Y-50, Y-51, Y-61, Y-98 or Y-99 as Y2, wherein better is Y-31, Y-40, Y-98 or Y-99.
[changing 17]
Figure BDA00002403104200131
[changing 18]
Figure BDA00002403104200132
[changing 19]
Figure BDA00002403104200141
[changing 20]
[changing 21]
Figure BDA00002403104200143
[changing 22]
Figure BDA00002403104200144
[changing 23]
Figure BDA00002403104200145
[changing 24]
[changing 25]
Figure BDA00002403104200152
[changing 26]
Figure BDA00002403104200153
[changing 27]
Figure BDA00002403104200154
[changing 28]
Figure BDA00002403104200161
[changing 29]
Wherein, the Y in the above-mentioned formula (1) 1It better is the structure of following formula (7) expression.
[changing 30]
Figure BDA00002403104200163
In the formula (7), R 5Be singly-bound or carbon number 1～20, better be 1～12 divalent organic group.The divalent organic group better is alkylidene, arlydene or their combination that can contain ehter bond, amido link, ester bond, thioester bond or thioether bond.R 6It is at least a structure that is selected from following formula (5) and (6).A is 1～4 integer, better is 1 or 2 integer.
In addition, in the following formula (1), better be that the Y1 of formula (1) has at least a structure that is selected from the structure that following formula represents.
[changing 31]
Figure BDA00002403104200171
In addition, wherein, the Y in the above-mentioned formula (4) 2Particularly preferably be selected from least a of structure that following formula represents.
[changing 32]
The manufacture method of＜poly amic acid ester 〉
By the poly amic acid ester of above-mentioned formula (1) expression can by by the tetracarboxylic acid derivatives of following formula (10)～(12) expression any and obtained by the polycondensation reaction of the diamine compound of formula (13) expression.
[changing 33]
[changing 34]
Figure BDA00002403104200183
(in the formula, X 1, Y 1, R 1, A 1And A 2Identical with the definition in the above-mentioned formula (1) respectively)
Poly amic acid ester by above-mentioned formula (1) expression can be by using above-mentioned monomer, and the method for (1)～(3) of expression is synthetic below adopting.
(1) by the synthetic situation of polyamic acid
Poly amic acid ester can be by being synthesized by the polyamic acid esterification that tetracarboxylic dianhydride and diamines obtain.
[changing 35]
Particularly, in the presence of organic solvent, in-20 ℃～150 ℃, better be under 0 ℃～50 ℃, make polyamic acid and esterifying agent reaction 30 minutes～24 hours, better be that reaction was synthesized in 1～4 hour.
Better be can be by purifying and the esterifying agent of easily removing as esterifying agent, can exemplify N, dinethylformamide dimethylacetal, N, dinethylformamide diethyl acetal, N, dinethylformamide dipropyl acetal, N, dinethylformamide neopentyl butyl acetal, N, dinethylformamide di-t-butyl acetal, 1-methyl-3-p-methylphenyl triazenes, 1-ethyl-3-p-methylphenyl triazenes, 1-propyl group-3-p-methylphenyl triazenes, 4-(4, the 6-dimethoxy)-1,3,5-triazine-2 base)-the 4-methyl morpholine hydrochloride etc.The repetitive of the polyamic acid of the addition of esterifying agent with respect to 1 mole is 2～6 molar equivalents preferably.
From the structure adaptability consideration, the solvent that uses in the above-mentioned reaction better is DMF, METHYLPYRROLIDONE or gamma-butyrolacton, and these can use one kind or two or more mixing to use.From being difficult for causing the viewpoint consideration of separating out and obtain easily the high molecular thing of polymkeric substance, the concentration when synthetic better is 1～30 quality %, is more preferably 5～20 quality %.
(2) by the synthetic situation of the reaction of dichloride tetrabasic carboxylic acid diester and diamines
Poly amic acid ester can be synthetic by the polycondensation reaction of dichloride tetrabasic carboxylic acid diester and diamines.
[changing 36]
Figure BDA00002403104200191
Particularly, in the presence of alkali and organic solvent, in-20 ℃～150 ℃, better be under 0 ℃～50 ℃, make dichloride tetrabasic carboxylic acid diester and diamine reactant 30 minutes～24 hours, it is synthetic better to be that reaction came in 1～4 hour.
Described alkali can use pyridine, triethylamine, 4-dimethylaminopyridine etc., in order to make reaction temperature and to carry out, preferred pyridine.From being the amount of easily removing and the viewpoint consideration that obtains easily the high molecular thing, the addition of alkali better is 2～4 times of moles with respect to dichloride tetrabasic carboxylic acid diester.
From monomer and structure adaptability consideration, employed solvent better is METHYLPYRROLIDONE, gamma-butyrolacton in the above-mentioned reaction, and these can use in one kind or two or more mixing.From being difficult for causing the viewpoint consideration of separating out and obtain easily the high molecular thing of polymkeric substance, the concentration when synthetic better is 1～30 quality %, is more preferably 5～20 quality %.In addition, in order to prevent the hydrolysis of dichloride tetrabasic carboxylic acid diester, the solvent that uses in the synthesizing polyamides acid esters better is dehydrated as far as possible, better is in nitrogen atmosphere, prevents sneaking into of external gas.
(3) by the situation of tetrabasic carboxylic acid diester and the acid of diamines synthesizing polyamides
Poly amic acid ester can synthesize by polycondensation tetrabasic carboxylic acid diester and diamines.
[changing 37]
Figure BDA00002403104200201
Particularly, in the presence of condensation agent, alkali and organic solvent, in 0 ℃～150 ℃, better be under 0 ℃～100 ℃, make tetrabasic carboxylic acid diester and diamine reactant 30 minutes～24 hours, it is synthetic better to be that reaction came in 3～15 hours.
Described condensation agent can use triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazine methyl morpholine, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea (TMU) tetrafluoro boric acid ester, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea (TMU) hexafluorophosphoric acid ester, (2,3-dihydroxy-2-sulfo--3-benzoxazolyl) phosphonic acid diphenyl ester etc.The addition of condensation agent better is 2～3 times of moles with respect to the tetrabasic carboxylic acid diester.
Described alkali can use the tertiary amines such as pyridine, triethylamine.From being the amount of easily removing and the viewpoint consideration that obtains easily the high molecular thing, the addition of alkali better is 2～4 times of moles with respect to two amine components.
In addition, in above-mentioned reaction, by adding lewis acid as adjuvant, reaction is effectively carried out.As lewis acid, better be the lithium halides such as lithium chloride, lithium bromide.Lewis acidic addition better is 0～1.0 times of mole with respect to two amine components.
In the synthetic method of above-mentioned 3 kinds of poly amic acid esters, in order to obtain the poly amic acid ester of high molecular, the spy is well the synthetic method of above-mentioned (1) or above-mentioned (2).
The solution of the poly amic acid ester that makes as mentioned above can make polymkeric substance separate out by well-beaten being injected into simultaneously in the Weak solvent.After separating out for several times and cleaning with Weak solvent, at normal temperatures or heat drying, can obtain the powder of sublimed poly amic acid ester.Weak solvent is not particularly limited, can exemplifies water, methyl alcohol, ethanol, hexane, butyl cellosolve, acetone, toluene etc.
The manufacture method of＜polyamic acid 〉
The polyamic acid of above-mentioned formula (4) expression can obtain by the polycondensation reaction of the tetracarboxylic dianhydride who is represented by following formula (14) and the diamine compound that is represented by formula (15).
[changing 38]
Figure BDA00002403104200211
Particularly, in the presence of organic solvent, in-20 ℃～150 ℃, better be under 0 ℃～50 ℃, make tetracarboxylic dianhydride and diamine reactant 30 minutes～24 hours, it is synthetic better to be that reaction came in 1～12 hour.
From monomer and structure adaptability consideration, the organic solvent that uses in the above-mentioned reaction better is DMF, METHYLPYRROLIDONE, gamma-butyrolacton, and these can use one kind or two or more mixing to use.From being difficult for causing the viewpoint consideration of separating out and obtain easily the high molecular thing of polymkeric substance, the concentration of polymkeric substance better is 1～30 quality %, is more preferably 5～20 quality %.
Injecting Weak solvent when the polyamic acid that makes as mentioned above can be by abundant stirring reaction solution makes polymkeric substance separate out and reclaim.In addition, after carrying out that several is separated out and cleaning with Weak solvent, can by at normal temperatures or heat drying obtain the powder of sublimed polyamic acid.Weak solvent is not particularly limited, can exemplifies water, methyl alcohol, ethanol, hexane, butyl cellosolve, acetone, toluene etc.
＜have a poly amic acid ester of hot detachment protecting group 〉
The poly amic acid ester with hot detachment protecting group of putting down in writing among the present invention is the poly amic acid ester with repetitive of above-mentioned formula (1) expression, and is the poly amic acid ester that satisfies each condition in following (i)～(iii).
(i) X of formula (1) 1, Y 2Or the two has 1 valency or the divalent substituting group that is selected from least a structure in following formula (2) and (3).
The (ii) A of formula (1) 1, A 2Or the two has 1 valency or the divalent substituting group that is selected from least a structure in following formula (2) and (3).
The (iii) X of formula (1) 1, Y 2Or the two has 1 valency or the divalent substituting group that is selected from least a structure in following formula (2) and (3), and A 1, A 2Or the two has 1 valency or the divalent substituting group that is selected from least a structure in following formula (2) and (3).
[changing 39]
In the formula (2), D 1Amino protecting group, so long as the functional group that is replaced by hydrogen atom by heating then is not particularly limited.As D 1, better be the structure that efficiently breaks away from reaction under 150 ℃～300 ℃ of the firing temperatures when obtaining liquid crystal orientation film, be more preferably tert-butoxycarbonyl or 9-fluorenyl methoxy carbonyl, particularly preferably tert-butoxycarbonyl.
In the formula (3), B 1Singly-bound or divalent organic group.As the better example of divalent organic group, can exemplify alkylidene, arlydene or their combination that can contain ehter bond, amido link, ester bond, thioester bond or thioether bond.In addition, the atom of the ester group institute bonding in the formula (3) is carbon.
D 1For 1 valency of the structure of the formula (2) of tert-butoxycarbonyl or 9-fluorenyl methoxy carbonyl expression or divalent substituting group can be by the methods that the compound with primary amino radical or secondary amino group that following formula represents and di-tert-butyl dicarbonate are acted in the presence of alkali, or the compound with primary amino radical or secondary amino group and the method that carbonochloridic acid-9-fluorenyl methyl ester acts in the presence of alkali are made, so long as known method then is not particularly limited.
[changing 40]
Figure BDA00002403104200222
To have substituent compound and tetracarboxylic acid derivatives or its precursor and an addition of diamine compound or derivatives thereof by what said method made; synthetic substituent tetracarboxylic acid derivatives and/or the diamines that has with the functional group that under the effect of heat, is replaced by hydrogen atom; with its raw material as poly amic acid ester, obtain thus the poly amic acid ester with hot detachment protecting group of the present invention.
In the formula (3), D 2The protecting group of carboxyl, so long as the functional group that is replaced by hydrogen atom by heating then its structure be not particularly limited.As D 2, better be the structure that efficiently breaks away from reaction under 150 ℃～300 ℃ of the firing temperatures when obtaining liquid crystal orientation film, be more preferably the functional group of following formula (D2-1)～(D2-5), particularly preferably following formula (D2-1).
[changing 41]
Figure BDA00002403104200231
In the formula (D2-2), R 10The alkyl of carbon number 1～5, as concrete example can exemplified by methyl (M e), ethyl, propyl group, butyl, amyl group or the tert-butyl group.
D 2For 1 valency substituting group of the structure of the formula (3) of above-mentioned (D2-1) expression can be by making carboxyl that following formula represents and tert-butyl alcohol reaction method, make the method for chlorocarbonylation compound and tert-butyl alcohol reaction or make carboxyl and the method for tert-butyl group halide reaction makes, so long as known method just is not particularly limited.To have substituent compound and tetracarboxylic acid derivatives or its precursor and diamine compound or its a precursor addition by what said method made; synthetic substituent tetracarboxylic acid derivatives and/or the diamines that has with the functional group that under the effect of heat, is replaced by hydrogen atom; with its raw material as poly amic acid ester, make thus the poly amic acid ester with hot detachment protecting group of the present invention.
[changing 42]
Figure BDA00002403104200241
In the structural unit that poly amic acid ester with hot detachment protecting group of the present invention comprises, the position that is selected from least a substituting group existence of formula (2) and (3) can be the X of formula (1) 1, Y 2, A 1, A 2Any position.Wherein, the viewpoint of the simplicity during from the monomer of the synthetic raw material that consists of poly amic acid ester and the operation complexity of this monomer is considered, better is the Y of formula (1) 1The A that has at least a substituent mode and the formula (1) of the formula of being selected from (2) and (3) in the structure 1, A 2Or the two has at least a substituent mode of the formula of being selected from (2) and formula (3).
Poly amic acid ester with hot detachment protecting group of the present invention also can contain formula (1) expression and at X 1, Y 1, A 1, A 2Any position do not have the substituent structural unit of formula (2) and (3) expression.If the substituent introducing amount of formula (2) and (3) expression is very few, the effect that then suppresses the micro concavo-convex that caused by being separated of poly amic acid ester and polyamic acid is little, therefore, and at X 1, Y 1, A 1, A 2The formula (2) that exists of any position and the structural unit that represents take formula (1) of the substituent containing ratio of (3) expression as benchmark better be more than 0.05, the spy is more than 0.10 well.
In the above-mentioned definition, the structural unit of the formula that for example contains in the poly amic acid ester (1) expression only is " the X of formula (1) 1And Y 1Middle respectively have respectively an a kind of substituting group that is selected from formula (2) and (3), and A 1Or A 2A kind of substituent structural unit that is selected from formula (2) and (3) " time, the substituent containing ratio of the formula in this poly amic acid ester (2) and (3) expression is 4.00.
The substituent concrete example with the functional group that is replaced by hydrogen atom under the effect of heat as above-mentioned formula (2) and (3) expression can exemplify following (D-1)～(D-24), but be not limited to this.
[changing 43]
[changing 44]
Figure BDA00002403104200252
[changing 45]
Figure BDA00002403104200253
[changing 46]
Figure BDA00002403104200261
[changing 47]
Figure BDA00002403104200262
In addition, the substituent diamine compound with the functional group that is replaced by hydrogen atom under the effect of heat that contains as above-mentioned formula (2) and (3) expression can exemplify the diamine compound of following formula (D-25)～(D-35) expression, but be not limited to this.
[changing 48]
Figure BDA00002403104200263
[changing 50]
Figure BDA00002403104200271
[changing 51]
Figure BDA00002403104200272
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention has above-mentioned the have poly amic acid ester of hot detachment protecting group and the form that polyamic acid is dissolved in the solution in the organic solvent.It is 2000～500000 that molecular weight with poly amic acid ester of hot detachment protecting group is haggled over weight-average molecular weight, is more preferably 5000～300000, is 10000～100000 well further.In addition, number-average molecular weight better is 1000～250000, is more preferably 2500～150000, is 5000～50000 well further.
On the other hand, the weight-average molecular weight of polyamic acid better is 2000～500000, is more preferably 5000～300000, is 10000～100000 well further.In addition, number-average molecular weight better is 1000～250000, is more preferably 2500～150000, is 5000～50000 well further.
Molecular weight by making the poly amic acid ester with hot detachment protecting group can further reduce cause because being separated small concavo-convex less than polyamic acid.Difference with weight-average molecular weight of the poly amic acid ester of hot detachment protecting group and polyamic acid better is 1000～200000, is more preferably 5000～150000, and the spy is 10000～100000 well.
In the aligning agent for liquid crystal of the present invention, have the poly amic acid ester of hot detachment protecting group and polyamic acid to contain that ratio (poly amic acid ester/polyamic acid) haggles over quality criteria be 1/9～9/1.Described ratio is more preferably 2/8, and the spy is 3/7～7/3 well.By making described ratio in this scope, can provide all good aligning agent for liquid crystal of liquid crystal aligning and electrical characteristics.
Aligning agent for liquid crystal of the present invention is so long as have the poly amic acid ester of hot detachment protecting group and the solution morphology that polyamic acid is dissolved in organic solvent, and then its manufacture method without limits.The powder of mixed polyamide acid esters and polyamic acid is for example arranged and be dissolved in the method for organic solvent, the method of the powder of mixed polyamide acid esters and the solution of polyamic acid, the method of the solution of mixed polyamide acid esters and the powder of polyamic acid, the method for mixed polyamide acid esters solution and polyamic acid solution.Because even the good solvent of dissolving poly amic acid ester and polyamic acid can not obtain uniform poly amic acid ester-polyamic acid mixed solution simultaneously yet, so be more preferably the method for mixed polyamide acid esters solution and polyamic acid solution.
In addition, when in organic solvent, making poly amic acid ester with hot detachment protecting group and/or polyamic acid, can be the reaction solution itself that makes, also can be with the suitable broad liquid of this reaction of solvent dilution must solution.In addition, when obtaining having the poly amic acid ester of hot detachment protecting group as powder, also can make it be dissolved in the solution that forms in the organic solvent.
