CN102893206A - Liquid crystal alignment agent containing end-modified polyamic acid ester, and liquid crystal alignment film - Google Patents

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

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CN102893206A
CN102893206A CN2011800240298A CN201180024029A CN102893206A CN 102893206 A CN102893206 A CN 102893206A CN 2011800240298 A CN2011800240298 A CN 2011800240298A CN 201180024029 A CN201180024029 A CN 201180024029A CN 102893206 A CN102893206 A CN 102893206A
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liquid crystal
acid ester
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polyamic acid
poly amic
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CN102893206B (en
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作本直树
堀隆夫
饭沼洋介
野口勇步
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films

Abstract

Disclosed is a liquid crystal alignment agent which can reduce microscopic irregularities on the surface of liquid crystal alignment films, improves liquid crystal alignment properties, and has improved electrical characteristics, such as the relaxation of residual DC voltage, and VHR/ion density. The liquid crystal alignment agent is characterised in containing: a polyamic acid ester having a structural unit represented by general formula (1), and having an end modified such that an amino group on the end has a specific structure represented by general formula (3); a polyamic acid having a structural unit represented by general formula (2); and an organic solvent. (R1 represents a C1-5 alkyl group, A1 and A2 independently represent a hydrogen atom or an optionally substituted C1-10 alkyl group, alkenyl group or alkynyl group, X1 and X2 represent a tetravalent organic group, and Y1 and Y2 represent a divalent organic group.) (In general formula (3), A represents a single bond, -O-, -S-, or -NR3-, and R2 and R3 independently represent a methyl group, an ethyl group, a vinyl group, a 1-propenyl group, an isopropenyl group, a C3-6 cycloalkyl group, a phenyl group, a naphthyl group, or a heterocyclic ring).

Description

Comprise the aligning agent for liquid crystal and the liquid crystal orientation film that end have been carried out the poly amic acid ester of modification
Technical field
The present invention relates to comprise liquid crystal orientation film and liquid crystal display cells that end has been carried out the aligning agent for liquid crystal of the poly amic acid ester modified and polyamic acid, obtained by this aligning agent for liquid crystal.
Background technology
The used liquid crystal display cells such as LCD TV, liquid crystal display is provided with the liquid crystal orientation film for the state of orientation of control liquid crystal usually in element.As liquid crystal orientation film, at present main employing will be coated take the solution of the polyimide precursor such as polyamic acid or soluble polyimide as the aligning agent for liquid crystal of principal ingredient glass substrate etc. and burn till the polyimide liquid crystal orientation film that gets.
Follow the high-precision refinement of liquid crystal display cells, requirement based on the contrast decline that suppresses liquid crystal display cells and minimizing ghost phenomena, the characteristics such as liquid crystal orientation film not only needs to present good liquid crystal aligning and stable tilt angle, and the mitigation of inhibition, the residual charge when applying DC voltage of high voltage holding ratio, the ghost that produces because of crosslinked driving residual charge few and/or that gather because of DC voltage is fast also become more and more important.
For the polyimide liquid crystal orientation film, in order to tackle aforesaid requirement, various schemes have been proposed.For example, short liquid crystal orientation film of time till disappearing as the ghost that produces because of DC voltage, propose to have the aligning agent for liquid crystal that uses the tertiary amine that except the polyamic acid of polyamic acid or imido-, also comprises ad hoc structure liquid crystal orientation film (reference example such as patent documentation 1), use and comprise the specific diamine compound that will have a pyridine skeleton etc. as the liquid crystal orientation film (reference example such as patent documentation 2) of the aligning agent for liquid crystal of the soluble polyimide of raw material etc.In addition, short liquid crystal orientation film of time till ghost high and that produce because of DC voltage disappears as voltage retention proposes to have and uses the liquid crystal orientation film (reference example such as patent documentation 3) of aligning agent for liquid crystal that compound, molecule that molecule includes 1 carboxyl include the compound of 1 acid anhydride's compound and the compound that molecule includes 1 tertiary amine groups that is selected from that also comprises minute quantity except polyamic acid or its imide amination polymer etc.In addition, good as liquid crystal aligning, voltage retention is high, ghost is few, reliability is good and present the liquid crystal orientation film of high tilt angle, known use comprises the liquid crystal orientation film (reference example such as patent documentation 4) by the aligning agent for liquid crystal of the tetracarboxylic dianhydride of ad hoc structure, the tetracarboxylic dianhydride with cyclo-butane, polyamic acid that specific diamine compound obtains or its imide amination polymer.In addition, as produce in the liquid crystal display cells that suppresses the transverse electric field type of drive by exchanging the method that drives the ghost that causes, propose to have use liquid crystal aligning good and with the method (with reference to patent documentation 5) of the large specific liquid crystal orientation film of the interaction of liquid crystal molecule.
But large picture, high-precision LCD TV become main flow in recent years, become stricter for the requirement of ghost, and requirement can tolerate the characteristic of the long-term use under the harsh environment for use.Meanwhile, employed liquid crystal orientation film needs in the past higher product of reliability ratio, about the various characteristics of liquid crystal orientation film, requires also that not only initial characteristic is good, also keeps good characteristic after exposing at high temperature for example for a long time.
On the other hand, reported as the component of polymer that consists of the polyimide aligning agent for liquid crystal, the reliability of poly amic acid ester is high, can the heat treated when it is carried out imidizate not cause molecular weight and molecular weight, so the orientation stability of liquid crystal, reliability good (with reference to patent documentation 6).But the problems such as poly amic acid ester exists generally that specific insulation is high, the residual charge when applying DC voltage is many, the still unknown method of improving the characteristic of the described polyimide aligning agent for liquid crystal that comprises poly amic acid ester.
The prior art document
Patent documentation
Patent documentation 1: Japanese patent laid-open 9-316200 communique
Patent documentation 2: Japanese patent laid-open 10-104633 communique
Patent documentation 3: Japanese patent laid-open 8-76128 communique
Patent documentation 4: Japanese patent laid-open 9-138414 communique
Patent documentation 5: Japanese patent laid-open 11-38415 communique
Patent documentation 6: Japanese Patent Laid-Open 2003-26918 communique
The summary of invention
Invent technical matters to be solved
As the method for the characteristic of improving the above-mentioned polyimide aligning agent for liquid crystal that comprises poly amic acid ester, the aligning agent for liquid crystal of the polyamic acid that the present invention has been conceived to fusion poly amic acid ester and electrical characteristics aspect are good.But, by described fusion the liquid crystal orientation film that obtains of the aligning agent for liquid crystal of poly amic acid ester and polyamic acid all can't be satisfactory aspect liquid crystal aligning and electrical characteristics.
Namely, the liquid crystal orientation film that is obtained by the aligning agent for liquid crystal that comprises poly amic acid ester and polyamic acid not only causes the gonorrhoea phenomenon, and produce voltage retention when at high temperature using film low, the ghost that gathering of DC voltage cause occurs and occur by exchanging the problems such as ghost that cause that drive.
The object of the present invention is to provide the aligning agent for liquid crystal that comprises poly amic acid ester and polyamic acid, the liquid crystal aligning of this aligning agent for liquid crystal and electrical characteristics are all good, and can obtain the liquid crystal orientation film without the tool transparency of gonorrhoea.
The technical scheme that the technical solution problem adopts
According to the inventor's research, the liquid crystal orientation film that is formed by the aligning agent for liquid crystal that comprises poly amic acid ester and polyamic acid to be analyzed, results verification produces trickle concavo-convex on film surface.But, the inventor finds to produce on the film surface, and trickle concavo-convex can the employing by poly amic acid ester carried out modifying the poly amic acid ester that at least a portion that makes its terminal amino group that has has ad hoc structure as described below to end and suppressed significantly, and find to reduce in the described trickle concavo-convex situation that produces on the film surface, comprise the above-mentioned difficult point that the aligning agent for liquid crystal of poly amic acid ester and polyamic acid exists and eliminate.
In addition, even the inventor also finds in the high situation of the molecular weight of the poly amic acid ester after the amino quilt of above-mentioned end is modified, because the dissolubility in organic solvent improves, therefore comprising terminal aligning agent for liquid crystal by the polyamic acid after modifying and polyamic acid can be made in organic solvent and contains sometimes the also lower aligning agent for liquid crystal of viscosity with high concentration, for example adopt thus that the manufacturing of the liquid crystal orientation film of ink-jet method becomes easily, and the manufacturing of thicker liquid crystal orientation film also becomes easy.
So, the present invention is based on above-mentioned new discovery, have following technical essential.
1. aligning agent for liquid crystal, it is characterized in that, comprise have following formula (1) structural unit and to end carried out modifying and make terminal amino group have the structure of following formula (3) poly amic acid ester, have polyamic acid and the organic solvent of the structural unit of following formula (2);
[changing 1]
Figure BDA00002401499800031
R 1Be the alkyl of carbon number 1～5, A 1～A 2Represent independently that respectively hydrogen atom maybe can have alkyl, the alkenyl or alkynyl of substituent carbon number 1～10, X 1, X 2Be 4 valency organic groups, Y 1, Y 2Be the divalent organic group;
[changing 2]
In the formula, A be singly-bound ,-O-,-S-or-NR 3-, R 2, R 3Represent independently respectively carbon number 1～10 alkyl, alkenyl or alkynyl, carbon number 3～6 naphthenic base or can have substituent aryl or heterocyclic radical.
2. such as above-mentioned 1 described aligning agent for liquid crystal, wherein, the content of described poly amic acid ester and the content of polyamic acid count 1/9～9/1 with the mass ratio of (content of the content/polyamic acid of poly amic acid ester).
3. such as above-mentioned 1 or 2 described aligning agent for liquid crystal, wherein, comprise described poly amic acid ester and polyamic acid and organic solvent, the total amount of described poly amic acid ester and polyamic acid is 0.5 quality %～15 quality % with respect to organic solvent.
As above-mentioned 1～3 in each described aligning agent for liquid crystal, wherein, the described poly amic acid ester that end has been carried out modifying is by making at least a chlorocarbonylation compound that is selected from following formula (C-1)～(C-17) and the main chain terminal amino group of poly amic acid ester react the poly amic acid ester that gets.
[changing 3]
Figure BDA00002401499800051
As above-mentioned 1～4 in each described aligning agent for liquid crystal, wherein, the X in formula (1) and the formula (2) 1And X 2Expression is selected from least a of the structure that represents with following formula independently respectively.
[changing 4]
Figure BDA00002401499800061
As above-mentioned 1～5 in each described aligning agent for liquid crystal, wherein, in the described formula (1), Y 1For being selected from least a of the structure that represents with following formula.
[changing 5]
Figure BDA00002401499800071
As above-mentioned 1～6 in each described aligning agent for liquid crystal, wherein, in the described formula (2), Y 2For being selected from least a of the structure that represents with following formula.
[changing 6]
Figure BDA00002401499800081
8. a liquid crystal orientation film is coated with each the described aligning agent for liquid crystal in above-mentioned 1～7, burn till and obtains.
9. liquid crystal orientation film, to each the described aligning agent for liquid crystal coating in above-mentioned 1～7, burn till and the tunicle irradiation behind polarization radioactive ray and obtain.
The effect of invention
If employing the present invention, then can provide and to reduce the trickle concavo-convex of surface, improve by exchanging the interfacial characteristics that drives the liquid crystal orientation films such as ghost minimizing that cause, and the electrical characteristics such as residual of voltage retention, ion concentration and DC voltage also improve, Reliability Enhancement aligning agent for liquid crystal.
Among the present invention, by employing terminal amino group having been carried out modification makes it have the poly amic acid ester of ad hoc structure as described below, can reduce described produce on the film surface trickle concavo-convex, the above-mentioned difficult point that comprises the aligning agent for liquid crystal existence of poly amic acid ester and polyamic acid is eliminated, for its reason and unclear, but think roughly as follows.
Namely, from poly amic acid ester and polyamic acid be dissolved in the organic solvent and the aligning agent for liquid crystal desolventizing and in the liquid crystal orientation film that forms, the poly amic acid ester that surface free energy is lower than polyamic acid is concentrated and is present in the surface, but poly amic acid ester and polyamic acid are separated, thereby form the agglutination body of polyamic acid in mutually at poly amic acid ester, and/or form the agglutination body of poly amic acid ester in mutually at polyamic acid, therefore be formed on the surface and have a large amount of trickle concavo-convex films.
For this point, by employing end having been carried out modification in the aligning agent for liquid crystal of the present invention makes it have the poly amic acid ester of above-mentioned ad hoc structure, when forming liquid crystal orientation film from this aligning agent for liquid crystal desolventizing, being separated of poly amic acid ester and polyamic acid is promoted, poly amic acid ester is present in the film near surface and does not mix with polyamic acid, and polyamic acid is present in the inner and substrate interface of film and does not mix with poly amic acid ester.Therefore, the surface of the liquid crystal orientation film of gained not can because of being separated of poly amic acid ester and polyamic acid form concavo-convex, so that the surface becomes is level and smooth.And, do not form concavo-convex and liquid crystal orientation film with smooth surface because the good poly amic acid ester coverlay surface of orientation stability, reliability, and the good polyamic acid of electrical characteristics is present in film inside and electrode interface, therefore has good characteristic.In addition, the liquid crystal orientation film that has smooth surface also reduces because producing the concavo-convex film gonorrhoea that causes.
The mode that carries out an invention
＜poly amic acid ester and polyamic acid 〉
The poly amic acid ester that the present invention is used and polyamic acid are for the polyimide precursor that obtains polyimide, are to have the polymkeric substance that can carry out by heating the position of imidization reaction as follows.
[changing 7]
Figure BDA00002401499800091
[changing 8]
Figure BDA00002401499800092
The poly amic acid ester that aligning agent for liquid crystal of the present invention is contained and polyamic acid have respectively following formula (1) and following formula (2).
[changing 9]
Figure BDA00002401499800093
In the formula (1), R 1For carbon number 1～5, better be 1～2 alkyl.For poly amic acid ester, the temperature of carrying out imidizate raises along with the increase of the carbon number in the alkyl.Therefore, from carry out the angle of the difficulty of imidizate, R by heating 1Methyl particularly preferably.
In formula (1) and the formula (2), A 1And A 2Represent independently that respectively hydrogen atom maybe can have alkyl, thiazolinyl, the alkynyl of substituent carbon number 1～10.As the object lesson of abovementioned alkyl, but exemplified by methyl, ethyl, propyl group, butyl, the tert-butyl group, hexyl, octyl group, decyl, cyclopentyl, cyclohexyl, dicyclohexyl etc.As thiazolinyl, can exemplify the more than one CH that to exist in the above-mentioned alkyl 2-CH 2Structure replace with the CH=CH structure and group, but more specifically exemplified by vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl group, 1,3-butadiene base, 2-pentenyl, 2-hexenyl, cyclopropanyl, cyclopentenyl, cyclohexenyl group etc.As alkynyl, can exemplify the more than one CH that to exist in the above-mentioned alkyl 2-CH 2Structure replace with CH ≡ CH structure and group, more specifically can exemplify ethinyl, 1-propinyl, 2-propynyl etc.
