CN102893209B - 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

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CN102893209B
CN102893209B CN201180024058.4A CN201180024058A CN102893209B CN 102893209 B CN102893209 B CN 102893209B CN 201180024058 A CN201180024058 A CN 201180024058A CN 102893209 B CN102893209 B CN 102893209B
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acid ester
polyamic acid
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CN102893209A (en
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作本直树
饭沼洋介
长尾将人
野口勇步
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Nissan Chemical Corp
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    • 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
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    • 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
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    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
    • C—CHEMISTRY; METALLURGY
    • 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

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Abstract

Disclosed is a liquid crystal alignment agent characterised by containing component (A) and component (B), wherein the component (A) has a polyamic acid ester which has a repeating group represented by general formula (1), and which fulfils the condition below; the component (B) has a polyamic acid which has a repeating group represented by general formula (4). 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

Aligning agent for liquid crystal containing poly amic acid ester and liquid crystal orientation film
Technical field
The present invention relates to containing the liquid crystal orientation film that there is the hot poly amic acid ester of detachment protecting group and the aligning agent for liquid crystal of polyamic acid and obtained by this aligning agent for liquid crystal.
Background technology
Liquid crystal display cells for LCD TV, liquid crystal display etc. arranges the liquid crystal orientation film of the state of orientation for controlling liquid crystal usually in element.All the time, the aligning agent for liquid crystal by being principal ingredient with the solution of the polyimide precursors such as polyamic acid (polyamic acid) or soluble polyimide is mainly used to coat glass substrate etc. and the polyimide liquid crystal orientation film burnt till as liquid crystal orientation film.
Along with the high-precision refinement of liquid crystal display cells, require to consider from the reduction etc. of the suppression reduced the contrast of liquid crystal display cells or ghost phenomena, in liquid crystal orientation film, following characteristic becomes important gradually: namely except embodying excellent liquid crystal aligning and stable tilt angle, also comprise high voltage holding ratio, to by exchange drive the ghost caused suppression, apply DC voltage time less residual charge and/or the characteristic such as the quick release of residual charge of putting aside because of DC voltage.
To polyimide liquid crystal orientation film, propose various scheme to adapt to above-mentioned requirements.Such as, the liquid crystal orientation film that time needed for disappearing as the ghost caused by DC voltage is short, propose use except polyamic acid and containing imide polyamic acid except also containing ad hoc structure tertiary amine aligning agent for liquid crystal liquid crystal orientation film (such as, referenced patent document 1) and use containing having the liquid crystal orientation film (such as, referenced patent document 2) etc. of specific diamine compound as the aligning agent for liquid crystal of the soluble polyimide of raw material of pyridine skeleton etc.In addition, as voltage retention high and that caused by DC voltage ghost disappear needed for time short liquid crystal orientation film, propose use except polyamic acid or its imide amination polymer etc. except, also to contain minute quantity be selected from molecule the liquid crystal orientation film (such as, referenced patent document 3) in the compound with a carboxylic acid group, the compound in molecule with an acid anhydride and molecule with the aligning agent for liquid crystal of the compound of the compound of a tertiary amine groups.
In addition, excellent as liquid crystal aligning, voltage retention is high, ghost is few, excellent in reliability and show the liquid crystal orientation film of high tilt angle, the known liquid crystal orientation film employing aligning agent for liquid crystal containing polyamic acid or its imide amination polymer, described polyamic acid is by the tetracarboxylic dianhydride of the tetracarboxylic dianhydride and cyclo-butane with ad hoc structure and specific diamine compound obtained (such as, referenced patent document 4).In addition, as the method being driven the ghost caused by interchange suppressing to occur in the liquid crystal display cells of transverse electric field drive pattern, propose and use liquid crystal aligning well and the method (referenced patent document 5) of the specific liquid crystal orientation film large with the interaction of liquid crystal molecule.
But, giant-screen and the LCD TV of fine becomes main body in recent years, more and more stricter to the requirement of ghost, and require that there is the characteristic that can tolerate Long-Time Service under the environment for use of harshness.Simultaneously, require that the liquid crystal orientation film reliability compared with liquid crystal orientation film in the past used is higher gradually, for liquid crystal orientation film many characteristics also, not only require that initial characteristic is good, even if also good characteristic can be maintained after also requiring such as to be exposed to for a long time under high temperature.
On the other hand, report is had to claim, as the component of polymer forming polyimide aligning agent for liquid crystal, because poly amic acid ester can not because causing the reduction of molecular weight by heating during its imidizate, the therefore orientation stability of liquid crystal and (referenced patent document 6) excellent in reliability.But poly amic acid ester has that specific insulation is high, problems such as residual charge is many when applying DC voltage usually, but not yet knows the method for the characteristic of the aligning agent for liquid crystal of the polyimide improved containing described poly amic acid ester.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 9-316200 publication
Patent documentation 2: Japanese Patent Laid-Open 10-104633 publication
Patent documentation 3: Japanese Patent Laid-Open 8-76128 publication
Patent documentation 4: Japanese Patent Laid-Open 9-138414 publication
Patent documentation 5: Japanese Patent Laid-Open 11-38415 publication
Patent documentation 6: Japanese Patent Laid-Open 2003-26918 publication
Summary of the invention
As improving the above-mentioned method containing the characteristic of the aligning agent for liquid crystal of poly amic acid ester, the present invention is conceived to the aligning agent for liquid crystal of the polyamic acid being doped with poly amic acid ester and electrical characteristics aspect excellence.But the described liquid crystal orientation film obtained by the aligning agent for liquid crystal being doped with poly amic acid ester and polyamic acid all cannot be satisfactory in liquid crystal aligning and electrical characteristics.
Namely, by the obtained liquid crystal orientation film of the aligning agent for liquid crystal containing poly amic acid ester and polyamic acid except causing gonorrhoea phenomenon, when also occurring at high temperature to use film voltage retention reduce, the generation of ghost that caused by the accumulation of DC voltage and abnormal by exchanging the generation that drives the ghost caused etc.
The object of the present invention is to provide a kind of aligning agent for liquid crystal containing poly amic acid ester and polyamic acid, its can obtain liquid crystal aligning and electrical characteristics all good and there is no the liquid crystal orientation film with the transparency of gonorrhoea.
According to the research of the present inventor, the liquid crystal orientation film formed by the aligning agent for liquid crystal containing poly amic acid ester and polyamic acid is analyzed, trickle in film Surface Creation concavo-convex of results verification.But, inventor finds, by using the poly amic acid ester with the ad hoc structure with the functional group replaced by hydrogen atom under the action of heat as described below, significantly can suppress the micro concavo-convex of film Surface Creation, inventor also finds, when reducing the micro concavo-convex of described film Surface Creation, the above-mentioned shortcoming that the aligning agent for liquid crystal containing poly amic acid ester and polyamic acid has is eliminated.
And then, according to the Knowledge Discovery of the present inventor, when the poly amic acid ester of the above-mentioned functional group with being replaced by hydrogen atom is under the action of heat high molecular, dissolubility is in organic solvent also good, also viscosity lower aligning agent for liquid crystal can be made when containing the described aligning agent for liquid crystal containing poly amic acid ester with high concentration in organic solvent, thus, easily can manufacture liquid crystal orientation film by such as ink-jet method, also easily can manufacture the large liquid crystal orientation film of thickness.
Like this, the present invention is the invention completed based on above-mentioned knowledge, comprises following technology contents.
1. an aligning agent for liquid crystal, is characterized in that, containing, for example under (A) composition and (B) composition.
(A) composition: the poly amic acid ester with the repetitive that following formula (1) represents, and the poly amic acid ester meeting condition any one of following (i) ~ (iii).
[changing 1]
(in formula, X 14 valency organic groups, Y 1divalent organic group, R 1the alkyl of carbon number 1 ~ 5, A 1and A 2separately for hydrogen atom maybe can have alkyl, alkenyl, the alkyl of substituent carbon number 1 ~ 20)
(i) the X of formula (1) 1, Y 2or both has 1 valency or the divalent substituting group of at least one structure be selected from following formula (2) and (3).
(ii) the A of formula (1) 1, A 2or both has 1 valency or the divalent substituting group of at least one structure be selected from following formula (2) and (3).
(iii) the X of formula (1) 1, Y 2or both has 1 valency or the divalent substituting group of at least one structure be selected from following formula (2) and (3), and A 1, A 2or both has 1 valency or the divalent substituting group of at least one structure be selected from following formula (2) and (3).
[changing 2]
(the D of formula (2) and formula (3) 1and D 2under the action of heat by protecting group that hydrogen atom replaces respectively.B 1singly-bound or divalent organic group.Wherein, the atom of the ester group institute bonding in formula (3) is carbon atom)
(B) composition: the polyamic acid with the repetitive that following formula (4) represents.
[changing 3]
(in formula, X 24 valency organic groups, Y 2divalent organic group, A 1and A 2with the A in formula (1) 1and A 2define identical)
2. the aligning agent for liquid crystal as described in above-mentioned 1, is characterized in that, the content of (A) composition and the content of (B) composition count 1/9 ~ 9/1 with mass ratio A/B.
3. the aligning agent for liquid crystal as described in above-mentioned 1 or 2, is characterized in that, the total content of described (A) composition and (B) composition is 1 ~ 10 quality % relative to organic solvent.
4. aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 3, is characterized in that, protecting group D 1it is at least one group being selected from tert-butoxycarbonyl and 9-fluorenylmethoxycarbonyl groups.
5. aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 4, is characterized in that, protecting group D 2it is the tert-butyl group.
6., as the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 5, it is characterized in that, (A) composition is the substituent poly amic acid ester with at least one representation be selected from following formula (5) and (6).
[changing 4]
(in formula (5), B 2singly-bound or divalent organic group, R 2, R 3, R 4be separately 1 valency organic group of hydrogen atom or carbon number 1 ~ 20)
[changing 5]
(in formula (6), B 3singly-bound or divalent organic group.Wherein, the atom of tert-butoxycarbonyl institute bonding that formula (6) is expressed is carbon atom)
7., as the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 6, it is characterized in that, (A) composition is the Y of formula (1) 1there is in structure the substituent poly amic acid ester of at least one representation in the formula of being selected from (5) and (6).
8., as the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 7, it is characterized in that, (A) composition is the A of formula (1) 1, A 2or both has the substituent poly amic acid ester of at least one representation in the formula of being selected from (5) and (6).
9., as the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 8, it is characterized in that, (A) composition is the Y of formula (1) 1for the poly amic acid ester of the structure that following formula (7) represents.
[changing 6]
(in formula, R 5it is the divalent organic group of singly-bound or carbon number 1 ~ 20.R 6it is at least one structure being selected from formula (5) and (6).A is the integer of 1 ~ 4)
10 as the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 9, and it is characterized in that, (A) composition is the Y of formula (1) 1there is the poly amic acid ester of at least one structure being selected from the structure that following formula represents.
[changing 7]
11., as aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 10, is characterized in that, in above-mentioned formula (1) and (4), and X 1and X 2structure separately for being selected from least one in the structure that is expressed from the next.
[changing 8]
12., as the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 11, is characterized in that, in formula (4), and Y 2for being selected from least one of the structure that following formula represents.
[changing 9]
13. 1 kinds of liquid crystal orientation films, is characterized in that, are coated with the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 12 and burn till and obtain.
14. 1 kinds of liquid crystal orientation films, is characterized in that, are coated with the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 12, burn till, and irradiate the ultraviolet of polarization and obtain.
Pass through the present invention, a kind of surperficial micro concavo-convex that can reduce the liquid crystal orientation film obtained is provided, interchange drives the liquid crystal of the ghost reduction caused etc. and the interfacial characteristics of liquid crystal orientation film to be enhanced, and residual etc. the electrical characteristics of voltage retention, ion concentration and DC voltage are also enhanced, the aligning agent for liquid crystal that reliability improves.
In addition, when containing aligning agent for liquid crystal of the present invention with high concentration in organic solvent, viscosity is also lower, thus, easily can manufacture liquid crystal orientation film by such as ink-jet method, also easily can manufacture the large liquid crystal orientation film of thickness.
In the present invention, by using the poly amic acid ester of the ad hoc structure had with the functional group replaced by hydrogen atom under the action of heat, the shortcoming that fine concavo-convex, containing poly amic acid ester and polyamic acid the aligning agent for liquid crystal that can reduce that described film generates on the surface why has is that assorted meeting is eliminated and does not still understand, but inventor thinks following reason.
Namely, be dissolved in the aligning agent for liquid crystal of organic solvent except in the liquid crystal orientation film formed after desolventizing 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 surface, but be separated because poly amic acid ester and polyamic acid cause, poly amic acid ester mutually in formed polyamic acid condensed matter or polyamic acid mutually in form the condensed matter of poly amic acid ester, become the film that there is a large amount of fine irregularities on film surface thus.
In contrast, in aligning agent for liquid crystal of the present invention, by using the above-mentioned poly amic acid ester with ad hoc structure with the functional group replaced by hydrogen atom under the action of heat, time from this aligning agent for liquid crystal except desolventizing, formation liquid crystal orientation film, poly amic acid ester and being separated of polyamic acid are promoted, poly amic acid ester does not mix with polyamic acid at film near surface and exists, and polyamic acid does not mix with poly amic acid ester and exists on film inside and substrate interface.
Like this, the surface of obtained liquid crystal orientation film can not be formed by poly amic acid ester and polyamic acid be separated and cause concavo-convex, thus become level and smooth surface, the gonorrhoea of the film caused by concavo-convex generation also reduces.Further, think because orientation stability, poly amic acid ester excellent in reliability are present in surface, and the polyamic acid of electrical characteristics excellence is present in film inside and electrode interface, the liquid crystal orientation film therefore possessing 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 by imidizate subsequently and burn till the heating in process and replaced by hydrogen atom, therefore, above-mentioned functional group is there is not in obtained liquid crystal orientation film, there is not the impact brought by the existence of the functional group of these ad hoc structures yet, can obtain having with use there is no the poly amic acid ester of the functional group of ad hoc structure time same characteristic liquid crystal orientation film.
Embodiment
< poly amic acid ester and polyamic acid >
The poly amic acid ester used in the present invention and polyamic acid are the polyimide precursors for obtaining polyimide, for having the polymkeric substance that can be carried out the position of following imidization reaction by heating.
[changing 10]
[changing 11]
The poly amic acid ester contained in aligning agent for liquid crystal of the present invention and polyamic acid have following formula (1) and following formula (4) respectively.
[changing 12]
In above formula (1), R 1for carbon number 1 ~ 5, be better 1 ~ 2 alkyl.Along with the increase of the carbon number of alkyl in poly amic acid ester, the temperature of carrying out imidizate uprises.Therefore, be easy to viewpoint from the imidizate caused because of heat and consider, R 1spy is methyl well.In formula (1) and formula (4), A 1and A 2separately for hydrogen atom maybe can have the alkyl of substituent carbon number 1 ~ 20, alkenyl or alkynyl.As the concrete example of abovementioned alkyl, can 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 and will be present in more than one CH in 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 and will be present in more than one CH in described alkyl 2-CH 2structure is substituted by the group of C ≡ C-structure, more specifically can exemplify ethinyl, 1-propinyl, 2-propynyl etc.