The concentration of the poly amic acid ester in the aligning agent for liquid crystal of the present invention and polyamic acid (sometimes being also referred to as polymkeric substance among the present invention) can be according to the setting of the thickness of filming of wanting to form and appropriate change, from forming uniformly flawless viewpoint of filming, better being more than the 1 quality %, better is below the 10 quality % from the viewpoint of the storage stability of solution.
The above-mentioned organic solvent that contains in the aligning agent for liquid crystal of the present invention so long as have the amic acid esters of protecting group of hot detachment and the component of polymer uniform dissolution of polyamic acid, then is not particularly limited.Its concrete example can exemplify N, dinethylformamide, N, N-diethylformamide, N, N-dimethyl acetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, 2-Pyrrolidone, NVP, dimethyl sulfoxide, dimethyl sulfone, gamma-butyrolacton, 1,3-dimethyl-2-imidazolidinone, 3-methoxyl-N, 3-methoxyl-N, N-dimethyl propylene acid amides etc.These can use one kind or two or more mixing to use.In addition, even the independent solvent of dissolve polymer composition equably as long as in the scope that polymkeric substance is not separated out, also can mix with above-mentioned organic solvent.
When in aligning agent for liquid crystal of the present invention, adding silane coupling agent, can before mixed polyamide acid esters solution and polyamic acid solution, make an addition in polyamic acid ester solution, polyamic acid solution or polyamic acid ester solution and the polyamic acid solution.In addition, can be added in poly amic acid ester-polyamic acid mixed solution.Since be the adaptation that improves polymkeric substance and substrate be that purpose is added silane coupling agent, therefore as the adding method of silane coupling agent, better be to be added on the polyamic acid solution that can most be arranged in film inside and substrate interface, after polymkeric substance and silane coupling agent are fully reacted, the method for mixing with the polyamic acid ester solution.Therefore when the addition of silane coupling agent was too much, unreacted reactant caused harmful effect to liquid crystal aligning, when very few, can't embody the adaptation effect, and the solid constituent with respect to polymkeric substance better is 0.01～5.0 % by weight, is more preferably 0.1～1.0 % by weight.
Aligning agent for liquid crystal of the present invention also can comprise to improve the solvent that film uniformity is purpose that is coated with when aligning agent for liquid crystal coated substrate except comprising the organic solvent take dissolve polymer as purpose.Described solvent uses the solvent lower with described organic solvent phase specific surface tension usually.Can exemplify ethyl cellosolve as its concrete example, butyl cellosolve, ethyl carbitol, butyl carbitol, the ethyl carbitol acetic acid esters, ethylene glycol, the 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, single acetic acid propylene glycol ester, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, the single ethylether of propylene glycol-1--2-acetic acid esters, butyl cellosolve acetate, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc.These solvents can be also with more than 2 kinds.
Aligning agent for liquid crystal of the present invention can comprise the various adjuvants such as silane coupling agent and crosslinking chemical.Adding in the situation of silane coupling agent and crosslinking chemical, in order to prevent separating out of polymkeric substance, better is to add before adding to Weak solvent in the aligning agent for liquid crystal.In addition, for burning till the imidizate that effectively carries out poly amic acid ester when filming, also can add imidizate promoter.
Below exemplify the concrete example of silane coupling agent, but operable silane coupling agent is not limited to this in the aligning agent for liquid crystal of the present invention.The amine silane coupling agents such as APTES, 3-(2-amino-ethyl) TSL 8330,3-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, 3-TSL 8330,3-phenyl amino propyl trimethoxy silicane, 3-triethoxysilicane alkyl-N-(1,3-dimethyl-butylidene) propylamine, 3-aminopropyl diethoxymethyl silane; Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, vinyl methyl dimethoxysilane, vinyltriacetoxy silane, vinyl silane triisopropoxide, allyltrimethoxysilanis, to vinyl silane coupling agents such as styryl trimethoxy silanes; The epoxies silane coupling agents such as 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane; The methacrylic silane coupling agents such as 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane; The acrylic compounds silane coupling agents such as 3-acryloxy propyl trimethoxy silicane; The urea groups one type of silane coupling agents such as 3-urea groups propyl-triethoxysilicane; Two (3-(triethoxysilicane alkyl) propyl group) disulfide, two (3-(triethoxysilicane alkyl) propyl group) tetrasulfide sulfides one type of silane coupling agent; 3-sulfydryl propyl group methyl dimethoxysilane, 3-sulfydryl propyl trimethoxy silicane, the 3-caprylyl sulfo--sulfydryl one type of silane coupling agents such as 1-propyl-triethoxysilicane; The isocyanates silane coupling agents such as 3-isocyanate group propyl-triethoxysilicane, 3-isocyanate group propyl trimethoxy silicane; The aldehydes silane coupling agents such as triethoxysilicane alkyl butyraldehyde; Tri-ethoxy silylpropyl methyl carbamate, (3-tri-ethoxy silylpropyl)-carbamates silane coupling agents such as tert-butyl group carbamate.
Below exemplify the concrete example of the imidizate promoter of poly amic acid ester, but operable imidizate promoter is not limited to this in the aligning agent for liquid crystal of the present invention.
[changing 52]
[changing 53]
Figure BDA00002403104200312
D in the above-mentioned formula (B-1)～(B-17) is tert-butoxycarbonyl or 9-fluorenyl methoxy carbonyl respectively independently.In (B-14)～(B-17), there are a plurality of D in the formula, they can be identical or different.
The content of imidizate promoter is so long as in the scope of the effect of the hot-imide that can be promoted poly amic acid ester, then be not particularly limited.If represent its lower limit, with respect to 1 mole at the amic acid esters position of the following formula that contains in the poly amic acid ester (16), better be more than 0.01 mole then, be more preferably more than 0.05 mole, further be more preferably more than 0.1 mole.In addition, the harmful effect that residual imidizate promoter itself is caused each characteristic of liquid crystal orientation film the film after will burning till is controlled at MIN viewpoint and considers, if represent its upper limit, then with respect to 1 mole at the amic acid esters position of following formula contained in the poly amic acid ester of the present invention (16), imidizate promoter better is below 2 moles, be more preferably below 1 mole, further be more preferably below 0.5 mole.
[changing 54]
Figure BDA00002403104200321
When adding imidizate promoter, might carry out imidizate by heating, therefore better be with adding after good solvent and the Weak solvent dilution.
＜liquid crystal orientation film 〉
Liquid crystal orientation film of the present invention be the aligning agent for liquid crystal that will obtain as mentioned above be coated on the substrate, dry, burn till and filming of obtaining, as required to orientation process such as this coated surface rub.
As the substrate of coating aligning agent for liquid crystal of the present invention, so long as the high substrate of the transparency then is not particularly limited, can use the plastic bases such as glass substrate, silicon nitride board, acrylic acid substrate, polycarbonate substrate etc.From the viewpoint of work simplification, better be to use the substrate be formed with for the ITO electrode of liquid crystal drive etc.In addition, in the reflection type liquid crystal display element, can use the opaque materials such as silicon wafer, but only limit to the substrate of a side, the electrode of this moment also can use the reflectorized materials such as aluminium.Coating process as aligning agent for liquid crystal of the present invention can exemplify spin-coating method, print process, ink-jet method etc.
The drying, the firing process that are coated with behind the aligning agent for liquid crystal of the present invention can be selected arbitrarily temperature and time.Usually, in order fully to remove the organic solvent that contains, make its dry 1 minute～10 minutes at 50 ℃～120 ℃, then burnt till 5 minutes～120 minutes at 150 ℃～300 ℃.Therefore the thickness of filming after burning till is not particularly limited, if but excessively thin, then the reliability of liquid crystal display cells can reduce sometimes, and 5～300nm normally better is 10～200nm.
This method of filming as orientation process can exemplify rubbing manipulation, light orientation process method etc., but aligning agent for liquid crystal of the present invention is particularly useful in the situation that adopts light orientation process method.
As the concrete example of light orientation process method, can exemplify the radioactive ray of above-mentioned film coated surface irradiation towards the certain orientation polarization, according to circumstances further under 150～250 ℃ temperature, carry out heat treated, give the method for liquid crystal aligning ability.The wavelength of radioactive ray can use has 100nm～ultraviolet ray and the visible light of 800nm wavelength.Wherein, better be the ultraviolet ray with 100nm～400nm wavelength, the spy is well the ultraviolet ray with 200nm～400nm wavelength.In addition, in order to improve liquid crystal aligning, can when filming substrate, 50～250 ℃ of lower heating shine radioactive ray.Ultraviolet irradiation amount in the above-mentioned orientation process etc. better is 1～10000mJ/cm 2Scope, the spy is 100～5000mJ/cm well 2Scope.
The liquid crystal orientation film that as above obtains can make liquid crystal molecule stably be orientated towards certain orientation.
Embodiment
Below, the present invention will be described in more detail to exemplify embodiment, but the present invention is not limited thereto.
Below, the abbreviation of using in present embodiment and the comparative example and the assay method of each characteristic are as described below.
1,3DMCBDE-Cl:1, two (chlorocarbonyl)-1 of 3-, 3-dimethyl cyclo-butane-2,4-dimethyl dicarboxylate
DA-1: above-mentioned formula (D-25)
BDA:1,2,3,4-butane tetracarboxylic acid dianhydride
CBDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
The NMP:N-N-methyl-2-2-pyrrolidone N-
γ-BL: gamma-butyrolacton
BCS: butyl cellosolve
PAE: poly amic acid ester
PAA: polyamic acid
DA-2: above-mentioned formula (D-29)
DA-3: above-mentioned formula (D-30)
DA-4: above-mentioned formula (D-28)
DA-5: above-mentioned formula (DA-32)
DA-6: the n=5 of above-mentioned formula (DA-35)
DA-7: following formula (DA-7)
DA-8: following formula (DA-8)
DAH-1: following formula (DAH-1)
DAH-2: following formula (DAH-2)
AD-1: following formula (AD-1)
AD-2: following formula (AD-2)
AD-3: following formula (AD-3)
AD-4: following formula (AD-4)
[changing 55]
Figure BDA00002403104200341
[viscosity]
In synthesis example, the viscosity of poly amic acid ester and polyamic acid solution is E type viscosity meter TVE-22H ((East Machine industry society of Toki Sangyo Co., Ltd.) system utilized) under the condition of 25 ℃ of sample size 1.1mL, circular cone type rotor (コ one Application ロ one タ) TE-1 (1 ° 34 ', R24), temperature, measure.
[molecular weight]
In addition, the molecular weight of poly amic acid ester is to adopt GPC(normal temperature gel permeation chromatography) device measures, and calculates number-average molecular weight (below, be also referred to as Mn) and weight-average molecular weight (below, be also referred to as Mw) with polyglycol, polyethylene oxide scaled value.
GPC device: Shodex (Showa Denko K. K) company's system (GPC-101)
Post: Showa Denko K. K's system (series connection of KD803, KD805)
Column temperature: 50 ℃
Eluent: N, and the N'-dimethyl formamide (as adjuvant, lithium bromide-hydrate (LiBrH 2O) be that 30mmol/L, phosphoric anhydride crystallization (O-phosphoric acid) are 10ml/L for 30mmol/L, tetrahydrofuran (THF))
Flow velocity: 1.0ml/ minute
Calibration curve is made and to be used standard sample: (East ソ ー society of eastern Cao company) TSK standard polyethylene oxide processed (weight-average molecular weight (Mw) about 900000,150000,100000,30000) and polymkeric substance laboratory company (Port リ マ ー ラ ボ ラ ト リ ー society) polyglycol processed (peak top molecular weight (Mp) about 12000,4000,1000).For fear of overlap of peaks, measured respectively 2 samples, namely mix 900000,100000,12000,1000 these samples of 4 kinds and mixed 150000,30000,4000 these samples of 3 kinds.
[center line average roughness mensuration]
To obtain through spin coating film on the hot plate of 80 ℃ of temperature dry 5 minutes of aligning agent for liquid crystal, in the heated air circulation type stove of 250 ℃ of temperature, burn till 1 hour, form filming of thickness 100nm.Observe this film surface of filming with atomic force microscope (AFM), and measured the center line average roughness (Ra) on film surface, the flatness on evaluated for film surface.
Determinator: L-follows the trail of probe microscope (SII technology Co., Ltd. (エ ス ア イ ア イ テ Network ノ ロ ジ ー society) system)
[voltage retention]
Aligning agent for liquid crystal is spun on the glass substrate with transparency electrode, through in dry 5 minutes, heated air circulation type stove at 250 ℃ on the hot plate of 80 ℃ of temperature, burning till 60 minutes step, forms filming of thickness 100nm.Across the ultraviolet 100mJ/cm of polarization plates to this coated surface irradiation 254nm 2, obtain the substrate with liquid crystal orientation film.Prepare two substrates with above-mentioned liquid crystal orientation film, after the liquid crystal aligning face of a substrate scatters the granular sept of diameter 6 μ m, with the antiparallel condition of the orientation of two substrates with two substrate in combination, sealing on every side, but stay liquid crystal injecting port, making structure cell interval (cell gap) is the negative crystal born of the same parents of 6 μ m.Vacuum is injected liquid crystal (MLC-2041, Merck ﹠ Co., Inc. (メ Le Network society) system) in this negative crystal born of the same parents at normal temperatures, with the inlet sealing, makes the liquid crystal structure cell.
The voltage retention of the above-mentioned liquid crystal structure cell of following mensuration.
Measure voltage after applying voltage 60 μ s, the 16.67ms of 4V, calculate thus the variation with initial value, with this as voltage retention.During mensuration, the temperature of liquid crystal structure cell is made as 23 ℃, 60 ℃, 90 ℃, is measuring at each temperature.
[ion concentration]
The ion concentration of the above-mentioned liquid crystal structure cell of following mensuration.
The use (East Yang テ of Toyo Corp. Network ニ カ society) 6254 type liquid crystal evaluation of physical property devices are measured.Apply the triangular wave of 10V, 0.01Hz, calculate the area suitable with the ion concentration of gained waveform by the triangle method of approximation, with it as ion concentration.During mensuration, the temperature of liquid crystal structure cell is made as 23 ℃, 60 ℃, is measuring at each temperature.
[interchange that FFS drives the liquid crystal structure cell drives sintering]
On the glass substrate that is formed with fringe field conversion (Fringe Field Switching, hereinafter referred to as FFS) driving electrode, by spin-coating method coating of liquid crystalline alignment agent, described FFS driving electrode is to have ITO electrode as the thickness 50nm of the shape of electrode, have as the silicon nitride of the thickness 500nm of the shape of dielectric film, at the 3rd layer of ITO electrode (electrode width: 3 μ m, electrode gap: 6 μ m, electrode height: fringe field conversion driving electrode 50nm) that has as the comb teeth-shaped of electrode at the second layer at ground floor.After 80 ℃ hot plates make its dry 5 minutes, in 250 ℃ heated air circulation type stove, burnt till 60 minutes, forming thickness is filming of 100nm.Across the ultraviolet 100mJ/cm of polarization plates to this coated surface irradiation 254nm 2, obtain the substrate with liquid crystal orientation film.In addition, film the implementation orientation processing forming too on the glass substrate of column spacer that having of electrode highly is 4 μ m as not being formed with of substrate in opposite directions.
With above-mentioned two substrates as one group, printing and sealing agent on substrate, fit another piece substrate so that liquid crystal orientation film toward each other and direction of orientation be 0 °, then, make sealant cures and make the negative crystal born of the same parents.Inject liquid crystal MLC-2041 (Merck ﹠ Co., Inc. (メ Le Network society) system) by the decompression injection method in this negative crystal born of the same parents, the sealing inlet obtains FFS and drives the liquid crystal structure cell.
Measure this FFS and drive liquid crystal structure cell after the V-T characteristic (voltage-transmission characteristics) under 58 ℃ of temperature, apply 4 hours ± square wave of 4V/120Hz.After 4 hours, cut off voltage, after placing 60 minutes under 58 ℃ the temperature, again measure the V-T characteristic, calculate apply square wave before and after transmissivity become 50% voltage difference.
[evaluation of electric charge Accumulation]
Above-mentioned FFS is driven the liquid crystal structure cell is positioned on the light source, measure V-T characteristic (voltage-transmission characteristics) after, measured and applied ± transmissivity (T under the state of 1.5V/60Hz square wave a).Then, apply ± square wave of 1.5V/60Hz repeats to apply direct current 1V after 10 minutes, makes it drive 30 minutes.Cut off DC voltage, measure through exchanging the transmissivity (T after driving 10 minutes b), according to T bAnd T aDifference calculate the poor of the transmissivity that caused by the voltage that remains in the liquid crystal display cells.
(a.) 1, two (chlorocarbonyl)-1 of 3-, 3-dimethyl cyclo-butane-2, the 4-dimethyl dicarboxylate (1,3DMCBDE-Cl) synthetic
(a-1) tetrabasic carboxylic acid dialkyl group ester synthesis
[changing 56]
Figure BDA00002403104200371
Under stream of nitrogen gas, at the 3L(liter) add the 220g(0.981 mole in the four-hole boiling flask) 1,3-dimethyl cyclo-butane-1,2,3, (compound of formula (5-1) is hereinafter to be referred as 1,3-DM-CBDA), 2200g methyl alcohol (6.87mol for the 4-tetracarboxylic dianhydride, with respect to 1,3-DM-CBDA is 10 times of weight), under 65 ℃, add hot reflux, become uniform solution after 30 minutes.Reaction solution directly adds hot reflux 4 hours 30 minutes and stirs.(hereinafter to be referred as HPLC) measured this reactant liquor by high performance liquid chromatography.
