CN103097946A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same - Google Patents
Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same Download PDFInfo
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- CN103097946A CN103097946A CN2011800420591A CN201180042059A CN103097946A CN 103097946 A CN103097946 A CN 103097946A CN 2011800420591 A CN2011800420591 A CN 2011800420591A CN 201180042059 A CN201180042059 A CN 201180042059A CN 103097946 A CN103097946 A CN 103097946A
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- 0 COC(CC1)CC(OC)=C1C=CC(*C*(C1)=CC(N)=CC1N)=* Chemical compound COC(CC1)CC(OC)=C1C=CC(*C*(C1)=CC(N)=CC1N)=* 0.000 description 22
- RFCDTPWAWJFLFR-UHFFFAOYSA-N COc1ccc(CCC(O)OCCCc2cc(N)cc(N)c2)c(OC)c1 Chemical compound COc1ccc(CCC(O)OCCCc2cc(N)cc(N)c2)c(OC)c1 RFCDTPWAWJFLFR-UHFFFAOYSA-N 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Cc1ccc(C)cc1 Chemical compound Cc1ccc(C)cc1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
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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
-
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- 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
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- 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
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Liquid Crystal Substances (AREA)
Abstract
A liquid crystal aligning agent is characterised in having at least one polymer selected from a group comprising: polyamic acids obtained by reacting a diamine component containing a diamine compound represented by formula [1] with a tetracarboxylic acid dianhydride; and polyimides obtained by the imidization of said polyamic acids. (In the formula, X1 represents a single bond, -CH2O-, -O-, -COO-, -OCO-, -NHCO-, or -CONH-, X2 represents a C1-3 alkylene group, X3 represents -O-, -NH-, or -N(R1)-, X4 represents a single bond, -O-, -S-, or -NH-. X5 represents a single bond or a carbon ring selected from the group [X5-1] - [X5-5], X6 represents a C1-18 straight-chain or branched alkyl group, X7 represents a hydrogen atom, -R2-, -OR3, -NHR4, -N(R5)2, or -SR6. Here, R1-R6 each independently represent a C1-5 alkyl group. n represents an integer of 1 or 2.) (In the carbon ring structure, an arbitrary hydrogen atom can be substituted by CH3.)
Description
Technical field
The present invention relates to be suitable as new diamine compound, the polyamic acid that uses this compound to obtain and polyimide and the aligning agent for liquid crystal of the raw material of the polymkeric substance used in liquid crystal orientation film etc.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 can be by less exposure polarized light or the radioactive ray of nonpolarized light aligning agent for liquid crystal of forming the liquid crystal orientation film of vertical orientated use, this liquid crystal orientation film and forming method thereof, there is liquid crystal display cells and the optical component of such liquid crystal orientation film.
Background technology
Liquid crystal orientation film is the member of formation of the liquid crystal display cells that is widely used as display device, plays the effect of liquid crystal along certain direction orientation that make.Now, the liquid crystal orientation film of industrial use is mainly formed by the aligning agent for liquid crystal comprised as the solution of the polyamic acid of polyimide precursor or poly amic acid ester or polyimide.In general, after on substrate, the coating of liquid crystalline aligning agent is heated and is burnt till, implement for make liquid crystal phase for real estate the parallel or orientation process of orientation obliquely.As this orientation process, the surface treatment method of the so-called rubbing manipulation on the known cloth wiping organic film surface with cotton, nylon, regenerated fiber etc.; Method by the monox oblique evaporation in substrate surface; Use Langmuir-Blaw Ztel method (LB method) forms the method for the unimolecular film with chain alkyl etc. at substrate surface.Wherein, particularly from the viewpoint of the orientation uniformity of substrate size, liquid crystal, processing time, cost etc., consider, generally by friction treatment, give the liquid crystal aligning ability.
But, while by friction treatment, giving the liquid crystal aligning ability, there are the following problems: because the damaged of liquid crystal orientation film occurs in friction, produce thus display defect, or generation dust, or cause the circuit of TFT (thin film transistor (TFT)) element destroyed etc. because producing static.
In the liquid crystal display cells of vertical orientation mode, MVA (multi-domain vertical alignment) mode of the projection of the known toppling direction that is formed for controlling liquid crystal on TFT substrate or colored filter substrate; Form slit on the ITO of substrate (tin indium oxide) electrode, control PVA (image the is vertical orientated) mode of the toppling direction of liquid crystal by electric field; Use the substrate that is formed with slit on the ITO electrode and the liquid crystal that is added with the optical polymerism compound to manufacture liquid crystal panel, apply electric field, irradiation ultraviolet radiations under the state of toppling at liquid crystal (UV) etc., by the immobilized PSA of the orientation of liquid crystal (polymer stabilizing orientation) mode etc.
As the problem of these existing vertical orientation modes, have because using complicated substrate to cause expensiveization of panel, causing the lower degradation of the transmissivity of panel because of projection or slit etc.
On the other hand, as giving liquid crystal orientation film in the liquid crystal structure cell another kind of method with the liquid crystal aligning ability, known optical alignment method, the method is that the photosensitive film of poly-vinyl cinnamate to being formed at substrate surface, polyimide etc. irradiates the radioactive ray of polarized light or nonpolarized light, thereby gives the liquid crystal aligning ability.(with reference to patent documentation 1～8)
Known this optical alignment method also can be as control the method for the vergence direction of liquid crystal molecule in the liquid crystal display cells of vertical alignment mode.That is, knownly by use, utilize optical alignment method to give the vertical alignment layer of orientation control force, can control equably the vergence direction (with reference to patent documentation 9～11) of the liquid crystal molecule while applying voltage.
By using, utilize like this optical alignment method to give the vertical alignment layer of orientation control force, can make in advance slightly low dip of the direction of liquid crystal molecule in from the substrate normal direction towards real estate.
Liquid crystal orientation film by the optical alignment method manufacture is preferred for liquid crystal display cells as mentioned above.But, when the known up to now aligning agent for liquid crystal that contains cinnamate or polyimide etc. is applied to optical alignment method, have the many problems of exposure that obtain the required radioactive ray of liquid crystal aligning ability.As exposure caused problems more, have liquid crystal display cells manufacture pitch time increase, because irradiating for a long time, cause liquid crystal orientation film to produce defect etc., be accompanied by these problems, the reliability of liquid crystal panel reduces.
In the liquid crystal display cells of vertical orientation mode, while in liquid crystal orientation film, having unreacted photoreactive group, also there are the following problems: because liquid crystal panel is exposed under the light of backlight (BL) for a long time, unreacted photoreactive group reacts, and the tilt angle of liquid crystal changes.
The prior art document
Patent documentation
Patent documentation 1: Japanese patent laid-open 6-287453 communique
Patent documentation 2: Japanese patent laid-open 10-251646 communique
Patent documentation 3: Japanese patent laid-open 11-2815 communique
Patent documentation 4: Japanese patent laid-open 11-152475 communique
Patent documentation 5: Japanese Patent Laid-Open 2000-144136 communique
Patent documentation 6: Japanese Patent Laid-Open 2000-319510 communique
Patent documentation 7: Japanese Patent Laid-Open 2000-281724 communique
Patent documentation 8: Japanese patent laid-open 9-297313 communique
Patent documentation 9: Japanese Patent Laid-Open 2003-307736 communique
Patent documentation 10: No. 4088156 communique of Jap.P.
Patent documentation 11: Japanese Patent Laid-Open 2004-163646 communique
Summary of the invention
Invent technical matters to be solved
The object of the present invention is to provide the aligning agent for liquid crystal of the liquid crystal orientation film that is used to form vertical orientated use, the liquid crystal orientation film of formation and the liquid crystal display cells with this liquid crystal orientation film, this liquid crystal orientation film can show tilt angle by the polarized light of less exposure or the radioactive ray of nonpolarized light, even and be exposed to for a long time under the light of backlight and also can maintain stable tilt angle.
The technical scheme that the technical solution problem adopts
The inventor has carried out conscientiously research in order to achieve the above object, found that the diamine compound with specific new structure, and the aligning agent for liquid crystal of also finding to comprise the polymkeric substance that uses this diamine compound to obtain can achieve the above object.The present invention is based on this discovery and the invention that completes, comprises following technology contents.
(1) a kind of aligning agent for liquid crystal, it is characterized in that at least one polymkeric substance that comprises the polyamic acid that two amine components that are selected from the diamine compound by containing following formula [1] obtain with reacting of tetracarboxylic dianhydride's composition and the polyimide that this polyamic acid imidizate is obtained;
[changing 1]
In formula, X
1the expression singly-bound ,-CH
2o-,-O-,-COO-,-OCO-,-NHCO-or-CONH-, X
2the alkylidene that means carbon number 1～3, X
3expression-O-,-NH-or-N (R
1)-, X
4mean singly-bound ,-O-,-S-or-NH-; X
5mean singly-bound or be selected from following formula [X
5-1]～[X
5-5] carbocyclic ring, X
6mean the straight chain of carbon number 1～18 or the alkyl of branch-like, X
7the expression hydrogen atom ,-R
2,-OR
3,-NHR
4,-N (R
5)
2or-SR
6; Here, R
1～R
6mean independently respectively the alkyl of carbon number 1～5; N means 1 or 2 integer;
[changing 2]
Here, in above-mentioned carbocyclic ring structure, hydrogen atom can be by CH arbitrarily
3replace.
(2), as above-mentioned (1) described aligning agent for liquid crystal, wherein, the content of the diamine compound of the formula [1] in described two amine components is 30～100 % by mole.
