CN103097946B - Aligning agent for liquid crystal, liquid crystal orientation film and use its liquid crystal display cells - Google Patents

Aligning agent for liquid crystal, liquid crystal orientation film and use its liquid crystal display cells Download PDF

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CN103097946B
CN103097946B CN201180042059.1A CN201180042059A CN103097946B CN 103097946 B CN103097946 B CN 103097946B CN 201180042059 A CN201180042059 A CN 201180042059A CN 103097946 B CN103097946 B CN 103097946B
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CN103097946A (en
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芦泽亮一
川野勇太
原田佳和
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/90—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. amino-diphenylethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/32—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and esterified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
    • 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

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

The invention provides a kind of aligning agent for liquid crystal, it is characterized in that, comprise at least one polymkeric substance of the polyamic acid being selected from and being obtained by the diamine component of diamine compound containing following formula [1] and the reaction of tetracarboxylic dianhydride and the polyimide obtained by this polyamic acid imidizate.(changing 1) in formula, X 1represent singly-bound ,-CH 2o-,-O-,-COO-,-OCO-,-NHCO-or-CONH-, X 2represent the alkylidene of carbon number 1 ~ 3, X 3represent-O-,-NH-or-N (R 1)-, X 4represent singly-bound ,-O-,-S-or-NH-; X 5represent singly-bound or be selected from following formula [X 5-1] ~ [X 5-5] carbocyclic ring, X 6represent the straight chain of carbon number 1 ~ 18 or the alkyl of branch-like, X 7represent hydrogen atom ,-R 2,-OR 3,-NHR 4,-N (R 5) 2or-SR 6; Here, R 1~ R 6separately represent the alkyl of carbon number 1 ~ 5; N represents the integer of 1 or 2; (changing 2) here, in above-mentioned carbocyclic ring structure, arbitrary hydrogen atom can by CH 3replace.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and use its liquid crystal display cells
Technical field
The present invention relates to new diamine compound, the polyamic acid using this compound to obtain and polyimide and the aligning agent for liquid crystal of the raw material being suitable as the middle polymkeric substance used such as liquid crystal orientation film.Also relate to the liquid crystal display cells with the liquid crystal orientation film obtained by above-mentioned aligning agent for liquid crystal.More specifically, relate to and form the aligning agent for liquid crystal, this liquid crystal orientation film and forming method thereof of vertical orientated liquid crystal orientation film, the liquid crystal display cells with such liquid crystal orientation film and optical component by the polarized light of less exposure or the radioactive ray of nonpolarized light.
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, the liquid crystal orientation film of industrial use is formed primarily of the aligning agent for liquid crystal comprised as the polyamic acid of polyimide precursor or the solution of poly amic acid ester or polyimide.In general, after on substrate, coating of liquid crystalline aligning agent carries out heating and burn till, implement for make liquid crystal phase for real estate orientation process that is parallel or orientation obliquely.As this orientation process, the surface treatment method of the so-called rubbing manipulation on the cloth wiping organic film surface of known cotton, nylon, regenerated fiber etc.; By the method for monox oblique evaporation in substrate surface; Langmuir-Blaw Ztel method (LB method) is used to form the method etc. with the unimolecular film of chain alkyl at substrate surface.Wherein, particularly from the viewpoint of the orientation uniformity, processing time, cost etc. of substrate size, liquid crystal, generally liquid crystal aligning ability is given by friction treatment.
But, when giving liquid crystal aligning ability by friction treatment, there are the following problems: the defect that liquid crystal orientation film occurs because of friction, produces display defect thus, or generation dust, or cause the circuit of TFT (thin film transistor (TFT)) element destroyed because producing electrostatic.
In the liquid crystal display cells of vertical orientation mode, known MVA (multi-domain vertical alignment) mode forming the projection of toppling direction for controlling liquid crystal in TFT substrate or colored filter substrate; ITO (tin indium oxide) electrode of substrate forms slit, is controlled PVA (image the is vertical orientated) mode of the toppling direction of liquid crystal by electric field; Be used in the substrate that ITO electrode is formed with slit and be added with the liquid crystal of photopolymerizable compound to manufacture liquid crystal panel, apply electric field, irradiation ultraviolet radiations (UV) etc. under the state that liquid crystal is toppled over, by immobilized for the orientation of liquid crystal PSA (polymer stabilizing orientation) mode etc.
As the problem of these existing vertical orientation modes, have and causing the high cost of panel because using complicated substrate, causing the lower degradation of the transmissivity of panel because of projection or slit etc.
On the other hand, as the liquid crystal orientation film given in liquid crystal cell with the another kind of method of liquid crystal aligning ability, known optical alignment method, the method is the radioactive ray photosensitive film of the poly-vinyl cinnamate, polyimide etc. that are formed at substrate surface being irradiated to polarized light or nonpolarized light, thus gives liquid crystal aligning ability.(with reference to patent documentation 1 ~ 8)
This optical alignment method known also can be used as the method for the vergence direction controlling liquid crystal molecule in the liquid crystal display cells of vertical alignment mode.That is, knownly utilizing optical alignment method to impart the vertical alignment layer of orientation control force by using, the vergence direction (with reference to patent documentation 9 ~ 11) of liquid crystal molecule when applying voltage can be controlled equably.
Utilizing optical alignment method to impart the vertical alignment layer of orientation control force like this by using, liquid crystal molecule can be made in advance slightly to tilt from substrate normal direction towards the direction of in real estate.
Liquid crystal orientation film as described above by optical alignment method manufacture is preferred for liquid crystal display cells.But, when the aligning agent for liquid crystal containing cinnamate or polyimide etc. known is up to now applied to optical alignment method, there is the problem that the exposure of the radioactive ray obtained needed for liquid crystal aligning ability is many.As exposure caused problem more, having the increase of the pitch time of the manufacture of liquid crystal display cells, causing because irradiating for a long time liquid crystal orientation film to produce defect etc., along with these problems, the reliability of liquid crystal panel reduces.
In the liquid crystal display cells of vertical orientation mode, when there is unreacted photoreactive group in liquid crystal orientation film, also there are the following problems: under liquid crystal panel is exposed to the light of backlight (BL) for a long time, unreacted photoreactive group reacts, and the tilt angle of liquid crystal changes.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 6-287453 publication
Patent documentation 2: Japanese Patent Laid-Open 10-251646 publication
Patent documentation 3: Japanese Patent Laid-Open 11-2815 publication
Patent documentation 4: Japanese Patent Laid-Open 11-152475 publication
Patent documentation 5: Japanese Patent Laid-Open 2000-144136 publication
Patent documentation 6: Japanese Patent Laid-Open 2000-319510 publication
Patent documentation 7: Japanese Patent Laid-Open 2000-281724 publication
Patent documentation 8: Japanese Patent Laid-Open 9-297313 publication
Patent documentation 9: Japanese Patent Laid-Open 2003-307736 publication
Patent documentation 10: Jap.P. No. 4088156 publication
Patent documentation 11: Japanese Patent Laid-Open 2004-163646 publication
Summary of the invention
Invent technical matters to be solved
The object of the present invention is to provide for the formation of the aligning agent for liquid crystal of vertical orientated liquid crystal orientation film, the liquid crystal orientation film of formation and the liquid crystal display cells with this liquid crystal orientation film, this liquid crystal orientation film shows tilt angle by the polarized light of less exposure or the radioactive ray of nonpolarized light, even and if also can maintain stable tilt angle under being exposed to the light of backlight for a long time.
The technical scheme that technical solution problem adopts
The present inventor has carried out conscientiously studying in order to achieve the above object, found that the diamine compound with specific new structure, and the aligning agent for liquid crystal also finding to comprise the polymkeric substance using this diamine compound to obtain can achieve the above object.The present invention is the invention completed based on this discovery, comprises following technology contents.
(1) a kind of aligning agent for liquid crystal, it is characterized in that, comprise at least one polymkeric substance of the polyamic acid being selected from and being obtained by the diamine component of the diamine compound containing following formula [1] and the reaction of tetracarboxylic dianhydride's composition and the polyimide obtained by this polyamic acid imidizate;
[changing 1]
In formula, X 1represent singly-bound ,-CH 2o-,-O-,-COO-,-OCO-,-NHCO-or-CONH-, X 2represent the alkylidene of carbon number 1 ~ 3, X 3represent-O-,-NH-or-N (R 1)-, X 4represent singly-bound ,-O-,-S-or-NH-; X 5represent singly-bound or be selected from following formula [X 5-1] ~ [X 5-5] carbocyclic ring, X 6represent the straight chain of carbon number 1 ~ 18 or the alkyl of branch-like, X 7represent hydrogen atom ,-R 2,-OR 3,-NHR 4,-N (R 5) 2or-SR 6; Here, R 1~ R 6separately represent the alkyl of carbon number 1 ~ 5; N represents the integer of 1 or 2;
[changing 2]
Here, in above-mentioned carbocyclic ring structure, arbitrary hydrogen atom can by CH 3replace.
(2) aligning agent for liquid crystal as described in above-mentioned (1), wherein, the content of the diamine compound of the formula [1] in described diamine component is 30 ~ 100 % by mole.
(3) aligning agent for liquid crystal as described in above-mentioned (1) or (2), wherein, the X of above-mentioned formula [1] 3-O-, X 7it is hydrogen atom.
(4) aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (3), wherein, the X of above-mentioned formula [1] 5it is singly-bound.
(5) aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (4), wherein, the X of above-mentioned formula [1] 1singly-bound, X 4-O-.
(6) aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (5), wherein, the n of above-mentioned formula [1] is 1.
(7) aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (6), wherein, the X of above-mentioned formula [1] 2-CH 2-, X 6it is the alkyl of carbon number 8 ~ 12.
(8) liquid crystal orientation film, is characterized in that, the aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (7) obtains.
(9) liquid crystal orientation film, it is aligning agent for liquid crystal according to any one of above-mentioned (1) ~ (7) and the liquid crystal orientation film obtained, and gives liquid crystal aligning ability by the irradiation of the radioactive ray of polarized light or nonpolarized light.
(10) liquid crystal display cells, is characterized in that, has above-mentioned (8) or the liquid crystal orientation film described in (9).
(11) diamine compound that represents of following formula [1];
[changing 3]
In formula, X 1represent singly-bound ,-CH 2o-,-O-,-COO-,-OCO-,-NHCO-or-CONH-, X 2represent the alkylidene of carbon number 1 ~ 3, X 3represent-O-,-NH-or-N (R 1)-, X 4represent singly-bound ,-O-,-S-or-NH-; X 5represent singly-bound or be selected from following formula [X 5-1] ~ [X 5-5] carbocyclic ring, X 6represent the straight chain of carbon number 1 ~ 18 or the alkyl of branch-like, X 7represent hydrogen atom ,-R 2,-OR 3,-NHR 4,-N (R 5) 2or-SR 6; Here, R 1~ R 6separately represent the alkyl of carbon number 1 ~ 5; N represents the integer of 1 or 2;
[changing 4]
Here, in above-mentioned carbocyclic ring structure, arbitrary hydrogen atom can by CH 3replace.
(12) diamine compound as described in above-mentioned (11), wherein, the X of above-mentioned formula [1] 3-O-, X 7it is hydrogen atom.
(13) diamine compound as described in above-mentioned (11) or (12), wherein, the X of above-mentioned formula [1] 5it is singly-bound.
(14) diamine compound according to any one of above-mentioned (11) ~ (13), wherein, the X of above-mentioned formula [1] 1singly-bound, X 4-O-.
(15) diamine compound according to any one of above-mentioned (11) ~ (14), wherein, the n of above-mentioned formula [1] is 1.
(16) diamine compound according to any one of above-mentioned (11) ~ (15), wherein, the X of above-mentioned formula [1] 2-CH 2-, X 6it is the alkyl of carbon number 8 ~ 12.
(17) polyimide that maybe obtained by this polyamic acid imidizate of polyamic acid, described polyamic acid reacts by making the diamine component containing the diamine compound according to any one of above-mentioned (1) ~ (16) and tetracarboxylic dianhydride's composition and obtains.
The effect of invention
Utilize aligning agent for liquid crystal of the present invention, can with the liquid crystal orientation film of the radiation exposure amount more less than existing optical alignment method acquisition for showing tilt angle.Even if the liquid crystal display cells with liquid crystal orientation film of the present invention also can show stable tilt angle under being exposed to the light of backlight for a long time, the high liquid crystal display cells of reliability can be used as.
The mode carried out an invention
The diamine compound > that < formula [1] represents
Diamine compound of the present invention (below sometimes also referred to as specific diamine compound) represents with following formula [1].
[changing 5]
In formula, X 1represent singly-bound ,-CH 2o-,-O-,-COO-,-OCO-,-NHCO-or-CONH-.
X 2represent the alkylidene of carbon number 1 ~ 3.
X 3represent-O-,-NH-or-N (R 1)-.
X 4represent singly-bound ,-O-,-S-or-NH-.
X 5represent singly-bound or be selected from following formula [X 5-1] ~ [X 5-5] carbocyclic ring.
X 6represent the straight chain of carbon number l ~ 18 or the alkyl of branch-like.
X 7represent hydrogen atom ,-R 2,-OR 3,-NHR 4,-N (R 5) 2or-SR 6.Here, R 1~ R 6separately represent the alkyl of carbon number l ~ 5.
N represents the integer of l or 2.
[changing 6]
Above-mentioned formula [X 5-1] ~ [X 5-5], in carbocyclic ring structure, arbitrary hydrogen atom can by CH 3replace.
Two amino (-NH in formula [1] 2) bonding position do not limit.Specifically, relative to the concatenating group (X of side chain 1), 2 on phenyl ring can be exemplified, 3,2,4,2,5,2,6,3,4 or 3,5.Wherein, from the viewpoint of complexity when reactivity during synthesizing polyamides acid and synthesis diamine compound, two amino bonding positions particularly preferably 2,4,2,5 or 3,5.
When diamine compound of the present invention is used as vertical orientated liquid crystal orientation film, in order to give tilt angle by ultraviolet irradiation, the part that following formula [2] contained in formula [1] represents is the part manifested determining tilt angle.By optimizing this structure, desirable tilt angle size can be obtained.