From this reactant liquor, after the distillation desolventizing, add the ethyl acetate of 1301g with the evaporator distillation, be heated to 80 ℃, it was refluxed 30 minutes.Then, be cooled to interior temperature with per 10 minutes 2～3 ℃ speed and reach 25 ℃, keep intact and under 25 ℃, stirred 30 minutes.By filter taking out the white crystals of separating out, and after washing this crystallization 2 times with the ethyl acetate of 141g, by the white crystals of drying under reduced pressure acquisition 103.97g.
According to the result of 1HNMR analysis and X ray analysis of crystal structure, confirming this crystallization is compound (1-1) (the HPLC relative area is 97.5%) (yield is 36.8%).
1H?NMR(DMSO-d6，δppm)；12.82(s，2H)，3.60(s，6H)，3.39(s，2H)，1.40(s，6H).
(a-2) 1,3-DM-CBDE-C1's is synthetic
[changing 57]
Figure BDA00002403104200381
Under stream of nitrogen gas, in the four-hole boiling flask of 3L, add 234.15g(0.81mol) compound (1-1), 1170.77g(11.68mol, 5 times of weight) after the normal heptane, add 0.64g(0.01mol) pyridine, heating is stirred to 75 ℃ under the stirring of magnetic stirring apparatus.Then, with dripping 289.93g(11.68mol in 1 hour) thionyl chloride.Begin immediately foaming after the dropping, drip 30 minutes afterreaction solution becomes of end and get evenly, stopped foaming.Then, directly 75 ℃ lower stir 1 hour 30 minutes after, the inner capacities of utilizing evaporator that the solvent distillation is removed to 40 ℃ of water-baths reaches 924.42g.Be heated to 60 ℃, the dissolving crystallized that distillation is separated out during desolventizing, and by carrying out with per 10 minutes 1 ℃ speed filtrate being cooled to 25 ℃ after thermosol filters insolubles under 60 ℃.Keep intact and, take out the white crystals of separating out by filtering, and wash this crystallization with the normal heptane of 264.21g after 30 minutes 25 ℃ of lower stirrings.By with its drying under reduced pressure, obtain the white crystals of 226.09g.
Then, under stream of nitrogen gas, after the normal heptane of the white crystals of adding 226.09g obtained above and 452.18g, heating is stirred to 60 ℃, makes dissolving crystallized in the four-hole boiling flask of 3L.Afterwards, with per 10 minutes speed cooling and stirring to 25 of 1 ℃ ℃, make crystallization.Keep intact 25 ℃ lower stir 1 hour after, take out the white crystals of separating out by filtering, and after washing this crystallization with the normal hexane of 113.04g, by the white crystals of drying under reduced pressure acquisition 203.91g.According to the 1HNMR analysis result, confirming this crystallization is compound (3-1), namely 1, two (chlorocarbonyl)-1 of 3-, 3-dimethyl cyclo-butane-2, and 4-two dimethyl carbonates (1,3-DM-CBDE-C1) (the HPLC relative area is 99.5%) (yield 77.2%).
1H?NMR(CDCl3,δppm):3.78(s,6H),3.72(s,2H),1.69(s,6H).
(synthesis example 1)
Directly synthesize diamine compound (DA-1) by four steps as follows.
The first step: compound (A5) synthetic
[changing 58]
Figure BDA00002403104200391
In the eggplant type flask of 500mL, sequentially add propargyl amine (8.81g, 160mmol), N, dinethylformamide (112mL), sal tartari (18.5g, 134mmol), be 0 ℃, while stirring to drip the monobromo-acetic acid tert-butyl ester (21.9g, 112mmol) was dissolved in the solution that DMF (80mL) obtains with about 1 hour.After dripping end, making reaction solution is room temperature, stirs 20 hours.Then, by the solids removed by filtration composition, in filtrate, add ethyl acetate 1L, use the water of 300mL to clean 4 times, use the saturated aqueous common salt of 300mL to clean 1 time.Then, use the dried over mgso organic layer, the decompression distillation desolventizing.At last, by at 0.6Torr, 70 ℃ of grease that lower decompression distillation is residual, obtain the colourless liquid N-propargyl aminoacetic acid tert-butyl ester (compound (A5)).The receipts amount is 12.0g, and yield is 63%.
The 2nd step: compound (A6) synthetic
[changing 59]
Figure BDA00002403104200392
In the eggplant type flask of 1L, add the above-mentioned N-propargyl aminoacetic acid tert-butyl ester (12.0g, 70.9mmol), methylene chloride (600mL) makes solution, stir ice-cold on one side, dripped with 1 hour on one side di-tert-butyl dicarbonate (15.5g, 70.9mmol) is dissolved in the solution that methylene chloride (100mL) obtains.After dripping end, making reaction solution is room temperature, stirs 20 hours.After reaction finishes, with the saturated aqueous common salt cleaning reaction solution of 300mL, use dried over mgso.Then, by the decompression distillation desolventizing, obtain weak yellow liquid N-propargyl-N-tert-butoxycarbonyl aminoacetic acid tert-butyl ester (compound (A6)).The receipts amount is 18.0g, and yield is 94%.
The 3rd step: compound (A7) synthetic
[changing 60]
Figure BDA00002403104200401
In the four-hole boiling flask of 300mL, add 2-iodo-4-nitroaniline (22.5g, 85.4mmol), two (triphenylphosphine) palladium chloride (1.20g, 1.71mmol), cupric iodide (0.651g, 3.42mmol), after being replaced into nitrogen, add diethylamine (43.7g, 598mmol), N, dinethylformamide (128mL), ice-cooled stirring on one side, add above-mentioned N-propargyl amino-N-tert-butoxycarbonyl tert-butyl acetate (27.6g, 102mmol) on one side, stirred 20 hours under the room temperature.After reaction finishes, add 1L ethyl acetate, clean 3 times with the aqueous ammonium chloride solution 150mL of 1mol/L, clean 1 time with the saturated aqueous common salt of 150mL, use dried over mgso.Then, the dissolution of solid that will separate out by the decompression distillation desolventizing carries out recrystallization by the hexane that adds 1L in the ethyl acetate of 200mL.This solid of leaching by drying under reduced pressure, obtains yellow solid 2-{3-(N-tert-butoxycarbonyl-N-tert-butoxycarbonyl methylamino)-1-propinyl) }-4-nitroaniline (compound (A7)).The receipts amount is 23.0g, and yield is 66%.
The 4th step: the reduction of compound (A7)
In the four-hole boiling flask of 500mL, add above-mentioned 2-{3-(N-tert-butoxycarbonyl-N-tert-butoxycarbonyl methylamino)-1-propinyl) }-4-nitroaniline (22.0g, 54.2mmol) and ethanol (200g), after being replaced into nitrogen in the system, add palladium carbon (2.20g), hydrogen will be replaced into, 50 ℃ of lower stirrings 48 hours in the system.Reaction is removed palladium carbon by diatomite filtration after finishing, and adds activated charcoal in filtrate, 50 ℃ of lower stirrings 30 minutes.Then, the filter activity charcoal, organic solvent is removed in decompression distillation, and the grease that drying under reduced pressure is residual obtains diamine compound (DA-1) thus.The receipts amount is 19.8g, and yield is 96%.
Diamine compound (DA-1) passes through 1H NMR confirms.
1H NMR (DMSO-d 6): δ 6.54-6.42 (m, 3H, Ar), 3.49,3.47 (all be s, 2H, NCH 2CO 2T-Bu), 3.38-3.30 (m, 2H, CH 2CH 2N), 2.51-2.44 (m, 2H, ArCH 2), 1.84-1.76 (m, 2H, CH 2CH 2CH 2), 1.48-1.44 (m, 18H, NCO 2T-Bu and CH 2CO 2T-Bu).
(synthesis example 2)
Making the 300mL four-hole boiling flask with stirring apparatus is nitrogen atmosphere, add 4, the DA-1 of 4 '-diaminodiphenyl-methane 4.486g (22.63mmol), 2.147g (5.658mmol), add NMP 121.37g and as the pyridine 5.16g(65.19mmol of alkali), make its dissolving through stirring.Then 1 of this two amine aqueous solutions limit interpolation 8.8384g (27.16mmol) is stirred on the limit, and 3DM-CBDE-Cl makes its reaction 4 hours under water-cooled.After 4 hours, in reaction solution, add NMP 134.86g, the lower stirring of room temperature (20 ℃) 15 minutes.The polyamic acid ester solution that obtains is added in the water of 1349g while stirring, filters and take out the white precipitate of separating out, then, water with 1349g cleans 1 time, ethanol with 1349g cleans 1 time, uses the ethanol of 337g to clean 3 times, and drying obtains the white poly amic acid ester toner of 11.04g.Yield is 81.9%.In addition, the molecular weight of this poly amic acid ester is Mn=15205, Mw=30219.
The poly amic acid ester toner 10.9690g that obtains is taken in the Erlenmeyer flask of 200ml, adds the NMP of 98.7394g, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-1).
(relatively synthesis example 1)
Making the 300mL four-hole boiling flask with stirring apparatus is nitrogen atmosphere, add 4,4 '-diaminodiphenyl-methane 8.0102g (40.35mmol) adds the NMP of 158.1g and the pyridine as alkali of 7.20g (91.03mmol), makes its dissolving through stirring.Then 1 of this two amine aqueous solutions limit interpolation 12.3419g (37.93mmol) is stirred on the limit, and 3DM-CBDE-Cl makes its reaction 4 hours under water-cooled.The polyamic acid ester solution that obtains is added in the water of 1757g while stirring, filters and take out the white precipitate of separating out, then, water with 1757g cleans 1 time, ethanol with 1757g cleans 1 time, uses the ethanol of 439g to clean 3 times, and drying obtains the white poly amic acid ester toner of 16.63g.Yield is 94.6%.In addition, the molecular weight of this poly amic acid ester is Mn=10180, Mw=21476.
The poly amic acid ester toner 14.8252 that obtains is taken in the Erlenmeyer flask of 200ml, adds the NMP of 99.3048g, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-2).
(synthesis example 3)
With 4 of 7.9693g (40mmol), 4 '-diamino-diphenylamine is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, adds the NMP of 31.7g, and the limit is supplied with the nitrogen limit and stirred and make its dissolving.BDA while stirring this two amine aqueous solution and add 7.1339g (36.01mmol) adds NMP again and makes solid component concentration reach 25 quality %, at room temperature stirs 24 hours, obtains the solution of polyamic acid (PAA-1).The viscosity of this polyamic acid solution under 25 ℃ of temperature is 2680mPas.In addition, the molecular weight of this polyamic acid is Mn=8176, Mw=16834.
(synthesis example 4)
With 4 of 5.9791g (30.01mmol), 3 of 4 '-diamino-diphenylamine and 3.0446g (20.01mmol), the 5-diaminobenzoic acid is taken in the four-hole boiling flask with the 100mL of stirring apparatus and nitrogen ingress pipe, add the NMP of 39.69g, stir and make its dissolving while supply with nitrogen.BDA while stirring this two amine aqueous solution and add 9.8379g (49.65mmol) adds NMP again and makes solid component concentration reach 25 quality %, at room temperature stirs 24 hours, obtains polyamic acid solution.The viscosity of this polyamic acid solution under 25 ℃ of temperature is 8000mPas.In addition, the molecular weight of this polyamic acid is Mn=13696, Mw=28619.
The polyamic acid solution that 5.5355g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 8.3744g, at room temperature stirs to make its dissolving in 24 hours, obtains the polyamic acid solution (PAA-2) of 10 quality %.
(synthesis example 5)
With 4 of 3.6652g (18.39mmol), 3 of 4 '-diamino-diphenylamine and 0.6992g (4.595mmol), the 5-diaminobenzoic acid is taken in the four-hole boiling flask with the 100mL of stirring apparatus and nitrogen ingress pipe, add the NMP of 39.36g, stir and make its dissolving while supply with nitrogen.CBDA while stirring this two amine aqueous solution and add 4.3326g (22.09mmol) adds NMP again and makes solid component concentration reach 15 quality %, at room temperature stirs 24 hours, obtains the solution of polyamic acid (PAA-3).The viscosity of this polyamic acid solution under 25 ℃ of temperature is 669mPas.In addition, the molecular weight of this polyamic acid is Mn=16902, Mw=34865.
(synthesis example 6)
With 4 of 1.848g (9.23mmol), 3 of 4 '-diamino-diphenylamine and 2.1025g (13.82mmol), the 5-diaminobenzoic acid is taken in the four-hole boiling flask with the 100mL of stirring apparatus and nitrogen ingress pipe, add the NMP of 39.7g, stir and make its dissolving while supply with nitrogen.PMDA while stirring this two amine aqueous solution and add 4.8162g (22.08mmol) adds NMP again and makes solid component concentration reach 15 quality %, at room temperature stirs 24 hours, obtains the solution of polyamic acid (PAA-4).The viscosity of this polyamic acid solution under 25 ℃ of temperature is 257mPas.In addition, the molecular weight of this polyamic acid is Mn=13620, Mw=28299.
(embodiment 1)
The polyamic acid solution (PAA-1) that obtains in the polyamic acid ester solution (PAE-1) that obtains in the synthesis example 2 with 1.5289g and the synthesis example 3 of 0.5184g is taken in the Erlenmeyer flask, add NMP, the BCS of 1.0011g of 2.0050g, obtained aligning agent for liquid crystal (I) in 30 minutes with magnetic stirrer.
(embodiment 2)
The polyamic acid solution (PAA-2) that obtains in the polyamic acid ester solution (PAE-1) that obtains in the synthesis example 2 with 1.5246g and the synthesis example 4 of 1.4067g is taken in the Erlenmeyer flask, add NMP, the BCS of 1.0112g of 1.0960g, obtained aligning agent for liquid crystal (II) in 30 minutes with magnetic stirrer.
(embodiment 3)
The polyamic acid solution (PAA-3) that obtains in the polyamic acid ester solution (PAE-1) that obtains in the synthesis example 2 with 1.5119g and the synthesis example 5 of 1.0074g is taken in the Erlenmeyer flask, add NMP, the BCS of 1.0313g of 1.5183g, obtained aligning agent for liquid crystal (III) in 30 minutes with magnetic stirrer.
(embodiment 4)
The polyamic acid solution (PAA-4) that obtains in the polyamic acid ester solution (PAE-1) that obtains in the synthesis example 2 with 1.5018g and the synthesis example 6 of 1.1008g is taken in the Erlenmeyer flask, add NMP, the BCS of 1.0214g of 1.4859g, obtained aligning agent for liquid crystal (IV) in 30 minutes with magnetic stirrer.
(comparative example 1)
The polyamic acid solution (PAA-1) that obtains in the polyamic acid ester solution (PAE-2) that obtains in the comparison synthesis example 1 with 3.00g and the synthesis example 3 of 1.021g is taken in the Erlenmeyer flask, add NMP, the BCS of 2.0128g of 3.99g, obtained aligning agent for liquid crystal (a) in 30 minutes with magnetic stirrer.
(comparative example 2)
The polyamic acid solution (PAA-2) that obtains in the polyamic acid ester solution (PAE-2) that obtains in the comparison synthesis example 1 with 1.5119g and the synthesis example 4 of 1.4334g is taken in the Erlenmeyer flask, add NMP, the BCS of 1.0271g of 1.0903g, obtained aligning agent for liquid crystal (b) in 30 minutes with magnetic stirrer.
(comparative example 3)
The polyamic acid solution (PAA-3) that obtains in the polyamic acid ester solution (PAE-2) that obtains in the comparison synthesis example 1 with 3.00g and the synthesis example 5 of 2.0141g is taken in the Erlenmeyer flask, add NMP, the BCS of 2.0111g of 3.01g, obtained aligning agent for liquid crystal (c) in 30 minutes with magnetic stirrer.
(comparative example 4)
The polyamic acid solution (PAA-4) that obtains in the polyamic acid ester solution (PAE-2) that obtains in the comparison synthesis example 1 with 1.5206g and the synthesis example 6 of 1.0258g is taken in the Erlenmeyer flask, add NMP, the BCS of 1.0418g of 1.4838g, obtained aligning agent for liquid crystal (d) in 30 minutes with magnetic stirrer.
(comparative example 5)
The polyamic acid ester solution (PAE-1) that obtains in the synthesis example 2 with 3.1281g was taken in the there-necked flask, adds NMP, the BCS of 1.0532g of 1.0911g, obtained aligning agent for liquid crystal (e) with magnetic stirrer 30 minutes.
(embodiment 5)
Behind the aligning agent for liquid crystal (I) that obtains among the filtrator filtration embodiment 1 with 1.0 μ m, be spun on the glass substrate with transparency electrode, through on the hot plate of 80 ℃ of temperature dry 5 minutes and under 250 ℃ of temperature, burnt till 1 hour, form filming of thickness 100nm.Measured the center line average roughness (Ra) of respectively filming.Measurement result is shown in table 1 described later.
(embodiment 6～9 and comparative example 7～10)
Each aligning agent for liquid crystal (II)～(IV) that in using above-described embodiment 2～4, comparative example 1～4, obtains and (a)～(d), use the method identical with embodiment 5 to form respectively and film.Observed the film surface of respectively filming with AFM.In addition, measured the center line average roughness (Ra) of respectively filming.These measurement results are shown in table 1 described later.
[table 1]
Figure BDA00002403104200441
Can be confirmed that by the embodiment 5～9 of table 1 expression and the result of comparative example 7～10 aligning agent for liquid crystal of the present invention can reduce because the small concavo-convex of generation that be separated of poly amic acid ester and polyamic acid obtains level and smooth film surface.
(embodiment 10)
Behind the aligning agent for liquid crystal (I) that obtains among the filtrator filtration embodiment 1 with 1.0 μ m, be spun on the glass substrate with transparency electrode, through on the hot plate of 80 ℃ of temperature dry 5 minutes and under 250 ℃ of temperature, burnt till 1 hour, form filming of thickness 100nm.Across the ultraviolet 100mJ/cm of polarization plates to this coated surface irradiation 254nm 2, obtain the substrate with liquid crystal orientation film.Prepare two substrates with above-mentioned liquid crystal orientation film, after the liquid crystal aligning face of a substrate scatters the sept of 6 μ m, with the antiparallel condition of the orientation of two substrates with two substrate in combination, sealing on every side, but stay liquid crystal injecting port, make the negative crystal born of the same parents that structure cell is spaced apart 6 μ m.Vacuum is injected liquid crystal (MLC-2041, Merck ﹠ Co., Inc.'s system) in this structure cell at normal temperatures, with the inlet sealing, makes the liquid crystal structure cell.To this liquid crystal structure cell, measure voltage retention, then carried out the mensuration of ion concentration.The measurement result of voltage retention and ion concentration is shown in table 2 described later.
(embodiment 11～13 and comparative example 11～15)
Each aligning agent for liquid crystal (II)～(IV) that in using above-described embodiment 2～4, comparative example 1～5, obtains and (a)～(e), use the method identical with embodiment 10 to make each liquid crystal structure cell.To this liquid crystal structure cell, measure voltage retention, then carried out the mensuration of ion concentration.The measurement result of these voltage retention and ion concentration is shown in table 2 described later.
[table 2]
Figure BDA00002403104200461
Can confirm that by the embodiment 10～13 of table 2 expression and the result of comparative example 15 aligning agent for liquid crystal of the present invention can obtain having the liquid crystal orientation film of or better reliability equal with the aligning agent for liquid crystal that only contains poly amic acid ester.In addition, result by embodiment 10～13 and comparative example 11～14 can confirm, aligning agent for liquid crystal of the present invention can obtain the poly amic acid ester of the low polar substituent that breaks away from not containing Yin Re and the aligning agent for liquid crystal of polyamic acid is compared the higher liquid crystal orientation film of reliability.
(embodiment 14)