Above-mentioned alkyl, thiazolinyl, alkynyl can have substituting group as long as carbon number on the whole is 1～10, also can form ring structure by substituting group.Form that ring structure refers to mutually combine between the substituting group or substituting group is combined with the part of female skeleton and is formed ring structure by substituting group.
As this substituent example, can exemplify halogen group, hydroxyl, sulfydryl, nitro, aryl, organic oxygen base, organic sulfenyl, organosilicon alkyl, acyl group, ester group, sulfo-ester group, phosphate-based, amide group, alkyl, thiazolinyl, alkynyl etc.
Can exemplify fluorine atom, chlorine atom, bromine atoms, iodine atom as substituent halogen group.
But as substituent aryl exemplified by phenyl.This aryl can further be replaced by other above-mentioned substituting group.
As substituent organic oxygen base the structure that represents with O-R can be shown.This R can be identical or different, but the above-mentioned alkyl of example, thiazolinyl, alkynyl, aryl etc.These R can further be replaced by above-mentioned substituting group.As the object lesson of alkoxy, can exemplify methoxyl, ethoxy, propoxyl group, butoxy, amoxy, own oxygen base, heptan oxygen base, octyloxy etc.
Can illustrate with-structure that S-R represents as substituent organic sulfenyl.As this R, but the above-mentioned alkyl of example, thiazolinyl, alkynyl, aryl etc.These R can further be replaced by above-mentioned substituting group.As the object lesson of alkylthio group, can exemplify methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl, heptan sulfenyl, hot sulfenyl etc.
Can illustrate with-Si-(R) as substituent organosilicon alkyl 3The structure of expression.This R can be identical or different, but the above-mentioned alkyl of example, thiazolinyl, alkynyl, aryl etc.These R can further be replaced by above-mentioned substituting group.As the object lesson of alkyl tin groups, alkyl silane groups, can exemplify TMS, triethyl silyl, tripropyl silylation, tributyl silylation, three amyl group silylation, three hexyl silane bases, amyl group dimethylsilyl, hexyl dimethylsilyl etc.
Can illustrate with-structure that C (O)-R represents as substituent acyl group.As this R, but the above-mentioned alkyl of example, thiazolinyl, aryl etc.These R can further be replaced by above-mentioned substituting group.As the object lesson of acyl group, can exemplify formoxyl, acetyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl, benzoyl etc.
As substituent ester group can illustrate with-C (O) O-R or-structure that OC (O)-R represents.As this R, but the above-mentioned alkyl of example, thiazolinyl, alkynyl, aryl etc.These R can further be replaced by above-mentioned substituting group.
As substituent sulfo-ester group can illustrate with-C (S) O-R or-structure that OC (S)-R represents.As this R, but the above-mentioned alkyl of example, thiazolinyl, alkynyl, aryl etc.These R can further be replaced by above-mentioned substituting group.
As substituent phosphate-based illustrating with-OP (O)-(OR) 2The structure of expression.This R can be identical or different, but the above-mentioned alkyl of example, thiazolinyl, alkynyl, aryl etc.These R can further be replaced by above-mentioned substituting group.
Can illustrate with-C (O) NH as substituent amide group 2Or-C (O) NHR ,-NHC (O) R ,-C (O) N (R) 2The structure that ,-NRC (O) R represents.This R can be identical or different, but the above-mentioned alkyl of example, thiazolinyl, alkynyl, aryl etc.These R can further be replaced by above-mentioned substituting group.
Can exemplify the group identical with above-mentioned aryl as substituent aryl.This aryl can further be replaced by other above-mentioned substituting group.
Can exemplify the group identical with above-mentioned alkyl as substituent alkyl.This alkyl can further be replaced by other above-mentioned substituting group.
Can exemplify the group identical with above-mentioned thiazolinyl as substituent thiazolinyl.This thiazolinyl can further be replaced by other above-mentioned substituting group.
Can exemplify the group identical with above-mentioned alkynyl as substituent alkynyl.This alkynyl can further be replaced by other above-mentioned substituting group.
Usually, if introduce bulky structure, then may make amino reactivity or liquid crystal aligning decline, therefore as A 1And A 2, be more preferably the alkyl that hydrogen atom maybe can have substituent carbon number 1～5, particularly preferably hydrogen atom, methyl or ethyl.
In addition, in above-mentioned formula (1) and the formula (2), X 1, X 2Be 4 valency organic groups, be not particularly limited.In the polyimide precursor, X 1, X 2Can exist simultaneously more than 2 kinds.If X is shown 1, X 2Object lesson, can exemplify independently respectively X-1～X-46 shown below.
[changing 10]
Figure BDA00002401499800121
[changing 11]
Figure BDA00002401499800122
[changing 12]
Figure BDA00002401499800123
[changing 13]
Wherein, from obtaining the difficulty of monomer, X 1And X 2Difference is preferred 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 independently.Have these preferred X 1And X 2Tetracarboxylic dianhydride's use amount better be 20～100 % by mole of whole tetracarboxylic dianhydrides, be more preferably 40～100 % by mole.
In addition, in above-mentioned formula (1) and the formula (2), Y 1And Y 2Represent independently respectively the divalent organic group, be not particularly limited.If Y is shown 1And Y 2Object lesson, can exemplify following Y-1～Y-103.As Y 1And Y 2, can exist simultaneously more than 2 kinds independently respectively.
[changing 14]
Figure BDA00002401499800131
[changing 15]
Figure BDA00002401499800132
[changing 16]
Figure BDA00002401499800133
[changing 17]
Figure BDA00002401499800141
[changing 18]
Figure BDA00002401499800142
[changing 19]
Figure BDA00002401499800143
[changing 20]
[changing 21]
Figure BDA00002401499800151
[changing 22]
Figure BDA00002401499800152
[changing 23]
[changing 24]
Figure BDA00002401499800161
[changing 25]
Figure BDA00002401499800162
[changing 26]
Figure BDA00002401499800171
Wherein, introducing poly amic acid ester for the diamines that linear degree is high and obtain good liquid crystal aligning, better is as Y 1Diamines with 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.As Y 1Better be 1～100 % by mole of whole diamines for the use amount of the preferred diamines of above example, be more preferably 50～100 % by mole.
Wherein, increase in the situation of tilt angle, better be to be introduced in the diamines that side chain has the structure that chain alkyl, aromatic ring, aliphatics ring, steroid skeleton or they combine in poly amic acid ester, at this moment as Y 1Be more preferably 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.
As described Y 1, be preferably selected from least a of the structure that represents with following formula.
[changing 27]
Figure BDA00002401499800181
To have the diamines that contains heteroatomic structure, Ppolynuclear aromatic structure or biphenyl backbone in order in polyamic acid, introducing, thereby can to reduce the ghost that gathering of DC voltage causes by the specific insulation that reduces polyamic acid, as Y 2Be 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 or Y-61, preferred Y 2Diamines for Y-31 or Y-40.As Y 2Better be 1～100 % by mole of whole diamines for the use amount of the preferred diamines of above example, be more preferably 50～100 % by mole.
Wherein, by improving the surface free energy of polyamic acid, being separated of poly amic acid ester and polyamic acid further is promoted, the film surface of the liquid crystal orientation film that is coated with, burns till and get becomes more level and smooth, therefore better is to introduce the diamines that contains secondary amino group, hydroxyl, amide group, urea groups or carboxyl in polyamic acid.Therefore, as Y 2, be more preferably Y-19, Y-31, Y-40, Y-45, Y-98 or Y-99, particularly preferably carboxylic Y-98 or Y-99.Wherein, Y 2Be preferably selected from least a of the structure that represents with following formula.
[changing 28]
Figure BDA00002401499800191
The manufacture method of＜poly amic acid ester 〉
Above-mentioned poly amic acid ester with formula (1) expression can be by obtaining with any reaction with the diamine compound that represents with formula (9) in the tetracarboxylic acid derivatives of following formula (6)～(8) expression.
[changing 29]
[changing 30]
In formula (6)～(9), X 1, Y 1, R 1, A 1And A 2Definition respectively with above-mentioned formula (1) in identical.
Above-mentioned poly amic acid ester with formula (1) expression can use above-mentioned monomer synthetic by the method for (1) shown below～(3).
(1) method of being made by polyamic acid
Poly amic acid ester can be by being made by the polyamic acid esterification that tetracarboxylic dianhydride and diamines obtain.
Specifically, can by make polyamic acid and esterifying agent in the presence of organic solvent in-20 ℃～150 ℃, better be 0 ℃～50 ℃ reactions 30 minutes～24 hours, better be to make in 1～4 hour.
As esterifying agent, better be the reagent that easily to remove by purifying, can exemplify N, dinethylformamide dimethylacetal, N, dinethylformamide diethyl acetal, N, dinethylformamide two propylal, N, dinethylformamide di neo-pentyl 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, chlorination-4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-the 4-methyl morpholine
Figure BDA00002401499800201
Deng.The addition of esterifying agent better is 2～6 molar equivalents with respect to the repetitive of 1 mole of polyamic acid.
From structure adaptability, the solvent that is used for above-mentioned reaction better is DMF, METHYLPYRROLIDONE, gamma-butyrolacton, and these solvents can use one kind or two or more mixing to use.Separate out and easily obtain the polymeric viewpoint of macromolecule from what polymkeric substance be difficult for to occur, the concentration during manufacturing better is 1～30 quality %, is more preferably 5～20 quality %.
(2) method of making by the reaction of tetrabasic carboxylic acid diester diacid chloride and diamines
Poly amic acid ester can be by making tetrabasic carboxylic acid diester diacid chloride and diamines polycondensation.
Specifically, can by make tetrabasic carboxylic acid diester diacid chloride and diamines in the presence of alkali and organic solvent in-20 ℃～150 ℃, better be 0 ℃～50 ℃ reactions 30 minutes～24 hours, better be to make in 1～4 hour.
Described alkali can use pyridine, triethylamine or 4-dimethylaminopyridine etc., carries out in order to make reacting balance ground, and better be pyridine.Easily remove and easily obtain the polymeric viewpoint of macromolecule from its amount, it is 2～4 times that the addition of alkali is haggled over mole with respect to tetrabasic carboxylic acid diester diacid chloride.
From monomer and structure adaptability, the solvent that is used for above-mentioned reaction better is METHYLPYRROLIDONE, gamma-butyrolacton, and these solvents can use one kind or two or more mixing to use.From being difficult for occuring the viewpoint of separating out and easily obtain heavy polymer of polymkeric substance, the polymer concentration during manufacturing better is 1～30 quality %, is more preferably 5～20 quality %.In addition, in order to prevent the hydrolysis of tetrabasic carboxylic acid diester diacid chloride, the solvent that is used for the manufacturing of poly amic acid ester better is to dewater as far as possible, better is to prevent sneaking into of extraneous gas in nitrogen atmosphere.
(3) made the method for polyamic acid by tetrabasic carboxylic acid diester and diamines
Poly amic acid ester can be by making tetrabasic carboxylic acid diester and diamines polycondensation.
Specifically, can by make tetrabasic carboxylic acid diester and diamines in the presence of condensation agent, alkali, organic solvent in 0 ℃～150 ℃, better be 0 ℃～100 ℃ reactions 30 minutes～24 hours, better be to make in 3～15 hours.
Described condensation agent can use triphenyl phosphite, dicyclohexyl carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazines ylmethyl morpholine
Figure BDA00002401499800211
O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea tetrafluoroborate, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea hexafluorophosphate, (2,3-dihydro-2-sulfo--3-benzo
Figure BDA00002401499800212
The azoles base) phosphonic acid diphenyl ester etc.It is 2～3 times that the addition of condensation agent is haggled over mole with respect to the tetrabasic carboxylic acid diester.
Described alkali can use the tertiary amines such as pyridine, triethylamine.Easily remove and easily obtain the polymeric viewpoint of macromolecule from its amount, it is 2～4 times that the addition of alkali is haggled over mole with respect to two amine components.
In addition, in the above-mentioned reaction, by adding lewis acid as adjuvant, reaction is carried out efficiently.As lewis acid, better be the lithium halides such as lithium chloride, lithium bromide.It is 0～1.0 times that lewis acidic addition is haggled over mole with respect to diamines.
In the manufacture method of above-mentioned 3 kinds of poly amic acid esters, owing to can obtain the poly amic acid ester of high molecular, the particularly preferably manufacture method of above-mentioned (1) or (2).
The solution of the poly amic acid ester that obtains as mentioned above can be by making polymkeric substance separate out well-beaten being injected into simultaneously in the poor solvent.Carry out several and separate out, normal temperature or heat drying after cleaning with poor solvent, thereby the poly amic acid ester powder behind the acquisition purifying.Poor solvent is not particularly limited, and can exemplify water, methyl alcohol, ethanol, hexane, butyl cellosolve, acetone, toluene etc.
The manufacture method of＜polyamic acid 〉
Above-mentioned polyamic acid with formula (2) expression can obtain by the reaction of the tetracarboxylic dianhydride who represents with following formula (10) and the diamine compound that represents with formula (11).
[changing 31]
Specifically, can by make tetracarboxylic dianhydride and diamines in the presence of organic solvent in-20 ℃～150 ℃, better be 0 ℃～50 ℃ reactions 30 minutes～24 hours, better be to make in 1～12 hour.
From monomer and structure adaptability, the organic solvent that is used for above-mentioned reaction better is DMF, METHYLPYRROLIDONE, gamma-butyrolacton, and these solvents can use one kind or two or more mixing to use.Separate out and easily obtain the polymeric viewpoint of macromolecule from what polymkeric substance be difficult for to occur, the concentration of the polymkeric substance of generation better is 1～30 quality %, is more preferably 5～20 quality %.
The polyamic acid that obtains as mentioned above makes polymkeric substance separate out recovery by being injected in abundant stirring reaction solution in the poor solvent.In addition, carry out several and separate out, normal temperature or heat drying after cleaning with poor solvent, thereby the polyamic acid powder behind the acquisition purifying.Poor solvent is not particularly limited, and can exemplify water, methyl alcohol, ethanol, hexane, butyl cellosolve, acetone, toluene etc.
＜for end modified chlorocarbonylation compound 〉
End can be reacted to obtain with the poly amic acid ester that has endways amino that obtains as mentioned above by making the chlorocarbonylation compound with following formula (12) expression by the poly amic acid ester after modifying.
Figure BDA00002401499800221
In the formula (12), A be singly-bound ,-O-,-S-or-NR 3-.R 2, R 3Represent independently respectively carbon number 1～10 alkyl, alkenyl or alkynyl, carbon number 3～6 naphthenic base or can have substituent aryl or heterocyclic radical.As the object lesson of the alkyl of carbon number 1～10, but exemplified by methyl, ethyl, vinyl, 1-propenyl or isopropenyl.Wherein, better be the short alkyl of carbon number 1～3, and compare with the alkyl of branch-like, be more preferably the alkyl of straight chain shape.As the naphthenic base of carbon number 3～6, better be cyclopropyl or cyclobutyl.As aryl, better be phenyl, naphthyl.As heterocyclic radical, better be pyridine, imidazoles, different Azoles, thiophene, furans, indoles, benzimidazole, pyrroles or piperidines.