[changing 7]
In formula [2], X 1singly-bound ,-CH 2the concatenating group of O-,-O-,-COO-,-OCO-,-NHCO-or-CONH-, X 2it is the alkylidene of carbon number 1 ~ 3.
X 2the length of alkylidene chain be very important for showing with less exposure for tilt angle, if this alkylidene chain is long, then the exposure to showing tilt angle increases.This is because the side chain of amine contained in the polymkeric substance forming vertical orientated liquid crystal orientation film is (from the X of above formula [2] 3the position that the carbonyl of upper bonding starts) root position there is light reaction, by this, the anisotropy caused because of light reaction has influence on whole side chain, and the orientation control force that side chain puts on liquid crystal increases.Consequently, even if also can show the tilt angle of liquid crystal with less exposure.
In formula [2], X 3represent-O-,-NH-or-N (R 1)-, X 4represent singly-bound ,-O-,-S-or-NH-.
R 1represent the alkyl of carbon number 1 ~ 5.
X 3and X 4be the concatenating group of photoreactivity part, consider from the angle of the complexity of the length of the light absorption wavelength of photoreactive group and synthesis, X 3and X 4particularly preferably-O-.
In formula [2], X 5be singly-bound or be selected from following formula [X 5-1] ~ [X 5-5] carbocyclic ring, X 6the straight chain of carbon number 1 ~ 18 or the alkyl of branch-like.
X 5and X 6for making liquid crystal be vertically very important for orientation, X 5when being singly-bound, consider from the angle of vertical orientated ability, X 6preferred chain alkyl.X now 6carbon number be better 6 ~ 18, be more preferably 8 ~ 12.
X 5be selected from following formula [X 5-1] ~ [X 5during carbocyclic ring-5], because vertical orientated ability improves, therefore X 4it is better slightly short alkyl.X now 4carbon number be better 1 ~ 12, be more preferably 3 ~ 8.
[changing 8]
In formula [2], X 7represent hydrogen atom ,-R 2,-OR 3,-NHR 4,-N (R 5) 2or-SR 6.Here, R 2~ R 6separately represent the alkyl of carbon number 1 ~ 5.N represents the integer of 1 or 2.
X 7with n for determine photoreactive group wavelength photoreceptor for be very important, if use to electro substituting group as X 7, then the absorbing wavelength of photoreactive group is elongated.If n is 2, then can obtain same effect.X 7with the wavelength that n can make the wavelength photoreceptor of photoreactive group reach desirable.
From the viewpoint of wavelength photoreceptor when being used as vertical orientated liquid crystal orientation film and photoreactive sensitivity, the X in formula [1] 1~ X 7preferred concrete combination as follows.
[changing 9]
[changing 10]
[changing 11]
[changing 12]
[changing 13]
[changing 14]
[changing 15]
[changing 16]
[changing 17]
[changing 18]
[changing 19]
[changing 20]
[changing 21]
[changing 22]
[changing 23]
[changing 24]
[changing 25]
[changing 26]
The C recorded in the diamine compound exemplified above nh 2n+1in part, n is the integer of 1 ~ 18.
The synthetic method > of < specific diamine compound
Method for making 1
By the acrylate body that obtained by dinitro matrix 12 and the reaction of benzene derivative 3 with leaving away property functional group Y, make the dinitro matrix 4 side chain with cinnamic acid position.For the dinitro matrix 4 of gained, by selecting to implement not have influential method of reducing to the double bond part of side chain, be convertible into targeted diamine 5.
[changing 27]
The method for making of compound 1
<X 1for the situation of singly-bound, (m is the integer of 1 ~ 3, X 3represent-O-,-NH-or-NR 1-) >
Several raw material can be buied as commercial goods.When being difficult to obtain as commercial goods, if carry out reduction reaction with borane reduction agent to the carboxylic acid shown in compound 6, then X can be synthesized 3correspond to the raw material of-O-.In addition, if make the carboxylic moiety of borane reduction agent and compound 6 be that compound, the i.e. compound 7 of cyano group acts on, then X can be synthesized 3for the raw material of the diamine compound of-NH-.
[changing 28]
By X 3after the hydroxyl of the compound 1a ' of-O-converts the leaving group such as halogen or sulphonic acid ester to, make it react with azide and obtain corresponding azide derivatives, this azide derivatives is reduced, also can obtain X 3for the compound 1a ' ' of-NH-.In addition, after converting leaving group to, synthesize by adopting so-called Jia Buliaier and synthesize amine, also can obtain X 3for the compound 1a ' ' of-NH-, this Jia Buliaier synthesis is reacted with succinimide or phthalimide, then with hydrazine, the N-alkylimide generated is decomposed.
For X 3for the compound 1a ' ' of-NH-, by making the reaction under the coexisting of alkali of alkyl halide or alkyl sulfonic ester, X can be obtained 3for-NR 1(R 1represent the alkyl of carbon number 1 ~ 5) compound 1a ' '.In addition, utilize reductive amination to react, also can obtain X 3for-NR 1(R 1represent the alkyl of carbon number 1 ~ 5) compound 1a ' ' ', the reaction of this reductive amination makes aldehyde compound effect and makes corresponding group with imine moiety, reduced by its imine moiety with boranes reductive agent etc.During the former alkylation, can obtain the accessory substance introducing multiple alkyl, and the method for the latter does not have accessory substance, the introducing for alkyl is effective.
<X 1for the situation of-O-, (m is the integer of 1 ~ 3, X 3represent-O-,-NH-or-NR 1-) >
By using the compound 9 with protecting group P that dinitrophenol 8 alkylation of commercial goods acquisition will be can be used as, thus obtain the dinitro matrix 10 with side chain.By making protecting group P deprotection contained in dinitro matrix 10, dinitro intermediate 1b can be manufactured.
[changing 29]
In compound 9, Y represents the sulfonic acid esters such as the halogen atoms such as F, Cl, Br, I or methanesulfonyloxy group, phenylsulfonyloxy, tosyloxy, trifluoromethane sulfonyl group.
Protecting group P can exemplify the ester class protecting groups such as formoxyl, acetyl group, propiono, benzoyl; the acetals protecting groups such as methoxy, ethoxyethyl group, THP trtrahydropyranyl, tetrahydrofuran base; the silane base class protecting groups such as TMS, triethyl silyl, tri isopropyl silane base, tri-phenyl-silane base, t-butyldimethylsilyi, tert-butyldiphenylsilanyl, cumyl diphenyl silane base, the carbonates protecting groups such as methoxycarbonyl, ethoxy carbonyl, benzyloxycarbonyl, phenyloxycarbonyl, tert-butoxycarbonyl.From the viewpoint of control subsidiary reaction, the protecting group of preferred acetals or silane base class.
When obtaining the reaction of dinitro matrix 10 by compound 8 and compound 9, alkali is coexisted, as used alkali, the inorganic bases such as sal tartari, sodium bicarbonate, sodium hydride, hydrofining can be used, the amine such as triethylamine, diisopropylethylamine etc.When carrying out this reaction, in order to make reaction carry out swimmingly, be better add sodium iodide, potassium iodide or tetrabutylammonium iodide.
The deprotection reaction of compound 10 selects the deprotection condition adapted with the protecting group used to implement.When using the protecting group of ester class or carbonates, the hydrolysis reaction of any one acid or alkaline fluidity is all effective.Also can utilize and carry out deprotection with the ester exchange reaction of lower alcohol.When using acetals protecting group, the organic acid deprotection reactions such as the mineral acid of preferred use catalytic amount or formic acid, acetic acid, toluenesulfonic acid.When using silane base class protecting group, it is better the deprotection using the fluorides such as tetra-n-butyl ammonium fluoride under the condition same with the deprotection of acetals protecting group.
For the X obtained as mentioned above 3for the compound of-NH-, by implementing reductive amination reaction, X can be synthesized 3correspond to-NR 1(R 1represent the alkyl of carbon number 1 ~ 5) compound 1b.
The hydroxylic moiety of the compound, the i.e. compound 8 that obtain by making above-claimed cpd 8 exchange mutually with Y base with the OH base of compound 9 is fluorine or chlorine and the compound that the Y of compound 9 is OH base reacts in the presence of base, also can obtain compound 10.
<X 1for the situation of-COO-or-CONH-, (m is the integer of 1 ~ 3, X 3represent-O-,-NH-or-NR 1-) >
By carboxylic acid or derivatives thereof 11 and the reaction of compound 12 with protecting group P, obtain dinitro-ester body 13 (Q=O) or the dinitro-acid amides body 13 (Q is-NH-) with side chain.By making protecting group deprotection contained in dinitro-ester body 13 (Q is-O-) or dinitro-acid amides body 13 (Q is-NH-), can be made into the dinitro intermediate 1c with ester bond base.
[changing 30]
In compound 11, Hal represents OH base or halogen atom, if the stability of considering, then preferably uses the compound 11 that Hal is OH base or chloro.
The preferred protecting group of the protecting group P in compound 12 is also with above identical.
Z in compound 12 represents hydroxyl, amino, halogen or sulfonyl.
Q in compound 13 represents-O-or-NH-.Consider that the structure of the Hal part of used compound 11 is to select the functional group represented by the Z in compound 12.Such as, Hal is OH base, selects OH base or NH 2when base is as Z, if use dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) condensation agent such as carbodiimide, carbonyl dimidazoles react, then can obtain the compound 13 with ester bond (Q is-O-) or amido link (Q is-NH-).Hal is OH base, when selecting halogen or sulfonyl as Z, if use the inorganic bases such as sal tartari, sodium bicarbonate, sodium hydride, hydrofining, the amine such as triethylamine, diisopropylethylamine reacts, then can obtain ester compounds 13 (Q is-O-).In order to make reaction carry out swimmingly, it is also effective for adding sodium iodide, potassium iodide or tetrabutylammonium iodide.
Hal is when taking chloro as the halogen atom of representative, and the compound using Z in compound 12 to be hydroxyl or amino, obtains ester compounds 13 (Q is-O-) or amide compound 13 (Q is-NH-).The amine such as triethylamine, pyridine is added as alkali in this reaction.
By making the protecting group P deprotection of the compound 13 of gained, compound 1c can be obtained, as the condition of deprotection, identical with the condition of the deprotection of above-claimed cpd 10.
For X 3for the compound 1a ' ' of-NH-, by making the reaction under the coexisting of alkali of alkyl halide or alkyl sulfonic ester, X can be obtained 3for NR 1(R 1represent the alkyl of carbon number 1 ~ 5) compound 1c.Utilize reductive amination to react, also can obtain X 3for NR 1(R 1represent the alkyl of carbon number 1 ~ 5) compound 1c, the reaction of this reductive amination makes aldehyde compound effect and makes corresponding group with imine moiety, reduced by its imine moiety with boranes reductive agent etc.During the former alkylation, can obtain the accessory substance introducing multiple alkyl, and the method for the latter does not have accessory substance, the introducing for alkyl is effective.
<X 1for the situation of-OCO-or-NHCO-, (m is the integer of 1 ~ 3, X 3represent-O-,-NH-or-NR-) >
Esterification or amidation is carried out with the reaction of the carboxylic acid derivates 15 with protecting group P by dinitrophenol (Q is-O-) or dinitroaniline (Q is-NH-) 14; after making the dinitro matrix 16 with ester or amide side chains; by protecting group deprotection contained in dinitro matrix 16, thus can be made into the dinitro intermediate 1d with ester bond or amido link.
[changing 31]
Q in compound 14 and dinitro matrix 16 and dinitro intermediate 1d represents-O-or-NH-.
In carboxylic acid derivates 15, Hal represents OH base or halogen atom, if the stability of considering, then preferably uses the compound 15 that Hal is OH base or chloro.The preferred protecting group of protecting group P is also with above identical.
Make that Hal is compound, the i.e. carboxylic acid 15 of OH base, dinitrophenol 14 (Q is-O-) or dinitroaniline 14 (Q is-NH-) be when reacting, usually use dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) condensation agent such as carbodiimide, carbonyl dimidazoles.Further, the acid or N, the N-dimethylamino naphthyridine that add catalytic amount are also beneficial to for the carrying out reacted.Also the acyl halide derivative preferably using Hal to represent chloro etc. carries out the method for reacting, and now, adds the alkali such as the amine of triethylamine, pyridine and so on and reacts.
By making the protecting group P deprotection of the compound 16 of gained, dinitro intermediate 1d can be obtained, as the condition of deprotection, identical with the condition of the deprotection of above-claimed cpd 10.
The method for making of compound 2
Compound 2 manufactures by the esterification between raw material 1 and acrylic acid derivative such as dinitro benzylalcohol of correspondence.
As acrylic acid derivative, preferably use the carboxylic acid halides class such as acryloyl chloride, propylene acylbromide, acrylic anhydride etc.
In esterification, as alkali, the inorganic base such as NaOH, potassium hydroxide, lithium hydroxide, sodium bicarbonate, saleratus, potassium phosphate, sodium carbonate, sal tartari, lithium carbonate, cesium carbonate, NaH, KOH can be used, the amines such as trimethylamine, triethylamine, tripropyl amine (TPA), tri-isopropyl amine, tri-n-butylamine, diisopropylethylamine, pyridine, quinoline, trimethylpyridine, the organic base such as sodium tert-butoxide, potassium tert-butoxide.
Solvent can suitably be selected, as long as under the reaction conditions in inertia, stable, the solvent that do not hinder reaction.Such as amine, aprotic polar organic solvent (dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, 1-METHYLPYRROLIDONE etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, cyclopentyl-methyl ether, tetrahydrofuran, two can be used alkane etc.), aliphatic hydrocarbon (pentane, hexane, heptane, sherwood oil etc.), aromatic hydrocarbon based (benzene,toluene,xylene, 1,3,5-trimethylbenzene, chlorobenzene, dichloro-benzenes, nitrobenzene, tetralin etc.), halogenated hydrocarbon (chloroform, methylene chloride, phenixin, ethylene dichloride etc.), low-grade fatty acid ester class (methyl acetate, ethyl acetate, butyl acetate, methyl propionate etc.), nitrile (acetonitrile, propionitrile, butyronitrile etc.).These solvents can be considered reaction conditions and react the complexity etc. of carrying out and suitably select, and can be used alone that one or more are used in combination.In addition, use after also according to circumstances can making non-aqueous solvent with dewatering agent or drying agent.