(3) as above-mentioned (1) or (2) described aligning agent for liquid crystal, wherein, the X of above-mentioned formula [1]
3be-O-X
7it is hydrogen atom.
(4) as the described aligning agent for liquid crystal of any one in above-mentioned (1)～(3), wherein, the X of above-mentioned formula [1]
5it is singly-bound.
(5) as the described aligning agent for liquid crystal of any one in above-mentioned (1)～(4), wherein, the X of above-mentioned formula [1]
1singly-bound, X
4be-O-.
(6) as the described aligning agent for liquid crystal of any one in above-mentioned (1)～(5), wherein, the n of above-mentioned formula [1] is 1.
(7) as the described aligning agent for liquid crystal of any one in above-mentioned (1)～(6), wherein, the X of above-mentioned formula [1]
2be-CH
2-, X
6it is the alkyl of carbon number 8～12.
(8) a kind of liquid crystal orientation film, is characterized in that, in above-mentioned (1)～(7), the described aligning agent for liquid crystal of any one obtains.
(9) a kind of liquid crystal orientation film, its be in above-mentioned (1)～(7) the described aligning agent for liquid crystal of any one and liquid crystal orientation film, the liquid crystal aligning ability is given in the irradiation of the radioactive ray by polarized light or nonpolarized light.
(10) a kind of liquid crystal display cells, is characterized in that, has above-mentioned (8) or (9) described liquid crystal orientation film.
(11) diamine compound that following formula [1] means;
[changing 3]
In formula, X
1the expression singly-bound ,-CH
2o-,-O-,-COO-,-OCO-,-NHCO-or-CONH-, X
2the alkylidene that means carbon number 1～3, X
3expression-O-,-NH-or-N (R
1)-, X
4mean singly-bound ,-O-,-S-or-NH-; X
5mean singly-bound or be selected from following formula [X
5-1]～[X
5-5] carbocyclic ring, X
6mean the straight chain of carbon number 1～18 or the alkyl of branch-like, X
7the expression hydrogen atom ,-R
2,-OR
3,-NHR
4,-N (R
5)
2or-SR
6; Here, R
1～R
6mean independently respectively the alkyl of carbon number 1～5; N means 1 or 2 integer;
[changing 4]
Here, in above-mentioned carbocyclic ring structure, hydrogen atom can be by CH arbitrarily
3replace.
(12) as above-mentioned (11) described diamine compound, wherein, the X of above-mentioned formula [1]
3be-O-X
7it is hydrogen atom.
(13) as above-mentioned (11) or (12) described diamine compound, wherein, the X of above-mentioned formula [1]
5it is singly-bound.
(14) as the described diamine compound of any one in above-mentioned (11)～(13), wherein, the X of above-mentioned formula [1]
1singly-bound, X
4be-O-.
(15) as the described diamine compound of any one in above-mentioned (11)～(14), wherein, the n of above-mentioned formula [1] is 1.
(16) as the described diamine compound of any one in above-mentioned (11)～(15), wherein, the X of above-mentioned formula [1]
2be-CH
2-, X
6it is the alkyl of carbon number 8～12.
(17) a kind of polyamic acid maybe by this polyamic acid imidizate and polyimide, described polyamic acid reacts and obtains with tetracarboxylic dianhydride's composition by two amine components that make to contain the described diamine compound of any one in above-mentioned (1)～(16).
The effect of invention
Utilize aligning agent for liquid crystal of the present invention, can be so that than existing optical alignment method, radiation exposure amount still less obtains for showing the liquid crystal orientation film of tilt angle.Be exposed to for a long time under the light of backlight and also can show stable tilt angle even there is the liquid crystal display cells of liquid crystal orientation film of the present invention, can be used as the high liquid crystal display cells of reliability.
The mode carried out an invention
The diamine compound that<formula [1] means >
Diamine compound of the present invention (following sometimes also referred to as specific diamine compound) means with following formula [1].
[changing 5]
In formula, X
1the expression singly-bound ,-CH
2o-,-O-,-COO-,-OCO-,-NHCO-or-CONH-.
X
2the alkylidene that means carbon number 1～3.
X
3expression-O-,-NH-or-N (R
1)-.
X
4mean singly-bound ,-O-,-S-or-NH-.
X
5mean singly-bound or be selected from following formula [X
5-1]～[X
5-5] carbocyclic ring.
X
6mean carbon number l～18 straight chain or alkyl of branch-like.
X
7the expression hydrogen atom ,-R
2,-OR
3,-NHR
4,-N (R
5)
2or-SR
6.Here, R
1～R
6mean independently respectively the alkyl of carbon number l～5.
N means the integer of l or 2.
[changing 6]
Above-mentioned formula [X
5-1]～[X
5-5], in carbocyclic ring structure, hydrogen atom can be by CH arbitrarily
3replace.
Two amino (NH in formula [1]
2) bonding position do not limit.Particularly, with respect to the concatenating group (X of side chain
1), can exemplify 2,3,2,4,2,5,2,6,3,4 or 3,5 on phenyl ring.Wherein, the viewpoint of the complexity when reactivity during from synthesizing polyamides acid and synthetic diamine compound is considered, particularly preferably 2,4,2,5 or 3,5 of the bonding positions of two amino.
When diamine compound of the present invention is used as to the liquid crystal orientation film of vertical orientated use, in order by ultraviolet irradiation, to give tilt angle, the part that in formula [1], contained following formula [2] means is the part manifested that determines tilt angle.By optimizing this structure, can obtain desirable tilt angle size.
[changing 7]
In formula [2], X
1be singly-bound ,-CH
2o-,-O-,-COO-,-OCO-,-NHCO-or-concatenating group of CONH-, X
2it is the alkylidene of carbon number 1～3.
X
2the length of alkylidene chain for the exposure with less shows tilt angle, be very important, if this alkylidene chain is long, to the exposure shown till tilt angle, increase.This is because the side chain of contained amine is (from the X of above formula [2] in the polymkeric substance of the liquid crystal orientation film that forms vertical orientated use
3light reaction occurs in the root position position that the carbonyl of upper bonding starts), and 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 also can show the tilt angle of liquid crystal with less exposure.
In formula [2], X
3expression-O-,-NH-or-N (R
1)-, X
4mean singly-bound ,-O-,-S-or-NH-.
R
1the alkyl that means carbon number 1～5.
X
3and X
4be the concatenating group of photoreactivity part, consider X from the angle of the length of the light absorption wavelength of photoreactive group and synthetic complexity
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 very important for vertically being orientated, X
5while being singly-bound, consider X from the angle of vertical orientated ability
6preferred chain alkyl.X now
6carbon number be better 6～18, be more preferably 8～12.
X
5to be selected from following formula [X
5-1]～[X
5during carbocyclic ring-5], because vertical orientated ability improves, so 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
7the expression hydrogen atom ,-R
2,-OR
3,-NHR
4,-N (R
5)
2or-SR
6.Here, R
2～R
6mean independently respectively the alkyl of carbon number 1～5.N means 1 or 2 integer.
X
7with n for the wavelength photoreceptor that determines photoreactive group, be very important, if use substituting group to electronics as X
7, the absorbing wavelength of photoreactive group is elongated.If n is 2, can obtain same effect.X
7with n, can make the wavelength photoreceptor of photoreactive group reach desirable wavelength.
Wavelength photoreceptor during from the liquid crystal orientation film as vertical orientated use and the viewpoint of photoreactive sensitivity are considered, 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 put down in writing in the diamine compound that the above exemplifies
nh
2n+1in part, n is 1～18 integer.
The synthetic method of<specific diamine compound >
Method for making 1
By reacting of the acrylate body 2 obtained by dinitro matrix 1 and the benzene derivative 3 with the Y of leaving away property functional group, make on side chain the dinitro matrix 4 with cinnamic acid position.For the dinitro matrix 4 of gained, implement that by selection two keys of side chain are not partly had to influential method of reducing, be convertible into targeted diamine 5.
[changing 27]
The method for making of compound 1
<X
1for the situation of singly-bound, (m is 1～3 integer, X
3expression-O-,-NH-or-NR
1-)
Several raw materials can be used as commercial goods and buy.In the situation that is difficult to obtain as commercial goods, if with the borane reduction agent, the carboxylic acid shown in compound 6 is carried out to reduction reaction, can synthesize X
3the raw material of correspond to-O-.In addition, if make compound that the carboxylic moiety of borane reduction agent and compound 6 is cyano group, be compound 7 effects, can synthesize X
3raw material for the diamine compound of-NH-.
[changing 28]
By X
3for after the hydroxyl of the compound 1a ' of-O-converts the leaving groups such as halogen or sulphonic acid ester to, make it with the azide reaction and obtain corresponding azide derivatives, by this azide derivatives reduction, also can obtain X
3compound 1a ' ' for-NH-.In addition, after converting leaving group to, by adopting so-called Jia Buliaier, synthesize to synthesize amine, also can obtain X
3for the compound 1a ' ' of-NH-, this Jia Buliaier is synthetic is react with succinimide or phthalimide, then with hydrazine by the N-alkylimide decomposition generated.
For X
3compound 1a ' ' for-NH-, by making the reaction under the coexisting of alkali of alkyl halide or alkyl sulfonic ester, can obtain X
3for-NR
1(R
1the alkyl that means carbon number 1～5) compound 1a ' '.In addition, utilize the reductive amination reaction, also can obtain X
3for-NR
1(R
1the alkyl that means carbon number 1～5) compound 1a ' ' ', this reductive amination reaction is to make the aldehyde compound effect and make corresponding group with imine moiety, with boranes reductive agent etc. by its imines partial reduction.During the former alkylation, can obtain having introduced the accessory substance of a plurality of alkyl, and the latter's method does not have accessory substance, effective for the introducing of alkyl.
