CN103154808B - Aligning agent for liquid crystal, liquid crystal orientation film and use the liquid crystal display cells of this liquid crystal orientation film - Google Patents

Aligning agent for liquid crystal, liquid crystal orientation film and use the liquid crystal display cells of this liquid crystal orientation film Download PDF

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CN103154808B
CN103154808B CN201180040348.8A CN201180040348A CN103154808B CN 103154808 B CN103154808 B CN 103154808B CN 201180040348 A CN201180040348 A CN 201180040348A CN 103154808 B CN103154808 B CN 103154808B
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CN103154808A (en
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野田尚宏
森内正人
筒井皇晶
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Nissan Chemical Corp
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    • 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
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Even if the invention provides to obtain and be exposed to the aligning agent for liquid crystal of liquid crystal orientation film and the new diamine for obtaining polymkeric substance contained in liquid crystal treating agent that decline that illumination penetrates lower voltage retention is also inhibited.Aligning agent for liquid crystal comprises at least one polymkeric substance being selected from the polyimide obtained through imidizate by the polyimide precursor of the diamines gained of following formula [1] and this polyimide precursor.(changing 1) (X is the organic group represented with following formula [2]; Y 1, Y 2represent phenyl ring or cyclohexane ring independently; P, q represent the integer of 0 or 1 independently; S 1, S 2represent singly-bound or bivalence linking base group independently; S during p=0 1for singly-bound, S during q=0 2for singly-bound; R 1represent hydrogen atom, fluorine atom, the alkyl of carbon number 1 ~ 22 or fluoroalkyl or steroid radical.) (changing 2) (in formula, C 1, C 2represent singly-bound or divalent organic group independently; A represents hot detachment organic group; B 1represent and be selected from-CH 2-, the divalent organic group of-O-,-NH-and-S-; N is 0 or 1; The link direction of X is not limited.)。

Description

Aligning agent for liquid crystal, liquid crystal orientation film and use the liquid crystal display cells of this liquid crystal orientation film
Technical field
The present invention relates to aligning agent for liquid crystal, use the liquid crystal orientation film of this aligning agent for liquid crystal and liquid crystal display cells.
Background technology
Liquid crystal orientation film is the member of formation of the liquid crystal display cells be widely used as display device, plays the effect making liquid crystal along certain direction orientation.Now, industrial used main liquid crystal orientation film is formed by aligning agent for liquid crystal, and this aligning agent for liquid crystal is formed by as the polyamic acid (polyamic acid) of polyimide precursor or the solution of polyimide.Specifically, after being undertaken heating and burn till by coating of liquid crystalline aligning agent on substrate, implementation orientation process and obtaining, the surface treatment that utilizes and rub and carry out can be exemplified and make liquid crystal phase for real estate orientation process that is parallel or orientation obliquely.
In recent years, there is the tendency of the enlarged areas of substrate, concavo-convex increase etc. in the maximization, high-definition, cost degradation etc. of the substrate used along with panel.When this substrate forms alignment films, can following problems be there is: occur during printing that the printing such as pore is bad, during friction treatment, be difficult to carry out impartial orientation process, the orientation of liquid crystal occur bad etc.In addition, in liquid crystal aligning process, main enforcement utilizes the surface treatment rubbing and carry out now, but can there is the defect that liquid crystal orientation film occurs, and produces the display defect caused thus, the problem producing dust etc.
On the other hand, utilize rubbing manipulation to carry out as an alternative the method for orientation process, the liquid crystal aligning process utilizing light reaction to carry out is proposed.Specifically, known following method: formed on the surface of the substrate and there is the film that the polymkeric substance of the privileged site of light reaction can occur polyvinyl cinnamate etc., by irradiate polarisation or non-polarized radioactive ray and give liquid crystal aligning can method (optical alignment method).According to the method, can realize not producing electrostatic, dust, and uniform liquid crystal aligning can be realized, orientation can also be realized and split (referenced patent documents 1,2) such as the angle of visibility improvement caused.
When liquid crystal cell such as TN (Twisted Nematic: twisted nematic), STN (Super Twisted Nematic: super twisted nematic), liquid crystal orientation film must have makes liquid crystal molecule relative to real estate with the function of angle (tilt angle) tilted alignment of regulation (with reference to patent documentation 15).In order to show tilt angle, known use comprises the polyamic acid, polyimide etc. of alkyl side chain, the side chain of steroid skeleton, the side chain with ring structure etc. and the liquid crystal orientation film (patent documentation 3,4,5) obtained.Making in the liquid crystal aligning process of using up, usually giving tilt angle (reference patent documentation 1) by irradiating the radioactive ray that tilt to the incident direction of real estate towards substrate normal.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 6-287453 publication
Patent documentation 2: Japanese Patent Laid-Open 9-297313 publication
Patent documentation 3: Japanese Patent Laid-Open 05-043687 publication
Patent documentation 4: Japanese Patent Laid-Open 04-281427 publication
Patent documentation 5: Japanese Patent Laid-Open 02-223916 publication
Summary of the invention
Invent technical matters to be solved
In the past, most liquid crystal orientation film utilizes the aligning agent for liquid crystal by forming as the polyamic acid of polyimide precursor or the solution of polyimide to be formed as mentioned above, even if use the preparation method comprising the liquid crystal orientation film of the solution of soluble polyimide to have to burn till at a lower temperature, the advantage of the superperformance as liquid crystal orientation film also can be obtained.But, use when comprising the polyimide of the diamines in a large number with side chain, have problems such as the coating film forming variation of substrate.
In order to address this is that, also following method can be implemented: a small amount of there is the diamines of the ring structure that can obtain larger tilt angle (such as at side chain by using, with reference to patent documentation 5), reduce the amount of side chain, improve the method for the coating on substrate., likely can there is the problem of the streaking of the polymkeric substance of gained etc. in poorly soluble in most cases in 1-METHYLPYRROLIDONE (hereinafter also referred to NMP) this polar solvent of the diamines that side chain has a ring structure.
In addition, in the material that light orientation uses, also mostly use the polymkeric substance etc. of the side chain had containing cinnamic acid ester group etc., in addition, in vertical orientated purposes, also need to import the diamines with other side chains.Usually, because side chain is hydrophobic mostly, decline with to the affinity of the high polar solvent of the wellability of substrate etc., the polymkeric substance therefore with a large amount of side chain position has the problem of the coating film forming difference to substrate.
In addition, along with the high performance of liquid crystal display cells in recent years, liquid crystal display cells is used at large picture in the LCD TV of high-resolution or the vehicle-mounted purposes such as purposes such as navigational system and indicator panel.In this purposes, sometimes for obtaining the backlight that high brightness uses thermal value large, and require, to backlight, there is high stability.Particularly, if penetrate as the voltage retention of one of electrical specification and decline because of the illumination of backlight, then easily can there is the sintering bad (line sintering) that display as liquid crystal display cells is one of bad, thus the high liquid crystal display cells of reliability cannot be obtained.So, in liquid crystal orientation film, except the initial stage characteristic of requirement well except, even if after also requiring that being such as exposed to illumination under long-time penetrates, the characteristic that voltage retention also not easily declines.
The present invention, in view of above-mentioned condition, its object is to provide the treatability of the polymkeric substance contained by a kind of aligning agent for liquid crystal good and coating is excellent, the aligning agent for liquid crystal that can obtain high reliability.In addition, the present invention also aims to, a kind of favorable solubility of solvent to using when obtaining polymkeric substance is provided and the diamines with side chain of the aligning agent for liquid crystal of printing excellence can be obtained, even and if provide a kind of and be exposed to the liquid crystal orientation film that the decline of voltage retention is also inhibited under the irradiation of light.
The technical scheme that technical solution problem adopts
The present inventor has carried out conscientiously studying for achieving the above object, and result completes the present invention.That is, the present invention has following main points.
(1) a kind of aligning agent for liquid crystal, comprise at least one polymkeric substance being selected from the polyimide obtained through imidizate by the polyimide precursor of the diamine component of the diamines represented containing following formula [1] and the reaction gained of tetracarboxylic dianhydride and this polyimide precursor
[changing 1]
(in formula, X is the organic group represented with following formula [2]; Y 1, Y 2represent phenyl ring or cyclohexane ring independently; P, q represent the integer of 0 or 1 independently; S 1, S 2represent singly-bound or bivalence linking base group independently; S during p=0 1for singly-bound, S during q=0 2for singly-bound; R 1represent hydrogen atom, fluorine atom, the alkyl of carbon number 1 ~ 22, the fluoroalkyl of carbon number 1 ~ 22 or steroid radical),
[changing 2]
(in formula, C 1, C 2represent singly-bound or divalent organic group independently; A represents the organic group departed from by heating; B 1represent and be selected from-CH 2-, the divalent organic group of-O-,-NH-and-S-; N is 0 or 1; The link direction of X is not limited).
(2) aligning agent for liquid crystal as described in above-mentioned (1), wherein, the content of the diamines that the formula [1] in above-mentioned diamine component represents is 5 ~ 95 % by mole.
(3) aligning agent for liquid crystal as described in above-mentioned (1) or (2), wherein, the A in above-mentioned formula [2] is the tert-butoxycarbonyl represented with formula [3],
[changing 3]
(4) aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (3), wherein, the C in above-mentioned formula [2] 1, C 2the divalent organic group represented with following formula [6],
[changing 4]
-S 3-R 2-S 4-R 3- [6]
(in formula, S 3, S 4be bivalence linking base group independently; R 2, R 3be the bivalent hydrocanbon radical of singly-bound or carbon number 1 ~ 20 independently).
(5) aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (4), wherein, the [-S of above-mentioned formula [6] 4-R 3-] represent with following formula [4], and C 1, C 2in either party there is the structure of formula [4],
[changing 5]
(in formula, B 2represent and be selected from singly-bound, phenyl ,-CH 2-,-O-,-NH-,-NR 10-and the divalent organic group of-S-; R 10represent the divalence hydrocarbon of carbon number 1 ~ 6; The structure of the alkene of formula [4] can be any one in E formula, Z formula; C in the key be represented by dotted lines and formula [2] 1the phenyl ring linked or C 2the carbonyl carbon linked links).
(6) aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (4), wherein, in above-mentioned formula [2], n=0.
(7) aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (5), wherein, the C in above-mentioned formula [2] 1it is singly-bound.
(8) aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (7), wherein, the B in above-mentioned formula [2] 1-O-or NH-.
(9) aligning agent for liquid crystal as described in above-mentioned (5), wherein, the B in above-mentioned formula [4] 2-O-or NH-.
(10) aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (9), wherein, the diamines represented by above-mentioned formula [1] is any one compound in following formula [1-a] ~ [1-k],
[changing 6]
[changing 7]
(11) liquid crystal orientation film, obtains by using the aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (10).
(12) liquid crystal orientation film, its liquid crystal orientation film obtained for using the aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (10), is penetrated by illumination and carries out orientation process.
(13) liquid crystal display cells, it possesses above-mentioned (11) or the liquid crystal orientation film described in (12).
(14) one has the diamines of the structure represented with following formula [1],
[changing 8]
(in formula, X is the organic group represented with following formula [2]; Y 1, Y 2represent phenyl ring or cyclohexane ring independently; P, q represent the integer of 0 or 1 independently; S 1, S 2represent singly-bound or bivalence linking base group independently; S during p=0 1for singly-bound, S during q=0 2for singly-bound; R 1represent hydrogen atom, fluorine atom, the alkyl of carbon number 1 ~ 22, the fluoroalkyl of carbon number 1 ~ 22 or steroid radical),
[changing 9]
(in formula, C 1, C 2represent singly-bound or divalent organic group independently; A represents the organic group departed from by heating; B 1represent and be selected from-CH 2-, the divalent organic group of-O-,-NH-and-S-; N is 0 or 1; The link direction of X is not limited).
(15) diamines as described in above-mentioned (14), wherein, the A in formula [2] is the tert-butoxycarbonyl represented with formula [3],
[changing 10]
(16) diamines as described in above-mentioned (14) or (15), wherein, the C in formula [2] 1, C 2the divalent organic group represented with following formula [6],
[changing 11]
-S 3-R 2-S 4-R 3- [6]
(in formula [6], S 3, S 4be bivalence linking base group independently; R 2, R 3be the bivalent hydrocanbon radical of singly-bound or carbon number 1 ~ 20 independently).
(17) diamines according to any one of above-mentioned (14) ~ (16), wherein, the [-S of above-mentioned formula [6] 4-R 3-] represent with following formula [4], and C 1, C 2in either party there is the structure of formula [4],
[changing 12]
(in formula, B 2represent and be selected from singly-bound, phenyl ,-CH 2-,-O-,-NH-,-NR 10-and the divalent organic group of-S-; R 10represent the divalence hydrocarbon of carbon number 1 ~ 6; The structure of the alkene of formula [4] can be any one in E formula, Z formula; C in the key be represented by dotted lines and formula [2] 1the phenyl ring linked or C 2the carbonyl carbon linked links).
(18) diamines, it is represented by any one in following formula [1-a] ~ [1-k],
[changing 13]
[changing 14]
(19) polyimide that obtains through imidizate of polyamide, polyamic acid or this polyamic acid, is that raw material obtains by the diamines described in any one in above-mentioned (14) ~ (18).
The effect of invention
As aligning agent for liquid crystal of the present invention raw material and use the dissolubility of diamines in NMP polar solvent very high, treatability during polymerization is good, containing the aligning agent for liquid crystal of polyimide obtain through imidization by polyamic acid or this polyamic acid acyl of this diamines gained, there is excellent coating film forming, though also formed be exposed to illumination penetrate under time voltage retention the liquid crystal orientation film be lowly also inhibited.In addition, above-mentioned diamines can also provide the aligning agent for liquid crystal of applicable optical alignment method.
Embodiment
< diamines > of the present invention
As aligning agent for liquid crystal of the present invention raw material and the diamines that uses is the diamines (hereinafter also referred to as diamines of the present invention) represented with following formula [1] as above.
[changing 15]
Diamines of the present invention has the phenylenediamine skeleton by hot detachment radical protections such as tert-butoxycarbonyls (hereinafter also referred to Boc yl) in side-chain structure.Usually, amino is hyperergic organic group, is therefore difficult to keep the state as a part for the side chain of diamines and exist, and can reduce amino reactivity by carrying out with hot detachment group protecting.In addition, if heated by the temperature of amino more than about 150 DEG C of hot detachment radical protection, then hot detachment group deprotection and can amino be changed to.
In addition, known amino is reactive high organic group, can react with the functional sites of unsaturated link, carboxylic acid, carboxylic acid anhydrides, epoxy compound, carbonyl etc.On the other hand, as shown below, if configure by the amino of hot detachment radical protection in the mode adjoined containing the concatenating group of carbonyl with amido link, ester bond etc., then the molecule internal ratio of diamines is intermolecular more easily reacts, thus can be formed imidazole ring, the heterocycles such as azoles ring, thiazole ring.
By this, in diamines of the present invention, the disengaging caused by making the thermal treatment in the sintering process of aligning agent for liquid crystal and the amino that generates in inner molecular reaction, thus form heterocycle, generate the side chain of rigidity, this side-chain structure is as good the bringing out position and play a role of tilt angle.
[changing 16]
In addition, the amino after hot detachment group comes off not is all for cyclization, but a part is also for intermolecular reaction, contributes to the improvement of film strength and improves reliability by being cross-linked with the low molecular composition in polymkeric substance.Therefore, film abrasive dust when using the polyamic acid of diamines of the present invention or polyimide that friction treatment is less likely to occur, even if be exposed to long-term high temperature, backlight irradiation etc., is also difficult to the decline of voltage retention or the increase of ion concentration occur.
Further, in diamines of the present invention, have bulky Boc base etc. as hot detachment group, so the dissolubility of organic solvent, particularly NMP polar solvent when being polymerized for diamines (contracting) is very high, treatability during polymerization is good.
In addition, adopt and use diamines of the present invention and the aligning agent for liquid crystal that obtains polyimide precursor or polyimide and obtain has the coating film forming of excellence, even if can obtain being exposed to illumination penetrate under time voltage retention the liquid crystal orientation film that is also inhibited of decline, further, aligning agent for liquid crystal also can use in optical alignment method.
Diamines of the present invention has the side chain represented with following formula [A].
[changing 17]
In formula [A], X is the organic group represented with following formula [2]; Y 1, Y 2represent phenyl ring or cyclohexane ring independently; P, q represent the integer of 0 or 1 independently; S 1, S 2represent singly-bound or bivalence linking base group independently; S during p=0 1for singly-bound, S during q=0 2for singly-bound; R 1represent hydrogen atom, fluorine atom, the alkyl of carbon number 1 ~ 22, the fluoroalkyl of carbon number 1 ~ 22 or steroid radical.In formula, DA represents phenylenediamine skeleton.
[changing 18]
Here, C 1, C 2represent singly-bound or divalent organic group independently; A represents the organic group departed from by heating; B 1represent and be selected from-CH 2-, the divalent organic group of-O-,-NH-and-S-; N is 0 or 1.In the link direction of X, i.e. above-mentioned [A], the C of X 1can with Y 1side links, or and C 1side links.
In diamines of the present invention, DA has phenylenediamine skeleton, can form the diamines with large-scale amount of side chains and side chain density by this.But when the larger grade of the molecular weight of diamine skeleton, the molecular weight of diamines can become large, and the amount of monomer required for polymkeric substance increases, and is industrially difficult to use.In addition, when diamine skeleton is aliphatic diamine, reactivity becomes too high, and the problem of the precipitation that causes or gelation etc. because salt is formed can occur when the preparation of polymkeric substance.
The amino with phenylenediamine skeleton is preferably primary amino radical, but also can be secondary amino group, such as, also can be methyl, ethyl, propyl group, alkyl that butyl equimolecular quantity is less replaced by amino.
In diamines of the present invention, the side chain position in formula [1] represents with following formula [5], and this position is the part manifesting tilt angle, determine its size, can be obtained the desirable amount of tilt angle by optimization.
[changing 19]
In formula [5], Y 1, Y 2be phenyl ring or cyclohexane ring independently.Phenyl ring and cyclohexane ring also can have substituting group as required.In addition, in any one in phenyl ring and cyclohexane ring of substituent coupling position, all preferably Isosorbide-5-Nitrae replaces.P, q represent the integer of 0 or 1 independently.Cyclohexane ring is preferably transconfiguration (i.e. chair form).
In formula [5], S 1, S 2be singly-bound or bivalence linking base group independently, S during p=0 1for singly-bound, S during q=0 2for singly-bound.
S 1, S 2object lesson be shown in (S-1) ~ (S-11), but be not limited to this.
[changing 20]
In above-mentioned formula (S-5) ~ (S-8), (S-10) and (S-11), R 4, R 5be 1 valency alkyl of hydrogen atom or carbon number 1 ~ 20, preferably 1 ~ 15 independently.
Here, as 1 valency alkyl, can the alkyl such as exemplified by methyl, ethyl, propyl group, butyl, the tert-butyl group, hexyl, octyl group, decyl; The naphthenic base such as cyclopentyl, cyclohexyl; The bicyclic alkyls such as dicyclohexyl; The alkenyls such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-, 2-or 3-butenyl group, hexenyl; The aryl such as phenyl, xylyl, tolyl, xenyl, naphthyl; The aralkyl etc. such as benzyl, phenethyl, phenylcyclohexyl.
In addition, part or all of the hydrogen atom of these 1 valency alkyl can by the replacement such as halogen atom, hydroxyl, sulfydryl, amino, phosphate-based, ester group, carboxyl, phosphate, thioester substrate, amide group, nitro, organic oxygen base, Organosilyl, organic thiol, organic amino, carbamate groups, acyl group, alkyl, naphthenic base, bicyclic alkyl, alkenyl, aryl, aralkyl.In addition, they also can be ring texturees.
R 4, R 5if aromatic rings or the large structure of alicyclic structure equal-volume, then likely can make that liquid crystal aligning declines, the shape of monomer becomes sticky body shape, be difficult to operation, therefore alkyl or the hydrogen atom such as preferable methyl, ethyl, propyl group, butyl, more preferably hydrogen atom.Particularly preferred S 1, S 2singly-bound ,-O-,-NHCO-or-COO-.
In formula [5], R 1represent hydrogen atom, fluorine atom, there is alkyl or fluoroalkyl or steroid radical that carbon number is 1 ~ 22.Alkyl, fluoroalkyl can be straight-chain or branch-like, also can form contracting ring structure as steroid radical.R 1during for alkyl, be preferably straight-chain, in addition, also can have suitable substituting group.From the viewpoint of synthesis easness and obtain difficulty, preferred R 1for alkyl.To R 1the carbon number of alkyl be not particularly limited, owing to declining when in formula [5], p, q are 0, without tilt angle presentation capability during ring structure, therefore preferred chain alkyl, preferred R 1carbon number be 5 ~ 18, more preferably 7 ~ 15.
In addition, when importing phenyl ring or cyclohexane ring, in order to improve the presentation capability of tilt angle, R 1be preferably the alkyl that carbon number is few.Preferred R 1carbon number be 1 ~ 12, more preferably 3 ~ 10.
The preferred concrete example of the structure represented with formula [5] is shown below.