Behind the aligning agent for liquid crystal (I) that obtains among the filtrator filtration embodiment 1 with 1.0 μ m, by spin coating it is coated on the glass substrate that is formed with the FFS driving electrode, described FFS driving electrode be have ITO electrode as the thickness 50nm of ground floor, as the silicon nitride as the thickness 500nm of dielectric film of the second layer, as the ITO electrode (electrode width: 3 μ m, electrode gap: 6 μ m, electrode height: FFS driving electrode 50nm) of the 3rd layer comb teeth-shaped.After 80 ℃ hot plates make its dry 5 minutes, in 250 ℃ heated air circulation type stove, burnt till 60 minutes, forming thickness is filming of 100nm.Across the ultraviolet 100mJ/cm of polarization plates to this coated surface irradiation 254nm 2, obtain the substrate with liquid crystal orientation film.In addition, film the implementation orientation processing forming too on the glass substrate of column spacer that having of electrode highly is 4 μ m as not being formed with of substrate in opposite directions.
With above-mentioned two substrates as one group, printing and sealing agent on substrate, fit another piece substrate so that liquid crystal orientation film toward each other and direction of orientation be 0 °, then, make sealant cures and make the negative crystal born of the same parents.Inject liquid crystal MLC-2041 (Merck ﹠ Co., Inc.'s system) by the decompression injection method in this negative crystal born of the same parents, the sealing inlet obtains FFS and drives the liquid crystal structure cell.
Estimate interchange driving sintering characteristic and electric charge Accumulation that this FFS drives the liquid crystal structure cell.The results are shown in table 3 described later.
(embodiment 15～17 and comparative example 16)
Each aligning agent for liquid crystal (II)～(IV) that in using above-described embodiment 2～4, comparative example 5, obtains and (e), use the method identical with embodiment 14 to make each FFS and drive liquid crystal structure cell.Estimate interchange driving sintering characteristic and electric charge Accumulation that each FFS drives the liquid crystal structure cell.The results are shown in table 3 described later.
[table 3]
Can be confirmed that by the embodiment 14～17 of table 3 expression and the result of comparative example 16 it is little to obtain exchanging driving sintering degree by aligning agent for liquid crystal of the present invention, and the few liquid crystal orientation film of residual voltage.
Synthesizing of (synthesis example 7) diamine compound (DA-2)
(precursor synthetic 1)
[changing 61]
Figure BDA00002403104200472
The four-hole boiling flask of 1L is linked to each other with Di Muluo cooling tube, 100mL tap funnel, add 2-amino-4-nitroaniline (15g, 92mmol), after being replaced into nitrogen in the system, add THF 400mL, be cooled to 0 ℃.Then, dripped borine-THF complex compound (the 1M borine being arranged, 100mL, 100mmol among THF) with 30 minutes from tap funnel.Confirm and produce gas in the reaction system, separate out yellow solid.After dripping end, at room temperature stirred 2 days.After reaction finishes, add hydrochloric acid (2N, 200mL), at room temperature stir 2 hours after, make its aobvious alkalescence at 10 ℃ of lower sodium hydrate aqueous solutions (2N, 250mL) that add, use dichloromethane extraction.Clean organic layer with saturated aqueous common salt (500mL), after dried over mgso, concentrate, vacuum drying, obtain thus yellow solid cyano reduction body.The receipts amount is 11.9g, and yield is 77%.
(precursor synthetic 2)
[changing 62]
Figure BDA00002403104200481
In 1L eggplant type bottle, add above-mentioned cyano reduction body (4.60g, 27.5mmol) and methylene chloride (900mL), make solution, to wherein adding di-tert-butyl dicarbonate (6.00g, 27.5mmol), the lower stirring of room temperature (20 ℃) 3 days.Reaction is directly used saturated aqueous common salt cleaning reaction solution after finishing, and uses dried over mgso.With ethyl acetate-hexane the solid of separating out by the reduced pressure concentration organic layer is carried out recrystallization, obtain yellow solid tert-butoxycarbonyl (Boc) and add adult.The receipts amount is 5.25g, and yield is 71%.
(DA-2's is synthetic)
[changing 63]
Figure BDA00002403104200482
Add above-mentioned Boc in the eggplant-shape bottle of 100mL and add adult (5.0g, 18.7mmol) and ethanol (40ml), after being replaced into nitrogen in the system, add platinum oxide (500mg), will be replaced into hydrogen in the system.At room temperature stirring becomes yellow outstanding turbid reaction mixture 15 hours.Reaction is added ethanol after finishing, and the white solid that dissolving is separated out is removed catalyzer by diatomite filtration.Concentrated filtrate carries out recrystallization with ethyl acetate-hexane to the peachiness solid that obtains, and obtains the pinkish solid.The receipts amount is 3.40g, and yield is 77%.
The solid that mensuration obtains 1H-NMR confirms and generates DA-2.
1H-NMR(DMSO-d 6，δppm)：1.44(s，9H)、3.87(d，J＝6.3Hz，2H)、4.10～4.30(m，4H)、6.27(dd，J=2.4Hz，8.1Hz，1H)、6.31(d，J=2.4Hz，1H)、6.38(d，J=8.1Hz)、7.14(t，J＝6.3Hz，1H).
Synthesizing of (synthesis example 8) diamine compound (DA-3)
(synthesizing of N-tert-butoxycarbonyl-propargyl amine)
[changing 64]
Figure BDA00002403104200491
In four-hole boiling flask, add propargyl amine (25.18g, 0.448mol), triethylamine (55.52g, 0.549mol), behind the methylene chloride 400ml, one side cooled reaction solution in water-bath (20 ℃), on one side with 30 minutes dropping di-tert-butyl dicarbonates (118.15g, 0.541mol).After dripping end, stirred 2 hours, then in reaction solution, add saturated aqueous common salt 300ml, methylene chloride 200ml, extraction.The organic layer that obtains with dried over mgso.After removing drying agent, the solvent of the solution that obtains is removed in distillation, obtains faint yellow oily thing.By recrystallization (hexane) purifying, obtain white solid N-tert-butoxycarbonyl-propargyl amine (receipts amount: 47.01g, yield: 67.6%).
(synthesizing of nitro-body)
[changing 65]
Figure BDA00002403104200492
In being replaced into the four-hole boiling flask of nitrogen, add 2-iodo-4-nitroaniline (5.11g, 19.4mmol), two (triphenylphosphine) palladium chloride (II) (281.7mg, 0.401mmol), cupric iodide (160.7mg, 0.844mmol) and diethylamine 30ml, at room temperature (20 ℃) stirred 20 minutes.Then, add tert-butoxycarbonyl-propargyl amine (3.72g, 24.0mmol), at room temperature (20 ℃) stirred 4 hours.After the disappearance of HPLC affirmation raw material, add ethyl acetate 200ml, 1M aqueous ammonium chloride solution 200ml, extraction.Clean the organic layer that obtains with the 1M aqueous ammonium chloride solution, clean 2 times, use anhydrous magnesium sulfate drying.After removing drying agent, concentrated filtrate is with silica gel column chromatography (ethyl acetate: the purifying of hexane=3:7).The receipts amount is 4.97g, and yield is 88.0%.
(DA-3's is synthetic)
[changing 66]
Figure BDA00002403104200501
In four-hole boiling flask, add above-mentioned nitro-body (12.45g, 42.7mmol), make it outstanding turbid with 200ml ethanol.After degassed, nitrogen replaces, add palladium carbon (1.23g), the hydrogen displacement was the lower stirring of room temperature (20 ℃) 20 days.Remove palladium carbon by diatomite filtration, the distillation desolventizing.After making the dissolution of solid that obtains in toluene 100ml, add hexane 50ml, recrystallization.The solid that drying under reduced pressure obtains obtains shallow dark brown solid.(receipts amount: 9.13g, yield: 80.6%).The solid that mensuration obtains 1H-NMR confirms and generates DA-B.
1H-NMR(DMSO-d 6,δppm):1.38(s,9H)、1.57(q,J=7.2Hz,2H)、2.30(t,J=7.2Hz,2H)、2.94(quin,J=6.0Hz,2H)、3.88～4.22(m,4H)、6.22(dd,J=2.1Hz,8.1Hz,1H)、6.25(d,J=2.1Hz,1H)、6.37(d,J=8.1Hz,1H)、6.84(t,J=6.0Hz,1H).
Synthesizing of (synthesis example 9) diamine compound (DA-4)
[changing 67]
Figure BDA00002403104200502
In the eggplant-shape bottle of 500mL, add p-phenylenediamine (PPD) (16.2g, 150mmol), N, dinethylformamide (200mL), sal tartari (49.8g, 360mmol),-20 ℃ of lower coolings, with dropping in 3 hours monobromo-acetic acid butyl ester (58.5g, 300mmol) is dissolved in the solution that obtains in the DMF (100mL).Then, at room temperature stir 20 hours.By removing by filter the solid in this reaction mixture, then, filtrate is injected 6L water, reclaim the thick product of the diamine compound (D) of separating out.The thick product that obtains is dissolved in the DMF of 100mL, re-injects in the water of 2L, solid is separated out.With this solid of washed with methanol, obtain pinkish solid diamine compound (DA-4) by drying under reduced pressure.The receipts amount is 25.1g, and yield is 50%.
The structure of diamine compound (D-4) is passed through 1H NMR confirms.
1H?NMR(DMSO-d 6)：δ6.39(s，4H，Ar)，5.09(t，J=6.6Hz，2H，NH)，3.64(d，J=6.6Hz，4H，CH 2)，1.39(s，18H，t-Bu).
Synthesizing of (synthesis example 10) diamine compound (DA-5)
(synthesizing of nitro-body)
[changing 68]
Figure BDA00002403104200511
In being replaced into the four-hole boiling flask of nitrogen, add tert-butoxycarbonyl glycocoll (10.17g, 58.05mmol), it is dissolved among the THF 150ml.To wherein adding N-methylmorpholine (11.93g, 117.9mmol), be cooled to-20 ℃.In this solution, drip carbonochloridic acid isobutyl ester (9.99g, 73.14mmol).At this moment, notice that not making the temperature of reaction solution is more than 0 ℃.After the dropping ,-20 ℃ of lower stirrings 10 minutes.At this moment, reaction solution is gonorrhoea.After 10 minutes, drip the THF solution 360ml of 2-amino-4-nitroaniline (8.86g, 57.86mmol) with tap funnel.After dripping end ,-20 ℃ of lower stirrings 1 hour, then under room temperature (20 ℃), stirred 18 hours.After 18 hours, filter the solid of separating out, the solvent of the filtrate that obtains is removed in distillation, obtains concentrate.In this concentrate, add ethyl acetate 200ml, 1M potassium dihydrogen phosphate aqueous solution 200ml, extraction.Clean the organic layer obtain 1 time with the 1M potassium dihydrogen phosphate aqueous solution, clean 1 time with saturated aqueous common salt, clean 2 times with saturated sodium bicarbonate aqueous solution, clean 1 time with saturated aqueous common salt.The organic layer that obtains with anhydrous magnesium sulfate drying.After removing drying agent, from filtrate, distill desolventizing, obtain orange solid.This Solid Suspension in toluene 300ml, was added thermal agitation 30 minutes.The suction filtration solid, the NMR of the solid that mensuration obtains, the result is object nitro-body (receipts amount: 9.85g, yield: 54.9%) as can be known.
(DA-5's is synthetic)
[changing 69]
Figure BDA00002403104200521
In eggplant-shape bottle, add above-mentioned nitro-body (9.85g, 31.75mmol), add ethanol 150ml.After being replaced into nitrogen in the reaction vessel, add palladium carbon (1.11g is 10 quality % with respect to the quality of nitro-body), again be replaced into nitrogen.Then, hydrogen will be replaced in the reaction vessel, 20 ℃ of lower stirrings 48 hours.Reaction is removed palladium carbon by diatomite filtration, desolventizing from filtrate after finishing.Add toluene 150ml in the concentrate that obtains, add hot reflux, the result separates out solid.Thermosol filters the solid of separating out, and obtains the lavender solid.The receipts amount is 8.05g, and yield is 90.4%.The solid that mensuration obtains 1H-NMR confirms and generates DA-5.
1H-NMR(DMSO-d 6，δppm)：1.40(s，9H)、3.70(d，J＝6.0Hz，2H)、4.04(bs，2H)、4.35(bs，2H)、6.23(dd，J=2.4Hz，8.0Hz，1H)、6.48(d，J=8.0Hz，1H)、6.61(d，J=2.4Hz，1H)、7.05(t，J=6.0Hz，1H)、8.94(s，1H)．
Synthesizing of (synthesis example 11) diamine compound (DA-6)
(precursor synthetic 1)
[changing 70]
In the four-hole boiling flask of 2L, add 1,5-diaminopropanes 50.00g (489.3mmol), sal tartari 270.5g (1.957mol), dimethyl sulfoxide 400g, under 100 ℃, add thermal agitation.Then, add 4-Fluoronitrobenzene 138.09g (978.7mmol), dimethyl sulfoxide 100g, under 100 ℃, added thermal agitation 4 hours.After 4 hours, while stir reaction solution is dropped in the 5L water yellow solid that leaching is separated out.With the solid that the washed with methanol of the water of 3L, 556g obtains, drying obtains yellow solid (precursor-1).The receipts amount is 152.71g.The solid that obtains (precursor-1) is used for following reaction.
(precursor synthetic 2)
[changing 71]
Figure BDA00002403104200531
Add above-mentioned (precursor-1) 100g (290.4mmol), N in the four-hole boiling flask of 2L, N-dimethyl aminopyridine 7.10g (58.08mmol), tetrahydrofuran 800g 10 ℃ of lower stirrings, make its dissolving.Then, di-tert-butyl dicarbonate 152.10g (697.0mmol) is joined in the tap funnel, be added drop-wise in the interior solution of four-hole boiling flask with 1 hour.After dripping end, remove reactant liquor with the evaporator distillation, obtain yellow oil.In this yellow oil, add ethyl acetate, add 10 % by weight hydrogen chloride solution 500ml, extraction.Clean the organic layer obtain with 10 % by weight hydrochloride aqueous solution 500ml, the water with 500ml cleans 2 times again, the organic layer that obtains with dried over mgso.After removing drying agent, the distillation desolventizing obtains yellow oil.After this yellow oil placed an evening, the yellowing solid.Add 2-propyl alcohol 400g in this solid, clean, the leaching solid makes its drying, obtains the solid (precursor-2) of yellow-white.The receipts amount is 124.32g.The solid that obtains (precursor-2) is directly used in following reaction.
(DA-6's is synthetic)
[changing 72]
Figure BDA00002403104200532
In the four-hole boiling flask of 2L, add the above-mentioned precursor-2 of 100.0g (183.6mmol), the Isosorbide-5-Nitrae-two of 1500g
Figure BDA00002403104200533
Alkane.After being replaced into nitrogen in the reaction vessel, add palladium carbon (10.00g is 10 quality % with respect to the quality of nitro-body), again be replaced into nitrogen.Then, hydrogen will be replaced in the reaction vessel, 20 ℃ of lower stirrings 24 hours.Add the acetonitrile 800g that separates out white solid, make its dissolving.With film filter (1.0 μ m) filtering reacting liquid, remove palladium carbon.Desolventizing from filtrate obtains white solid.In this white solid, add 2-propyl alcohol 350g, stirred 1 hour.After 1 hour, the leaching solid adds the 2-propyl alcohol of 300g in the solid that obtains, after disperseing to clean with ultrasonic unit, filter, and carries out drying, obtains white solid DA-6.The receipts amount is 65.50g, and yield is 74%.The solid that mensuration obtains 1H-NMR confirms and generates DA-6.
1H-NMR(DMSO-d 6，δppm):1.10～1.23(m,6H)、1.32(s,18H)、3.40(t,J=6.8Hz,4H)、5.03(s,4H)、6.49(d,8.0Hz,1H)、6.48(d,J=8.4Hz,4H)、6.77(d,J=8.4Hz,4H).
(synthesis example 12) 1, two (the 4-aminobenzene ethyl) ureas of 3-synthetic
[changing 73]
Figure BDA00002403104200541
In the four-hole boiling flask of nitrogen replacement, adding 2-(4-nitrobenzophenone) ethylamine hydrochloride [A] (52.50g, 259mmol), two (4-nitrobenzophenone) esters [B] (37.53g, 123mmol) of carbonic acid and THF (1877g) under the room temperature, add therein triethylamine (74.90g, 740mmol) and 4-N, N-dimethyl aminopyridine (3.01g, 24.7mmol) stirs with mechanical stirrer.Follow the tracks of reaction by HPLC, reaction joins reaction solution in the pure water (9L) after finishing, and carries out 30 minutes stirring.Then filter, clean with pure water (1L), obtain the crude product of white solid.After this gained white solid disperse cleaned with ultrasonic unit in methyl alcohol (488g), filter, drying, obtain the dinitro compound [C] (must measure 42.3g, yield 96%) of white solid.
1H-NMR(400MHz，DMSO-d6，δppm)：8.11-8.08(4H，m)，7.43-7.40(4H，m)，5.89(2H，t)，3.24-3.19(4H，q)，2.76(4H，t).
With compound [C] (42.32g, 118mmol), 5% palladium carbon (4.23g, 10 % by weight) and Isosorbide-5-Nitrae-two
Figure BDA00002403104200551
The potpourri of alkane (2031g) behind nitrogen replacement, is replaced again with hydrogen, stirs under room temperature in the presence of hydrogen.Follow the tracks of reaction by HPLC, after reaction finished, behind the diatomite filtration catalyzer, filtrate was removed under reduced pressure distillation, and the result obtains the crude product of white solid.In this crude product, add 2-propyl alcohol (85g), after disperseing to clean with ultrasonic unit, filter, drying, obtain white solid 1, two (the 4-aminobenzene ethyl) ureas (must measure 31.9g, yield 91%) of 3-.
1H-NMR(400MHz，DMSO-d6，δppm)：6.85-6.82(4H，m)，6.51-6.48(4H，m)，5.78(2H，t)，4.83(4H，s)，3.14-3.09(4H，m)，2.50-2.45(4H，m).
(synthesis example 13)
[changing 74]
Figure BDA00002403104200552
In the reaction vessel of 500ml, add compound (b) (50.00g, 229mmol), pyridine (0.500g, 0.632mmol), compound (c) (63.02,504mmol), acetonitrile (300g), under nitrogen atmosphere, react adding under the hot reflux.After reaction finishes, be cooled to 20 ℃ after, filter, clean with acetonitrile (100g), the acquisition crude product.Then, in crude product, add 2-propyl alcohol (300g), distilled water (100g), add hot reflux.Afterwards, be cooled to 20 ℃, cross filter solid, with 2-propyl alcohol (100g) cleaning, dry, acquisition compound (d) (receipts amount: 37.8g, yield: 37%).
1H-NMR ( 1The H nuclear magnetic resonance spectrum) (400MHz, DMSO-d 6, σ (ppm)): 8.07 (2H, s), 5.15-5.14 (2H, m), 4.62 (2H, t), 4.59-4.49 (4H, m), 4.38 (2H, q).
In the 500mL reaction vessel, add compound (d) (20.00g, 44.0mmol), thionyl chloride (120.0g, 1.01mol), add hot reflux.After 30 minutes, be cooled to 20 ℃ after, append thionyl chloride 120.0g, 1.01mol), further carry out 2 hours the hot reflux that adds.After reaction finished, superfluous thionyl chloride was removed in decompression distillation, cleaned with hexane (200g).Then, under 20 ℃, in crude product, add methylene chloride (200g) and stir, to wherein slowly dripping compound (c) (12.1g, 96.8mmol), pyridine (13.93g, 176mmol), methylene chloride (100g) solution.Stir after 1 hour, further add compound (c) (12.1g, 96.8mmol), pyridine (13.93g, 176mmol).After reaction finished, the distillation desolventizing was cleaned with distilled water (144g), obtains crude product.In this crude product, add tetrahydrofuran (144g), disperse to clean, filter at 23 ℃, it is rear, dry to use respectively tetrahydrofuran (130g), distilled water (170g), methyl alcohol (150g) to clean, and obtains (AD-4) (receipts amount: 17.72g, yield: 62%).
1H-NMR ( 1The H nuclear magnetic resonance spectrum) (400MHz, DMSO-d 6, σ (ppm)): 8.17 (2H, s), 5.18-5.13 (2H, m), 4.64-4.53 (6H, m), 4.37 (2H, q).
(synthesis example 14)
With 2 of 10.2046g (39.22mmol), two (methoxycarbonyl) cyclo-butane-1 of 4-, 3-dicarboxylic acid are taken in the 300ml four-hole boiling flask with stirring apparatus, add the NMP of 181.2g, stir and make its dissolving.Then, add the triethylamine of 8.90g (87.90mmol), the p-phenylenediamine (PPD) of 3.8987g (36.05mmol), the DA-2 of 0.9528g (4.02mmol), make its dissolving through stirring.Stir this solution on one side, Yi Bian add (2, the 3-dihydroxy-2-sulfo--3-benzo of 33.74g (88.01mmol)
Figure BDA00002403104200561
The azoles base) phosphonic acid diphenyl ester adds the NMP of 32g again, makes its reaction 4 hours under water-cooled.Join in the 2-propyl alcohol of 1090g while stirring the polyamic acid ester solution that will obtain, the sediment that leaching is separated out, then the 2-propyl alcohol with 540g cleans 5 times, and drying obtains the poly amic acid ester toner.