<X
1for the situation of-O-, (m is 1～3 integer, X
3expression-O-,-NH-or-NR
1-)
The compound 9 that has protecting group P by use will can be used as dinitrophenol 8 alkylations that commercial goods obtains, thereby obtain the dinitro matrix 10 with side chain.By making protecting group P deprotection contained in dinitro matrix 10, can manufacture dinitro intermediate 1b.
[changing 29]
In compound 9, Y means the sulfonic acid esterses 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, tert-butyl group dimethylsilyl, tert-butyl diphenyl silylation, cumyl diphenyl silane base, the carbonates protecting groups such as methoxycarbonyl, ethoxy carbonyl, benzyloxycarbonyl, phenyloxycarbonyl, tert-butoxycarbonyl.From the viewpoint of controlling subsidiary reaction, consider, preferably the protecting group of acetals or silane base class.
While by compound 8 and compound 9, obtaining the reaction of dinitro matrix 10, alkali is coexisted, as used alkali, can use the inorganic bases such as sal tartari, sodium bicarbonate, sodium hydride, hydrofining, the amines such as triethylamine, diisopropylethylamine etc.While carrying out this reaction, in order to make reaction, carrying out swimmingly, is better to add sodium iodide, potassium iodide or tetrabutylammonium iodide.
The deprotection reaction of compound 10 selects the deprotection condition adapted with the protecting group of using to implement.While using the protecting group of ester class or carbonates, the hydrolysis reaction of any acid or alkaline fluidity is all effective.Also can utilize with the ester exchange reaction of lower alcohol and carry out deprotection.While using the acetals protecting group, preferably use the organic acid deprotection reactions such as the mineral acid of catalytic amount or formic acid, acetic acid, toluenesulfonic acid.While using silane base class protecting group, it is better the deprotection that uses the fluoride such as tetra-n-butyl ammonium fluoride under the condition same at the deprotection with the acetals protecting group.
For the X obtained as mentioned above
3for the compound of-NH-, by implementing the reductive amination reaction, can synthesize X
3correspond to-NR
1(R
1the alkyl that means carbon number 1～5) compound 1b.
The OH base of above-claimed cpd 8 and compound 9 and Y base are exchanged mutually to the compound that obtains, are that the hydroxylic moiety of compound 8 is that fluorine or chlorine and compound that the Y of compound 9 is the OH base react under the existence of alkali by making, also can obtain compound 10.
<X
1for-COO-or-(m is 1～3 integer, X for the situation of CONH-
3expression-O-,-NH-or-NR
1-)
By reacting of carboxylic acid or derivatives thereof 11 and the compound 12 with protecting group P, obtain having the dinitro-ester body 13 (Q=O) of side chain or dinitro-acid amides body 13 (Q for-NH-).By making contained protecting group deprotection 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 means OH base or halogen atom, if the stability of considering is preferably used the compound 11 that Hal is OH base or chloro.
The preferred protecting group of protecting group P in compound 12 is also with above identical.
Z in compound 12 means hydroxyl, amino, halogen or sulfonyl.
Mean-O-of Q in compound 13 or-NH-.Consider that the structure of the Hal part of used compound 11 selects the represented functional group of Z in compound 12.For example, Hal is OH base, selection OH base or NH
2base is during as Z, if use the condensation agents such as dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide, carbonyl dimidazoles to be reacted, can obtain and there is ester bond the compound 13 of (Q for-O-) or amido link (Q for-NH-).Hal is the OH base, while selecting halogen or sulfonyl as Z, if use the inorganic bases such as sal tartari, sodium bicarbonate, sodium hydride, hydrofining, the amines such as triethylamine, diisopropylethylamine are reacted, and can obtain ester compounds 13 (Q for-O-).For reaction is carried out swimmingly, it is also effective adding sodium iodide, potassium iodide or tetrabutylammonium iodide.
Hal is when take the halogen atom that chloro is representative, and using the Z in compound 12 is hydroxyl or amino compound, obtains ester compounds 13 (Q for-O-) or amide compound 13 (Q for-NH-).Add the amines such as triethylamine, pyridine in this reaction as alkali.
The protecting group P deprotection of the compound 13 by making gained, can obtain compound 1c, as the condition of deprotection, identical with the condition of the deprotection of above-claimed cpd 10.
For X
3compound 1a ' ' for-NH-, by making the reaction under the coexisting of alkali of alkyl halide or alkyl sulfonic ester, can obtain X
3for NR
1(R
1the alkyl that means carbon number 1～5) compound 1c.Utilize the reductive amination reaction, also can obtain X
3for NR
1(R
1the alkyl that means carbon number 1～5) compound 1c, this reductive amination reaction is to make the aldehyde compound effect and make corresponding group with imine moiety, with boranes reductive agent etc. by its imines partial reduction.During the former alkylation, can obtain having introduced the accessory substance of a plurality of alkyl, and the latter's method does not have accessory substance, effective for the introducing of alkyl.
<X
1for-OCO-or-(m is 1～3 integer, X for the situation of NHCO-
3expression-O-,-NH-or-NR-)
React to carry out esterification or amidation by dinitrophenol (Q for-O-) or dinitroaniline (Q for-NH-) 14 and the carboxylic acid derivates 15 with protecting group P; after making the dinitro matrix 16 with ester or amide side chains; by protecting group deprotection contained in dinitro matrix 16, thereby can be made into the dinitro intermediate 1d with ester bond or amido link.
[changing 31]
Mean-O-of Q in compound 14 and dinitro matrix 16 and dinitro intermediate 1d or-NH-.
In carboxylic acid derivates 15, Hal means OH base or halogen atom, if the stability of considering is preferably used the compound 15 that Hal is OH base or chloro.The preferred protecting group of protecting group P is also with above identical.
Make compound that Hal is the OH base, while being carboxylic acid 15, dinitrophenol 14 (Q for-O-) or dinitroaniline 14 (Q for-NH-) reaction, usually use the condensation agents such as dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide, carbonyl dimidazoles.Also have, add acid or the N of catalytic amount, the N-dimethylamino naphthyridine also is beneficial to for the carrying out of reaction.Also preferably with Hal, represent the method that the acyl halide derivative of chloro etc. is reacted, now, the alkali such as amine that add triethylamine, pyridine and so on are reacted.
The protecting group P deprotection of the compound 16 by making gained, can obtain dinitro intermediate 1d, 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 can be manufactured by the esterification between the raw materials 1 such as corresponding dinitro benzylalcohol and acrylic acid derivative.
As acrylic acid derivative, preferably use the carboxylic acid halides classes such as acryloyl chloride, propylene acylbromide, acrylic anhydride etc.
In esterification, as alkali, can use the inorganic bases such as NaOH, potassium hydroxide, lithium hydroxide, sodium bicarbonate, saleratus, potassium phosphate, sodium carbonate, sal tartari, lithium carbonate, cesium carbonate, NaH, KOH, the amines such as trimethylamine, triethylamine, tripropyl amine (TPA), tri-isopropyl amine, tri-n-butylamine, diisopropylethylamine, pyridine, quinoline, trimethylpyridine, the organic bases such as sodium tert-butoxide, potassium tert-butoxide.
Solvent can suitably be selected, so long as under this reaction conditions, be inertia, stable, do not hinder the solvent of reaction to get final product.Can use such as amine, non-proton property 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
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 reaction conditions and the reaction complexity of carrying out etc. suitably select, and can use separately one or more to mix and use.In addition, use after also can according to circumstances with dewatering agent or drying agent, making non-aqueous solvent.
Temperature of reaction is better in the scope of the boiling point of the solvent of-100 ℃～use, is more preferably in the scope of-50～150 ℃.
Reaction time is better 0.1～1000 hour.
The compound 2 obtained as mentioned above can carry out purifying by recrystallization, distillation, silica gel column chromatography, activated charcoal etc.
Compound 2 also can pass through the ester exchange reaction of the acrylate such as methyl acrylate, ethyl acrylate and dinitro benzylalcohol, or acrylic acid and the dinitro benzyl halides such as dinitro benzyl chloride, dinitro benzyl bromide a-bromotoluene react synthesize.
The method for making of compound 3
[changing 32]
In above-claimed cpd 17 and compound 18, U mean the halogen atoms such as F, Cl, Br, I ,-OH ,-SH or-NH
2, X
5mean singly-bound or be selected from above-mentioned [X
5-1]～[X
5-5] carbocyclic ring, X
6mean the straight chain of carbon number 1～18 or the alkyl of branch-like.
X
7the expression hydrogen atom ,-R
2,-OR
3,-NHR
4,-N (R
5)
2or-SR
6.Here, R
2～R
6mean independently respectively the alkyl of carbon number 1～5.
N means 1 or 2 integer.
Y and L are respectively halogen or pseudohalogen independently, such as meaning alkylsulfonyloxy or the aromatic series sulfonyloxies such as F, Cl, Br, I, methanesulfonyloxy group, phenylsulfonyloxy, tosyloxy, trifluoromethane sulfonyl group.
Compound 3 for example can by the compound shown in 17 and the compound shown in 18 react manufacture.Several compounds 17 and compound 18 can obtain easily as commercial goods.
<X
4for-O-,-S-or-situation of 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 under the existence of alkali, obtain compound 3.As used alkali, alkali-metal oxyhydroxide or carbonate such as lithium, sodium, potassium are arranged, the organic base of organic fatty family, aromatic series and the heterocycles such as triethylamine, diazabicyclo octane, diazabicycloundecene, pyridine, DMAP etc.Also can use the potpourri of these alkali.Sal tartari particularly preferably.