[table 1]
The structure of side chain Y1 S1 Y2 S2 R1
5-1 － － Phenyl － The alkyl of carbon number 7 ~ 15
5-2 － － Phenyl Singly-bound The alkyl of hydrogen atom or carbon number 1 ~ 12
5-3 － － Phenyl -O- The alkyl of carbon number 5 ~ 12
5-4 － － Phenyl -NHCO- The alkyl of carbon number 5 ~ 12
5-5 － － Phenyl -CONH- The alkyl of carbon number 5 ~ 12
5-6 － － Phenyl -COO- The alkyl of carbon number 5 ~ 12
5-7 － － Phenyl -OCO- The alkyl of carbon number 5 ~ 12
5-8 － － Cyclohexyl Singly-bound The alkyl of hydrogen atom or carbon number 1 ~ 12
5-9 － － Cyclohexyl Singly-bound The alkyl of carbon number 5 ~ 12
5-10 － － Cyclohexyl Singly-bound The alkyl of carbon number 5 ~ 12
5-11 － － Cyclohexyl Singly-bound The alkyl of carbon number 5 ~ 12
5-12 － － Cyclohexyl Singly-bound The alkyl of carbon number 5 ~ 12
5-13 － － Cyclohexyl Singly-bound The alkyl of carbon number 5 ~ 12
5-14 Phenyl Singly-bound Phenyl Singly-bound The alkyl of hydrogen atom or carbon number 1 ~ 10
5-15 Phenyl -O- Phenyl Singly-bound The alkyl of hydrogen atom or carbon number 1 ~ 10
5-16 Phenyl -NHCO- Phenyl Singly-bound The alkyl of hydrogen atom or carbon number 1 ~ 10
5-17 Phenyl -CONH- Phenyl Singly-bound The alkyl of hydrogen atom or carbon number 1 ~ 10
5-18 Phenyl -COO- Phenyl Singly-bound The alkyl of hydrogen atom or carbon number 1 ~ 10
5-19 Phenyl -OCO- Phenyl Singly-bound The alkyl of hydrogen atom or carbon number 1 ~ 10
5-20 Phenyl Singly-bound Phenyl -O- The alkyl of carbon number 3 ~ 10
5-21 Phenyl -O- Phenyl -O- The alkyl of carbon number 3 ~ 10
5-22 Phenyl -NHCO- Phenyl -O- The alkyl of carbon number 3 ~ 10
5-23 Phenyl -CONH- Phenyl -O- The alkyl of carbon number 3 ~ 10
5-24 Phenyl -COO- Phenyl -O- The alkyl of carbon number 3 ~ 10
5-25 Phenyl -OCO- Phenyl -O- The alkyl of carbon number 3 ~ 10
5-26 Phenyl Singly-bound Phenyl -NHCO- The alkyl of carbon number 3 ~ 10
5-27 Phenyl -O- Phenyl -NHCO- The alkyl of carbon number 3 ~ 10
5-28 Phenyl -NHCO- Phenyl -NHCO- The alkyl of carbon number 3 ~ 10
5-29 Phenyl -CONH- Phenyl -NHCO- The alkyl of carbon number 3 ~ 10
5-30 Phenyl -COO- Phenyl -NHCO- The alkyl of carbon number 3 ~ 10
5-31 Phenyl -OCO- Phenyl -NHCO- The alkyl of carbon number 3 ~ 10
5-32 Phenyl Singly-bound Phenyl -COO- The alkyl of carbon number 3 ~ 10
5-33 Phenyl -O- Phenyl -COO- The alkyl of carbon number 3 ~ 10
5-34 Phenyl -NHCO- Phenyl -COO- The alkyl of carbon number 3 ~ 10
5-35 Phenyl -CONH- Phenyl -COO- The alkyl of carbon number 3 ~ 10
5-36 Phenyl -COO- Phenyl -COO- The alkyl of carbon number 3 ~ 10
5-37 Phenyl -OCO- Phenyl -COO- The alkyl of carbon number 3 ~ 10
5-38 Phenyl Singly-bound Phenyl -OCO- The alkyl of carbon number 3 ~ 10
5-39 Phenyl -O- Phenyl -OCO- The alkyl of carbon number 3 ~ 10
5-40 Phenyl -NHCO- Phenyl -OCO- The alkyl of carbon number 3 ~ 10
5-41 Phenyl -CONH- Phenyl -OCO- The alkyl of carbon number 3 ~ 10
5-42 Phenyl -COO- Phenyl -OCO- The alkyl of carbon number 3 ~ 10
5-43 Phenyl -OCO- Phenyl -OCO- The alkyl of carbon number 3 ~ 10
5-44 Phenyl Singly-bound Cyclohexyl Singly-bound The alkyl of hydrogen atom or carbon number 1 ~ 10
5-45 Cyclohexyl Singly-bound Cyclohexyl Singly-bound The alkyl of hydrogen atom or carbon number 1 ~ 10
5-46 － － － － Steroid radical
From the viewpoint of synthesis easness and raw material obtain difficulty, the structure represented with formula [5] is preferably [5-1] ~ [5-3], [5-8], [5-14] ~ [5-19], [5-20], [5-44], [5-45] etc., more preferably [5-1], [5-2], [5-8] etc.
In diaminobenzene skeleton in formula [1], the coupling position of the amino on phenyl ring is not limited.The position of concrete amino can exemplify, and is 2,3,2,4,2,5,2,6,3,4 or 3,5 relative to the position of substitution of side chain.Wherein, consider from reactive viewpoint during synthesizing polyamides acid, preferably 2,4,2,5 or 3,5.If also consider the complexity of synthesizing, then preferably 2,4 (formula 1-1) or 3,5 (formula 1-2).
[changing 21]
Diamines generation thermal cyclization reaction of the present invention: namely, carrying out the deprotection of the hot detachment group of Boc base etc. as above, generating amino when burning till, the amino of generation carries out nucleophilic attack to carbonyl carbon thus forms heterocycle.Therefore, as diamines of the present invention, in diamines, comprise the structure shown in following formula [2].
[changing 22]
Here, C 1, C 2represent singly-bound or divalent organic group independently; A represents the organic group departed from by heating; B 1represent and be selected from-CH 2-, the divalent organic group of-O-,-NH-and-S-; N is 0 or 1; The direction of the linking portion of X is not limited.
With above-mentioned formula [2] as long as in the hot detachment group that represents of A aligning agent for liquid crystal of the present invention firing temperature namely preferably more than 150 DEG C, at more preferably 170 ~ 300 DEG C, particularly preferably 180 ~ 250 DEG C by heating the organic group that can depart from, be not particularly limited.
As hot detachment group, the organic group of the carbamates being representative can be exemplified with benzyloxycarbonyl, 9-fluorenylmethoxycarbonyl groups, allyloxy carbonyl, tert-butoxycarbonyl (Boc yl) etc.Good from the viewpoint of the efficiency departed from by heating, can depart from a lower temperature, gas harmless when departing from, particularly preferably Boc base.
As the preferred example of general formula [2], be shown in following formula [2-1] ~ [2-16].
In addition, the B in formula [2] 1represent and be selected from-CH 2-, the divalent organic group of-O-,-NH-and-S-, to be not particularly limited, but from the viewpoint of obtaining difficulty, the yield of cyclization, the electrical characteristics etc. of alignment films, particularly preferably-O-or NH-.
For the n in formula [2], when coming off by burning till Boc base and generate amino, 5 membered ring heterocyclic can be formed during n=0, during n=1,6 membered ring heterocyclic can be formed.But, during n=1, amino to become far with the distance of carbonyl carbon, be difficult to generation cyclization, therefore from the viewpoint of the efficiency of cyclization, preferred n=0.
[changing 23]
[changing 24]
In formula [2], C 1, C 2represent singly-bound or divalent organic group.If divalent organic group, be not particularly limited, various selection can be carried out according to the acquisition difficulty etc. of the easness of synthesis and raw material.C 1, C 2when being divalent organic group, can represent by the structure represented by formula [6] shown below.
[changing 25]
-S 3-R 2-S 4-R 3- [6]
In formula [6], S 3, S 4be singly-bound or bivalence linking base group independently; R 2, R 3be the divalence hydrocarbon of singly-bound or carbon number 1 ~ 20 independently.
S 3, S 4object lesson identical with above-mentioned formula [S-1] ~ [S-11], but also can be link group in addition.
In formula [6], R 2, R 3when being the divalent hydrocarbon of carbon number 1 ~ 20, following object lesson can be exemplified.
The alkylidenes such as such as methylene, 1,1-ethylidene, 1,2-ethylidene, 1,1-propylidene, 1,2-propylidene, 1,3-propylidene, 1,2-butylidene, Isosorbide-5-Nitrae-butylidene, 2,3-butylidenes, 1,6-hexylidene, 1,8-sub-octyl group, 1,10-sub-decyl can be exemplified; The cycloalkylidenes such as 1,2-cyclopropylidene, 1,2-sub-cyclobutyl, 1,3-sub-cyclobutyl, 1,2-cyclopentylene, 1,1-cyclohexylidene, 1,2-cyclohexylidene, Isosorbide-5-Nitrae-cyclohexylidene; 1,1-ethenylidene, 1,2-ethenylidene, 1,2-ethenylidene methylene, 1-methyl isophthalic acid, 2-ethenylidene, 1,2-ethenylidene-1,1-ethylidene, 1,2-ethenylidene-1,2-ethylidene, 1,2-ethenylidene-1,2-propylidene, 1,2-ethenylidene-1,3-propylidene, 1,2-ethenylidene-Isosorbide-5-Nitrae-butylidene, 1,2-ethenylidene-1,2-butylidene, 1,2-ethenylidene-1, the alkylene groups such as the sub-heptyl of 2-, the sub-decyl of 1,2-ethenylidene-1,2-; Ethynylene, ethynylene methylene, ethynylene-1,1-ethylidene, ethynylene-1,2-ethylidene, ethynylene-1,2-propylidene, ethynylene-1,3-propylidene, ethynylene-Isosorbide-5-Nitrae-butylidene, ethynylene-1,2-butylidene, ethynylene-1, the alkynylenes such as the sub-heptyl of 2-, the sub-decyl of ethynylene-1,2-; 1,2-phenylene, 1,3-phenylene, Isosorbide-5-Nitrae-phenylene, 1,2-naphthylene, 1,4-naphthylene, 1,5-naphthylene, 2,3-naphthylenes, 2,6-naphthylenes, 3-phenyl-1,2-phenylene, 2,2 '-biphenylene, 2, the arlydene such as 2 '-dinaphtho-1,1 '-Ji; 1,2-phenylene methylene, 1,3-phenylene methylene, 1,4-phenylene methylene, 1,2-phenylene-1,1-ethylidene, 1,2-phenylene-1,2-ethylidene, 1,2-phenylene-1,2-propylidene, 1,2-phenylene-1,3-propylidene, 1,2-phenylene-Isosorbide-5-Nitrae-butylidene, 1,2-phenylene-1,2-butylidene, 1,2-phenylene-1,2-hexylidene, methylene-1,2-phenylene methylene, methylene-1, two functional hydrocarbon groups that 3-phenylene methylene, methylene-Isosorbide-5-Nitrae-phenylene methylene etc. are made up of arlydene and alkylidene.
In addition, part or all of the hydrogen atom of above-mentioned divalent alkyl can by the replacement such as halogen atom, hydroxyl, sulfydryl, phosphate-based, ester group, carboxyl, phosphate, thioester substrate, amide group, nitro, organic oxygen base, Organosilyl, organic thiol, organic amino, carbamate groups, acyl group, alkyl, naphthenic base, bicyclic alkyl, alkenyl, aryl, aralkyl.In addition, they also can be ring texturees.
R 2, R 3carbon number fewer, monomer more easily becomes solid, when using as liquid crystal orientation film, in order to improve the stability of tilt angle, the alkynylene of the alkylidene of preferred carbon number 1 ~ 6, the alkylene group of carbon number 1 ~ 6 or carbon number 1 ~ 6.
In formula [6], as C 1coupling position, preferably from 4 or 5 of the position of substitution of the amino protected by Boc base, but which position no matter in 4,5, the structure after cyclisation is all identical, is therefore not particularly limited.
In addition, in formula [6], [-S 4-R 3-] structure represent and C with following formula [4] 1, C 2in either party when there is the structure of formula [4], become the structure that can use in optical alignment method.
[changing 26]
Here, B 2represent and be selected from singly-bound, phenyl ,-CH 2-,-O-,-NH-,-NR 10-and the divalent organic group of-S-; R 10represent the divalence hydrocarbon of carbon number 1 ~ 6.
The olefinic sites of formula [4] can be any one in E formula, Z formula, represents the C of dotted line and the general formula [2] linked with alkene 1the phenyl ring linked or C 2the carbonyl carbon linked links.
The position utilizing light and various reaction occurs with the structure that formula [4] represents.In formula, B 2represent and be selected from singly-bound, phenyl ,-CH 2-,-O-,-NH-,-NR 10-and the divalent organic group of-S-, consider from the easness of synthesis and the difficulty that obtains of raw material, particularly preferably-O-or-NH-.R 10represent the divalence hydrocarbon of carbon number 1 ~ 6.
Consider from the easness of synthesis, the olefinic sites of formula [4] is at C 1place is preferably E formula.In this situation, formula [2] and cinnamate derivates synonym, therefore from easily carrying out light reaction consideration, are particularly preferred.
On the other hand, to C 2the olefinic sites at place is not particularly limited.In addition, C 2when comprising the structure represented with formula [4], become by utilizing heat to carry out cyclisation and there is light reaction.On the contrary, when carrying out cyclisation, light reaction is less likely to occur, and thinks monomer or use the aligning agent for liquid crystal of this monomer and liquid crystal orientation film to affect more less than cinnamate derivative in the past by UV-induced deterioration etc., consider from this viewpoint, more preferably C 2it is the structure of formula [4].
As the preferred object lesson of formula [2], following formula [2-17] ~ [2-32] is shown.
[changing 27]
Formula [2-17] ~ [2-20] and [2-25] ~ [2-28] is changing into following shown formula [2-33] ~ [2-40] when burning till, think and can obtain the effect identical with cinnamate by this.
[changing 28]
The structure of particularly preferred diamines is shown below, but is not limited thereto.
[changing 29]
[changing 30]
In formula [7-1] ~ [7-6], B 1represent-O-or NH-; C 1, C 2represent singly-bound or divalent organic group independently; Y 1, Y 2for phenyl ring or cyclohexyl ring; S 1, S 2for singly-bound or bivalence linking base group; P, q represent the integer of 0 or 1; S during p=0 1for singly-bound, S during q=0 2for singly-bound; R 1represent the alkyl of proton or carbon number 1 ~ 22.
The object lesson of the structure of diamines is shown below.
[changing 31]
[changing 32]
[changing 33]
The synthesis > of < diamines of the present invention
[changing 34]
Substituent X synthesizes the precursor of object construction by following method: the compound for the protection of hot detachment groups such as Boc bases making di-tert-butyl dicarbonate etc. and the o-phenylenediamine, Ortho-Aminophenol, 2-aminobenzene mercaptan etc. (substrate) that are substituted act in a solvent.Now, as required, yield and reaction velocity can be improved by making the alkali such as itself and pyridine, DMAP, triethylamine coexist.On the other hand, if reacted by coexisting with these alkali, then become and import the product of the hot detachment group of 2 unit relative to amino or in hydroxyl, be imported with the product of hot detachment group, therefore, preferably adopt more suitably condition corresponding to the substrate carrying out reacting.
[changing 35]
The position making to represent with formula [2], namely there is cyclisation position towards diaminobenzene side time; following method can be exemplified: obtaining X is the substituent material not replacing or have side chain shape; amino with hot detachment radical protection by said method, change into the method for diamines after importing dinitro benzene.Concrete synthesis example is shown below.
[changing 36]
On the other hand; when making the position of generation cyclisation towards side chain side; following method can be exemplified: protect the X of above-mentioned formula in advance or the substituent state of the inertia transformed can occur after becoming in advance; the amino adjacent with the amino by hot detachment radical protection or hydroxyl import side chain; then X is changed into active substituting group etc., after being imported by dinitro benzene, change into the method for diamines again.Concrete synthesis example is shown below.
[changing 37]
Can synthesizing amide key by the condensation reaction of carboxylic acid and amine, carrying out condensation reaction by making carboxylic acid and alcohol or phenol can synthesize ester bond.This reaction obtains by following method: in the solvent do not reacted with carboxylic acid, amine and alcohol, and in the presence of base, makes the method that carboxylic acid halides and amine, alcohol or phenol react; Or under the existence of condensation agent, make the method that carboxylic acid and amine, alcohol or phenol react.
Carboxylic acid halides reacts by making carboxylic acid and suitable halogenating agent and obtains.From the viewpoint of versatility, the carboxylic acid halides used is preferably carbonyl chloride compound, such as phosgene.Phosgene is by making carboxylic acid and chlorination reaction and obtaining.As the example of chlorating agent, thionyl chloride, phosphoryl chloride phosphorus oxychloride, sulfonic acid chloride, oxalyl chloride, phosphorus trichloride, phosphorous pentachloride etc. can be exemplified, angularly consider from the easness of versatility, removing, preferred thionyl chloride, sulfonic acid chloride, oxalyl chloride etc., particularly preferably thionyl chloride or oxalyl chloride.
In addition, as the solvent that above-mentioned reaction uses, METHYLPYRROLIDONE, gamma-butyrolacton, DMF, N can be exemplified, N-dimethyl acetamide, tetrahydrofuran, chloroform, ethylene dichloride, methylene chloride, tetrahydrofuran, oxinane, Isosorbide-5-Nitrae-two alkane etc.As the alkali used during condensation reaction, the organic bases such as pyridine, DMAP, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine, N-methylmorpholine can be exemplified, also can exemplify according to circumstances and use the method (Xiao Teng-Bao Man reaction method) of the inorganic base aqueous solution such as sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
When carrying out condensation reaction under the existence of condensation agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride, N can be used, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazines methyl morpholine , O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylurea (TMU) tetrafluoro boric acid ester, O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylurea (TMU) hexafluorophosphoric acid ester, (2,3-dihydro-2-sulfo--3-benzo azoles) condensation agent such as phosphonic acid diphenyl ester, 4-(4,6-dimethoxy-1,3,5-triazines-2-base) 4-methoxyl morpholine hydrochloride n hydrate.
In addition, in the method using above-mentioned condensation agent, by adding lewis acid as adjuvant, reaction can be carried out efficiently.As lewis acid, the lithium halides such as preferred lithium chloride, lithium bromide.Lewis acidic addition is relative to C 1molal quantity be preferably 0.1 ~ 1.0 times mole.
With the C of general formula [2] 1, C 2in the link group represented, as preferred C 1, C 2structure, the divalent organic group that following formula [6] represents can be exemplified.
[changing 38]
－Ｓ ３－Ｒ ２－Ｓ ４－Ｒ ３［６］
Here, S 3, S 4be singly-bound or bivalence linking base group independently; R 2, R 3be the divalence hydrocarbon of singly-bound or carbon number 1 ~ 20 independently.As concrete example, the diamines of formula [1-c], formula [1-i], formula [1-h] can be exemplified.
[changing 39]
The diamines of formula [4-c] can synthesize towards the method for side chain according to above-mentioned cyclisation position.
[changing 40]
In the synthesis of the diamines of formula [4-i] and formula [4-h], can synthesize according to the method for above-mentioned cyclisation position towards diamines side, but synthetic method also can be method in addition, so there is no be particularly limited to.
When importing alkene structures in diamines, the constitutional isomer of E (instead) formula and Z (suitable) formula can obtain same effect.By using fumaric acid to synthesize during synthesis E formula, Z formula is synthesized by using maleic acid.As the synthetic method of E formula, utilize the isomerization reaction of Z formula to carry out the method for synthesizing in addition, due to compared with the synthetic method via fumaric acid, selectivity, good yield that can be more excellent synthesize, therefore no matter be E formula or Z formula, all preferably use the method for maleic acid.
In the diamines synthesis example of formula [4-i] and formula [4-h], have and form the step of ehter bond, ehter bond is by Williamson ether synthesis, namely make alkyl halide or aryl halide and alcohol obtain with the synthetic method of carrying out reacting in their nonreactive solvents in the presence of a base.In addition, also can by using the method for palladium catalyst etc., copper is used for the method etc. of catalyzer and obtains.Preferred method can be selected according to the substrate carrying out reacting.If consider reacted aftertreatment and cost aspect, then preferred Williamson ether synthesis.Used alkali is not particularly limited, the inorganic bases such as sodium hydride, hydrofining, sal tartari, NaOH, sodium alkoxide, potassium alcoholate can be used, or the organic base such as triethylamine, trimethylamine, tri-n-butylamine, trioctylamine.
By using above-mentioned synthetic method etc., synthesis dinitro benzene derivant [8], changes into amino by common reduction reaction by nitro, thus can obtain targeted diamine.To the method for reduction dinitro compound, there is no particular limitation, usually has by using palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-aluminium oxide, platinum sulfide carbon etc. as catalyzer, at ethyl acetate, toluene, tetrahydrofuran, two in alkane, alcohols solvent equal solvent, carry out the method for reducing with hydrogen, hydrazine, hydrogen chloride etc.As required, also reactor etc. can be used.On the other hand, when comprising unsaturated link position in structure, if use palladium carbon, platinum carbon etc., then likely unsaturated link position is reduced and becomes saturated bond, therefore as desirable condition, preferably use the transition metal such as reduced iron, tin, tin chloride as the reducing condition of catalyzer.