As long as the overall carbon number of abovementioned alkyl, alkenyl, alkynyl is 1 ~ 20 also can have substituting group, ring structure can also be formed by substituting group.Formed by substituting group ring structure represent between substituting group or substituting group and main body framework a part of bonding and become ring structure.
As this substituent example, 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 can be exemplified.
The alternatively halogen group of base, can exemplify fluorine atom, chlorine atom, bromine atoms, atomic iodine.
Alternatively the aryl of base can exemplified by phenyl.This aryl can be replaced by other above-mentioned substituting groups further.
The structure that alternatively organic oxygen base of base can be represented by-O-R-represents.This R may be the same or different, and can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.Can also replace further in these R and have above-mentioned substituting group.As the concrete example of organic oxygen base, can exemplify methoxyl, ethoxy, propoxyl group, butoxy, amoxy, own oxygen base, heptan oxygen base, octyloxy etc.
The structure that alternatively organic sulfenyl of base can be represented by-S-R represents.As this R, above-mentioned alkyl, alkenyl, alkynyl, aryl etc. can be exemplified.Can also replace further in these R and have above-mentioned substituting group.As the concrete example of organic sulfenyl, can exemplify methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl, heptan sulfenyl, pungent sulfenyl etc.
Alternatively the organosilicon alkyl of base can by-Si-(R) 3the structure represented represents.This R may be the same or different, and can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.Can also replace further in these R and have above-mentioned substituting group.As the concrete example of organosilicon alkyl, TMS, triethyl silyl, tripropyl silylation, tributyl silylation, three pentylsilane bases, three hexyl silane bases, amyl dimethyl silylation, hexyl dimethylsilyl etc. can be exemplified.
Alternatively the acyl group of base can by-C(O) structure that represents of-R represents.As this R, above-mentioned alkyl, alkenyl, aryl etc. can be exemplified.Can also replace further in these R and have above-mentioned substituting group.As the concrete example of acyl group, formoxyl, acetyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl, benzoyl etc. can be exemplified.
Alternatively the ester group of base can by-C(O) structure that represents of O-R or-OC (O)-R represents.As this R, above-mentioned alkyl, alkenyl, alkynyl, aryl etc. can be exemplified.Can also replace further in these R and have above-mentioned substituting group.
Alternatively the thioester substrate of base can by-C(S) structure that represents of O-R or-OC (S)-R represents.As this R, above-mentioned alkyl, alkenyl, alkynyl, aryl etc. can be exemplified.Can also replace further in these R and have above-mentioned substituting group.
Alternatively the phosphate-based of base can by-OP(O)-(OR) 2the structure represented represents.This R may be the same or different, and can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.Can also replace further in these R and have above-mentioned substituting group.
Alternatively the amide group of base can by-C (O) NH 2, or-C (O) NHR ,-NHC (O) R ,-C (O) N (R) 2, the structure that represents of-NRC (O) R represents.This R may be the same or different, and can exemplify above-mentioned alkyl, alkenyl, alkynyl, aryl etc.Can also replace further in these R and have above-mentioned substituting group.
The alternatively aryl of base, can exemplify the group identical with above-mentioned aryl.This aryl can be replaced by other above-mentioned substituting groups further.
The alternatively alkyl of base, can exemplify the group identical with above-mentioned alkyl.This alkyl can be replaced by other above-mentioned substituting groups further.
The alternatively alkenyl of base, can exemplify the group identical with above-mentioned alkenyl.This alkenyl can be replaced by other above-mentioned substituting groups further.
The alternatively alkynyl of base, can exemplify the group identical with above-mentioned alkynyl.This alkynyl can be replaced by other above-mentioned substituting groups further.
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, spy is well hydrogen atom, methyl or ethyl.
In above-mentioned formula (1) and formula (4), X 1and X 2be separately the organic group of 4 valencys, Y1 and Y 2it is separately the organic group of divalent.X 1, X 2be the organic group of 4 valencys, be not particularly limited.In polyimide precursor, X 1, X 2can mix and have two or more.If enumerate X 1, X 2concrete example, then separately can exemplify the X-1 ~ X-46 of following expression.Wherein, consider from the complexity obtaining monomer, X 1, X 2better be separately 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]
[changing 14]
[changing 15]
[changing 16]
In addition, in formula (1) and (4), Y 1, Y 2be separately the organic group of divalent, be not particularly limited.In polyimide precursor, Y 1and Y 2separately can mix and have two or more.If enumerate Y 1, Y 2concrete example, then can exemplify following Y-1 ~ Y-103.
Wherein, in order to obtain good liquid crystal aligning, be better that linearly high diamines is incorporated in 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, be better by side chain has chain alkyl, aromatic ring, aliphatics ring, steroid skeleton or their combination the diamines of structure be incorporated in 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, arbitrary tilt angle can be embodied.
By reducing the specific insulation of polyamic acid, the ghost caused by the savings of DC voltage can be reduced, therefore be better that the diamines having heteroatomic structure, Ppolynuclear aromatic structure or have a biphenyl backbone is incorporated in 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]
[changing 18]
[changing 19]
[changing 20]
[changing 21]
[changing 22]
[changing 23]
[changing 24]
[changing 25]
[changing 26]
[changing 27]
[changing 28]
[changing 29]
Wherein, the Y in above-mentioned formula (1) 1it is better the structure that following formula (7) represents.
[changing 30]
In formula (7), R 5be singly-bound or carbon number 1 ~ 20, be better 1 ~ 12 divalent organic group.Divalent organic group is better to contain the alkylidene of ehter bond, amido link, ester bond, thioester bond or thioether bond, arlydene or their combination.R 6it is at least one structure being selected from above formula (5) and (6).A is the integer of 1 ~ 4, is better the integer of 1 or 2.
In addition, in above formula (1), be better that the Y1 of formula (1) has at least one structure be selected from structure that following formula represents.
[changing 31]
In addition, wherein, the Y in above-mentioned formula (4) 2particularly preferably be selected from least one of the structure that following formula represents.
[changing 32]
The manufacture method > of < poly amic acid ester
The poly amic acid ester represented by above-mentioned formula (1) obtains by any one and the polycondensation reaction of diamine compound that represented by formula (13) of the tetracarboxylic acid derivatives that represented by following formula (10) ~ (12).
[changing 33]
[changing 34]
(in formula, X 1, Y 1, R 1, A 1and A 2identical with the definition in above-mentioned formula (1) respectively)
The poly amic acid ester represented by above-mentioned formula (1), by using above-mentioned monomer, adopts the method synthesis of following (1) ~ (3) represented.
(1) situation of being synthesized by polyamic acid
Poly amic acid ester is by synthesizing the polyamic acid esterification obtained by tetracarboxylic dianhydride and diamines.
[changing 35]
Particularly, in presence of organic solvent in-20 DEG C ~ 150 DEG C, being better at 0 DEG C ~ 50 DEG C, making polyamic acid and esterifying agent react 30 minutes ~ 24 hours, is better that reaction is synthesized for 1 ~ 4 hour.
It is better the esterifying agent easily removed by purifying as esterifying agent, N can be exemplified, 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-(4,6-dimethoxy)-1,3,5-triazine-2 base)-4-methyl morpholine hydrochloride etc.The addition of esterifying agent is relative to repetitive preferably 2 ~ 6 molar equivalents of the polyamic acid of 1 mole.
Consider from structure adaptability, the solvent used in above-mentioned reaction is better DMF, METHYLPYRROLIDONE or gamma-butyrolacton, and these can use one kind or two or more used in combination.From the viewpoint of not easily causing the precipitation of polymkeric substance and easily obtaining high molecular thing, concentration during synthesis is better 1 ~ 30 quality %, is more preferably 5 ~ 20 quality %.
(2) by the situation of the Reactive Synthesis of dichloride tetrabasic carboxylic acid diester and diamines
Poly amic acid ester can be synthesized by the polycondensation reaction of dichloride tetrabasic carboxylic acid diester and diamines.
[changing 36]
Particularly, in-20 DEG C ~ 150 DEG C under the existence of alkali and organic solvent, be better at 0 DEG C ~ 50 DEG C, making dichloride tetrabasic carboxylic acid diester and diamine reactant 30 minutes ~ 24 hours, is better that reaction is synthesized for 1 ~ 4 hour.
Described alkali can use pyridine, triethylamine, 4-dimethylaminopyridine etc., in order to make reaction temperature and carry out, preferred pyridine.Easily obtain high molecular thing from the viewpoint of the amount for easily removing, the addition of alkali is better 2 ~ 4 times moles relative to dichloride tetrabasic carboxylic acid diester.
Consider from monomer and structure adaptability, the solvent used in above-mentioned reaction is better METHYLPYRROLIDONE, gamma-butyrolacton, and these can be one kind or two or more used in combination.From the viewpoint of not easily causing the precipitation of polymkeric substance and easily obtaining high molecular thing, concentration during synthesis is better 1 ~ 30 quality %, is more preferably 5 ~ 20 quality %.In addition, in order to prevent dichloride tetrabasic carboxylic acid two ester hydrolysis, the solvent used in synthesizing polyamides acid esters is better dehydrated as far as possible, is better in nitrogen atmosphere, prevents being mixed into of foreign gas.
(3) by the situation of tetrabasic carboxylic acid diester and the acid of diamines synthesizing polyamides
Poly amic acid ester synthesizes by polycondensation tetrabasic carboxylic acid diester and diamines.
[changing 37]
Particularly, in 0 DEG C ~ 150 DEG C under the existence of condensation agent, alkali and organic solvent, be better at 0 DEG C ~ 100 DEG C, making tetrabasic carboxylic acid diester and diamine reactant 30 minutes ~ 24 hours, is better that reaction is synthesized for 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-base)-N, N, N ', N '-tetramethylurea (TMU) tetrafluoro boric acid ester, O-(benzotriazole-1-base)-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 is better 2 ~ 3 times moles relative to tetrabasic carboxylic acid diester.
Described alkali can use the tertiary amine such as pyridine, triethylamine.Easily obtain high molecular thing from the viewpoint of the amount for easily removing, the addition of alkali is better 2 ~ 4 times moles relative to diamine component.
In addition, in above-mentioned reaction, by adding lewis acid as adjuvant, reaction is effectively carried out.As lewis acid, it is better the lithium halide such as lithium chloride, lithium bromide.Lewis acidic addition is better 0 ~ 1.0 times mole relative to diamine component.
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, spy is well the synthetic method of above-mentioned (1) or above-mentioned (2).
The solution of poly amic acid ester obtained as mentioned above makes polymkeric substance separate out by well-beaten being injected in Weak solvent simultaneously.By to separate out for several times and after cleaning with Weak solvent, at normal temperatures or heat drying, the powder of sublimed poly amic acid ester can be obtained.Weak solvent is not particularly limited, water, methyl alcohol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. can be exemplified.
The manufacture method > of < polyamic acid
The polyamic acid that above-mentioned formula (4) represents obtains with the polycondensation reaction of the diamine compound represented by formula (15) by the tetracarboxylic dianhydride represented by following formula (14).
[changing 38]
Particularly, in presence of organic solvent in-20 DEG C ~ 150 DEG C, be better at 0 DEG C ~ 50 DEG C, making tetracarboxylic dianhydride and diamine reactant 30 minutes ~ 24 hours, is better that reaction is synthesized for 1 ~ 12 hour.
Consider from monomer and structure adaptability, the organic solvent used in above-mentioned reaction is better DMF, METHYLPYRROLIDONE, gamma-butyrolacton, and these can use one kind or two or more used in combination.From the viewpoint of not easily causing the precipitation of polymkeric substance and easily obtaining high molecular thing, the concentration of polymkeric substance is better 1 ~ 30 quality %, is more preferably 5 ~ 20 quality %.
Polyamic acid obtained as mentioned above makes polymkeric substance separate out by injecting Weak solvent while abundant stirring reaction solution and reclaims.In addition, carry out several and to separate out and after cleaning with Weak solvent, can by normal temperatures or heat drying obtain the powder of sublimed polyamic acid.Weak solvent is not particularly limited, water, methyl alcohol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. can be exemplified.
< has the poly amic acid ester > of hot detachment protecting group
The poly amic acid ester with hot detachment protecting group recorded in the present invention is the poly amic acid ester with the repetitive that above-mentioned formula (1) represents, and be meet (i) following ~ (iii) any one of the poly amic acid ester of condition.
(i) the X of formula (1) 1, Y 2or both has 1 valency or the divalent substituting group of at least one structure be selected from following formula (2) and (3).
(ii) the A of formula (1) 1, A 2or both has 1 valency or the divalent substituting group of at least one structure be selected from following formula (2) and (3).
(iii) the X of formula (1) 1, Y 2or both has 1 valency or the divalent substituting group of at least one structure be selected from following formula (2) and (3), and A 1, A 2or both has 1 valency or the divalent substituting group of at least one structure be selected from following formula (2) and (3).
[changing 39]
In formula (2), D 1amino protecting group, as long as be then not particularly limited by the functional group that hydrogen atom replaces by heating.As D 1, being better the structure of efficiently carrying out departing from reaction at the firing temperature 150 DEG C ~ 300 DEG C when obtaining liquid crystal orientation film, being more preferably tert-butoxycarbonyl or 9-fluorenylmethoxycarbonyl groups, particularly preferably tert-butoxycarbonyl.
In formula (3), B 1singly-bound or divalent organic group.As the better example of divalent organic group, can exemplify can contain ehter bond, amido link, ester bond, thioester bond or thioether bond alkylidene, arlydene or their combination.In addition, the atom of the ester group institute bonding in formula (3) is carbon.
D 1the method that 1 valency of the structure represented for the formula (2) of tert-butoxycarbonyl or 9-fluorenylmethoxycarbonyl groups or divalent substituting group can be acted in the presence of a base by the compound with primary amino radical or secondary amino group that makes following formula represent and di-tert-butyl dicarbonate, or make to have the method that the compound of primary amino radical or secondary amino group and carbonochloridic acid-9-fluorenylmethvl ester act in the presence of a base and obtain, as long as known method is then not particularly limited.
[changing 40]
By what obtained by said method, there is substituent compound and tetracarboxylic acid derivatives or its precursor and the addition of diamine compound or derivatives thereof; synthesize the substituent tetracarboxylic acid derivatives and/or diamines that have with the functional group replaced by hydrogen atom under the action of heat; it can be used as the raw material of poly amic acid ester, obtain the poly amic acid ester with hot detachment protecting group of the present invention thus.
In formula (3), D 2the protecting group of carboxyl, as long as the functional group replaced by hydrogen atom by heating then its structure be not particularly limited.As D 2, being better the structure of efficiently carrying out departing from reaction at the firing temperature 150 DEG C ~ 300 DEG C when obtaining liquid crystal orientation film, being more preferably the functional group of following formula (D2-1) ~ (D2-5), particularly preferably following formula (D2-1).