Temperature of reaction be better-100 DEG C ~ use solvent boiling point scope in, be more preferably in the scope of-50 ~ 150 DEG C.
Reaction time is better 0.1 ~ 1000 hour.
The compound 2 obtained as mentioned above carrys out purifying by recrystallization, distillation, silica gel column chromatography, activated charcoal etc.
Compound 2 is also by the ester exchange reaction of the acrylate such as methyl acrylate, ethyl acrylate and dinitro benzylalcohol, or the reaction of acrylic acid and the dinitrobenzyl halogen such as dinitrobenzyl chlorine, dinitrobenzyl bromine is synthesized.
The method for making of compound 3
[changing 32]
In above-claimed cpd 17 and compound 18, U represents halogen atom ,-OH ,-SH or the-NH such as F, Cl, Br, I 2, X 5represent singly-bound or be selected from above-mentioned [X 5-1] ~ [X 5-5] carbocyclic ring, X 6represent the straight chain of carbon number 1 ~ 18 or the alkyl of branch-like.
X 7represent hydrogen atom ,-R 2,-OR 3,-NHR 4,-N (R 5) 2or-SR 6.Here, R 2~ R 6separately represent the alkyl of carbon number 1 ~ 5.
N represents the integer of 1 or 2.
Y and L is separately halogen or pseudohalogen, such as, represent alkylsulfonyloxy or the aromatic sulfonyl oxygen bases such as F, Cl, Br, I, methanesulfonyloxy group, phenylsulfonyloxy, tosyloxy, trifluoromethane sulfonyl group.
Compound 3 such as manufactures by the reaction of the compound shown in the compound shown in 17 and 18.Several compound 17 and compound 18 can obtain easily as commercial goods.
<X 4for the situation > of-O-,-S-or-NH-
The substituting group U of compound 17 is-OH ,-SH or-NH 2, compound 18 X 5for singly-bound or be selected from above-mentioned [X 5-1] ~ [X 5during carbocyclic ring-5], two kinds of compounds are reacted in the presence of base, obtains compound 3.As used alkali, there are alkali-metal oxyhydroxide or the carbonate such as such as lithium, sodium, potassium, the organic base etc. of the organic fatty races such as triethylamine, diazabicyclo octane, diazabicycloundecene, pyridine, DMAP, aromatic series and heterocycle.Also the potpourri of these alkali can be used.Particularly preferably sal tartari.
Solvent can suitably be selected, as long as under the reaction conditions stable, in inertia, do not hinder the solvent of reaction.Such as ketones solvent (acetone, 2-butanone, methyl isobutyl ketone etc.), aprotic polar organic solvent (dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, 1-METHYLPYRROLIDONE etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, cyclopentyl-methyl ether, tetrahydrofuran, two can be used alkane etc.), aliphatic hydrocarbon (pentane, hexane, heptane, sherwood oil etc.), aromatic hydrocarbon based (benzene,toluene,xylene, 1,3,5-trimethylbenzene, chlorobenzene, dichloro-benzenes, nitrobenzene, tetralin etc.), halogenated hydrocarbon (chloroform, methylene chloride, phenixin, ethylene dichloride etc.), low-grade fatty acid ester class (methyl acetate, ethyl acetate, butyl acetate, methyl propionate etc.), nitrile (acetonitrile, propionitrile, butyronitrile etc.).These solvents can consider that reacting the complexity etc. of carrying out suitably selects, and can be used alone that one or more are used in combination.In addition, use after also according to circumstances can making non-aqueous solvent with dewatering agent or drying agent.
Temperature of reaction is better the boiling point of the solvent of-100 DEG C ~ use, is more preferably in the scope of-50 ~ 150 DEG C.
Reaction time is better 0.1 ~ 1000 hour.
The compound 3 obtained as mentioned above carrys out purifying by recrystallization, distillation, silica gel column chromatography etc.
The substituting group U of compound 17 is-OH ,-SH or-NH 2, compound 18 X 5for singly-bound or [X 5-5], time, can, using metal complex and part as catalyzer under the existence of suitable alkali, utilize coupling reaction to synthesize compound 3.As metal complex, preferably use copper complex, palladium complex or nickel complex.Particularly preferably use using tertiary phosphine or tertiary phosphite ester (Japanese: 3 Grade ホ ス Off ア イ ト) as the zero valent complex of part.Also the suitable precursor easily converting zero valent complex to can be used in reaction system.In reaction system can also using not containing tertiary phosphine or tertiary phosphite ester as the complex compound of part and tertiary phosphine or the mixing of tertiary phosphite ester, generate using tertiary phosphine or tertiary phosphite ester as the low quantivalency complex compound of part.
As tertiary phosphine or the tertiary phosphite ester of part, such as triphenyl phasphine, tri-o-tolyl phosphine, diphenyl methyl phosphine, phenyldimethylphosphine, 1 can be exemplified, two (diphenylphosphino) ethane, 1 of 2-, two (diphenylphosphino) propane, 1 of 3-, two (diphenylphosphino) butane, 1 of 4-, 1 '-bis-(diphenylphosphino) ferrocene, Trimethyl phosphite, triethyl phosphite, triphenyl phosphite etc., also preferably use mixing to comprise the complex compound of these two or more parts.As catalyzer, the copper complex or palladium complex that do not contain tertiary phosphine or tertiary phosphite ester can be used.Also preferred above-mentioned part and the complex compound that comprises tertiary phosphine or tertiary phosphite ester to be combinationally used.As with above-mentioned ligand combination use not containing the complex compound of tertiary phosphine or tertiary phosphite ester, copper catalyst has CuCl, CuBr, CuI, Cu 2o, CuCN, CuO etc., palladium catalyst has two (BENZYLIDENE ACETONE) palladium, three (BENZYLIDENE ACETONE) two palladium, two (acetonitrile) palladium chloride, two (benzonitrile) palladium chloride, acid chloride, palladium bichloride, palladium bichloride-acetonitrile complex compound, palladium-activated charcoal etc.As comprising tertiary phosphine or the tertiary phosphite ester complex compound as part, two (triphenylphosphine) palladium of dimethyl, dimethyl two (diphenyl methyl phosphine) palladium, (ethylidene) two (triphenylphosphine) palladium, tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chlorides etc. can be exemplified, but be not limited to this.As long as the so-called catalytic amount of consumption of copper complex, palladium complex, nickel complex etc. as catalyzer, in general 20 % by mole below of compound of reaction with regard to enough, be generally less than 10 % by mole.
As alkali, also the inorganic bases such as NaOH, potassium hydroxide, lithium hydroxide, sodium bicarbonate, saleratus, potassium phosphate, sodium carbonate, sal tartari, lithium carbonate, cesium carbonate can be used, the amines etc. such as methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, propylamine, di-n-propylamine, tripropyl amine (TPA), isopropylamine, diisopropylamine, tri-isopropyl amine, butylamine, dibutylamine, tri-n-butylamine, diisopropylethylamine, pyridine, imidazoles, quinoline, trimethylpyridine, and sodium acetate, potassium acetate, lithium acetate etc.
Solvent can suitably be selected, as long as under the reaction conditions stable, in inertia, do not hinder the solvent of reaction.Such as water, alcohols, amine, aprotic polar organic solvent (dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, 1-METHYLPYRROLIDONE etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, cyclopentyl-methyl ether, tetrahydrofuran, two can be exemplified alkane etc.), aliphatic hydrocarbon (pentane, hexane, heptane, sherwood oil etc.), aromatic hydrocarbon based (benzene,toluene,xylene, 1,3,5-trimethylbenzene, chlorobenzene, dichloro-benzenes, nitrobenzene, tetralin etc.), halogenated hydrocarbon (chloroform, methylene chloride, phenixin, ethylene dichloride etc.), low-grade fatty acid ester class (methyl acetate, ethyl acetate, butyl acetate, methyl propionate etc.), nitrile (acetonitrile, propionitrile, butyronitrile etc.).These solvents can consider that reacting the complexity etc. of carrying out suitably selects, and can be used alone that one or more are used in combination.In addition, use after also according to circumstances can making non-aqueous solvent with dewatering agent or drying agent.
Temperature of reaction is the boiling point of the solvent of-100 DEG C ~ use, is better in the scope of-50 ~ 150 DEG C.
Reaction time is better 0.1 ~ 1000 hour.
The compound 3 obtained as mentioned above carrys out purifying by recrystallization, distillation, silica gel column chromatography etc.
<X 4for the situation > of singly-bound
The substituting group U of compound 17 is the X of F, Cl, Br or I, compound 3 4during for singly-bound, can, using metal complex and part as catalyzer under the existence of suitable alkali, utilize coupling reaction to synthesize compound 3.As metal complex, preferred iron complex, palladium complex or nickel complex.Particularly preferably use using tertiary phosphine or tertiary phosphite ester as the zero valent complex of part.Also the suitable precursor easily converting zero valent complex to can be used in reaction system.In reaction system can also using not containing tertiary phosphine or tertiary phosphite ester as the complex compound of part and tertiary phosphine or the mixing of tertiary phosphite ester, generate using tertiary phosphine or tertiary phosphite ester as the low quantivalency complex compound of part.
As tertiary phosphine or the tertiary phosphite ester of part, such as triphenyl phasphine, tri-o-tolyl phosphine, diphenyl methyl phosphine, phenyldimethylphosphine, 1 can be exemplified, two (diphenylphosphino) ethane, 1 of 2-, two (diphenylphosphino) propane, 1 of 3-, two (diphenylphosphino) butane, 1 of 4-, 1 '-bis-(diphenylphosphino) ferrocene, Trimethyl phosphite, triethyl phosphite, triphenyl phosphite etc., also preferably use mixing to comprise the complex compound of these two or more parts.As catalyzer, the iron complex or palladium complex that do not contain tertiary phosphine or tertiary phosphite ester can be used.Also preferred above-mentioned part and the complex compound that comprises tertiary phosphine or tertiary phosphite ester to be combinationally used.As with above-mentioned ligand combination use not containing the complex compound of tertiary phosphine or tertiary phosphite ester, iron catalyst has FeBr 3, FeBr 2, FeCl 3, FeCl 2, FeF 3, FeF 2, tri acetylacetonato iron, two (diacetone) iron etc., palladium catalyst has two (BENZYLIDENE ACETONE) palladium, three (BENZYLIDENE ACETONE) two palladium, two (acetonitrile) palladium chloride, two (benzonitrile) palladium chloride, acid chloride, palladium bichloride, palladium bichloride-acetonitrile complex compound, palladium-activated charcoal etc.As comprising tertiary phosphine or the tertiary phosphite ester complex compound as part, two (triphenylphosphine) palladium of dimethyl, dimethyl two (diphenyl methyl phosphine) palladium, (ethylidene) two (triphenylphosphine) palladium, tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chlorides etc. can be exemplified, but be not limited to this.As long as the so-called catalytic amount of consumption of iron complex, palladium complex, nickel complex etc. as catalyzer, in general 20 % by mole below of compound of reaction with regard to enough, be generally less than 10 % by mole.
As alkali, also the inorganic bases such as NaOH, potassium hydroxide, lithium hydroxide, sodium bicarbonate, saleratus, potassium phosphate, sodium carbonate, sal tartari, lithium carbonate, cesium carbonate can be used, N, the amines such as N-dimethyl-ethylenediamine, methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, propylamine, di-n-propylamine, tripropyl amine (TPA), isopropylamine, diisopropylamine, tri-isopropyl amine, butylamine, dibutylamine, tri-n-butylamine, diisopropylethylamine, pyridine, imidazoles, quinoline, trimethylpyridine, and sodium acetate, potassium acetate, lithium acetate etc.
Solvent can suitably be selected, as long as under the reaction conditions stable, in inertia, do not hinder the solvent of reaction.Such as water, alcohols, amine, aprotic polar organic solvent (dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, 1-METHYLPYRROLIDONE etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, cyclopentyl-methyl ether, tetrahydrofuran, two can be used alkane etc.), aliphatic hydrocarbon (pentane, hexane, heptane, sherwood oil etc.), aromatic hydrocarbon based (benzene,toluene,xylene, 1,3,5-trimethylbenzene, chlorobenzene, dichloro-benzenes, nitrobenzene, tetralin etc.), halogenated hydrocarbon (chloroform, methylene chloride, phenixin, ethylene dichloride etc.), low-grade fatty acid ester class (methyl acetate, ethyl acetate, butyl acetate, methyl propionate etc.), nitrile (acetonitrile, propionitrile, butyronitrile etc.).These solvents can consider that reacting the complexity etc. of carrying out suitably selects, and can be used alone that one or more are used in combination.In addition, use after also according to circumstances can making non-aqueous solvent with dewatering agent or drying agent.
Temperature of reaction is the boiling point of the solvent of-100 DEG C ~ use, is better in the scope of-50 ~ 150 DEG C.
Reaction time is better 0.1 ~ 1000 hour.
The compound 3 obtained as mentioned above carrys out purifying by recrystallization, distillation, silica gel column chromatography etc.
The method for making of compound 4
Compound 4 synthesizes by coupling reactions such as compound 2 and the compound 3 He Ke reactions under the coexisting of metal complex catalyst, part and alkali.
As the Y in compound 3; as long as have the substituting group of leaving capability; the halogen atoms such as such as F, Cl, Br, I can be used; the alkylsulfonyloxies such as methanesulfonyloxy group, phenylsulfonyloxy, tosyloxy, trifluoromethane sulfonyl group, aromatic sulfonyl oxygen base etc.; if the reactivity of considering, then preferred Br, I or trifluoromethane sulfonyl group.
Coupling reaction preferably uses metal complex and part as catalyzer.Usual use palladium complex, nickel complex etc. are as metal complex.
As catalyzer, the catalyzer of various structure can be used, preferably use so-called low valent palladium complex or nickel complex, particularly preferably using tertiary phosphine or tertiary phosphite ester as the zero valent complex of part.Also the suitable precursor easily converting zero valent complex to can be used in reaction system.In reaction system can also using not containing tertiary phosphine or tertiary phosphite ester as the complex compound of part and tertiary phosphine or the mixing of tertiary phosphite ester, generate using tertiary phosphine or tertiary phosphite ester as the low quantivalency complex compound of part.