[changing 41]
< polymkeric substance > of the present invention
Polymkeric substance of the present invention refers to polyimide precursor, this polyimide precursor obtains through imidizate polyimide, polyamide.Here, polyimide precursor refers to polyamic acid and poly amic acid ester.Diamines of the present invention is by reacting to obtain polyamic acid side chain with ad hoc structure with tetrabasic carboxylic acid or derivatives thereofs such as tetrabasic carboxylic acid, tetrabasic carboxylic acid two carboxylic acid halides, tetracarboxylic dianhydrides.In addition, by tetrabasic carboxylic acid diester diacid chloride and diamines reaction or tetrabasic carboxylic acid diester and diamines are reacted under the existence of suitable condensation agent and alkali, thus obtain poly amic acid ester.Further, by making above-mentioned polyamic acid dehydration closed-loop or at high temperature heating poly amic acid ester to promote dealcoholysis, to carry out closed loop, thus polyimide side chain with ad hoc structure can be obtained.
< polyamic acid and poly amic acid ester >
Polyamic acid of the present invention is by obtaining containing the diamine component of diamines represented with formula [1] and the reaction of tetracarboxylic dianhydride.In addition, poly amic acid ester of the present invention carries out reacting obtaining under the existence of suitable condensation agent and alkali by making the diamine component containing the diamines represented with formula [1] and tetrabasic carboxylic acid diester diacid chloride carry out in the presence of a base to react or make tetrabasic carboxylic acid diester and diamines.Polyimide of the present invention is by making this polyamic acid carry out dehydration closed-loop or heating to make its closed loop to obtain to poly amic acid ester.As the polymkeric substance for obtaining liquid crystal orientation film, any one in above-mentioned polyamic acid, poly amic acid ester and polyimide is all useful.
For by reacting to obtain in the diamine component (hereinafter also referred to diamine component) of polyamic acid with above-mentioned tetracarboxylic dianhydride, proportional less than limiting to containing of the diamines represented with formula [1].Use above-mentioned polyamic acid or polyimide and in the liquid crystal orientation film of the present invention that obtains, the diamines represented with formula [1] in above-mentioned diamine component containing proportional higher, the tilt angle of liquid crystal is larger.
With regard to reaching the object of the tilt angle increasing liquid crystal, more than 1 % by mole of preferred diamine component is the diamines represented with formula [1].With the side-chain structure of formula [1] or the alignment mode difference of liquid crystal, content has difference, therefore the preferred content of unnecessary setting, but in TN pattern, ocb mode etc., also must consider horizontal alignment constraining force, that is therefore polymerized the diamines represented with formula [1] in the diamine component that uses is preferably 1 ~ 50 % by mole, particularly preferably 5 ~ 30 % by mole containing proportional.
With regard to reach make liquid crystal vertically orientation object with regard to, also can be 100 % by mole of diamines represented for formula [1] of diamine component.Diamines due to formula [1] can make the polymeric viscosity of polymkeric substance greatly reduce, and causes the viscosity of aligning agent for liquid crystal, and therefore in flexographic printing etc., for obtaining required thickness, the content of the diamines of preferred formula [1] is 30 ~ 70 % by mole.
In above-mentioned diamine component, when the diamines represented with formula (1) is lower than 100 % by mole, the concrete example of the diamines (hereinafter also referred to other diamines) beyond the diamines represented with formula (1) used is as follows.
The example of alicyclic diamine class can exemplify: Isosorbide-5-Nitrae-diamino-cyclohexane, 1,3-diamino-cyclohexane, 4,4 '-diamino-dicyclohexyl methane, 4,4 '-diamido-3,3 '-dimethyidicyclohexyl amine, isophorone diamine etc.
The example of aromatic diamines can exemplify: o-phenylenediamine, m-phenylene diamine, p-phenylenediamine (PPD), 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, Isosorbide-5-Nitrae-diamido-2-methoxybenzene, 2,5-diamido P-xylene, 1,3-diamido-4-chlorobenzene, 3,5-diaminobenzoic acid, Isosorbide-5-Nitrae-diamido-2,5-dichloro-benzenes, 4,4 '-diaminostilbene, 2-diphenylethane, 4,4 '-diamido-2,2 '-dimethyl bibenzyl, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diamido-3,3 '-dimethyl diphenylmethane, 2,2 '-diamido Stilbene, 4,4 '-diamido Stilbene, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diamino diphenyl sulfide, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diaminobenzophenone, two (3-amino-benzene oxygen) benzene of 1,3-, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzoic acid of 3,5-, 4,4 '-bis-(4-amino-benzene oxygen) bibenzyl, two [(4-amino-benzene oxygen) methyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two (4-aminophenyl) cyclohexane of 1,1-, α, α '-bis-(4-aminophenyl)-Isosorbide-5-Nitrae-diisopropyl benzene, two (4-aminophenyl) fluorenes of 9,9-, two (3-aminophenyl) HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-diamino-diphenyl amine, 2,4-diamino-diphenyl amine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diamino-anthraquinone, 1,3-diamido pyrene, 1,6-diamido pyrene, 1,8-diamido pyrene, 2,7-diamino-fluorene, two (4-aminophenyl) tetramethyl disiloxane of 1,3-, biphenylamine, 2,2 '-dimethylbenzidine, two (4-aminophenyl) ethane of 1,2-, two (4-aminophenyl) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) butane, two (4-aminophenyl) pentane of 1,5-, two (4-aminophenyl) hexane of 1,6-, two (4-aminophenyl) heptane of 1,7-, two (4-aminophenyl) octane of 1,8-, two (4-aminophenyl) nonane of 1,9-, two (4-aminophenyl) decane of 1,10-, two (4-amino-benzene oxygen) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) butane, two (4-amino-benzene oxygen) pentane of 1,5-, two (4-amino-benzene oxygen) hexane of 1,6-, two (4-amino-benzene oxygen) heptane of 1,7-, two (4-amino-benzene oxygen) octane of 1,8-, two (4-amino-benzene oxygen) nonane of 1,9-, two (4-amino-benzene oxygen) decane of 1,10-, two (4-aminophenyl) 1,3-malonate, two (4-aminophenyl) 1, 4-succinic acid ester, two (4-aminophenyl) 1,5-glutarate, two (4-aminophenyl) 1,6-adipate, two (4-aminophenyl) 1,7-pimelate, two (4-aminophenyl) 1,8-suberate, two (4-aminophenyl) 1,9-azelate, two (4-aminophenyl) 1,10-sebacate, two [4-(4-amino-benzene oxygen) phenoxy group] propane of 1,3-, Isosorbide-5-Nitrae-bis-[4-(4-amino-benzene oxygen) phenoxy group] butane, two [4-(4-amino-benzene oxygen) phenoxy group] pentane of 1,5-, two [4-(4-amino-benzene oxygen) phenoxy group] hexane of 1,6-, two [4-(4-amino-benzene oxygen) phenoxy group] heptane of 1,7-, two [4-(4-amino-benzene oxygen) phenoxy group] octane of 1,8-, two [4-(4-amino-benzene oxygen) phenoxy group] nonane of 1,9-, two [4-(4-amino-benzene oxygen) phenoxy group] decane of 1,10-etc.
The example of aromatic-aliphatic diamines can exemplify: 3-aminobenzene methyl amine, 4-aminobenzene methyl amine, 3-Amino-N-methyl benzyl amine, 4-Amino-N-methyl benzyl amine, 3-aminophenethyl amine, 4-aminophenethyl amine, 3-Amino-N-methyl phenethyl amine, 4-Amino-N-methyl phenethyl amine, 3-(3-aminopropyl) aniline, 4-(3-aminopropyl) aniline, 3-(3-dimethylaminopropyl) aniline, 4-(3-dimethylaminopropyl) aniline, 3-(4-aminobutyl) aniline, 4-(4-aminobutyl) aniline, 3-(4-methylamino butyl) aniline, 4-(4-methylamino butyl) aniline, 3-(5-Aminopentyl) aniline, 4-(5-Aminopentyl) aniline, 3-(5-methylamino-pentyl) aniline, 4-(5-methylamino-pentyl) aniline, 2-(the amino naphthyl of 6-) methyl amine, 3-(the amino naphthyl of 6-) methyl amine, 2-(the amino naphthyl of 6-) ethylamine, 3-(the amino naphthyl of 6-) ethylamine etc.
The example of hetero ring type Diamines can exemplify: DAP, 2,4-diamino-pyridines, 2,4-diamino-1,3,5-triazines, 2,7-diamido dibenzofurans, 3,6-diaminocarbazole, 2,4-diamido-6-isopropyls-1,3,5-triazine, 2, two (the 4-aminophenyl)-1,3,4-of 5- diazole etc.
The example of aliphatic diamine class can exemplify: 1, 2-diaminoethanes, 1, 3-diaminopropanes, 1, 4-diaminobutane, 1, 5-1,5-DAP, 1, 6-diamino hexane, 1, 7-diaminoheptane, 1, 8-diamino-octane, 1, 9-diamino nonane, 1, 10-diamino decane, 1, 3-diamido-2, 2-dimethylpropane, 1, 6-diamido-2, 5-dimethylhexane, 1, 7-diamido-2, 5-dimethyl heptane, 1, 7-diamido-4, 4-dimethyl heptane, 1, 7-diamido-3-methylheptane, 1, 9-diamido-5-methylheptane, 1, 12-diamino dodecane, 1, 18-diamido octadecane, 1, 2-two (the amino propoxyl group of 3-) ethane etc.
Also can be used together and there is alkyl on side chain, containing fluoroalkyl, aromatic rings, aliphatics ring, heterocycle or the diamine compound of large ring-type substituent that is made up of them.Specifically, the diamines represented with following formula [DA1] ~ formula [DA26] can be illustrated.
[changing 42]
(R 6to be carbon number be 1 ~ 22 alkyl or containing fluoroalkyl.)
[changing 43]
(S 5represent-COO-,-OCO-,-CONH-,-NHCO-,-CH 2-,-O-,-CO-or-NH-; R 6represent that carbon number is the alkyl of 1 ~ 22 or contains fluoroalkyl.)
[changing 44]
(S 6represent-O-,-OCH 2-,-CH 2o-,-COOCH 2-or-CH 2oCO-; R 7to be carbon number be 1 ~ 22 alkyl, alkoxy, containing fluoroalkyl or fluoroalkoxy.)
[changing 45]
(S 7represent-COO-,-OCO-,-CONH-,-NHCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-or-CH 2-; R 8to be carbon number be 1 ~ 22 alkyl, alkoxy, containing fluoroalkyl or fluoroalkoxy.)
[changing 46]
(S 8represent-COO-,-OCO-,-CONH-,-NHCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-,-CH 2-,-O-or-NH-; R 9for fluorine-based, cyano group, trifluoromethyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group or hydroxyl.)
[changing 47]
[changing 48]
(R 10to be carbon number be 3 ~ 12 alkyl, the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene is respectively trans.)
[changing 49]
When utilizing light to carry out orientation process, by also with the diamines of general formula [1] and the diamines of above-mentioned [DA-1] ~ [DA-26], more stable tilt angle can be obtained, therefore preferably.As can and preferred diamines, the diamines of preferred formula [DA-10] ~ [DA-26], the more preferably diamines of formula [DA-10] ~ [DA-16].The preferred content of these diamines is not particularly limited, but is preferably 5 ~ 50 % by mole in diamine component, from the viewpoint of printing, preferably 5 ~ 30 % by mole.
In addition, also can be used together following diamines.
[changing 52]
(m is the integer of 0 ~ 3; In formula [DA-34], n is the integer of 1 ~ 5).
By the diamines containing formula [DA-27], formula [DA-28] etc., can improve voltage retention performance when making liquid crystal orientation film, the diamines of formula [DA-29] ~ [DA-34] has to reduce accumulates charged effect.
Further, as other diamines, the diamido siloxane etc. represented with following formula [DA-35] also can be exemplified.
[changing 53]
(m is the integer of 1 ~ 10.)
Other diamine compound according to the characteristic such as liquid crystal aligning, voltage retention performance, accumulated charge when making liquid crystal orientation film, can use a kind or two or more is used in combination.
Be not particularly limited with the tetracarboxylic dianhydride that diamine component reacts for for obtaining polyamic acid of the present invention.Exemplify its object lesson below:
The tetracarboxylic dianhydride with ester ring type structure or aliphatic structure can exemplify 1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 2-dimethyl-1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 3-dimethyl-1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 2, 3, 4-tetramethyl-1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentane tetracarboxylic dianhydride, 2, 3, 4, 5-tetrahydrofuran tetracarboxylic dianhydride, 1, 2, 4, 5-cyclopentanetetracarboxylic dianhydride, 3, 4-dicarboxyl-1-cyclohexyl succinic acid dianhydride, 3, 4-dicarboxyl-1, 2, 3, 4-tetrahydrochysene-1-naphthalene succinic dianhydride, 1, 2, 3, 4-butane tetracarboxylic acid dianhydride, two rings [3, 3, 0] octane-2, 4, 6, 8-tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-dicyclohexyl tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, cis-3, 7-dibutyl ring pungent-1, 5-diene-1, 2, 5, 6-tetracarboxylic dianhydride, three ring [4.2.1.0 2,5] nonane-3,4,7,8-tetrabasic carboxylic acid-3,4:7,8-dianhydride, six ring [6.6.0.1 2,7.0 3,6.1 9,14.0 10,13] hexadecane-4,5,11,12-tetrabasic carboxylic acid-4,5:11,12-dianhydride, 4-(2,5-dioxotetrahydro furans-3-base)-1,2,3,4-tetrahydro-naphthalene-1,2-dicarboxylic anhydride etc.
Further, if also use aromatic tetracarboxylic acid's dianhydride outward the above-mentioned tetracarboxylic dianhydride with ester ring type structure or aliphatic structure, then can improve liquid crystal aligning, and the accumulated charge of liquid crystal cell can be reduced, therefore preferably.
As aromatic tetracarboxylic acid's dianhydride, pyromellitic acid anhydride, 3 can be exemplified, 3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyphenyi) ether dianhydride, two (3,4-dicarboxyphenyi) sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydrides etc.
Tetracarboxylic dianhydride can according to the characteristic such as liquid crystal aligning, voltage retentivity, accumulated charge when making liquid crystal orientation film, uses one or and with two or more.
Be not particularly limited with the tetrabasic carboxylic acid dialkyl that diamine component reacts for for obtaining poly amic acid ester of the present invention.Exemplify its object lesson below:
The object lesson of aliphatics tetrabasic carboxylic acid diester can exemplify 1, 2, 3, 4-cyclo-butane tetrabasic carboxylic acid dialkyl, 1, 2-dimethyl-1, 2, 3, 4-cyclo-butane tetrabasic carboxylic acid dialkyl, 1, 3-dimethyl-1, 2, 3, 4-cyclo-butane tetrabasic carboxylic acid dialkyl, 1, 2, 3, 4-tetramethyl-1, 2, 3, 4-cyclo-butane tetrabasic carboxylic acid dialkyl, 1, 2, 3, 4-cyclopentane tetrabasic carboxylic acid dialkyl, 2, 3, 4, 5-tetrahydrofuran tetrabasic carboxylic acid dialkyl, 1, 2, 4, 5-cyclopentanetetracarboxylic dialkyl, 3, 4-dicarboxyl-1-cyclohexyl dialkyl succinate, 3, 4-dicarboxyl-1, 2, 3, 4-tetrahydrochysene-1-naphthalene succinic dialkyl, 1, 2, 3, 4-butane tetracarboxylic acid dialkyl ester, two rings [3, 3, 0] octane-2, 4, 6, 8-tetrabasic carboxylic acid dialkyl, 3, 3 ', 4, 4 ' dicyclohexyl tetrabasic carboxylic acid dialkyl, 2, 3, 5-tricarboxylic cyclopentyl dialkyl acetates, cis-3, 7-dibutyl ring pungent-1, 5-diene-1, 2, 5, 6-tetrabasic carboxylic acid dialkyl, three ring [4.2.1.0 2,5] nonane-3,4,7,8-tetrabasic carboxylic acid-3,4:7,8-dialkyl, six ring [6.6.0.1 2,7.0 3,6.1 9,14.0 10,13] hexadecane-4,5,11,12-tetrabasic carboxylic acid-4,5:11,12-dialkyl, 4-(2,5-dioxotetrahydro furans-3-base)-1,2,3,4-tetrahydro-naphthalene-1,2-dicarboxylic acid dialkyl esters etc.
As aromatic tetracarboxylic acid's dialkyl, Pyromellitic Acid dialkyl, 3 can be exemplified, 3 ', 4,4 '-biphenyltetracarboxyacid acid dialkyl, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid dialkyl, 2,3,3 ', 4-biphenyltetracarboxyacid acid dialkyl, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dialkyl, 2,3,3 ', 4-benzophenone tetrabasic carboxylic acid dialkyl, two (3,4-dicarboxyphenyi) ether dialkyl, two (3,4-dicarboxyphenyi) sulfone dialkyl, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl etc.
The synthesis > of < polyamide
Be not particularly limited with the dicarboxylic acid that diamine component reacts for for obtaining polyamide of the present invention.As the object lesson of the aliphatic dicarboxylic acid of dicarboxylic acid or derivatives thereof, malonic acid, oxalic acid, dimethyl malonic acid, succinic acid, fumaric acid, glutaric acid, hexane diacid, muconic acid, 2-methyl hexane diacid, trimethyladipic acid, heptandioic acid, 2 can be exemplified, 2-dimethylated pentanedioic acid, 3,3-diethyl succinic acids, azelaic acid, decanedioic acid, suberic acid etc.
As the dicarboxylic acid of ester ring type class, 1,1-cyclopropane dicarboxylic acid can be exemplified, 1,2-cyclopropane dicarboxylic acid, 1,1-cyclobutane dicarboxylic acid, 1,2-cyclobutane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 3,4-diphenyl-1,2-cyclobutane dicarboxylic acid, 2,4-diphenyl-1,3-cyclobutane dicarboxylic acid, 1-cyclobutane-1,2-dicarboxylic acid, 1-cyclobutane-3,4-dicarboxylic acid, 1,1-cyclopentane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,1-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-(2-norborene) dicarboxylic acid, norborene-2,3-dicarboxylic acid, two rings [2.2.2] octane-Isosorbide-5-Nitrae-dicarboxylic acid, two rings [2.2.2] octane-2,3-dicarboxylic acid, 2,5-dioxo-Isosorbide-5-Nitrae-two ring [2.2.2] octane dicarboxylic acid, 1,3-diamantane dicarboxylic acid, 4,8-dioxo-1,3-diamantane dicarboxylic acid, 2,6-spiral shell [3.3] heptane dicarboxylic acid, 1,3-diamantane oxalic acid, camphoric acid etc.
As aromatic dicarboxylic acid, phthalic acid can be exemplified, m-phthalic acid, terephthalic acid (TPA), oreinol dioctyl phthalate, 5-tert-butyl isophthalic acid, 5-amino isophthalic acid, 5-Hydroxy M Phthalic Acid, 2,5-dimethyl terephthalic acid, tetramethyl terephthalic acid (TPA), Isosorbide-5-Nitrae-naphthalene dicarboxylic acids, 2,5-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, 2,7-naphthalene dicarboxylic acids, Isosorbide-5-Nitrae-anthracene dicarboxylic acid, Isosorbide-5-Nitrae-anthraquinone dicarboxylic acid, 2,5-diphenyl dicarboxylic acid, 4,4 '-diphenyl dicarboxylic acid, 1,5-diphenylene dicarboxylic acids, 4,4 "-terphenyl dicarboxylic acid, 4,4 '-diphenyl methane dicarboxylic acid, 4,4 '-diphenylethane dicarboxylic acid, 4,4 '-diphenyl propane dicarboxylic acid, 4,4 '-diphenyl HFC-236fa dicarboxylic acid, 4,4 '-diphenyl ether dicarboxylic acid, 4,4 '-dibenzyl dicarboxylic acid, 4,4 '-stilbene dicarboxylic acid, 4,4 '-tolane dicarboxylic acid, 4,4 '-carbonyl dibenzoic acid, 4,4 '-sulfonyl dibenzoic acid, 4,4 '-dithiodibenzoic acid, to phenylenediacetic acid, 3,3 '-to phenylene dipropionic acid, 4-o-carboxy cinnamic acid, to phenylene diacrylate, 3,3 '-[4,4 '-(methylene two pairs of phenylenes)] dipropionic acid, 4,4 '-[4,4 '-(oxygen base two pairs of phenylenes)] dipropionic acid, 4,4 '-[4,4 '-(oxygen base two pairs of phenylenes)] two butyric acid, (isopropylidene two pairs of phenylene dioxy bases) two butyric acid, two (to carboxyl phenyl) dimethylsilane etc.
As the dicarboxylic acid containing heterocycle, 1,5-(9-oxo fluorenes) dicarboxylic acid, 3,4-furans dicarboxylic acid, 4,5-thiazole dicarboxylic acid, 2-phenyl-4,5-thiazole dicarboxylic acid, 1,2,5-thiadiazoles-3,4-dicarboxylic acid, 1,2,5-can be exemplified diazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acids, 2,4-pyridinedicarboxylic acids, 2,5-Pyridinedicarboxylic acid, 2, dipicolimic acid 2,3,4-pyridinedicarboxylic acids, 3,5-pyridinedicarboxylic acids etc.
Above-mentioned various dicarboxylic acid also can have the structure of sour two carboxylic acid halides or acid anhydrides.In these omega-dicarboxylic acids, particularly can provide the omega-dicarboxylic acids of the polyamide of linear structure, from keeping the orientation of liquid crystal molecule to consider, be preferred.Wherein, preferred use terephthalic acid (TPA), m-phthalic acid (acid of イ ソ テ レ Off タ Le), 1,4-cyclohexane dicarboxylic acid, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-diphenyl methane dicarboxylic acid, 4,4 '-diphenylethane dicarboxylic acid, 4,4 '-diphenyl propane dicarboxylic acid, 4,4 '-diphenyl HFC-236fa dicarboxylic acid, 2,2-bis-(phenyl) propane dicarboxylic acid, 4,4-terphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acids, 2,5-Pyridinedicarboxylic acid or their acid two carboxylic acid halides etc.Sometimes also there is isomeride in these compounds, also can be the potpourri comprising isomeride.In addition, the compound that also two or more kinds may be used.