[changing 41]
In 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 21 valency substituting group of the structure represented for the formula (3) of above-mentioned (D2-1) can by the method for the carboxyl that makes following formula represent and tert-butyl alcohol reaction, make the method for chlorocarbonylation compound and tert-butyl alcohol reaction or the method for carboxyl and tert-butyl group halide reaction obtained, as long as known method is just not particularly limited.By what obtained by said method, there is substituent compound and tetracarboxylic acid derivatives or its precursor and diamine compound or its precursor addition; synthesize the substituent tetracarboxylic acid derivatives and/or diamines that have with the functional group replaced by hydrogen atom under the action of heat; it can be used as the raw material of poly amic acid ester, thus the obtained poly amic acid ester with hot detachment protecting group of the present invention.
[changing 42]
In the structural unit that the poly amic acid ester with hot detachment protecting group of the present invention comprises, the position that at least one substituting group being selected from formula (2) and (3) exists can be the X of formula (1) 1, Y 2, A 1, A 2any position.Wherein, simplicity when forming the monomer of raw material of poly amic acid ester from the viewpoint of synthesis and the operation complexity of this monomer are better the Y of formula (1) 1there is in structure the substituent mode of at least one of the formula of being selected from (2) and (3) and the A of formula (1) 1, A 2or both has the substituent mode of at least one of the formula of being selected from (2) and formula (3).
The poly amic acid ester with hot detachment protecting group of the present invention also can contain that formula (1) represents and at X 1, Y 1, A 1, A 2any position there is not the substituent structural unit that formula (2) and (3) represent.If the substituent introduction volume that formula (2) and (3) represent is very few, then suppress little by the effect of the micro concavo-convex caused that is separated of poly amic acid ester and polyamic acid, therefore, at X 1, Y 1, A 1, A 2the formula (2) that exists of any position and (3) substituent containing ratio of representing be benchmark with the structural unit that formula (1) represents be better more than 0.05, spy is more than 0.10 well.
In above-mentioned definition, the structural unit that the formula (1) such as, contained in poly amic acid ester represents is only " the X of formula (1) 1and Y 1middle respectively have a kind of substituting group that is selected from formula (2) and (3) respectively, and A 1or A 2the substituent structural unit of one being selected from formula (2) and (3) " time, the substituent containing ratio that the formula (2) in this poly amic acid ester and (3) represent is 4.00.
As the substituent concrete example with the functional group replaced by hydrogen atom under the action of heat that above-mentioned formula (2) and (3) represent, following (D-1) ~ (D-24) can be exemplified, but be not limited thereto.
[changing 43]
[changing 44]
[changing 45]
[changing 46]
[changing 47]
In addition, as above-mentioned formula (2) and (3) represent containing the substituent diamine compound with the functional group replaced by hydrogen atom under the action of heat, the diamine compound that following formula (D-25) ~ (D-35) represents can be exemplified, but be not limited thereto.
[changing 48]
[changing 50]
[changing 51]
< aligning agent for liquid crystal >
Aligning agent for liquid crystal of the present invention have above-mentioned there is hot detachment protecting group poly amic acid ester and polyamic acid be dissolved in the form of the solution in organic solvent.It is 2000 ~ 500000 that the molecular weight with the poly amic acid ester of hot detachment protecting group is haggled over weight-average molecular weight, and being more preferably 5000 ~ 300000, is 10000 ~ 100000 well further.In addition, number-average molecular weight is better 1000 ~ 250000, is more preferably 2500 ~ 150000, is 5000 ~ 50000 well further.
On the other hand, the weight-average molecular weight of polyamic acid is better 2000 ~ 500000, is more preferably 5000 ~ 300000, is 10000 ~ 100000 well further.In addition, number-average molecular weight is better 1000 ~ 250000, is more preferably 2500 ~ 150000, is 5000 ~ 50000 well further.
By making the molecular weight of the poly amic acid ester with hot detachment protecting group be less than polyamic acid, the minute asperities caused because being separated can be reduced further.The difference with the hot poly amic acid ester of detachment protecting group and the weight-average molecular weight of polyamic acid is better 1000 ~ 200000, is more preferably 5000 ~ 150000, and spy is 10000 ~ 100000 well.
In aligning agent for liquid crystal of the present invention, poly amic acid ester and the haggling over quality criteria containing ratio (poly amic acid ester/polyamic acid) of polyamic acid with hot detachment protecting group are 1/9 ~ 9/1.Described ratio is more preferably 2/8, and spy is 3/7 ~ 7/3 well.By making described ratio within the scope of this, the aligning agent for liquid crystal that liquid crystal aligning and electrical characteristics are all good can be provided.
As long as aligning agent for liquid crystal of the present invention has the solution morphology that the poly amic acid ester of hot detachment protecting group and polyamic acid are dissolved in organic solvent, then its manufacture method does not limit.Such as there is the powder of mixed polyamide acid esters and polyamic acid 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.Even if because uniform poly amic acid ester-polyamic acid mixed solution also can be obtained, so be more preferably the method for mixed polyamide acid esters solution and polyamic acid solution when dissolving poly amic acid ester is different with the good solvent of polyamic acid.
In addition, when manufacture has poly amic acid ester and/or the polyamic acid of hot detachment protecting group in organic solvent, can be obtained reaction solution itself, also can be the solution obtained with the suitable broad liquid of this reaction of solvent dilution.In addition, when obtaining the poly amic acid ester with hot detachment protecting group as powder, it also can be made to be dissolved in solution in organic solvent.
The concentration of the poly amic acid ester in aligning agent for liquid crystal of the present invention and polyamic acid (sometimes also referred to as polymkeric substance in the present invention) suitably can change according to wanting the setting of the thickness of the film formed, from the viewpoint forming uniform flawless film, being better more than 1 quality %, is better below 10 quality % from the viewpoint of the storage stability of solution.
The above-mentioned organic solvent contained in aligning agent for liquid crystal of the present invention, as long as have the amic acid esters of the protecting group of hot detachment and the component of polymer uniform dissolution of polyamic acid, is then 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-dimethylpropionamide etc.These can use one kind or two or more used in combination.In addition, even separately cannot the 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 adding silane coupling agent in aligning agent for liquid crystal of the present invention, before mixed polyamide acid esters solution and polyamic acid solution, can make an addition in polyamic acid ester solution, polyamic acid solution or polyamic acid ester solution and polyamic acid solution.In addition, can be added in poly amic acid ester-polyamic acid mixed solution.Owing to being add silane coupling agent for the purpose of the adaptation improving polymkeric substance and substrate, therefore as the adding method of silane coupling agent, better be added on the polyamic acid solution that most can be arranged in film inside and substrate interface, after polymkeric substance and silane coupling agent are fully reacted, the method mixed with polyamic acid ester solution.When the addition of silane coupling agent is too much, unreacted reactant causes harmful effect to liquid crystal aligning, time very few, cannot embody adaptation effect, is therefore better 0.01 ~ 5.0 % by weight relative to the solid constituent of polymkeric substance, is more preferably 0.1 ~ 1.0 % by weight.
Aligning agent for liquid crystal of the present invention, except comprising the organic solvent for the purpose of dissolve polymer, also can comprise the solvent for the purpose of the painting film uniformity improved when aligning agent for liquid crystal being coated substrate.Described solvent uses the solvent lower with described organic solvent phase specific surface tension usually.Ethyl cellosolve can be exemplified as its concrete example, butyl cellosolve, ethyl carbitol, butyl carbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, single propylene glycol acetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, propylene glycol-1-single ethylether-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 and use two or more.
Aligning agent for liquid crystal of the present invention can comprise the various adjuvant such as silane coupling agent and crosslinking chemical.When adding silane coupling agent and crosslinking chemical, in order to prevent the precipitation of polymkeric substance, be better added before Weak solvent is added in aligning agent for liquid crystal.In addition, in order to effectively carry out the imidizate of poly amic acid ester when burning till film, also imidizate promoter can be added.
Below exemplify the concrete example of silane coupling agent, but in aligning agent for liquid crystal of the present invention, operable silane coupling agent is not limited thereto.APTES, 3-(2-amino-ethyl) TSL 8330,3-(2-amino-ethyl) amino propyl methyl dimethoxysilane, 3-TSL 8330,3-phenyl amino propyl trimethoxy silane, amine silane coupling agent such as 3-triethoxysilicane alkyl-N-(1,3-dimethyl-butylidene) propylamine, 3-aminopropyl diethoxymethylsilane etc.; 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-glycidoxypropyl group triethoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl dimethoxysilane, 2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane; The methacrylic silane coupling agents such as 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloyloxypropyl methyl diethoxy silane, 3-methacryloxypropyl; The acrylic-silane coupling agents such as 3-acryloxypropyl trimethoxy silane; The urea groups one type of silane coupling agents such as 3-ureidopropyltriethoxysilane; Two (3-(triethoxysilicane alkyl) propyl group) disulfide, two (3-(triethoxysilicane alkyl) propyl group) tetrasulfide sulfides one type of silane coupling agent; The sulfydryl one type of silane coupling agents such as 3-mercaptopropyi methyl dimethoxysilane, 3-mercaptopropyi trimethoxy silane, 3-Octanoylthio-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; The carbamates silane coupling agents such as tri-ethoxy silylpropyl methyl carbamate, (3-tri-ethoxy silylpropyl)-t-butylcarbamate.
Below exemplify the concrete example of the imidizate promoter of poly amic acid ester, but in aligning agent for liquid crystal of the present invention, operable imidizate promoter is not limited thereto.
[changing 52]
[changing 53]
D in above-mentioned formula (B-1) ~ (B-17) is separately tert-butoxycarbonyl or 9-fluorenylmethoxycarbonyl groups.In (B-14) ~ (B-17), there is multiple D in a formula, they can be identical or different.
As long as the content of imidizate promoter can be promoted poly amic acid ester hot-imide effect scope in, be then not particularly limited.If represent its lower limit, then relative to 1 mole, the amic acid esters position of the following formula contained in poly amic acid ester (16), be better more than 0.01 mole, be more preferably more than 0.05 mole, be more preferably more than 0.1 mole further.In addition, control to consider in MIN viewpoint from the harmful effect that each characteristic of imidizate promoter itself to liquid crystal orientation film residual the film after burning till is caused, if represent its upper limit, then relative to 1 mole, the amic acid esters position of following formula (16) contained in poly amic acid ester of the present invention, imidizate promoter is better less than 2 moles, be more preferably less than 1 mole, be more preferably less than 0.5 mole further.
[changing 54]
When adding imidizate promoter, likely carrying out imidizate by heating, is therefore better add with after good solvent and Weak solvent dilution.
< liquid crystal orientation film >
Liquid crystal orientation film of the present invention be the aligning agent for liquid crystal obtained as mentioned above to be coated on substrate, dry, burn till and the film that obtains, as required this coated surface is carried out rubbing etc. orientation process.
As the substrate of coating aligning agent for liquid crystal of the present invention, as long as the high substrate of the transparency is then not particularly limited, the plastic bases etc. such as glass substrate, silicon nitride board, acrylic acid substrate, polycarbonate substrate can be used.From the viewpoint that technique simplifies, it is better the substrate using the ITO electrode etc. be formed with for liquid crystal drive.In addition, in reflection type liquid crystal display element, can use the opaque materials such as silicon wafer, but be only limitted to the substrate of side, electrode now 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.
Be coated with the drying after aligning agent for liquid crystal of the present invention, firing process can select arbitrary temperature and time.Usually, in order to fully remove the organic solvent contained, making its dry 1 minute ~ 10 minutes at 50 DEG C ~ 120 DEG C, then burning till 5 minutes ~ 120 minutes at 150 DEG C ~ 300 DEG C.The thickness of the film after burning till is not particularly limited, if but excessively thin, then the reliability of liquid crystal display cells can reduce sometimes, therefore normally 5 ~ 300nm, is better 10 ~ 200nm.
As the method for this film of orientation process, rubbing manipulation, light orientation process method etc. can be exemplified, but aligning agent for liquid crystal of the present invention is particularly useful when adopting light orientation process method.
As the concrete example of light orientation process method, can exemplify and radioactive ray towards certain orientation polarization are irradiated to above-mentioned film coated surface, according to circumstances heat at the temperature of 150 ~ 250 DEG C further, give the method for liquid crystal aligning ability.The wavelength of radioactive ray can use the ultraviolet and visible ray with 100nm ~ 800nm wavelength.Wherein, be better the ultraviolet with 100nm ~ 400nm wavelength, spy is well the ultraviolet with 200nm ~ 400nm wavelength.In addition, in order to improve liquid crystal aligning, while film substrate can being heated at 50 ~ 250 DEG C, irradiate radioactive ray.Ultraviolet irradiation amount in above-mentioned orientation process etc. is better 1 ~ 10000mJ/cm 2scope, spy is 100 ~ 5000mJ/cm well 2scope.
As above the liquid crystal orientation film obtained can make liquid crystal molecule towards certain orientation stably 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 used in the present embodiment and comparative example and the assay method of each characteristic as described below.
1,3DMCBDE-Cl:1,3-two (chlorocarbonyl)-1,3-dimethylcyclobutane-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
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]
[viscosity]
In synthesis example, the viscosity of poly amic acid ester and polyamic acid solution utilizes E type viscosity meter TVE-22H ((East Machine industry society of Toki Sangyo Co., Ltd.) to make) measure under the condition of sample size 1.1mL, circular cone type rotor (コ mono-Application ロ mono-タ) TE-1 (1 ° 34 ', R24), temperature 25 DEG C.
[molecular weight]
In addition, the molecular weight of poly amic acid ester adopts GPC(normal temperature gel permeation chromatography) device measures, and calculates number-average molecular weight (hereinafter also referred to as Mn) and weight-average molecular weight (hereinafter also referred to as Mw) with polyglycol, polyethylene oxide scaled value.
GPC device: Shodex (Showa Denko K. K) Inc. (GPC-101)
Post: Showa Denko K. K's system (series connection of KD803, KD805)
Column temperature: 50 DEG C
Eluent: N, N'-dimethyl formamide (as adjuvant, lithium bromide-hydrate (LiBrH 2o) for 30mmol/L, phosphoric anhydride crystallization (O-phosphoric acid) be 30mmol/L, tetrahydrofuran (THF) is 10ml/L)
Flow velocity: 1.0ml/ minute
Calibration curve making standard sample: Dong Cao company (East ソ ー society) TSK standard polyethylene oxide processed (weight-average molecular weight (Mw) about 900000,150000,100000,30000) and Polymer Laboratory company (Port リ マ ー ラ ボ ラ ト リ ー society) polyglycol processed (peak top molecular weight (Mp) about 12000,4000,1000).In order to avoid overlap of peaks, determine 2 samples respectively, be namely mixed with 900000,100000,12000,1000 these samples of 4 kinds and be mixed with 150000,30000,4000 these samples of 3 kinds.