As tertiary phosphine or the tertiary phosphite ester of part, such as triphenyl phasphine, tri-o-tolyl phosphine, diphenyl methyl phosphine, phenyldimethylphosphine, 1 can be exemplified, two (diphenylphosphino) ethane, 1 of 2-, two (diphenylphosphino) propane, 1 of 3-, two (diphenylphosphino) butane, 1 of 4-, 1 '-bis-(diphenylphosphino) ferrocene, Trimethyl phosphite, triethyl phosphite, triphenyl phosphite etc., also preferably use mixing to comprise the complex compound of these two or more parts.As catalyzer, the mode above-mentioned part and palladium complex and/or the complex compound that comprises tertiary phosphine or tertiary phosphite ester not containing tertiary phosphine or tertiary phosphite ester combinationally used also is preferred mode.As with above-mentioned ligand combination use not containing the complex compound of tertiary phosphine or tertiary phosphite ester, two (BENZYLIDENE ACETONE) palladium, three (BENZYLIDENE ACETONE) two palladium, two (acetonitrile) palladium chloride, two (benzonitrile) palladium chloride, acid chloride, palladium bichloride, palladium-activated charcoal etc. can be exemplified.As comprising tertiary phosphine or the tertiary phosphite ester complex compound as part, two (triphenylphosphine) palladium of dimethyl, dimethyl two (diphenyl methyl phosphine) palladium, (ethylidene) two (triphenylphosphine) palladium, tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chlorides etc. can be exemplified, but be not limited to this.As long as the so-called catalytic amount of the consumption of these palladium complexs, in general 20 % by mole below of compound of reaction with regard to enough, be generally less than 10 % by mole.
As alkali, also the amine etc. such as inorganic base or methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, propylamine, di-n-propylamine, tripropyl amine (TPA), isopropylamine, diisopropylamine, tri-isopropyl amine, butylamine, dibutylamine, tri-n-butylamine, diisopropylethylamine, pyridine, imidazoles, quinoline, trimethylpyridine can be used, and sodium acetate, potassium acetate, lithium acetate etc.
Solvent can suitably be selected, as long as under the reaction conditions stable, in inertia, do not hinder the solvent of reaction.Such as water, alcohols, amine, aprotic polar organic solvent (dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, 1-METHYLPYRROLIDONE etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, cyclopentyl-methyl ether, tetrahydrofuran, two can be used alkane etc.), aliphatic hydrocarbon (pentane, hexane, heptane, sherwood oil etc.), aromatic hydrocarbon based (benzene,toluene,xylene, 1,3,5-trimethylbenzene, chlorobenzene, dichloro-benzenes, nitrobenzene, tetralin etc.), halogenated hydrocarbon (chloroform, methylene chloride, phenixin, ethylene dichloride etc.), low-grade fatty acid ester class (methyl acetate, ethyl acetate, butyl acetate, methyl propionate etc.), nitrile (acetonitrile, propionitrile, butyronitrile etc.).These solvents can be considered reaction conditions and react the complexity etc. of carrying out and suitably select, and now can be used alone that one or more are used in combination.In addition, use after also according to circumstances can making non-aqueous solvent with dewatering agent or drying agent.
Temperature of reaction is the boiling point of the solvent of-100 DEG C ~ use, is better in the scope of-50 ~ 150 DEG C.
Reaction time is better 0.1 ~ 1000 hour.
The compound 4 obtained as mentioned above carrys out purifying by recrystallization, distillation, silica gel column chromatography, activated charcoal etc.
The method for making of compound 5
The dinitro matrix 4 obtained as mentioned above can select the reduction reaction conditions of the double bond not damaging side chain to carry out the reduction of nitro, thus converts the diamine compound 5 as target product to.
In the reduction of the nitro that the double bond of side chain is maintained the original state, be better that the metals such as Fe, Sn, Zn or their slaine are used together with proton source.Metal and slaine can use separately or jointly.
As proton source, the acid such as hydrochloric acid can be used, the ammonium salts such as ammonium chloride, the protonic solvent such as methyl alcohol, ethanol.
As long as solvent can tolerate the solvent of the environment under reducing atmosphere, aprotic polar organic solvent (dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, 1-METHYLPYRROLIDONE etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, cyclopentyl-methyl ether, tetrahydrofuran, two can be used alkane etc.), aliphatic hydrocarbon (pentane, hexane, heptane, sherwood oil etc.), aromatic hydrocarbon based (benzene,toluene,xylene, 1,3,5-trimethylbenzene, chlorobenzene, dichloro-benzenes, nitrobenzene, tetralin etc.), low-grade fatty acid ester class (methyl acetate, ethyl acetate, butyl acetate, methyl propionate etc.), nitrile (acetonitrile, propionitrile, butyronitrile etc.).These solvents can be considered reaction conditions and react the complexity etc. of carrying out and suitably select, and can be used alone that one or more are used in combination.In addition, use after also according to circumstances can making non-aqueous solvent with suitable dewatering agent or drying agent.
Temperature of reaction is the boiling point of the solvent of-100 DEG C ~ use, is better in the scope of-50 ~ 150 DEG C.
Reaction time is better 0.1 ~ 1000 hour.
The compound 5 obtained as mentioned above carrys out purifying by recrystallization, distillation, silica gel column chromatography, activated charcoal etc.
Method for making 2
By the reaction of dinitro matrix 1 and acrylic acid derivative 19 or the compound 20 as etheride, can be made into the dinitro matrix 4 that side chain has cinnamic acid position.For the dinitro matrix 4 of gained, by selecting to implement not have influential method of reducing to the double bond part of side chain, be convertible into the diamine compound 5 as target product.
[changing 33]
The method for making of compound 20
[changing 34]
In compound 19 and compound 20, X represents F, Cl, Br or I as halogen, X 4represent singly-bound ,-O-,-S-or-NH-.
X 5, X 6, X 7with the implication of n with above identical.
The method for making of compound 20 is methods that compound 19 and carboxylic acid halides agent are reacted.From reagent obtain complexity, reactive viewpoint consider, preferred Cl or Br of X.As used carboxylic acid halides agent, such as thionyl chloride, oxalyl chloride, phosgene, chlorine, phosphoryl chloride phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, N-chlorosuccinimide, boron chloride, thionyl bromide, oxalyl bromine, bromine, phosphoryl bromide, phosphorus tribromide, phosphorus pentabromide, N-bromosuccinimide etc. can be exemplified.Preferred use thionyl chloride or thionyl bromide.The consumption of carboxylic acid halides agent is generally 2 ~ 100 times moles relative to compound 19, is preferably 2 ~ 30 times moles, is more preferably 2 ~ 3 times moles.
Above-mentioned reaction also can be carried out in the carboxylic acid halides agents such as thionyl chloride, can use solvent as required.
As long as solvent is to the solvent of reaction in inertia, be not particularly limited, such as aprotic polar organic solvent (dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, 1-METHYLPYRROLIDONE etc.), ethers (diethyl ether, diisopropyl ether, tetrabutyl methyl ether, cyclopentyl-methyl ether, tetrahydrofuran, two can be used alkane etc.), aliphatic hydrocarbon (pentane, hexane, heptane, sherwood oil etc.), aromatic hydrocarbon based (benzene,toluene,xylene, 1,3,5-trimethylbenzene, chlorobenzene, dichloro-benzenes, nitrobenzene, tetralin etc.), halogenated hydrocarbon (chloroform, methylene chloride, phenixin, ethylene dichloride etc.), low-grade fatty acid ester class (methyl acetate, ethyl acetate, butyl acetate, methyl propionate etc.), nitrile (acetonitrile, propionitrile, butyronitrile etc.).These solvents can consider that reacting the complexity etc. of carrying out suitably selects, and can be used alone that one or more are used in combination.In addition, use after also according to circumstances can making non-aqueous solvent with suitable dewatering agent or drying agent.
Above-mentioned reaction also can be carried out under the condition not having catalyzer, but by adding catalyzer, can reduce the consumption of chlorating agent, and can add the carrying out of fast response.Be not particularly limited as catalyzer, organic bases such as such as triethylamine, pyridine, quinoline, DMA, dimethyl formamide can be exemplified, the metal alkoxide classes such as sodium methoxide, potassium methoxide or potassium tert-butoxide.Preferably exemplify triethylamine, pyridine, dimethyl formamide.More preferably pyridine is exemplified.The consumption of these catalyzer is generally 0 ~ 100 times mole relative to etheride, is preferably 0.01 ~ 10 times mole.
Temperature of reaction is the boiling point of the solvent of-100 DEG C ~ use, is better in the scope of-50 ~ 150 DEG C.
Reaction time is generally 0.1 ~ 1000 hour.
The compound 20 obtained as mentioned above carrys out purifying by operations such as recrystallization, distillation, silica gel column chromatographies.
The method for making-1 of compound 19
[changing 35]
In compound 21, A represents alkyl, silylation or hydrogen, such as, be methyl, ethyl, propyl group, normal-butyl, isopropyl, the tert-butyl group, sec-butyl, phenyl, benzyl, silylation, THP trtrahydropyranyl, tetrahydrofuran base, methoxy, methoxy ethoxy, vinyl etc.
Above-mentioned reaction by coupling reactions such as compound 3 and the compound 21 He Ke reactions under the coexisting of metal complex catalyst, part and alkali to synthesize compound 19.Method shown in the synthetic method of reaction conditions and the compound 4 of method for making 1 is identical.
A be alkyl or silylation time, by utilizing water to be hydrolyzed by ester group-COOA after the reaction in the presence of acids and bases, the compound 19 for correspondence can be derived.As used acid, the organic acid such as the mineral acids such as dilute sulfuric acid or p-toluenesulfonic acid, formic acid, acetic acid can be exemplified.As alkali, the carbonates such as saleratus, sodium bicarbonate, sal tartari, sodium carbonate can be exemplified, the alkali metal hydroxide such as NaOH, potassium hydroxide, the alkaline earth metal hydroxide such as calcium hydroxide, magnesium hydroxide, the phosphoric acid salt such as sodium dihydrogen phosphate, potassium dihydrogen phosphate, the metal carboxylate such as sodium acetate, potassium acetate, organic bases such as triethylamine, pyridine, the metal alkoxide such as sodium methoxide, caustic alcohol class, the metal hydride classes etc. such as sodium hydride.
For hydrolysis, carry out swimmingly to make reaction, can carry out in the solvent that can mix with water, as used solvent, the aprotic polar organic solvents such as dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide can be exemplified, the nitriles such as acetonitrile, propionitrile, butyronitrile, the organic weak base solvents such as pyridine, the alcohols such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, the tert-butyl alcohol.In addition, by heating, reaction can be made to carry out quickly.
Temperature of reaction is the boiling point of the solvent of-100 DEG C ~ use, is better in the scope of-50 ~ 150 DEG C.
Reaction time is generally 0.1 ~ 1000 hour.
The compound 19 obtained as mentioned above carrys out purifying by operations such as recrystallization, distillation, silica gel column chromatographies.
The method for making-2 of compound 19
[changing 36]
In compound 22 and compound 23, X 4, X 5, X 6, X 7, n with A implication with above identical.The group that A exemplifies is also with above identical.
Such as A be alkyl or silylation time, the method for making of compound 19 makes compound 22 and compound 23 in the presence of base after dehydrating condensation, by diester partial hydrolysis, makes the method for its decarbonate.When A is hydrogen, the method for making of compound 19 makes compound 22 and compound 23 in the presence of base after dehydrating condensation, makes the method for its decarbonate.
When A is hydrogen, though be not particularly limited, such as, by reacting in pyridine solvent, under the existence of piperidines, at 60 ~ 100 DEG C, aldehyde radical and malonic acid dehydrating condensation can be made, then be heated to 100 ~ 150 DEG C to carry out decarbonate reaction, obtain compound 19.
As long as the alkali used in dehydration condensation uses the alkali with the base strength (basicity) making reaction carry out swimmingly, be not particularly limited.Such as there is lithium, sodium, the alkali-metal oxyhydroxide of potassium and so on or carbonate, lithium amide, sodium amide, the alkali metal amino compound of amination potassium and so on, lithium hydride, sodium hydride, the alkali metal hydride of hydrofining and so on, earth alkali metal, the methoxide of sodium or potassium, ethylate, n-propanol salt, isopropoxide, normal butyl alcohol salt, sec-butyl alcohol salt, tert butoxide, 2-methyl-2-butylate, 2-methyl-2-amylalcohol salt, 3-methyl-3-amylalcohol salt, 3-ethyl-3-amylalcohol salt and so on by the aliphatic primary alcohol of carbon number 1 ~ 10, the alkali metal alcoholates that secondary alcohol or the tertiary alcohol derive, diazabicyclo octane, diazabicycloundecene, DMAP, pyrrolidine, the organic fatty races such as piperidines, aromatic series, the nitrogenous base of heterocycle.These alkali also can use as a mixture.As alkali, preferred alcohol sodium, sodium hydride.The consumption of alkali is generally 0.1 ~ 10 times mole relative to compound 22, is preferably 0.1 ~ 5 times mole.
As long as the solvent that solvent does not react with compound 22 and compound 23 just can use.The aprotic polar organic solvents such as such as dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, 1-METHYLPYRROLIDONE can be used, diethyl ether, diisopropyl ether, tetrabutyl methyl ether, cyclopentyl-methyl ether, tetrahydrofuran, two the ethers such as alkane, the aliphatic hydrocarbons such as pentane, hexane, heptane, sherwood oil, benzene,toluene,xylene, 1,3,5-trimethylbenzene, chlorobenzene, dichloro-benzenes, nitrobenzene, tetralin etc. are aromatic hydrocarbon based, the nitriles such as acetonitrile, propionitrile, butyronitrile, the organic weak base such as pyridine, quinoline solvent etc.Also the alcohols such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, the tert-butyl alcohol can be used.These solvents can consider that reacting the complexity etc. of carrying out suitably selects, and can be used alone that one or more are used in combination.In addition, use after also according to circumstances can making non-aqueous solvent with suitable dewatering agent or drying agent.
Method shown in the method for making-1 of the condition utilizing water to be hydrolyzed and compound 19 is identical.