When obtaining polyamide of the present invention by the reaction of dicarboxylic acid and diamine component, known synthetic method can be adopted.Normally make the method that dicarboxylic acid and diamine component react in organic solvent.
The synthesis > of < polyamic acid
Obtained the method for polyamic acid of the present invention by the reaction of tetracarboxylic dianhydride and diamine component, known method can be adopted.Normally make the method that tetracarboxylic dianhydride and diamine component react in organic solvent.The reaction of tetracarboxylic dianhydride and diamines is carried out than being easier in organic solvent, and is favourable not generating in accessory substance this point.
As the organic solvent of the reaction for tetracarboxylic dianhydride and diamines, as long as the solvent of the polyamic acid of solubilized generation is not particularly limited.Exemplify its object lesson below:
DMF can be exemplified, DMA, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton, isopropyl alcohol, methoxy amylalcohol, cinene, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, DPGME, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethylether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic acid esters, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, two alkane, normal hexane, normal heptane, normal octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, lactic acid ethyl, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethylether, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy-propionic acid methyl ethyl ester, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxyl-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide etc.These can be used alone, also can be used in combination.Further, even the solvent of polyamic acid can not be dissolved, in the scope that the polyamic acid generated is not separated out, may be combined in above-mentioned solvent and use.
In addition, the moisture in organic solvent hinders polyreaction, and the polyamic acid of generation can be made to be hydrolyzed, and therefore organic solvent preferably uses the organic solvent through farthest dehydrating.
Following method can be exemplified: the solution that stirring makes diamine component be dispersed or dissolved in organic solvent and obtains, the method for then directly adding tetracarboxylic dianhydride or adding again after making tetracarboxylic dianhydride be dispersed or dissolved in organic solvent when tetracarboxylic dianhydride and diamine component are reacted in organic solvent; The method of diamine component is added in the solution obtained tetracarboxylic dianhydride is dispersed or dissolved in organic solvent on the contrary; Alternately add the method etc. of tetracarboxylic dianhydride and diamine component, also can use any one method wherein.In addition, when tetracarboxylic dianhydride or diamine component are made up of multiple compounds, can it be made to react under the state be pre-mixed, it also can be made to react successively respectively, can also make to react respectively and the low-molecular weight hybrid reaction obtained and obtain high molecular body.
Polymerization temperature now can select the arbitrary temp of-20 ~ 150 DEG C, preferably the scope of-5 ~ 100 DEG C.In addition, reaction can be carried out with arbitrary concentration, if but concentration is too low, be difficult to the polymkeric substance obtaining high molecular, if excessive concentration, the viscosity of reactant liquor becomes too high and is difficult to stir uniformly, therefore tetracarboxylic dianhydride and the diamine component total concentration in reaction solution is preferably 1 ~ 50 quality %, more preferably 5 ~ 30 quality %.Initial reaction stage is carried out in higher concentrations, can add organic solvent afterwards.
In the polyreaction of polyamic acid, the ratio of the total mole number of tetracarboxylic dianhydride and the total mole number of diamine component is preferably 0.8 ~ 1.2, and more preferably 0.9 ~ 1.1.Identical with common polycondensation reaction, this mol ratio is more close to 1.0, and the molecular weight of the polyamic acid of generation is larger.
The synthesis > of < polyimide
Polyimide of the present invention is the polyimide making above-mentioned polyamic acid dehydration closed-loop and obtain, and is useful as the polymkeric substance for obtaining liquid crystal orientation film.
In polyimide of the present invention, the dehydration closed-loop rate (acid imide rate) of acid amides acidic group does not need one to be decided to be 100%, can adjust arbitrarily according to purposes or object.
The hot-imide method of the solution of directly heating polyamic acid can be exemplified as the method making polyamic acid carry out imidizate and in the solution of polyamic acid, add the catalysis imidizate method of catalyzer.
Temperature when making polyamide acid heat carry out imidizate is in the solution 100 ~ 400 DEG C, and preferably 120 ~ 250 DEG C is better carry out imidizate while draining into outside system by the water generated by imidization reaction.
The catalysis imidizate of polyamic acid is by adding base catalyst and acid anhydrides in polyamic acid solution, and stirs at-20 ~ 250 DEG C, preferably 0 ~ 180 DEG C and carry out.The amount of base catalyst is 0.5 ~ 30 mole times of acid amides acidic group, preferably 2 ~ 20 moles times, and the amount of acid anhydrides is 1 ~ 50 mole times of acid amides acidic group, preferably 3 ~ 30 moles times.As base catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be exemplified, wherein pyridine have for make reaction carry out for appropriateness alkalescence, therefore preferably.As acid anhydrides, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc. can be exemplified, wherein, use during acetic anhydride and be easy to carry out reacting the purifying after terminating, therefore preferably.Adopt the acid imide rate of catalysis imidizate can be controlled by adjustment catalytic amount, temperature of reaction, the reaction time etc.
The synthesis > of < poly amic acid ester
As the method for synthesizing polyamides acid esters, the method that can exemplify tetrabasic carboxylic acid diester diacid chloride and diamine reactant and the method that tetrabasic carboxylic acid diester and diamines are reacted under the existence of suitable condensation agent and alkali, or in advance polyamic acid is polymerized, recycling high molecular weight reactive carries out esterification method to the carboxylic acid in amic acid.
Specifically, can by making tetrabasic carboxylic acid diester diacid chloride and diamines under the existence of alkali and organic solvent, and reaction 30 minutes at-20 ~ 150 DEG C, preferably 0 ~ 50 DEG C ~ 24 hours, preferably 1 ~ 4 hour, synthesize.
Above-mentioned alkali can use pyridine, triethylamine, 4-dimethylaminopyridine etc., in order to make reaction leniently carry out, and preferred pyridine.Can easily obtain high molecular body from the viewpoint of with the amount easily removed, the addition of alkali is preferably 2 ~ 4 times moles relative to tetrabasic carboxylic acid diester diacid chloride.
When carrying out polycondensation reaction under the existence of condensation agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride, N can be used, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazines methyl morpholine , O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylurea (TMU) tetrafluoro boric acid ester, O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylurea (TMU) hexafluorophosphoric acid ester, (2,3-dihydroxy-2-sulfo--3-benzo azoles) condensation agent such as phosphonic acid diphenyl ester, 4-(4,6-dimethoxy-1,3,5-triazines-2-base) 4-methoxyl morpholine hydrochloride n hydrate.
In addition, in the method using above-mentioned condensation agent, by adding lewis acid as adjuvant, reaction can be carried out efficiently.As lewis acid, the lithium halides such as preferred lithium chloride, lithium bromide.Lewis acidic addition is preferably 0.1 ~ 1.0 times of molar weight relative to diamine component.
As the solvent used in above-mentioned reaction, the solvent identical with the solvent used when above-mentioned polyamic acid is polymerized can be used, consider from monomer and structure adaptability, preferred METHYLPYRROLIDONE, gamma-butyrolacton etc., can use in them a kind or two or more is used in combination.From the viewpoint of not easily causing the precipitation of polymkeric substance and easily obtaining high molecular body, concentration preferably 1 ~ 30 quality % of polymkeric substance during synthesis, more preferably 5 ~ 20 quality %.In addition, in order to prevent tetrabasic carboxylic acid diester diacid chloride to be hydrolyzed, the state that the solvent for the synthesis of poly amic acid ester preferably farthest dewaters to the greatest extent, preferably prevents the foreign gas reacted in blanket of nitrogen to be mixed into.
The recovery > of < polymkeric substance
When reclaiming from the reaction solution of polyamic acid, poly amic acid ester, polyimide etc. the polymkeric substance generated, preferably reaction solution is dropped in poor solvent to make it precipitate.As the poor solvent for precipitating, methyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water etc. can be exemplified.The polymkeric substance putting in poor solvent precipitation can after filtered and recycled, under normal or reduced pressure, carries out drying under normal temperature or heating.In addition, if the polymkeric substance making precipitation reclaim is dissolved in again organic solvent, precipitate the operation of recovery again and repeat 2 ~ 10 times, then the impurity in polymkeric substance can be reduced.As poor solvent now, can exemplify such as alcohols, ketone, hydro carbons etc., if use the poor solvent being selected from more than 3 kinds of these solvents, then purification efficiency improves further, therefore desirable.
The molecular weight of the polymkeric substance contained in aligning agent for liquid crystal of the present invention, consider the homogeneity of operability when the painting film strength of gained, film are formed and film, the weight-average molecular weight utilizing GPC (gel permeation chromatography) method to measure is preferably 5000 ~ 1000000, is more preferably 10000 ~ 150000.
< aligning agent for liquid crystal >
Aligning agent for liquid crystal of the present invention is the coating fluid for the formation of liquid crystal orientation film, and is be dissolved in for the formation of the resinous principle of resin coating the solution formed in organic solvent.Here, above-mentioned resinous principle comprises at least one polymkeric substance of the polymkeric substance being selected from the invention described above.The content of resinous principle in aligning agent for liquid crystal is preferably 1 ~ 20 quality %, more preferably 3 ~ 15 quality %, particularly preferably 3 ~ 10 quality %.
Resinous principle can be all polymkeric substance of the present invention, also can mix other polymkeric substance in addition.Now, other the content of polymkeric substance above-mentioned in resinous principle is 0.5 ~ 15 quality %, preferably 1 ~ 10 quality %.
Other described polymkeric substance, can exemplify such as the diamine component reacted with tetracarboxylic dianhydride's composition, use the diamine compound beyond specific diamine compound and the polyamic acid obtained or polyimide etc.
As long as the organic solvent of the organic solvent energy dissolving resin composition used in aligning agent for liquid crystal of the present invention, is not particularly limited.Exemplify its object lesson below:
N can be exemplified, dinethylformamide, N, N-dimethyl acetamide, METHYLPYRROLIDONE, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrolidone, NVP, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton, 3-methoxyl-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1, 3-dimethyl-2-imidazolidinone, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone etc.These can be used alone, also can be used in combination.
Aligning agent for liquid crystal of the present invention can comprise composition other than the above.Object lesson has, and film thickness uniformity when improving coating of liquid crystalline aligning agent or the vehicle substance etc. of surface smoothness, improves the compound etc. of the adaptation of liquid crystal orientation film and substrate.
As the concrete example of the solvent (poor solvent) of the homogeneity or surface smoothness that can improve thickness, following material can be exemplified.
Such as, isopropyl alcohol can be exemplified, methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, DPGME, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethylether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic acid esters, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, 1-hexanol, normal hexane, n-pentane, normal octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethylether, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy-propionic acid Methylethyl ester, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, propylene glycol-1-single ethylether-2-acetic acid esters, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate or isoamyl lactate etc. have the solvent etc. of low surface tension.
These poor solvents can use a kind, or by multiple used in combination.When using above-mentioned solvent, its content is preferably 5 ~ 80 quality % of the solvent total amount comprised in aligning agent for liquid crystal, more preferably 20 ~ 60 quality %.
As the raising homogeneity of thickness or the compound of surface smoothness, fluorine class surfactant, siloxane type surfactants, nonionic surfactant etc. can be exemplified.
More specifically, such as エ Off ト ッ プ EF301 can be exemplified, EF303, EF352 (illuminating product Co., Ltd. (ト ー ケ system プ ロ ダ クツ society) system), メ ガ Off ァ ッ Network F171, F173, R-30 (Dainippon Ink and Chemicals, Inc (large Japanese イ Application キ society) system), Off ロ ラ ー De FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo ス リ ー エ system society) system), ア サ ヒ ガ ー De AG710, サ ー Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd (Asahi Glass society) system) etc.The usage rate of these surfactants, relative to resinous principle 100 mass parts comprised in aligning agent for liquid crystal, is better 0.01 ~ 2 mass parts, is more preferably 0.01 ~ 1 mass parts.
As the concrete example of compound of adaptation improving liquid crystal orientation film and substrate, can exemplify shown below containing the compound of functional silanes, the compound etc. containing epoxy radicals.
Such as, 3-TSL 8330 can be exemplified, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (the oxyethylene group)-3-TSL 8330 of N-, two (the oxyethylene group)-APTES of N-, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2,4-hexanediol, N, N, N ', N ' ,-four glycidyl group-m-xylene diamine, two (N, the N-diglycidyl amino methyl) cyclohexane of 1,3-, N, N, N ', N ' ,-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.
Except improving the adaptation of substrate and film, in order to prevent degradation under the electrical characteristics that caused by backlight, preferably also contain the adjuvant of phenoplast class as follows.Concrete phenoplast class adjuvant is shown below.
[changing 54]
When use can improve the compound with the adaptation of substrate, its use amount is preferably 0.1 ~ 30 mass parts relative to 100 mass parts of resinous principle, more preferably 1 ~ 20 mass parts.If use amount is less than 0.1 mass parts, then cannot expect the effect that adaptation improves, if more than 30 mass parts, then the orientation of liquid crystal is deteriorated sometimes.
In aligning agent for liquid crystal of the present invention, in addition to the foregoing, in the scope not damaging effect of the present invention, can add be changed liquid crystal orientation film the electrical characteristics such as specific inductive capacity, electric conductivity for the purpose of dielectric, conductive materials, can also add to improve the hardness of film when forming liquid crystal orientation film or the cross-linked compound etc. for the purpose of density.
< liquid crystal orientation film and liquid crystal display cells >
Aligning agent for liquid crystal of the present invention to be coated on substrate and after burning till, the orientation process such as can carry out that friction treatment or illumination are penetrated, or is used as liquid crystal orientation film without orientation process in vertical orientated purposes etc.Now, as long as the substrate that the substrate transparency of use is high, be not particularly limited, the plastic bases etc. such as glass substrate, acrylic acid substrate, polycarbonate substrate can be used.In addition, from the viewpoint that technique simplifies, preferably use the substrate of the ITO electrode etc. be formed with for liquid crystal drive.In addition, in reflection type liquid crystal display element, if be only limitted to the substrate of side, also can use the opaque materials such as silicon wafer, electrode now also can use the material of the reflected light such as aluminium.
Be not particularly limited the coating process of aligning agent for liquid crystal, the method be coated with is carried out in industrial usual employing by serigraphy, hectographic printing, flexographic printing, ink-jet etc.As other coating process, also have dip coating, rolling method, slot coated, spin-coating method etc., these methods can be used according to object.
Aligning agent for liquid crystal is coated burning till after on substrate to be carried out at 50 ~ 300 DEG C, preferably 80 ~ 250 DEG C by heating arrangements such as heating plates, solvent is evaporated, thus forms film.If the thickness burning till rear formed film is blocked up, then unfavorable in the power consumption of liquid crystal display cells, if excessively thin, then the reliability of liquid crystal display cells reduces sometimes, therefore preferably 5 ~ 300nm, more preferably 10 ~ 100nm.When making liquid crystal horizontal alignment or tilted alignment, by friction or polarisation Ultraviolet radiation etc., the film after burning till is processed.
Liquid crystal display cells of the present invention is after being with the substrate of liquid crystal orientation film by said method by aligning agent for liquid crystal acquisition of the present invention, the liquid crystal display cells formed by known method manufacture liquid crystal cell.
An example of liquid crystal cell is manufactured if exemplify, following method can be illustrated: a pair substrate preparing to be formed with liquid crystal orientation film, the liquid crystal orientation film of a plate base scatters sept, makes liquid crystal aligning face become interior rear flank the laminating of another plate base, decompression injects liquid crystal and the method for sealing; Or drip liquid crystal on the liquid crystal aligning face being scattered with sept after, baseplate-laminating is carried out the method etc. sealed.Now, the thickness of sept preferably 1 ~ 30 μm, more preferably 2 ~ 10 μm.
Embodiment
Below, the present invention will be described in more detail to exemplify embodiment and comparative example, but explanation of the invention is not limited to these embodiments.
< embodiment 1>
The synthesis of 3,5-diaminobenzoic acid-2-(tertbutyloxycarbonylamino)-4-decoyl amido phenyl ester (HC-01)
[changing 55]
Step 1
The synthesis of 4-decoyl amido-2-nitrophenol
[changing 56]
4-amino-2-nitrophenol 15.9g (103 mM), tetrahydrofuran 300mL and pyridine 7.9g (103 mM) is added in the four-hole boiling flask of 500mL (milliliter).By system internal cooling to 0 DEG C, add positive caprylyl chloride 16.3g (103 mM), at room temperature stir.After reaction terminates, add after 50mL pure water stirs, add ethyl acetate after reaction terminates, be separated organic layer, with water and saturated aqueous common salt cleaning organic layer.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.Use the mixed solvent (3:7 (volume ratio, identical below)) of ethyl acetate and normal hexane to carry out recrystallization to the solid of gained, obtain flaxen solid 27.0g (yield 94%).
Step 2
The synthesis of 4-decoyl amido-Ortho-Aminophenol
[changing 57]
In the four-hole boiling flask of 500mL, add N-(3-nitro-4-hydroxy phenyl) caprylamide 15.0g (53.5 mM), ethanol 40mL and 5% palladium carbon 1.0g, stir under a hydrogen atmosphere, in room temperature.After reaction terminates, filtering palladium carbon by crossing, using rotary evaporator distillation except desolventizing.With the mixed solvent (1:9) of ethyl acetate and normal hexane, recrystallization is carried out to residue, obtain white solid 13.0g (yield 97%).
Step 3
The synthesis of 4-decoyl amido-2-tertbutyloxycarbonylamino phenol
[changing 58]
In the four-hole boiling flask of 300mL, add N-(3-amino-4-hydroxylphenyl) caprylamide 12.5g (49.9 mM), tetrahydrofuran 200mL, di-tert-butyl dicarbonate 11.9g (54.9 mM) and DMAP 0.61g (4.99 mM), at room temperature stir.After reaction terminates, add ethyl acetate, clean with water and saturated aqueous common salt.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.With silica gel column chromatography (ethyl acetate: hexane=1:3 (volume ratio, also identical in following embodiment) purifying is carried out to residue, use the mixed solvent (1:9) of ethyl acetate and normal hexane to carry out recrystallization, obtain white solid 16.5g (yield 94%).
Step 4
The synthesis of 3,5-dinitrobenzoic acid-2-(tertbutyloxycarbonylamino)-4-decoyl amido phenyl ester
[changing 59]
The HC-03-1 of 7.0g (20.0 mM), tetrahydrofuran 80mL and pyridine 1.6g (20.0 mM) is added in the four-hole boiling flask of 300mL.By system internal cooling to 0 DEG C, add 3,5-dinitrobenzoyl chloride 5.5g (20.0 mM), at room temperature stir.After reaction terminates, add 10 quality % wet chemicals, pH is adjusted to 8 ~ 9, adds ethyl acetate, be separated organic layer, with water and saturated aqueous common salt cleaning organic layer.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.With silica gel column chromatography (ethyl acetate: hexane=1:4) Purification, use the mixed solvent (1:9) of ethyl acetate and normal hexane to carry out recrystallization, obtain faint yellow solid 5.9g (yield 54%).
Step 5
The synthesis of HC-01
[changing 60]
3 are added in the four-hole boiling flask of 500mL, 5-dinitrobenzoic acid-2-(tertbutyloxycarbonylamino-4-caprylamide benzene) ester 5.9g (10.8 mM), tetrahydrofuran 150mL and 5% palladium/carbon 0.6g, stir under a hydrogen atmosphere, in room temperature.After reaction terminates, filtering palladium carbon by crossing, using rotary evaporator distillation except desolventizing.With the mixed solvent (1:9) of ethyl acetate and normal hexane, recrystallization is carried out to residue, obtain the solid 5.2g (yield 99%) of grey.The solid of gained 1the result of H-NMR is as follows.According to this result, be confirmed to be object HC-01.
In addition, the qualification of the compound of embodiments of the invention utilizes 1h-NMR ( 1the nuclear magnetic resonance of H, Varian Associates, Inc. (US) 611 Hansen Way, Palo Alto, California 94303, U.S.A. (Varian society) makes, INSTRUMENT MODEL: INOVA400) carry out.
1H NMR(400MHz,[D 6]-DMSO):δ9.92(s,1H),8.73(s,1H),7.89(s,1H),7.40-7.43(d,1H),6.99-7.01(d,1H),6.58(s,2H),6.09(s,1H),5.04(s,4H),2.27-2.31(t,2H),1.56-1.60(t,2H),1.40(s,9H),1.25-1.29(m,8H),0.85-0.88(t,3H)
< embodiment 2>
The synthesis of the synthesis (HC-02) of N-4-(4-amylbenzene formamido group)-3-tbutoxycarbonylaminophenyl-3,5-diaminobenzene formamide
[changing 61]
Step 1
The synthesis of 3-tertbutyloxycarbonylamino-4-aminonitrobenzene
[changing 62]
3,4-diamido nitrobenzene 25.0g (163 mM), tetrahydrofuran 250mL and di-tert-butyl dicarbonate 35.6g (163 mM), under nitrogen atmosphere return stirring 4 hours is added in the four-hole boiling flask of 300mL.After reaction terminates, with rotary evaporator except desolventizing, with the solid of washed with methanol gained, and carry out recrystallization with the mixed solvent (5:5) of ethyl acetate and normal hexane, obtain yellow solid 33.8g (yield 82%).