[center line average roughness mensuration]
By the film on the hot plate of temperature 80 DEG C dry 5 minutes obtaining aligning agent for liquid crystal through spin coating, in the heated air circulation type stove of temperature 250 DEG C, burn till 1 hour, form the film of thickness 100nm.Observe the film surface of this film with atomic force microscope (AFM), and measure 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 of band transparency electrode, passes through drying 5 minutes on the hot plate of temperature 80 DEG C, in the heated air circulation type stove of 250 DEG C, burn till the step of 60 minutes, form the film of thickness 100nm.Across polarization plates, the ultraviolet 100mJ/cm of 254nm is irradiated to this coated surface 2, obtain the substrate of band liquid crystal orientation film.Prepare two pieces of substrates with above-mentioned liquid crystal orientation film, after the liquid crystal aligning face of one piece of substrate scatters the granular sept of diameter 6 μm, with the antiparallel condition of the orientation of two pieces of substrates by two pieces of substrate in combination, by environmental seal, but leave liquid crystal injecting port, make the negative crystal born of the same parents that structure cell interval (cell gap) is 6 μm.Inject liquid crystal (MLC-2041, Merck & Co., Inc. (メ ルク society) makes) to vacuum in this negative crystal born of the same parents at normal temperatures, inlet is sealed, makes liquid crystal cell.
The voltage retention of the above-mentioned liquid crystal cell of following mensuration.
Measure voltage after applying voltage 60 μ s, 16.67ms of 4V, calculate the change with initial value thus, in this, as voltage retention.During mensuration, the temperature of liquid crystal cell is set to 23 DEG C, 60 DEG C, 90 DEG C, measures at each temperature.
[ion concentration]
The ion concentration of the above-mentioned liquid crystal cell of following mensuration.
Use Toyo Corp. (East Yang テ Network ニ カ society) 6254 type liquid crystal evaluation of physical property devices measure.Apply the triangular wave of 10V, 0.01Hz, calculate the area suitable with the ion concentration of gained waveform by triangle method of approximation, it can be used as ion concentration.During mensuration, the temperature of liquid crystal cell is set to 23 DEG C, 60 DEG C, measures at each temperature.
[FFS drives the interchange of liquid crystal cell to drive sintering]
On the glass substrate being 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 be ground floor have the thickness 50nm of the shape as electrode ITO electrode, have at the second layer thickness 500nm of the shape as dielectric film silicon nitride, have in third layer the comb teeth-shaped as electrode ITO electrode (electrode width: 3 μm, electrode gap: 6 μm, electrode height: 50nm) fringe field conversion driving electrode.The hot plate of 80 DEG C makes they after dry 5 minutes, in the heated air circulation type stove of 250 DEG C, burn till 60 minutes, forming thickness is the film of 100nm.Across polarization plates, the ultraviolet 100mJ/cm of 254nm is irradiated to this coated surface 2, obtain the substrate being with liquid crystal orientation film.In addition, film is being formed too, implementation orientation process as on the glass substrate with the column spacer being highly 4 μm not being formed with electrode of substrate in opposite directions.
Using above-mentioned two pieces of substrates as one group, printing and sealing agent on substrate, another block substrate of fitting, to make liquid crystal orientation film toward each other and direction of orientation is 0 °, then, makes sealant cures and makes negative crystal born of the same parents.In this negative crystal born of the same parents, inject liquid crystal MLC-2041 (Merck & Co., Inc. (メ ルク society) system) by decompression injection method, sealing inlet, obtain FFS and drive liquid crystal cell.
Measure after this FFS drives the V-T characteristic of liquid crystal cell at 58 DEG C of temperature (voltage-transmission rate characteristic), apply 4 hours ± square wave of 4V/120Hz.After 4 hours, cut off voltage, place after 60 minutes at the temperature of 58 DEG C, again measure V-T characteristic, calculate transmissivity before and after applying square wave and become the voltage difference of 50%.
[evaluation of charge accumulation characteristic]
Liquid crystal cell is driven to be positioned on light source above-mentioned FFS, after measuring V-T characteristic (voltage-transmission rate characteristic), the transmissivity (T under the state determining applying ± 1.5V/60Hz square wave a).Then, the square wave of applying ± 1.5V/60Hz, after 10 minutes, repeats to apply direct current 1V, makes it drive 30 minutes.Cutting off DC voltage, measuring through exchanging the transmissivity (T of driving after 10 minutes b), according to T band T adifference calculate the difference of the transmissivity caused by the voltage remained in liquid crystal display cells.
(a.) 1,3-two (chlorocarbonyl)-1,3-synthesis of dimethylcyclobutane-2,4-dimethyl dicarboxylate (1,3DMCBDE-Cl)
(a-1) synthesis of tetrabasic carboxylic acid dialkyl
[changing 56]
Under stream of nitrogen gas, at 3L(liter) add 220g(0.981 mole in four-hole boiling flask) 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (compound of formula (5-1), hereinafter referred to as 1,3-DM-CBDA), 2200g methyl alcohol (6.87mol, relative to 1,3-DM-CBDA is 10 times of weight), carry out adding hot reflux at 65 DEG C, after 30 minutes, become uniform solution.Reaction solution directly adds hot reflux 4 hours 30 minutes and stirs.This reactant liquor is determined by high performance liquid chromatography (hereinafter referred to as HPLC).
Except after desolventizing with evaporator distillation distillation from this reactant liquor, add the ethyl acetate of 1301g, be heated to 80 DEG C, make it reflux 30 minutes.Then, be cooled to interior temperature with the every 10 minutes speed of 2 ~ 3 DEG C and reach 25 DEG C, keep intact and stirred 30 minutes at 25 DEG C.By filtering the white crystals taking out and separate 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.
Analyze and the result of X ray analysis of crystal structure according to 1HNMR, confirming this crystallization is compound (1-1) (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) synthesis of 1,3-DM-CBDE-C1
[changing 57]
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) normal heptane after, add 0.64g(0.01mol) pyridine, under the stirring of magnetic stirring apparatus heating be stirred to 75 DEG C.Then, dripped 289.93g(11.68mol with 1 hour) thionyl chloride.Start immediately after dropping foaming, drip end after 30 minutes reaction solution become even, stopped foaming.Then, directly stir after 1 hour 30 minutes at 75 DEG C, utilize evaporator that solvent distillation removing is reached 924.42g to the inner capacities in 40 DEG C of water-baths.Be heated to 60 DEG C, the dissolving crystallized of separating out when making distillation remove desolventizing, and by carrying out thermosol filtration and after filtering insolubles, with the every 10 minutes speed of 1 DEG C, filtrate is cooled to 25 DEG C at 60 DEG C.Keeping intact and stir after 30 minutes at 25 DEG C, by filtering the white crystals taking out and separate out, and washing this crystallization with the normal heptane of 264.21g.By by its drying under reduced pressure, obtain the white crystals of 226.09g.
Then, under stream of nitrogen gas, add the white crystals of 226.09g obtained above and the normal heptane of 452.18g in the four-hole boiling flask of 3L after, heating is stirred to 60 DEG C, makes dissolving crystallized.Afterwards, with every 10 minutes speed cooling and stirring to 25 DEG C of 1 DEG C, crystallization is made.Keeping intact and stir after 1 hour at 25 DEG C, by filtering the white crystals taking out and separate out, and with after this crystallization of n-hexane of 113.04g, being obtained the white crystals of 203.91g by drying under reduced pressure.According to 1HNMR analysis result, confirming this crystallization is compound (3-1), namely 1, two (chlorocarbonyl)-1 of 3-, 3-dimethylcyclobutane-2,4-bis-dimethyl carbonate (1,3-DM-CBDE-C1) (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)
By four footpaths, step synthesis diamine compound (DA-1) as follows.
The first step: the synthesis of compound (A5)
[changing 58]
Propargyl amine (8.81g is sequentially added in the eggplant type flask of 500mL, 160mmol), N, dinethylformamide (112mL), sal tartari (18.5g, 134mmol), be 0 DEG C, stirred with about 1 hour while drip solution Bromo-t-butylacetate (21.9g, 112mmol) being dissolved in DMF (80mL) and obtaining.After dropping terminates, make reaction solution be room temperature, stir 20 hours.Then, by solids removed by filtration composition, in filtrate, add ethyl acetate 1L, clean 4 times with the water of 300mL, clean 1 time with the saturated aqueous common salt of 300mL.Then, with dry over magnesium sulfate, decompression distillation is except desolventizing.Finally, by 0.6Torr, decompression distillation is residual at 70 DEG C grease, colourless liquid N-propargyl-amino tert-butyl acetate (compound (A5)) is obtained.Receipts amount is 12.0g, and yield is 63%.
2nd step: the synthesis of compound (A6)
[changing 59]
Above-mentioned N-propargyl-amino tert-butyl acetate (12.0g is added in the eggplant type flask of 1L, 70.9mmol), methylene chloride (600mL) makes solution, while stir ice-cold, while dripped with 1 hour solution di-tert-butyl dicarbonate (15.5g, 70.9mmol) being dissolved in methylene chloride (100mL) and obtaining.After dropping terminates, make reaction solution be room temperature, stir 20 hours.After reaction terminates, with the saturated aqueous common salt cleaning reaction solution of 300mL, use dried over mgso.Then, by decompression distillation except desolventizing, weak yellow liquid N-propargyl-N-tertbutyloxycarbonylamino tert-butyl acetate (compound (A6)) is obtained.Receipts amount is 18.0g, and yield is 94%.
3rd step: the synthesis of compound (A7)
[changing 60]
2-iodo-4-nitroaniline (22.5g is added in the four-hole boiling flask of 300mL, 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, while add above-mentioned N-propargyl-amino-N-tert-butoxycarbonyl tert-butyl acetate (27.6g, 102mmol), stirred at ambient temperature 20 hours.After reaction terminates, 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 of separating out removing desolventizing by decompression distillation, in the ethyl acetate of 200mL, carries out recrystallization by the hexane adding 1L.This solid of leaching, by drying under reduced pressure, obtains yellow solid 2-{3-(N-tert-butoxycarbonyl-N-tert-Butoxycarbonyl-methyl is amino)-1-propinyl) }-4-nitroaniline (compound (A7)).Receipts amount is 23.0g, and yield is 66%.
4th step: the reduction of compound (A7)
Above-mentioned 2-{3-(N-tert-butoxycarbonyl-N-tert-Butoxycarbonyl-methyl is amino)-1-propinyl is added in the four-hole boiling flask of 500mL) }-4-nitroaniline (22.0g, 54.2mmol) with ethanol (200g), after being replaced into nitrogen in system, add palladium carbon (2.20g), be replaced into hydrogen by system, stir 48 hours at 50 DEG C.After reaction terminates, by diatomite filtration removing palladium carbon, in filtrate, add activated charcoal, stir 30 minutes at 50 DEG C.Then, filter activity charcoal, decompression distillation removing organic solvent, the grease that drying under reduced pressure is residual, obtains diamine compound (DA-1) thus.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 (is all 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)
The 300mL four-hole boiling flask with stirring apparatus is made to be nitrogen atmosphere, add 4, the DA-1 of 4 '-diaminodiphenyl-methane 4.486g (22.63mmol), 2.147g (5.658mmol), add NMP 121.37g and the pyridine 5.16g(65.19mmol as alkali), make it dissolve through stirring.Then limit stirs 1,3DM-CBDE-Cl of this two amine aqueous solutions limit interpolation 8.8384g (27.16mmol), makes it react 4 hours under water-cooled.After 4 hours, in reaction solution, add NMP 134.86g, stir 15 minutes under room temperature (20 DEG C).The polyamic acid ester solution obtained is added in the water of 1349g while stirring, filters the white precipitate taking out and separate out, then, 1 time is cleaned with the water of 1349g, with the ethanol purge 1 time of 1349g, with the ethanol purge 3 times of 337g, 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 obtained is taken in the Erlenmeyer flask of 200ml, adds the NMP of 98.7394g, at room temperature stir and make it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-1).
(comparing synthesis example 1)
The 300mL four-hole boiling flask with stirring apparatus is made to be nitrogen atmosphere, add 4,4 '-diaminodiphenyl-methane 8.0102g (40.35mmol), adds the pyridine as alkali of NMP and 7.20g (91.03mmol) of 158.1g, makes it dissolve through stirring.Then limit stirs 1,3DM-CBDE-Cl of this two amine aqueous solutions limit interpolation 12.3419g (37.93mmol), makes it react 4 hours under water-cooled.The polyamic acid ester solution obtained is added in the water of 1757g while stirring, filters the white precipitate taking out and separate out, then, 1 time is cleaned with the water of 1757g, with the ethanol purge 1 time of 1757g, with the ethanol purge 3 times of 439g, 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 obtained is taken in the Erlenmeyer flask of 200ml, adds the NMP of 99.3048g, at room temperature stir and make it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-2).
(synthesis example 3)
By 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 supply nitrogen limit, limit is stirred and made it dissolve.Stir this two amine aqueous solution while add the BDA of 7.1339g (36.01mmol), then add NMP and make solid component concentration reach 25 quality %, at room temperature stir 24 hours, obtain the solution of polyamic acid (PAA-1).The viscosity of this polyamic acid solution at temperature 25 DEG C is 2680mPas.In addition, the molecular weight of this polyamic acid is Mn=8176, Mw=16834.
(synthesis example 4)
By 4 of 5.9791g (30.01mmol), 3 of 4 '-diamino-diphenylamine and 3.0446g (20.01mmol), 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, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add the BDA of 9.8379g (49.65mmol), then add NMP and make solid component concentration reach 25 quality %, at room temperature stir 24 hours, obtain polyamic acid solution.The viscosity of this polyamic acid solution at temperature 25 DEG C is 8000mPas.In addition, the molecular weight of this polyamic acid is Mn=13696, Mw=28619.
The polyamic acid solution obtained by 5.5355g is taken in the Erlenmeyer flask of 50ml, adds the NMP of 8.3744g, at room temperature stirs and makes it dissolve in 24 hours, obtain the polyamic acid solution (PAA-2) of 10 quality %.
(synthesis example 5)
By 4 of 3.6652g (18.39mmol), 3 of 4 '-diamino-diphenylamine and 0.6992g (4.595mmol), 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, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add the CBDA of 4.3326g (22.09mmol), then add NMP and make solid component concentration reach 15 quality %, at room temperature stir 24 hours, obtain the solution of polyamic acid (PAA-3).The viscosity of this polyamic acid solution at temperature 25 DEG C is 669mPas.In addition, the molecular weight of this polyamic acid is Mn=16902, Mw=34865.
(synthesis example 6)
By 4 of 1.848g (9.23mmol), 3 of 4 '-diamino-diphenylamine and 2.1025g (13.82mmol), 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, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add the PMDA of 4.8162g (22.08mmol), then add NMP and make solid component concentration reach 15 quality %, at room temperature stir 24 hours, obtain the solution of polyamic acid (PAA-4).The viscosity of this polyamic acid solution at temperature 25 DEG C is 257mPas.In addition, the molecular weight of this polyamic acid is Mn=13620, Mw=28299.
(embodiment 1)
The polyamic acid solution (PAA-1) obtained in the synthesis example 3 of the polyamic acid ester solution (PAE-1) obtained in the synthesis example 2 of 1.5289g and 0.5184g is taken in Erlenmeyer flask, add the BCS of NMP, 1.0011g of 2.0050g, within 30 minutes, obtain aligning agent for liquid crystal (I) by magnetic stirrer.