Temperature of reaction is the boiling point of the solvent of-100 DEG C ~ use, is better in the scope of-50 ~ 150 DEG C.
Reaction time is generally 0.1 ~ 1000 hour.
The compound 19 obtained as mentioned above carrys out purifying by operations such as recrystallization, distillation, silica gel column chromatographies.
The method for making of compound 22
[changing 37]
In compound 24, the implication of U with n is with above identical.
The method for making of compound 22 is such as the method that compound 24 and compound 18 are reacted.Several compound 24 and compound 18 can obtain easily as commercial goods.
The substituting group U of compound 24 is-OH ,-SH or-NH 2, compound 18 X 5for singly-bound or be selected from above-mentioned [X 5-1] ~ [X 5during carbocyclic ring-4], compound 24 and compound 18 are reacted in the presence of base, thus obtains compound 22.Reaction conditions can adopt the X in the synthetic method of the compound 3 of method for making 1 5for being selected from above-mentioned [X 5-1] ~ [X 5method during structure-4].
The substituting group U of compound 24 is-OH ,-SH or-NH 2, compound 18 X 5for singly-bound or [X 5during carbocyclic ring-5], can, in the presence of base using metal complex and part as catalyzer, coupling reaction be utilized to synthesize.Reaction conditions can adopt the X in the synthetic method of the compound 3 of method for making 1 5for above-mentioned [X 5-5] method time.
The substituting group U of compound 24 is X of F, Cl, Br or I as halogen, compound 22 4during for singly-bound, can, in the presence of base using metal complex and part as catalyzer, coupling reaction be utilized to synthesize.Reaction conditions can adopt the X in the synthetic method of the compound 3 of method for making 1 4for method during singly-bound.
The method for making-3 of compound 19
[changing 38]
In compound 25, the implication of A is with above identical, and the group exemplified is also with above identical.
The method for making of compound 19 is such as, after making compound 22 and compound 25 carry out dehydration condensation in the presence of base, utilize the method that ester group-COOA is hydrolyzed by water.
As long as the alkali used in above-mentioned reaction uses the alkali with the base strength (basicity) making reaction carry out swimmingly, be not particularly limited.Such as there is the alkali-metal oxyhydroxide of lithium, sodium, potassium and so on, the alkali metal amino compound of lithium amide, sodium amide, amination potassium and so on, the alkali metal hydride of lithium hydride, sodium hydride, hydrofining and so on, the alkali metal alcoholates etc. derivative by the aliphatic primary alcohol of carbon number 1 ~ 10, secondary alcohol or the tertiary alcohol of the methoxide, ethylate, n-propanol salt, isopropoxide, normal butyl alcohol salt, sec-butyl alcohol salt, tert butoxide, 2-methyl-2-butylate, 2-methyl-2-amylalcohol salt, 3-methyl-3-amylalcohol salt, 3-ethyl-3-amylalcohol salt and so on of earth alkali metal, sodium or potassium.These alkali also can use as a mixture.As alkali, preferred alcohol sodium, sodium hydride.The consumption of these alkali is generally 0.1 ~ 10 times mole relative to compound 22, is preferably 0.1 ~ 5 times mole.
As long as the solvent that solvent does not react with compound 22 and compound 25 just can use.The aprotic polar organic solvents such as such as dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, 1-METHYLPYRROLIDONE can be used, diethyl ether, diisopropyl ether, tetrabutyl methyl ether, cyclopentyl-methyl ether, tetrahydrofuran, two the ethers such as alkane, the aliphatic hydrocarbons such as pentane, hexane, heptane, sherwood oil, benzene,toluene,xylene, 1,3,5-trimethylbenzene, chlorobenzene, dichloro-benzenes, nitrobenzene, tetralin etc. are aromatic hydrocarbon based, the nitriles such as acetonitrile, propionitrile, butyronitrile, the organic weak base such as pyridine, quinoline solvent etc.Also the alcohols such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, the tert-butyl alcohol can be used.These solvents can consider that reacting the complexity etc. of carrying out suitably selects, and can be used alone that one or more are used in combination.In addition, use after also according to circumstances can making non-aqueous solvent with suitable dewatering agent or drying agent.
Method shown in the method for making-1 of the condition utilizing water to be hydrolyzed and compound 19 is identical.
Temperature of reaction is the boiling point of the solvent of-100 DEG C ~ use, is better in the scope of-50 ~ 150 DEG C.
Reaction time is generally 0.1 ~ 1000 hour.
The compound 19 obtained as mentioned above carrys out purifying by operations such as recrystallization, distillation, silica gel column chromatographies.
The method for making-4 of compound 19
[changing 39]
In compound 26, the implication of A is with above identical, and the group exemplified is also with above identical.W is triphenylphosphine or phosphonate ester.
The method for making of compound 19 is such as after making compound 22 and compound 26 carry out witig reaction or Huo Naer-Wordsworth-Ai Mengsi reaction (Horner-Wadsworth-Emmons reaction), by the method that ester group-COOA is hydrolyzed.Reaction is better use alkali to carry out in a solvent.
Alkali used in reaction preferably uses the alkali having and can generate the intensity of phosphonium ylide swimmingly.As alkali, such as lithium can be used, sodium, the alkali-metal oxyhydroxide of potassium and so on or carbonate, butyl lithium, s-butyl lithium, the lithium alkyl of tert-butyl lithium and so on, lithium amide, sodium amide, the alkali metal amino compound of amination potassium and so on, lithium hydride, sodium hydride, the alkali metal hydride of hydrofining and so on, lithium hexamethyldisilazide, sodium hexamethyldisilazide, the silica-based amides class of alkaline metal hexamethyl two of potassium hexamethyldisilazide and so on, earth alkali metal, the methoxide of sodium or potassium, ethylate, n-propanol salt, isopropoxide, normal butyl alcohol salt, sec-butyl alcohol salt, tert butoxide, 2-methyl-2-butylate, 2-methyl-2-amylalcohol salt, 3-methyl-3-amylalcohol salt, 3-ethyl-3-amylalcohol salt and so on by the aliphatic primary alcohol of carbon number 1 ~ 10, the alkali metal alcoholates that secondary alcohol or the tertiary alcohol derive, diazabicyclo octane, diazabicycloundecene, DMAP, pyrrolidine, the organic fatty races such as piperidines, aromatic series, the nitrogenous base etc. of heterocycle.Particularly preferably butyl lithium, tert-butyl lithium.
As long as the solvent that solvent does not react with compound 22 and compound 26 just can use.Such as ethers (diethyl ether, diisopropyl ether, tetrabutyl methyl ether, cyclopentyl-methyl ether, tetrahydrofuran, two can be used alkane etc.), aprotic polar organic solvent (dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, 1-METHYLPYRROLIDONE etc.), aliphatic hydrocarbon (pentane, hexane, heptane, sherwood oil etc.), aromatic hydrocarbon based (benzene,toluene,xylene, 1,3,5-trimethylbenzene, chlorobenzene, dichloro-benzenes, nitrobenzene, tetralin etc.), nitrile (acetonitrile, propionitrile, butyronitrile etc.).These solvents can consider that reacting the complexity etc. of carrying out suitably selects, and can be used alone that one or more are used in combination.In addition, use after also according to circumstances can making non-aqueous solvent with dewatering agent or drying agent.
Method shown in the method for making-1 of the condition utilizing water to be hydrolyzed and compound 19 is identical.
Temperature of reaction is the boiling point of the solvent of-100 DEG C ~ use, is better in the scope of-50 ~ 150 DEG C.
Reaction time is 0.1 ~ 1000 hour.
The compound 19 obtained as mentioned above carrys out purifying by operations such as recrystallization, distillation, silica gel column chromatographies.
The method for making-5 of compound 19
[changing 40]
In compound 27 and compound 28, X 4, X 5, X 6, X 7with the implication of n with above identical.
M is organometallic reaction agent Li, MgCl, MgBr or MgI.
The implication of A is with above identical, and the group exemplified is also with above identical.
The method for making of compound 19 is such as make compound 27 and the mixing of mantoquita, zinc salt or dialkyl group zinc in a solvent, make cuprate or diaryl zine compound, after carrying out Isosorbide-5-Nitrae-addition reaction with the compound shown in compound 28, utilize the method that ester group-COOA is hydrolyzed by water.
The mantoquita used in this reaction, zinc salt or dialkyl group zinc both can be used alone, and also these mantoquitas, zinc salt, dialkyl group zinc can be combinationally used.
As the example of the mantoquita used in reaction, there are CuCl, CuBr, CuI, CuCN or CuCl 2with the salt-mixture etc. of LiCl, particularly preferably CuI.
As the example of the zinc salt used in reaction, there is ZnCl 2, ZnBr 2or ZnI 2, particularly preferably ZnCl 2.
As the example of the dialkyl group zinc used in reaction, there are dibutyl zinc, diethyl zinc or dibutene base zinc, particularly preferably diethyl zinc.
As long as the solvent that solvent does not react with organometallic reaction agent just can use.
Such as ethers (diethyl ether, diisopropyl ether, tetrabutyl methyl ether, cyclopentyl-methyl ether, tetrahydrofuran, two can be used alkane etc.), aprotic polar organic solvent (dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, 1-METHYLPYRROLIDONE etc.), aliphatic hydrocarbon (pentane, hexane, heptane, sherwood oil etc.), aromatic hydrocarbon based (benzene,toluene,xylene, 1,3,5-trimethylbenzene, chlorobenzene, dichloro-benzenes, nitrobenzene, tetralin etc.).These solvents can consider that reacting the complexity etc. of carrying out suitably selects, and can be used alone that one or more are used in combination.In addition, use after also according to circumstances can making non-aqueous solvent with suitable dewatering agent or drying agent.
Method shown in the method for making-1 of the condition utilizing water to be hydrolyzed and compound 19 is identical.
Temperature of reaction is the boiling point of the solvent of-100 DEG C ~ use, is better in the scope of-50 ~ 150 DEG C.
Reaction time is 0.1 ~ 1000 hour.
The compound 10 obtained as mentioned above carrys out purifying by operations such as recrystallization, distillation, silica gel column chromatographies.
The method for making of compound 27
[changing 41]
In compound 29 and compound 30, U, X, X 4, X 5, X 6, X 7with the implication of n with above identical.
The method for making of compound 27 is such as synthesize compound 30 by compound 29 and the reaction of compound 18, then makes the method that compound 30 reacts with magnesium metal or lithiumation agent.Several compound 29 and compound 18 can obtain easily as commercial goods.
The substituting group U of compound 29 is-OH ,-SH or-NH 2, compound 18 X 5for singly-bound or be selected from above-mentioned [X 5-1] ~ [X 5during carbocyclic ring-4], compound 29 and compound 18 are reacted in the presence of base, thus obtains compound 30.Reaction conditions can adopt the X in the synthetic method of the compound 3 of method for making 1 5for being selected from above-mentioned [X 5-1] ~ [X 5method during carbocyclic ring-4].
The substituting group U of compound 29 is-OH ,-SH or-NH 2, compound 18 X 5for singly-bound or [X 5during carbocyclic ring-5], can, in the presence of base using metal complex and part as catalyzer, coupling reaction be utilized to synthesize.Reaction conditions can adopt the X in the synthetic method of the compound 3 of method for making 1 5for above-mentioned [X 5-5] method time.
The substituting group U of compound 29 is X of F, Cl, Br or I as halogen, compound 27 4during for singly-bound, can, in the presence of base using metal complex and part as catalyzer, coupling reaction be utilized to synthesize.Reaction conditions can adopt the X in the synthetic method of the compound 3 of method for making 1 4for method during singly-bound.
In the compound 30 of gained, add metal M g, react in ether solvents, obtain the compound 27 (M=MgF, MgCl, MgBr, MgI) that can be used for grignard reaction.In addition, make lithium metal react in a solvent, the compound 27 that M is Li can be obtained.
The method for making-6 of compound 19
[changing 42]
In compound 31, the implication of U with n is with above identical.
The method for making of compound 19 is such as that compound 31 and compound 18 are reacted, and utilizes the method that ester group-COOA is hydrolyzed by water after reaction.Several compound 31 and compound 18 can obtain easily as commercial goods.
The substituting group U of compound 31 is-OH ,-SH or-NH 2, compound 18 X 5for singly-bound or be selected from above-mentioned [X 5-1] ~ [X 5during carbocyclic ring-4], compound 31 and compound 18 are reacted in the presence of base, as shown in the method for making-1 of compound 19, utilizes water to be hydrolyzed after reaction, thus obtain compound 19.Reaction conditions can adopt the X in the synthetic method of the compound 3 of method for making 1 5for being selected from above-mentioned [X 5-1] ~ [X 5method during carbocyclic ring-4].
The substituting group U of compound 31 is-OH ,-SH or-NH 2, compound 18 X 5for singly-bound or above-mentioned [X 5-5], time, carry out coupling reaction using metal complex and part as catalyzer in the presence of base, after reaction, as shown in the method for making-1 of compound 19, utilize water to be hydrolyzed, thus obtain compound 19.Reaction conditions can adopt the X in the synthetic method of the compound 3 of method for making 1 5for above-mentioned [X 5-5] method time.
The substituting group U of compound 31 is X of F, Cl, Br or I as halogen, compound 19 4during for singly-bound, carry out coupling reaction using metal complex and part as catalyzer in the presence of base, after reaction, as shown in the method for making-1 of compound 19, utilize water to be hydrolyzed, thus obtain compound 19.Reaction conditions can adopt the X in the synthetic method of the compound 3 of method for making 1 4for method during singly-bound.
The method for making of compound 4
Compound 4 is by the compound 1 in solvent and manufacture as the compound 19 of acrylic acid derivative or the esterification of compound 20.
Particularly in the reaction of the such etheride of compound 20 and compound 1, the carboxylic acid halides classes such as the preferred acyl chlorides of etheride, acylbromide, and also because reaction is carried out, swimmingly so be better react in the presence of base.As alkali, the inorganic bases such as such as NaOH, potassium hydroxide, lithium hydroxide, sodium bicarbonate, saleratus, potassium phosphate, sodium carbonate, sal tartari, lithium carbonate, cesium carbonate, sodium hydride, hydrofining can be used, the amines such as trimethylamine, triethylamine, tripropyl amine (TPA), tri-isopropyl amine, tri-n-butylamine, diisopropylethylamine, pyridine, quinoline, trimethylpyridine, the organic base such as sodium tert-butoxide, potassium tert-butoxide.