The molecular weight of this poly amic acid ester is Mn=5210, Mw=8755.
The poly amic acid ester toner that 2.4495g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 22.1541g, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-3).
(synthesis example 15)
With 2 of 1.2736g (4.51mmol), 2 of two (methoxycarbonyl) terephthalic acid (TPA)s of 5-, 2.6915g (10.34mmol), two (methoxycarbonyl) cyclo-butane-1 of 4-, the 3-dicarboxylic acid is taken in the 200ml four-hole boiling flask with stirring apparatus, add the NMP of 73.20g, stir and make its dissolving.Then, 1 of the triethylamine of interpolation 3.34g (33.01mmol), 3.4376g (12.01mmol), the DA-2 of two (4-amino-benzene oxygen) propane of 3-, 0.7122g (3.00mmol) makes its dissolving through stirring.While (2, the 3-dihydroxy-2-sulfo--3-benzo that stirs this solution and add 12.65g (33.0mmol) The azoles base) phosphonic acid diphenyl ester adds the NMP of 10g again, makes its reaction 4 hours under water-cooled.Join in the 2-propyl alcohol of 530g while stirring the polyamic acid ester solution that will obtain, the sediment that leaching is separated out, then the 2-propyl alcohol with 210g cleans 5 times, and drying obtains the poly amic acid ester toner.
The molecular weight of this poly amic acid ester is Mn=10281, Mw=23163.
The poly amic acid ester toner that 2.5429g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 22.9458g, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-4).
(synthesis example 16)
Making the 300mL four-hole boiling flask with stirring apparatus is nitrogen atmosphere, add 4 of 5.0067g (25.25mmol), the triethylamine as alkali of NMP, the 5.57g (70.36mmol) of DA-6, the 139g of 4 '-diaminodiphenyl-methane, 3.0573g (6.31mmol) stirs and makes its dissolving.Then add 1 of 9.5299g (29.31mmol) while stirring this two amine aqueous solution, 3DM-CBDE-Cl makes its reaction 4 hours under water-cooled.Be added in the pure water of 1545g while stirring the polyamic acid ester solution that will obtain, the white precipitate that leaching is separated out, then, pure water with 1545g cleans 1 time, ethanol with 1545g cleans 1 time, and the ethanol with 386g cleans 3 times again, and drying obtains white poly amic acid ester toner.The molecular weight of this poly amic acid ester is Mn=14359, Mw=31558.
The poly amic acid ester toner that 12.31g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 110.79g, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-5).
(synthesis example 17)
With 2 of 5.5958g (19.83mmol), two (methoxycarbonyl) terephthalic acid (TPA)s of 5-are taken in the 200ml four-hole boiling flask with stirring apparatus, add the NMP of 68.70g, stir and make its dissolving.Then, add the triethylamine of 4.01g (39.63mmol), the 3-aminobenzene methylamine of 1.9611g (16.05mmol), the DA-2 of 0.9493g (4.00mmol), stir and make its dissolving.While the 4-(4,6-dimethoxy-1,3,5-triazines-2-yl) that stirs this solution and add 16.40g-4-methyl morpholine hydrochloride (15 ± 2 % by weight hydrate), add again the NMP of 7.72g, under water-cooled, make its reaction 4 hours.Join in the 2-propyl alcohol of 633g while stirring the polyamic acid ester solution that will obtain, the sediment that leaching is separated out, then the 2-propyl alcohol with 210g cleans 5 times, and drying obtains the poly amic acid ester toner.The molecular weight of this poly amic acid ester is Mn=5152, Mw=8788.
The poly amic acid ester toner that 2.5630g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 23.0971g, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-6).
(synthesis example 18)
Making the 300mL four-hole boiling flask with stirring apparatus is nitrogen atmosphere, add 4 of 1.5163g (7.65mmol), the DA-1 of 4 '-diaminodiphenyl-methane, 2.8712g (7.57mmol), add NMP 73.3g and as the pyridine 2.82g (35.59mmol) of alkali, stir and make its dissolving.Then add 1 of 4.8583g (14.94mmol) while stirring this two amine aqueous solution, 3DM-CBDE-Cl makes its reaction 4 hours under water-cooled.After 4 hours, in reaction solution, add NMP81.44g, the lower stirring of room temperature (20 ℃) 15 minutes.Join in the 2-propyl alcohol of 850g while stirring the polyamic acid ester solution that will obtain, the white precipitate that leaching is separated out, then the 2-propyl alcohol with 170g cleans 5 times, and drying obtains the poly amic acid ester toner of white.The molecular weight of this poly amic acid ester is Mn=21514, Mw=43900.
The poly amic acid ester toner that 2.1684g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 19.2226g, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-7).
(synthesis example 19)
The DA-2 of the p-phenylenediamine (PPD) of 1.7312g (16.01mmol) and 0.9444g (3.98mmol) is taken in the four-hole boiling flask with the 200ml of stirring apparatus and nitrogen ingress pipe, adds the NMP of 32.47g, the limit is supplied with the nitrogen limit and is stirred and make its dissolving.Add 4.4841g (20.0mmol) 2.3.5-tricarboxylic basic ring amyl group acetic acid dianhydride while stirring this two amine aqueous solution, further add NMP and make the concentration of solid constituent reach 15 quality %, at room temperature stirred 24 hours.The viscosity of this solution under 25 ℃ of temperature is 580mPas.After in this solution, adding NMP 23.28g, making solid component concentration be 10 quality %, add 1-methyl-3-p-methylphenyl triazenes 6.04g (40.5mmol), stirred 4 hours under the room temperature.After 4 hours, while stir reactant liquor is joined in the 2-propyl alcohol of 286g, the sediment that leaching is separated out, then the 2-propyl alcohol with 140g cleans 5 times, and drying obtains the poly amic acid ester toner.The molecular weight of this poly amic acid ester is Mn=16532, Mw=50698.
The poly amic acid ester toner that 2.2078g is obtained is taken in the 50ml test tube with stirrer, adds the NMP of 19.7894g, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-8).
(synthesis example 20)
Making the 300mL four-hole boiling flask with stirring apparatus is nitrogen atmosphere, add 4, the DA-5 of 4 '-diamino-N-Methylphenethylamine 1.9995g (13.28mmol), 0.9379g (3.35mmol), add NMP 130.70g and as the pyridine 3.80g (37.54mmol) of alkali, stir and make its dissolving.Then add 1 of 5.0894g (15.65mmol) while stirring this two amine aqueous solution, 3DM-CBDE-Cl makes its reaction 4 hours under water-cooled.Join in the 2-propyl alcohol of 688g while stirring the polyamic acid ester solution that will obtain, the white precipitate that leaching is separated out, then the 2-propyl alcohol with 172g cleans 5 times, and drying obtains the poly amic acid ester toner of white.The molecular weight of this poly amic acid ester is Mn=7331, Mw=14716.
The poly amic acid ester toner that 1.9755g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 17.7314g, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-9).
(synthesis example 21)
Making the 100mL four-hole boiling flask with stirring apparatus is nitrogen atmosphere, the DA-3 of the p-phenylenediamine (PPD) of adding 0.6005g (5.55mmol), DA-4, the 0.1849g (0.693mmol) of 0.2334g (0.694mmol) adds the pyridine as alkali of NMP, the 1.15g (14.56mmol) of 49.80g, stirs to make its dissolving.Then add 1 of 2.2550g (6.94mmol) while stirring this two amine aqueous solution, 3DM-CBDE-Cl makes its reaction 4 hours under water-cooled.Join in the water of 277g while stirring the polyamic acid ester solution that will obtain, the white precipitate that leaching is separated out, then the water with 69g cleans 5 times, and drying obtains the poly amic acid ester toner of white.The molecular weight of this poly amic acid ester is Mn=16919, Mw=27982.
The poly amic acid ester toner that 2.0204g is obtained is taken in the Erlenmeyer flask of 50ml, adds the GBL of 18.1836g, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-10).
(synthesis example 22)
With 2 of 2.2570g (8.00mmol), 2 of two (methoxycarbonyl) terephthalic acid (TPA)s of 5-, 3.0206g (11.61mmol), two (methoxycarbonyl) cyclo-butane-1 of 4-, the 3-dicarboxylic acid is taken in the 300ml four-hole boiling flask with stirring apparatus, add the NMP of 100.35g, stir and make its dissolving.Then, 1 of the triethylamine of interpolation 4.45g (43.98mmol), 3.0934g (11.98mmol), 1 of two (4-amino-benzene oxygen) propane of 5-, 1.2018g (4.03mmol), the DA-3 of two (the 4-aminobenzene ethyl) ureas of 3-, 1.0653g (4.02mmol) stirs and makes its dissolving.While (2, the 3-dihydroxy-2-sulfo--3-benzo that stirs this solution and add 16.92g (44.14mmol)
Figure BDA00002403104200601
The azoles base) phosphonic acid diphenyl ester, add the NMP of 13.14g again, under water-cooled, make its reaction 4 hours.Join in the 2-propyl alcohol of 890g while stirring the polyamic acid ester solution that will obtain, the sediment that leaching is separated out, then the 2-propyl alcohol with 300g cleans 5 times, drying acquisition poly amic acid ester toner.
The molecular weight of this poly amic acid ester is Mn=9170, Mw=19990.
The poly amic acid ester toner that 1.8720g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 16.9543g, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-11).
(synthesis example 23)
Making the 300mL four-hole boiling flask with stirring apparatus is nitrogen atmosphere, gets the p-phenylenediamine (PPD) of 3.02g (27.93mmol), adds NMP, the 5.16g (65.25mmol) of 173.0g as the pyridine of alkali, stirs and makes its dissolving.Then, add 2 of 8.09g (27.23mmol) while stir this two amine aqueous solution, two (chlorocarbonyl) cyclo-butane-1 of 4-, the 3-dimethyl dicarboxylate makes its reaction 2 hours under water-cooled.The polyamic acid ester solution that obtains is joined in the water of 1000g, the white precipitate that leaching is separated out, then the 2-propyl alcohol with 300g cleans 5 times, the white poly amic acid ester toner of drying acquisition.The molecular weight of this poly amic acid ester is Mn=10820, Mw=29197.
The poly amic acid ester toner that 1.5309g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 13.7781g, the DMF of 16.9279g, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-12).
(synthesis example 24)
With 2 of 1.7779g (6.30mmol), 2 of two (methoxycarbonyl) terephthalic acid (TPA)s of 5-, 3.7712g (14.49mmol), two (methoxycarbonyl) cyclo-butane-1 of 4-, the 3-dicarboxylic acid is taken in the 200ml four-hole boiling flask with stirring apparatus, add the NMP of 146.71g, stir and make its dissolving.Then, 1 of the triethylamine of interpolation 4.25g (42.0mmol), 5.4239g (21.0mmol), two (4-amino-benzene oxygen) propane of 3-stir and make its dissolving.While (2, the 3-dihydroxy-2-sulfo--3-benzo that stirs this solution and add 16.91g (44.11mmol)
Figure BDA00002403104200611
The azoles base) phosphonic acid diphenyl ester, add the NMP of 25.81g again, under water-cooled, make its reaction 4 hours.Join in the methyl alcohol of 1224g while stirring the polyamic acid ester solution that will obtain, the sediment that leaching is separated out, then with the washed with methanol of 408g 4 times, drying obtains the poly amic acid ester toner.The molecular weight of this poly amic acid ester is Mn=15103, Mw=32483.
The poly amic acid ester toner that 1.0172g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 9.4167g, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-13).
(synthesis example 25)
Making the 300mL four-hole boiling flask with stirring apparatus is nitrogen atmosphere, add 4 of 5.0086g (25.26mmol), 1 of 4 '-diaminodiphenyl-methane, 1.8064g (6.31mmol), two (4-amino-benzene oxygen) pentanes of 5-, the pyridine as alkali that adds NMP, the 5.69g (71.88mmol) of 272g stirs and makes its dissolving.Then add 1 of 9.7356g (29.94mmol) while stirring this two amine aqueous solution, 3DM-CBDE-Cl makes its reaction 4 hours under water-cooled.Be added in the pure water of 1436g while stirring the polyamic acid ester solution that will obtain, the white precipitate that leaching is separated out, then, pure water with 1436g cleans 1 time, ethanol with 1436g cleans 1 time, and the ethanol with 386g cleans 3 times again, and drying obtains white poly amic acid ester toner.The molecular weight of this poly amic acid ester is Mn=15205, Mw=30219.
The poly amic acid ester toner that 11.89g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 107.01g, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-14).
(synthesis example 26)
With 2 of 3.7141g (13.16mmol), two (methoxycarbonyl) terephthalic acid (TPA)s of 5-are taken in the 200ml four-hole boiling flask with stirring apparatus, add the NMP of 72.31g, stir and make its dissolving.Then, add the triethylamine of 0.71g (7.01mmol), the 3-aminobenzene methylamine of 1.7112g (14.01mmol), stir and make its dissolving.While the 4-(4,6-dimethoxy-1,3,5-triazines-2-yl) that stirs this solution and add 11.6258g-4-methyl morpholine hydrochloride (15 ± 2 % by weight hydrate), add again the NMP of 12.91g, under water-cooled, make its reaction 4 hours.Join in the methyl alcohol of 616g while stirring the polyamic acid ester solution that will obtain, the sediment that leaching is separated out, then with the washed with methanol of 616g 4 times, drying obtains the poly amic acid ester toner.The molecular weight of this poly amic acid ester is Mn=7234, Mw=15577.
The poly amic acid ester toner that 1.1325g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 10.1925g, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-15).
(synthesis example 27)
Making the 300mL four-hole boiling flask with stirring apparatus is nitrogen atmosphere, adds the p-phenylenediamine (PPD) of 7.0100g (64.82mmol), and γ-BL, the 11.55g (146mmol) of NMP, the 324g of adding 108g stirs and make its dissolving as the pyridine of alkali.Then 1 of this two amine aqueous solutions limit interpolation 19.7838g (60.85mmol) is stirred on the limit, and 3DM-CBDE-Cl makes its reaction 4 hours under water-cooled.Join in the 2-propyl alcohol of 1881g while stirring the polyamic acid ester solution that will obtain, the white precipitate that leaching is separated out, then the 2-propyl alcohol with 940g cleans 5 times, and drying obtains the poly amic acid ester toner of white.The molecular weight of this poly amic acid ester is Mn=11325, Mw=24387.
The poly amic acid ester toner that 1.2019g is obtained is taken in the Erlenmeyer flask of 50ml, adds the N of 10.8171g, and the N-diethylformamide at room temperature stirs and made its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-16).
(synthesis example 28)
Making the 300mL four-hole boiling flask with stirring apparatus is nitrogen atmosphere, and the 4-amino of adding 3.0144g (20.07mmol)-N-Methylphenethylamine adds the NMP of 148.88g and the pyridine as alkali of 4.65g (46.01mmol), stirs to make its dissolving.Then add 1 of 6.2390g (19.19mmol) while stirring this two amine aqueous solution, 3DM-CBDE-Cl makes its reaction 4 hours under water-cooled.Join in the water of 784g while stirring the polyamic acid ester solution that will obtain, the white precipitate that leaching is separated out then cleans 3 times with the water of 784g, the 2-propyl alcohol of 196g, and drying obtains the poly amic acid ester toner of white.The molecular weight of this poly amic acid ester is Mn=8691, Mw=20311.
The poly amic acid ester toner that 1.9144g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 17.2026g, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-17).
(synthesis example 29)
With 20.0838g(132.0mmol) 3, the DA-7 of 5-diaminobenzoic acid and 21.3254g (88.0mmol) is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 268.48g, stir and make its dissolving while supply with nitrogen.Stir this two amine aqueous solutions limit on one side and add 1,2,3 of 42.4946g (216.7mmol), 4-cyclo-butane tetracarboxylic dianhydride, add again NMP and make solid component concentration reach 20 quality %, at room temperature stirred 24 hours, obtain the solution of polyamic acid (PAA-5).The viscosity of this polyamic acid solution under 25 ℃ of temperature is 2156mPas.In addition, the molecular weight of this polyamic acid is Mn=18794, Mw=63387.
(synthesis example 30)
With 3.5843g(17.99mmol) 4, the DA-7 of 4 '-diamino-diphenylamine, 2.9064g (12.0mmol) is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 55.58g, stir and make its dissolving while supply with nitrogen.Add 5.7653g (29.40mmol) 1,2,3 while stirring this two amine aqueous solution, 4-cyclo-butane tetracarboxylic dianhydride further adds NMP and makes the concentration of solid constituent reach 15 quality %, at room temperature stirs 24 hours.The viscosity of the polyamic acid solution that obtains under 25 ℃ of temperature is 1269mPas.In addition, the molecular weight of this polyamic acid is Mn=15559, Mw=43490.
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0368g, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-6).
(synthesis example 31)
With 3 of 1.2133g (7.97mmol), 4 of 5-diaminobenzoic acid, 6.8216g (31.98mmol), 4 '-diamino-diphenyl-N-methyl-amine is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 44.03g, stir and make its dissolving while supply with nitrogen.BDA while stirring this two amine aqueous solution and add 7.1310g (36.0mmol) at room temperature stirred 2 hours.Then, add the NMP of 14.62g, add the pyromellitic acid anhydride of 0.8713g (3.99mmol).Further add NMP so that the concentration of solid constituent reaches 18 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that obtains under 25 ℃ of temperature is 577mPas.In addition, the molecular weight of this polyamic acid is Mn=12656, Mw=28487.
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0480g, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-7).
(synthesis example 32)
With 3.6541g(24.02mmol) 3,5-diaminobenzoic acid, 4.2931g(16.00mmol) 1, two (4-aminophenyl) piperazines of 4-are taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 36.48g, stir and make its dissolving while supply with nitrogen.Add 4.7522g(23.99mmol while stirring this two amine aqueous solution) BDA, at room temperature stirred 2 hours.Then, add the NMP of 36.50g, add 3.4084g(15.63mmol) pyromellitic acid anhydride.Further add NMP so that the concentration of solid constituent reaches 15 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that obtains under 25 ℃ of temperature is 1166mPas.In addition, the molecular weight of this polyamic acid is Mn=19307, Mw=42980.
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0483g, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-4).
(synthesis example 33)
With 3.6536g(24.01mmol) 3,5-diaminobenzoic acid, 3.8715g(15.98mmol) DA-7 be taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 31.75g, stir and make its dissolving while supply with nitrogen.Add 3.9621g(20.0mmol while stirring this two amine aqueous solution) BDA, at room temperature stirred 2 hours.Then, add the NMP of 25.42g, add 1,2,4 of 4.4776g (19.97mmol), 5-cyclohexane tetracarboxylic dianhydride.Further add NMP so that the concentration of solid constituent reaches 20 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that obtains under 25 ℃ of temperature is 417mPas.In addition, the molecular weight of this polyamic acid is Mn=13291, Mw=54029.
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0476g, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-9).
(synthesis example 34)