(embodiment 2)
The polyamic acid solution (PAA-2) obtained in the synthesis example 4 of the polyamic acid ester solution (PAE-1) obtained in the synthesis example 2 of 1.5246g and 1.4067g is taken in Erlenmeyer flask, add the BCS of NMP, 1.0112g of 1.0960g, within 30 minutes, obtain aligning agent for liquid crystal (II) by magnetic stirrer.
(embodiment 3)
The polyamic acid solution (PAA-3) obtained in the synthesis example 5 of the polyamic acid ester solution (PAE-1) obtained in the synthesis example 2 of 1.5119g and 1.0074g is taken in Erlenmeyer flask, add the BCS of NMP, 1.0313g of 1.5183g, within 30 minutes, obtain aligning agent for liquid crystal (III) by magnetic stirrer.
(embodiment 4)
The polyamic acid solution (PAA-4) obtained in the synthesis example 6 of the polyamic acid ester solution (PAE-1) obtained in the synthesis example 2 of 1.5018g and 1.1008g is taken in Erlenmeyer flask, add the BCS of NMP, 1.0214g of 1.4859g, within 30 minutes, obtain aligning agent for liquid crystal (IV) by magnetic stirrer.
(comparative example 1)
The polyamic acid solution (PAA-1) obtained in the synthesis example 3 of the polyamic acid ester solution (PAE-2) obtained in the comparison synthesis example 1 of 3.00g and 1.021g is taken in Erlenmeyer flask, add the BCS of NMP, 2.0128g of 3.99g, within 30 minutes, obtain aligning agent for liquid crystal (a) by magnetic stirrer.
(comparative example 2)
The polyamic acid solution (PAA-2) obtained in the synthesis example 4 of the polyamic acid ester solution (PAE-2) obtained in the comparison synthesis example 1 of 1.5119g and 1.4334g is taken in Erlenmeyer flask, add the BCS of NMP, 1.0271g of 1.0903g, within 30 minutes, obtain aligning agent for liquid crystal (b) by magnetic stirrer.
(comparative example 3)
The polyamic acid solution (PAA-3) obtained in the synthesis example 5 of the polyamic acid ester solution (PAE-2) obtained in the comparison synthesis example 1 of 3.00g and 2.0141g is taken in Erlenmeyer flask, add the BCS of NMP, 2.0111g of 3.01g, within 30 minutes, obtain aligning agent for liquid crystal (c) by magnetic stirrer.
(comparative example 4)
The polyamic acid solution (PAA-4) obtained in the synthesis example 6 of the polyamic acid ester solution (PAE-2) obtained in the comparison synthesis example 1 of 1.5206g and 1.0258g is taken in Erlenmeyer flask, add the BCS of NMP, 1.0418g of 1.4838g, within 30 minutes, obtain aligning agent for liquid crystal (d) by magnetic stirrer.
(comparative example 5)
The polyamic acid ester solution (PAE-1) obtained in the synthesis example 2 of 3.1281g is taken in there-necked flask, adds the BCS of NMP, 1.0532g of 1.0911g, obtain aligning agent for liquid crystal (e) by magnetic stirrer 30 minutes.
(embodiment 5)
After the aligning agent for liquid crystal (I) obtained in the filter. EXAMPLE 1 of 1.0 μm, be spun on the glass substrate of band transparency electrode, through on the hot plate of temperature 80 DEG C dry 5 minutes and burn till 1 hour at temperature 250 DEG C, form the film of thickness 100nm.Determine the center line average roughness (Ra) of each film.Measurement result is shown in table 1 described later.
(embodiment 6 ~ 9 and comparative example 7 ~ 10)
Except using above-described embodiment 2 ~ 4, except each aligning agent for liquid crystal (II) ~ (IV) that obtain in comparative example 1 ~ 4 and (a) ~ (d), define each film by the method identical with embodiment 5.The film surface of each film is observed with AFM.In addition, the center line average roughness (Ra) of each film is determined.These measurement results are shown in table 1 described later.
[table 1]
The embodiment 5 ~ 9 represented by table 1 and the result of comparative example 7 ~ 10 can confirm, aligning agent for liquid crystal of the present invention can reduce the minute asperities produced that is separated due to poly amic acid ester and polyamic acid, obtains level and smooth film surface.
(embodiment 10)
After the aligning agent for liquid crystal (I) obtained in the filter. EXAMPLE 1 of 1.0 μm, be spun on the glass substrate of band transparency electrode, through on the hot plate of temperature 80 DEG C dry 5 minutes and burn till 1 hour at temperature 250 DEG C, form the film of thickness 100nm.Across polarization plates, the ultraviolet 100mJ/cm of 254nm is irradiated to this coated surface 2, obtain the substrate being with liquid crystal orientation film.Prepare two pieces of substrates with above-mentioned liquid crystal orientation film, after the liquid crystal aligning face of one piece of substrate scatters the sept of 6 μm, with the antiparallel condition of the orientation of two pieces of substrates by two pieces of substrate in combination, by environmental seal, but leave liquid crystal injecting port, make the negative crystal born of the same parents that structure cell is spaced apart 6 μm.Inject liquid crystal (MLC-2041, Merck & Co., Inc.'s system) to vacuum in this structure cell at normal temperatures, inlet is sealed, makes liquid crystal cell.To this liquid crystal 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)
Except using above-described embodiment 2 ~ 4, except each aligning agent for liquid crystal (II) ~ (IV) that obtain in comparative example 1 ~ 5 and (a) ~ (e), make each liquid crystal cell by the method identical with embodiment 10.To this liquid crystal 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]
The embodiment 10 ~ 13 represented by table 2 and the result of comparative example 15 can confirm, aligning agent for liquid crystal of the present invention can obtain having the liquid crystal orientation film with the equal or better reliability of aligning agent for liquid crystal only containing poly amic acid ester.In addition, can be confirmed by the result of embodiment 10 ~ 13 and comparative example 11 ~ 14, aligning agent for liquid crystal of the present invention can obtain comparing the higher liquid crystal orientation film of reliability with the poly amic acid ester of low polar substituent do not departed from containing Yin Re with the aligning agent for liquid crystal of polyamic acid.
(embodiment 14)
After the aligning agent for liquid crystal (I) obtained in the filter. EXAMPLE 1 of 1.0 μm, be coated on by spin coating on the glass substrate being formed with FFS driving electrode, described FFS driving electrode is the FFS driving electrode of the ITO electrode of the thickness 50nm had as ground floor, the silicon nitride as the thickness 500nm as dielectric film of the second layer, the ITO electrode as the comb teeth-shaped of third layer (electrode width: 3 μm, electrode gap: 6 μm, electrode height: 50nm).The hot plate of 80 DEG C makes they after dry 5 minutes, in the heated air circulation type stove of 250 DEG C, burn till 60 minutes, forming thickness is the film of 100nm.Across polarization plates, the ultraviolet 100mJ/cm of 254nm is irradiated to this coated surface 2, obtain the substrate being with liquid crystal orientation film.In addition, film is being formed too, implementation orientation process as on the glass substrate with the column spacer being highly 4 μm not being formed with electrode of substrate in opposite directions.
Using above-mentioned two pieces of substrates as one group, printing and sealing agent on substrate, another block substrate of fitting, to make liquid crystal orientation film toward each other and direction of orientation is 0 °, then, makes sealant cures and makes negative crystal born of the same parents.In this negative crystal born of the same parents, inject liquid crystal MLC-2041 (Merck & Co., Inc.'s system) by decompression injection method, sealing inlet, obtain FFS and drive liquid crystal cell.
Evaluating this FFS drives the interchange of liquid crystal cell to drive sintering characteristic and charge accumulation characteristic.Result is shown in table 3 described later.
(embodiment 15 ~ 17 and comparative example 16)
Except using above-described embodiment 2 ~ 4, except each aligning agent for liquid crystal (II) ~ (IV) that obtain in comparative example 5 and (e), make each FFS by the method identical with embodiment 14 and driven liquid crystal cell.Evaluating each FFS drives the interchange of liquid crystal cell to drive sintering characteristic and charge accumulation characteristic.Result is shown in table 3 described later.
[table 3]
The embodiment 14 ~ 17 represented by table 3 and the result of comparative example 16 can confirm, can be obtained exchanging driving sintering degree little by aligning agent for liquid crystal of the present invention, and the liquid crystal orientation film that residual voltage is few.
The synthesis of (synthesis example 7) diamine compound (DA-2)
(precursor synthesis 1)
[changing 61]
The four-hole boiling flask of 1L is connected with Di Muluo cooling tube, 100mL tap funnel, adds 2-amino-4-nitroaniline (15g, 92mmol), after being replaced into nitrogen in system, add THF 400mL, be cooled to 0 DEG C.Then, Borane-THF complex (having 1M borine among THF, 100mL, 100mmol) was dripped with 30 minutes from tap funnel.Confirm in reaction system and produce gas, separate out yellow solid.After dropping terminates, at room temperature stir 2 days.After reaction terminates, add hydrochloric acid (2N, 200mL), at room temperature stir after 2 hours, at 10 DEG C, add sodium hydrate aqueous solution (2N, 250mL) make its aobvious alkalescence, use dichloromethane extraction.Clean organic layer with saturated aqueous common salt (500mL), after dried over mgso, carry out concentrating, vacuum drying, obtain yellow solid cyano reduction body thus.Receipts amount is 11.9g, and yield is 77%.
(precursor synthesis 2)
[changing 62]
Above-mentioned cyano reduction body (4.60g is added in 1L eggplant type bottle, 27.5mmol) with methylene chloride (900mL), make solution, add di-tert-butyl dicarbonate (6.00g wherein, 27.5mmol), stir 3 days under room temperature (20 DEG C).After reaction terminates, directly with saturated aqueous common salt cleaning reaction solution, use dried over mgso.With ethylacetate-hexane, recrystallization is carried out to the solid of being separated out by reduced pressure concentration organic layer, obtain yellow solid tert-butoxycarbonyl (Boc) and add adult.Receipts amount is 5.25g, and yield is 71%.
(synthesis of DA-2)
[changing 63]
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 system, adding platinum oxide (500mg), be replaced into hydrogen by system.At room temperature stir and become the reaction mixture 15 hours that yellow is suspended.After reaction terminates, add ethanol, the white solid of solution modeling, removes catalyzer by diatomite filtration.Concentrated filtrate, carries out recrystallization with ethylacetate-hexane to the peachiness solid obtained, obtains pinkish solid.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).
The synthesis of (synthesis example 8) diamine compound (DA-3)
(synthesis of N-tert-butoxycarbonyl-propargyl amine)
[changing 64]
Propargyl amine (25.18g is added in four-hole boiling flask, 0.448mol), triethylamine (55.52g, 0.549mol), after methylene chloride 400ml, while in water-bath (20 DEG C) cooled reaction solution, while dripped di-tert-butyl dicarbonate (118.15g, 0.541mol) with 30 minutes.After dropping terminates, stir 2 hours, in reaction solution, then add saturated aqueous common salt 300ml, methylene chloride 200ml, extraction.With the organic layer that dried over mgso obtains.After removing drying agent, distillation removes the solvent of the solution obtained, and obtains pale yellow oil.By recrystallization (hexane) purifying, obtain white solid N-tert-butoxycarbonyl-propargyl amine (receipts amount: 47.01g, yield: 67.6%).
(synthesis of nitro-body)
[changing 65]
The iodo-4-nitroaniline of 2-(5.11g is added in the four-hole boiling flask being replaced into nitrogen, 19.4mmol), two (triphenylphosphine) palladium chloride (II) (281.7mg, 0.401mmol), cupric iodide (160.7mg, 0.844mmol) with diethylamine 30ml, at room temperature (20 DEG C) stir 20 minutes.Then, add tert-butoxycarbonyl-propargyl amine (3.72g, 24.0mmol), at room temperature (20 DEG C) stir 4 hours.After confirming that raw material disappears by HPLC, add ethyl acetate 200ml, 1M aqueous ammonium chloride solution 200ml, extraction.Clean the organic layer obtained with 1M aqueous ammonium chloride solution, clean 2 times, use anhydrous magnesium sulfate drying.After removing drying agent, concentrated filtrate, with silica gel column chromatography (ethyl acetate: hexane=3:7) purifying.Receipts amount is 4.97g, and yield is 88.0%.
(synthesis of DA-3)
[changing 66]
In four-hole boiling flask, add above-mentioned nitro-body (12.45g, 42.7mmol), make it be suspended with 200ml ethanol.After degassed, nitrogen replaces, add palladium carbon (1.23g), hydrogen is replaced, and stirs 20 days under room temperature (20 DEG C).By diatomite filtration removing palladium carbon, distillation is except 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 tan 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).
The synthesis of (synthesis example 9) diamine compound (DA-4)
[changing 67]
P-phenylenediamine (PPD) (16.2g is added in the eggplant-shape bottle of 500mL, 150mmol), N, dinethylformamide (200mL), sal tartari (49.8g, 360mmol), cool at-20 DEG C, dripped with 3 hours and monobromo-acetic acid butyl ester (58.5g, 300mmol) is dissolved in the solution obtained in DMF (100mL).Then, at room temperature stir 20 hours.By crossing the solid filtered in this reaction mixture, then, filtrate being injected 6L water, reclaiming the thick product of the diamine compound (D) of separating out.Make the thick product obtained be dissolved in the DMF of 100mL, re-inject 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.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).
The synthesis of (synthesis example 10) diamine compound (DA-5)
(synthesis of nitro-body)
[changing 68]
In the four-hole boiling flask being replaced into nitrogen, add tert-butoxycarbonyl glycocoll (10.17g, 58.05mmol), make it be dissolved in THF 150ml.Add N-methylmorpholine (11.93g, 117.9mmol) wherein, be cooled to-20 DEG C.Carbonochloridic acid isobutyl ester (9.99g, 73.14mmol) is dripped in this solution.Now, note not making the temperature of reaction solution be more than 0 DEG C.After dropping, stir 10 minutes at-20 DEG C.Now, 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 dropping terminates, stir 1 hour at-20 DEG C, then stir 18 hours under room temperature (20 DEG C).After 18 hours, filter the solid of separating out, distillation removes the solvent of the filtrate obtained, and obtains concentrate.Ethyl acetate 200ml, 1M potassium dihydrogen phosphate aqueous solution 200ml is added, extraction in this concentrate.The organic layer obtained with the cleaning of 1M potassium dihydrogen phosphate aqueous solution 1 time, cleans 1 time with saturated aqueous common salt, cleans 2 times with saturated sodium bicarbonate aqueous solution, clean 1 time with saturated aqueous common salt.With the organic layer that anhydrous magnesium sulfate drying obtains.After removing drying agent, from filtrate, distillation is except desolventizing, obtains orange solid.By this Solid Suspension in toluene 300ml, add thermal agitation 30 minutes.Suction filtration solid, measure the NMR of the solid obtained, result is known is object nitro-body (receipts amount: 9.85g, yield: 54.9%).