If exemplify the example of chlorocarbonylation compound of the present invention, can exemplify the chlorocarbonylation compound of following (C-1)～(C-36), but be not limited in this.
As above-mentioned chlorocarbonylation compound, the structure that carbon number is fewer, the interaction between the end is less, can suppress the aggegation of poly amic acid ester.Therefore, as the chlorocarbonylation compound, better be C-1, C-2, C-3, C-16, C-17, C-19, C-20, C-21, C-27 or C-29, be more preferably C-1, C-2, C-3, C-16 or C-17.
The manufacture method of＜terminally modified poly amic acid ester 〉
The above-mentioned end that has endways the poly amic acid ester of the amino repetitive with formula (1) is modified, so that this amino has the structure of above-mentioned formula (3).
This can obtain by several method the poly amic acid ester that end has carried out modifying, can exemplify following method: will have endways the powder dissolution of amino poly amic acid ester behind organic solvent, and in the presence of alkali, add the chlorocarbonylation compound and make the method for its reaction; Perhaps, two amine components and tetrabasic carboxylic acid dialkyl derivant (two (chlorocarbonyl) compound, dicarboxylic acid dialkyl esters etc.) are reacted in organic solvent and obtain to have endways in the situation of amino poly amic acid ester, do not separate this poly amic acid ester, add the chlorocarbonylation compound in this reaction system, make it and be present in the method that has endways amino poly amic acid ester reaction in the reaction system etc.Wherein, a kind ofly add the method for chlorocarbonylation compound in the reaction system owing to adopting the purifying of reppd poly amic acid ester only get final product for 1 time afterwards, can shorten production process, so more preferably.
In order to obtain the poly amic acid ester that end has been carried out modification of the present invention, must be manufactured on the terminal poly amic acid ester that has amino of main chain.Therefore, the mol ratio of two amine components and tetrabasic carboxylic acid dialkyl derivant better is 1:0.7～1:1, is more preferably 1:0.8～1:1.
Method as above-mentioned reaction system being added the chlorocarbonylation compound has following method: add simultaneously with tetrabasic carboxylic acid dialkyl derivant, make the method for itself and diamine reactant; Tetrabasic carboxylic acid dialkyl derivant and diamines are fully reacted and make terminally for behind the amino poly amic acid ester, add the method for chlorocarbonylation compound.The angle of the molecular weight of calm polymkeric substance easy to control is more preferably rear a kind of method.
End during poly amic acid ester that acquisition has been carried out modifying to end for the reaction of amino poly amic acid ester and chlorocarbonylation compound in the presence of alkali and organic solvent in-20～150 ℃, better be 0～50 ℃ carry out 30 minutes～24 hours, better be 30 minutes～4 hours.
The addition of chlorocarbonylation compound better is 0.5～60mol% with respect to end for 1 repetitive of amino poly amic acid ester, is more preferably 1～40mol%.If addition is many, then remaining unreacted chlorocarbonylation compound is difficult to remove, and therefore further is more preferably 1～20mol%.
Described alkali can preferably use pyridine, triethylamine, 4-dimethylaminopyridine, carries out in order to make reacting balance ground, and better be pyridine.Be difficult at most remove if the addition of alkali is crossed, molecular weight reduces if cross at least, and therefore haggling over molar weight with respect to the chlorocarbonylation compound is 2～4 times.
From monomer and structure adaptability, better be METHYLPYRROLIDONE, gamma-butyrolacton for the manufacture of the organic solvent of the poly amic acid ester that end has been carried out modify, these solvents can use one kind or two or more mixing to use.If the concentration during manufacturing is too high separating out of polymkeric substance occuring easily then, can't improve if cross low then molecular weight, so better be 1～30 quality %, is more preferably 5～20 quality %.In addition, in order to prevent the hydrolysis of chlorocarbonylation compound, better be to dewater as far as possible or be stored in to prevent sneaking into of extraneous gas in the nitrogen atmosphere for the manufacture of the organic solvent of the poly amic acid ester that end has been carried out modify.
Obtain thus end has been carried out the poly amic acid ester of modifying, but in the aligning agent for liquid crystal of the present invention, the described poly amic acid ester that end has been carried out modifying does not need the contained poly amic acid ester of aligning agent for liquid crystal all end to be modified, its content better is more than 15 quality % with respect to the total amount of contained poly amic acid ester, be more preferably more than 40 quality %, particularly preferably more than 60 quality %.Terminal amino group carried out the content of the poly amic acid ester modified when low, can't fully obtain target effect of the present invention.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention have above-mentioned to end carried out that the poly amic acid ester modified and polyamic acid are dissolved in the organic solvent and the form of solution.It is 2000～500000 that the molecular weight that end has been carried out the poly amic acid ester modified is haggled over its weight-average molecular weight, is more preferably 5000～300000, further is more preferably 10000～100000, endways in the not adorned situation of amino too.In addition, number-average molecular weight better is 1000～250000, is more preferably 2500～150000, further is more preferably 5000～50000.
On the other hand, the weight-average molecular weight of polyamic acid better is 2000～500000, is more preferably 5000～300000, further is more preferably 10000～100000.In addition, number-average molecular weight better is 1000～250000, is more preferably 2500～150000, further is more preferably 5000～50000.
That end has been carried out the molecular weight ratio polyamic acid of the poly amic acid ester modified is little by making, and can further reduce be separated and produce small concavo-convex.The difference of end having been carried out the weight-average molecular weight of the poly amic acid ester modified and polyamic acid better is 1000～1200000, is more preferably 3000～80000, particularly preferably 5000～60000.
The poly amic acid ester that aligning agent for liquid crystal of the present invention is contained and the mass ratio of polyamic acid (poly amic acid ester/polyamic acid) better are 1/9～9/1.Described ratio is more preferably 2/8, and particularly preferably 3/7～7/3.By making described ratio in this scope, can provide all good aligning agent for liquid crystal of liquid crystal aligning and electrical characteristics.
As long as aligning agent for liquid crystal of the present invention have to end carried out that the poly amic acid ester modified and polyamic acid are dissolved in the organic solvent and the form of solution, it is not made and limits.The method of for example, the method that is dissolved in organic solvent after the powder of poly amic acid ester and polyamic acid mixed, the method that the powder of poly amic acid ester is mixed with the solution of polyamic acid, the method that the polyamic acid ester solution is mixed with the powder of polyamic acid are arranged, the polyamic acid ester solution being mixed with polyamic acid solution.Owing in the different situation of the good solvent of dissolving poly amic acid ester and polyamic acid, also can obtain uniform poly amic acid ester-polyamic acid mixed solution, being more preferably the method that the polyamic acid ester solution is mixed with polyamic acid solution.
In addition, making in organic solvent end has been carried out in the situation of the poly amic acid ester modified and/or polyamic acid, can be the reaction solution of gained itself, also can be with this reaction solution with suitable solvent dilution must solution.In addition, obtain end has been carried out can making it be dissolved in organic solvent and make solution in the situation of the poly amic acid ester modified with powder type.At this moment, the concentration of polymkeric substance better is 10～30 quality %, particularly preferably 10～15 quality %.In addition, can heat during the powder of dissolving poly amic acid ester and/or polyamic acid.Heating-up temperature better is 20～150 ℃, particularly preferably 20～80 ℃.
The content (concentration) that in the aligning agent for liquid crystal of the present invention end has been carried out the poly amic acid ester modified can come appropriate change according to the thickness setting of the liquid crystal orientation film that will form, in order to form even and not have defective filming, better be more than 0.5 quality % with respect to organic solvent, angle from the stability of solution, better be below 15 quality %, 1～10 quality % particularly preferably.
In the aligning agent for liquid crystal of the present invention, except the poly amic acid ester that end has been carried out modify, also can comprise as other aligning agent for liquid crystal with compound of liquid crystal aligning.As these other aligning agent for liquid crystal, can exemplify the various aligning agent for liquid crystal such as aligning agent for liquid crystal that comprise the not modified poly amic acid ester of terminal amino group, soluble polyimide and/or polyamic acid.
Wherein, because it is high to the dissolubility of organic solvent that end has been carried out the poly amic acid ester modified, institute so that its comprising orientation characteristic and electrical characteristics well but the dissolubility of organic solvent contained sometimes particularly useful in the aligning agent for liquid crystal of low for example polyamic acid or soluble polyimide.
The above-mentioned organic solvent that aligning agent for liquid crystal of the present invention is contained is not particularly limited so long as the solvent that at least a portion of terminal amino group has been carried out the component of polymer uniform dissolution of the amic acid esters modified and polyamic acid gets final product.If exemplify its object lesson, 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-imidazolinone, 3-methoxyl-N, N-dimethyl propylene acid amides etc.They can use one kind or two or more mixing to use.In addition, even the independent solvent of dissolve polymer composition equably as long as in the scope of not separating out polymkeric substance, also can be sneaked into above-mentioned organic solvent.
As described later, in the situation that add silane coupling agent in the aligning agent for liquid crystal of the present invention, can with the polyamic acid ester solution with before polyamic acid solution mixes, make an addition to polyamic acid ester solution or polyamic acid solution or make an addition to simultaneously polyamic acid ester solution and polyamic acid solution.In addition, silane coupling agent can make an addition to poly amic acid ester-polyamic acid mixed solution.Silane coupling agent adds for the adaptation that improves polymkeric substance and substrate, therefore as the adding method of silane coupling agent, be more preferably following method: make an addition to and to concentrate in the polyamic acid solution that is present in film inside and substrate interface, after polymkeric substance and silane coupling agent are fully reacted, mix with the polyamic acid ester solution.Unreacted reagent may cause harmful effect to aligning agent for liquid crystal if the addition of above-mentioned silane coupling agent is crossed at most, if cross the effect that to bring into play at least adaptation, therefore the solid constituent with respect to polymkeric substance better is 0.01～5.0 quality %, is more preferably 0.1～1.0 quality %.
Aligning agent for liquid crystal of the present invention also can comprise for the inhomogeneity solvent of filming that improves when aligning agent for liquid crystal coated substrate except comprising the organic solvent for the dissolve polymer composition.Described solvent generally adopts the surface tension solvent lower than above-mentioned organic solvent.If exemplify object lesson, can exemplify ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, the ethyl carbitol acetic acid esters, ethylene glycol, the 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, the propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, the single ether of propylene glycol-1--2-acetic acid esters, butyl cellosolve acetate, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc.These solvents can be also with more than 2 kinds.
Aligning agent for liquid crystal of the present invention can comprise the various adjuvants such as silane coupling agent or crosslinking chemical.Adding in the situation of silane coupling agent or crosslinking chemical, in order to prevent separating out of polymkeric substance, better is to add before this in the situation of aligning agent for liquid crystal adding poor solvent.In addition, carry out efficiently in order when burning till filming, to make the imidizate of poly amic acid ester, can add imidizate promoter.
Below exemplify the object lesson of silane coupling agent, the silane coupling agent that can be used for aligning agent for liquid crystal of the present invention is not limited in this.APTES; 3-(2-amino-ethyl) TSL 8330; 3-(2-amino-ethyl) aminopropyl methyl dimethoxysilane; the 3-TSL 8330; 3-phenyl amino propyl trimethoxy silicane; 3-triethoxysilicane alkyl-N-(1; 3-dimethyl-butylidene) propylamine; the amine silane coupling agents such as 3-aminopropyl diethoxymethyl silane; vinyltrimethoxy silane; vinyltriethoxysilane; vinyl three (2-methoxy ethoxy) silane; the vinyl methyl dimethoxysilane; vinyltriacetoxy silane; vinyl silane triisopropoxide; allyltrimethoxysilanis; the vinyl-based silane coupling agents such as p-styryl trimethoxy silane; the 3-glycidoxypropyltrime,hoxysilane; 3-glycidoxy propyl-triethoxysilicane; 3-glycidoxy propyl group methyldiethoxysilane; 3-glycidoxy propyl group methyl dimethoxysilane; 2-(3; the 4-epoxycyclohexyl) the epoxy radicals one type of silane coupling agent such as ethyl trimethoxy silane; 3-methacryloxypropyl methyl dimethoxysilane; the 3-methacryloxypropyl trimethoxy silane; 3-methacryloxypropyl methyldiethoxysilane; the methacryl one type of silane coupling agents such as 3-methacryloxypropyl triethoxysilane; the acryloyl one type of silane coupling agents such as 3-acryloxy propyl trimethoxy silicane; the urea groups one type of silane coupling agents such as 3-urea groups propyl-triethoxysilicane; two (3-(triethoxysilicane alkyl) propyl group) disulfide; the thioether one type of silane coupling agents such as two (3-(triethoxysilicane alkyl) propyl group) four thioethers; 3-sulfydryl propyl group methyl dimethoxysilane; 3-sulfydryl propyl trimethoxy silicane; the 3-caprylyl sulfenyl-sulfydryl one type of silane coupling agents such as 1-propyl-triethoxysilicane; 3-isocyanate group propyl-triethoxysilicane; the isocyanate group one type of silane coupling agents such as 3-isocyanate group propyl trimethoxy silicane; the aldehydes silane coupling agents such as triethoxysilicane alkyl butyraldehyde, carbamic acid tri-ethoxy silylpropyl methyl ester; the carbamates silane coupling agents such as carbamic acid (3-tri-ethoxy silylpropyl) tertiary butyl ester.
Liquid crystal aligning is not caused harmful effect and manifest the viewpoint of the effect of adaptation from unreacted reagent, the addition of above-mentioned silane coupling agent better is 0.01～5.0 quality % with respect to component of polymer, is more preferably 0.1～1.0 quality %.Adding in the situation of silane coupling agent, in order to prevent separating out of polymkeric substance, better is to add before adding the described inhomogeneity solvent of filming for raising.
Below exemplify the object lesson of the imidizate promoter of poly amic acid ester, but the spendable imidizate promoter of aligning agent for liquid crystal of the present invention is not limited in this.
[changing 32]
Figure BDA00002401499800281
[changing 33]
Figure BDA00002401499800291
D in the above-mentioned formula (B-1)～(B-17) represents respectively tert-butoxycarbonyl or 9-fluorenyl methoxy carbonyl independently.In the formula (B-14)～(B-17), have a plurality of D in the structural formula, these D can be identical, also can be different.
So long as in the scope of the effect of the hot-imide that can obtain to promote poly amic acid ester, the content of imidizate promoter is not particularly limited.If its lower limit is shown, can exemplify 1 mole at the amic acid esters position of the following formula contained with respect to poly amic acid ester (13), better be more than 0.01 mole, be more preferably more than 0.05 mole, further be more preferably more than 0.1 mole.In addition, residual imidizate promoter self is controlled at MIN angle to the harmful effect that each characteristic of liquid crystal orientation film causes the film after will burning till, if its upper limit is shown, can exemplify 1 mole at the amic acid esters position of the following formula contained with respect to poly amic acid ester (13), imidizate promoter better is below 2 moles, be more preferably below 1 mole, further be more preferably below 0.5 mole.