Step 2
The synthesis of N-4-(4-amylbenzene formamido group)-3-tertbutyloxycarbonylamino nitrobenzene
[changing 63]
4-amylbenzene formic acid 18.3g (95.0 mM), tetrahydrofuran 150mL and dimethyl formamide 20mL is added in the four-hole boiling flask of 300mL, by system internal cooling to 0 DEG C, add thionyl chloride 14.1g (119 mM), return to stirring at room temperature 2 hours, thus preparation 4-pentylbenzoyl chloride solution.On the other hand, 3-tertbutyloxycarbonylamino-4-aminonitrobenzene 20.0g (79.0 mM), tetrahydrofuran 100mL and pyridine 7.5g (95.0 mM) is added in the four-hole boiling flask of 500mL, by system internal cooling to 0 DEG C, the 4-pentylbenzoyl chloride solution of preparation before slowly dripping, at room temperature stirs.After reaction terminates, with rotary evaporator except desolventizing, add ethyl acetate, clean with the sodium bicarbonate aqueous solution of 10 quality %, water and saturated aqueous common salt.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.Use washed with methanol residue, carry out recrystallization with the mixed solvent (2:8) of ethyl acetate and normal hexane, obtain yellow solid 24.7g (yield 73%).
Step 3
The synthesis of N-4-(4-amylbenzene formamido group)-3-tertbutyloxycarbonylamino aniline
[changing 64]
In the four-hole boiling flask of 500mL, add N-4-(4-amylbenzene formamido group)-3-tertbutyloxycarbonylamino nitrobenzene 20.0g (46.8 mM), tetrahydrofuran 200mL and 10% palladium carbon 2.0g, stir under a hydrogen atmosphere, in room temperature.After reaction terminates, palladium carbon is filtered by crossing, with rotary evaporator distillation except desolventizing, again dissolve with acetone, add after activated charcoal at room temperature stirs a period of time, filter activity charcoal, distillation removing acetone, carry out vacuum drying, thus obtain the vitreous solid 17.7g (yield 95%) of pistac.
Step 4
The synthesis of N-4-(4-amylbenzene formamido group)-3-tbutoxycarbonylaminophenyl-3,5-dinitrobenzamide
[changing 65]
N-4-(4-amylbenzene formamido group)-3-tertbutyloxycarbonylamino aniline 10.0g (25.2 mM), tetrahydrofuran 150mL, dimethyl formamide 20mL and pyridine 2.4g (30.2 mM) is added in the four-hole boiling flask of 300mL.By system internal cooling to 0 DEG C, add 3,5-dinitrobenzoyl chloride 5.8g (25.2 mM), at room temperature stir.After reaction terminates, with rotary evaporator except desolventizing, add ethyl acetate, clean with the sodium bicarbonate aqueous solution of 10 quality %, water and saturated aqueous common salt.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.Use washed with methanol residue, carry out recrystallization with the mixed solvent (3:7) of ethyl acetate and normal hexane, obtain faint yellow solid 11.8g (yield 79%).
Step 5
The synthesis of HC-02
[changing 66]
N-4-(4-amylbenzene formamido group)-3-tbutoxycarbonylaminophenyl-3 is added in the four-hole boiling flask of 300mL, 5-dinitrobenzamide 10.0g (16.9 mM), tetrahydrofuran 100mL and 10% palladium carbon 1.0g, stir under a hydrogen atmosphere, in room temperature.After reaction terminates, filtering palladium carbon by crossing, using rotary evaporator distillation except desolventizing.With the mixed solvent (3:7) of ethyl acetate and normal hexane, recrystallization is carried out to residue, then clean with normal hexane dispersion, thus obtain the solid 8.6g (yield 96%) of white.The solid of gained 1the result of H-NMR is as follows.According to this result, be confirmed to be object HC-02.
1H NMR(400MHz,[D 6]-DMSO):δ10.0(s,1H),9.71(s,1H),8.62(s,1H),8.01(d,1H),7.89-7.87(d,2H),7.54-7.52(dd,1H),7.42-7.40(d,1H),7.37-7.35(d,2H),6.30(d,2H),6.00-5.90(t,1H),4.96(s-br,4H),2.68-2.64(m,2H),1.64-1.57(m,2H),1.45(s,9H),1.39-1.17(m,4H),0.89-0.85(t,3H)
< embodiment 3>
The synthesis (HC-03) of N-4-(4-amylbenzene formamido group)-3-tbutoxycarbonylaminophenyl-2,4-diaminobenzene formamide
[changing 67]
Step 1
The synthesis of N-4-(4-amylbenzene formamido group)-3-tbutoxycarbonylaminophenyl-2,4-dinitrobenzamide
[changing 68]
2 are added in the four-hole boiling flask of 300mL, 4-dinitrobenzoic acid 4.10g (19.4 mM), methylene chloride 150mL and dimethyl formamide 20mL, by system internal cooling to 0 DEG C, slowly add oxalyl chloride 2.46g (19.4 mM), return to room temperature and stir 2 hours, prepare 2,4-dinitrobenzoyl chloride solution.On the other hand, 4-(4-amylbenzene formamido group)-3-tertbutyloxycarbonylamino aniline 7.00g (17.6 mM), tetrahydrofuran 100mL and pyridine 2.09g (26.4 mM) is added in the four-hole boiling flask of 500mL, by system internal cooling to 0 DEG C, prepare before slowly dripping 2,4-dinitrobenzoyl chloride solution, stirs in 40 DEG C under nitrogen atmosphere.After reaction terminates, with rotary evaporator except desolventizing, add ethyl acetate, clean with the sodium bicarbonate aqueous solution of 10 quality %, water and saturated aqueous common salt.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.With methyl alcohol dispersion cleaning residue, carry out recrystallization with the mixed solvent (2:8) of ethylene dichloride and normal hexane, obtain faint yellow solid 6.56g (yield 63%).
Step 2
The synthesis of N-4-(4-amylbenzene formamido group)-3-tbutoxycarbonylaminophenyl-2,4-diaminobenzene formamide
[changing 69]
N-4-(4-amylbenzene formamido group)-3-tbutoxycarbonylaminophenyl-2 is added in the four-hole boiling flask of 300mL, 4-dinitrobenzamide 6.00g (10.2 mM), tetrahydrofuran 100mL and 10% palladium carbon 0.60g, stir under a hydrogen atmosphere, in room temperature.After reaction terminates, filtering palladium carbon by crossing, using rotary evaporator distillation except desolventizing.Clean residue with the mixed solvent dispersion of methyl alcohol and 2-propyl alcohol, then use the mixed solvent (2:8) of ethyl acetate and normal hexane to carry out recrystallization, obtain flaxen solid 4.88g (yield 90%).The solid of gained 1the result of H-NMR is as follows.According to this result, be confirmed to be object HC-02.
1H NMR(400MHz,[D 6]-DMSO):δ10.4(s,1H),9.56(s,1H),8.63(s,1H),8.01(d,1H),7.89―7.87(d,2H),7.54-7.52(dd,1H),7.42-7.40(d,1H),7.37-7.35(d,1H),7.28(d,1)、6.72(d,1H),6.75(d,1H),6.40(s-br,2H),5.84(s,1H),5.44(s-br,2H),2.68-2.64(m,2H),1.64-1.57(m,2H),1.45(s,9H),1.39-1.17(m,4H),0.89-0.85(t,3H)
< embodiment 4>
The synthesis of the synthesis (HC-04) of N-4-(4-amylbenzene formyloxy)-3-tbutoxycarbonylaminophenyl-3,5-diaminobenzene formamide
[changing 70]
Step 1
The synthesis of 2-tertbutyloxycarbonylamino-4-nitrophenol
[changing 71]
In the four-hole boiling flask of 300mL, add 2-Amino-4-nitrophenol 12.3g (79.8 mM), tetrahydrofuran 250mL, di-tert-butyl dicarbonate 14.2g (87.9 moles) and DMAP 2.00g (7.98 moles), at room temperature stir.After reaction terminates, add ethyl acetate, clean with water and saturated aqueous common salt.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.With silica gel column chromatography (ethyl acetate: hexane=1:1) Purification, use the mixed solvent (1:9) of ethyl acetate and normal hexane to carry out recrystallization, obtain faint yellow solid 15.0g (yield 73%).
Step 2
The synthesis of 4-(4-amylbenzene formyloxy)-3-tertbutyloxycarbonylamino-nitrobenzene
[changing 72]
4-amylbenzene formic acid 6.4g (32.8 moles) and tetrahydrofuran 60mL is added in the four-hole boiling flask of 200mL, by system internal cooling to 0 DEG C, add thionyl chloride 4.3g (35.3 moles), return to room temperature and stir 1 hour, obtain 4-pentylbenzoyl chloride solution.On the other hand, 2-tertbutyloxycarbonylamino-4-nitrophenol 6.3g (25.2 mM), tetrahydrofuran 60mL and pyridine The 4.0g (50.4 mM) is added in the four-hole boiling flask of 500mL, by system internal cooling to 0 DEG C, the 4-pentylbenzoyl chloride solution of preparation before slowly dripping, at room temperature stirs.After reaction terminates, add 10 quality % wet chemicals, pH is adjusted to 8 ~ 9.Add ethyl acetate, be separated organic layer, with water and saturated aqueous common salt cleaning organic layer.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.With the mixed solvent (7:3) of ethyl acetate and normal hexane, recrystallization is carried out to residue, obtain yellow solid 6.9g (yield 64%).
Step 3
The synthesis of 4-(4-amylbenzene formyloxy)-3-tertbutyloxycarbonylamino-aniline
[changing 73]
In the four-hole boiling flask of 300mL, add 4-(4-amylbenzene the formyloxy)-3-tertbutyloxycarbonylamino nitrobenzene 2 of 8.8g (20.5 moles), tetrahydrofuran 100mL and 5% palladium carbon 0.9g, stir under a hydrogen atmosphere, in room temperature.After reaction terminates, filtering palladium carbon by crossing, using rotary evaporator distillation except desolventizing.With the mixed solvent (7:3) of ethyl acetate and normal hexane, recrystallization is carried out to residue, obtain white solid 6.8g (yield 84%).
Step 4
The synthesis of N-4-(4-amylbenzene formyloxy)-3-tbutoxycarbonylaminophenyl-3,5-dinitrobenzamide
[changing 74]
4-(4-amylbenzene formyloxy)-3-tertbutyloxycarbonylamino aniline 6.8g (17.1 mM), tetrahydrofuran 100mL and pyridine 1.5g (18.8 mM) is added in the four-hole boiling flask of 300mL.By system internal cooling to 0 DEG C, add 3,5-dinitrobenzoyl chloride 4.6g (20.0 moles), at room temperature stir.After reaction terminates, add 10 quality % wet chemicals, pH is adjusted to 8 ~ 9.Add ethyl acetate, be separated organic layer, with water and saturated aqueous common salt cleaning organic layer.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.With the mixed solvent (3:7) of ethyl acetate and normal hexane, recrystallization is carried out to residue, obtain faint yellow solid 11.0g (yield 99%).
Step 5
The synthesis of HC-04
[changing 75]
N-4-(4-amylbenzene formyloxy)-3-tbutoxycarbonylaminophenyl-3 is added in the four-hole boiling flask of 300mL, 5-dinitrobenzamide 11.0g (18.6 mM), tetrahydrofuran 100mL and 5% palladium carbon 1.0g, stir under a hydrogen atmosphere, in room temperature.After reaction terminates, filtering palladium carbon by crossing, using rotary evaporator distillation except desolventizing.With the mixed solvent (1:9) of ethyl acetate and normal hexane, recrystallization is carried out to residue, obtain the solid 9.7g (yield 98%) of grey.The solid of gained 1the result of H-NMR is as follows.According to this result, be confirmed to be object HC-04.
1H NMR(400MHz,[D 6]-DMSO):δ9.99(s,1H),8.88(s,1H),7.99-8.01(m,3H),7.48-7.51(d,1H),7.34-7.38(d,2H),7.10-7.11(d,1H),6.26(s,2H),5.96(s,1H),4.93(s-br,4H),2.63-2.67(t,2H),1.55-1.59(t,2H),1.22-1.34(m,13H),0.81-0.84(t,3H),
The synthesis of < embodiment 5>2-methyl-6-tert butoxy carbonylamino phenyl-3,5-diaminobenzoic acid (HC-05)
[changing 76]
Step 1
The synthesis of 6-tertbutyloxycarbonylamino metacresol
[changing 77]
In the four-hole boiling flask of 300mL, add amino metacresol 6.2g (50.3 mM) of 6-, tetrahydrofuran 150mL and di-tert-butyl dicarbonate 14.2g (55.3 mM), at room temperature stir.After reaction terminates, add ethyl acetate, clean with water and saturated aqueous common salt.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing, obtain white solid 11.2g (yield 99%).
Step 2
3,5-dinitrobenzoic acid-3-methyl-6-tert butoxy carbonylamino phenyl ester
[changing 78]
6-tertbutyloxycarbonylamino metacresol 11.2g (50.2 mM), tetrahydrofuran 200mL and pyridine 4.0g (50.2 mM) is added in the four-hole boiling flask of 300mL.By system internal cooling to 0 DEG C, add 3,5-dinitrobenzoyl chloride 11.5g (50.2 mM), at room temperature stir.After reaction terminates, reaction solution is poured in the mixed solvent (9:1) of first alcohol and water, solid is separated out, by solid filtering.Then, with the mixed solvent (1:9) of ethyl acetate and normal hexane, recrystallization is carried out to solid, obtain yellow solid 20.2g (yield 97%).
Step 3
The synthesis of HC-05
[changing 79]
In the four-hole boiling flask of 300mL, add 3,5-dinitrobenzoic acid-3-methyl-6-tert butoxy carbonylamino phenyl ester 10.0g (24.0 mM), tetrahydrofuran 100mL and 5% palladium/carbon 1.0g, stir under a hydrogen atmosphere, in room temperature.After reaction terminates, filtering palladium carbon by crossing, using rotary evaporator distillation except desolventizing.With the mixed solvent (1:9) of ethyl acetate and normal hexane, recrystallization is carried out to residue, obtain the solid 8.7g (yield 99%) of grey.The solid of gained 1the result of H-NMR is as follows.According to this result, be confirmed to be object HC-05.
1H NMR(400MHz,[D 6]-DMSO):δ8.63(s,1H),7.43-7.45(d,2H),6.99-7.02(d,1H),6.93(s,1H),6.57(s,2H),6.08(s,1H),5.04(s,4H),2.27(s,1H),1.37(s,9H)
< embodiment 6>
The synthesis of 4-(4-amylbenzene formamido group)-2-tertbutyloxycarbonylamino-3,5-diaminobenzoic acid ester (HC-06)
[changing 80]
Step 1
The synthesis of 4-(4-amylbenzene formamido group)-2-nitrophenol
[changing 81]
4-amylbenzene formic acid 12.5g (64.9 mM), tetrahydrofuran 100mL and DMF (N is added in the four-hole boiling flask of 200mL, dinethylformamide) 20mL, by system internal cooling to 0 DEG C, add thionyl chloride 7.80g (65.5 moles), stir 2 hours at 60 DEG C, prepare 4-pentylbenzoyl chloride solution.On the other hand, 4-amino-2-nitrophenol 10.0g (64.9 mM), tetrahydrofuran 150mL and pyridine 6.3g (64.9 mM) is added in the four-hole boiling flask of 300mL, by system internal cooling to 0 DEG C, the 4-pentylbenzoyl chloride solution of preparation before slowly adding, return to room temperature, stir 1 day under nitrogen atmosphere.After reaction terminates, with evaporator distillation except desolventizing, add ethyl acetate and add pure water 50mL, after stirring, being separated organic layer, with water and saturated aqueous common salt cleaning organic layer.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.By column chromatography (mixed solvent (8:2) of ethyl acetate and normal hexane), purifying is carried out to residue, use the mixed solvent (2:8) of ethyl acetate and normal hexane to carry out dispersion cleaning again, obtain yellow solid 15.6g (yield 73%).
Step 2
The synthesis of 4-(4-amylbenzene formamido group)-Ortho-Aminophenol
[changing 82]
In the four-hole boiling flask of 200mL, add 4-(4-amylbenzene formamido group)-2-nitrophenol 10.0g (30.5 moles), tetrahydrofuran 100mL and 10% palladium carbon 1.0g, stir under a hydrogen atmosphere, in room temperature.After reaction terminates, filtering palladium carbon by crossing, with rotary evaporator distillation except desolventizing, making it dissolve again with acetone, adding activated charcoal and stir.Then, filtering activated charcoal by crossing, with rotary evaporator, solvent being distilled removing from filtrate, thus obtain light brown sugar shape solid 8.4g (yield 93%).
Step 3
The synthesis of 4-(4-amylbenzene formamido group)-2-tertbutyloxycarbonylamino phenol
[changing 83]
In the four-hole boiling flask of 200mL, add 4-(4-amylbenzene formamido group)-Ortho-Aminophenol 6.0g (20.1 mM), tetrahydrofuran 100mL, di-tert-butyl dicarbonate 4.4g (20.1 mM) and pyridine 0.16g (2.01 mM), at room temperature stir.After reaction terminates, with rotary evaporator distillation except desolventizing, add ethyl acetate, clean with water and saturated aqueous common salt.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.With the mixed solvent (3:7) of ethyl acetate and normal hexane, recrystallization is carried out to residue, obtain white solid 5.8g (yield 72%).
Step 4
The synthesis of 3,5-dinitrobenzoic acid-4-(4-amylbenzene formamido group)-2-tertbutyloxycarbonylamino phenyl ester
[changing 84]
4-amylbenzene formamido group-2-tertbutyloxycarbonylamino phenol 5.00g (12.5 mM), tetrahydrofuran 80mL and pyridine 0.99g (12.5 mM) is added in the four-hole boiling flask of 200mL.By system internal cooling to 0 DEG C, add 3,5-dinitrobenzoyl chloride 2.9g (12.5 mM), at room temperature stir.After reaction terminates, add ethyl acetate, clean with the sodium bicarbonate aqueous solution of 10 quality %, water and saturated aqueous common salt successively.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.Clean residue with mixed solvent (3:7) dispersion of methyl alcohol and 2-propyl alcohol, carry out recrystallization with the mixed solvent (2:8) of ethyl acetate and normal hexane, thus obtain faint yellow solid 5.09g (yield 90%).
Step 5
The synthesis of HC-06
[changing 85]
4-(4-amylbenzene formamido group)-2-tertbutyloxycarbonylamino-3,5-dinitrobenzoic acid 4.52g (7.59 mM), Isosorbide-5-Nitrae-two is added in the four-hole boiling flask of 100mL alkane 50mL and 10% palladium carbon 0.45g, stirs under a hydrogen atmosphere, in room temperature.After reaction terminates, filtering palladium carbon by crossing, using rotary evaporator distillation except desolventizing.With the mixed solvent (5:5) of ethylene dichloride and normal hexane, recrystallization is carried out to residue, obtain grayish solid 3.62g (yield 90%).The solid of gained 1the result of H-NMR is as follows.According to this result, be confirmed to be object HC-07.
1H NMR(400MHz,[D 6]-DMSO):δ9.82(s,1H),8.73(s,1H),7.96-7.85(dd,3H),7.40-7.43(d,1H),7.37-7.35(d,2H)、6.99-7.01(d,1H),6.54(s,2H),6.12(s,1H),4.99(s-br,4H),2.68-2.64(m,2H),1.65-1.56(m,2H),1.46(s,9H),1.37-1.16(m,4H),0.88-0.84(t,3H)
< embodiment 7>
The synthesis of [4-(4-amylbenzene formamido group)-2-(tertbutyloxycarbonylamino) phenyl]-2-(2,4-diamino-phenyl) acetamide (HC-07)
[changing 86]
Step 1
The synthesis of [4-(4-amylbenzene formamido group)-3-(tertbutyloxycarbonylamino) phenyl]-(2,4-dinitrophenyl) acetamide
[changing 87]
2 are added in the four-hole boiling flask of 100mL, 4-dinitro benzene acetic acid 3.0g (12.3 mM), methylene chloride 50mL and dimethyl formamide 5mL, by system internal cooling to 0 DEG C, slowly add oxalyl chloride 1.6g (12.3 mM), return to room temperature, stir 2 hours, thus preparation 2,4-dinitro benzene chloride solution.On the other hand, N-4-(4-amylbenzene formamido group)-3-tertbutyloxycarbonylamino aniline 4.5g (11.2 mM), methylene chloride 50mL and pyridine 1.1g (13.4 mM) is added in the four-hole boiling flask of 200mL, by system internal cooling to 0 DEG C, prepare before slowly adding 2,4-dinitrobenzoyl chloride solution, stirs under nitrogen atmosphere, in room temperature.After reaction terminates, with rotary evaporator except desolventizing, add ethyl acetate, clean with the sodium bicarbonate aqueous solution of 10 quality %, water and saturated aqueous common salt successively.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.With methyl alcohol dispersion cleaning residue, carry out recrystallization with the mixed solvent (2:8) of ethyl acetate and normal hexane, obtain faint yellow solid 5.2g (yield 77%).
Step 2
The synthesis of HC-07
[changing 88]
N-[4-(4-amylbenzene formamido group)-3-(tertbutyloxycarbonylamino) phenyl]-(2,4-dinitrophenyl) acetamide 4.5g (7.43 mM), Isosorbide-5-Nitrae-two is added in the four-hole boiling flask of 100mL alkane 50mL and platinum oxide 0.45g, stirs under a hydrogen atmosphere, in room temperature.After reaction terminates, filtering platinum oxide by crossing, using rotary evaporator distillation except desolventizing.With the mixed solvent (5:5) of ethyl acetate and normal hexane, recrystallization is carried out to residue, obtain the solid 3.6g (yield 89%) of light brown.The solid of gained 1the result of H-NMR is as follows.According to this result, be confirmed to be object HC-07.