With 3 of 2.7365g (17.99mmol), 2 of 5-diaminobenzoic acid, 2.5471g (12.0mmol), 2 '-dimethyl-4,4 '-benzidine is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 27.32g, stir and make its dissolving while supply with nitrogen.While dicyclo [3.3.0] octane-2,4,6 that stirs this two amine aqueous solution and add 2.2562g (9.02mmol), 8-tetracarboxylic dianhydride, in 80 ℃ of lower stirrings 3 hours.After reaction solution is cooled to room temperature, add the NMP of 27.32g, add 4.5715g(20.96mmol) pyromellitic acid anhydride.Further add NMP so that the concentration of solid constituent reaches 15 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that obtains under 25 ℃ of temperature is 2190mPas.In addition, the molecular weight of this polyamic acid is Mn=23632, Mw=56881.
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0360g, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-10).
(synthesis example 35)
With 6.0854g(40.0mmol) 3, the 5-diaminobenzoic acid is taken in the four-hole boiling flask with the 100mL of stirring apparatus and nitrogen ingress pipe, adds the NMP of 65.56g, stirs and makes its dissolving while supply with nitrogen.Add 8.5449g(39.18mmol while stirring this two amine aqueous solution) pyromellitic acid anhydride, further add NMP and make the concentration of solid constituent reach 15 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that obtains under 25 ℃ of temperature is 523mPas.In addition, the molecular weight of this polyamic acid is Mn=20565, Mw=47912.
The nmp solution of the 3-glycidoxy propyl group methyldiethoxysilane of the 0.3 quality % of interpolation 13.79g in this solution obtains polyamic acid solution (PAA-11) again.
(synthesis example 36)
With 4 of 3.2080g (16.02mmol), the DA-7 of 4 '-diamino-diphenyl ether, 5.8147 (24.0mmol) is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 60.42g, stir and make its dissolving while supply with nitrogen.Add 7.7658g (39.60mmol) 1,2,3 while stirring this two amine aqueous solution, 4-cyclo-butane tetracarboxylic dianhydride further adds NMP and makes the concentration of solid constituent reach 20 quality %, at room temperature stirs 24 hours.The viscosity of the polyamic acid solution that obtains under 25 ℃ of temperature is 1972mPas.In addition, the molecular weight of this polyamic acid is Mn=15159, Mw=38251.
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0504g, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-12).
(synthesis example 37)
With 3 of 2.4301g (15.97mmol), the DA-8 of 5-diaminobenzoic acid, 9.4204g (24.0mmol) is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 44.60g, stir and make its dissolving while supply with nitrogen.Add 4.7505g(23.98mmol while stirring this two amine aqueous solution) BDA, at room temperature stirred 2 hours.Then, add the NMP of 44.59g, add 1,2,3 of 3.1054g (15.84mmol), 4-cyclo-butane tetracarboxylic dianhydride.Further add NMP so that the concentration of solid constituent reaches 15 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that obtains under 25 ℃ of temperature is 802mPas.In addition, the molecular weight of this polyamic acid is Mn=13261, Mw=32578,
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0590g, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-13).
(synthesis example 38)
With 3.6504g(23.69mmol) 3,5-diaminobenzoic acid, 3.8718g(15.98mmol) DA-7 be taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 68.6g, stir and make its dissolving while supply with nitrogen.While the DAH-1 that stirs this two amine aqueous solution and add 11.5387g (39.21mmol).Further add NMP so that the concentration of solid constituent reaches 20 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that obtains under 25 ℃ of temperature is 736mPas.In addition, the molecular weight of this polyamic acid is Mn=10091, Mw=19511.
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0572g, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-14).
(synthesis example 39)
With 3.6603g(24.06mmol) 3,5-diaminobenzoic acid, 4.7740g(16.0mmol) 1, two (the 4-aminobenzene ethyl) ureas of 3-are taken in the four-hole boiling flask with the 100mL of stirring apparatus and nitrogen ingress pipe, add the NMP of 28.59g, stir and make its dissolving while supply with nitrogen.Add 2.3782g(12.0mmol while stirring this two amine aqueous solution) BDA, at room temperature stirred 2 hours.Then, add the NMP of 38.13g, add 6.0903g(27.92mmol) pyromellitic acid anhydride.Further add NMP so that the concentration of solid constituent reaches 15 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that obtains under 25 ℃ of temperature is 744mPas.In addition, the molecular weight of this polyamic acid is Mn=17771, Mw=38991.
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0505g, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-15).
(synthesis example 40)
With 0.6123g(4.00mmol) 3,4 of 5-diaminobenzoic acid, 3.199g (16.06mmol), the 4-diamino-diphenylamine is taken in the four-hole boiling flask with the 100mL of stirring apparatus and nitrogen ingress pipe, adds the NMP of 19.64g, stirs and makes its dissolving while supply with nitrogen.Add 3.1780g(16.04mmol while stirring this two amine aqueous solution) BDA, at room temperature stirred 2 hours.Then, add the NMP of 8.93g, add 0.8736g(4.01mmol) pyromellitic acid anhydride.Further add NMP so that the concentration of solid constituent reaches 18 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that obtains under 25 ℃ of temperature is 8100mPas.In addition, the molecular weight of this polyamic acid is Mn=22537, Mw=72601.
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0235g, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-16).
(synthesis example 41)
With 3 of 3.6516g (24.0mmol), the 4-amino of 5-diaminobenzoic acid, 2.4070g (16.02mmol)-N-Methylphenethylamine is taken in the four-hole boiling flask with the 100mL of stirring apparatus and nitrogen ingress pipe, add the NMP of 66.21g, stir and make its dissolving while supply with nitrogen.While the pyromellitic acid anhydride that stirs this two amine aqueous solution and add 8.5972g (39.42mmol).Further add NMP so that the concentration of solid constituent reaches 15 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that obtains under 25 ℃ of temperature is 488mPas.In addition, the molecular weight of this polyamic acid is Mn=13205, Mw=33511.
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0438g, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-17).
(synthesis example 42)
With 3.6532g(24.01mmol) 3,5-diaminobenzoic acid, 3.8790g(16.01mmol) DA-7 be taken in the four-hole boiling flask with the 100mL of stirring apparatus and nitrogen ingress pipe, add the NMP of 70.32g, stir and make its dissolving while supply with nitrogen.While the DAH-2 that stirs this two amine aqueous solution and add 12.0709g (39.41mmol).Further add NMP so that the concentration of solid constituent reaches 20 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that obtains under 25 ℃ of temperature is 207mPas.In addition, the molecular weight of this polyamic acid is Mn=5269, Mw=12875.
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0586g, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-18).
(embodiment 18)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-5) that obtains in the synthesis example 29 of the polyamic acid ester solution (PAE-3) that obtains in the synthesis example 14 of 3.6139g, 2.7012g, add NMP, the BCS of 3.01g of 5.7093g, further add the 4-as imidizate promoter (tert-butoxycarbonyl the is amino) pyridine (below be abbreviated as Boc-AP) of 0.1284g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (I-1).
(embodiment 19)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-6) that obtains in the synthesis example 30 of the polyamic acid ester solution (PAE-4) that obtains in the synthesis example 15 of 2.4040g, 2.4687g, add NMP, the BCS of 2.0348g of 3.2072g, further add the Boc-AP as imidizate promoter of 0.0542g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (I-2).
(embodiment 20)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-6) that obtains in the synthesis example 31 of the polyamic acid ester solution (PAE-4) that obtains in the synthesis example 15 of 2.4548g, 2.0213g, add NMP, the BCS of 2.0116g of 3.6200g, that further add 0.0415g is the Boc-AP of imidizate promoter, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (I-3).
(embodiment 21)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-9) that obtains in the synthesis example 33 of the polyamic acid ester solution (PAE-5) that obtains in the synthesis example 16 of 2.4232g, 2.4189g, add NMP, the BCS of 2.0272g of 3.2928g, further add the N-α as imidizate promoter of 0.0416g-(9-fluorenyl methoxy carbonyl)-N-tert-butoxycarbonyl-L-Histidine (below be abbreviated as Fmoc-His), with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (I-4).
(embodiment 22)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-9) that obtains in the synthesis example 33 of the polyamic acid ester solution (PAE-5) that obtains in the synthesis example 16 of 2.4232g, 1.8681g, add NMP, the BCS of 2.0158g of 3.6548g, further add the Fmoc-His as imidizate promoter of 0.0372g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (I-5).
(embodiment 23)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-10) that obtains in the synthesis example 34 of the polyamic acid ester solution (PAE-6) that obtains in the synthesis example 17 of 2.4356g, 2.5278g, add NMP, the BCS of 2.0366g of 3.2644g, further add the Fmoc-His as imidizate promoter of 0.0550g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (I-6).
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-11) that obtains in the synthesis example 35 of the polyamic acid ester solution (PAE-7) that obtains in the synthesis example 18 of 2.4012g, 2.4115g, add NMP, the BCS of 2.0052g of 2.6514g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-1).
(embodiment 25)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-11) that obtains in the synthesis example 35 of the polyamic acid ester solution (PAE-7) that obtains in the synthesis example 18 of 2.4130g, 2.4216g, add NMP, the BCS of 2.0198g of 2.6780g, further add the multi-functional epoxy compound's as crosslinking chemical (AD-1) of 0.3062g 20 quality %NMP solution, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-2).
(embodiment 26)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-12) that obtains in the synthesis example 36 of the polyamic acid ester solution (PAE-4) that obtains in the synthesis example 15 of 2.4302g, 1.8678g, add NMP, the BCS of 2.0060g of 3.8086g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-3).
(embodiment 27)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-12) that obtains in the synthesis example 36 of the polyamic acid ester solution (PAE-4) that obtains in the synthesis example 15 of 2.4144g, 1.8062g, add NMP, the BCS of 2.0168g of 3.8184g, further add the multifunctional hydroxy-containing compounds (AD-2) as crosslinking chemical of 0.040g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-4).
(embodiment 28)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-13) that obtains in the synthesis example 37 of the polyamic acid ester solution (PAE-4) that obtains in the synthesis example 15 of 2.4015g, 1.8005g, add NMP, the BCS of 2.0011g of 3.8063g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-5).
(embodiment 29)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-14) that obtains in the synthesis example 38 of the polyamic acid ester solution (PAE-8) that obtains in the synthesis example 19 of 2.4120g, 1.8389g, add NMP, the BCS of 2.0181g of 3.8639g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-6).
(embodiment 30)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-14) that obtains in the synthesis example 38 of the polyamic acid ester solution (PAE-8) that obtains in the synthesis example 19 of 2.4120g, 1.8389g, add NMP, the BCS of 2.0181g of 3.8639g, further add the multifunctional cyclic carbonate compound (AD-4) as crosslinking chemical of 0.0318g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-7).
(embodiment 31)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-15) that obtains in the synthesis example 39 of the polyamic acid ester solution (PAE-9) that obtains in the synthesis example 20 of 1.2268g, 3.2688g, add NMP, the BCS of 2.0591g of 3.6154g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-8).
(embodiment 32)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-16) that obtains in the synthesis example 40 of the polyamic acid ester solution (PAE-10) that obtains in the synthesis example 21 of 2.4236g, 2.3539g, add γ-BL, the BCS of 2.0178g of NMP, the 3.0639g of 0.3782g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-9).
(embodiment 33)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-17) that obtains in the synthesis example 41 of the polyamic acid ester solution (PAE-5) that obtains in the synthesis example 16 of 4.2045g, 1.2281g, add NMP, the BCS of 2.0112g of 2.6041g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-10).
(embodiment 34)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-5) that obtains in the synthesis example 29 of the polyamic acid ester solution (PAE-11) that obtains in the synthesis example 22 of 2.4195g, 1.8484g, add NMP, the BCS of 2.0204g of 3.8069g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-11).
(embodiment 35)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-18) that obtains in the synthesis example 42 of the polyamic acid ester solution (PAE-6) that obtains in the synthesis example 17 of 2.4176g, 2.0148g, add NMP, the BCS of 2.0129g of 3.8182g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-12).
(embodiment 36)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-18) that obtains in the synthesis example 42 of the polyamic acid ester solution (PAE-6) that obtains in the synthesis example 17 of 2.3987g, 2.1543g, add NMP, the BCS of 2.0374g of 3.8130g, further add the multifunctional oxetane compound (AD-3) as crosslinking chemical of 0.0460g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (I-13).
(comparative example 17)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-5) that obtains in the synthesis example 29 of the polyamic acid ester solution (PAE-12) that obtains in the synthesis example 23 of 7.2164g, 2.7470g, add NMP, the BCS of 3.0264g of 2.1068g, further add the Boc-AP as imidizate promoter of 0.1396g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (a-1).
(comparative example 18)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-6) that obtains in the synthesis example 30 of the polyamic acid ester solution (PAE-13) that obtains in the synthesis example 24 of 2.4504g, 2.4805g, add NMP, the BCS of 2.0226g of 3.2447g, further add the Boc-AP as imidizate promoter of 0.0547g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (a-2).
(comparative example 19)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-9) that obtains in the synthesis example 33 of the polyamic acid ester solution (PAE-14) that obtains in the synthesis example 25 of 2.4012g, 1.8320g, add NMP, the BCS of 2.0195g of 3.8172g, further add the Fmoc-His as imidizate promoter of 0.0433g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (a-5).
(comparative example 20)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-9) that obtains in the synthesis example 33 of the polyamic acid ester solution (PAE-15) that obtains in the synthesis example 26 of 2.4017g, 2.5777g, add NMP, the BCS of 2.000g of 3.2518g, further add the Fmoc-His as imidizate promoter of 0.0550g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (a-6).
(comparative example 21)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-11) that obtains in the synthesis example 35 of the polyamic acid ester solution (PAE-2) that obtains in the comparison synthesis example 1 of 2.4335g, 2.4013g, add NMP, the BCS of 2.0105g of 2.6238g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (b-1).
(comparative example 22)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-12) that obtains in the synthesis example 36 of the polyamic acid ester solution (PAE-13) that obtains in the synthesis example 24 of 2.4264g, 1.8157g, add NMP, the BCS of 2.0448g of 3.8352g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (b-3).
(comparative example 23)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-15) that obtains in the synthesis example 39 of the polyamic acid ester solution (PAE-17) that obtains in the synthesis example 28 of 1.2049g, 3.2102g, add NMP, the BCS of 2.0694g of 3.6342g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (b-9).
(comparative example 24)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-16) that obtains in the synthesis example 40 of the polyamic acid ester solution (PAE-16) that obtains in the synthesis example 27 of 2.4025g, 2.2514g, add γ-BL, the BCS of 2.0015g of NMP, the 3.0007g of 0.3792g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (b-10).
(comparative example 25)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-17) that obtains in the synthesis example 41 of the polyamic acid ester solution (PAE-14) that obtains in the synthesis example 25 of 4.2242g, 1.2473g, add NMP, the BCS of 2.0664g of 2.6481g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (b-11).
(comparative example 26)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (PAA-18) that obtains in the synthesis example 42 of the polyamic acid ester solution (PAE-15) that obtains in the synthesis example 26 of 2.4260g, 2.2122g, add NMP, the BCS of 2.0585g of 3.8118g, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (b-13).
(embodiment 37)
Behind the aligning agent for liquid crystal (I-1) that obtains among the filtrator filtration embodiment 18 with 1.0 μ m, be spun on the glass substrate with transparency electrode, through on the hot plate of 80 ℃ of temperature dry 5 minutes and in the heated air circulation type stove of 230 ℃ of temperature, burnt till 20 minutes, obtained the film of the imidizate of thickness 100nm.Measured the center line average roughness (Ra) of this imidizate film.Measurement result is shown in table 4 described later.
(embodiment 38～52 and comparative example 27～35)
Except use above-described embodiment 19,22,24～27,29～36 and comparative example 17～19,21～26 in each aligning agent for liquid crystal of obtaining, use the method identical with embodiment 37 to form respectively and film.Observed the film surface of respectively filming with AFM.In addition, measured the center line average roughness (Ra) of respectively filming.These measurement results are shown in table 4 described later.
[table 4]
Figure BDA00002403104200741
The possibility of utilizing on the industry
Aligning agent for liquid crystal of the present invention, surperficial micro concavo-convex by the liquid crystal orientation film that reduces to obtain, exchange to drive the liquid crystal of the ghost reduction that causes etc. and the interfacial characteristics of liquid crystal orientation film and be enhanced, and residual etc. the electrical characteristics of voltage retention, ion concentration and DC voltage also are enhanced.The result can be widely used in TN element, STN element, TFT liquid crystal cell, and the liquid crystal display cells of vertical orientating type etc.
Quote the full content of Japanese patent application 2010-058552 number instructions, claims and the specification digest of filing an application on March 15th, 2010 here as the announcement of instructions of the present invention.