Solvent can suitably be selected, so long as stablize, be inertia under this reaction conditions, do not hinder the solvent of reaction to get final product.Can use such as ketones solvent (acetone, 2-butanone, methyl isobutyl ketone etc.), non-proton property 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
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 the reaction complexity of carrying out etc. suitably selects, and can use separately one or more to mix and use.In addition, use after also can according to circumstances with dewatering agent or drying agent, making non-aqueous solvent.
Temperature of reaction is better the boiling point of the solvent of-100 ℃～use, is more preferably in the scope of-50～150 ℃.
Reaction time is better 0.1～1000 hour.
The compound 3 obtained as mentioned above can carry 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 under the existence of suitable alkali, using metal complex and part as catalyzer, utilize coupling reaction to carry out synthetic compound 3.As metal complex, preferably use copper complex, palladium complex or nickel complex.Particularly preferably use and using tertiary phosphine or tertiary phosphite ester (Japanese: 3 Grade ホ ス Off ア イ ト) as the zero valent complex of part.Also can use the suitable precursor that easily converts zero valent complex in reaction system.Can also will be not in reaction system containing tertiary phosphine or tertiary phosphite ester, as the complex compound of part and tertiary phosphine or tertiary phosphite ester, do not mix, generate and using tertiary phosphine or the tertiary phosphite ester low quantivalency complex compound as part.
Tertiary phosphine or tertiary phosphite ester as part, can exemplify for example triphenyl phasphine, tri-o-tolyl phosphine, diphenyl methyl phosphine, phenyl dimethyl phosphine, 1, 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 used and mix the complex compound that comprises these two or more parts.As catalyzer, can use the copper complex or the palladium complex that do not contain tertiary phosphine or tertiary phosphite ester.Also preferably above-mentioned part and the complex compound that comprises tertiary phosphine or tertiary phosphite ester are used in combination.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) palladiums, three (BENZYLIDENE ACETONE) two palladiums, 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, can exemplify two (triphenylphosphine) palladiums of dimethyl, two (diphenyl methyl phosphine) palladiums of dimethyl, (ethylidene) two (triphenylphosphine) palladium, tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride etc., but be not limited to this.As the consumption of the copper complex of catalyzer, palladium complex, nickel complex etc., so long as so-called catalytic amount gets final product, in general just enough below 20 % by mole at the compound of reaction, be generally below 10 % by mole.
As alkali, also can use the inorganic bases such as NaOH, potassium hydroxide, lithium hydroxide, sodium bicarbonate, saleratus, potassium phosphate, sodium carbonate, sal tartari, lithium carbonate, cesium carbonate, the amines 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 etc., and sodium acetate, potassium acetate, lithium acetate etc.
Solvent can suitably be selected, so long as stablize, be inertia under this reaction conditions, do not hinder the solvent of reaction to get final product.Can exemplify such as water, alcohols, amine, non-proton property 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
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 the reaction complexity of carrying out etc. suitably selects, and can use separately one or more to mix and use.In addition, use after also can according to circumstances with dewatering agent or drying agent, making non-aqueous solvent.
Temperature of reaction is the boiling point of the solvent of-100 ℃～use, is better in the scope of-50～150 ℃.
Reaction time is better 0.1～1000 hour.
The compound 3 obtained as mentioned above can carry out purifying by recrystallization, distillation, silica gel column chromatography etc.
<X
4situation for singly-bound>
The X that the substituting group U of compound 17 is F, Cl, Br or I, compound 3
4during for singly-bound, can under the existence of suitable alkali, using metal complex and part as catalyzer, utilize coupling reaction to carry out synthetic compound 3.As metal complex, preferred iron complex, palladium complex or nickel complex.Particularly preferably use and using tertiary phosphine or the tertiary phosphite ester zero valent complex as part.Also can use the suitable precursor that easily converts zero valent complex in reaction system.Can also will be not in reaction system containing tertiary phosphine or tertiary phosphite ester, as the complex compound of part and tertiary phosphine or tertiary phosphite ester, do not mix, generate and using tertiary phosphine or the tertiary phosphite ester low quantivalency complex compound as part.
Tertiary phosphine or tertiary phosphite ester as part, can exemplify for example triphenyl phasphine, tri-o-tolyl phosphine, diphenyl methyl phosphine, phenyl dimethyl phosphine, 1, 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 used and mix the complex compound that comprises these two or more parts.As catalyzer, can use the iron complex or the palladium complex that do not contain tertiary phosphine or tertiary phosphite ester.Also preferably above-mentioned part and the complex compound that comprises tertiary phosphine or tertiary phosphite ester are used in combination.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) palladiums, three (BENZYLIDENE ACETONE) two palladiums, 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, can exemplify two (triphenylphosphine) palladiums of dimethyl, two (diphenyl methyl phosphine) palladiums of dimethyl, (ethylidene) two (triphenylphosphine) palladium, tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride etc., but be not limited to this.As the consumption of the iron complex of catalyzer, palladium complex, nickel complex etc., so long as so-called catalytic amount gets final product, in general just enough below 20 % by mole at the compound of reaction, be generally below 10 % by mole.
As alkali, also can use the inorganic bases such as NaOH, potassium hydroxide, lithium hydroxide, sodium bicarbonate, saleratus, potassium phosphate, sodium carbonate, sal tartari, lithium carbonate, cesium carbonate, 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, so long as stablize, be inertia under this reaction conditions, do not hinder the solvent of reaction to get final product.Can use such as water, alcohols, amine, non-proton property 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
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 the reaction complexity of carrying out etc. suitably selects, and can use separately one or more to mix and use.In addition, use after also can according to circumstances with dewatering agent or drying agent, making non-aqueous solvent.
Temperature of reaction is the boiling point of the solvent of-100 ℃～use, is better in the scope of-50～150 ℃.
Reaction time is better 0.1～1000 hour.
The compound 3 obtained as mentioned above can carry out purifying by recrystallization, distillation, silica gel column chromatography etc.
The method for making of compound 4
Compound 4 can synthesize in the coupling reactions such as He Ke reaction under the coexisting of metal complex catalyst, part and alkali by compound 2 and compound 3.
As the Y in compound 3; so long as there is the substituting group of the ability of leaving away, get final product; can use halogen atoms such as F, Cl, Br, I; the alkylsulfonyloxies such as methanesulfonyloxy group, phenylsulfonyloxy, tosyloxy, trifluoromethane sulfonyl group, aromatic series sulfonyloxy etc.; if the reactivity of considering, preferred Br, I or trifluoromethane sulfonyl group.
Coupling reaction is preferably used metal complex and part as catalyzer.Usually use palladium complex, nickel complex etc. as metal complex.
As catalyzer, can use the catalyzer of various structures, preferably use so-called low valent palladium complex or nickel complex, particularly preferably using tertiary phosphine or the tertiary phosphite ester zero valent complex as part.Also can use the suitable precursor that easily converts zero valent complex in reaction system.Can also will be not in reaction system containing tertiary phosphine or tertiary phosphite ester, as the complex compound of part and tertiary phosphine or tertiary phosphite ester, do not mix, generate and using tertiary phosphine or the tertiary phosphite ester low quantivalency complex compound as part.
Tertiary phosphine or tertiary phosphite ester as part, can exemplify for example triphenyl phasphine, tri-o-tolyl phosphine, diphenyl methyl phosphine, phenyl dimethyl phosphine, 1, 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 used and mix the complex compound that comprises these two or more parts.As catalyzer, by above-mentioned part with containing the palladium complex of tertiary phosphine or tertiary phosphite ester and/or comprise tertiary phosphine or mode that the complex compound of tertiary phosphite ester is used in combination is also preferred mode.As with above-mentioned ligand combination use not containing the complex compound of tertiary phosphine or tertiary phosphite ester, can exemplify two (BENZYLIDENE ACETONE) palladiums, three (BENZYLIDENE ACETONE) two palladiums, two (acetonitrile) palladium chloride, two (benzonitrile) palladium chloride, acid chloride, palladium bichloride, palladium-activated charcoal etc.As comprising tertiary phosphine or the tertiary phosphite ester complex compound as part, can exemplify two (triphenylphosphine) palladiums of dimethyl, two (diphenyl methyl phosphine) palladiums of dimethyl, (ethylidene) two (triphenylphosphine) palladium, tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride etc., but be not limited to this.The consumption of these palladium complexs is so long as so-called catalytic amount gets final product, and in general just enough below 20 % by mole at the compound of reaction, be generally below 10 % by mole.
As alkali, also can use the amines 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 etc., and sodium acetate, potassium acetate, lithium acetate etc.
Solvent can suitably be selected, so long as stablize, be inertia under this reaction conditions, do not hinder the solvent of reaction to get final product.Can use such as water, alcohols, amine, non-proton property 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
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 reaction conditions and the reaction complexity of carrying out etc. suitably select, and now can use separately one or more to mix and use.In addition, use after also can according to circumstances with dewatering agent or drying agent, making non-aqueous solvent.
Temperature of reaction is the boiling point of the solvent of-100 ℃～use, is better in the scope of-50～150 ℃.
Reaction time is better 0.1～1000 hour.
The compound 4 obtained as mentioned above can carry out purifying by recrystallization, distillation, silica gel column chromatography, activated charcoal etc.