1H NMR(400MHz,[D 6]-DMSO):δ9.98(s,1H),9.67(s,1H),8.68(s,1H),8.00(d,1H),7.85―7.83(d,2H),7.53-7.50(m,1H),7.32-7.28(m,2H),7.22(d,2H),6.43-6.40(d,1H),6.00-5.90(d,1H),4.96(s-br,2H),3.52(s-br,2H),3.08(s,2H),2.67-2.65(m,2H),1.62-1.55(m,2H),1.46(s,9H),1.39-1.17(m,4H),0.89-0.85(t,3H)
< embodiment 8>
The synthesis of 4-(2-(tertbutyloxycarbonylamino) phenyl amino)-4-oxo but-2-ene acid-(Z)-3,5-dinitro benzyl ester (HC-08)
[changing 89]
Step 1
The synthesis of 2-(tertbutyloxycarbonylamino) aniline
[changing 90]
In the four-hole boiling flask of 500mL, add o-phenylenediamine 50.0g (462 mM), tetrahydrofuran 300mL and di-tert-butyl dicarbonate 100.8g (462 mM), reflux 4 hours under nitrogen atmosphere.After reaction terminates, with rotary evaporator except desolventizing, with the solid of methyl alcohol dispersion cleaning gained, and carry out recrystallization with the mixed solvent (3:7) of ethyl acetate and normal hexane, obtain light tan solid 77.0g (yield 80%).
Step 2
The synthesis of (E)-butenedioic acid (2Z)-3,5-dinitro benzyl ester
[changing 91]
3 are added in the four-hole boiling flask of 500mL, 5-dinitro benzylalcohol 25.0g (126 mM), chloroform 300mL and triethylamine 19.1g (189 mM), under nitrogen atmosphere by system internal cooling to 0 DEG C, add maleic anhydride 14.8g (151 mM), stir 2 hours, return to room temperature and react 6 hours.After reaction terminates, be again cooled to 10 DEG C, after the sodium bicarbonate aqueous solution 200mL adding 10 quality % stirs 1 hour, separate aqueous layer, cleans water layer with ethylene dichloride, is again cooled to 10 DEG C, pH is adjusted to 4 ~ 5 by the aqueous hydrochloric acid solution adding 10 quality %, separates out white solid.With the solid of acetic acid ethyl dissolution gained, after extraction, with water and saturated aqueous common salt cleaning ethyl acetate layer.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.With ethanol dispersion cleaning residue, make its recrystallization with the mixed solvent (3:7) of ethyl acetate and normal hexane, thus obtain the solid 32.1g (yield 86%) of white.
Step 3
The synthesis of 4-(2-(tertbutyloxycarbonylamino) phenyl amino)-4-oxo but-2-ene acid-(Z)-3,5-dinitro benzyl ester
[changing 92]
(E)-butenedioic acid (2Z)-3 is measured in the four-hole boiling flask of 300mL, 5-dinitro benzyl ester 10.00g (33.7 mM), add THF200mL, triethylamine 1.71g (16.9 mM) and 4-(4,6-dimethoxy-1,3,5-triazine-2-base) 4-methoxyl morpholine hydrochloride n hydrate (DMT-MM) 13.99g (50.6 mM), at room temperature stir after 30 minutes, little by little add 2-(tertbutyloxycarbonylamino) aniline 7.67g(36.8 mM), under nitrogen atmosphere, in room temperature reaction 6 hours.
After reaction terminates, use rotary evaporator concentrated reaction solution, add ethyl acetate 200ml, stir after 1 hour at 50 DEG C, filter insolubles, clean with water, saturated aqueous common salt successively.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.With methyl alcohol, recrystallization is carried out to residue, obtain flaxen solid 14.59 (yield 89%).
Step 4
The synthesis of HC-08
[changing 93]
4-(2-(tertbutyloxycarbonylamino) phenyl amino)-4-oxo but-2-ene acid-(Z)-3 is added in the four-hole boiling flask of 300mL, the aqueous ammonium chloride solution 107g (ammonium chloride 200 mM) of 5-dinitro benzyl ester 10.0g (20.6 mM), reduced iron 11.5g (200 mM), 10 quality % and toluene 150mL, is reacting while 1 day under nitrogen atmosphere, in 70 DEG C of stirrings with mechanical stirrer.After reaction terminates, add ethyl acetate, then iron is filtered, with the organic layer of water, saturated aqueous common salt wash filtrate.Then use dried over mgso, filtering magnesium sulfate by crossing, in organic layer, adding activated charcoal, stir a period of time.Then, filter activated charcoal by crossing, with rotary evaporator distillation except desolventizing.Carry out purifying by column chromatography (mixed solvent (3:7) of ethyl acetate and ethylene dichloride), under reduced pressure carry out drying, obtain flaxen vitreous solid 8.0g (yield 91%).
The solid of gained 1the result of H-NMR is as follows.According to this result, be confirmed to be object HC-08.
1H NMR(400MHz,CDCl 3):δ8.78(s-br,1H),7.56-7.53(d,1H),7.38-7.37(dd,1H),7.20-7.12(m,2H),7.04-6.92(q,2H),6.93(s-br,1H),6.10(d,2H),5.98-5.97(t,1H),5.01(s,2H),3.63(s-br,4H),1.51(s,9H)
< embodiment 9>
4-(2-(tertbutyloxycarbonylamino) phenyl amino)-4-oxo but-2-ene acid-(E)-(2,4-diamino phenoxy) ethyl ester (HC-09) and
The synthesis of 4-(2-(tertbutyloxycarbonylamino) phenyl amino)-4-ketobutyric acid-2-(2,4-diamino phenoxy) ethyl ester (HC-10)
[changing 94]
[changing 95]
Step 1
The synthesis of 2-(2,4-dinitrophenoxy) ethanol
[changing 96]
Triethylamine 13.6g (134 mM), ethylene glycol 50mL and tetrahydrofuran 150mL is added in the four-hole boiling flask of 300mL, be cooled to 10 DEG C under nitrogen atmosphere, then add DNF 25.0g (134 mM), be heated to 60 DEG C, carry out the reaction of 16 hours.After reaction terminates, with rotary evaporator except desolventizing, add ethyl acetate, after water, saturated aqueous common salt cleaning, use dried over mgso.Then, filter magnesium sulfate by crossing, with rotary evaporator distillation except desolventizing.Carry out recrystallization with the mixed solvent (3:7) of methyl alcohol and 2-propyl alcohol, carry out dispersion cleaning with normal hexane, thus obtain white solid 26.0g (yield 85%).
Step 2 (1)
The synthesis of (E)-butenedioic acid (2E)-2-(2,4-dinitrophenoxy) ethanol ester (with maleic anhydride and utilize the method for isomerization reaction)
[changing 97]
2-(2 is measured in the four-hole boiling flask of 300mL, 4-dinitrophenoxy) ethanol 10.0g (43.8 mM), add chloroform 200mL and triethylamine 4.43g (43.8 mM), maleic anhydride 5.15g (52.6 mM) is added under ice bath, slowly return to room temperature, stir 6 hours.Add ethyl acetate 100mL after reaction terminates, clean with the aqueous hydrochloric acid solution of 10 quality %, water and saturated aqueous common salt successively.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.Residue is dissolved in the Isosorbide-5-Nitrae-two of 200mL in alkane, add hydrochloric acid 1.00g, stir 2 hours in 100 DEG C.Then, with rotary evaporator distillation except desolventizing, carry out recrystallization with the mixed solvent (7:3) of ethyl acetate and hexane, obtain the solid 12.86g (yield 90%) of white.
Step 2 (2)
The synthesis of (E)-butenedioic acid (2E)-2-(2,4-dinitrophenoxy) ethanol ester
[changing 98]
Fumaryl chloride 10.0 (65.7 mM) and chloroform 150mL is added in the four-hole boiling flask of 300mL, under nitrogen atmosphere by system internal cooling to 0 DEG C, slowly add 2-(2 again, 4-dinitrophenoxy) dimethylacetamide solution (DMAc50mL) of ethanol 10.0g (43.8 mM) and the chloroformic solution of triethylamine 4.43g (43.8 mM), stir 2 hours, return to room temperature and carry out reaction 1 day.After reaction terminates, add water 50mL, then be cooled to 10 DEG C, add the sodium bicarbonate aqueous solution 100mL of 10 quality %, stir 1 hour, separate aqueous layer, cleans water layer with ethyl acetate.Then, after being cooled to 10 DEG C, adding the aqueous hydrochloric acid solution of 10 quality %, pH is adjusted to 4 ~ 5, separate out the solid of white.By the dissolution of solid of gained in ethyl acetate, after extraction, with water and saturated aqueous common salt cleaning ethyl acetate layer.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.With ethanol dispersion cleaning residue, make its recrystallization with the mixed solvent (2:8) of ethyl acetate and normal hexane, thus obtain the solid 12.1g (yield 85%) of white.
Step 3
The synthesis of 4-(2-(tertbutyloxycarbonylamino) phenyl amino)-4-oxo but-2-ene acid-(E)-(2,4-dinitrophenoxy) ethyl ester
[changing 99]
(E)-butenedioic acid (2E)-2-(2 is added in the four-hole boiling flask of 200mL, 4-dinitrophenoxy) ethanol ester 10.0g (30.7 mM), chloroform 100mL and DMF30mL, again under nitrogen atmosphere under, add oxalyl chloride 4.3g (33.8 mM) at leisure in 0 DEG C after, return to room temperature, stir 2 hours.Then, 2-(tertbutyloxycarbonylamino) aniline 9.6g (46.1 mM) is added, under nitrogen atmosphere, in room temperature reaction 24 hours.After reaction terminates, add ethyl acetate and be separated organic layer, with the sodium bicarbonate aqueous solution of the aqueous hydrochloric acid solution of water, 10 quality %, 10 quality %, water and saturated aqueous common salt, organic layer is cleaned successively.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.With the mixed solvent (3:7) of ethyl acetate and normal hexane, recrystallization is carried out to residue, after ethanol dispersion cleaning, obtain flaxen solid 12.1g (yield 76%).
Step 4
The synthesis of HC-09
[changing 100]
4-(2-(tertbutyloxycarbonylamino) phenyl amino)-4-oxo but-2-ene acid-(E)-(2 are added in the four-hole boiling flask of 200mL, 4-dinitrophenoxy) ethyl ester 5.0g (9.68 mM), reduced iron 5.4g (96.8 mM), the aqueous ammonium chloride solution 51.8g (ammonium chloride 96.8 mM) of 10 quality % and toluene 70mL, with mechanical stirrer under nitrogen atmosphere, to stir while 1 day in 70 DEG C and reacting.After reaction terminates, add ethyl acetate, iron is filtered, with the organic layer of water and saturated aqueous common salt wash filtrate.Then use dried over mgso, filtering magnesium sulfate by crossing, in organic layer, adding activated charcoal, stir a period of time.Then, filter activated charcoal by crossing, with rotary evaporator distillation except desolventizing.Carry out purifying by column chromatography (mixed solvent (5:5) of ethyl acetate and ethylene dichloride), under reduced pressure carry out drying, obtain flaxen vitreous solid 3.5g (yield 80%).
The solid of gained 1the result of H-NMR is as follows.According to this result, be confirmed to be object HC-09.
1H NMR(400MHz,CDCl 3):δ8.80(s-br,1H),7.61-7.59(d,1H),7.40-7.38(d,1H),7.21-7.14(m,2H),6.99(s-br,1H),6.94-6.81(q,2H),6.69-6.67(d,1H),6.15-6.13(d,1H),6.09-6.07(dd,1H),4.54-4.52(t,2H),4.21-4.19(t,2H),3.66(s-br,4H),1.52(s,9H)
Step 5
The synthesis of HC-10
[changing 101]
4-(2-(tertbutyloxycarbonylamino) phenyl amino)-4-oxo but-2-ene acid-(E)-(2 are added in the four-hole boiling flask of 300mL, 4-dinitrophenoxy) ethyl ester 5.0g (9.68 mM), tetrahydrofuran 50mL and 10% palladium carbon 0.50g, stir under a hydrogen atmosphere, in room temperature.After reaction terminates, filtering palladium carbon by crossing, then using rotary evaporator distillation except desolventizing.With the mixed solvent (2:8) of ethyl acetate and normal hexane, recrystallization is carried out to residue, obtain the solid 4.00g (yield 90%) of white.
The solid of gained 1the result of H-NMR is as follows.According to this result, be confirmed to be object HC-09.
1H NMR(400MHz,CDCl 3):δ8.21(s-br,1H),7.43-7.42(d,1H),7.37-7.36(d,1H),7.16-7.08(m,3H),6.57-6.56(d,1H),6.05-6.03(d,1H),5.97-5.96(dd,1H),4.38-4.35(t,2H),4.14-4.11(t,2H),3.22(s-br,4H),2.76-2.74(t,2H),2.59-2.56(t,2H),1.46(s,9H)
The evaluating characteristics > of < liquid crystal orientation film
The abbreviation of the compound used in this instructions is as follows.
< tetracarboxylic dianhydride >
CBDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
PMDA: pyromellitic acid anhydride
CBDE:1,2,3,4-cyclo-butane tetrabasic carboxylic acid dimethyl ester
[changing 102]
< diamines >
P-PDA: p-phenylenediamine (PPD)
3-ABA:3-amino-benzylamine
Amino-2, the 4-diaminobenzenes of 2,4-DAA:N, N-diallyl
C14DAB:4-tetradecyloxyaniline-1,3-diaminobenzene
C16DAB:4-hexadecane Oxy-1,3-diaminobenzene
Amino-2, the 4-diaminobenzenes of CAB-2:N-(4-(trans-4-n-heptyl cyclohexyl) benzoyl)
PCH-7AB:N-(4-(trans-4-n-heptyl cyclohexyl) phenoxy group)-2,4-diaminobenzenes
M-TDA a: tolyl-3,5-diaminobenzoic acid
HC-01:3,5-diaminobenzoic acid-2-(tertbutyloxycarbonylamino)-4-decoyl amido phenyl ester
HC-02:N-4-(4-amylbenzene formamido group)-3-tbutoxycarbonylaminophenyl-3,5-diaminobenzene formamide
HC-03:N-4-(4-amylbenzene formamido group)-3-tbutoxycarbonylaminophenyl-2,4-diaminobenzene formamide
HC-04:N-4-(4-amylbenzene formyloxy)-3-tbutoxycarbonylaminophenyl-3,5-diaminobenzene formamide
HC-05:3,5-diaminobenzoic acid-2-methyl-6-tert butoxy carbonylamino phenyl ester
HC-06:4-(4-amylbenzene formamido group)-2-tertbutyloxycarbonylamino-3,5-diaminobenzoic acid
HC-07:[4-(4-amylbenzene formamido group)-2-(tertbutyloxycarbonylamino) phenyl]-2-(2,4-diamino-phenyl) acetamide
HC-08:4-(2-(tertbutyloxycarbonylamino) phenyl amino)-4-oxo but-2-ene acid-(Z)-3,5-dinitro benzyl ester
HC-09:4-(2-(tertbutyloxycarbonylamino) phenyl amino)-4-oxo but-2-ene acid-(E)-(2,4-diamino phenoxy) ethyl ester
HC-10:4-(2-(tertbutyloxycarbonylamino) phenyl amino)-4-ketobutyric acid-2-(2,4-diamino phenoxy) ethyl ester
HC-11:4-(trans-4-amyl group hexamethylene acylamino-)-3-(tertbutyloxycarbonylamino) phenyl-3,5-diaminobenzene formamide
HC-12:4-[4-(trans-4-pentylcyclohexyl) benzamido]-3-(tertbutyloxycarbonylamino) phenyl-3,5-diaminobenzene formamide
[changing 103]
[changing 104]
[changing 105]
< condensation agent >
DMT-MM:4-(4,6-dimethoxy-1,3,5-triazines-2-base) 4-methoxyl morpholine hydrochloride n hydrate
< organic solvent >
NMP:N-N-methyl-2-2-pyrrolidone N-
γ-BL: gamma-butyrolacton
BC: butyl cellosolve
DPM: DPGME
The mensuration > of < molecular weight
The molecular weight of the polymkeric substance obtained by polyreaction measures as follows: measure this polyimide by GPC (normal temperature gel permeation chromatography) device, calculate number-average molecular weight and weight-average molecular weight as polyglycol and polyethylene oxide scaled value.
GPC device: Shodex company (Showa Denko K. K) system (GPC-101)
Post: Showa Denko K. K's system (series connection of KD803, KD805)
Column temperature: 50 DEG C
Eluent: DMF (as adjuvant, lithium bromide-hydrate (LiBrH 2o) be 30 mMs/L, phosphoric anhydride crystallization (o-phosphoric acid) is 30 mMs/L, tetrahydrofuran (THF) is 10ml/L)
Flow velocity: 1.0ml/ minute
Calibration curve making standard sample: Dong Cao company (East ソ ー society) TSK standard polyethylene oxide processed (molecular weight about 900000,150000,100000,30000) and Polymer Laboratory company (polymer ラ ボ ラ ト リ ー society) polyglycol processed (molecular weight about 12000,4000,1000).
The mensuration > of < acid imide rate
The acid imide rate of the polyimide in synthesis example measures as follows.The polyimide powder of 20mg is joined NMR stopple coupon (specification of wasteland's science Co., Ltd. NMR stopple coupon), add the deuterated dimethylsulfoxide (DMSO-d6,0.05 quality %TMS potpourri) of 0.53ml, make it dissolve completely with ultrasound wave.The proton N MR of the 500MHz of this solution is determined with the NMR analyzer (JNW-ECA500) that NEC Dan Ding Co., Ltd. (Japanese Electricity デ ー タ system society) makes.Acid imide rate is tried to achieve as follows: the proton coming from unconverted structure before and after imidizate is decided to be reference proton, uses the peak integrated value of this proton and the proton peak integrated value of the NH base from amic acid that occurs near 9.5 ~ 10.0ppm to be tried to achieve by following formula.
Acid imide rate (%)=(1-α x/y) × 100
In above-mentioned formula, x is the integrated value of the proton peak of the NH base coming from amic acid, and y is the integrated value at standard proton peak, and α is the number ratio relative to the standard proton of 1 NH matrix of amic acid time polyamic acid (acid imide rate is 0%).
The making > of < liquid crystal cell
The aligning agent for liquid crystal prepared by embodiment and comparative example is made liquid crystal cell as follows.
Be spun on by aligning agent for liquid crystal on the glass substrate of band transparency electrode, on the heating plate of 80 DEG C after dry 70 seconds, the heating plate of 210 DEG C carries out 10 minutes burn till, and forming thickness is the film of 100nm.For utilizing the aligning agent for liquid crystal rubbing and carry out, with rayon cloth, this coated surface is rubbed under the condition of roller rotating speed 1000rpm, roller gait of march 50mm/ second, intrusion 0.3mm with the rubbing device of roller footpath 120mm, obtain the substrate being with liquid crystal orientation film.For the liquid crystal aligning process utilizing light to carry out, with the normal slope 40 relative to flat board °condition to this coated surface irradiate linear polarization UV light (UV wavelength 313nm, is equivalent to 500mJ) carry out.
Prepare 2 substrates through the band liquid crystal orientation film of as above liquid crystal aligning process, 1 liquid crystal aligning face scatters the sept of 6 μm wherein, then printing and sealing agent thereon, fit another plate base to make liquid crystal aligning face relatively and frictional direction craspedodrome (Twisted Nematic liquid crystal structure cell), or for the substrate irradiated through UV, carry out fit (vertical alignment mode) in the mode that the direction of the polarisation making irradiation is parallel, make sealant cures to make negative crystal born of the same parents.During for stable twisted nematic structure cell, liquid crystal MLC-2003 (Merck & Co., Inc. (メ ルク society) system) is injected by decompression injection method in negative crystal born of the same parents, during for vertical alignment mode, inject liquid crystal MLC-6608 (Merck & Co., Inc.'s system), sealing inlet, obtains Twisted Nematic liquid crystal structure cell.
Mensuration and the evaluating characteristics of the physical property of each liquid crystal cell made are as described below.
In addition, the result of the composition of each aligning agent for liquid crystal, the physical property measurement of each liquid crystal orientation film and evaluating characteristics etc. in embodiment 1 ~ 9 and comparative example 1 ~ 3 is shown in table 2 ~ table 4.
The evaluation > of < rub resistance
When the method recorded in making > with above-mentioned < liquid crystal cell makes the substrate of band liquid crystal orientation film, the intrusion of friction condition is changed into 0.5mm to carry out, make the liquid crystal orientation film of rub resistance evaluation, with confocal laser microscopic examination surface, carry out following evaluation.
Zero: do not observe abrasive dust attachment and friction scar.
△: observe abrasive dust attachment and friction scar.
×: film is peeled off or is observed visually friction scar.
The mensuration > of < tilt angle
To the Twisted Nematic liquid crystal structure cell of the method making recorded in the making > with above-mentioned < liquid crystal cell or after heating 5 minutes to antiparallel structure cell at 105 DEG C, carry out the mensuration of tilt angle.Tilt angle passes through " the Axo Scan " with Axo Metrix Inc. and measures by Muller matrix method (ミ ュ ラ ー マ ト リ Network ス method).