Solvent can suitably be selected, as long as under the reaction conditions stable, in inertia, do not hinder the solvent of reaction.Such as amine, aprotic polar organic solvent (dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, 1-METHYLPYRROLIDONE etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, cyclopentyl-methyl ether, tetrahydrofuran, two can be used alkane etc.), aliphatic hydrocarbon (pentane, hexane, heptane, sherwood oil etc.), aromatic hydrocarbon based (benzene,toluene,xylene, 1,3,5-trimethylbenzene, chlorobenzene, dichloro-benzenes, nitrobenzene, tetralin etc.), halogenated hydrocarbon (chloroform, methylene chloride, phenixin, ethylene dichloride etc.), low-grade fatty acid ester class (methyl acetate, ethyl acetate, butyl acetate, methyl propionate etc.), nitrile (acetonitrile, propionitrile, butyronitrile etc.).These solvents can be considered reaction conditions and react the complexity etc. of carrying out and suitably select, and can be used alone that one or more are used in combination.In addition, use after also according to circumstances can making non-aqueous solvent with dewatering agent or drying agent.
Temperature of reaction is the boiling point of the solvent of-100 DEG C ~ use, is better in the scope of-50 ~ 150 DEG C.
Reaction time is better 0.1 ~ 1000 hour.
The compound 4 obtained as mentioned above carrys out purifying by recrystallization, distillation, silica gel column chromatography, activated charcoal etc.
In the reaction of compound 19 and compound 1, usually use dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) condensation agent such as carbodiimide, carbonyl dimidazoles.Now, the acid of catalytic amount or the interpolation of N, N-dimethylamino naphthyridine are effective for the carrying out of reaction, therefore preferably.
The method for making of compound 5
The manufacture of the compound 5 of compound 4 is used to be undertaken by the method described in method for making 1.
< polyamic acid, poly amic acid ester, polyimide >
Diamine compound 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.Except tetrabasic carboxylic acid or derivatives thereof, by the reaction of tetrabasic carboxylic acid diester diacid chloride and diamine compound, or by making tetrabasic carboxylic acid diester and diamine compound react under the existence of condensation agent, alkali etc., the poly amic acid ester as polyimide precursor can be obtained.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 >
Polyamic acid of the present invention is the polyamic acid by obtaining containing the diamine component of diamine compound represented with formula [1] and the reaction of tetracarboxylic dianhydride.
Poly amic acid ester of the present invention is the poly amic acid ester by making the diamine component containing the diamine compound represented with formula [1] and tetrabasic carboxylic acid diester diacid chloride carry out in the presence of a base reacting or make tetrabasic carboxylic acid diester and diamine compound to carry out reacting under the existence of condensation agent, alkali etc. and obtain.
Polyimide of the present invention is the polyimide obtained by making this polyamic acid carry out dehydration closed-loop or to make poly amic acid ester carry out heating closed loop.
As the polymkeric substance for obtaining liquid crystal orientation film, any one in 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 tetracarboxylic dianhydride, proportional less than limiting to containing of the diamine compound represented with formula [1].The diamine compound represented with formula [1] containing proportional be such as more than 10 % by mole of diamine component, preferably more than 20 % by mole, more preferably more than 30 % by mole.Also can 100 % by mole of diamine component be all the diamine compound represented with formula [1].Containing of the diamine compound represented with formula [1] is proportional larger, then when making liquid crystal orientation film, the ability that liquid crystal is stood vertically is stronger, and the efficiency of light orientation process is higher.Tilt angle during light orientation process because of the structure of the side chain of diamine compound represented with formula [1] and the liquid crystal used vertical orientated ability and change, therefore in order to obtain desired tilt angle, can selecting in preferable range containing proportional of the diamine compound represented with formula [1].
In diamine component, when the diamine compound represented with formula [1] is lower than 100 % by mole, diamine compound (below sometimes also referred to as other diamine compound) beyond the diamine compound represented with formula [1] used is not particularly limited, and its concrete example 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 and the diamine compound of large ring-type substituent that is made up of them.Particularly, the diamines represented with following formula [DA-1] ~ formula [DA-26] can be illustrated.
[changing 43]
(R 6be carbon number 1 ~ 22 alkyl or containing fluoroalkyl.)
[changing 44]
(S 5represent-COO-,-OCO-,-CONH-,-NHCO-,-CH 2-,-O-,-CO-or-NH-, R 6represent the alkyl of carbon number 1 ~ 22 or contain fluoroalkyl.)
[changing 45]
(S 6represent-O-,-OCH 2-,-CH 2o-,-COOCH 2-or-CH 2oCO-, R 7be the alkyl of carbon number 1 ~ 22, alkoxy, containing fluoroalkyl or fluoroalkoxy.)
[changing 46]
(S 7represent-COO-,-OCO-,-CONH-,-NHCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-or-CH 2-, R 8be the alkyl of carbon number 1 ~ 22, alkoxy, containing fluoroalkyl or fluoroalkoxy.)
[changing 47]
(S 8represent-COO-,-OCO-,-CONH-,-NHCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-,-CH 2-,-O-or-NH-, R 9fluorine-based, cyano group, trifluoromethyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group or hydroxyl.)
[changing 48]
(R 10be the alkyl of carbon number 3 ~ 12, the cis-trans isomerism of Isosorbide-5-Nitrae-cyclohexylidene is respectively trans.)
[changing 49]
[changing 50]
[changing 51]
In order to make up vertical orientated ability, also can by the diamine compound of above-mentioned [DA-1] ~ [DA-26] and the diamine compound represented with general formula [1] simultaneously and use.As can and preferred diamines, consider from the angle of voltage retention and residual accumulation voltage etc., the diamine compound of preferred formula [DA-10] ~ [DA-26], the more preferably diamine compound of formula [DA-10] ~ [DA-16].The preferred content of these diamine compounds is not particularly limited, but is preferably 5 ~ 50 % by mole in diamine component, more preferably 5 ~ 30 % by mole.
In addition, also can be used together following diamine compound.
[changing 52]
(m is the integer of 0 ~ 3, and n is the integer of 1 ~ 5).
By containing [DA-27] or [DA-28], can improve voltage retention (VHR), [DA-29] ~ [DA-34] has the effect reducing accumulated charge, therefore preferably.
Further, as other diamine compound, 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 can, according to as characteristics such as liquid crystal aligning during liquid crystal orientation film, voltage retention performance, accumulated charge, use one or more 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 alicyclic 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 alicyclic 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.
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:
As aliphatics tetrabasic carboxylic acid diester, can 1 be exemplified, 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.
For in order to diamine compound of the present invention for raw material obtains polyimide and being not particularly limited with the dicarboxylic acid that diamine component reacts.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, the dicarboxylic acid such as 2-dimethylated pentanedioic acid, 3,3-diethyl succinic acids, azelaic acid, decanedioic acid, suberic acid.
As the dicarboxylic acid of alicyclic structure, 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, the sub-diphenyl dicarboxylic acid of 1,5-, 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 '-ethynylene dibenzoic 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 '-(oxo two pairs of phenylenes)] dipropionic acid, 4,4 '-[4,4 '-(oxo two pairs of phenylenes)] two butyric acid, (isopropylidene two pairs of phenylene dioxies) 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 be sour two carboxylic acid halides or acid anhydrides.In these dicarboxylic acid, particularly can give the dicarboxylic acid of the polyamide of linear structure, be preferred from the viewpoint of the orientation of maintenance liquid crystal molecule.Wherein, preferred use terephthalic acid (TPA), m-phthalic acid, Isosorbide-5-Nitrae-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, also can be used together two or more compounds.
The omega-dicarboxylic acids used in the present invention is not limited to the compound above exemplified.
Tetracarboxylic dianhydride can according to the characteristic such as liquid crystal aligning, voltage retention performance, accumulated charge when making liquid crystal orientation film, uses one or and with two or more.
When obtaining polyamic acid of the present invention by the reaction of diamine component and tetracarboxylic dianhydride, known synthetic method can be adopted.Normally make the method that tetracarboxylic dianhydride and diamine component react in organic solvent.The reaction of tetracarboxylic dianhydride and diamine compound 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 diamine compound, as long as generate the soluble solvent of polyamic acid, be 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, 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 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 insoluble solution polyamic acid, as long as in the scope that the polyamic acid generated can not be separated out, also can be used in combination with above-mentioned solvent.
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.
Can exemplify when tetracarboxylic dianhydride and diamine component are reacted in organic solvent: 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; 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, can by any one method wherein.In addition, when tetracarboxylic dianhydride or diamine component comprise 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, is better the scope of-5 ~ 100 DEG C.In addition, reaction can be carried out with arbitrary concentration, if but concentration is too low, then be difficult to the polymkeric substance obtaining high molecular, if excessive concentration, the viscosity of reactant liquor is too high, be difficult to stir uniformly, therefore tetracarboxylic dianhydride and the diamine component total concentration in reaction solution is preferably 1 ~ 50 quality %, is more preferably 5 ~ 30 quality %.Initial reaction stage is carried out in higher concentrations, can add organic solvent afterwards.
In above-mentioned reaction, 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.
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.
< polyimide >
As the method making polyamic acid imidizate, the hot-imide of the solution of directly heating polyamic acid can be exemplified, in the solution of polyamic acid, add the catalysis imidizate of catalyzer.
Making temperature during polyamic acid hot-imide be 100 ~ 400 DEG C in the solution, is better 120 ~ 250 DEG C, is better to carry out while the water will generated by imidization reaction is got rid of to system.
The catalysis imidizate of polyamic acid is by adding base catalyst and acid anhydrides in polyamic acid solution, and at-20 ~ 250 DEG C, is better stir at 0 ~ 180 DEG C and carry out.The amount of base catalyst is mole to count 0.5 ~ 30 times of acid amides acidic group, preferably 2 ~ 20 times, and the amount of acid anhydrides is mole to count 1 ~ 50 times of acid amides acidic group, preferably 3 ~ 30 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, reaction time.
< poly amic acid ester >
As the method for synthesizing polyamides acid esters, by the reaction of tetrabasic carboxylic acid diester diacid chloride and diamine compound, or by making tetrabasic carboxylic acid diester and diamine compound react under the existence of condensation agent, alkali etc., a kind of poly amic acid ester as polyimide precursor can be obtained.Or by making polyamic acid be polymerized in advance, utilizing high molecular weight reactive to make the method for the carboxylic esterification in amic acid, also can obtain poly amic acid ester.
Specifically, can make tetrabasic carboxylic acid diester diacid chloride and diamine compound 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, thus synthesize.
Alkali can use pyridine, triethylamine, DMAP etc., because reacting balance ground carries out, so preferred pyridine.Easily obtain high molecular body from the viewpoint of with the amount easily removed, the addition of alkali is better 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-dihydro-2-sulfo--3-benzo azoles) phosphonic acid diphenyl ester, 4-(4,6-dimethoxy-1,3,5-triazines-2-base) 4-methoxyl morpholine hydrochloride n hydrate etc. be as condensation agent.
In addition, in the method using 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 mole relative to tetrabasic carboxylic acid diester.
As solvent, solvent used when the carrying out above recorded can be used to be polymerized and obtain polyamic acid, considers from the angle of monomer and structure adaptability, preferred METHYLPYRROLIDONE, gamma-butyrolacton etc.These solvents can use one or more used in combination.In addition, in order to prevent the hydrolysis of tetrabasic carboxylic acid diester diacid chloride, the solvent for the synthesis of poly amic acid ester is better dehydration as far as possible.
From the viewpoint of being difficult to cause the precipitation of polymkeric substance and easily obtaining high molecular body, tetrabasic carboxylic acid diester diacid chloride and the diamine component total concentration in reaction solution is better 1 ~ 30 quality %, is more preferably 5 ~ 20 quality %.
Reaction is better carry out in nitrogen atmosphere, prevents being mixed into of foreign gas.
< polyamide >
Polyamide also can synthesize in the same manner as poly amic acid ester.
The recovery > of < polymkeric substance
When reclaiming the polyamic acid, poly amic acid ester, polyimide etc. of generation from the reaction solution of polyamic acid, poly amic acid ester, polyimide etc., reaction solution can be put into Weak solvent and polymkeric substance is precipitated.As the Weak 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 into precipitation in Weak solvent after filtered and recycled, can carry out drying in normal temperature or heating under normal or reduced pressure.In addition, if the polymkeric substance repeating to make precipitation reclaim is dissolved in organic solvent and precipitate the operation 2 ~ 10 times of recovery more again, then the impurity in polymkeric substance can be reduced.As Weak solvent now, can exemplify such as alcohols, ketone, hydro carbons etc., if use the Weak solvent being selected from more than 3 kinds of these solvents, then purification efficiency improves further, therefore desirable.
Polyamic acid contained in aligning agent for liquid crystal of the present invention and the molecular weight of polyimide, when the operability when considering that gained is coated with film strength, film is formed and the homogeneity of film, the weight-average molecular weight utilizing GPC (gel permeation chromatography) method to measure is better 2000 ~ 1000000, is more preferably 5000 ~ 100000.
< 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, is to be dissolved in for the formation of the resinous principle of resin coating the solution formed in organic solvent.Here, above-mentioned resinous principle is the resinous principle of at least one polymkeric substance comprising the polymkeric substance being selected from the invention described above.Now, content preferably 1 ~ 20 quality % of resinous principle, more preferably 3 ~ 15 quality %, particularly preferably 3 ~ 10 quality %.
In the present invention, described resinous principle can be all polymkeric substance of the present invention, also can mix other polymkeric substance beyond polymkeric substance of the present invention in polymkeric substance of the present invention.Now, the content of other polymkeric substance beyond the polymkeric substance of the present invention in resinous principle is 0.5 ~ 15 quality %, is better 1 ~ 10 quality %.
This other polymkeric substance can exemplify such as the diamine component reacted with tetracarboxylic dianhydride's composition, uses 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.Its example has, film thickness uniformity during raising coating of liquid crystalline aligning agent or the compound etc. of the solvent of surface smoothness or the adaptation of compound, raising liquid crystal orientation film and substrate.