[changing 34]
Figure BDA00002401499800292
Adding in the situation of imidizate promoter, may imidizate occur because of heating, therefore better is to add after with good solvent or poor solvent dilution.
＜liquid crystal orientation film 〉
Liquid crystal orientation film of the present invention be with the aligning agent for liquid crystal that obtains as mentioned above coat substrate and dry, burn till and film, as required to orientation process such as this coated surface rub.
Substrate as coating aligning agent for liquid crystal of the present invention, so long as the high substrate of the transparency gets final product, be not particularly limited, can use the plastic bases such as glass substrate, silicon nitride board, acrylic acid substrate or polycarbonate substrate etc., from the viewpoint of work simplification, better be to use the substrate be formed with for the ITO electrode that drives liquid crystal etc.In addition, in the liquid crystal display cells of reflection-type, can only use the opaque article such as silicon wafer in a side of substrate, the electrode in this situation also can use the catoptrical materials such as aluminium.
As the coating process of aligning agent for liquid crystal of the present invention, can exemplify spin-coating method, print process, ink-jet method etc.
The drying, the firing process that are coated with behind the aligning agent for liquid crystal of the present invention can be selected arbitrarily temperature and time.Usually, in order fully to remove contained organic solvent, make its drying 1～10 minute at 50～120 ℃, then carry out 5～120 minutes burn till at 150～300 ℃.The thickness of filming after burning till is not particularly limited, if but too thin, then the reliability of liquid crystal display cells may descend, so thickness is 5～300nm, better is 10～200nm.
Carry out the method for orientation process as this is filmed, can exemplify rubbing manipulation, light orientation process method etc., aligning agent for liquid crystal of the present invention is particularly useful when using by light orientation process method.
As the object lesson of light orientation process method, can exemplify following method: to the radioactive ray of described film coated surface irradiation to the certain orientation polarisation, further under 150～250 ℃ temperature, carry out as required heat treated, give the liquid crystal aligning ability.As radioactive ray, can use ultraviolet ray and the visible light of the wavelength with 100～800nm.Wherein, better be the ultraviolet ray with wavelength of 100～400nm, particularly preferably have the ultraviolet ray of the wavelength of 200～400nm.In addition, in order to improve liquid crystal aligning, the substrate of filming also can be shone radioactive ray simultaneously 50～250 ℃ of heating.The exposure of described radioactive ray better is at 1～10000mJ/cm 2Scope in, particularly preferably at 100～5000mJ/cm 2Scope in.
The liquid crystal orientation film of making as mentioned above can stably make liquid crystal molecule towards the direction orientation of regulation.
Embodiment
Below, exemplify embodiment and further the present invention is specifically described.But the present invention certainly should not be construed as and only limits to these embodiment.
The abbreviation of using among the embodiment and the assay method of each characteristic are as follows.
1,3DMCBDE-Cl:1, two (chlorocarbonyl)-1 of 3-, 3-dimethyl cyclo-butane-2,4-dimethyl dicarboxylate
BDA:1,2,3,4-butane tetracarboxylic acid dianhydride
CBDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
The NMP:N-N-methyl-2-2-pyrrolidone N-
γ-BL: gamma-butyrolacton
BCS: butyl cellosolve
PAE: poly amic acid ester
PAA: polyamic acid
DA-7: following formula (DA-7)
DA-8: following formula (DA-8)
[changing 35]
[viscosity]
In the synthesis example, the viscosity of poly amic acid ester and polyamic acid solution is used E type viscosity meter TVE-22H ((East Machine industry society of Toki Sangyo Co., Ltd.) system) with sample size 1.1mL, cone rotor TE-1 (1 ° 34 ', R24), the condition of 25 ℃ of temperature measures.
[molecular weight]
In addition, the molecular weight of poly amic acid ester is measured by GPC (normal temperature gel permeation chromatography) device, in polyglycol, polyethylene oxide scaled value, calculates number-average molecular weight (the following Mn that also claims) and weight-average molecular weight (the following Mw that also claims).
GPC device: Showa Denko K. K (Shodex society) system (GPC-101)
Post: Showa Denko K. K's (series connection of KD803, KD805)
Column temperature: 50 ℃
Eluent: DMF (as adjuvant, lithium bromide monohydrate (LiBrH 2O) be 30mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) is 30mmol/L, and tetrahydrofuran (THF) is 10ml/L)
Flow velocity: 1.0ml/ minute
Calibration curve is made and to be used standard model: (East ソ ー society of TOSOH Co., Ltd) TSK standard polyethylene oxide processed (weight-average molecular weight (Mw) approximately 900000,150000,100000,30000) and polymkeric substance laboratory company (Port リ マ ー ラ ボ ラ ト リ ー society) polyglycol processed (peak top molecular weight (Mp) approximately 12000,4000,1000).For fear of overlap of peaks, measure and respectively 2 groups of samples to be carried out, namely mix 900000,100000,12000,1000 these 4 kinds and sample and mix 150000,30000,4000 these 3 kinds and sample.
[center line average roughness mensuration]
Filming on the heating plate of 80 ℃ of temperature dry 5 minutes of the aligning agent for liquid crystal that will obtain by spin coating the heated air circulation type kiln roasting of 250 ℃ of temperature 1 hour, obtains filming of thickness 100nm.Observe the film surface that this is filmed by atomic force microscope (AFM), measure the center line average roughness (Ra) on film surface, estimated the flatness on film surface.
Determinator: the L-trace probe microscope (Seiko be full of the department electronics technology Co., Ltd. (エ ス ア イ ア イ テ Network ノ ロ ジ ー society) system)
[voltage retention]
Aligning agent for liquid crystal is spun on the glass substrate with transparency electrode, on the heating plate of 80 ℃ of temperature dry 5 minutes, in 250 ℃ heated air circulation type stove, through 60 minutes burn till, obtains the imidizate film of thickness 100nm.Across polarization plates this coated surface is shone 100mJ/cm 2254nm ultraviolet ray, obtain the substrate with liquid crystal orientation film.Prepare 2 such substrates with liquid crystal orientation film, after the liquid crystal aligning face of a substrate scatters the sept of 6 μ m, make up in the antiparallel mode of the orientation of 2 substrates, stay liquid crystal injecting port, the sylphon that the box spacing is 6 μ m is made in sealing on every side.To this sylphon at normal temperatures vacuum inject liquid crystal (MLC-2041, Merck Co., Ltd. (メ Le Network Co., Ltd.) system), sealing inlet and make liquid crystal cell.
Being determined as follows of the voltage retention of above-mentioned liquid crystal cell carried out.
Apply 4V voltage 60 μ s, measure the voltage behind the 16.67ms, thereby calculate variation from initial value as voltage retention.During mensuration, the temperature of liquid crystal cell is made as 23 ℃, 60 ℃, 90 ℃, is measuring respectively at each temperature.
[ion concentration]
Being determined as follows of the ion concentration of above-mentioned liquid crystal cell carried out.
The use Dongyang science and technology (East Yang テ of Co., Ltd. Network ニ カ society) 6254 type liquid crystal evaluation of physical property devices of system are measured.Apply the triangular wave of 10V, 0.01Hz, calculate the area corresponding to ion concentration of the waveform of gained by the triangle method of approximation, as ion concentration.During mensuration, the temperature of liquid crystal cell is made as 23 ℃, 60 ℃, is measuring respectively at each temperature.
[interchange that FFS drives liquid crystal cell drives sintering (Japanese: the baked I is paid I)]
Pass through the spin application aligning agent for liquid crystal at the glass substrate that is formed with fringe field switching (Fringe Field Switching: hereinafter referred to as FFS) driving electrode; In the described fringe field switching driving electrode, be formed with the ITO electrode of the thickness 50nm of shape as shown in Figure 1 as electrode at ground floor, be formed with the silicon nitride of the thickness 500nm of shape as shown in Figure 2 as dielectric film at the second layer, at the 3rd layer of ITO electrode (electrode width: 3 μ m that is formed with pectination as shown in Figure 3 as electrode, electrode gap: 6 μ m, electrode height: 50nm).After on 80 ℃ the heating plate dry 5 minutes, in 250 ℃ heated air circulation type stove, burnt till 60 minutes, form filming of thickness 100nm.Across polarization plates this coated surface is shone 100mJ/cm 2254nm ultraviolet ray, obtain the substrate with liquid crystal orientation film.In addition, form similarly on the glass substrate as the relative column spacer that does not form the high 4 μ m of having of electrode of substrate and film, implementation orientation is processed.
As one group, printing and sealing agent on substrate behind bonding another piece substrate of 0 ℃ mode, makes sealant cures take the relative direction of orientation of liquid crystal aligning face, makes the sky liquid crystal cell with above-mentioned 2 substrates.Inject liquid crystal MLC-2041 (Merck Japanese firm system) to this sylphon by the decompression injection method, with the filling orifice sealing, obtain FFS and drive liquid crystal cell.
After measuring the V-T characteristic (voltage-transmission characteristics) under 58 ℃ of temperature that this FFS drives liquid crystal cell, apply ± square wave of 4V/120Hz 4 hours.Cut off voltage after 4 hours, after placing 60 minutes under 58 ℃ the temperature, again measure the V-T characteristic, calculate the transmissivity of square wave before and after applying and reach the poor of 50% voltage.
[evaluation of electric charge accumulation characteristic]
Above-mentioned FFS is driven liquid crystal cell places on the light source, measure V-T characteristic (voltage-transmission characteristics) after, measure and apply ± transmissivity (T under the state of the square wave of 1.5V/60Hz a).Then, apply ± square wave of 1.5V/60Hz is after 10 minutes, and overlapping direct current 1V drives 30 minutes.Cut off DC voltage, measure the transmissivity (T that exchanged after driving through 10 minutes b), by T bAnd T aDifference calculate the poor of transmissivity that the voltage that remains in the liquid crystal display cells produces.
Two (chlorocarbonyl)-1 of 1,3-, 3-dimethyl cyclo-butane-2, the 4-dimethyl dicarboxylate (1,3DMCBDE-Cl) synthetic
A-1: tetrabasic carboxylic acid dialkyl group ester synthesis
[changing 36]
Figure BDA00002401499800341
In stream of nitrogen gas, in the four-hole boiling flask of 3L (liter), add 1 of 220g (0.981mol), 3-dimethyl cyclo-butane-1,2,3, the 4-tetracarboxylic dianhydride (compound of formula (5-1), below slightly 1,3-DM-CBDA) and 2200g (6.87mol, with respect to 1,3-DM-CBDA is 10 times in mass) methyl alcohol, add hot reflux at 65 ℃, the result is through forming uniform solution in 30 minutes.Reaction solution stirred 4 hours 30 minutes adding under the hot reflux like this.This reactant liquor is measured by high performance liquid chromatography (following slightly HPLC).The analysis of this measurement result as described later.
After heating up in a steamer desolventizing by evaporator from this reactant liquor, add 1301g ethyl acetate and also be heated to 80 ℃, refluxed 30 minutes.Then, with 10 minutes 2～3 ℃ speed interior temperature is cooled to 25 ℃, directly stirred 30 minutes at 25 ℃.By filter taking out the white crystals of separating out, this crystallization cleaned 2 times with 141g ethyl acetate after drying under reduced pressure, thereby obtain the 103.97g white crystals.
This crystallization basis 1H NMR analyzes and the results verification of X ray analysis of crystal structure is compound (1-1) (HPLC relative area 97.5%) (yield 36.8%).
1H?NMR(DMSO-d6,δppm);12.82(s,2H),3.60(s,6H),3.39(s,2H),1.40(s,6H).
A-2.1,3-DM-CBDE-Cl's is synthetic
[changing 37]
Figure BDA00002401499800342
In stream of nitrogen gas, the compound (1-1) and the 1170.77g (11.68mol that add 234.15g (0.81mol) in the four-hole boiling flask of 3L, 5 times in mass) normal heptane after, add 0.64g (0.01mol) pyridine, heating is stirred to 75 ℃ under the stirring of magnetic stirring apparatus.Then, with splashing into 289.93g (11.68mol) thionyl chloride in 1 hour.Just begin foaming after just having dripped, drip 30 minutes afterreaction solution becomes of end and get evenly, foaming stops.Then,, in 40 ℃ water-bath, heating up in a steamer desolventizing to inner capacities with evaporator and reaching 924.42g after 1 hour 30 minutes in 75 ℃ of stirrings under this state.Be heated to 60 ℃, make the dissolving crystallized of separating out when heating up in a steamer desolventizing, behind the elimination insolubles, filtrate is cooled to 25 ℃ with 10 minutes 1 ℃ speed 60 ℃ of while hot filtrations., after 30 minutes the white crystals of separating out being taken out by filtering in 25 ℃ of stirrings under this state, with this crystallization 264.21g normal heptane cleaning.With its drying under reduced pressure, thereby obtain the 226.09g white crystals.
Then, in stream of nitrogen gas, add 226.09g white crystals obtained above and 452.18g normal heptane in the four-hole boiling flask of 3L after, heating is stirred to 60 ℃ makes dissolving crystallized.Then, with 10 minutes speed cooling and stirring to 25 of 1 ℃ ℃, make crystallization.After 1 hour, the white crystals of separating out is passed through to filter taking-up in 25 ℃ of stirrings under this state, with this crystallization rear drying under reduced pressure of 113.04g normal hexane cleaning, thereby obtaining the 203.91g white crystals.This crystallization is confirmed as compound (3-1) according to 1H NMR analysis result, namely 1, two (chlorocarbonyl)-1 of 3-, 3-dimethyl cyclo-butane-2, the 4-dimethyl dicarboxylate (1,3-DM-CBDE-Cl) (HPLC relative area 99.5%) (yield 77.2%).
1H?NMR(CDCl 3,δppm):3.78(s,6H),3.72(s,2H),1.69(s,6H).
(Production Example 1)
Make the 300mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 6.40g (32.3mmol) 4,4 '-diaminodiphenyl-methane adds 131gNMP and 6.16g (77.86mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 9.8641g (27.16mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.380g (4.20mmol) acryloyl chloride, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 144.33g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.With the solution of the poly amic acid ester of gained while stirring in the water that drops into 1443g, the white precipitate that leaching is separated out, then the water with 1443g cleans 1 time, clean 1 time with 1443g ethanol, 361g ethanol cleans 3 times, dry and obtain 14.37g white end has been carried out the poly amic acid ester toner of modifying.Yield is 99.6%.In addition, this is Mn=13335 to the molecular weight that end has carried out the poly amic acid ester of modification, Mw=23824.
That gets the 3.3076g gained in the 50ml Erlenmeyer flask has carried out the poly amic acid ester toner of modifying to end, adds 30.4854g NMP, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-1).