Claims (14)

1. an aligning agent for liquid crystal is characterized in that, contains following (A) composition and (B) composition,
(A) composition: have the repetitive of following formula (1) expression and satisfy the poly amic acid ester of each condition in following (i)～(iii),
[changing 1]
Figure FDA00002403104100011
In the formula, X 14 valency organic groups, Y 1The divalent organic group, R 1The alkyl of carbon number 1～5, A 1And A 2Alkyl, alkenyl, the alkyl that maybe can have independently respectively substituent carbon number 1～20 for hydrogen atom,
(i) X of formula (1) 1, Y 2Or the two has 1 valency or the divalent substituting group that is selected from least a structure in following formula (2) and (3),
The (ii) A of formula (1) 1, A 2Or the two has 1 valency or the divalent substituting group that is selected from least a structure in following formula (2) and (3),
The (iii) X of formula (1) 1, Y 2Or the two has 1 valency or the divalent substituting group that is selected from least a structure in following formula (2) and (3), and A 1, A 2Or the two has 1 valency or the divalent substituting group that is selected from least a structure in following formula (2) and (3),
[changing 2]
Figure FDA00002403104100012
The D of formula (2) and formula (3) 1And D 2Respectively the protecting group that under the effect of heat, is replaced by hydrogen atom, B 1Be singly-bound or divalent organic group, wherein, the atom of the ester group institute bonding in the formula (3) is carbon atom,
(B) composition: have the polyamic acid of the repetitive of following formula (4) expression,
[changing 3]
In the formula, X 24 valency organic groups, Y 2The divalent organic group, A 1And A 2With the A in the formula (1) 1And A 2Define identical.
2. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, (A) content of composition and (B) content of composition count 1/9～9/1 with mass ratio A/B.
3. aligning agent for liquid crystal as claimed in claim 1 or 2 is characterized in that, (A) composition and (B) the total content of composition be 1～10 quality % with respect to organic solvent.
4. such as each described aligning agent for liquid crystal in the claim 1～3, it is characterized in that protecting group D 1It is at least a group that is selected from tert-butoxycarbonyl and 9-fluorenyl methoxy carbonyl.
5. such as each described aligning agent for liquid crystal in the claim 1～4, it is characterized in that protecting group D 2It is the tert-butyl group.
6. such as each described aligning agent for liquid crystal in the claim 1～5, it is characterized in that (A) composition is to have a substituent poly amic acid ester that is selected from least a representation in following formula (5) and (6),
[changing 4]
In the formula (5), B 2Singly-bound or divalent organic group, R 2, R 3, R 4Be 1 valency organic group of hydrogen atom or carbon number 1～20 independently respectively,
[changing 5]
Figure FDA00002403104100023
In the formula (6), B 3Be singly-bound or divalent organic group, wherein, the atom of the tert-butoxycarbonyl institute bonding in the formula (6) is carbon atom.
7. such as each described aligning agent for liquid crystal in the claim 1～6, it is characterized in that (A) composition is the Y of formula (1) 1The substituent poly amic acid ester that has at least a representation in the formula of being selected from (5) and (6) in the structure.
8. such as each described aligning agent for liquid crystal in the claim 1～7, it is characterized in that (A) composition is the A of formula (1) 1, A 2Or the two has the substituent poly amic acid ester of at least a representation in the formula of being selected from (5) and (6).
9. such as each described aligning agent for liquid crystal in the claim 1～8, it is characterized in that (A) composition is the Y of formula (1) 1Be the poly amic acid ester of the structure of following formula (7) expression,
[changing 6]
Figure FDA00002403104100031
In the formula, R 5The divalent organic group of singly-bound or carbon number 1～20, R 6Be at least a structure that is selected from formula (5) and (6), a is 1～4 integer.
10. such as each described aligning agent for liquid crystal in the claim 1～9, it is characterized in that (A) composition is the Y of formula (1) 1Poly amic acid ester with at least a structure that is selected from the structure that following formula represents,
[changing 7]
Figure FDA00002403104100041
11. such as each described aligning agent for liquid crystal in the claim 1～10, it is characterized in that, in above-mentioned formula (1) and (4), X 1And X 2Respectively independently for being selected from least a in the structure that is expressed from the next,
[changing 8]
Figure FDA00002403104100042
12. such as each described aligning agent for liquid crystal in the claim 1～11, it is characterized in that, in the formula (4), Y 2For being selected from least a of structure that following formula represents,
Figure FDA00002403104100051
13. a liquid crystal orientation film is characterized in that, each described aligning agent for liquid crystal and burn till and obtain in the coating claim 1～12.
14. a liquid crystal orientation film is characterized in that, the coating claim 1～12 in each described aligning agent for liquid crystal, burn till, and the irradiation polarization ultraviolet ray and obtain.
CN201180024058.4A 2010-03-15 2011-03-15 Liquid crystal alignment agent containing polyamic acid ester, and liquid crystal alignment film Active CN102893209B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2010058552 2010-03-15
JP2010-058552 2010-03-15
PCT/JP2011/056072 WO2011115118A1 (en) 2010-03-15 2011-03-15 Liquid crystal alignment agent containing polyamic acid ester, and liquid crystal alignment film