(synthesis of DA-5)
[changing 69]
In eggplant-shape bottle, add above-mentioned nitro-body (9.85g, 31.75mmol), add ethanol 150ml.After being replaced into nitrogen in reaction vessel, adding palladium carbon (1.11g is 10 quality % relative to the quality of nitro-body), be again replaced into nitrogen.Then, be replaced into hydrogen by reaction vessel, stir 48 hours at 20 DEG C.After reaction terminates, by diatomite filtration removing palladium carbon, except desolventizing from filtrate.In the concentrate obtained, add toluene 150ml, add hot reflux, result separates out solid.Thermosol filters the solid of separating out, and obtains lavender solid.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)．
The synthesis of (synthesis example 11) diamine compound (DA-6)
(precursor synthesis 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, at 100 DEG C, add thermal agitation.Then, add 4-Fluoronitrobenzene 138.09g (978.7mmol), dimethyl sulfoxide 100g, at 100 DEG C, add thermal agitation 4 hours.After 4 hours, stir and reaction solution is dropped in 5L water, the yellow solid that leaching is separated out.With the solid that the water of 3L, the washed with methanol of 556g obtain, dry, obtain yellow solid (precursor-1).Receipts amount is 152.71g.The solid (precursor-1) obtained is for following reaction.
(precursor synthesis 2)
[changing 71]
In the four-hole boiling flask of 2L, add above-mentioned (precursor-1) 100g (290.4mmol), N, N-dimethyl aminopyridine 7.10g (58.08mmol), tetrahydrofuran 800g, stir at 10 DEG C, make it dissolve.Then, di-tert-butyl dicarbonate 152.10g (697.0mmol) is joined in tap funnel, was added drop-wise to 1 hour in the solution in four-hole boiling flask.After dropping terminates, with evaporator distillation removing reactant liquor, obtain yellow oil.In this yellow oil, add ethyl acetate, add 10 % by weight hydrogen chloride solution 500ml, extraction.Clean the organic layer obtained with 10 % by weight hydrochloride aqueous solution 500ml, then clean 2 times with the water of 500ml, the organic layer obtained by dried over mgso.After removing drying agent, distillation, except desolventizing, obtains yellow oil.After this yellow oil is placed an evening, yellowing solid.In this solid, add 2-propyl alcohol 400g, cleaning, leaching solid, make it dry, obtain the solid (precursor-2) of yellow-white.Receipts amount is 124.32g.The solid (precursor-2) obtained is directly used in following reaction.
(synthesis of DA-6)
[changing 72]
The above-mentioned precursor-2 of 100.0g (183.6mmol), the Isosorbide-5-Nitrae-two of 1500g is added in the four-hole boiling flask of 2L alkane.After being replaced into nitrogen in reaction vessel, adding palladium carbon (10.00g is 10 quality % relative to the quality of nitro-body), be again replaced into nitrogen.Then, be replaced into hydrogen by reaction vessel, stir 24 hours at 20 DEG C.Add the acetonitrile 800g separating out white solid, make it dissolve.With film filter (1.0 μm) filtering reacting liquid, removing palladium carbon.Except desolventizing from filtrate, obtain white solid.In this white solid, add 2-propyl alcohol 350g, stir 1 hour.After 1 hour, leaching solid, adds the 2-propyl alcohol of 300g in the solid obtained, and after carrying out dispersion cleaning, filters, carries out drying, obtain white solid DA-6 with ultrasonic unit.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).
The synthesis of (synthesis example 12) 1,3-pair of (4-aminophenethyl) urea
[changing 73]
In the four-hole boiling flask of replacing through nitrogen, 2-(4-nitrobenzophenone) ethylamine hydrochloride [A] (52.50g, 259mmol), two (4-nitrobenzophenone) ester [B] (37.53g, the 123mmol) and THF (1877g) of carbonic acid is added under room temperature, add triethylamine (74.90g, 740mmol) and 4-N wherein, N-dimethyl aminopyridine (3.01g, 24.7mmol), stirs with mechanical stirrer.Follow the tracks of reaction by HPLC, after reaction terminates, reaction solution is joined in pure water (9L), carry out the stirring of 30 minutes.Then filter, with pure water (1L) cleaning, obtain the crude product of white solid.By this gained white solid in methyl alcohol (488g) with after ultrasonic unit dispersion cleaning, carry out filtering, dry, obtain the dinitro compound [C] (must 42.3g be measured, 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).
By compound [C] (42.32g, 118mmol), 5% palladium carbon (4.23g, 10 % by weight) and Isosorbide-5-Nitrae-two the potpourri of alkane (2031g), after nitrogen displacement, replaces with hydrogen, again in the presence of the hydrogen in stirred at ambient temperature.Follow the tracks of reaction by HPLC, after reaction terminates, after diatomite filtration catalyzer, under reduced pressure distillation removing filtrate, result obtains the crude product of white solid.In this crude product, add 2-propyl alcohol (85g), after carrying out dispersion cleaning with ultrasonic unit, carry out filtering, dry, obtain two (4-aminophenethyl) urea (must 31.9g be measured, yield 91%) of white solid 1,3-.
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]
Compound (b) (50.00g is added in the reaction vessel of 500ml, 229mmol), pyridine (0.500g, 0.632mmol), compound (c) (63.02,504mmol), acetonitrile (300g), in a nitrogen atmosphere, react adding under hot reflux.After reaction terminates, after being cooled to 20 DEG C, filtering, clean with acetonitrile (100g), obtain crude product.Then, add 2-propyl alcohol (300g), distilled water (100g) in the crude product, add hot reflux.Afterwards, be cooled to 20 DEG C, filtering solids, with 2-propyl alcohol (100g) cleaning, dry, acquisition compound (d) (receipts amount: 37.8g, yield: 37%).
1h-NMR ( 1h 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 500mL reaction vessel, add compound (d) (20.00g, 44.0mmol), thionyl chloride (120.0g, 1.01mol), carry out adding hot reflux.After 30 minutes, after being cooled to 20 DEG C, add thionyl chloride 120.0g, 1.01mol), carry out further 2 hours add hot reflux.After reaction terminates, the thionyl chloride that decompression distillation removing is superfluous, cleans with hexane (200g).Then, at 20 DEG C, add methylene chloride (200g) in the crude product stir, slowly drip compound (c) (12.1g, 96.8mmol), pyridine (13.93g, 176mmol), methylene chloride (100g) solution wherein.Stir after 1 hour, add compound (c) (12.1g, 96.8mmol), pyridine (13.93g, 176mmol) further.After reaction terminates, distillation, except desolventizing, with distilled water (144g) cleaning, obtains crude product.Tetrahydrofuran (144g) is added in this crude product, 23 DEG C of dispersion cleanings, filter, tetrahydrofuran (130g), distilled water (170g), methyl alcohol (150g) is used to clean respectively rear, dry, obtain (AD-4) (receipts amount: 17.72g, yield: 62%).
1h-NMR ( 1h 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)
2,4-of 10.2046g (39.22mmol) two (methoxycarbonyl) cyclo-butane-1,3-dicarboxylic acid are taken in the 300ml four-hole boiling flask with stirring apparatus, add the NMP of 181.2g, stir and make it dissolve.Then, adding triethylamine, the p-phenylenediamine (PPD) of 3.8987g (36.05mmol), the DA-2 of 0.9528g (4.02mmol) of 8.90g (87.90mmol), making it dissolve through stirring.While stir this solution, add (2, the 3-dihydroxy-2-sulfo--3-benzo of 33.74g (88.01mmol) azoles base) phosphonic acid diphenyl ester, then add the NMP of 32g, under water-cooled, make it react 4 hours.Stir while join in the 2-propyl alcohol of 1090g by the polyamic acid ester solution obtained, the sediment that leaching is separated out, then clean 5 times with the 2-propyl alcohol of 540g, drying obtains 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 obtained by 2.4495g is taken in the Erlenmeyer flask of 50ml, adds the NMP of 22.1541g, at room temperature stirs and makes it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-3).
(synthesis example 15)
By 2 of 1.2736g (4.51mmol), 2 of two (methoxycarbonyl) terephthalic acid (TPA) of 5-, 2.6915g (10.34mmol), two (methoxycarbonyl) cyclo-butane-1 of 4-, 3-dicarboxylic acid is taken in the 200ml four-hole boiling flask with stirring apparatus, add the NMP of 73.20g, stir and make it dissolve.Then, adding the triethylamine of 3.34g (33.01mmol), 1,3-two (4-amino-benzene oxygen) propane of 3.4376g (12.01mmol), the DA-2 of 0.7122g (3.00mmol), making it dissolve through stirring.Stir this solution while add (2, the 3-dihydroxy-2-sulfo--3-benzo of 12.65g (33.0mmol) azoles base) phosphonic acid diphenyl ester, then add the NMP of 10g, under water-cooled, make it react 4 hours.Stir while join in the 2-propyl alcohol of 530g by the polyamic acid ester solution obtained, the sediment that leaching is separated out, then clean 5 times with the 2-propyl alcohol of 210g, drying obtains 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 obtained by 2.5429g is taken in the Erlenmeyer flask of 50ml, adds the NMP of 22.9458g, at room temperature stirs and makes it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-4).
(synthesis example 16)
The 300mL four-hole boiling flask with stirring apparatus is made to be nitrogen atmosphere, add 4 of 5.0067g (25.25mmol), the triethylamine as alkali of NMP, 5.57g (70.36mmol) of DA-6,139g of 4 '-diaminodiphenyl-methane, 3.0573g (6.31mmol), stirs and makes it dissolve.Then stir this two amine aqueous solution while add 1,3DM-CBDE-Cl of 9.5299g (29.31mmol), under water-cooled, make it react 4 hours.Stir while the polyamic acid ester solution obtained is added in the pure water of 1545g, the white precipitate that leaching is separated out, then, 1 time is cleaned with the pure water of 1545g, with the ethanol purge 1 time of 1545g, then use the ethanol purge 3 times of 386g, 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 obtained by 12.31g is taken in the Erlenmeyer flask of 50ml, adds the NMP of 110.79g, at room temperature stirs and makes it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-5).
(synthesis example 17)
2,5-of 5.5958g (19.83mmol) two (methoxycarbonyl) terephthalic acid (TPA)s are taken in the 200ml four-hole boiling flask with stirring apparatus, add the NMP of 68.70g, stir and make it dissolve.Then, add triethylamine, the 3-aminobenzene methylamine of 1.9611g (16.05mmol), the DA-2 of 0.9493g (4.00mmol) of 4.01g (39.63mmol), stir and make it dissolve.Stir this solution while add 4-(4,6-dimethoxy-1,3,5-triazines-2-base)-4-methyl morpholine hydrochloride (15 ± 2 % by weight hydrate) of 16.40g, then add the NMP of 7.72g, under water-cooled, make it react 4 hours.Stir while join in the 2-propyl alcohol of 633g by the polyamic acid ester solution obtained, the sediment that leaching is separated out, then clean 5 times with the 2-propyl alcohol of 210g, drying obtains 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 obtained by 2.5630g is taken in the Erlenmeyer flask of 50ml, adds the NMP of 23.0971g, at room temperature stirs and makes it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-6).
(synthesis example 18)
The 300mL four-hole boiling flask with stirring apparatus is made to be 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 the pyridine 2.82g (35.59mmol) as alkali, stir and make it dissolve.Then stir this two amine aqueous solution while add 1,3DM-CBDE-Cl of 4.8583g (14.94mmol), under water-cooled, make it react 4 hours.After 4 hours, in reaction solution, add NMP81.44g, stir 15 minutes under room temperature (20 DEG C).Stir while join in the 2-propyl alcohol of 850g by the polyamic acid ester solution obtained, the white precipitate that leaching is separated out, then clean 5 times with the 2-propyl alcohol of 170g, 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 obtained by 2.1684g is taken in the Erlenmeyer flask of 50ml, adds the NMP of 19.2226g, at room temperature stirs and makes it dissolve in 24 hours, obtain 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, add the NMP of 32.47g, supply nitrogen limit, limit is stirred and is made it dissolve.Stir this two amine aqueous solution while add 4.4841g (20.0mmol) 2.3.5-tricarboxylic cyclopentyl acetic acid dianhydride, add NMP further and make the concentration of solid constituent reach 15 quality %, at room temperature stir 24 hours.The viscosity of this solution at temperature 25 DEG C is 580mPas.In this solution, add NMP 23.28g, make solid component concentration be after 10 quality %, add 1-methyl-3-p-methylphenyl triazenes 6.04g (40.5mmol), stirred at ambient temperature 4 hours.After 4 hours, stir and joined by reactant liquor in the 2-propyl alcohol of 286g, the sediment that leaching is separated out, then clean 5 times with the 2-propyl alcohol of 140g, drying obtains 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 obtained by 2.2078g is taken in the 50ml test tube with stirrer, adds the NMP of 19.7894g, at room temperature stirs and makes it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-8).
(synthesis example 20)
The 300mL four-hole boiling flask with stirring apparatus is made to be 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 the pyridine 3.80g (37.54mmol) as alkali, stir and make it dissolve.Then stir this two amine aqueous solution while add 1,3DM-CBDE-Cl of 5.0894g (15.65mmol), under water-cooled, make it react 4 hours.Stir while join in the 2-propyl alcohol of 688g by the polyamic acid ester solution obtained, the white precipitate that leaching is separated out, then clean 5 times with the 2-propyl alcohol of 172g, 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 obtained by 1.9755g is taken in the Erlenmeyer flask of 50ml, adds the NMP of 17.7314g, at room temperature stirs and makes it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-9).
(synthesis example 21)
The 100mL four-hole boiling flask with stirring apparatus is made to be nitrogen atmosphere, add the p-phenylenediamine (PPD) of 0.6005g (5.55mmol), the pyridine as alkali that the DA-3 of DA-4,0.1849g (0.693mmol) of 0.2334g (0.694mmol) adds NMP, 1.15g (14.56mmol) of 49.80g, stir and make it dissolve.Then stir this two amine aqueous solution while add 1,3DM-CBDE-Cl of 2.2550g (6.94mmol), under water-cooled, make it react 4 hours.Stir while join in the water of 277g by the polyamic acid ester solution obtained, the white precipitate that leaching is separated out, then clean 5 times with the water of 69g, 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 obtained by 2.0204g is taken in the Erlenmeyer flask of 50ml, adds the GBL of 18.1836g, at room temperature stirs and makes it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-10).
(synthesis example 22)
By 2 of 2.2570g (8.00mmol), 2 of two (methoxycarbonyl) terephthalic acid (TPA) of 5-, 3.0206g (11.61mmol), two (methoxycarbonyl) cyclo-butane-1 of 4-, 3-dicarboxylic acid is taken in the 300ml four-hole boiling flask with stirring apparatus, add the NMP of 100.35g, stir and make it dissolve.Then, add the triethylamine of 4.45g (43.98mmol), 1 of 3.0934g (11.98mmol), 1 of two (4-amino-benzene oxygen) propane of 5-, 1.2018g (4.03mmol), the DA-3 of two (4-aminophenethyl) urea of 3-, 1.0653g (4.02mmol), stirs and makes it dissolve.Stir this solution while add (2, the 3-dihydroxy-2-sulfo--3-benzo of 16.92g (44.14mmol) azoles base) phosphonic acid diphenyl ester, add the NMP of 13.14g again, under water-cooled, make it react 4 hours.Stir while the polyamic acid ester solution obtained is joined in the 2-propyl alcohol of 890g, the sediment that leaching is separated out, then clean 5 times, drying acquisition poly amic acid ester toner with the 2-propyl alcohol of 300g.