(Production Example 2)
Make the 300mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 5.00g (25.22mmol) 4,4 '-diaminodiphenyl-methane adds 102g NMP and 4.81g (60.83mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 7.707g (23.71mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.4302g (3.30mmol) 2-furyl chlorine, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 114g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.With the solution of the poly amic acid ester of gained while stirring in the water that drops into 1141g, the white precipitate that leaching is separated out, then the water with 1141g cleans 1 time, clean 1 time with 1141g ethanol, 285g ethanol cleans 3 times, dry and obtain 11.12g white end has been carried out the poly amic acid ester toner of modifying.Yield is 97.5%.In addition, this is Mn=12864 to the molecular weight that end has carried out the poly amic acid ester of modification, Mw=22513.
That gets the 3.1266g gained in the 50ml Erlenmeyer flask has carried out the poly amic acid ester toner of modifying to end, adds 28.1581g NMP, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-2).
(Production Example 3)
Make the 300mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 5.00g (25.22mmol) 4,4 '-diaminodiphenyl-methane adds 103gNMP and 4.81g (60.83mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 7.7075g (23.71mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.4702g (3.35mmol) chlorobenzoyl chloride, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 114g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.With the solution of the poly amic acid ester of gained while stirring in the water that drops into 1144g, the white precipitate that leaching is separated out, then the water with 1144g cleans 1 time, cleans 1 time with 1144g ethanol, 286g ethanol cleans 3 times, and is dry and obtain the poly amic acid ester toner of 11.10g white.Yield is 97.0%.In addition, this is Mn=11260 to the molecular weight that end has carried out the poly amic acid ester of modification, Mw=19060.
That gets the 3.6625g gained in the 50ml Erlenmeyer flask has carried out the poly amic acid ester toner of modifying to end, adds 32.9616g NMP, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-3).
(Production Example 4)
Make the 300mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 5.00g (25.22mmol) 4,4 '-diaminodiphenyl-methane adds 103gNMP and 4.81g (60.83mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 7.7014g (23.70mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.5140g (3.28mmol) phenyl chloroformate, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 115g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.With the solution of the poly amic acid ester of gained while stirring in the water that drops into 1149g, the white precipitate that leaching is separated out, then the water with 1503g cleans 1 time, clean 1 time with 1149g ethanol, 287g ethanol cleans 3 times, dry and obtain 11.01g white end has been carried out the poly amic acid ester toner of modifying.Yield is 95.8%.In addition, this is Mn=11772 to the molecular weight that end has carried out the poly amic acid ester of modification, Mw=20564.
That gets the 3.6176g gained in the 50ml Erlenmeyer flask has carried out the poly amic acid ester toner of modifying to end, adds 32.5597g NMP, at room temperature stirs and makes its dissolving in 24 hours, obtains polyamic acid ester solution (PAE-4).
(Production Example 5)
In the 100mL four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, get 2.7469g (13.79mmol) 4,4 '-diamino-diphenyl amine and 1.4007g (9.206mmol) 3, the 5-diaminobenzoic acid adds 38.85g NMP, stirs in supplying nitrogen and makes its dissolving.Add 4.4319g (22.60mmol) CBDA when stirring this two amine aqueous solution, adding NMP, to make solid component concentration be 15 quality % again, at room temperature stirred 24 hours, obtains the solution of polyamic acid (PAA-1).Viscosity during 25 ℃ of the temperature of this polyamic acid solution is 1055mPas.In addition, the molecular weight of this polyamic acid is Mn=21482, Mw=49280.
(Production Example 6)
In the 100mL four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, get 7.9719g (40.01mmol) 4,4 '-diamino-diphenyl amine and 1.5246g (10.02mmol) 3, the 5-diaminobenzoic acid adds 40.64g NMP, stirs in supplying nitrogen and makes its dissolving.Add 9.8377g (49.65mmol) BDA when stirring this two amine aqueous solution, adding NMP, to make solid component concentration be 25 quality % again, at room temperature stirred 24 hours, obtains the solution of polyamic acid.Viscosity during 25 ℃ of the temperature of this polyamic acid solution is 14550mPas.In addition, the molecular weight of this polyamic acid is Mn=16230, Mw=34539.
The polyamic acid solution of 45.1642g gained is taken in the 100ml Erlenmeyer flask, adds 33.87gNMP, at room temperature stirred 4 hours, obtain the polyamic acid solution (PAA-2) of 15 quality %.
(relatively Production Example 1)
Make the 300mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 8.0102 (40.35mmol) 4,4 '-diaminodiphenyl-methane adds 158.1gNMP and 7.20g (91.03mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 12.3419g (37.93mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.With the solution of the poly amic acid ester of gained while stirring in the water that drops into 1757g, the white precipitate that leaching is separated out, then the water with 1757g cleans 1 time, cleans 1 time with 1757g ethanol, 439g ethanol cleans 3 times, and is dry and obtain the poly amic acid ester toner of 16.63g white.Yield is 94.6%.In addition, the molecular weight of this poly amic acid ester is Mn=10180, Mw=21476.
In the 200ml Erlenmeyer flask, get the poly amic acid ester toner of 14.8252g gained, add 99.3048g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-5).
(embodiment 1)
In having added the 20ml sample hose of stirrer, get the polyamic acid solution (PAA-1) that obtains in the polyamic acid ester solution (PAE-1) that obtains in the 1.5016g Production Example 1 and the 1.0469g Production Example 5, add 1.4916g NMP and 1.0249g BCS, obtain aligning agent for liquid crystal (I) with magnetic stirrer 30 minutes.
(embodiment 2)
In having added the 20ml sample hose of stirrer, get the polyamic acid solution (PAA-2) that obtains in the polyamic acid ester solution (PAE-2) that obtains in the 1.5050g Production Example 2 and the 0.9091g Production Example 6, add 1.6291gNMP and 1.0032g BCS, obtain aligning agent for liquid crystal (II) with magnetic stirrer 30 minutes.
(embodiment 3)
In having added the 20ml sample hose of stirrer, get the polyamic acid solution (PAA-2) that obtains in the polyamic acid ester solution (PAE-3) that obtains in the 1.5138g Production Example 3 and the 0.8932g Production Example 6, add 1.6438g NMP and 1.0231g BCS, obtain aligning agent for liquid crystal (III) with magnetic stirrer 30 minutes.
(embodiment 4)
In having added the 20ml sample hose of stirrer, get the polyamic acid solution (PAA-2) that obtains in the polyamic acid ester solution (PAE-4) that obtains in the 1.5097g Production Example 4 and the 0.8953g Production Example 6, add 1.6372g NMP and 1.0101gBCS, obtain aligning agent for liquid crystal (IV) with magnetic stirrer 30 minutes.
(comparative example 1)
In having added the 20ml sample hose of stirrer, get the polyamic acid solution (PAA-1) that obtains in polyamic acid ester solution (PAE-5) that 1.4911g relatively obtains in the Production Example 1 and the 1.1118g Production Example 5, add 1.4881gNMP and 1.0315gBCS, obtain aligning agent for liquid crystal (a) with magnetic stirrer 30 minutes.
(comparative example 3)
In having added the 20ml sample hose of stirrer, get the polyamic acid solution (PAA-2) that obtains in polyamic acid ester solution (PAE-5) that 1.5095g relatively obtains in the Production Example 1 and the 1.0391g Production Example 6, add 1.4964g NMP and 1.0011g BCS, obtain aligning agent for liquid crystal (c) with magnetic stirrer 30 minutes.
(embodiment 5)
After obtaining the filter filtration of aligning agent for liquid crystal (I) with 1.0 μ m among the embodiment 1, be spun on the glass substrate with transparency electrode, drying is 5 minutes on the heating plate of 80 ℃ of temperature, in the heated air circulation type stove of 250 ℃ of temperature through 60 minutes burn till, obtain thickness 100nm imidizate film.For this film, measured center line average roughness (Ra).Measurement result is shown in the table 1 described later.
(embodiment 6)
The aligning agent for liquid crystal (II) that in using embodiment 2, obtains, by method similarly to Example 5 make imidizate film.For this film, measured center line average roughness (Ra).Measurement result is shown in the table 1 described later.
(embodiment 7)
The aligning agent for liquid crystal (III) that in using embodiment 3, obtains, by method similarly to Example 5 make imidizate film.For this film, measured center line average roughness (Ra).Measurement result is shown in the table 1 described later.
(embodiment 8)
The aligning agent for liquid crystal (IV) that in using embodiment 4, obtains, by method similarly to Example 5 make imidizate film.For this film, measured center line average roughness (Ra).Measurement result is shown in the table 1 described later.
(comparative example 4)
The aligning agent for liquid crystal that in usage comparison example 1, obtains (a), by method similarly to Example 5 make imidizate film.For this film, measured center line average roughness (Ra).Measurement result is shown in the table 1 described later.
(comparative example 6)
The aligning agent for liquid crystal that in usage comparison example 3, obtains (c), by method similarly to Example 5 make imidizate film.For this film, measured center line average roughness (Ra).Measurement result is shown in the table 1 described later.
[table 1]
Figure BDA00002401499800401
According to embodiment 5 and the result of comparative example 4 and the results verification of embodiment 6～8 and comparative example 6, comprise end has been carried out the poly amic acid ester of modification and the aligning agent for liquid crystal of polyamic acid, by small concavo-convex being inhibited that is separated and produces of poly amic acid ester and polyamic acid.
(embodiment 9)
After obtaining the filter filtration of aligning agent for liquid crystal (I) with 1.0 μ m among the embodiment 1, be spun on the glass substrate with transparency electrode, drying is 5 minutes on the heating plate of 80 ℃ of temperature, in the heated air circulation type stove of 250 ℃ of temperature through 60 minutes burn till, obtain thickness 100nm imidizate film.Across polarization plates this coated surface is shone 100mJ/cm 2254nm ultraviolet ray, obtain the substrate with liquid crystal orientation film.Prepare 2 such substrates with liquid crystal orientation film, after the liquid crystal aligning face of a substrate scatters the sept of 6 μ m, make up in the antiparallel mode of the orientation of 2 substrates, stay liquid crystal injecting port, the sylphon that the box spacing is 6 μ m is made in sealing on every side.To this sylphon at normal temperatures vacuum inject liquid crystal (MLC-2041, Merck Co., Ltd. (メ Le Network Co., Ltd.) system), sealing inlet and make liquid crystal cell.For this liquid crystal cell, measured voltage retention, then carried out the mensuration of ion concentration.The measurement result of voltage retention and ion concentration is shown in the table 2 described later.
(comparative example 7)
The aligning agent for liquid crystal that in usage comparison example 1, obtains (a), make liquid crystal cell by method similarly to Example 9.For this liquid crystal cell, measured voltage retention, then carried out the mensuration of ion concentration.The measurement result of voltage retention and ion concentration is shown in the table 2 described later.
[table 2]
Figure BDA00002401499800411
According to the result of embodiment 9 with comparative example 7, confirm that the liquid crystal orientation film that is obtained by aligning agent for liquid crystal of the present invention is the high liquid crystal orientation film of reliability.
(embodiment 10)
With after obtaining aligning agent for liquid crystal (I) among the embodiment 1 and filtering with the filter of 1.0 μ m, by spin application on the glass substrate that is formed with fringe field switching (Fringe Field Switching: hereinafter referred to as FFS) driving electrode; In the described fringe field switching driving electrode, be formed with the ITO electrode of thickness 50nm as ground floor, be formed with the silicon nitride of thickness 500nm as the dielectric film of the second layer, as the 3rd layer of ITO electrode (electrode width: 3 μ m that is formed with pectination, electrode gap: 6 μ m, electrode height: 50nm).After on 80 ℃ the heating plate dry 5 minutes, in 250 ℃ heated air circulation type stove, burnt till 60 minutes, form filming of thickness 130nm.Across polarization plates this coated surface is shone 100mJ/cm 2254nm ultraviolet ray, obtain the substrate with liquid crystal orientation film.In addition, form similarly on the glass substrate as the relative column spacer that does not form the high 4 μ m of having of electrode of substrate and film, implementation orientation is processed.
As one group, printing and sealing agent on substrate behind bonding another piece substrate of 0 ℃ mode, makes sealant cures take the relative direction of orientation of liquid crystal aligning face, makes the sky liquid crystal cell with above-mentioned 2 substrates.Inject liquid crystal MLC-2041 (Merck Japanese firm system) to this sylphon by the decompression injection method, with the filling orifice sealing, obtain FFS and drive liquid crystal cell.
Drive liquid crystal cell for this FFS, carried out exchanging the mensuration of driving and the evaluation that electric charge is put aside characteristic.The results are shown in the table 3 described later.
(comparative example 8)
The aligning agent for liquid crystal that in usage comparison example 1, obtains (a), make FFS by method similarly to Example 10 and drive liquid crystal cell.Drive liquid crystal cell for this FFS, carried out exchanging the evaluation that drives sintering and electric charge savings characteristic.The results are shown in the table 3 described later.
[table 3]
Figure BDA00002401499800421
To exchange to drive the aligning agent for liquid crystal that the sintering degree is low and residual voltage is few according to the results verification of embodiment 10 and comparative example 8, the liquid crystal orientation film that is obtained by aligning agent for liquid crystal of the present invention.
Synthesizing of diamine compound (DA-1)
By the synthetic diamine compound (DA-1) in the path in 4 steps shown below.
The 1st step: compound (A5) synthetic
[changing 38]
Figure BDA00002401499800422
In the eggplant-shape bottle of 500mL, add successively propargyl amine (8.81g, 160mmol), N, dinethylformamide (112mL), sal tartari (18.5g, 134mmol), temperature is made as 0 ℃, with approximately 1 hour while stir drip bromoacetic acid tertiary butyl ester (21.9g, 112mmol) is dissolved in DMF (80mL) and solution.After dripping end, the temperature that makes reaction solution is room temperature, stirs 20 hours.Then, by the solids removed by filtration material, in filtrate, add 1L ethyl acetate, clean 4 times with 300mL water, clean 1 time with the 300mL saturated aqueous common salt again.Then, with the organic layer dried over mgso, desolventizing is heated up in a steamer in decompression.At last, with residual grease with 0.6Torr, 70 ℃ condition decompression distillation, thereby obtain to be the N-propargyl aminoacetic acid tert-butyl ester (compound (A5)) of colourless liquid.Receipts amount 12.0g, yield 63%.
The 2nd step: compound (A6) synthetic
[changing 39]
Figure BDA00002401499800423
In the eggplant-shape bottle of 1L, add the above-mentioned N-propargyl aminoacetic acid tert-butyl ester (12.0g, 70.9mmol), methylene chloride (600mL) makes solution, stir ice-cold on one side, the solution that with dropping in 1 hour di-tert-butyl dicarbonate (15.5g, 70.9mmol) is dissolved in methylene chloride (100mL) on one side and gets.After dripping end, the temperature that makes reaction solution is room temperature, stirs 20 hours.After reaction finishes, reaction solution is cleaned with the 300mL saturated aqueous common salt, use dried over mgso.Then, desolventizing is heated up in a steamer in decompression, thereby obtains to be the N-propargyl of weak yellow liquid-N-tert-butoxycarbonyl aminoacetic acid tert-butyl ester (compound (A6)).Receipts amount 18.0g, yield 94%.