The method for making of compound 5
The reduction reaction conditions that the dinitro matrix 4 obtained as mentioned above can select not damage two keys of side chain carries out the reduction of nitro, thereby converts the diamine compound 5 as target product to.
In the reduction of the nitro that two keys of side chain are 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 be used separately or jointly.
As proton source, can use the acid such as hydrochloric acid, the ammonium salts such as ammonium chloride, the protonic solvents such as methyl alcohol, ethanol.
Solvent so long as can tolerate the solvent of the environment under reducing atmosphere and get final product, can be used non-proton property 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
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 consider that reaction conditions and the reaction complexity of carrying out etc. suitably select, and can use separately one or more to mix and use.In addition, use after also can according to circumstances with suitable dewatering agent or drying agent, making non-aqueous solvent.
Temperature of reaction is the boiling point of the solvent of-100 ℃～use, is better in the scope of-50～150 ℃.
Reaction time is better 0.1～1000 hour.
The compound 5 obtained as mentioned above can carry out purifying by recrystallization, distillation, silica gel column chromatography, activated charcoal etc.
Method for making 2
By dinitro matrix 1 and acrylic acid derivative 19 or as the reacting of the compound 20 of etheride, can be made into the dinitro matrix 4 that side chain has the cinnamic acid position.For the dinitro matrix 4 of gained, implement that by selection two keys of side chain are not partly had to influential method of reducing, 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 means F, Cl, Br or the I as halogen, X
4mean 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 is reacted with the carboxylic acid halides agent.Consider the preferred Cl of X or Br from the acquisition complexity of reagent, reactive viewpoint.As used carboxylic acid halides agent, can exemplify 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.Preferably use thionyl chloride or thionyl bromide.The consumption of carboxylic acid halides agent is generally 2～100 times moles with respect to compound 19, is preferably 2～30 times moles, 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.
Solvent so long as the solvent that reaction is to inertia get final product, be not particularly limited, can use such as non-proton property 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
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 the reaction complexity of carrying out etc. suitably selects, and can use separately one or more to mix and use.In addition, use after also can according to circumstances with suitable dewatering agent or drying agent, making non-aqueous solvent.
Above-mentioned reaction also can be carried out under the condition of catalyzer not having, 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, can exemplify the metal alkoxide classes such as organic bases such as triethylamine, pyridine, quinoline, DMA, dimethyl formamide, sodium methoxide, potassium methoxide or potassium tert-butoxide.Preferably exemplify triethylamine, pyridine, dimethyl formamide.More preferably exemplify pyridine.The consumption of these catalyzer is generally 0～100 times mole with respect to etheride, is preferably 0.01～10 times mole.
Temperature of reaction is the boiling point of the solvent of-100 ℃～use, is better in the scope of-50～150 ℃.
Reaction time is generally 0.1～1000 hour.
The compound 20 obtained as mentioned above can carry out purifying by operations such as recrystallization, distillation, silica gel column chromatographies.
The method for making of compound 19-1
[changing 35]
In compound 21, A means alkyl, silylation or hydrogen, such as being 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 can carry out synthetic compound 19 in the coupling reactions such as He Ke reaction under the coexisting of metal complex catalyst, part and alkali by compound 3 and compound 21.Method shown in the synthetic method of reaction conditions and the compound 4 of method for making 1 is identical.
When A is alkyl or silylation, by utilizing water by ester group-COOA hydrolysis after reaction under the existence of acid or alkali, can derive as corresponding compound 19.As used acid, can exemplify the organic acids such as the mineral acids such as dilute sulfuric acid or p-toluenesulfonic acid, formic acid, acetic acid.As alkali, can exemplify the carbonates such as saleratus, sodium bicarbonate, sal tartari, sodium carbonate, 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 carboxylates 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 such as sodium hydride etc.
For hydrolysis, in order to make reaction, carry out swimmingly, can in the solvent that can mix with water, carry out, as used solvent, can exemplify the non-proton property polar organic solvents such as dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, 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, can make reaction carry out quickly.
Temperature of reaction is the boiling point of the solvent of-100 ℃～use, is better in the scope of-50～150 ℃.
Reaction time is generally 0.1～1000 hour.
The compound 19 obtained as mentioned above can carry out purifying by operations such as recrystallization, distillation, silica gel column chromatographies.
The method for making of compound 19-2
[changing 36]
In compound 22 and compound 23, X
4, X
5, X
6, X
7, n and A implication with above identical.The group that A exemplifies is also with above identical.
For example, when A is alkyl or silylation, the method for making of compound 19 is to make compound 22 and compound 23 after dehydrating condensation, by the diester partial hydrolysis, make the method for its decarbonate under the existence of alkali.When A is hydrogen, the method for making of compound 19 is to make compound 22 and compound 23 after dehydrating condensation, make the method for its decarbonate under the existence of alkali.
When A is hydrogen, for example, though be not particularly limited, can, by pyridine solvent, under the existence of piperidines, reacted, make aldehyde radical and malonic acid dehydrating condensation under 60～100 ℃, then be heated to 100～150 ℃ and carry out the decarbonate reaction, obtain compound 19.
The alkali used in dehydration condensation, as long as use has the alkali that makes to react the base strength (basicity) carried out swimmingly, is not particularly limited.Lithium is for example arranged, sodium, alkali-metal oxyhydroxide or the carbonate of potassium 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, 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, the aliphatic primary alcohol by carbon number 1～10 of 3-ethyl-3-amylalcohol salt and so on, the alkali metal alcoholates that secondary alcohol or the tertiary alcohol are derivative, the diazabicyclo octane, diazabicycloundecene, DMAP, pyrrolidine, the organic fatty families such as piperidines, aromatic series, the nitrogenous base of heterocycle.These alkali also can be used with the form of potpourri.As alkali, preferred alcohol sodium, sodium hydride.The consumption of alkali is generally 0.1～10 times mole with respect to compound 22, is preferably 0.1～5 times mole.
Solvent so long as the solvent do not reacted with compound 22 and compound 23 just can use.Can use non-proton property polar organic solvents such as dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, 1-METHYLPYRROLIDONE, 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 solvents such as pyridine, quinoline etc.Also can use the alcohols such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, the tert-butyl alcohol.These solvents can consider that the reaction complexity of carrying out etc. suitably selects, and can use separately one or more to mix and use.In addition, use after also can according to circumstances with suitable dewatering agent or drying agent, making non-aqueous solvent.
Method shown in the method for making-1 of the condition of utilizing water to be hydrolyzed and compound 19 is identical.
Temperature of reaction is the boiling point of the solvent of-100 ℃～use, is better in the scope of-50～150 ℃.
Reaction time is generally 0.1～1000 hour.
The compound 19 obtained as mentioned above can carry 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 and n is with above identical.
The method for making of compound 22 is for example the method that compound 24 is reacted with compound 18.Several compounds 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 under the existence of alkali, thereby obtain compound 22.Reaction conditions can adopt the X in the synthetic method of 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 under the existence of alkali, using metal complex and part as catalyzer, utilize coupling reaction to be synthesized.Reaction conditions can adopt the X in the synthetic method of compound 3 of method for making 1
5for above-mentioned [X
5-5] method time.
The substituting group U of compound 24 is F, Cl, Br or the I as halogen, the X of compound 22
4during for singly-bound, can under the existence of alkali, using metal complex and part as catalyzer, utilize coupling reaction to be synthesized.Reaction conditions can adopt the X in the synthetic method of compound 3 of method for making 1
4method during for singly-bound.
The method for making of compound 19-3
[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 for example after making compound 22 and compound 25 carry out dehydration condensation under the existence of alkali, utilizes water by the method for ester group-COOA hydrolysis.
The alkali used in above-mentioned reaction, as long as use has the alkali that makes to react the base strength (basicity) carried out swimmingly, is not particularly limited.The alkali-metal oxyhydroxide that lithium, sodium, potassium and so on are for example arranged, 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 that the aliphatic primary alcohol by carbon number 1～10, secondary alcohol or the tertiary alcohol of the methoxide of earth alkali metal, 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 is derivative etc.These alkali also can be used with the form of potpourri.As alkali, preferred alcohol sodium, sodium hydride.The consumption of these alkali is generally 0.1～10 times mole with respect to compound 22, is preferably 0.1～5 times mole.
Solvent so long as the solvent do not reacted with compound 22 and compound 25 just can use.Can use non-proton property polar organic solvents such as dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, 1-METHYLPYRROLIDONE, 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 solvents such as pyridine, quinoline etc.Also can use the alcohols such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, the tert-butyl alcohol.These solvents can consider that the reaction complexity of carrying out etc. suitably selects, and can use separately one or more to mix and use.In addition, use after also can according to circumstances with suitable dewatering agent or drying agent, making non-aqueous solvent.
Method shown in the method for making-1 of the condition of utilizing water to be hydrolyzed and compound 19 is identical.
Temperature of reaction is the boiling point of the solvent of-100 ℃～use, is better in the scope of-50～150 ℃.
Reaction time is generally 0.1～1000 hour.
The compound 19 obtained as mentioned above can carry out purifying by operations such as recrystallization, distillation, silica gel column chromatographies.
The method for making of compound 19-4
[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 for example 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 for ester group-COOA hydrolysis.Reaction is better in solvent, to use alkali to carry out.