The molecular weight of this poly amic acid ester is Mn=9170, Mw=19990.
The poly amic acid ester toner obtained by 1.8720g is taken in the Erlenmeyer flask of 50ml, adds the NMP of 16.9543g, at room temperature stirs and makes it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-11).
(synthesis example 23)
Make the 300mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, get the p-phenylenediamine (PPD) of 3.02g (27.93mmol), add NMP, 5.16g (65.25mmol) pyridine as alkali of 173.0g, stir and make it dissolve.Then, stir 2,4-two (chlorocarbonyl) cyclo-butane-1,3-dimethyl dicarboxylates that this two amine aqueous solution adds 8.09g (27.23mmol), under water-cooled, make it react 2 hours.The polyamic acid ester solution obtained is joined in the water of 1000g, the white precipitate that leaching is separated out, then with the 2-propyl alcohol of 300g clean 5 times, drying obtains white poly amic acid ester toner.The molecular weight of this poly amic acid ester is Mn=10820, Mw=29197.
The poly amic acid ester toner obtained by 1.5309g is taken in the Erlenmeyer flask of 50ml, adds the DMF of NMP, 16.9279g of 13.7781g, at room temperature stirs and makes it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-12).
(synthesis example 24)
By 2 of 1.7779g (6.30mmol), 2 of two (methoxycarbonyl) terephthalic acid (TPA) of 5-, 3.7712g (14.49mmol), two (methoxycarbonyl) cyclo-butane-1 of 4-, 3-dicarboxylic acid is taken in the 200ml four-hole boiling flask with stirring apparatus, add the NMP of 146.71g, stir and make it dissolve.Then, add 1,3-two (4-amino-benzene oxygen) propane of the triethylamine of 4.25g (42.0mmol), 5.4239g (21.0mmol), stir and make it dissolve.Stir this solution while add (2, the 3-dihydroxy-2-sulfo--3-benzo of 16.91g (44.11mmol) azoles base) phosphonic acid diphenyl ester, add the NMP of 25.81g again, under water-cooled, make it react 4 hours.Stir while join in the methyl alcohol of 1224g by the polyamic acid ester solution obtained, the sediment that leaching is separated out, then use the washed with methanol 4 times of 408g, drying obtains 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 obtained by 1.0172g is taken in the Erlenmeyer flask of 50ml, adds the NMP of 9.4167g, at room temperature stirs and makes it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-13).
(synthesis example 25)
The 300mL four-hole boiling flask with stirring apparatus is made to be nitrogen atmosphere, add 4 of 5.0086g (25.26mmol), 1 of 4 '-diaminodiphenyl-methane, 1.8064g (6.31mmol), two (4-amino-benzene oxygen) pentane of 5-, add the pyridine as alkali of NMP, 5.69g (71.88mmol) of 272g, stir and make it dissolve.Then stir this two amine aqueous solution while add 1,3DM-CBDE-Cl of 9.7356g (29.94mmol), under water-cooled, make it react 4 hours.Stir while the polyamic acid ester solution obtained is added in the pure water of 1436g, the white precipitate that leaching is separated out, then, 1 time is cleaned with the pure water of 1436g, with the ethanol purge 1 time of 1436g, then use the ethanol purge 3 times of 386g, 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 obtained by 11.89g is taken in the Erlenmeyer flask of 50ml, adds the NMP of 107.01g, at room temperature stirs and makes it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-14).
(synthesis example 26)
2,5-of 3.7141g (13.16mmol) two (methoxycarbonyl) terephthalic acid (TPA)s are taken in the 200ml four-hole boiling flask with stirring apparatus, add the NMP of 72.31g, stir and make it dissolve.Then, add the triethylamine of 0.71g (7.01mmol), the 3-aminobenzene methylamine of 1.7112g (14.01mmol), stir and make it dissolve.Stir this solution while add 4-(4,6-dimethoxy-1,3,5-triazines-2-base)-4-methyl morpholine hydrochloride (15 ± 2 % by weight hydrate) of 11.6258g, then add the NMP of 12.91g, under water-cooled, make it react 4 hours.Stir while join in the methyl alcohol of 616g by the polyamic acid ester solution obtained, the sediment that leaching is separated out, then use the washed with methanol 4 times of 616g, drying obtains 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 obtained by 1.1325g is taken in the Erlenmeyer flask of 50ml, adds the NMP of 10.1925g, at room temperature stirs and makes it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-15).
(synthesis example 27)
The 300mL four-hole boiling flask with stirring apparatus is made to be nitrogen atmosphere, add the p-phenylenediamine (PPD) of 7.0100g (64.82mmol), add γ-BL, 11.55g (146mmol) pyridine as alkali of NMP, 324g of 108g, stir and make it dissolve.Then limit stirs 1,3DM-CBDE-Cl of this two amine aqueous solutions limit interpolation 19.7838g (60.85mmol), makes it react 4 hours under water-cooled.Stir while join in the 2-propyl alcohol of 1881g by the polyamic acid ester solution obtained, the white precipitate that leaching is separated out, then clean 5 times with the 2-propyl alcohol of 940g, 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 obtained by 1.2019g is taken in the Erlenmeyer flask of 50ml, adds the N of 10.8171g, N-diethylformamide, at room temperature stirs and makes it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-16).
(synthesis example 28)
The 300mL four-hole boiling flask with stirring apparatus is made to be nitrogen atmosphere, add the 4-Amino-N-methyl phenyl ethylamine of 3.0144g (20.07mmol), add the pyridine as alkali of NMP and 4.65g (46.01mmol) of 148.88g, stir and make it dissolve.Then stir this two amine aqueous solution while add 1,3DM-CBDE-Cl of 6.2390g (19.19mmol), under water-cooled, make it react 4 hours.Stir while join in the water of 784g by the polyamic acid ester solution obtained, the white precipitate that leaching is separated out, then clean 3 times with the water of 784g, the 2-propyl alcohol of 196g, 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 obtained by 1.9144g is taken in the Erlenmeyer flask of 50ml, adds the NMP of 17.2026g, at room temperature stirs and makes it dissolve in 24 hours, obtain polyamic acid ester solution (PAE-17).
(synthesis example 29)
By 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, supply nitrogen and stir and make it dissolve.While stir 1,2,3 of this two amine aqueous solutions limit interpolation 42.4946g (216.7mmol), 4-cyclo-butane tetracarboxylic dianhydride, adding NMP again makes solid component concentration reach 20 quality %, at room temperature stirs 24 hours, obtains the solution of polyamic acid (PAA-5).The viscosity of this polyamic acid solution at temperature 25 DEG C is 2156mPas.In addition, the molecular weight of this polyamic acid is Mn=18794, Mw=63387.
(synthesis example 30)
By 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, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add 5.7653g (29.40mmol) 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, add NMP further and make the concentration of solid constituent reach 15 quality %, at room temperature stir 24 hours.The viscosity of the polyamic acid solution obtained at temperature 25 DEG C is 1269mPas.In addition, the molecular weight of this polyamic acid is Mn=15559, Mw=43490.
In this solution, add the 3-glycidoxypropyl diethoxy silane of 0.0368g further, at room temperature stir 24 hours, obtain polyamic acid solution (PAA-6).
(synthesis example 31)
By 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, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add the BDA of 7.1310g (36.0mmol), at room temperature stir 2 hours.Then, add the NMP of 14.62g, add the pyromellitic acid anhydride of 0.8713g (3.99mmol).Further interpolation NMP makes the concentration of solid constituent reach 18 quality %, at room temperature stirs 24 hours.The viscosity of the polyamic acid solution obtained at temperature 25 DEG C is 577mPas.In addition, the molecular weight of this polyamic acid is Mn=12656, Mw=28487.
In this solution, add the 3-glycidoxypropyl diethoxy silane of 0.0480g further, at room temperature stir 24 hours, obtain polyamic acid solution (PAA-7).
(synthesis example 32)
By 3.6541g(24.02mmol) 3,5-diaminobenzoic acid, 4.2931g(16.00mmol) 1, two (4-aminophenyl) piperazine of 4-is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 36.48g, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add 4.7522g(23.99mmol) BDA, at room temperature stir 2 hours.Then, add the NMP of 36.50g, add 3.4084g(15.63mmol) pyromellitic acid anhydride.Further interpolation NMP makes the concentration of solid constituent reach 15 quality %, at room temperature stirs 24 hours.The viscosity of the polyamic acid solution obtained at temperature 25 DEG C is 1166mPas.In addition, the molecular weight of this polyamic acid is Mn=19307, Mw=42980.
In this solution, add the 3-glycidoxypropyl diethoxy silane of 0.0483g further, at room temperature stir 24 hours, obtain polyamic acid solution (PAA-4).
(synthesis example 33)
By 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, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add 3.9621g(20.0mmol) BDA, at room temperature stir 2 hours.Then, add the NMP of 25.42g, add 1,2,4,5-cyclopentanetetracarboxylic's dianhydride of 4.4776g (19.97mmol).Further interpolation NMP makes the concentration of solid constituent reach 20 quality %, at room temperature stirs 24 hours.The viscosity of the polyamic acid solution obtained at temperature 25 DEG C is 417mPas.In addition, the molecular weight of this polyamic acid is Mn=13291, Mw=54029.
In this solution, add the 3-glycidoxypropyl diethoxy silane of 0.0476g further, at room temperature stir 24 hours, obtain polyamic acid solution (PAA-9).
(synthesis example 34)
By 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, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add 2.2562g (9.02mmol) dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, at 80 DEG C stir 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 interpolation NMP makes the concentration of solid constituent reach 15 quality %, at room temperature stirs 24 hours.The viscosity of the polyamic acid solution obtained at temperature 25 DEG C is 2190mPas.In addition, the molecular weight of this polyamic acid is Mn=23632, Mw=56881.
In this solution, add the 3-glycidoxypropyl diethoxy silane of 0.0360g further, at room temperature stir 24 hours, obtain polyamic acid solution (PAA-10).
(synthesis example 35)
By 6.0854g(40.0mmol) 3,5-diaminobenzoic acids be taken in the four-hole boiling flask with the 100mL of stirring apparatus and nitrogen ingress pipe, add the NMP of 65.56g, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add 8.5449g(39.18mmol) pyromellitic acid anhydride, add further NMP and make the concentration of solid constituent reach 15 quality %, at room temperature stir 24 hours.The viscosity of the polyamic acid solution obtained at temperature 25 DEG C is 523mPas.In addition, the molecular weight of this polyamic acid is Mn=20565, Mw=47912.
In this solution, add the nmp solution of the 3-glycidoxypropyl diethoxy silane of the 0.3 quality % of 13.79g again, obtain polyamic acid solution (PAA-11).
(synthesis example 36)
By 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, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add 7.7658g (39.60mmol) 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, add NMP further and make the concentration of solid constituent reach 20 quality %, at room temperature stir 24 hours.The viscosity of the polyamic acid solution obtained at temperature 25 DEG C is 1972mPas.In addition, the molecular weight of this polyamic acid is Mn=15159, Mw=38251.
In this solution, add the 3-glycidoxypropyl diethoxy silane of 0.0504g further, at room temperature stir 24 hours, obtain polyamic acid solution (PAA-12).
(synthesis example 37)
By 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, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add 4.7505g(23.98mmol) BDA, at room temperature stir 2 hours.Then, add the NMP of 44.59g, add 1,2,3, the 4-cyclo-butane tetracarboxylic dianhydride of 3.1054g (15.84mmol).Further interpolation NMP makes the concentration of solid constituent reach 15 quality %, at room temperature stirs 24 hours.The viscosity of the polyamic acid solution obtained at temperature 25 DEG C is 802mPas.In addition, the molecular weight of this polyamic acid is Mn=13261, Mw=32578,
In this solution, add the 3-glycidoxypropyl diethoxy silane of 0.0590g further, at room temperature stir 24 hours, obtain polyamic acid solution (PAA-13).
(synthesis example 38)
By 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, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add the DAH-1 of 11.5387g (39.21mmol).Further interpolation NMP makes the concentration of solid constituent reach 20 quality %, at room temperature stirs 24 hours.The viscosity of the polyamic acid solution obtained at temperature 25 DEG C is 736mPas.In addition, the molecular weight of this polyamic acid is Mn=10091, Mw=19511.
In this solution, add the 3-glycidoxypropyl diethoxy silane of 0.0572g further, at room temperature stir 24 hours, obtain polyamic acid solution (PAA-14).
(synthesis example 39)
By 3.6603g(24.06mmol) 3,5-diaminobenzoic acid, 4.7740g(16.0mmol) 1, two (4-aminophenethyl) urea of 3-is taken in the four-hole boiling flask with the 100mL of stirring apparatus and nitrogen ingress pipe, add the NMP of 28.59g, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add 2.3782g(12.0mmol) BDA, at room temperature stir 2 hours.Then, add the NMP of 38.13g, add 6.0903g(27.92mmol) pyromellitic acid anhydride.Further interpolation NMP makes the concentration of solid constituent reach 15 quality %, at room temperature stirs 24 hours.The viscosity of the polyamic acid solution obtained at temperature 25 DEG C is 744mPas.In addition, the molecular weight of this polyamic acid is Mn=17771, Mw=38991.
In this solution, add the 3-glycidoxypropyl diethoxy silane of 0.0505g further, at room temperature stir 24 hours, obtain polyamic acid solution (PAA-15).
(synthesis example 40)
By 0.6123g(4.00mmol) 3,4 of 5-diaminobenzoic acid, 3.199g (16.06mmol), 4-diamino-diphenylamine is taken in the four-hole boiling flask with the 100mL of stirring apparatus and nitrogen ingress pipe, add the NMP of 19.64g, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add 3.1780g(16.04mmol) BDA, at room temperature stir 2 hours.Then, add the NMP of 8.93g, add 0.8736g(4.01mmol) pyromellitic acid anhydride.Further interpolation NMP makes the concentration of solid constituent reach 18 quality %, at room temperature stirs 24 hours.The viscosity of the polyamic acid solution obtained at temperature 25 DEG C is 8100mPas.In addition, the molecular weight of this polyamic acid is Mn=22537, Mw=72601.
In this solution, add the 3-glycidoxypropyl diethoxy silane of 0.0235g further, at room temperature stir 24 hours, obtain polyamic acid solution (PAA-16).
(synthesis example 41)
By 3 of 3.6516g (24.0mmol), the 4-Amino-N-methyl phenyl ethylamine of 5-diaminobenzoic acid, 2.4070g (16.02mmol) is taken in the four-hole boiling flask with the 100mL of stirring apparatus and nitrogen ingress pipe, add the NMP of 66.21g, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add the pyromellitic acid anhydride of 8.5972g (39.42mmol).Further interpolation NMP makes the concentration of solid constituent reach 15 quality %, at room temperature stirs 24 hours.The viscosity of the polyamic acid solution obtained at temperature 25 DEG C is 488mPas.In addition, the molecular weight of this polyamic acid is Mn=13205, Mw=33511.
In this solution, add the 3-glycidoxypropyl diethoxy silane of 0.0438g further, at room temperature stir 24 hours, obtain polyamic acid solution (PAA-17).