The 3rd step: compound (A7) synthetic
[changing 40]
Figure BDA00002401499800431
In the four-hole boiling flask of 300mL, add 2-iodo-4-nitroaniline (22.5g, 85.4mmol), molybdenyl dichloride (triphenyl phasphine) palladium (1.20g, 1.71mmol), cupric iodide (0.651g, 3.42mmol), add diethylamine (43.7g behind the nitrogen replacement, 598mmol), N, dinethylformamide (128mL), ice-cold stirring on one side, add the described N-propargyl-N-tert-butoxycarbonyl aminoacetic acid tert-butyl ester (27.6g on one side, 102mmol), at room temperature stir 20 hours.After reaction finishes, add 1L ethyl acetate, use the aqueous ammonium chloride solution of 150mL1mol/L to clean 3 times, clean 1 time with the 150mL saturated aqueous common salt again, use dried over mgso.Then, decompression heated up in a steamer desolventizing and the dissolution of solid of separating out in 200mL ethyl acetate, add the 1L hexane and carry out recrystallization.This solid of leaching, drying under reduced pressure, thereby obtain to be the 2-{3-(N-tert-butoxycarbonyl-N-tert-butoxycarbonyl methylamino) of yellow solid-1-propinyl }-4-nitroaniline (compound (A7)).Receipts amount 23.0g, yield 66%.
The 4th step: the reduction of compound (A7)
In the four-hole boiling flask of 500mL, add described 2-{3-(N-tert-butoxycarbonyl-N-tert-butoxycarbonyl methylamino)-1-propinyl }-4-nitroaniline (22.0g, 54.2mmol) or ethanol (200g), system is interior with behind the nitrogen replacement, add palladium carbon (2.20g), use hydrogen exchange in the system, stirred 48 hours at 50 ℃.Reaction is removed palladium carbon by diatomite filtration after finishing, and adds activated charcoal in filtrate, stirs 30 minutes at 50 ℃.Then, the filter activity charcoal, organic solvent is heated up in a steamer in decompression, the grease that drying under reduced pressure is residual, thus obtain diamine compound (DA-1).Receipts amount 19.8g, yield 96%.
Diamine compound (DA-1) passes through 1H NMR confirms.
1H?NMR(DMSO-d 6):δ6.54-6.42(m,3H,Ar),3.49,3.47(each?s,2H,NCH 2CO 2?t-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?andCH 2CO 2?t-Bu).
(Production Example 7)
Make the four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 40.73g NMP and 1.9246g (24.3317mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.192g (1.3114mmol) 2-thiophene chloride, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 45.2499g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 498g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 226g ethanol, clean 2 times with 452g water, clean 1 time with 453g ethanol, clean 3 times with 113g ethanol, dry and obtain the poly amic acid ester toner of 4.4587g white.Yield is 98.53%.In addition, the molecular weight of this poly amic acid ester is Mn=12256, Mw=21405.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.1520g gained, add 19.3658g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-7).
(Production Example 8)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 40.42g NMP and 1.9246g (24.3317mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.1555g (1.3114mmol) 3, the 3-dimethyl acryloyl chloride, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 44.9236g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 494g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 225g ethanol, clean 2 times with 449g water, clean 1 time with 449g ethanol, clean 3 times with 112g ethanol, dry and obtain the poly amic acid ester toner of 3.9916g white.Yield is 88.98%.In addition, the molecular weight of this poly amic acid ester is Mn=13673, Mw=22739.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.3883g gained, add 21.5218g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-8).
(Production Example 9)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 40.94g NMP and 1.9246g (24.3317mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.2185g (1.3114mmol) cinnamoyl chloride, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 45.54g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 500g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 227g ethanol, clean 2 times with 455g water, clean 1 time with 455g ethanol, clean 3 times with 114g ethanol, dry and obtain the poly amic acid ester toner of 4.2721g white.Yield is 93.91%.In addition, the molecular weight of this poly amic acid ester is Mn=13033, Mw=23520.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.4517g gained, add 22.0656g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-9).
(Production Example 10)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 40.94g NMP and 1.9246g (24.3317mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, adding 0.1725g (1.3114mmol) is different
Figure BDA00002401499800451
Azoles-5-formyl chloride, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 45.06g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 495g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 226g ethanol, clean 2 times with 451g water, clean 1 time with 451g ethanol, clean 3 times with 113g ethanol, dry and obtain the poly amic acid ester toner of 4.3714g white.Yield is 96.99%.In addition, the molecular weight of this poly amic acid ester is Mn=13418, Mw=22819.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.2172g gained, add 19.9964g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-10).
(Production Example 11)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 40.75g NMP and 1.9246g (24.3317mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.1948g (1.3114mmol) 2-oxo-1-imidazolidine phosgene, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 45.23g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 498g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 226g ethanol, clean 2 times with 453g water, clean 1 time with 453g ethanol, clean 3 times with 113g ethanol, dry and obtain the poly amic acid ester toner of 3.98g white.Yield is 87.92%.In addition, the molecular weight of this poly amic acid ester is Mn=12119, Mw=23633.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.1446g gained, add 19.2937g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-11).
(Production Example 12)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 40.14g NMP and 1.9246g (24.3317mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.1213g (1.3114mmol) propionyl chloride, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 44.60g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 491g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 223g ethanol, clean 2 times with 446g water, clean 1 time with 446g ethanol, clean 3 times with 111g ethanol, dry and obtain the poly amic acid ester toner of 3.74g white.Yield is 83.86%.In addition, the molecular weight of this poly amic acid ester is Mn=13082, Mw=23048.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.1867g gained, add 19.6897g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-12).
(Production Example 13)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 40.14g NMP and 1.9246g (24.3317mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.2079g (1.3114mmol) 4-fluorobenzoyl chloride, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 45.39g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 499g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 227g ethanol, clean 2 times with 454g water, clean 1 time with 454g ethanol, clean 3 times with 114g ethanol, dry and obtain the poly amic acid ester toner of 3.87g white.Yield is 85.26%.In addition, the molecular weight of this poly amic acid ester is Mn=12207, Mw=22609.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 1.9882g gained, add 17.908g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-13).
(Production Example 14)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 41.49g NMP and 1.9246g (24.3317mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.2841g (1.3114mmol) 4-phenyl chlorobenzoyl chloride, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 46.10g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 507g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 230g ethanol, clean 2 times with 461g water, clean 1 time with 461g ethanol, clean 3 times with 115g ethanol, dry and obtain the poly amic acid ester toner of 4.02g white.Yield is 87.20%.In addition, the molecular weight of this poly amic acid ester is Mn=11563, Mw=22120.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.1231g gained, add 19.1000g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-14).
(Production Example 15)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 40.86g NMP and 1.9246g (24.3317mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.2079g (1.3114mmol) trimethylene phosgene, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 45.39g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 499g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 227g ethanol, clean 2 times with 454g water, clean 1 time with 454g ethanol, clean 3 times with 114g ethanol, dry and obtain the poly amic acid ester toner of 3.8463g white.Yield is 84.7%.In addition, the molecular weight of this poly amic acid ester is Mn=12995, Mw=23470.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.3403g gained, add 21.0717g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-15).
(Production Example 16)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 45.39g NMP and 1.9246g (24.3317mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.2079g (0.897mmol) diphenyl amino formyl chloride, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 45.39g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 499g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 227g ethanol, clean 2 times with 454g water, clean 1 time with 454g ethanol, clean 3 times with 114g ethanol, dry and obtain the poly amic acid ester toner of 3.7689g white.Yield is 83.0%.In addition, the molecular weight of this poly amic acid ester is Mn=9543, Mw=21337.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.0849g gained, add 18.7717g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-16).
(Production Example 17)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 40.86g NMP and 1.9246g (24.3317mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.2079g (2.6484mmol) acetyl chloride, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 45.39g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 499g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 227g ethanol, clean 2 times with 454g water, clean 1 time with 454g ethanol, clean 3 times with 114g ethanol, dry and obtain the poly amic acid ester toner of 4.2288g white.Yield is 93.2%.In addition, the molecular weight of this poly amic acid ester is Mn=13739, Mw=24113.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.2812g gained, add 20.5236g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-17).
(Production Example 18)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 40.86g NMP and 1.9246g (24.3317mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.2079g (1.9889mmol) methacrylic chloride, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 45.39g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 499g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 227g ethanol, clean 2 times with 454g water, clean 1 time with 454g ethanol, clean 3 times with 114g ethanol, dry and obtain the poly amic acid ester toner of 4.5616g white.Yield is 99.0%.In addition, the molecular weight of this poly amic acid ester is Mn=14046, Mw=23471.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.2641g gained, add 20.3711g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-18).
(Production Example 19)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 40.86g NMP and 1.9246g (24.3317mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.2079g (1.8804mmol) chlorine bamic acid methyl esters, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 45.39g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 499g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 227g ethanol, clean 2 times with 454g water, clean 1 time with 454g ethanol, clean 3 times with 114g ethanol, dry and obtain the poly amic acid ester toner of 4.2667g white.Yield is 94.0%.In addition, the molecular weight of this poly amic acid ester is Mn=13857, Mw=24200.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.2436g gained, add 20.1778g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-19).
(Production Example 20)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 40.86g NMP and 1.9246g (24.3317mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.2079g (1.2187mmol) 4-methoxy benzoyl chloride, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 45.39g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 499g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 227g ethanol, clean 2 times with 454g water, clean 1 time with 454g ethanol, clean 3 times with 114g ethanol, dry and obtain the poly amic acid ester toner of 4.2667g white.Yield is 95.7%.In addition, the molecular weight of this poly amic acid ester is Mn=12439, Mw=23256.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.4178g gained, add 21.7607g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-20).
(Production Example 21)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 40.86g NMP and 2.0759g (26.2443mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.6003g (2.90528mmol) chloro-carbonic acid-2-naphthyl ester, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 45.98g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 552g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 227g ethanol, clean 2 times with 460g water, clean 1 time with 228g ethanol, clean 3 times with 115g ethanol, dry and obtain the poly amic acid ester toner of 4.24g white.Yield is 92.2%.In addition, the molecular weight of this poly amic acid ester is Mn=12498, Mw=22829.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 1.9683g gained, add 17.7163gNMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-21).
(Production Example 22)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 40.86g NMP and 2.0759g (26.2443mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.4726g (2.90528mmol) 2-n-pro-pyl n-amyl chloride, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 45.44g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 545g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 227g ethanol, clean 2 times with 454g water, clean 1 time with 227g ethanol, clean 3 times with 114g ethanol, dry and obtain the poly amic acid ester toner of 3.89g white.Yield is 85.7%.In addition, the molecular weight of this poly amic acid ester is Mn=15211, Mw=25954.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.6046g gained, add 18.5329g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-22).
(Production Example 23)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.0000g (10.0878mmol) 4,4 '-diaminodiphenyl-methane adds 40.86g NMP and 2.0759g (26.2443mmol) as the pyridine of alkali, stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 3.0831g (9.4825mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.4637g (2.90528mmol) diallyl carbamyl chloride, reaction is 30 minutes under water-cooled.After 30 minutes, in reaction solution, add 45.41g NMP, the lower stirring of room temperature (20 ℃) 15 minutes.The solution of the poly amic acid ester of gained is dropped in the 545g ethanol while stirring, the white precipitate that leaching is separated out, then clean 1 time with 227g ethanol, clean 2 times with 454g water, clean 1 time with 227g ethanol, clean 3 times with 114g ethanol, dry and obtain the poly amic acid ester toner of 3.83g white.Yield is 84.3%.In addition, the molecular weight of this poly amic acid ester is Mn=9243, Mw=20232.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.2187g gained, add 19.9635gNMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-23).
(Production Example 24)
In the 100mL four-hole boiling flask with stirring apparatus, get 4.9034g (18.84mmol) 2, two (methoxycarbonyl) cyclo-butane-1 of 4-, the 3-dicarboxylic acid adds 68.12g NMP, stirs and makes its dissolving.Then, add 4.45g (43.98mmol) triethylamine, 1.7315g (16.01mmol) p-phenylenediamine (PPD), 0.7922g (4.00mmol) 4,4 '-diaminodiphenyl-methane stirs and makes its dissolving.Add 16.90g (44.08mmol) (2,3-dihydroxy-2-sulfo--3-benzo when stirring this solution
Figure BDA00002401499800521
The azoles base) phosphonic acid diphenyl ester adds 9.67g NMP again, and reaction is 4 hours under water-cooled.After 4 hours, add 0.2607g (2.88mmol) acryloyl chloride, reaction is 30 minutes under water-cooled.With the polyamic acid ester solution of gained while stirring in the 2-propyl alcohol that drops into 650g, the precipitation that leaching is separated out, then the 2-propyl alcohol with 210g cleans 5 times, and is dry and obtain the poly amic acid ester toner.
The molecular weight of this poly amic acid ester is Mn=3189, Mw=4783.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.3389g gained, add 22.6242g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-24).
(Production Example 25)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 3.0000g (15.13mmol) 4,4 '-diaminodiphenyl-methane, 1.38g (10.13mmol) 3-amino-N-methylbenzylamine, add 94.65g NMP and 5.75g (56.89mmol) as the triethylamine of alkali, stir and make its dissolving.Then, when stirring this two amine aqueous solution, add 7.7149g (23.73mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.6574g (7.2632mmol) acryloyl chloride, reaction is 30 minutes under water-cooled.With the solution of the poly amic acid ester of gained while stirring in the 2-propyl alcohol that drops into 450g, the white precipitate that leaching is separated out, then the 2-propyl alcohol with 220g cleans 5 times, and is dry and obtain the poly amic acid ester toner of white.The molecular weight of this poly amic acid ester is Mn=8861, Mw=20627.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 1.5913g gained, add 14.5979g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-25).
(Production Example 26)
In the 100mL four-hole boiling flask with stirring apparatus, get 1.2654g (4.48mmol) 2, two (methoxycarbonyl) terephthalic acid (TPA)s of 5-, 2.6157g (10.05mmol) 2, two (methoxycarbonyl) cyclo-butane-1 of 4-, the 3-dicarboxylic acid, add 73.16g NMP, stir and make its dissolving.Then, add 3.34g (33.01mmol) triethylamine, two (4-amino-benzene oxygen) propane of 3.8784g (15.01mmol) 1.3-, stir and make its dissolving.Add 12.68g (33.08mmol) (2,3-dihydroxy-2-sulfo--3-benzo when stirring this solution
Figure BDA00002401499800522
The azoles base) phosphonic acid diphenyl ester adds 10.05gNMP again, and reaction is 4 hours under water-cooled.After 4 hours, add 0.1508g (1.07mmol) acryloyl chloride, reaction is 30 minutes under water-cooled.With the polyamic acid ester solution of gained while stirring in the 2-propyl alcohol that drops into 650g, the precipitation that leaching is separated out, then the 2-propyl alcohol with 210g cleans 5 times, and is dry and obtain the poly amic acid ester toner.The molecular weight of this poly amic acid ester is Mn=15633, Mw=32874.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 1.2264g gained, add 11.4164g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-26).