The mensuration > of < voltage retention (VHR) and the aging patience of backlight
Voltage retention after the voltage retention of the original state of the liquid crystal cell that the method recorded in the making > with above-mentioned < liquid crystal cell makes and backlight aging (carry liquid crystal cell on LCD backlight, drive 2 weeks with AC10V) is measured.Being determined as of voltage retention, applies the voltage 60 μ s of 4V at the temperature of 90 DEG C, measures the voltage after 16.67ms, calculates voltage and can keep how many, using this as voltage retention.In addition, the mensuration of voltage retention adopts Toyo Corp. (East Yang テ Network ニ カ society) the voltage retention determinator (VHR-1) made.
(embodiment 10)
In the four-hole boiling flask of 50mL, add the NMP of HC-01 and 28.2g of p-PDA, the 0.72g (1.50 mM) of the 1.46g (13.5 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 2.79g (14.3 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-1) is the solution of 15 quality %.
The solution 30g of this polyamic acid (PAA-1) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 15.0g of 30.0g dilutes, the solution of to make polyamic acid (PAA-1) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-1.The number-average molecular weight of this polyamic acid is 14300, and weight-average molecular weight is 41200.
(embodiment 11)
In the four-hole boiling flask of 50mL, add the NMP of HC-02 and 28.6g of p-PDA, the 0.80g (1.5 mM) of the 1.46g (13.5 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 2.79g (14.3 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-2) is the solution of 15 quality %.
The solution 30g of this polyamic acid (PAA-2) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 15.0g of 30.0g dilutes, the solution of to make polyamic acid (PAA-2) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-2.The number-average molecular weight of this polyamic acid is 12300, and weight-average molecular weight is 26700.
(embodiment 12)
In the four-hole boiling flask of 50mL, add the NMP of HC-03 and 28.6g of p-PDA, the 0.80g (1.5 mM) of the 1.46g (13.5 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 2.79g (14.3 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-3) is the solution of 15 quality %.
The solution 30g of this polyamic acid (PAA-3) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 15.0g of 30.0g dilutes, the solution of to make polyamic acid (PAA-3) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-3.The number-average molecular weight of this polyamic acid is 9800, and weight-average molecular weight is 26900.
(embodiment 13)
In the four-hole boiling flask of 50mL, add the NMP of HC-04 and 28.6g of p-PDA, the 0.80g (1.5 mM) of the 1.46g (13.5 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 2.79g (14.3 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-4) is the solution of 15 quality %.
The solution 30g of this polyamic acid (PAA-4) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 15.0g of 30.0g dilutes, the solution of to make polyamic acid (PAA-4) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-4.The number-average molecular weight of this polyamic acid is 11300, and weight-average molecular weight is 25800.
(embodiment 14)
In the four-hole boiling flask of 50mL, add the NMP of HC-05 and 27.1g of p-PDA, the 0.54g (1.5 mM) of the 1.46g (13.5 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 2.79g (14.3 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-5) is the solution of 15 quality %.
The solution 30g of this polyamic acid (PAA-5) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 15.0g of 30.0g dilutes, the solution of to make polyamic acid (PAA-5) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-5.The number-average molecular weight of this polyamic acid is 12600, and weight-average molecular weight is 30200.
(embodiment 15)
In the four-hole boiling flask of 50mL, add the NMP of HC-06 and 28.6g of p-PDA, the 0.80g (1.5 mM) of the 1.46g (13.5 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 2.79g (14.3 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-6) is the solution of 15 quality %.
The solution 30g of this polyamic acid (PAA-6) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 15.0g of 30.0g dilutes, the solution of to make polyamic acid (PAA-6) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-6.The number-average molecular weight of this polyamic acid is 12700, and weight-average molecular weight is 27700.
(embodiment 16)
In the four-hole boiling flask of 50mL, add the NMP of HC-07 and 28.7g of p-PDA, the 0.82g (1.5 mM) of the 1.46g (13.5 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 2.79g (14.3 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-7) is the solution of 15 quality %.
The solution 30g of this polyamic acid (PAA-7) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 15.0g of 30.0g dilutes, the solution of to make polyamic acid (PAA-7) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-7.The number-average molecular weight of this polyamic acid is 10200, and weight-average molecular weight is 26500.
(embodiment 17)
In the four-hole boiling flask of 50mL, add the NMP of HC-10 and 28.1g of p-PDA, the 0.71g (1.5 mM) of the 1.46g (13.5 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 2.79g (14.3 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-8) is the solution of 15 quality %.
The solution 30g of this polyamic acid (PAA-8) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 15.0g of 30.0g dilutes, the solution of to make polyamic acid (PAA-8) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-8.The number-average molecular weight of this polyamic acid is 9900, and weight-average molecular weight is 23500.
(embodiment 18)
In the four-hole boiling flask of 50mL, add the NMP of HC-05 and 17.4g of the 2.00g (5.60 mM) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 1.08g (5.49 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-9) is the solution of 15 quality %.
The solution 15g of this polyamic acid (PAA-9) is transferred in the Erlenmeyer flask of 50mL, the BC adding NMP, 7.5g of 15.0g dilutes, the solution of to make polyamic acid (PAA-9) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-9.The number-average molecular weight of this polyamic acid is 21200, and weight-average molecular weight is 50900.
(embodiment 19)
In the four-hole boiling flask of 50mL, add the NMP of PCH-7AB and 20.3g of HC-08, the 0.45g (1.17 mM) of the 2.00g (4.70 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 1.13g (5.81 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-10) is the solution of 15 quality %.
The solution 20g of this polyamic acid (PAA-10) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 10.0g of 20.0g dilutes, the solution of to make polyamic acid (PAA-10) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-10.The number-average molecular weight of this polyamic acid is 13300, and weight-average molecular weight is 42800.
(embodiment 20)
In the four-hole boiling flask of 50mL, add the NMP of PCH-7AB and 19.7g of HC-09, the 0.45g (1.10 mM) of the 2.00g (4.38 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 1.06g (5.43 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-11) is the solution of 15 quality %.
The solution 20g of this polyamic acid (PAA-11) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 10.0g of 20.0g dilutes, the solution of to make polyamic acid (PAA-11) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-11.The number-average molecular weight of this polyamic acid is 10700, and weight-average molecular weight is 35300.
(embodiment 21)
2 of 3-ABA, the 0.384g (1.89 mM) of the 0.307g (2.52 mM) as diamine component are added in the four-hole boiling flask of 100mL, the NMP of HC-02 and 12.3g of 4-DAA, 1.00g (1.89 moles), is cooled to about 10 DEG C.Then, add the PMDA of 0.412g (1.89 mM), return to room temperature, react 1 hour under nitrogen atmosphere.Add the CBDA of 0.964g (4.91 mM) again, react 16 hours under room temperature, blanket of nitrogen, the concentration obtaining polyamic acid (PAA-12) is the solution of 20 quality %.
The NMP adding 22.5g in the solution 15.0g of polyamic acid (PAA-12) dilutes, then adds 1.96g acetic anhydride and 0.84g pyridine, reacts 3 hours at 50 DEG C.After this reaction solution is cooled to room temperature, stirs in the methyl alcohol 150mL slowly pouring into and be cooled to about 10 DEG C, solid is separated out.Reclaim the solid of separating out, then carry out with methyl alcohol 100mL the dispersion cleaning amounting to 2 times, at 100 DEG C, carry out drying under reduced pressure, obtain the tawny powder of polyimide (SPI-1).The number-average molecular weight of this polyimide is 11200, and weight-average molecular weight is 30800.In addition, acid imide rate is 89%.
In the polyimide (SPI-1) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.The DPM of the γ-BL of 8.0g, BC and 6.0g of 6.0g is added again in this solution, stir 20 hours in 50 DEG C, obtain that polyimide (SPI-1) is 5 quality %, the aligning agent for liquid crystal-12 of γ-BL be 65 quality %, BC to be 15 quality %, DPM be 15 quality %.
(embodiment 22)
2 of 3-ABA, the 0.384g (1.89 mM) of the 0.307g (2.52 mM) as diamine component are added in the four-hole boiling flask of 100mL, the NMP of HC-03 and 12.3g of 4-DAA, 1.00g (1.89 moles), is cooled to about 10 DEG C.Then, add the PMDA of 0.412g (1.89 mM), return to room temperature, react 1 hour under nitrogen atmosphere.Add the CBDA of 0.964g (4.91 mM) again, react 16 hours under room temperature, blanket of nitrogen, the concentration obtaining polyamic acid (PAA-13) is the solution of 20 quality %.
The NMP adding 22.5g in the solution 15.0g of polyamic acid (PAA-13) dilutes, then adds 1.96g acetic anhydride and 0.84g pyridine, reacts 3 hours at 50 DEG C.After this reaction solution is cooled to room temperature, stirs in the methyl alcohol 150mL slowly pouring into and be cooled to about 10 DEG C, solid is separated out.Reclaim the solid of separating out, then carry out with methyl alcohol 100mL the dispersion cleaning amounting to 2 times, at 100 DEG C, carry out drying under reduced pressure, obtain the orange powder of polyimide (SPI-2).The number-average molecular weight of this polyimide is 9800, and weight-average molecular weight is 23500.In addition, acid imide rate is 89%.
In the polyimide (SPI-2) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.The DPM of the γ-BL of 8.0g, BC and 6.0g of 6.0g is added again in this solution, stir 20 hours in 50 DEG C, obtain that polyimide (SPI-2) is 5 quality %, the aligning agent for liquid crystal-13 of γ-BL be 65 quality %, BC to be 15 quality %, DPM be 15 quality %.
(embodiment 23)
2 of 3-ABA, the 0.384g (1.89 mM) of the 0.308g (2.52 mM) as diamine component are added in the four-hole boiling flask of 100mL, the NMP of HC-04 and 12.3g of 4-DAA, 1.00g (0.89 mole), is cooled to about 10 DEG C.Then, add the PMDA of 0.412g (1.89 mM), return to room temperature, react 1 hour under nitrogen atmosphere.Add the CBDA of 0.964g (4.91 mM) again, react 16 hours under room temperature, blanket of nitrogen, the concentration obtaining polyamic acid (PAA-14) is the solution of 20 quality %.
The NMP adding 22.5g in the solution 15.0g of polyamic acid (PAA-14) dilutes, then adds 1.96g acetic anhydride and 0.84g pyridine, reacts 3 hours at 50 DEG C.After this reaction solution is cooled to room temperature, stirs in the methyl alcohol 150mL slowly pouring into and be cooled to about 10 DEG C, solid is separated out.Reclaim the solid of separating out, then carry out with methyl alcohol 100mL the dispersion cleaning amounting to 2 times, at 100 DEG C, carry out drying under reduced pressure, obtain the tawny powder of polyimide (SPI-3).The number-average molecular weight of this polyimide is 11800, and weight-average molecular weight is 25100.In addition, acid imide rate is 88%.
In the polyimide (SPI-3) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.The DPM of the γ-BL of 8.0g, BC and 6.0g of 6.0g is added again in this solution, stir 20 hours in 50 DEG C, obtain that polyimide (SPI-3) is 5 quality %, the aligning agent for liquid crystal-14 of γ-BL be 65 quality %, BC to be 15 quality %, DPM be 15 quality %.
(embodiment 24)
2 of 3-ABA, the 0.384g (1.89 mM) of the 0.308g (2.52 mM) as diamine component are added in the four-hole boiling flask of 100mL, the NMP of HC-06 and 12.3g of 4-DAA, 1.00g (0.89 mole), is cooled to about 10 DEG C.Then, add the PMDA of 0.412g (1.89 mM), return to room temperature, react 1 hour under nitrogen atmosphere.Add the CBDA of 0.964g (4.91 mM) again, react 16 hours under room temperature, blanket of nitrogen, the concentration obtaining polyamic acid (PAA-15) is the solution of 20 quality %.
The NMP adding 22.5g in the solution 15.0g of polyamic acid (PAA-15) dilutes, then adds 1.96g acetic anhydride and 0.84g pyridine, reacts 3 hours at 50 DEG C.After this reaction solution is cooled to room temperature, stirs in the methyl alcohol 150mL slowly pouring into and be cooled to about 10 DEG C, solid is separated out.Reclaim the solid of separating out, then carry out with methyl alcohol 100mL the dispersion cleaning amounting to 2 times, at 100 DEG C, carry out drying under reduced pressure, obtain the tawny powder of polyimide (SPI-4).The number-average molecular weight of this polyimide is 13200, and weight-average molecular weight is 29400.In addition, acid imide rate is 85%.
In the polyimide (SPI-4) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.The DPM of the γ-BL of 8.0g, BC and 6.0g of 6.0g is added again in this solution, stir 20 hours in 50 DEG C, obtain that polyimide (SPI-4) is 5 quality %, the aligning agent for liquid crystal-15 of γ-BL be 65 quality %, BC to be 15 quality %, DPM be 15 quality %.
(embodiment 25)
2 of 3-ABA, the 0.372g (1.83 mM) of the 0.298g (2.44 mM) as diamine component are added in the four-hole boiling flask of 100mL, the NMP of HC-04 and 12.0g of 4-DAA, 1.00g (0.83 mole), is cooled to about 10 DEG C.Then, add the PMDA of 0.399g (1.83 mM), return to room temperature, react 1 hour under nitrogen atmosphere.Add the CBDA of 0.933g (4.76 mM) again, react 16 hours under room temperature, blanket of nitrogen, the concentration obtaining polyamic acid (PAA-16) is the solution of 20 quality %.
The NMP adding 22.5g in the solution 15.0g of polyamic acid (PAA-16) dilutes, then adds 1.94g acetic anhydride and 0.83g pyridine, reacts 3 hours at 50 DEG C.After this reaction solution is cooled to room temperature, stirs in the methyl alcohol 150mL slowly pouring into and be cooled to about 10 DEG C, solid is separated out.Reclaim the solid of separating out, then carry out with methyl alcohol 100mL the dispersion cleaning amounting to 2 times, at 100 DEG C, carry out drying under reduced pressure, obtain the tawny powder of polyimide (SPI-5).The number-average molecular weight of this polyimide is 10700, and weight-average molecular weight is 22800.In addition, acid imide rate is 87%.
In the polyimide (SPI-5) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.The DPM of the γ-BL of 8.0g, BC and 6.0g of 6.0g is added again in this solution, stir 20 hours in 50 DEG C, obtain that polyimide (SPI-5) is 5 quality %, the aligning agent for liquid crystal-16 of γ-BL be 65 quality %, BC to be 15 quality %, DPM be 15 quality %.
(embodiment 26)
In the four-hole boiling flask of 100mL, add the CBDE of 2.37g (9.12 mM), triethylamine as NMP and 0.475g (4.70 mM) of HC-02,30.7g of p-PDA, 1.00g (1.88 mM) of the 0.813g (7.52 mM) of diamine component, be cooled to about 10 DEG C.Then, add the DMT-MM of 7.80g (28.2 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining poly amic acid ester (PAE-1) is the solution of 12 quality %.
In the solution of this polyamic acid (PAE-1), add the NMP of 34.9g, stir in the methyl alcohol 500mL pouring at leisure and be cooled to about 10 DEG C, solid is separated out.Reclaim the solid of separating out, then carry out with methyl alcohol 300mL the dispersion cleaning amounting to 2 times, at 100 DEG C, carry out drying under reduced pressure, obtain the white powder of poly amic acid ester (PAE-1).The number-average molecular weight of this poly amic acid ester is 15300, and weight-average molecular weight is 38800.
γ-the BL of 18.0g is added, in stirring at room temperature 20 hours in the poly amic acid ester (PAE-1) of 2.00g.At the end of stirring, polyimide dissolves completely.The DPM of the γ-BL of 8.0g, BC and 6.0g of 6.0g is added again in this solution, stir 20 hours in 50 DEG C, obtain that polyimide (PAE-1) is 5 quality %, the aligning agent for liquid crystal-17 of γ-BL be 65 quality %, BC to be 15 quality %, DPM be 15 quality %.
(comparative example 1)
In the four-hole boiling flask of 50mL, add the NMP of C16DAB and 28.2g of p-PDA, the 0.52g (1.50 mM) of the 1.45g (13.5 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 2.79g (14.3 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-17) is the solution of 15 quality %.
The solution 30g of this polyamic acid (PAA-17) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 15.0g of 30.0g dilutes, the solution of to make polyamic acid (PAA-17) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-18.The number-average molecular weight of this polyamic acid is 18300, and weight-average molecular weight is 43200.
(comparative example 2)
In the four-hole boiling flask of 50mL, add the NMP of CAB-2 and 28.2g of p-PDA, the 0.64g (1.50 mM) of the 1.45g (13.5 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 2.79g (14.3 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-18) is the solution of 15 quality %.
The solution 30g of this polyamic acid (PAA-18) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 15.0g of 30.0g dilutes, the solution of to make polyamic acid (PAA-18) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-19.The number-average molecular weight of this polyamic acid is 9700, and weight-average molecular weight is 19200.
(comparative example 3)
In the four-hole boiling flask of 50mL, add the NMP of the mTDA and 20.3 of the 2.00g (8.26 mM) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 1.59g (8.09 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-19) is the solution of 15 quality %.
The solution 15g of this polyamic acid (PAA-19) is transferred in the Erlenmeyer flask of 50mL, the BC adding NMP, 7.5g of 15.0g dilutes, the solution of to make polyamic acid (PAA-19) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-20.The number-average molecular weight of this polyamic acid is 22000, and weight-average molecular weight is 49600.
(comparative example 4)
2 of 3-ABA, the 0.634g (3.12 mM) of the 0.508g (4.16 mM) as diamine component are added in the four-hole boiling flask of 100mL, the NMP of C14DAB and 17.7g of 4-DAA, 1.00g (3.12 mM), is cooled to about 10 DEG C.Then, add the PMDA of 0.680g (3.12 mM), return to room temperature, react 1 hour under nitrogen atmosphere.Add the CBDA of 1.59g (8.11 mM) again, react 16 hours under room temperature, blanket of nitrogen, the concentration obtaining polyamic acid (PAA-20) is the solution of 20 quality %.
The NMP adding 30.0g in the solution 20.0g of polyamic acid (PAA-20) dilutes, then adds 3.01g acetic anhydride and 1.29g pyridine, reacts 3 hours at 50 DEG C.After this reaction solution is cooled to room temperature, stirs in the methyl alcohol 200mL slowly pouring into and be cooled to about 10 DEG C, solid is separated out.Reclaim the solid of separating out, then carry out with methyl alcohol 150mL the dispersion cleaning amounting to 2 times, at 100 DEG C, carry out drying under reduced pressure, obtain the tawny powder of polyimide (SPI-6).The number-average molecular weight of this polyimide is 10700, and weight-average molecular weight is 22800.In addition, acid imide rate is 88%.
In the polyimide (SPI-6) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.The DPM of the γ-BL of 8.0g, BC and 6.0g of 6.0g is added again in this solution, stir 20 hours in 50 DEG C, make that polyimide (SPI-6) is 5 quality %, the solution of γ-BL be 65 quality %, BC to be 15 quality %, DPM be 15 quality %, obtain aligning agent for liquid crystal-21.
(comparative example 5)
2 of 3-ABA, the 0.482g (2.37 mM) of the 0.386g (3.16 mM) as diamine component are added in the four-hole boiling flask of 100mL, the NMP of CAB-2 and 14.4g of 4-DAA, 1.00g (2.37 mM), is cooled to about 10 DEG C.Then, add the PMDA of 0.517g (2.37 mM), return to room temperature, react 1 hour under nitrogen atmosphere.Add the CBDA of 1.21g (6.16 mM) again, react 16 hours under room temperature, blanket of nitrogen, the concentration obtaining polyamic acid (PAA-21) is the solution of 20 quality %.
The NMP adding 22.5g in the solution 15.0g of polyamic acid (PAA-21) dilutes, then adds 2.10g acetic anhydride and 0.90g pyridine, reacts 3 hours at 50 DEG C.After this reaction solution is cooled to room temperature, stirs in the methyl alcohol 150mL slowly pouring into and be cooled to about 10 DEG C, solid is separated out.Reclaim the solid of separating out, then carry out with methyl alcohol 100mL the dispersion cleaning amounting to 2 times, at 100 DEG C, carry out drying under reduced pressure, obtain the yellowish orange powder of polyimide (SPI-7).The number-average molecular weight of this polyimide is 9900, and weight-average molecular weight is 28800.In addition, acid imide rate is 91%.
In the polyimide (SPI-7) of 2.00g, add the γ-BL of 18.0g, stir 20 hours in 50 DEG C.At the end of stirring, polyimide dissolves completely.The DPM of the γ-BL of 8.0g, BC and 6.0g of 6.0g is added again in this solution, stir 20 hours in 50 DEG C, make that polyimide (SPI-7) is 5 quality %, the solution of γ-BL be 65 quality %, BC to be 15 quality %, DPM be 15 quality %, obtain aligning agent for liquid crystal-22.
(comparative example 6)
In the four-hole boiling flask of 50mL, add the NMP of PCH-7AB and 23.3g of m-PDA, the 0.883g (2.32 mM) of the 1.00g (9.28 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 2.23g (11.4 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-22) is the solution of 15 quality %.
The solution 20g of this polyamic acid (PAA-22) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 10.0g of 20.0g dilutes, the solution of to make polyamic acid (PAA-22) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-23.The number-average molecular weight of this polyamic acid is 16300, and weight-average molecular weight is 40200.