In reaction, alkali used is preferably used and has the alkali that can generate swimmingly the intensity of phosphonium ylide.As alkali, can use for example lithium, sodium, alkali-metal oxyhydroxide or the carbonate of potassium and so on, 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, the silica-based lithium amide of hexamethyl two, the silica-based Sodamide of hexamethyl two, the silica-based amides class of the alkaline metal hexamethyl two of hexamethyl two silica-based potassamides 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, the aliphatic primary alcohol by carbon number 1～10 of 3-ethyl-3-amylalcohol salt and so on, the alkali metal alcoholates that secondary alcohol or the tertiary alcohol are derivative, the diazabicyclo octane, diazabicycloundecene, DMAP, pyrrolidine, the organic fatty families such as piperidines, aromatic series, the nitrogenous base of heterocycle etc.Particularly preferably butyl lithium, tert-butyl lithium.
Solvent so long as the solvent do not reacted with compound 22 and compound 26 just can use.Can use for example ethers (diethyl ether, diisopropyl ether, tetrabutyl methyl ether, cyclopentyl-methyl ether, tetrahydrofuran, two
alkane etc.), non-proton property 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 the reaction complexity of carrying out etc. suitably selects, and can use separately one or more to mix and use.In addition, use after also can according to circumstances with dewatering agent or drying agent, making non-aqueous solvent.
Method shown in the method for making-1 of the condition of utilizing water to be hydrolyzed and compound 19 is identical.
Temperature of reaction is the boiling point of the solvent of-100 ℃～use, is better in the scope of-50～150 ℃.
Reaction time is 0.1～1000 hour.
The compound 19 obtained as mentioned above can carry out purifying by operations such as recrystallization, distillation, silica gel column chromatographies.
The method for making of compound 19-5
[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 for example in solvent, to make compound 27 and mantoquita, zinc salt or dialkyl group zinc mix, make cuprate or diaryl zine compound, after carrying out Isosorbide-5-Nitrae-addition reaction with the compound shown in compound 28, utilize water by the method for ester group-COOA hydrolysis.
The mantoquita, zinc salt or the dialkyl group zinc that in this reaction, use both can be used separately, also these mantoquitas, zinc salt, dialkyl group zinc can be used in combination.
Example as the mantoquita used in reaction, have CuCl, CuBr, CuI, CuCN or CuCl
2with salt-mixture of LiCl etc., particularly preferably CuI.
Example as the zinc salt used in reaction, have ZnCl
2, ZnBr
2or ZnI
2, ZnCl particularly preferably
2.
Example as the dialkyl group zinc used in reaction, have dibutyl zinc, diethyl zinc or dibutene base zinc, particularly preferably diethyl zinc.
Solvent so long as the solvent do not reacted with the organometallic reaction agent just can use.
Can use for example ethers (diethyl ether, diisopropyl ether, tetrabutyl methyl ether, cyclopentyl-methyl ether, tetrahydrofuran, two
alkane etc.), non-proton property 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 the reaction complexity of carrying out etc. suitably selects, and can use separately one or more to mix and use.In addition, use after also can according to circumstances with suitable dewatering agent or drying agent, making non-aqueous solvent.
Method shown in the method for making-1 of the condition of utilizing water to be hydrolyzed and compound 19 is identical.
Temperature of reaction is the boiling point of the solvent of-100 ℃～use, is better in the scope of-50～150 ℃.
Reaction time is 0.1～1000 hour.
The compound 10 obtained as mentioned above can carry 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 for example to react synthetic compound 30, the method that then makes compound 30 react with magnesium metal or lithiumation agent by compound 29 and compound 18.Several compounds 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 under the existence of alkali, thereby obtain compound 30.Reaction conditions can adopt the X in the synthetic method of 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 under the existence of alkali, using metal complex and part as catalyzer, utilize coupling reaction to be synthesized.Reaction conditions can adopt the X in the synthetic method of compound 3 of method for making 1
5for above-mentioned [X
5-5] method time.
The substituting group U of compound 29 is F, Cl, Br or the I as halogen, the X of compound 27
4during for singly-bound, can under the existence of alkali, using metal complex and part as catalyzer, utilize coupling reaction to be synthesized.Reaction conditions can adopt the X in the synthetic method of compound 3 of method for making 1
4method during for singly-bound.
Add metal M g in the compound 30 of gained, react in ether solvents, obtaining can be for the compound 27 (M=MgF, MgCl, MgBr, MgI) of grignard reaction.In addition, make lithium metal reaction in solvent, the compound 27 that can to obtain M be Li.
The method for making of compound 19-6
[changing 42]
In compound 31, the implication of U and n is with above identical.
The method for making of compound 19 is for example that compound 31 and compound 18 are reacted, and after reaction, utilizes water by the method for ester group-COOA hydrolysis.Several compounds 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 under the existence of alkali, after reaction, as shown in the method for making-1 of compound 19, utilize water to be hydrolyzed, thereby obtain compound 19.Reaction conditions can adopt the X in the synthetic method of 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], the time, usining metal complex and part under the existence of alkali carries out coupling reaction as catalyzer, after reaction, as shown in the method for making-1 of compound 19, utilizes water to be hydrolyzed, thereby obtains compound 19.Reaction conditions can adopt the X in the synthetic method of compound 3 of method for making 1
5for above-mentioned [X
5-5] method time.
The substituting group U of compound 31 is F, Cl, Br or the I as halogen, the X of compound 19
4during for singly-bound, usining metal complex and part under the existence of alkali carries out coupling reaction as catalyzer, after reaction, as shown in the method for making-1 of compound 19, utilizes water to be hydrolyzed, thereby obtains compound 19.Reaction conditions can adopt the X in the synthetic method of compound 3 of method for making 1
4method during for singly-bound.
The method for making of compound 4
Compound 4 can and be manufactured as the compound 19 of acrylic acid derivative or the esterification of compound 20 by the compound 1 in solvent.
Particularly at compound 20 in the reacting of such etheride and compound 1, the carboxylic acid halides classes such as the preferred acyl chlorides of etheride, acylbromide, and because reaction carry out swimmingly, so reacted under the existence of alkali.As alkali, can use inorganic bases such as NaOH, potassium hydroxide, lithium hydroxide, sodium bicarbonate, saleratus, potassium phosphate, sodium carbonate, sal tartari, lithium carbonate, cesium carbonate, sodium hydride, hydrofining, the amines such as trimethylamine, triethylamine, tripropyl amine (TPA), tri-isopropyl amine, tri-n-butylamine, diisopropylethylamine, pyridine, quinoline, trimethylpyridine, the organic bases such as sodium tert-butoxide, potassium tert-butoxide.
Solvent can suitably be selected, so long as stablize, be inertia under this reaction conditions, do not hinder the solvent of reaction to get final product.Can use such as amine, non-proton property 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
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 reaction conditions and the reaction complexity of carrying out etc. suitably select, and can use separately one or more to mix and use.In addition, use after also can according to circumstances with dewatering agent or drying agent, making non-aqueous solvent.
Temperature of reaction is the boiling point of the solvent of-100 ℃～use, is better in the scope of-50～150 ℃.
Reaction time is better 0.1～1000 hour.
The compound 4 obtained as mentioned above can carry out purifying by recrystallization, distillation, silica gel column chromatography, activated charcoal etc.
In the reaction of compound 19 and compound 1, usually use the condensation agents such as dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide, carbonyl dimidazoles.Now, the acid of catalytic amount or N, the interpolation of N-dimethylamino naphthyridine is effective for the carrying out of reaction, therefore preferably.
The method for making of compound 5
With the manufacture of the compound 5 of compound 4, can be undertaken by the described method of method for making 1.
<polyamic acid, poly amic acid ester, polyimide >
Diamine compound of the present invention can be by reacting to obtain on side chain the polyamic acid 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 the tetrabasic carboxylic acid or derivatives thereof, by reacting of tetrabasic carboxylic acid diester diacid chloride and diamine compound, or, by tetrabasic carboxylic acid diester and diamine compound are reacted under the existence of condensation agent, alkali etc., can obtain the poly amic acid ester as polyimide precursor.Also have, 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, thereby can obtain on side chain the polyimide with ad hoc structure.
<polyamic acid >
Polyamic acid of the present invention is the polyamic acid that two amine components by containing the diamine compound meaned with formula [1] obtain with reacting of tetracarboxylic dianhydride.
Poly amic acid ester of the present invention is that two amine components by making to contain the diamine compound meaned with formula [1] are reacted or make the tetrabasic carboxylic acid diester be reacted the poly amic acid ester obtained with diamine compound under the existence of condensation agent, alkali etc. under alkali exists with tetrabasic carboxylic acid diester diacid chloride.
Polyimide of the present invention is by making this polyamic acid carry out dehydration closed-loop or making poly amic acid ester be heated the polyimide that closed loop obtains.
As for obtaining the polymkeric substance of liquid crystal orientation film, any in polyamic acid, poly amic acid ester and polyimide is all useful.
Be used for by two amine components (following also referred to as two amine components) that react to obtain polyamic acid with the tetracarboxylic dianhydride, to not limiting containing proportional of the diamine compound with formula [1] expression.The diamine compound that the formula [1] of take means containing proportional be for example more than 10 % by mole of two amine components, preferably more than 20 % by mole, more preferably more than 30 % by mole.Also can two amine components 100 % by mole be all the diamine compound meaned with formula [1].Containing of the diamine compound meaned with formula [1] is proportional larger, and while 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 the light orientation process changes because of the vertical orientated ability of the structure of the side chain of the diamine compound that means with formula [1] and the liquid crystal that used, therefore in order to obtain desired tilt angle, the diamine compound meaned with formula [1] containing proportional can the selection in preferable range.