(Production Example 28)
Make the 300mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 3.1516g (29.14mmol) p-phenylenediamine (PPD), 1.2301g (3.24mmol) DA-1, add 58.11g NMP, 174.34g γ-BL, 5.78g (73.13mmol) as the pyridine of alkali, stir and make its dissolving.Then, when stirring this two amine aqueous solution, add 9.9137g (30.49mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 0.7329g (9.34mmol) acetyl chloride, reaction is 30 minutes under water-cooled.With the polyamic acid ester solution of gained while stirring in the 2-propyl alcohol that drops into 1012g, the precipitation that leaching is separated out, then the 2-propyl alcohol with 823g cleans 5 times, and is dry and obtain the poly amic acid ester toner.
The molecular weight of this poly amic acid ester is Mn=17834, Mw=33755.
In the 200ml Erlenmeyer flask, get the poly amic acid ester toner of 10.18g gained, add 91.61g γ-BL, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-27).
(Production Example 28)
Make the 300mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 3.1524g (29.15mmol) p-phenylenediamine (PPD), 1.2301g (3.24mmol) DA-1, add 60.48g NMP, 181.44g γ-BL, 5.78g (73.13mmol) as the pyridine of alkali, stir and make its dissolving.Then, when stirring this two amine aqueous solution, add 9.9032g (30.46mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add 1.9290g (9.34mmol) chloro-carbonic acid-2-naphthyl ester, reaction is 30 minutes under water-cooled.With the polyamic acid ester solution of gained while stirring in the 2-propyl alcohol that drops into 1055g, the precipitation that leaching is separated out, then the 2-propyl alcohol with 522g cleans 5 times, and is dry and obtain the poly amic acid ester toner.
The molecular weight of this poly amic acid ester is Mn=16701, Mw=33541.
In the 200ml Erlenmeyer flask, get the poly amic acid ester toner of 10.21g gained, add 92.52g γ-BL, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-28).
(Production Example 29)
Make the 300mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.9935g (27.68mmol) p-phenylenediamine (PPD), 1.1674g (3.08mmol) DA-1, add 56.89g NMP, 170.68g γ-BL, 12.62g (104.1mmol) as 2 of alkali, 4, the 6-trimethylpyridine stirs and makes its dissolving.Then, when stirring this two amine aqueous solution, add 9.4058g (28.93mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.After 4 hours, add the different nicotinoyl chlorine hydrochloride of 1.5772g (8.86mmol), reaction is 30 minutes under water-cooled.With the polyamic acid ester solution of gained while stirring in the 2-propyl alcohol that drops into 1004g, the precipitation that leaching is separated out, then the 2-propyl alcohol with 497g cleans 5 times, and is dry and obtain the poly amic acid ester toner.
The molecular weight of this poly amic acid ester is Mn=14972, Mw=31405.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 1.6073g gained, add 14.4534g γ-BL, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-29).
(Production Example 30)
In the 100mL four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, get 1.848g (9.23mmol) 4,4 '-diamino-diphenyl ether and 2.1025g (13.82mmol) 3, the 5-diaminobenzoic acid adds 39.7g NMP, stirs in supplying nitrogen and makes its dissolving.Add 4.8162g (22.08mmol) pyromellitic acid dianhydride when stirring this two amine aqueous solution, adding NMP, to make solid component concentration be 15 quality % again, at room temperature stirred 24 hours, obtains the solution of polyamic acid (PAA-3).Viscosity during 25 ℃ of the temperature of this polyamic acid solution is 257mPas.In addition, the molecular weight of this polyamic acid is Mn=13620, Mw=28299.
(Production Example 31)
Get 2.4301g (15.97mmol) 3 in the 100mL four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, 5-diaminobenzoic acid, 9.4204g (24.0mmol) DA-8 add 44.60g NMP, stir in supplying nitrogen and make its dissolving.When stirring this two amine aqueous solution, add 4.7505g (23.98mmol) BDA, at room temperature stirred 2 hours.Then, add 44.59g NMP, 3.1054g (15.84mmol) 1,2,3,4-cyclo-butane tetracarboxylic dianhydride.Adding NMP, to make solid component concentration be 15 quality % again, at room temperature stirred 24 hours.Viscosity during 25 ℃ of the temperature of the polyamic acid solution of gained is 802mPas.In addition, the molecular weight of this polyamic acid is Mn=13261, Mw=32578.
Then in this solution, add 0.0590g 3-glycidoxy propyl group methyldiethoxysilane, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-4).
(Production Example 32)
Get 20.0838g (132.0mmol) 3 in the 100mL four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, 5-diaminobenzoic acid and 21.3254g (88.0mmol) DA-7 adds 268.48g NMP, stirs in supplying nitrogen and makes its dissolving.When stirring this two amine aqueous solution, add 42.4946g (216.7mmol) 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, adding NMP, to make solid component concentration be 20 quality % again, at room temperature stirred 24 hours, obtains the solution of polyamic acid (PAA-5).Viscosity during 25 ℃ of the temperature of this polyamic acid solution is 2156mPas.In addition, the molecular weight of this polyamic acid is Mn=18794, Mw=63387.
(Production Example 33)
Get 3.6536g (24.01mmol) 3 in the 100mL four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, 5-diaminobenzoic acid, 3.8715g (15.98mmol) DA-7 add 31.75g NMP, stir in supplying nitrogen and make its dissolving.When stirring this two amine aqueous solution, add 3.9621g (20.0mmol) BDA, at room temperature stirred 2 hours.Then, add 25.42g NMP, 4.4776g (19.97mmol) 1,2,3,4-cyclohexane tetracarboxylic dianhydride.Adding NMP, to make solid component concentration be 20 quality % again, at room temperature stirred 24 hours.Viscosity during 25 ℃ of the temperature of the polyamic acid solution of gained is 417mPas.In addition, the molecular weight of this polyamic acid is Mn=13291, Mw=54029.
Then in this solution, add 0.0476g 3-glycidoxy propyl group methyldiethoxysilane, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-6).
(Production Example 34)
In the 100mL four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, get 3.6516g (24.0mmol) 3,5-diaminobenzoic acid, 2.4070g (16.02mmol) 4-amino-N-Methylphenethylamine, add 66.21g NMP, in supplying nitrogen, stir and make its dissolving.When stirring this two amine aqueous solution, add 8.5972g (39.42mmol) pyromellitic acid dianhydride.Adding NMP, to make solid component concentration be 15 quality % again, at room temperature stirred 24 hours.Viscosity during 25 ℃ of the temperature of the polyamic acid solution of gained is 488mPas.In addition, the molecular weight of this polyamic acid is Mn=13205, Mw=33511.
Then in this solution, add 0.0438g 3-glycidoxy propyl group methyldiethoxysilane, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-7).
(Production Example 35)
In the 100mL four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, get 3.6603g (24.06mmol) 3,5-diaminobenzoic acid, 4.7740g (16.0mmol) 1, two (the 4-aminobenzene ethyl) ureas of 3-add 28.59g NMP, stir in supplying nitrogen and make its dissolving.When stirring this two amine aqueous solution, add 2.3782g (12.0mmol) BDA, at room temperature stirred 2 hours.Then, add 38.13g NMP, add 6.0903g (27.92mmol) pyromellitic acid dianhydride.Adding NMP, to make solid component concentration be 15 quality % again, at room temperature stirred 24 hours.Viscosity during 25 ℃ of the temperature of the polyamic acid solution of gained is 744mPas.In addition, the molecular weight of this polyamic acid is Mn=17771, Mw=38991.
Then in this solution, add 0.0505g 3-glycidoxy propyl group methyldiethoxysilane, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-8).
(Production Example 36)
In the 100mL four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, get 3.2080g (16.02mmol) 4,4 '-diamino-diphenyl ether, 5.8147g (24.0mmol) DA-7, add 60.42g NMP, in supplying nitrogen, stir and make its dissolving.When stirring this two amine aqueous solution, add 7.7658g (39.60mmol) 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, adding NMP, to make solid component concentration be 20 quality % again, at room temperature stirred 24 hours.Viscosity during 25 ℃ of the temperature of the polyamic acid solution of gained is 1972mPas.In addition, the molecular weight of this polyamic acid is Mn=15159, Mw=38251.
Then in this solution, add 0.0504g 3-glycidoxy propyl group methyldiethoxysilane, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-9).
(Production Example 37)
In the 100mL four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, get 1.2133g (7.97mmol) 3,5-diaminobenzoic acid, 6.8216g (31.98mmol) 4,4 '-diamino-diphenyl-N-methyl amine adds 44.03g NMP, stirs in supplying nitrogen and makes its dissolving.When stirring this two amine aqueous solution, add 7.1310g (36.0mmol) BDA, at room temperature stirred 2 hours.Then, add 14.62gNMP, add 0.8713g (3.99mmol) pyromellitic acid dianhydride.Adding NMP, to make solid component concentration be 18 quality % again, at room temperature stirred 24 hours.Viscosity during 25 ℃ of the temperature of the polyamic acid solution of gained is 577mPas.In addition, the molecular weight of this polyamic acid is Mn=12656, Mw=28487.
Then in this solution, add 0.0480g 3-glycidoxy propyl group methyldiethoxysilane, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-10).
(Production Example 38)
In the 100mL four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, get 3.5843g (17.99mmol) 4,4 '-diamino-diphenyl amine, 2.9064g (12.0mmol) DA-7, add 55.58g NMP, in supplying nitrogen, stir and make its dissolving.When stirring this two amine aqueous solution, add 5.7653g (29.40mmol) 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, adding NMP, to make solid component concentration be 15 quality % again, at room temperature stirred 24 hours.Viscosity during 25 ℃ of the temperature of the polyamic acid solution of gained is 1269mPas.In addition, the molecular weight of this polyamic acid is Mn=15559, Mw=43490.
Then in this solution, add 0.0368g 3-glycidoxy propyl group methyldiethoxysilane, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-11).
(Production Example 39)
Get 6.087g (40.01mmol) 3 in the 500mL four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, the 5-diaminobenzoic acid adds 71.04g NMP, stirs in supplying nitrogen and makes its dissolving.Then, add 31.88g (160mmol) 4,4 '-diamino-diphenyl amine, 124.30g γ-BL stir in supplying nitrogen and make its dissolving.When stirring this two amine aqueous solution, add 31.70g (160mmol) BDA, under water-cooled, stirred 2 hours.Then, add 88.78g γ-BL, stirs after 10 minutes, add 8.51g (39.0mmol) pyromellitic acid dianhydride in the time of stirring reaction solution, adding γ-BL, to make solid component concentration be 18 quality % again, and stirring is 24 hours under water-cooled.Viscosity during 25 ℃ of the temperature of the polyamic acid solution of gained is 2864mPas.In addition, the molecular weight of this polyamic acid is Mn=14435, Mw=30525.
Then in this solution, add 77.81g is diluted to 0.3 quality % than the mixed solvent that is 2/8 with NMP/ γ-BL 3-glycidoxy propyl group methyldiethoxysilane solution, obtain polyamic acid solution (PAA-12).
(Production Example 40)
Add 3.6543g (24.02mmol) 3 in the 100mL four-hole boiling flask with stirring apparatus and nitrogen ingress pipe, 5-diaminobenzoic acid, 18.82g NMP stir in supplying nitrogen and make its dissolving.Then, add 3.8765g (16.0mmol) DA-7,18.82g γ-BL, in supplying nitrogen, stir and make its dissolving.When stirring this two amine aqueous solution, add 5.4708g (27.61mmol) BDA, under water-cooled, stirred 2 hours.Then, add 4.71g γ-BL, stirs after 10 minutes, add 2.700g (12.04mmol) 1,2,4 in the time of stirring reaction solution, 5-cyclohexane tetracarboxylic dianhydride, adding γ-BL, to make solid component concentration be 20 quality % again, stirring is 24 hours under water-cooled.Viscosity during 25 ℃ of the temperature of the polyamic acid solution of gained is 2142mPas.In addition, the molecular weight of this polyamic acid is Mn=6509, Mw=11481.
Then in this solution, add 0.0470g 3-glycidoxy propyl group methyldiethoxysilane, at room temperature stirred 24 hours, obtain polyamic acid solution (PAA-13).
(relatively Production Example 3)
In the 100mL four-hole boiling flask with stirring apparatus, get 5.1584g (19.82mmol) 2, two (methoxycarbonyl) cyclo-butane-1 of 4-, the 3-dicarboxylic acid adds 68.12g NMP, stirs and makes its dissolving.Then, add 4.45g (43.98mmol) triethylamine, 1.7315g (16.01mmol) p-phenylenediamine (PPD), 0.7922g (3.99mmol) 4,4 '-diaminodiphenyl-methane stirs and makes its dissolving.Add 16.90g (44.08mmol) (2,3-dihydroxy-2-sulfo--3-benzo when stirring this solution
Figure BDA00002401499800581
The azoles base) phosphonic acid diphenyl ester adds 9.67g NMP again, and reaction is 4 hours under water-cooled.With the polyamic acid ester solution of gained while stirring in the 2-propyl alcohol that drops into 650g, the precipitation that leaching is separated out, then the 2-propyl alcohol with 210g cleans 5 times, and is dry and obtain the poly amic acid ester toner.
The molecular weight of this poly amic acid ester is Mn=3860, Mw=5384.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.0332g gained, add 18.4708g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-30).
(relatively Production Example 4)
Make the 100mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 2.01g (10.09mmol) 4,4 '-diaminodiphenyl-methane, 0.92g (6.73mmol) 3-amino-N-methylbenzylamine, add 131.14g NMP, 3.83g (37.93mmol) as the triethylamine of alkali, stir and make its dissolving.Then, when stirring this two amine aqueous solution, add 5.1407g (15.81mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.With the solution of the poly amic acid ester of gained while stirring in the 2-propyl alcohol that drops into 690g, the white precipitate that leaching is separated out, then the 2-propyl alcohol with 220g cleans 5 times, and is dry and obtain the poly amic acid ester toner of white.The molecular weight of this poly amic acid ester is Mn=5064, Mw=11348.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 2.0014g gained, add 18.2912g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-31).
(relatively Production Example 5)
In the 200mL four-hole boiling flask with stirring apparatus, get 1.7779g (6.30mmol) 2, two (methoxycarbonyl) terephthalic acid (TPA)s of 5-, 3.7712g (14.49mmol) 2, two (methoxycarbonyl) cyclo-butane-1 of 4-, the 3-dicarboxylic acid, add 146.71gNMP, stir and make its dissolving.Then, add 4.25g (42.0mmol) triethylamine, 5.4239g (21.0mmol) 1, two (4-amino-benzene oxygen) propane of 3-stir and make its dissolving.Add 16.91g (44.11mmol) (2,3-dihydroxy-2-sulfo--3-benzo when stirring this solution
Figure BDA00002401499800582
The azoles base) phosphonic acid diphenyl ester adds 25.81g NMP again, and reaction is 4 hours under water-cooled.With the polyamic acid ester solution of gained while stirring in the methyl alcohol that drops into 1224g, the precipitation that leaching is separated out, then with the washed with methanol of 408g 4 times, dry and obtain the poly amic acid ester toner.The molecular weight of this poly amic acid ester is Mn=15103, Mw=32483.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 1.0172g gained, add 9.4167g NMP, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-32).