(comparative example 7)
In the four-hole boiling flask of 100mL, add the CBDE of 2.98g (11.4 mM), triethylamine as NMP and 0.60g (5.90 mM) of CAB-2,36.6g of p-PDA, 1.00g (2.36 mM) of the 1.02g (9.44 mM) of diamine component, be cooled to about 10 DEG C.Then, add the DMT-MM of 9.80g (35.4 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining poly amic acid ester (PAE-2) is the solution of 12 quality %.
In the solution of this polyamic acid (PAE-2), add the NMP of 41.7g, stir in the methyl alcohol 500mL pouring at leisure and be cooled to about 10 DEG C, solid is separated out.Reclaim the solid of separating out, then carry out with methyl alcohol 300mL the dispersion cleaning amounting to 2 times, at 100 DEG C, carry out drying under reduced pressure, obtain the baby pink powder of poly amic acid ester (PAE-2).The number-average molecular weight of this poly amic acid ester is 13200, and weight-average molecular weight is 35700.
γ-the BL of 18.0g is added, in stirring at room temperature 20 hours in the poly amic acid ester (PAE-2) of 2.00g.At the end of stirring, polyimide dissolves completely.The DPM of the γ-BL of 8.0g, BC and 6.0g of 6.0g is added again in this solution, stir 20 hours in 50 DEG C, make that polyimide (PAE-2) is 5 quality %, the solution of γ-BL be 65 quality %, BC to be 15 quality %, DPM be 15 quality %, obtain aligning agent for liquid crystal-24.
[table 2]
[table 3]
[table 4]
When embodiment 10 ~ 18 and comparative example 1,2 being compared, the rub resistance in known embodiment 10 ~ 18 improves, VHR is high, the aging patience of backlight is excellent.
When embodiment 17 and comparative example 3 being compared, compared with embodiment 17, tilt angle is little for known comparative example 3 (structure of cyclization does not occur), also excellent in the raising of the aging patience of rub patience and VHR.
When embodiment 19,20 and comparative example 6 being compared, confirm to show tilt angle in embodiment 19,20, known aligning agent for liquid crystal is useful in optical alignment method.
When embodiment 21 ~ 25 and comparative example 4,5 are compared, when aligning agent for liquid crystal being printed on substrate in comparative example 4,5, confirm have pore and rhombus unequal, printing in embodiment 21 ~ 25 is excellent, do not confirm this defect, in addition, also confirm that tilt angle manifests and the effect of raising of the aging patience of backlight of VHR.
When embodiment 26 and comparative example 7 being compared, the printing in embodiment 26 is good, and the result that the aging patience of the backlight obtaining rub resistance and VHR improves.
< embodiment 27>
The synthesis of the synthesis (HC-11) of 4-(trans-4-amyl group hexamethylene acylamino-)-3-(tertbutyloxycarbonylamino) phenyl-3,5-diaminobenzene formamide
[changing 106]
Step 1
The synthesis of 4-(trans-4-amyl group hexamethylene acylamino-)-3-(tertbutyloxycarbonylamino)-nitrobenzene
[changing 107]
Trans-4-pentylcyclohexane carboxylic acid 5.16g (20.0 mM) is measured in the eggplant type flask of the band branch of 100mL, the THF adding 50mL makes it dissolve, and slowly drips the 50 quality %THF solution of thionyl chloride 3.33g (28.0 mM) under ice bath.Then, return to room temperature, react 2 hours, generate 4-amyl group Cyclohexanoyl chloride.
On the other hand, 3-tertbutyloxycarbonylamino-4-aminonitrobenzene 5.07g (20.0 mM) is measured in the four-hole boiling flask of 200mL, add THF50.0mL and triethylamine 4.05g (40.0 mM), less than 10 DEG C are adjusted to, the 4-amyl group Cyclohexanoyl chloride of preparation before dripping under nitrogen atmosphere with ice bath.Then, return to room temperature, react 24 hours under nitrogen atmosphere.
After reaction terminates, add ethyl acetate, clean with the sodium bicarbonate aqueous solution of 10 quality %, acetic acid water, pure water and saturated aqueous common salt successively.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.With the mixed solvent (6:4) of ethyl acetate and normal hexane, recrystallization is carried out to residue, obtain white-yellowish solid 5.31g (yield 61%).
Step 2
The synthesis of 4-(trans-4-amyl group hexamethylene acylamino-)-3-(tertbutyloxycarbonylamino)-aniline
[changing 108]
In the four-hole boiling flask of 100mL, add 4-(trans-4-amyl group hexamethylene acylamino-)-3-(tertbutyloxycarbonylamino)-nitrobenzene 4.28g (9.88 mM), tetrahydrofuran 50mL, pure water 50mL and tin chloride 9.48g (50.0 mM), reflux 24 hours under nitrogen atmosphere.After reaction terminates, adding ethyl acetate 100mL, then add the sodium bicarbonate aqueous solution of 10 quality %, filtering precipitate by crossing.Then, the organic layer of separating filtrate, cleans with pure water, saturated aqueous common salt, carries out drying with anhydrous sodium sulfate.Filtering anhydrous sodium sulfate by crossing, with rotary evaporator except desolventizing, obtaining yellow solid 3.95g (yield 99%).
Step 3
The synthesis of 4-(trans-4-amyl group hexamethylene acylamino-)-3-(tertbutyloxycarbonylamino) phenyl-3,5-dinitrobenzamide
[changing 109]
4-(trans-4-amyl group hexamethylene acylamino-)-3-(tertbutyloxycarbonylamino) aniline 4.79g (11.9 mM), tetrahydrofuran 80mL and pyridine 1.10g (13.9 mM) is added in the four-hole boiling flask of 200mL, under nitrogen atmosphere, in ice bath less than 10 DEG C, drip 3 at leisure again, the 10 quality %THF solution of 5-dinitrobenzoyl chloride 3.22g (14.0 mM), react 24 hours after returning to room temperature.By system internal cooling to 0 DEG C, then add 3,5-dinitrobenzoyl chloride 5.8g (14.0 mM), at room temperature stir.After reaction terminates, with rotary evaporator except desolventizing, add ethyl acetate, clean with the aqueous sodium carbonate of 10 quality %, water and saturated aqueous common salt.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.With the mixed solvent (1:9) of ethyl acetate and normal hexane, recrystallization is carried out to residue, obtain faint yellow solid 5.26g (yield 74%).
Step 4
The synthesis of HC-11
[changing 110]
4-(trans-4-amyl group hexamethylene acylamino-)-3-(tertbutyloxycarbonylamino) phenyl-3 is added in the four-hole boiling flask of 300mL, 5-dinitrobenzamide 5.00g (8.37 mM), tetrahydrofuran 30mL, ethanol 30mL and 5% palladium carbon 0.50g, stir under a hydrogen atmosphere, in room temperature.After reaction terminates, filtering palladium carbon by crossing, using rotary evaporator distillation except desolventizing.With the mixed solvent (1:9) of ethyl acetate and normal hexane, recrystallization is carried out to residue, then with normal hexane dispersion cleaning, thus obtain the solid 4.20g (yield 93%) of grey.
The solid of gained 1the result of H-NMR is as follows.According to this result, be confirmed to be object HC-10.
1H NMR(400MHz,[D 6]-DMSO):δ9.94(s,1H),9.22(s,1H),8.34(s,1H),8.34-7.93(d,1H),7.48-7.7.46(dd,1H),7.32-7.30(d,1H),7.28(d,2H),5.99-5.97(t,1H),4.93(s-br,4H),2.29(m,1H),1.88-1.81(m,4H),1.47(s,9H)1.47-1.40(m,2H),1.31-1.16(m,9H),0.94-0.91(m、2H)0.89-0.85(t,3H)
< embodiment 28>
The synthesis of the synthesis (HC-12) of 4-[4-(trans-4-pentylcyclohexyl) benzamido]-3-(tertbutyloxycarbonylamino) phenyl-3,5-diaminobenzene formamide
[changing 111]
Step 1
The synthesis of 4-[(trans-4-pentylcyclohexyl) benzamido]-3-tertbutyloxycarbonylamino-nitrobenzene
[changing 112]
100mL band branch eggplant type flask in measure 4-(trans-4-pentylcyclohexyl) benzoic acid 5.07g (22.0 mM), add THF50mL and DMF1mL, thionyl chloride 3.33g (28.0 mM) is dripped at leisure under ice bath, return to room temperature, react 2 hours, generate 4-(trans-4-pentylcyclohexyl) chlorobenzoyl chloride.
On the other hand, 3-tertbutyloxycarbonylamino-4-aminonitrobenzene 5.07g (20.0 mM) is measured in the four-hole boiling flask of 200mL, add THF50.0mL and triethylamine 2.43g (24.0 mM), less than 10 DEG C are adjusted to ice bath, 4-(trans-4-pentylcyclohexyl) chlorobenzoyl chloride of preparation before dripping under nitrogen atmosphere, return to room temperature, react 24 hours under nitrogen atmosphere.
After reaction terminates, add ethyl acetate, clean with the sodium bicarbonate aqueous solution of 10 quality %, acetic acid water, pure water and saturated aqueous common salt.Then using dried over mgso, filtering magnesium sulfate by crossing, use rotary evaporator distillation except desolventizing.With the mixed solvent (3:7) of ethyl acetate and normal hexane, recrystallization is carried out to residue, obtain white-yellowish solid 6.03g (yield 60%).
Step 2
The synthesis of 4-[(trans-4-pentylcyclohexyl) benzamido]-3-(tertbutyloxycarbonylamino) aniline
[changing 113]
4-[(trans-4-pentylcyclohexyl) benzamido]-3-(tertbutyloxycarbonylamino) nitrobenzene 6.03g (11.8 mM), tetrahydrofuran 50mL and 5% palladium carbon 0.60g is added, under a hydrogen atmosphere, in stirring at room temperature 24 hours in the four-hole boiling flask of 200mL.After reaction terminates, filtering palladium carbon by crossing, with rotary evaporator except desolventizing, obtaining the solid 5.94g (yield 99%) of white.
Step 3
The synthesis of 4-[(trans-4-pentylcyclohexyl) benzamido]-3-(tertbutyloxycarbonylamino) phenyl-3,5-dinitrobenzamide
[changing 114]
4-[(trans-4-pentylcyclohexyl) benzamido]-3-(tertbutyloxycarbonylamino) aniline 5.94g (12.4 mM), tetrahydrofuran 80mL and pyridine 1.10g (13.9 mM) is added in the four-hole boiling flask of 200mL, under nitrogen atmosphere, in ice bath less than 10 DEG C drip the 10 quality %THF solution of 3,5-dinitrobenzoyl chloride 3.22g (14.0 mM) at leisure.Then, return to room temperature, react 24 hours.After reaction terminates, with rotary evaporator except desolventizing, after washed with methanol residue, carry out recrystallization with the mixed solvent (1:9) of ethyl acetate and normal hexane, obtain faint yellow solid 7.82g (yield 94%).
Step 4
The synthesis of HC-11
[changing 115]
In the four-hole boiling flask of 300mL, make 4-[(trans-4-pentylcyclohexyl) benzamido)-3-(tertbutyloxycarbonylamino) phenyl-3,5-dinitrobenzamide 6.00g (8.9 mM) is dissolved in tetrahydrofuran 60mL, add 5% palladium carbon 0.60g, stir under a hydrogen atmosphere, in room temperature.After reaction terminates, filtering palladium carbon by crossing, using rotary evaporator distillation except desolventizing.With the mixed solvent (1:9) of ethyl acetate and normal hexane, recrystallization is carried out to residue, then with normal hexane dispersion cleaning, thus obtain the solid 5.45g (yield 99%) of grey.
The solid of gained 1the result of H-NMR is as follows.According to this result, be confirmed to be object HC-10.
1H NMR(400MHz,[D 6]-DMSO):δ10.00(s,1H),9.71(s,1H),8.59(s,1H),8.02-8.01(d,1H),7.89―7.87(d,2H),7.54-7.51(dd,1H),7.41-7.37(dd,3H),6.31-6.30(d,2H),6.00-5.99(t,1H),4.94(s-br,4H),2.60-2.51(t,1H),1.85-1.81(m,4H),1.51-1.45(t,2H)1.45(s,9H),1.32-1.2(m,10H)1.10-1.00(m,2H)0.89-0.86(t,3H)
(embodiment 29)
In the four-hole boiling flask of 50mL, add the NMP of HC-11 and 28.6g of p-PDA, the 0.81g (1.5 mM) of the 1.46g (13.5 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 2.79g (14.3 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-23) is the solution of 15 quality %.
The solution 30g of this polyamic acid (PAA-23) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 15.0g of 30.0g dilutes, the solution of to make polyamic acid (PAA-23) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-25.The number-average molecular weight of this polyamic acid is 10100, and weight-average molecular weight is 22500.
(embodiment 30)
In the four-hole boiling flask of 50mL, add the NMP of HC-12 and 29.4g of p-PDA, the 0.94g (1.5 mM) of the 1.46g (13.5 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 2.79g (14.3 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-24) is the solution of 15 quality %.
The solution 30g of this polyamic acid (PAA-24) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 15.0g of 30.0g dilutes, the solution of to make polyamic acid (PAA-24) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-26.The number-average molecular weight of this polyamic acid is 13700, and weight-average molecular weight is 28200.
(embodiment 31)
In the four-hole boiling flask of 50mL, add the NMP of HC-11 and 36.4g of p-PDA, the 2.48g (4.5 mM) of the 1.06g (10.5 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 2.88g (14.7 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-25) is the solution of 15 quality %.
The solution 30g of this polyamic acid (PAA-25) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 15.0g of 30.0g dilutes, the solution of to make polyamic acid (PAA-25) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-27.The number-average molecular weight of this polyamic acid is 17200, and weight-average molecular weight is 38900.
(embodiment 32)
In the four-hole boiling flask of 50mL, add the NMP of HC-12 and 38.3g of p-PDA, the 2.82g (4.5 mM) of the 1.06g (10.5 moles) as diamine component, be cooled to about 10 DEG C.Then, add the CBDA of 2.88g (14.7 mM), return to room temperature, react 24 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-26) is the solution of 15 quality %.
The solution 30g of this polyamic acid (PAA-26) is transferred in the Erlenmeyer flask of 100mL, the BC adding NMP, 15.0g of 30.0g dilutes, the solution of to make polyamic acid (PAA-26) be 6 quality %, NMP to be 74 quality %, BC be 20 quality %, obtains aligning agent for liquid crystal-28.The number-average molecular weight of this polyamic acid is 19600, and weight-average molecular weight is 42200.
Evaluation same as described above is carried out to the aligning agent for liquid crystal of embodiment 29 ~ 32.The results are shown in table 5 ~ table 8.
[table 5]
[table 6]
< side chain diamines dissolubility test >
As the deliquescent test of comparing monomer, add the NMP of 2.0g relative to side chain diamines 0.5g, stir 1 hour in 20 DEG C, whether the solution of preparation 20wt%, investigate and dissolve.The metewand of test is as follows.
Dissolve completely: zero
There is not molten thing: ×
[table 7]
Diamines Whether dissolve
HC-01 ○
HC-02 ○
HC-03 ○
HC-04 ○
HC-05 ○
HC-06 ○
HC-07 ○
HC-08 ○
HC-09 ○
HC-10 ○
HC-11 ○
HC-12 ○
CAB-2 ×
PCH-7AB ×
[table 8]
The possibility that industry utilizes
Use aligning agent for liquid crystal of the present invention and the reliability of the liquid crystal display cells manufactured is high, can be used for comprising large picture and the TN liquid crystal display cells of the LCD TV of high-resolution, stn liquid crystal display element, TFT liquid crystal display cells, VA liquid crystal display cells, IPS liquid crystal display cells, OCB liquid crystal display cells etc.
Quote the full content of the instructions of No. 2010-150054, the Japanese patent application that on June 30th, 2010 files an application, claims and specification digest here, as the announcement of instructions of the present invention.

Claims (19)

1. an aligning agent for liquid crystal, comprise at least one polymkeric substance being selected from the polyimide obtained through imidizate by the polyimide precursor of the diamine component of the diamines represented containing following formula [1] and the reaction gained of tetracarboxylic dianhydride and this polyimide precursor
[changing 1]
In formula, X is the organic group represented with following formula [2]; Y 1, Y 2represent phenyl ring or cyclohexane ring independently; P, q represent the integer of 0 or 1 independently; S 1, S 2represent singly-bound or bivalence linking base group independently; S during p=0 1for singly-bound, S during q=0 2for singly-bound; R 1represent hydrogen atom, fluorine atom, the alkyl of carbon number 1 ~ 22, the fluoroalkyl of carbon number 1 ~ 22 or steroid radical,
[changing 2]
In formula, C 1, C 2represent singly-bound or divalent organic group independently; A represents the organic group departed from by heating; B 1represent and be selected from-CH 2-, the divalent organic group of-O-,-NH-and-S-; N is 0 or 1; The link direction of X is not limited.
2. aligning agent for liquid crystal as claimed in claim 1, it is characterized in that, the content of the diamines that the formula [1] in described diamine component represents is 5 ~ 95 % by mole.
3. aligning agent for liquid crystal as claimed in claim 1 or 2, it is characterized in that, the A in described formula [2] is the tert-butoxycarbonyl represented with formula [3],
[changing 3]
4. aligning agent for liquid crystal as claimed in claim 1, is characterized in that, the C in described formula [2] 1, C 2the divalent organic group represented with following formula [6],
[changing 4]
-S 3-R 2-S 4-R 3-[6]
In formula, S 3, S 4be bivalence linking base group independently; R 2, R 3be the bivalent hydrocanbon radical of singly-bound or carbon number 1 ~ 20 independently.
5. aligning agent for liquid crystal as claimed in claim 4, is characterized in that, the [-S of described formula [6] 4-R 3-] represent with following formula [4], and C 1, C 2in either party there is the structure of formula [4],
[changing 5]
In formula, B 2represent and be selected from singly-bound, phenyl ,-CH 2-,-O-,-NH-,-NR 10-and the divalent organic group of-S-; R 10represent the divalence hydrocarbon of carbon number 1 ~ 6; The structure of the alkene of formula [4] can be any one in E formula, Z formula; C in the key be represented by dotted lines and formula [2] 1the phenyl ring linked or C 2the carbonyl carbon linked links.
6. aligning agent for liquid crystal as claimed in claim 1, is characterized in that, in described formula [2], and n=0.
7. aligning agent for liquid crystal as claimed in claim 1, is characterized in that, the C in described formula [2] 1it is singly-bound.
8. aligning agent for liquid crystal as claimed in claim 1, is characterized in that, the B in described formula [2] 1-O-or NH-.
9. aligning agent for liquid crystal as claimed in claim 5, is characterized in that, the B in described formula [4] 2-O-or NH-.
10. aligning agent for liquid crystal as claimed in claim 1, it is characterized in that, the diamines represented by described formula [1] is any one compound in following formula [1-a] ~ [1-k],
[changing 6]
[changing 7]
11. 1 kinds of liquid crystal orientation films, is characterized in that, obtain by using the aligning agent for liquid crystal according to any one of claim 1 ~ 10.
12. 1 kinds of liquid crystal orientation films, its liquid crystal orientation film obtained for using the aligning agent for liquid crystal according to any one of claim 1 ~ 10, is penetrated by illumination and carries out orientation process.
13. 1 kinds of liquid crystal display cells, it possesses the liquid crystal orientation film described in claim 11 or 12.
14. 1 kinds of diamines with the structure represented with following formula [1],
[changing 8]
In formula, X is the organic group represented with following formula [2]; Y 1, Y 2represent phenyl ring or cyclohexane ring independently; P, q represent the integer of 0 or 1 independently; S 1, S 2represent singly-bound or bivalence linking base group independently; S during p=0 1for singly-bound, S during q=0 2for singly-bound; R 1represent hydrogen atom, fluorine atom, the alkyl of carbon number 1 ~ 22, the fluoroalkyl of carbon number 1 ~ 22 or steroid radical,
[changing 9]
In formula, C 1, C 2represent singly-bound or divalent organic group independently; A represents the organic group departed from by heating; B 1represent and be selected from-CH 2-, the divalent organic group of-O-,-NH-and-S-; N is 0 or 1; The link direction of X is not limited.
15. diamines as claimed in claim 14, is characterized in that, the A in formula [2] is the tert-butoxycarbonyl represented with formula [3],
[changing 10]
16. diamines as described in claims 14 or 15, is characterized in that, the C in formula [2] 1, C 2the divalent organic group represented with following formula [6],
[changing 11]
-S 3-R 2-S 4-R 3-[6]
In formula, S 3, S 4be bivalence linking base group independently; R 2, R 3be the bivalent hydrocanbon radical of singly-bound or carbon number 1 ~ 20 independently.
17. diamines as claimed in claim 16, is characterized in that, the [-S of described formula [6] 4-R 3-] represent with following formula [4], and C 1, C 2in either party there is the structure of formula [4],
[changing 12]
In formula, B 2represent and be selected from singly-bound, phenyl ,-CH 2-,-O-,-NH-,-NR 10-and the divalent organic group of-S-; R 10represent the divalence hydrocarbon of carbon number 1 ~ 6; The structure of the alkene of formula [4] can be any one in E formula, Z formula; C in the key be represented by dotted lines and formula [2] 1the phenyl ring linked or C 2the carbonyl carbon linked links.
18. 1 kinds of diamines, it is represented by any one in following formula [1-a] ~ [1-k],
[changing 13]
[changing 14]
The polyimide that 19. 1 kinds of polyamide, polyamic acid or this polyamic acids obtain through imidizate, is characterized in that, is that raw material obtains by the diamines described in any one in claim 14 ~ 18.
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