As the concrete example of the solvent (Weak 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 methyl ethyl 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, isoamyl lactates etc. have the solvent etc. of low surface tension.
These Weak solvents can one or more be used in combination.When using solvent as above, be better 5 ~ 80 quality % of the solvent total amount comprised in aligning agent for liquid crystal, be 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 can exemplify エ Off ト Star プ EF301, EF303, EF352 (illuminating product Co., Ltd. (ト mono-ケ system プ Kouダクツ society) system), メ ガ Off ア Star Network F171, F173, R-30 (large Japanese ink Co., Ltd. (large Japanese イ Application キ society) system), Off mouth ラ mono-De FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo ス リ mono-エ system society) system), ア サ ヒ ガ mono-De AG710, サ mono-Off mouth Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd (Asahi Glass society) system) etc.The usage ratio 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, in aligning agent for liquid crystal, also phenoplast class adjuvant as follows can be contained.Concrete phenoplast class adjuvant is as follows, but is not limited to this structure.
[changing 54]
When using the compound improved with the adaptation of substrate, relative to resinous principle 100 mass parts contained in aligning agent for liquid crystal, its consumption is better 0.1 ~ 30 mass parts, is more preferably 1 ~ 20 mass parts.If consumption 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, the dielectric for the purpose of the electrical characteristics such as the specific inductive capacity that is changed liquid crystal orientation film or electric conductivity or conductive materials can be added, the cross-linked compound etc. for the purpose of the hardness improving film when forming liquid crystal orientation film or density can also be added.
< 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, glass substrate or the plastic base etc. such as acrylic acid substrate and 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, can use the opaque materials such as silicon wafer, but be only limitted to the substrate of side, electrode now can use the reflectorized materials such as aluminium.
The coating process of aligning agent for liquid crystal is not particularly limited, industrial usual employing 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 after on substrate burn till can by the heating arrangements such as heating plate 50 ~ 300 DEG C, be better 80 ~ 250 DEG C at carry out, to make solvent evaporate, thus formed film.If the thickness burning till the film of rear formation 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 cells.
An example of liquid crystal cells 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 substrate scatters sept, makes liquid crystal aligning face become interior rear flank another baseplate-laminating, 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.
As mentioned above, use the reliability of aligning agent for liquid crystal of the present invention and obtained liquid crystal display cells good, the LCD TV etc. of large picture and high-resolution can be performed well in.
Embodiment
Below, the present invention will be described in more detail to exemplify embodiment, but the present invention is not limited thereto.
[changing 55]
< embodiment 1>
In four-hole boiling flask, add 4-iodophenol 1 (22.0g, 0.100mol), sal tartari (20.7g, 0.150mol), dimethyl formamide 130ml (mM), after stirring in a nitrogen atmosphere, be warming up to 80 DEG C.After arriving 80 DEG C, drip 1-bromo-decane (17.9g, 0.0809mol) with the times of 30 minutes, drip after terminating and stir 1 hour again.After confirming that 1-bromo-decane disappears by GC (vapor-phase chromatography), steaming desolventizes, and adds toluene 120ml and pure water 150g extracts, removing water layer.Then in organic layer, add 1N NaOH100ml extract, removing water layer.By the organic over anhydrous dried over mgso of gained, then filtering magnesium sulfate, the organic layer of gained is under reduced pressure steamed and desolventizes, obtain compound 2 (26.9g, 0.0747mol, yield 92.3% must be measured).The structure of compound 2 is passed through 1h-NMR (nuclear magnetic resonance) analyzes and confirms.
1H-NMR（CDCl 3）:δ7.55-7.52(m,2H,Ar-H),6.69-6.65(m,2H,Ar-H),3.90(t,2H,Ｊ＝6.8Hz,Ar-O-CH 2),1.79-1.72(m,2H,Ar-O-CH 2-CH 2-),1.47-1.27(m,14H,Ar-O-CH 2-CH 2-C 7H 14-),0.87(t,3H,Ｊ＝6.8Hz,-CH 2-CH 3)
[changing 56]
< embodiment 2>
By 3, the solution that 5-dinitro benzylalcohol 3 (39.6g, 0.200mol), triethylamine (26.3g, 0.260mol) and tetrahydrofuran 200ml mix in 0 DEG C of stirring, drips the solution mixed by acryloyl chloride (21.7g, 0.240mol) and tetrahydrofuran 40ml in a nitrogen atmosphere in this solution with the times of 30 minutes.After dropping, then stir 4 hours, after reaction terminates, steaming desolventizes, and adds water 300g in the crude product of gained, stirs 30 minutes in the slurry state in 25 DEG C.Then filtering reacting liquid, by solid constituent under reduced pressure in 70 DEG C of dryings 3 hours, obtains compound 4 (must measure 48.7g, 0.193mol, yield 96.5%).The structure of compound 4 is passed through 1h-NMR analyzes and confirms.
1H-NMR（CDCl 3）:δ9.02(t,1H,J=2.4Hz,Ar-H),8.58(m,2H,Ar-H),6.54(dd,1H,J=17.6,1.2Hz,-CH=CH 2),6.27-6.20(m,1H,-CH=CH 2),5.99(dd,1H,J=10.8Hz,1.2Hz,-CH=CH 2),5.40(s,2H,Ar-CH 2-O)
[changing 57]
< embodiment 3>
After the suspension of compound 2 (25.3g, 0.0702mol), compound 4 (21.1g, 0.0837mol), palladium bichloride-acetonitrile complex compound (0.572g, 2.21mmol), three (o-tolyl) phosphine (1.28g, 4.21mmol), tripotassium phosphate (22.7g, 0.107mol), dimethyl acetamide 170g is decompressed to 50Torr with membrane pump at ambient temperature, use nitrogen Recovery and rebuild, repeat above action 10 times, the oxygen in removing reactor and contained by dimethyl acetamide.Then heat up, stir 3 hours in 110 DEG C in a nitrogen atmosphere.After reaction terminates, steaming desolventizes, and extracts with water 200g and chloroform 250g.The water layer that separatory goes out extracts 2 times with chloroform 250g again, by the organic over anhydrous dried over mgso of gained.Filtering magnesium sulfate, under reduced pressure steams the organic layer of gained and desolventizes, and washs the crude product of gained with acetonitrile 170g.Then filtering for crystallizing, by the solid constituent drying under reduced pressure of gained, thus obtains compound 5 (must measure 32.5g, 0.0671mol, yield 95.6%).The structure of compound 5 is passed through 1h-NMR analyzes and confirms.
1H-NMR（CDCl 3）:δ9.01(t,1H,Ar-H),8.61(d,2H,J=1.6Hz,Ar-H),7.74(d,1H,J=16.0Hz,-CH=CH-Ar),7.49(d,2H,J=7.6Hz,Ar-H),6.91(d,2H,J=7.6Hz,Ar-H),6.39(d,1H,J=16.0Hz,-CH=CH-Ar),5.42(s,2H,Ar-CH 2-O),3.99(t,2H,J=6.4Hz,Ar-O-CH 2),1.83-1.76(m,2H,Ar-O-CH 2-CH 2-),1.49-1.28(m,14H,Ar-O-CH 2-CH 2-C 7H 14-),0.89(t,3H,J=6.4Hz,-CH 2-CH 3)
[changing 58]
< embodiment 4>
Ammonium chloride (9.9g, 0.185mol) is dissolved in pure water 90.0g, the solution of gained is heated to 55 DEG C, stir.After arriving 55 DEG C, add iron powder (51.1g, 0.915mol), be warming up to 80 DEG C further.After arriving 80 DEG C, drip the compound 5 (29.0g, 0.0599mol) being dissolved in and heating in the toluene of the 145g of 80 DEG C.Stir 2 hours again after dropping terminates, after reaction terminates, under the condition of heating of 80 DEG C, carry out thermosol filtration, by the reactant liquor separatory of gained, removing water layer.In the organic layer of gained, add activated charcoal 1.2g, stir 30 minutes under the condition of heating of 80 DEG C.Then, under the condition of heating of 80 DEG C, carry out thermosol filtration, with the organic layer 2 times of pure water gained being heated to 80 DEG C in advance.By the organic over anhydrous dried over mgso of gained, then filtering magnesium sulfate, the organic layer of gained is under reduced pressure steamed and desolventizes, obtain compound 6 (18.7g, 0.0440mol, yield 73.5% must be measured).The structure of compound 6 is passed through 1h-NMR analyzes and confirms.
1H-NMR（CDCl 3）:δ7.67(d,1H,J=16.0Hz,-CH=CH-Ar),7.45(d,2H,J=8.4Hz,Ar-H),6.88(d,2H,J=8.4Hz,Ar-H),6.34(d,1H,J=16.0Hz,-CH=CH-Ar),6.15(d,2H,J=1.6Hz,Ar-H),5.98(t,1H,J=1.6Hz,Ar-H),5.05(s,2H,Ar-CH 2-O),3.97(t,2H,J=6.4Hz,Ar-O-CH 2),3.62(b,4H,NH 2),1.82-1.76(m,2H,Ar-O-CH 2-CH 2-),1.46-1.27(m,14H,Ar-O-CH 2-CH 2-C 7H 14-),0.88(t,3H,J=7.2Hz,-CH 2-CH 3)
[changing 59]
With the time of 1 hour 2, drip tetrahydrofuran (281g) solution of borane dimethylsulfide ether complexes (57.0g, 750mmol) in tetrahydrofuran (452g) solution of 4-dinitro benzene guanidine-acetic acid (56.6g, 250mmol), at room temperature stir 22 hours.Then at 0 DEG C, drip water (112g) with the time of 2 hours, at room temperature stir after 2 hours, extract with ethyl acetate and water, separate aqueous layer, use dry over magnesium sulfate.Filter magnesium sulfate by crossing, the organic layer of concentrated gained, makes the crude product of gained recrystallization from ethyl acetate and hexane, obtains 2,4-dinitrophenyl ethanol 1 (42.1g, 79% yield).
1H-NMR(CDCl 3):δ8.79(d,1H,J=2.4Hz,Ar-H),8.40(dd,1H,J=8.4,2.4Hz,Ar-H),7.70(d,1H,J=8.4Hz,Ar-H),4.01(dt,2H,J=5.2,6.0Hz,CH 2-OH),3.29(t,2H,J=6.0Hz,Ar-CH 2),1.63(t,1H,J=5.2Hz,-OH).
[changing 60]
Dimethyl formamide (90.1g) is added in iodobutane (30.0g, 163mmol), 4-iodophenol (39.4g, 179mmol) and sal tartari (27.0g, 196mmol), stir 2 hours at 85 DEG C, then passed through to filter sal tartari.Then, extract with the sodium hydrate aqueous solution of toluene and 1 equivalent.Separate aqueous layer, with the organic layer of dried over mgso gained, after excessively filtering magnesium sulfate, concentration of organic layers, obtains ether compound 2 (36.2g, 81% yield).
1H-NMR(CDCl 3):δ7.53(d,2H,J=8.8Hz,Ar-H),6.66(d,2H,J=8.8Hz,Ar-H),3.90(t,2H,J=6.6Hz,O-CH 2),1.76(m,2H,O-CH 2-CH 2,),1.47(m,2H,CH 2-CH 3),0.96(t,3H,J=7.6Hz,-CH 3).
[changing 61]
In ether compound 2 (36.2g, 131mmol), acrylic acid (13.0g, 180mmol), acid chloride (0.269g, 1.20mmol), three (o-tolyl) phosphine (0.730g, 2.40mmol) and tri-n-butylamine (67.9g, 366mmol), add dimethyl acetamide (362g), stir 2 hours at 140 DEG C.Then, extract with ethyl acetate and water, separate aqueous layer, use dry over magnesium sulfate.Filter magnesium sulfate by crossing, the organic layer of concentrated gained, makes the crude product of gained recrystallization from ethyl acetate and hexane, obtains cinnamic acid derivative 3 (21.1g, 73% yield).
1H-NMR(DMSO):δ12.2(s,1H,CO 2H),7.62(d,2H,Ｊ=8.8Hz,Ar-H),7.54(d,1H,Ｊ=16.0Hz,CO-CH=CH),6.95(d,2H,Ｊ=8.8Hz,Ar-H),6.36(d,1H,J=16.0Hz,CO-CH=CH),4.01(t,2H,Ｊ=6.6Hz,O-CH 2),1.69(m,2H,O-CH 2-CH 2),1.44(m,2H,CH 2-CH 3),0.93(t,3H,J=7.4Hz,-CH 3).
[changing 62]
By Cinnamic acid compounds 3 (16.2g, 73.5mmol), 2,4-dinitrophenyl ethanol 1 (15.6g, 73.5mmol) and dimethylamino naphthyridine (0.895g, 7.32mmol) are dissolved in tetrahydrofuran (232g), at 0 DEG C, add 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride (16.2g, 84.5mmol), at room temperature stir 15 hours.Then, extract with ethyl acetate and water, separate aqueous layer, use dry over magnesium sulfate.Filter magnesium sulfate by crossing, the organic layer of concentrated gained, with the crude product of column chromatography eluting gained, obtains dinitro compound 4 (19.9g, 65% yield).
1H-NMR(CDCl 3):δ8.83(d,1H,J=2.4Hz,Ar-H),8.40(dd,1H, J=8.8,2.4Hz,Ar-H),7.66(d,1H,J=8.8Hz,Ar-H),7.60(d,1H,J=16.0Hz,CO-CH=CH),7.46(d,2H,J=8.4Hz,Ar-H),6.89(d,2H,J=8.4Hz,Ar-H),6.21(d,1H,J=16.0Hz,CO-CH=CH)4.53(t,2H,J=6.4Hz,CH 2-OCO),4.00(t,2H,J=6.6Hz,C 6H 4-O-CH 2),3.45(m,2H,J=6.4Hz,Ar-CH 2),1.78(m,2H,O-CH 2-CH 2),1.52(m,2H,CH 2-CH 3),0.98(t,3H,J=7.4Hz,-CH 3).