(relatively Production Example 6)
Make the 300mL four-hole boiling flask with stirring apparatus be nitrogen atmosphere, add 3.0968g (28.64mmol) p-phenylenediamine (PPD), 1.2067g (3.18mmol) DA-1, add 58.81g NMP, 176.42g γ-BL, 5.67g (71.73mmol) as the pyridine of alkali, stir and make its dissolving.Then, when stirring this two amine aqueous solution, add 9.7184g (29.89mmol) 1,3DM-CBDE-Cl, reaction is 4 hours under water-cooled.With the polyamic acid ester solution of gained while stirring in the 2-propyl alcohol that drops into 1018g, the precipitation that leaching is separated out, then the 2-propyl alcohol with 504g cleans 5 times, and is dry and obtain the poly amic acid ester toner.
The molecular weight of this poly amic acid ester is Mn=16123, Mw=32976.
In the 50ml Erlenmeyer flask, get the poly amic acid ester toner of 1.8932g gained, add 17.0436g γ-BL, at room temperature stir and made its dissolving in 24 hours, obtain polyamic acid ester solution (PAE-33).
(embodiment 11)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-3) that obtains in the polyamic acid ester solution (PAE-7) that obtains in the 2.4106g Production Example 7, the 1.6477g Production Example 30, add 2.3811g NMP, 1.5934g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (V-1).
(embodiment 12)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-3) that obtains in the polyamic acid ester solution (PAE-10) that obtains in the 2.3986g Production Example 10, the 1.6926g Production Example 30, add 2.3700g NMP, 1.6042g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (V-2).
(embodiment 13)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-3) that obtains in the polyamic acid ester solution (PAE-11) that obtains in the 2.4102g Production Example 11, the 1.6552g Production Example 30, add 2.3643g NMP, 1.6339g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (V-3).
(embodiment 14)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-3) that obtains in the polyamic acid ester solution (PAE-12) that obtains in the 2.4153g Production Example 12, the 1.6606g Production Example 30, add 2.3594g NMP, 1.6067g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (V-4).
(embodiment 15)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-3) that obtains in the polyamic acid ester solution (PAE-13) that obtains in the 2.4079g Production Example 13, the 1.6504g Production Example 30, add 2.3762g NMP, 1.6062g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (V-5).
(embodiment 16)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-3) that obtains in the polyamic acid ester solution (PAE-9) that obtains in the 2.3990g Production Example 9, the 1.6445g Production Example 30, add 2.3564g NMP, 1.6084g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (V-6).
(embodiment 17)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-3) that obtains in the polyamic acid ester solution (PAE-14) that obtains in the 2.3984g Production Example 14, the 1.663g Production Example 30, add 2.3651gNMP, 1.6102g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (V-7).
(embodiment 18)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-3) that obtains in the polyamic acid ester solution (PAE-21) that obtains in the 2.3983g Production Example 21, the 1.6284g Production Example 30, add 2.3625gNMP, 1.5973g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (V-8).
(embodiment 19)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-3) that obtains in the polyamic acid ester solution (PAE-22) that obtains in the 2.4288g Production Example 22, the 1.6277g Production Example 30, add 2.3674g NMP, 1.6044g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (V-9).
(embodiment 20)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-2) that obtains in the polyamic acid ester solution (PAE-15) that obtains in the 2.4073g Production Example 15, the 1.4266g Production Example 6, add 2.5623gNMP, 1.6037g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VI-1).
(embodiment 21)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-2) that obtains in the polyamic acid ester solution (PAE-8) that obtains in the 2.4315g Production Example 8, the 1.4539g Production Example 6, add 2.5771gNMP, 1.6047g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VI-2).
(embodiment 22)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-2) that obtains in the polyamic acid ester solution (PAE-16) that obtains in the 2.4080g Production Example 16, the 1.5842g Production Example 6, add 2.5699g NMP, 1.6067g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VI-3).
(embodiment 23)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-2) that obtains in the polyamic acid ester solution (PAE-20) that obtains in the 2.4016g Production Example 20, the 1.5320g Production Example 6, add 2.5650g NMP, 1.5970g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VI-4).
(embodiment 24)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-2) that obtains in the polyamic acid ester solution (PAE-19) that obtains in the 2.4105g Production Example 19, the 1.4186g Production Example 6, add 2.5900g NMP, 1.6034g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VI-5).
(embodiment 25)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-2) that obtains in the polyamic acid ester solution (PAE-17) that obtains in the 2.4208g Production Example 17, the 1.4416g Production Example 6, add 2.5948g NMP, 1.6192g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VI-6).
(embodiment 26)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-2) that obtains in the polyamic acid ester solution (PAE-18) that obtains in the 2.4128g Production Example 18, the 1.4003g Production Example 6, add 2.5658g NMP, 1.6040g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VI-7).
(embodiment 27)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-2) that obtains in the polyamic acid ester solution (PAE-23) that obtains in the 2.4003g Production Example 23, the 1.4214g Production Example 6, add 2.5769g NMP, 1.6258g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VI-8).
(embodiment 28)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-13) that obtains in the polyamic acid ester solution (PAE-14) that obtains in the 1.4970g Production Example 14, the 0.6867g Production Example 40, add 1.8321gNMP, 0.9933g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VII-1).
(embodiment 29)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-13) that obtains in the polyamic acid ester solution (PAE-20) that obtains in the 1.4939g Production Example 20, the 0.6778g Production Example 40, add 1.8243g NMP, 0.9970g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VII-2).
(embodiment 30)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-13) that obtains in the polyamic acid ester solution (PAE-17) that obtains in the 1.4923g Production Example 17, the 0.6527g Production Example 40, add 1.8424g NMP, 1.0093g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VII-3).
(embodiment 31)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-4) that obtains in the polyamic acid ester solution (PAE-24) that obtains in the 2.4514g Production Example 24, the 2.6079g Production Example 31, add 3.2294g NMP, 2.0193gBCS and 0.0745g as 4-(tert-butoxycarbonyl the is amino) pyridine (following slightly Boc-AP) of imidizate promoter, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VIII-1).
(embodiment 32)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-6) that obtains in the polyamic acid ester solution (PAE-25) that obtains in the 2.4389g Production Example 25, the 2.0025g Production Example 33, add 3.8213g NMP, 2.0747g BCS and 0.0571g as the N-α of imidizate promoter-(9-fluorenyl methoxy carbonyl)-N-tert-butoxycarbonyl-L-Histidine (following slightly Fmoc-His), with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VIII-2).
(embodiment 33)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-7) that obtains in the polyamic acid ester solution (PAE-26) that obtains in the 2.4317g Production Example 26, the 2.4209g Production Example 34, add 3.2161gNMP, 2.0138g BCS and 0.0443 Fmoc-His as imidizate promoter, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VIII-3).
(embodiment 34)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-5) that obtains in the polyamic acid ester solution (PAE-24) that obtains in the 2.4033g Production Example 24, the 1.8146g Production Example 32, add 3.8062g NMP, 2.0598g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VIII-4).
(embodiment 35)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-8) that obtains in the polyamic acid ester solution (PAE-25) that obtains in the 2.4133g Production Example 25, the 2.4596g Production Example 35, add 3.2232g NMP, 2.0172g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VIII-5).
(embodiment 36)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-9) that obtains in the polyamic acid ester solution (PAE-25) that obtains in the 2.4188g Production Example 25, the 1.8056g Production Example 36, add 3.8213g NMP, 2.0016g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VIII-6).
(embodiment 37)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-10) that obtains in the polyamic acid ester solution (PAE-25) that obtains in the 2.4086g Production Example 25, the 2.0296g Production Example 37, add 3.6425gNMP, 2.0192g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VIII-7).
(embodiment 38)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-11) that obtains in the polyamic acid ester solution (PAE-26) that obtains in the 2.4038g Production Example 26, the 2.4958g Production Example 38, add 3.2333gNMP, 2.0473g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VIII-8).
(embodiment 39)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-12) that obtains in the polyamic acid ester solution (PAE-27) that obtains in the 2.4592g Production Example 27, the 2.3451g Production Example 39, add 0.3698g NMP, 3.0082g γ-BL and 2.0164g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VIII-9).
(embodiment 40)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-12) that obtains in the polyamic acid ester solution (PAE-28) that obtains in the 2.4180g Production Example 28, the 2.2640g Production Example 39, add 0.3912g NMP, 2.9920g γ-BL and 2.0276g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VIII-10).
(embodiment 41)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-13) that obtains in the polyamic acid ester solution (PAE-29) that obtains in the 2.4290g Production Example 29, the 2.1331g Production Example 40, add 1.1458g NMP, 2.4939g γ-BL and 2.0804g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (VIII-11).
(comparative example 9)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-3) that obtains in polyamic acid ester solution (PAE-2) that 1.5206g relatively obtains in the Production Example 1 and the Production Example 30, add 1.4838g NMP, 1.0418g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (d).
(comparative example 10)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-4) that obtains in polyamic acid ester solution (PAE-30) that 2.4052g relatively obtains in the Production Example 3, the 2.5709g Production Example 31, add 3.2177g NMP, 2.0115gBCS and 0.0466 Boc-AP as imidizate promoter, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (e-1).
(comparative example 11)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-6) that obtains in polyamic acid ester solution (PAE-31) that 2.4477g relatively obtains in the Production Example 4, the 2.0163g Production Example 31, add 3.8281gNMP, 2.0238g BCS and 0.0567 Fmoc-His as imidizate promoter, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (e-2).
(comparative example 12)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-7) that obtains in polyamic acid ester solution (PAE-32) that 2.4343g relatively obtains in the Production Example 5, the 2.4192g Production Example 34, add 3.2408g NMP, 2.0078g BCS and 0.0493 Fmoc-His as imidizate promoter, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (e-3).
(comparative example 13)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-5) that obtains in polyamic acid ester solution (PAE-30) that 2.4670g relatively obtains in the Production Example 3, the 1.8052g Production Example 32, add 3.8260g NMP, 1.994g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (e-4).
(comparative example 14)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-11) that obtains in polyamic acid ester solution (PAE-32) that 1.2196g relatively obtains in the Production Example 5, the 1.2191g Production Example 38, add 1.6214g NMP, 1.0094g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (e-8).
(comparative example 15)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-12) that obtains in polyamic acid ester solution (PAE-33) that 2.4001g relatively obtains in the Production Example 6, the 2.3161g Production Example 39, add 0.3740g NMP, 3.0250g γ-BL and 2.0167g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (e-9).
(comparative example 16)
In the 50ml Erlenmeyer flask, add stirrer, get the polyamic acid solution (PAA-13) that obtains in polyamic acid ester solution (PAE-33) that 2.4239g relatively obtains in the Production Example 6, the 2.1307g Production Example 40, add 1.1709g NMP, 2.5186g γ-BL and 2.0286g BCS, with magnetic stirrer 30 minutes, obtain aligning agent for liquid crystal (e-11).
(embodiment 42)
After obtaining the filter filtration of aligning agent for liquid crystal (V-1) with 1.0 μ m among the embodiment 11, be spun on the glass substrate with transparency electrode, drying is 5 minutes on the heating plate of 80 ℃ of temperature, in the heated air circulation type stove of 230 ℃ of temperature through 20 minutes burn till, obtain thickness 100nm imidizate film.For this imidizate film, measured center line average roughness (Ra).Measurement result is shown in the table 4 described later.
(embodiment 43～69 and comparative example 17～24)
The aligning agent for liquid crystal that in using respectively above-described embodiment 12～34,38～41, comparative example 9～16, obtains, respectively film by forming with the same method of embodiment 42.Observe the film surface of respectively filming by AFM.In addition, for respectively filming, measured center line average roughness (Ra).These measurement results are shown in the table 4 described later.
[table 4]
Figure BDA00002401499800671
The possibility of utilizing on the industry
If employing the present invention then can reduce the trickle concavo-convex of surface, improved by the interfacial characteristics that exchange to drive the liquid crystal such as the ghost minimizing that causes and liquid crystal orientation film, and the electrical characteristics such as residual of voltage retention, ion concentration and DC voltage also improve.Thereby can be widely used in liquid crystal display cells of TN element, STN element, TFT liquid crystal cell and vertical orientating type etc.
Quote all the elements of Japanese patent application 2010-058556 number instructions, claims and the summary of filing an application on March 15th, 2010 here as the announcement of instructions of the present invention.

Claims (9)

1. aligning agent for liquid crystal, it is characterized in that, comprise have following formula (1) structural unit and to end carried out modifying and make terminal amino group have the structure of following formula (3) poly amic acid ester, have polyamic acid and the organic solvent of the structural unit of following formula (2);
[changing 1]
Figure FDA00002401499700011
R 1Be the alkyl of carbon number 1～5, A 1, A 2Represent independently that respectively hydrogen atom maybe can have alkyl, the alkenyl or alkynyl of substituent carbon number 1～10, X 1, X 2Be 4 valency organic groups, Y 1, Y 2Be the divalent organic group;
[changing 2]
Figure FDA00002401499700012
In the formula, A be singly-bound ,-O-,-S-or-NR 3-, R 2, R 3Represent independently respectively carbon number 1～10 alkyl, alkenyl or alkynyl, carbon number 3～6 naphthenic base or can have substituent aryl or heterocyclic radical.
2. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, the content of described poly amic acid ester and the content of polyamic acid count 1/9～9/1 with the mass ratio of (content of the content/polyamic acid of poly amic acid ester).
3. aligning agent for liquid crystal as claimed in claim 1 or 2 is characterized in that, comprises described poly amic acid ester and polyamic acid and organic solvent, and the total amount of described poly amic acid ester and polyamic acid is 0.5 quality %～15 quality % with respect to organic solvent.
4. such as each the described aligning agent for liquid crystal in the claim 1～3, it is characterized in that, the described poly amic acid ester that end has been carried out modifying is by making at least a chlorocarbonylation compound that is selected from following formula (C-1)～(C-36) and the main chain terminal amino group of poly amic acid ester react the poly amic acid ester that gets;
[changing 3]
5. such as each the described aligning agent for liquid crystal in the claim 1～4, it is characterized in that, in described formula (1) and the formula (2), X 1And X 2Structure be selected from following structure at least a;
[changing 4]
Figure FDA00002401499700031
6. such as each the described aligning agent for liquid crystal in the claim 1～5, it is characterized in that, in the described formula (1), Y 1For being selected from least a of the structure that represents with following formula;
[changing 5]
Figure FDA00002401499700041
7. such as each the described aligning agent for liquid crystal in the claim 1～6, it is characterized in that, in the described formula (2), Y 2For being selected from least a of the structure that represents with following formula;
[changing 6]
Figure FDA00002401499700051
8. a liquid crystal orientation film is characterized in that, each the described aligning agent for liquid crystal in the claim 1～7 is coated with, burns till and obtains.
9. a liquid crystal orientation film is characterized in that, to the described aligning agent for liquid crystal coating of in the claim 1～7 each, burn till and the tunicle irradiation behind polarization radioactive ray and obtain.
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