(synthesis example 42)
By 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, supply nitrogen and stir and make it dissolve.Stir this two amine aqueous solution while add the DAH-2 of 12.0709g (39.41mmol).Further interpolation NMP makes the concentration of solid constituent reach 20 quality %, at room temperature stirs 24 hours.The viscosity of the polyamic acid solution obtained at temperature 25 DEG C is 207mPas.In addition, the molecular weight of this polyamic acid is Mn=5269, Mw=12875.
In this solution, add the 3-glycidoxypropyl diethoxy silane of 0.0586g further, at room temperature stir 24 hours, obtain polyamic acid solution (PAA-18).
(embodiment 18)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 14 of 3.6139g polyamic acid ester solution (PAE-3), 2.7012g synthesis example 29 in the polyamic acid solution (PAA-5) that obtains, add the BCS of NMP, 3.01g of 5.7093g, 4-as imidizate promoter (tertbutyloxycarbonylamino) pyridine (being abbreviated as Boc-AP below) of further interpolation 0.1284g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (I-1).
(embodiment 19)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 15 of 2.4040g polyamic acid ester solution (PAE-4), 2.4687g synthesis example 30 in the polyamic acid solution (PAA-6) that obtains, add the BCS of NMP, 2.0348g of 3.2072g, the Boc-AP as imidizate promoter of further interpolation 0.0542g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (I-2).
(embodiment 20)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 15 of 2.4548g polyamic acid ester solution (PAE-4), 2.0213g synthesis example 31 in the polyamic acid solution (PAA-6) that obtains, add the BCS of NMP, 2.0116g of 3.6200g, that further interpolation 0.0415g is the Boc-AP of imidizate promoter, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (I-3).
(embodiment 21)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 16 of 2.4232g polyamic acid ester solution (PAE-5), 2.4189g synthesis example 33 in the polyamic acid solution (PAA-9) that obtains, add the BCS of NMP, 2.0272g of 3.2928g, the N-α as imidizate promoter-(9-fluorenylmethoxycarbonyl groups)-N-tert-butoxycarbonyl-L-Histidine (being abbreviated as Fmoc-His below) of further interpolation 0.0416g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (I-4).
(embodiment 22)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 16 of 2.4232g polyamic acid ester solution (PAE-5), 1.8681g synthesis example 33 in the polyamic acid solution (PAA-9) that obtains, add the BCS of NMP, 2.0158g of 3.6548g, the Fmoc-His as imidizate promoter of further interpolation 0.0372g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (I-5).
(embodiment 23)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 17 of 2.4356g polyamic acid ester solution (PAE-6), 2.5278g synthesis example 34 in the polyamic acid solution (PAA-10) that obtains, add the BCS of NMP, 2.0366g of 3.2644g, the Fmoc-His as imidizate promoter of further interpolation 0.0550g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (I-6).
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 18 of 2.4012g polyamic acid ester solution (PAE-7), 2.4115g synthesis example 35 in the polyamic acid solution (PAA-11) that obtains, add the BCS of NMP, 2.0052g of 2.6514g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-1).
(embodiment 25)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 18 of 2.4130g polyamic acid ester solution (PAE-7), 2.4216g synthesis example 35 in the polyamic acid solution (PAA-11) that obtains, add the BCS of NMP, 2.0198g of 2.6780g, the 20 quality %NMP solution of the multi-functional epoxy compound as crosslinking chemical (AD-1) of further interpolation 0.3062g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-2).
(embodiment 26)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 15 of 2.4302g polyamic acid ester solution (PAE-4), 1.8678g synthesis example 36 in the polyamic acid solution (PAA-12) that obtains, add the BCS of NMP, 2.0060g of 3.8086g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-3).
(embodiment 27)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 15 of 2.4144g polyamic acid ester solution (PAE-4), 1.8062g synthesis example 36 in the polyamic acid solution (PAA-12) that obtains, add the BCS of NMP, 2.0168g of 3.8184g, the multifunctional hydroxy-containing compounds (AD-2) as crosslinking chemical of further interpolation 0.040g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-4).
(embodiment 28)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 15 of 2.4015g polyamic acid ester solution (PAE-4), 1.8005g synthesis example 37 in the polyamic acid solution (PAA-13) that obtains, add the BCS of NMP, 2.0011g of 3.8063g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-5).
(embodiment 29)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 19 of 2.4120g polyamic acid ester solution (PAE-8), 1.8389g synthesis example 38 in the polyamic acid solution (PAA-14) that obtains, add the BCS of NMP, 2.0181g of 3.8639g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-6).
(embodiment 30)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 19 of 2.4120g polyamic acid ester solution (PAE-8), 1.8389g synthesis example 38 in the polyamic acid solution (PAA-14) that obtains, add the BCS of NMP, 2.0181g of 3.8639g, the multifunctional cyclic carbonate compound (AD-4) as crosslinking chemical of further interpolation 0.0318g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-7).
(embodiment 31)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 20 of 1.2268g polyamic acid ester solution (PAE-9), 3.2688g synthesis example 39 in the polyamic acid solution (PAA-15) that obtains, add the BCS of NMP, 2.0591g of 3.6154g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-8).
(embodiment 32)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 21 of 2.4236g polyamic acid ester solution (PAE-10), 2.3539g synthesis example 40 in the polyamic acid solution (PAA-16) that obtains, add the γ-BL of NMP, 3.0639g, the BCS of 2.0178g of 0.3782g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-9).
(embodiment 33)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 16 of 4.2045g polyamic acid ester solution (PAE-5), 1.2281g synthesis example 41 in the polyamic acid solution (PAA-17) that obtains, add the BCS of NMP, 2.0112g of 2.6041g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-10).
(embodiment 34)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 22 of 2.4195g polyamic acid ester solution (PAE-11), 1.8484g synthesis example 29 in the polyamic acid solution (PAA-5) that obtains, add the BCS of NMP, 2.0204g of 3.8069g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-11).
(embodiment 35)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 17 of 2.4176g polyamic acid ester solution (PAE-6), 2.0148g synthesis example 42 in the polyamic acid solution (PAA-18) that obtains, add the BCS of NMP, 2.0129g of 3.8182g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (II-12).
(embodiment 36)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 17 of 2.3987g polyamic acid ester solution (PAE-6), 2.1543g synthesis example 42 in the polyamic acid solution (PAA-18) that obtains, add the BCS of NMP, 2.0374g of 3.8130g, the multifunctional oxetane compound (AD-3) as crosslinking chemical of further interpolation 0.0460g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (I-13).
(comparative example 17)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 23 of 7.2164g polyamic acid ester solution (PAE-12), 2.7470g synthesis example 29 in the polyamic acid solution (PAA-5) that obtains, add the BCS of NMP, 3.0264g of 2.1068g, the Boc-AP as imidizate promoter of further interpolation 0.1396g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (a-1).
(comparative example 18)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 24 of 2.4504g polyamic acid ester solution (PAE-13), 2.4805g synthesis example 30 in the polyamic acid solution (PAA-6) that obtains, add the BCS of NMP, 2.0226g of 3.2447g, the Boc-AP as imidizate promoter of further interpolation 0.0547g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (a-2).
(comparative example 19)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 25 of 2.4012g polyamic acid ester solution (PAE-14), 1.8320g synthesis example 33 in the polyamic acid solution (PAA-9) that obtains, add the BCS of NMP, 2.0195g of 3.8172g, the Fmoc-His as imidizate promoter of further interpolation 0.0433g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (a-5).
(comparative example 20)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 26 of 2.4017g polyamic acid ester solution (PAE-15), 2.5777g synthesis example 33 in the polyamic acid solution (PAA-9) that obtains, add the BCS of NMP, 2.000g of 3.2518g, the Fmoc-His as imidizate promoter of further interpolation 0.0550g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (a-6).
(comparative example 21)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the comparison synthesis example 1 of 2.4335g polyamic acid ester solution (PAE-2), 2.4013g synthesis example 35 in the polyamic acid solution (PAA-11) that obtains, add the BCS of NMP, 2.0105g of 2.6238g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (b-1).
(comparative example 22)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 24 of 2.4264g polyamic acid ester solution (PAE-13), 1.8157g synthesis example 36 in the polyamic acid solution (PAA-12) that obtains, add the BCS of NMP, 2.0448g of 3.8352g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (b-3).
(comparative example 23)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 28 of 1.2049g polyamic acid ester solution (PAE-17), 3.2102g synthesis example 39 in the polyamic acid solution (PAA-15) that obtains, add the BCS of NMP, 2.0694g of 3.6342g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (b-9).
(comparative example 24)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 27 of 2.4025g polyamic acid ester solution (PAE-16), 2.2514g synthesis example 40 in the polyamic acid solution (PAA-16) that obtains, add the γ-BL of NMP, 3.0007g, the BCS of 2.0015g of 0.3792g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (b-10).
(comparative example 25)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 25 of 4.2242g polyamic acid ester solution (PAE-14), 1.2473g synthesis example 41 in the polyamic acid solution (PAA-17) that obtains, add the BCS of NMP, 2.0664g of 2.6481g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (b-11).
(comparative example 26)
Stirrer is put in the Erlenmeyer flask of 50ml, be taken into obtain in the synthesis example 26 of 2.4260g polyamic acid ester solution (PAE-15), 2.2122g synthesis example 42 in the polyamic acid solution (PAA-18) that obtains, add the BCS of NMP, 2.0585g of 3.8118g, by magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (b-13).
(embodiment 37)
After the aligning agent for liquid crystal (I-1) obtained in the filter. EXAMPLE 18 of 1.0 μm, be spun on the glass substrate of band transparency electrode, through on the hot plate of temperature 80 DEG C dry 5 minutes and burn till 20 minutes in the heated air circulation type stove of temperature 230 DEG C, obtain the film of the imidizate of thickness 100nm.Determine 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 each aligning agent for liquid crystal obtained in use above-described embodiment 19,22,24 ~ 27,29 ~ 36 and comparative example 17 ~ 19,21 ~ 26, define each film by the method identical with embodiment 37.The film surface of each film is observed with AFM.In addition, the center line average roughness (Ra) of each film is determined.These measurement results are shown in table 4 described later.
[table 4]
The possibility that industry utilizes
Aligning agent for liquid crystal of the present invention, by reducing the surperficial micro concavo-convex of the liquid crystal orientation film obtained, exchange and drive the liquid crystal of the ghost reduction that causes etc. to be enhanced with the interfacial characteristics of liquid crystal orientation film, and the electrical characteristics to remain etc. of voltage retention, ion concentration and DC voltage are also enhanced.Result can be widely used in TN element, STN element, TFT liquid crystal cell, and the liquid crystal display cells etc. of vertical orientating type.
Quote the announcement of full content as instructions of the present invention of the instructions of No. 2010-058552, the Japanese patent application that on March 15th, 2010 files an application, claims and specification digest here.

Claims (14)

1. an aligning agent for liquid crystal, is characterized in that, containing, for example under (A) composition and (B) composition,
(A) composition: there is repetitive that following formula (1) represents and meet the poly amic acid ester of condition any one of following (i) ~ (iii),
[changing 1]
In formula, X 14 valency organic groups, Y 1divalent organic group, R 1the alkyl of carbon number 1 ~ 5, A 1and A 2separately for hydrogen atom maybe can have alkyl, alkenyl, the alkynyl of substituent carbon number 1 ~ 20,
The X of (i) formula (1) 1, Y 1or both has 1 valency or the divalent substituting group of at least one structure be selected from following formula (2) and (3),
(ii) A of formula (1) 1, A 2or both has 1 valency or the divalent substituting group of at least one structure be selected from following formula (2) and (3),
(iii) X of formula (1) 1, Y 1or both has 1 valency or the divalent substituting group of at least one structure be selected from following formula (2) and (3), and A 1, A 2or both has 1 valency or the divalent substituting group of at least one structure be selected from following formula (2) and (3),
[changing 2]
The D of formula (2) and formula (3) 1and D 2under the action of heat by the functional group that hydrogen atom replaces respectively, B 1be singly-bound or divalent organic group, wherein, the atom of the ester group institute bonding in formula (3) is carbon atom,
(B) composition: the polyamic acid with the repetitive that following formula (4) represents,
[changing 3]
In formula, X 24 valency organic groups, Y 2divalent organic group, A 1and A 2with the A in formula (1) 1and A 2define identical.
2. aligning agent for liquid crystal as claimed in claim 1, is characterized in that, the content of (A) composition and the content of (B) 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, the total content of (A) composition and (B) composition is 1 ~ 10 quality % relative to organic solvent.
4. aligning agent for liquid crystal as claimed in claim 1, is characterized in that, functional group D 1it is at least one group being selected from tert-butoxycarbonyl and 9-fluorenylmethoxycarbonyl groups.
5. aligning agent for liquid crystal as claimed in claim 1, is characterized in that, functional group D 2it is the tert-butyl group.
6. aligning agent for liquid crystal as claimed in claim 1, it is characterized in that, (A) composition is the substituent poly amic acid ester with at least one representation be selected from following formula (5) and (6),
[changing 4]
In formula (5), B 2singly-bound or divalent organic group, R 2, R 3, R 4be separately 1 valency organic group of hydrogen atom or carbon number 1 ~ 20,
[changing 5]
In formula (6), B 3be singly-bound or divalent organic group, wherein, the atom of the tert-butoxycarbonyl institute bonding in formula (6) is carbon atom.
7. aligning agent for liquid crystal as claimed in claim 6, it is characterized in that, (A) composition is the Y of formula (1) 1there is in structure the substituent poly amic acid ester of at least one representation in the formula of being selected from (5) and (6).
8. aligning agent for liquid crystal as claimed in claim 6, it is characterized in that, (A) composition is the A of formula (1) 1, A 2or both has the substituent poly amic acid ester of at least one representation in the formula of being selected from (5) and (6).
9. aligning agent for liquid crystal as claimed in claim 1, it is characterized in that, (A) composition is the Y of formula (1) 1for the poly amic acid ester of the structure that following formula (7) represents,
[changing 6]
In formula, R 5the divalent organic group of singly-bound or carbon number 1 ~ 20, R 6be at least one structure being selected from formula (5) and (6), a is the integer of 1 ~ 4.
10. aligning agent for liquid crystal as claimed in claim 1, it is characterized in that, (A) composition is the Y of formula (1) 1there is the poly amic acid ester of at least one structure being selected from the structure that following formula represents,
[changing 7]
11. aligning agent for liquid crystal as claimed in claim 1, is characterized in that, in above-mentioned formula (1) and (4), and X 1and X 2separately for being selected from least one in the structure that is expressed from the next,
[changing 8]
12. aligning agent for liquid crystal as described in claim 1 or 11, is characterized in that, in formula (4), and Y 2for being selected from least one of the structure that following formula represents,
13. 1 kinds of liquid crystal orientation films, is characterized in that, are coated with the aligning agent for liquid crystal according to any one of claim 1 ~ 12 and burn till and obtain.
14. 1 kinds of liquid crystal orientation films, is characterized in that, the aligning agent for liquid crystal of coating according to any one of claim 1 ~ 12, burns till, and irradiate the ultraviolet of polarization and obtain.
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