In two amine components, the diamine compound meaned with formula [1] is lower than in the situation of 100 % by mole, diamine compound (following sometimes also referred to as other diamine compound) beyond the diamine compound meaned 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 '-dimethyl dicyclohexyl 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, the 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 thioether, 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) cyclohexanes 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 disiloxanes 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) pentanes of 1,5-, two (4-aminophenyl) hexanes of 1,6-, two (4-aminophenyl) heptane of 1,7-, two (4-aminophenyl) octanes of 1,8-, two (4-aminophenyl) nonanes 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) pentanes of 1,5-, two (4-amino-benzene oxygen) hexanes of 1,6-, two (4-amino-benzene oxygen) heptane of 1,7-, two (4-amino-benzene oxygen) octanes of 1,8-, two (4-amino-benzene oxygen) nonanes of 1,9-, two (4-amino-benzene oxygen) decane of 1,10-, two (4-aminophenyls) 1, the 3-malonate, two (4-aminophenyl) 1, 4-succinic acid ester, two (4-aminophenyls) 1, the 5-glutarate, two (4-aminophenyls) 1, the 6-adipate, two (4-aminophenyls) 1, the 7-pimelate, two (4-aminophenyls) 1, the 8-suberate, two (4-aminophenyls) 1, the 9-azelate, two (4-aminophenyls) 1, the 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] pentanes of 1,5-, two [4-(4-amino-benzene oxygen) phenoxy group] hexanes of 1,6-, two [4-(4-amino-benzene oxygen) phenoxy group] heptane of 1,7-, two [4-(4-amino-benzene oxygen) phenoxy group] octanes of 1,8-, two [4-(4-amino-benzene oxygen) phenoxy group] nonanes 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-methylbenzene methyl amine, 4-amino-N-methylbenzene methyl amine, 3-aminobenzene ethylamine, 4-aminobenzene ethylamine, 3-amino-N-methylbenzene ethylamine, 4-amino-N-methylbenzene ethylamine, 3-(3-aminopropyl) aniline, 4-(3-aminopropyl) aniline, 3-(3-methylamino propyl group) aniline, 4-(3-methylamino propyl group) aniline, 3-(4-aminobutyl) aniline, 4-(4-aminobutyl) aniline, 3-(4-methylamino butyl) aniline, 4-(4-methylamino butyl) aniline, 3-(the amino amyl group of 5-) aniline, 4-(the amino amyl group of 5-) aniline, 3-(5-methylamino amyl group) aniline, 4-(5-methylamino amyl group) 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-pyridine, 2,4-diamino-1,3,5-triazines, 2,7-diamido dibenzofurans, 3,6-diamido carbazole, 2,4-diamido-6-isopropyl-1,3,5-triazine, 2, two (the 4-aminophenyls)-1,3 of 5-, 4-
diazole etc.
The example of aliphatic diamine class can exemplify: 1, the 2-diaminoethanes, 1, the 3-diaminopropanes, 1, the 4-diaminobutane, 1, the 5-1,5-DAP, 1, the 6-diamino hexane, 1, 7-diamido heptane, 1, the 8-diamino-octane, 1, 9-diamido nonane, 1, the 10-diamino decane, 1, 3-diamido-2, the 2-dimethylpropane, 1, 6-diamido-2, the 5-dimethylhexane, 1, 7-diamido-2, the 5-dimethyl heptane, 1, 7-diamido-4, the 4-dimethyl heptane, 1, 7-diamido-3-methylheptane, 1, 9-diamido-5-methylheptane, 1, 12-diamido dodecane, 1, 18-diamido octadecane, 1, 2-two (the amino propoxyl group of 3-) ethane etc.
Also can be used together there is alkyl on side chain, containing the diamine compound of fluoroalkyl, aromatic rings, aliphatics ring, heterocycle and the large ring-type substituent that formed by them.Particularly, the diamines can illustration meaned with following formula [DA-1]～formula [DA-26].
[changing 43]
(R
6it is the alkyl of carbon number 1～22 or containing fluoroalkyl.)
[changing 44]
(S
5expression-COO-,-OCO-,-CONH-,-NHCO-,-CH
2-,-O-,-CO-or-NH-, R
6mean the alkyl of carbon number 1～22 or contain fluoroalkyl.)
[changing 45]
(S
6expression-O-,-OCH
2-,-CH
2o-,-COOCH
2-or-CH
2oCO-, R
7the alkyl, alkoxy of carbon number 1～22, containing fluoroalkyl or fluoroalkoxy.)
[changing 46]
(S
7expression-COO-,-OCO-,-CONH-,-NHCO-,-COOCH
2-,-CH
2oCO-,-CH
2o-,-OCH
2-or-CH
2-, R
8the alkyl, alkoxy of carbon number 1～22, containing fluoroalkyl or fluoroalkoxy.)
[changing 47]
(S
8expression-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
10that the alkyl of carbon number 3～12, the cis-trans isomerism of Isosorbide-5-Nitrae-cyclohexylidene are respectively trans.)
[changing 49]
[changing 50]
[changing 51]
In order to make up vertical orientated ability, also the diamine compound of above-mentioned [DA-1]～[DA-26] and the diamine compound meaned with general formula [1] also can be used simultaneously.As can and the preferred diamines of use, consider the diamine compound of preferred formula [DA-10]～[DA-26], the more preferably diamine compound of formula [DA-10]～[DA-16] from voltage retention and the residual angle of accumulating voltage etc.Preferred content to these diamine compounds is not particularly limited, but is preferably 5～50 % by mole in two amine components, more preferably 5～30 % by mole.
In addition, also can be used together following diamine compound.
[changing 52]
(m is 0～3 integer, and n is 1～5 integer).
By containing [DA-27] or [DA-28], can improve voltage retention (VHR), [DA-29]～[DA-34] has the effect that electric charge is accumulated in minimizing, therefore preferably.
Also have, as other diamine compound, also can exemplify the diamido siloxane that means with following formula [DA-35] etc.
[changing 53]
(m is 1～10 integer.)
Other diamine compound can be according to as liquid crystal orientation film the time liquid crystal aligning, voltage retention performance, accumulate the characteristic such as electric charge, use one or more to mix and use.
For being not particularly limited with the tetracarboxylic dianhydride that two amine components react for obtaining polyamic acid of the present invention.Below exemplify its object lesson:
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-cyclohexane tetracarboxylic 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, the 8-tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-dicyclohexyl tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic basic ring amyl group acetic acid dianhydride, cis-3, 7-dibutyl ring hot-1, 5-diene-1, 2, 5, the 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-dioxo tetrahydrofuran-3-yl)-1,2,3,4-tetrahydro-naphthalene-1,2-dicarboxylic anhydride etc.
Also have, if also use aromatic tetracarboxylic acid's dianhydride outside the above-mentioned tetracarboxylic dianhydride with alicyclic structure or aliphatic structure, can improve liquid crystal aligning, and can reduce the electric charge of accumulating of liquid crystal structure cell, therefore preferably.As aromatic tetracarboxylic acid's dianhydride, can exemplify pyromellitic acid anhydride, 3,3 ', 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-dicarboxyl phenyl) ether dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride etc.
For being not particularly limited for obtaining the tetrabasic carboxylic acid dialkyl that poly amic acid ester of the present invention reacts with two amine components.Below exemplify its object lesson:
As aliphatics tetrabasic carboxylic acid diester, can exemplify 1, 2, 3, 4-cyclo-butane tetrabasic carboxylic acid dialkyl, 1, 2-dimethyl-1, 2, 3, 4-cyclo-butane tetrabasic carboxylic acid dialkyl, 1, 3-dimethyl-1, 2, 3, 4-cyclo-butane tetrabasic carboxylic acid dialkyl, 1, 2, 3, 4-tetramethyl-1, 2, 3, 4-cyclo-butane tetrabasic carboxylic acid dialkyl, 1, 2, 3, 4-cyclopentane tetrabasic carboxylic acid dialkyl, 2, 3, 4, 5-tetrahydrofuran tetrabasic carboxylic acid dialkyl, 1, 2, 4, 5-cyclohexane tetrabasic carboxylic acid 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 basic ring amyl group acetic acid dialkyl, cis-3, 7-dibutyl ring hot-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-dioxo tetrahydrofuran-3-yl)-1,2,3,4-tetrahydro-naphthalene-1,2-dicarboxylic acid dialkyl esters etc.
As aromatic tetracarboxylic acid's dialkyl, can exemplify Pyromellitic Acid dialkyl, 3,3 ', 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-dicarboxyl phenyl) ether dialkyl, two (3,4-dicarboxyl phenyl) sulfone dialkyl, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl etc.
For being not particularly limited with the dicarboxylic acid that two amine components react as raw material obtains polyimide in order to take diamine compound of the present invention.Object lesson as the aliphatic dicarboxylic acid of dicarboxylic acid or derivatives thereof, can exemplify 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, 2,2-dimethylated pentanedioic acid, 3, the dicarboxylic acid such as 3-diethyl succinic acid, azelaic acid, decanedioic acid, suberic acid.