[changing 63]
Dinitro compound 4 (19.9g, 48.0mmol), reduced iron (32.2g, 583mmol) and ammonium chloride (15.4g, 288mmol) are dissolved in ethyl acetate (200g) and water (77.1g), stir 14 hours at 70 DEG C.Then remain on 70 DEG C, filter with zeyssatite, with the organic layer of the filtrate of dried over mgso gained.Filter magnesium sulfate by crossing, the organic layer of concentrated gained, obtains crude product.The crude product of gained is dissolved in tetrahydrofuran (200g), adds activated charcoal (2.00g), at room temperature stir 18 hours.Filtering activated charcoal, concentration of organic layers by crossing, obtaining the diamine compound 5 (15.5g, 91% yield) as target product.
1H-NMR(CDCl 3):δ7.65(d,1H,J=16.0Hz,CO-CH=CH),7.41(d,2H,J=8.4Hz,Ar-H,),6.89(d,2H,J=8.4Hz,Ar-H),6.85(d,1H,J=8.0Hz,Ar-H),6.30(d,1H,J=16.0Hz,CO-CH=CH),6.10(dd,1H,J=8.0,2.4Hz,Ar-H),6.07(d,1H,J=2.4Hz Ar-H),4.30(t,2H,J=7.6Hz,CH 2-OCO),4.00(t,2H,J=6.4Hz,C 6H 4-O-CH 2),3.88(br-s,2H,NH 2),3.56(br-s,2H,NH 2),2.81(m,2H,J=7.6Hz,Ar-CH 2),1.78(m,2H,O-CH 2-CH 2),1.49(m,2H,CH 2-CH 3),0.98(t,3H,J=7.2Hz,-CH 3).
[synthesis of polyamic acid]
The abbreviation of the tetracarboxylic dianhydride and diamine compound etc. for the synthesis of polyamic acid is below shown.
(tetracarboxylic dianhydride)
PMDA: pyromellitic acid anhydride
CBDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
(diamine compound)
P-PDA: p-phenylenediamine (PPD)
DA1:3-(4-(4-oxygen in last of the ten Heavenly stems base) phenyl) acrylic acid-3,5-diamido benzyl ester
[changing 64]
(organic solvent)
NMP:N-N-methyl-2-2-pyrrolidone N-
BC: butyl cellosolve
The molecular weight determination > of < polyimide
The molecular weight of polyimide is the post (KD-803, KD-805) of normal temperature gel permeation chromatography (GPC) device (SSC-7200) and Showa electrician (Shodex) Co., Ltd. using eternal lasting science Co., Ltd. (セ Application シ ユ mono-science society) to make, and measures as follows.
Column temperature: 50 DEG C
Eluent: N, N'-dimethyl formamide (as adjuvant, lithium bromide monohydrate (LiBrH 2o) for 30mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) be 30mmol/L, tetrahydrofuran (THF) is 10ml/L)
Flow velocity: 1.0ml/ minute
Calibration curve making standard sample: Dong Cao company (East ソ ー society) TSK standard polyethylene oxide processed (molecular weight about 900000,150000,100000,30000) and Polymer Laboratory company (Port リ マ ー ラ ボ ラ ト リ ー society) polyglycol processed (molecular weight about 12000,4000,1000).
< embodiment 5>
By DA1 (0.637g, 1.50mmol) and p-PDA (0.162g, 1.50mmol) mixing in NMP (8.13g), at room temperature stir after within 1 hour, making it dissolve, add PMDA (0.635g, 2.91mmol), at room temperature react 12 hours, obtain polyamic acid solution.In this polyamic acid solution (9.56g), add NMP (9.56g) and BC (4.78g), stir 5 hours, thus obtain the aligning agent for liquid crystal (A) of 6 quality %.
The number-average molecular weight of this polyamic acid is 7000, and weight-average molecular weight is 17000.
< embodiment 6>
By DA1 (0.743g, 1.75mmol) and p-PDA (0.081g, 0.75mmol) mixing in NMP (7.67g), at room temperature stir after within 1 hour, making it dissolve, add PMDA (0.529g, 2.43mmol), at room temperature react 12 hours, obtain polyamic acid solution.In this polyamic acid solution (9.02g), add NMP (9.02g) and BC (4.51g), stir 5 hours, thus obtain the aligning agent for liquid crystal (B) of 6 quality %.
The number-average molecular weight of this polyamic acid is 6500, and weight-average molecular weight is 16000.
< embodiment 7>
By DA1 (0.849g, 2.0mmol) mixing in NMP (7.21g), at room temperature stir after within 1 hour, making it dissolve, add PMDA (0.424g, 1.94mmol), at room temperature react 12 hours, obtain polyamic acid solution.In this polyamic acid solution (8.48g), add NMP (8.48g) and BC (4.24g), stir 5 hours, thus obtain the aligning agent for liquid crystal (C) of 6 quality %.
The number-average molecular weight of this polyamic acid is 6000, and weight-average molecular weight is 16000.
< embodiment 8>
By DA1 (0.509g, 1.20mmol) and p-PDA (0.194g, 1.80mmol) mixing in NMP (7.22g), at room temperature stir after within 1 hour, making it dissolve, add CBDA (0.571g, 2.91mmol), at room temperature react 12 hours, obtain polyamic acid solution.In this polyamic acid solution (9.02g), add NMP (9.02g) and BC (4.51g), stir 5 hours, thus obtain the aligning agent for liquid crystal (D) of 6 quality %.
The number-average molecular weight of this polyamic acid is 8000, and weight-average molecular weight is 21000.
< embodiment 9>
By DA1 (0.637g, 1.50mmol) and p-PDA (0.163g, 1.50mmol) mixing in NMP (7.76g), at room temperature stir after within 1 hour, making it dissolve, add CBDA (0.571g, 2.91mmol), at room temperature react 12 hours, obtain polyamic acid solution.In this polyamic acid solution (9.13g), add NMP (9.13g) and BC (4.57g), stir 5 hours, thus obtain the aligning agent for liquid crystal (E) of 6 quality %.
The number-average molecular weight of this polyamic acid is 7000, and weight-average molecular weight is 19000.
< embodiment 10>
Use the aligning agent for liquid crystal (A) obtained in embodiment 5, carry out the manufacture of liquid crystal cell with step as follows.
[manufacture of liquid crystal cell]
The aligning agent for liquid crystal [A] obtained in embodiment 5 is spun on the ito surface of the glass substrate with the transparency electrode be made up of ito film, on the heating plate of 80 DEG C after dry 90 seconds, in the heated air circulation type baking oven of 200 DEG C, carry out 30 minutes burn till, forming thickness is the liquid crystal orientation film of 100nm.
Irradiating exposure intensity to this substrate is 8.0mW/cm 2the linear polarization UV of 313nm, exposure is 100mJ.The direction of incident ray has tilted 40 ° relative to substrate normal direction.Linear polarization UV adjusts by the following method: the bandpass filter of ultraviolet light by 313nm making high-pressure sodium lamp, then makes it by the polaroid of 313nm.
Prepare two pieces of aforesaid substrates, after the liquid crystal orientation film of one piece of substrate scatters the pearl sept of 6 μm, printing and sealing agent thereon.Then, make the liquid crystal aligning face of two pieces of substrates opposed, crimp, make the projecting direction of the optical axis of linear polarization UV on each substrate be antiparallel, in 150 DEG C of time chien shih sealant heat curings with 105 minutes.In this negative crystal born of the same parents, inject negative liquid crystal (Merck & Co., Inc. (メ ルク society) makes, MLC-6608) by decompression injection method, make liquid crystal cell.
In said method, change the exposure of the polarization UV of irradiation into 0mJ ~ 1000mJ, make same liquid crystal cell.
[evaluation of liquid crystal cell]
At 25 DEG C, apply/remove the voltage of 8V to liquid crystal cell, observing with polarizing microscope now has farmland without exception, will not have being evaluated as " liquid crystal aligning is good " of abnormal farmland.The liquid crystal cell made as mentioned above demonstrates good vertical orientated property not executing under alive state, and liquid crystal aligning when applying voltage is also good.
[evaluation of tilt angle]
The mensuration of the tilt angle of liquid crystal cell uses Axo Metrix Inc. " Axo Scan " to be measured by Muller matrix method.
< embodiment 11>
Except being changed into except aligning agent for liquid crystal (B) by aligning agent for liquid crystal (A), making liquid crystal cell similarly to Example 10, carrying out the orientation of liquid crystal and the mensuration of tilt angle.
< embodiment 12>
Except being changed into except aligning agent for liquid crystal (C) by aligning agent for liquid crystal (A), making liquid crystal cell in the same manner as embodiment 10, carrying out the orientation of liquid crystal and the mensuration of tilt angle.
< embodiment 13>
Except being changed into except aligning agent for liquid crystal (D) by aligning agent for liquid crystal (A), making liquid crystal cell similarly to Example 10, carrying out the orientation of liquid crystal and the mensuration of tilt angle.
< embodiment 14>
Except being changed into except aligning agent for liquid crystal (E) by aligning agent for liquid crystal (A), making liquid crystal cell similarly to Example 10, carrying out the orientation of liquid crystal and the mensuration of tilt angle.
The acid dianhydride used in the manufacture of above-mentioned aligning agent for liquid crystal (A) ~ (E) and each proportion of composing of diamine compound are shown in table 1.In table 1, the % in () to represent in whole acid dianhydride component or this acid dianhydride all in diamine component or diamine compound containing proportional (% by mole).
The tilt angle of liquid crystal cell obtained in each embodiment is shown in table 2.
[table 1]
[table 2]
Can be confirmed by the result of table 2, use novel diamine compound of the present invention and the liquid crystal display cells obtained demonstrates good vertical orientated property, and by irradiating the ultraviolet of polarization, even if also can liquid crystal aligning be made with the exposure that 100mJ is less like this, show larger tilt angle.Can also confirm, use the tilt angle of the liquid crystal orientation film of novel diamine compound of the present invention to keep constant, have nothing to do with ultraviolet irradiation amount.This just represents, even if be exposed to for a long time after under the light of backlight etc., also stably can keep tilt angle.
It can thus be appreciated that novel diamine compound of the present invention can be used for the liquid crystal orientation film used for liquid crystal display element of vertical orientation mode, be also preferred for the optical alignment method being given liquid crystal aligning ability by Ultraviolet radiation.
< comparative example 1>
[changing 65]
By the DA3 of DA2 and 0.11g (0.30mmol) of 1.11g (2.70mmol) mixing in NMP (10.22g), at room temperature stir after within 1 hour, making it dissolve, add the CBDA of 0.58g (2.94mmol), at room temperature react 12 hours, obtain polyamic acid solution.In this polyamic acid solution (12.0g), add NMP (9.0g) and BC (9.0g), stir 5 hours, thus obtain the aligning agent for liquid crystal (F) of 6 quality %.The number-average molecular weight of this polyamic acid is 12000, and weight-average molecular weight is 29000.
In above-described embodiment 10, except being changed into except aligning agent for liquid crystal (F) by aligning agent for liquid crystal (A), making liquid crystal cell similarly to Example 10, carrying out the orientation of liquid crystal and the mensuration of tilt angle.
The acid dianhydride used in the synthesis of above-mentioned aligning agent for liquid crystal (F) and each proportion of composing of diamine compound are shown in table 3.The tilt angle of liquid crystal cell obtained in comparative example 1 is shown in table 4.
[table 3]
[table 4]
The possibility that industry utilizes
Even if the liquid crystal display cells with the liquid crystal orientation film obtained by novel diamine compound of the present invention also stably can keep tilt angle under being exposed to the light of backlight etc. for a long time, reliability is good, can be preferred for the LCD TV etc. of large picture and high-resolution.
Quote the announcement of full content as instructions of the present invention of the instructions of No. 2010-153075, the Japanese patent application that on July 5th, 2010 files an application, claims and specification digest here.

Claims (10)

1. an aligning agent for liquid crystal, it is characterized in that, comprise at least one polymkeric substance of the polyamic acid being selected from and being obtained by the diamine component of the diamine compound containing following formula [1] and the reaction of tetracarboxylic dianhydride's composition and the polyimide obtained by this polyamic acid imidizate;
[changing 1]
In formula, X 1represent singly-bound ,-CH 2o-,-O-,-COO-,-OCO-,-NHCO-or-CONH-, X 2represent the alkylidene of carbon number 1 ~ 3, X 3represent-O-,-NH-or-N (R 1)-, X 4represent singly-bound ,-O-,-S-or-NH-; X 5represent singly-bound or be selected from following formula [X 5-1] ~ [X 5-5] carbocyclic ring, X 6represent the straight chain of carbon number 1 ~ 18 or the alkyl of branch-like, X 7represent hydrogen atom ,-R 2,-OR 3,-NHR 4,-N (R 5) 2or-SR 6; Here, R 1~ R 6separately represent the alkyl of carbon number 1 ~ 5; N represents the integer of 1 or 2;
[changing 2]
Here, in above-mentioned carbocyclic ring structure, arbitrary hydrogen atom can by CH 3replace.
2. aligning agent for liquid crystal as claimed in claim 1, wherein, the content of the diamine compound of the formula [1] in described diamine component is 30 ~ 100 % by mole.
3. aligning agent for liquid crystal as claimed in claim 1 or 2, wherein, the X of above-mentioned formula [1] 3-O-, X 7it is hydrogen atom.
4. the aligning agent for liquid crystal according to any one of claims 1 to 3, wherein, the X of above-mentioned formula [1] 5it is singly-bound.
5. the aligning agent for liquid crystal according to any one of Claims 1 to 4, wherein, the X of above-mentioned formula [1] 1singly-bound, X 4-O-.
6. the aligning agent for liquid crystal according to any one of Claims 1 to 5, wherein, the n of above-mentioned formula [1] is 1.
7. the aligning agent for liquid crystal according to any one of claim 1 ~ 6, wherein, the X of above-mentioned formula [1] 2-CH 2-, X 6it is the alkyl of carbon number 8 ~ 12.
8. a liquid crystal orientation film, is characterized in that, the aligning agent for liquid crystal according to any one of claim 1 ~ 7 obtains.
9. a liquid crystal orientation film, it is aligning agent for liquid crystal according to any one of claim 1 ~ 7 and the liquid crystal orientation film obtained, and gives liquid crystal aligning ability by the irradiation of the radioactive ray of polarized light or nonpolarized light.
10. a liquid crystal display cells, is characterized in that, has the liquid crystal orientation film described in claim 8 or 9.
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