Publications (2)

Publication Number Publication Date
CN102893209A true CN102893209A (en) 2013-01-23
CN102893209B CN102893209B (en) 2015-05-06

Family

ID=44649202

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180024058.4A Active CN102893209B (en) 2010-03-15 2011-03-15 Liquid crystal alignment agent containing polyamic acid ester, and liquid crystal alignment film

Country Status (5)

Country Link
JP (1) JP5915523B2 (en)
KR (1) KR101820981B1 (en)
CN (1) CN102893209B (en)
TW (1) TWI501998B (en)
WO (1) WO2011115118A1 (en)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104513669A (en) * 2013-10-03 2015-04-15 Jsr株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display device
CN105283801A (en) * 2013-03-25 2016-01-27 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
CN105593753A (en) * 2013-10-01 2016-05-18 日产化学工业株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using same
CN105593754A (en) * 2013-10-01 2016-05-18 日产化学工业株式会社 Liquid crystal aligning agent for in-plate switching, liquid crystal alignment film and liquid crystal display element using same
CN105849631A (en) * 2013-10-23 2016-08-10 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
CN105849630A (en) * 2013-10-23 2016-08-10 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
CN106047374A (en) * 2015-04-16 2016-10-26 Jsr株式会社 Liquid crystal aligning agent, liquid crystal aligning film, manufacturing method for liquid crystal aligning film, and liquid crystal element
CN107632461A (en) * 2016-07-19 2018-01-26 株式会社日本显示器 Optical alignment film varnish and liquid crystal display device
CN108139633A (en) * 2015-07-31 2018-06-08 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element
CN108604027A (en) * 2015-11-25 2018-09-28 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
CN108604028A (en) * 2015-11-30 2018-09-28 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
CN108604029A (en) * 2015-12-03 2018-09-28 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal expression element using it
CN109073935A (en) * 2016-01-07 2018-12-21 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal expression element using it
CN109196412A (en) * 2016-03-31 2019-01-11 日产化学株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
TWI665259B (en) * 2014-02-13 2019-07-11 日商日產化學工業股份有限公司 Novel liquid crystal alignment agents, diamines, and polyimide precursors
TWI673301B (en) * 2014-05-30 2019-10-01 日商日產化學工業股份有限公司 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
CN110300922A (en) * 2016-12-21 2019-10-01 日产化学株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
TWI675096B (en) * 2015-03-27 2019-10-21 日商Ｊｓｒ股份有限公司 Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, retardation film, and its production method, polymer and diamine
CN111936923A (en) * 2018-03-30 2020-11-13 日产化学株式会社 Novel liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
CN118005923A (en) * 2024-04-10 2024-05-10 浙江奥首材料科技有限公司 Polyamic acid ester varnish for flexible OLED display panel and preparation method thereof

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5929298B2 (en) * 2011-03-02 2016-06-01 Jnc株式会社 Diamine, liquid crystal aligning agent, liquid crystal display element using the same, and method for forming liquid crystal alignment film
JP5633714B2 (en) * 2011-07-14 2014-12-03 日産化学工業株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
TWI596137B (en) * 2011-10-27 2017-08-21 Nissan Chemical Ind Ltd Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
JP5939614B2 (en) * 2012-02-01 2016-06-22 株式会社ジャパンディスプレイ Alignment film and liquid crystal display device using the same
WO2013147083A1 (en) * 2012-03-30 2013-10-03 日産化学工業株式会社 Polyimide-based liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
CN104395820B (en) * 2012-04-18 2017-07-11 日产化学工业株式会社 The aligning agent for liquid crystal of optical alignment method, liquid crystal orientation film and liquid crystal display cells
CN104756001B (en) * 2012-08-29 2017-08-11 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells
DE102012223339A1 (en) 2012-12-17 2014-06-18 Henkel Ag & Co. Kgaa Surfactant combination for improved drying
CN105579897B (en) * 2013-07-24 2019-03-15 日产化学工业株式会社 Aligning agent for liquid crystal and the liquid crystal orientation film for having used it
JP6400284B2 (en) * 2013-10-22 2018-10-03 株式会社ジャパンディスプレイ Liquid crystal display
WO2015060360A1 (en) * 2013-10-23 2015-04-30 日産化学工業株式会社 Liquid crystal aligning agent containing polyimide precursor having thermally cleavable group and/or polyimide
CN105683827B (en) * 2013-10-23 2019-11-05 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal aligning element
CN105659156B (en) * 2013-10-23 2019-02-01 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
KR102346494B1 (en) * 2014-04-03 2021-12-31 닛산 가가쿠 가부시키가이샤 Liquid crystal alignment agent containing polyamic acid ester-polyamic acid copolymer, and liquid crystal alignment film using same
KR101732789B1 (en) 2014-04-04 2017-05-08 주식회사 엘지화학 Liquid Crystal Element
JP2016066053A (en) * 2014-09-19 2016-04-28 株式会社ジャパンディスプレイ Liquid crystal display device and material for alignment film
KR102512603B1 (en) * 2014-09-26 2023-03-21 닛산 가가쿠 가부시키가이샤 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
JP6701635B2 (en) * 2014-10-08 2020-05-27 Jsr株式会社 Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device
JP6461544B2 (en) * 2014-10-08 2019-01-30 株式会社ジャパンディスプレイ Liquid crystal display device and manufacturing method thereof
JP6776897B2 (en) * 2014-10-28 2020-10-28 日産化学株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
JP6631077B2 (en) * 2014-11-05 2020-01-15 Jsr株式会社 Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device
KR101989587B1 (en) 2016-03-28 2019-06-14 주식회사 엘지화학 Liquid crystal photoalignment agent, liquid crystal photoalignment film containing the same and method for preparing liquid crystal photoalignment film
JP6174194B2 (en) * 2016-05-12 2017-08-02 株式会社ジャパンディスプレイ Alignment film and liquid crystal display device using the same
JP6996509B2 (en) * 2016-08-30 2022-01-17 日産化学株式会社 Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element using it
KR20220046514A (en) * 2019-08-08 2022-04-14 닛산 가가쿠 가부시키가이샤 Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element using same
TW202142597A (en) * 2020-02-14 2021-11-16 日商日產化學股份有限公司 Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, and diamine

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05247209A (en) * 1992-03-05 1993-09-24 Chisso Corp Coating fluid for oriented liquid-crystal film and production thereof
CN1257587A (en) * 1998-03-19 2000-06-21 住友电木株式会社 Aligning agent for liquid crystal
CN1440516A (en) * 2000-07-07 2003-09-03 日产化学工业株式会社 Liquid crystal orientating agent and liquid crystal display element using the same
CN1585912A (en) * 2001-11-15 2005-02-23 日产化学工业株式会社 Liquid crystal aligning agent for vertical alignment, alignment layer for liquid crystal, and liquid crystal displays made by using the same
JP2007212542A (en) * 2006-02-07 2007-08-23 Asahi Kasei Electronics Co Ltd Laminate

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001089426A (en) 1999-09-14 2001-04-03 Fuji Photo Film Co Ltd New acetylene compound
WO2008153101A1 (en) * 2007-06-15 2008-12-18 Nissan Chemical Industries, Ltd. Resin composition for forming heat-cured film
CN101373296B (en) * 2007-08-24 2012-07-04 株式会社日立显示器 Liquid crystal display device and manufacturing method thereof
CN102067024B (en) 2008-06-17 2013-08-07 日产化学工业株式会社 Liquid-crystal alignment material, liquid-crystal display element employing same, and novel diamine
JP5355970B2 (en) * 2008-09-16 2013-11-27 株式会社ジャパンディスプレイ Liquid crystal display
KR101726456B1 (en) * 2009-03-10 2017-04-12 닛산 가가쿠 고교 가부시키 가이샤 Polyimide precursor, polyimide, and liquid-crystal alignment material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05247209A (en) * 1992-03-05 1993-09-24 Chisso Corp Coating fluid for oriented liquid-crystal film and production thereof
CN1257587A (en) * 1998-03-19 2000-06-21 住友电木株式会社 Aligning agent for liquid crystal
CN1440516A (en) * 2000-07-07 2003-09-03 日产化学工业株式会社 Liquid crystal orientating agent and liquid crystal display element using the same
CN1585912A (en) * 2001-11-15 2005-02-23 日产化学工业株式会社 Liquid crystal aligning agent for vertical alignment, alignment layer for liquid crystal, and liquid crystal displays made by using the same
JP2007212542A (en) * 2006-02-07 2007-08-23 Asahi Kasei Electronics Co Ltd Laminate

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105283801A (en) * 2013-03-25 2016-01-27 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
CN105283801B (en) * 2013-03-25 2019-07-09 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
CN105593753A (en) * 2013-10-01 2016-05-18 日产化学工业株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using same
CN105593754A (en) * 2013-10-01 2016-05-18 日产化学工业株式会社 Liquid crystal aligning agent for in-plate switching, liquid crystal alignment film and liquid crystal display element using same
CN105593754B (en) * 2013-10-01 2020-01-03 日产化学工业株式会社 Liquid crystal aligning agent for transverse electric field driving system, liquid crystal alignment film, and liquid crystal display element using same
CN104513669B (en) * 2013-10-03 2018-02-23 Jsr株式会社 Crystal aligning agent, liquid crystal orienting film and liquid crystal display cells
CN104513669A (en) * 2013-10-03 2015-04-15 Jsr株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display device
CN105849631B (en) * 2013-10-23 2019-04-16 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
CN105849631A (en) * 2013-10-23 2016-08-10 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
CN105849630A (en) * 2013-10-23 2016-08-10 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
CN105849630B (en) * 2013-10-23 2019-06-07 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
TWI665259B (en) * 2014-02-13 2019-07-11 日商日產化學工業股份有限公司 Novel liquid crystal alignment agents, diamines, and polyimide precursors
TWI673301B (en) * 2014-05-30 2019-10-01 日商日產化學工業股份有限公司 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
TWI675096B (en) * 2015-03-27 2019-10-21 日商Ｊｓｒ股份有限公司 Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, retardation film, and its production method, polymer and diamine
CN106047374A (en) * 2015-04-16 2016-10-26 Jsr株式会社 Liquid crystal aligning agent, liquid crystal aligning film, manufacturing method for liquid crystal aligning film, and liquid crystal element
CN108139633A (en) * 2015-07-31 2018-06-08 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element
CN108604027A (en) * 2015-11-25 2018-09-28 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
CN108604028A (en) * 2015-11-30 2018-09-28 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
TWI751995B (en) * 2015-12-03 2022-01-11 日商日產化學工業股份有限公司 Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element using the same
CN108604029A (en) * 2015-12-03 2018-09-28 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal expression element using it
CN109073935A (en) * 2016-01-07 2018-12-21 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal expression element using it
CN109196412A (en) * 2016-03-31 2019-01-11 日产化学株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
CN109196412B (en) * 2016-03-31 2021-08-24 日产化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
US10947345B2 (en) 2016-07-19 2021-03-16 Japan Display Inc. Varnish for photo alignment film and liquid crystal display device
CN107632461B (en) * 2016-07-19 2021-07-27 株式会社日本显示器 Varnish for photo-alignment film and liquid crystal display device
CN107632461A (en) * 2016-07-19 2018-01-26 株式会社日本显示器 Optical alignment film varnish and liquid crystal display device
US11384204B2 (en) 2016-07-19 2022-07-12 Japan Display Inc. Varnish for photo alignment film and liquid crystal display device
CN110300922A (en) * 2016-12-21 2019-10-01 日产化学株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
CN111936923A (en) * 2018-03-30 2020-11-13 日产化学株式会社 Novel liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
CN111936923B (en) * 2018-03-30 2023-12-22 日产化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
CN118005923A (en) * 2024-04-10 2024-05-10 浙江奥首材料科技有限公司 Polyamic acid ester varnish for flexible OLED display panel and preparation method thereof

Also Published As

Publication number Publication date
KR101820981B1 (en) 2018-01-22
TW201206994A (en) 2012-02-16
JPWO2011115118A1 (en) 2013-06-27
CN102893209B (en) 2015-05-06
TWI501998B (en) 2015-10-01
WO2011115118A1 (en) 2011-09-22
JP5915523B2 (en) 2016-05-11
KR20130048726A (en) 2013-05-10

Similar Documents

Publication Publication Date Title
CN102893209B (en) Liquid crystal alignment agent containing polyamic acid ester, and liquid crystal alignment film
CN102893208B (en) Liquid crystal alignment agent containing polyamic acid ester and polyamic acid, and liquid crystal alignment film
JP5708636B2 (en) End-modified polyamic acid ester-containing liquid crystal aligning agent and liquid crystal aligning film
CN103562784B (en) Aligning agent for liquid crystal and use the liquid crystal orientation film of this aligning agent for liquid crystal
WO2011115080A1 (en) Polyamic acid ester liquid crystal alignment agent, and liquid crystal alignment film using same
JP6064997B2 (en) Polyimide-based liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element
CN103282824B (en) Aligning agent for liquid crystal and liquid crystal orientation film
WO2013115228A1 (en) Novel diamine, polymer, liquid crystal alignment agent, and liquid crystal alignment film, and liquid crystal display element using same
CN102893210A (en) Liquid crystal alignment agent for use in photo-alignment process, and liquid crystal alignment film using same
CN103562783A (en) Liquid crystal aligning agent, and liquid crystal alignment film produced using same
WO2012102312A1 (en) Liquid crystal alignment agent containing both polyamic acid ester and polyamic acid
CN103797410B (en) Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells
JP6597645B2 (en) Liquid crystal alignment agent
CN102934011B (en) Comprise the aligning agent for liquid crystal to the poly amic acid ester that end is modified and liquid crystal orientation film
WO2014010402A1 (en) Liquid crystal alignment agent containing polyamic acid ester, liquid crystal alignment film, 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
C14 Grant of patent or utility model
GR01 Patent grant