Dicarboxylic acid as alicyclic structure, can exemplify 1, the 1-cyclopropane dicarboxylic acid, 1, the 2-cyclopropane dicarboxylic acid, 1, the 1-cyclobutane dicarboxylic acid, 1, the 2-cyclobutane dicarboxylic acid, 1, the 3-cyclobutane dicarboxylic acid, 3, 4-diphenyl-1, the 2-cyclobutane dicarboxylic acid, 2, 4-diphenyl-1, the 3-cyclobutane dicarboxylic acid, 1-cyclobutane-1, the 2-dicarboxylic acid, 1-cyclobutane-3, the 4-dicarboxylic acid, 1, 1-cyclopentane dicarboxylic acid, 1, 2-cyclopentane dicarboxylic acid, 1, 3-cyclopentane dicarboxylic acid, 1, the 1-cyclohexane dicarboxylic acid, 1, the 2-cyclohexane dicarboxylic acid, 1, the 3-cyclohexane dicarboxylic acid, 1, the 4-cyclohexane dicarboxylic acid, 1, 4-(2-norborene) dicarboxylic acid, norborene-2, the 3-dicarboxylic acid, two ring [2.2.2] octanes-1, the 4-dicarboxylic acid, two ring [2.2.2] octanes-2, the 3-dicarboxylic acid, 2, 5-dioxo-1, 4-bis-ring [2.2.2] octane dicarboxylic acid, 1, 3-diamantane dicarboxylic acid, 4, 8-dioxo-1, 3-diamantane dicarboxylic acid, 2, 6-spiroheptane dicarboxylic acid, 1, 3-diamantane oxalic acid, camphoric acid etc.
As aromatic dicarboxylic acid, can exemplify phthalic acid, m-phthalic acid, terephthalic acid (TPA), the oreinol dioctyl phthalate, the 5-tert-butyl isophthalic acid, the amino m-phthalic acid of 5-, the 5-Hydroxy M Phthalic Acid, 2,5-dimethyl terephthalic acid, the 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 inferior 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 the phenylene oxalic acid, 3,3 '-to the phenylene dipropionic acid, the 4-o-carboxy cinnamic acid, to the phenylene diacrylate, 3,3 '-[4,4 '-(two pairs of phenylenes of methylene)] dipropionic acid, 4,4 '-[4,4 '-(two pairs of phenylenes of oxo)] dipropionic acid, 4,4 '-[4,4 '-(two pairs of phenylenes of oxo)] two butyric acid, (two pairs of phenylene dioxies of isopropylidene) two butyric acid, two (to carboxyl phenyl) dimethylsilane etc.
Dicarboxylic acid as containing heterocycle, can exemplify 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-
diazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-Pyridinedicarboxylic acid, 2, dipicolimic acid 2,3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid etc.
Above-mentioned various dicarboxylic acid can be also sour two carboxylic acid halides or acid anhydrides.In these dicarboxylic acid, particularly can give the dicarboxylic acid of the polyamide of linear structure, from the orientation aspect that keeps liquid crystal molecule, consider it is preferred.Wherein, preferably 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 having isomeride in these compounds, can be also the potpourri that comprises 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.
The tetracarboxylic dianhydride can be when making liquid crystal orientation film liquid crystal aligning, voltage retention performance, accumulate the characteristic such as electric charge, use a kind of or and with two or more.
When the reaction by two amine components and tetracarboxylic dianhydride obtains polyamic acid of the present invention, can adopt known synthetic method.The method that normally makes tetracarboxylic dianhydride and two amine components 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 on the accessory substance this point.
As the organic solvent of the reaction for tetracarboxylic dianhydride and diamine compound, so long as the soluble solvent of polyamic acid generated, be not particularly limited.Below exemplify its object lesson:
Can exemplify DMF, DMA, METHYLPYRROLIDONE, the N-ethyl-2-pyrrolidone, the N-methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, the pregnancy sulfoxide, gamma-butyrolacton, isopropyl alcohol, the 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, the glycol monomethyl isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, the propylene glycol monoacetate, propylene glycol monomethyl ether, the glycol tertiary butyl ether, DPGME, diethylene glycol, the diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethylether, the single propyl ether of dipropylene glycol, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxyl butylacetic acid ester, the tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, the 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, acetic acid propylene glycol ester list ethylether, methyl pyruvate, ethyl pyruvate, the 3-methoxy methyl propionate, 3-ethoxy-propionic acid methyl ethyl ester, 3-methoxy propyl acetoacetic ester, the 3-ethoxy-propionic acid, the 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diethylene glycol dimethyl ether, the 4-hydroxy-4-methyl-2-pentanone, 3-methoxyl-N, N-dimethyl propylene acid amides, 3-ethoxy-N, N-dimethyl propylene acid amides, 3-butoxy-N, N-dimethyl propylene acid amides etc.These can be used alone, but also also mix together.Also have, even the solvent of insoluble solution polyamic acid, so long as, in the scope that can not separate out at the polyamic acid generated, also can use with above-mentioned solvent.
In addition, the moisture in organic solvent hinders polyreaction, and can make the polyamic acid hydrolysis generated, so organic solvent is preferably used the organic solvent through farthest dehydrating.
When being reacted in organic solvent, tetracarboxylic dianhydride and two amine components can exemplify: stir the solution that makes two amine components be dispersed or dissolved in organic solvent and obtain, then directly add the tetracarboxylic dianhydride or make the tetracarboxylic dianhydride be dispersed or dissolved in the method for adding again after organic solvent; Add the method for two amine components in the solution obtained the tetracarboxylic dianhydride is dispersed or dissolved in to organic solvent on the contrary; Alternately add the method for tetracarboxylic dianhydride and two amine components etc., can use any method wherein.In addition, when tetracarboxylic dianhydride or two amine components comprise multiple compounds, can under the state be pre-mixed, make its reaction, also can make its respectively reaction successively, can also make to react respectively and low-molecular-weight body hybrid reaction and obtain the high molecular body.
Polymerization temperature now can be selected the arbitrary temp of-20～150 ℃, is better the scope of-5～100 ℃.In addition, reaction can be carried out with concentration arbitrarily, if but concentration is too low, be difficult to obtain the polymkeric substance of high molecular, if excessive concentration the viscosity of reactant liquor is too high, be difficult to stir uniformly, so tetracarboxylic dianhydride and the total concentration of two amine components in reaction solution be preferably 1～50 quality %, be more preferably 5～30 quality %.Initial reaction stage is carried out under high concentration, can append organic solvent afterwards.
In above-mentioned reaction, the ratio of the total mole number of tetracarboxylic dianhydride's total mole number and two amine components 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 be make above-mentioned polyamic acid dehydration closed-loop and polyimide, as the polymkeric substance for obtaining liquid crystal orientation film, be useful.
In polyimide of the present invention, the dehydration closed-loop rate of acid amides acidic group (acid imide rate) does not need one to be decided to be 100%, can adjust arbitrarily according to purposes or purpose.
<polyimide >
As the method that makes the polyamic acid imidizate, can exemplify the hot-imide of the solution of direct heating polyamic acid, add the catalysis imidizate of catalyzer in the solution of polyamic acid.
Temperature while making the polyamic acid hot-imide in solution is 100～400 ℃, is better 120～250 ℃, is better to carry out when the water that will generate by imidization reaction is got rid of to system.
The catalysis imidizate of polyamic acid is by add base catalyst and acid anhydrides in polyamic acid solution, and at-20～250 ℃, is better to stir under 0～180 ℃ and carry out.The amount of base catalyst to be mole to count 0.5～30 times of acid amides acidic group, and preferably 2～20 times, the amount of acid anhydrides is mole to count 1～50 times of acid amides acidic group, preferably 3～30 times.
As base catalyst, can exemplify pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc., wherein pyridine have for make reaction carry out for appropriate alkalescence, therefore preferably.
As acid anhydrides, can exemplify acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc., wherein, be easy to react the purifying after finishing while using acetic anhydride, therefore preferably.Adopt the acid imide rate of catalysis imidizate to control by adjustment catalytic amount, temperature of reaction, reaction time.
<poly amic acid ester >
Method as the synthesizing polyamides acid esters, by reacting of tetrabasic carboxylic acid diester diacid chloride and diamine compound, perhaps, by tetrabasic carboxylic acid diester and diamine compound are reacted under the existence of condensation agent, alkali etc., can obtain a kind of poly amic acid ester as polyimide precursor.Perhaps, by making in advance the polyamic acid polymerization, utilize high molecular weight reactive to make the method for the carboxylic esterification in amic acid, also can obtain poly amic acid ester.
Particularly, can make tetrabasic carboxylic acid diester diacid chloride and diamine compound under the existence of alkali and organic solvent, and-20～150 ℃, preferably reaction 30 minutes～24 hours, preferably 1～4 hour under 0～50 ℃, thereby synthesized.
Alkali can be used pyridine, triethylamine, DMAP etc., because reacting balance ground carries out, so preferred pyridine.Easily obtain the viewpoint consideration of high molecular body from the amount easily to remove, the addition of alkali is better 2～4 times moles with respect to tetrabasic carboxylic acid diester diacid chloride.
While under the existence of condensation agent, carrying out polycondensation reaction, can use triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazines methyl morpholine
, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea (TMU) tetrafluoro boric acid ester, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea (TMU) hexafluorophosphoric acid ester, (2,3-dihydro-2-sulfo--3-benzo
azoles) phosphonic acid diphenyl ester, 4-(4,6-dimethoxy-1,3,5-triazines-2-yl) 4-methoxyl morpholine hydrochloride n hydrate etc. are as condensation agent.
In addition, in the method for 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 with respect to the tetrabasic carboxylic acid diester.
As solvent, can use above the carrying out polymerization of record and solvent used while obtaining polyamic acid, from the deliquescent angle of monomer and polymkeric substance, consider, preferably METHYLPYRROLIDONE, gamma-butyrolacton etc.These solvents can be used one or more to mix and use.In addition, in order to prevent the hydrolysis of tetrabasic carboxylic acid diester diacid chloride, for the synthesis of the solvent of poly amic acid ester, be better dehydration as far as possible.
From being difficult to cause the viewpoint consideration of separating out and easily obtain the high molecular body of polymkeric substance, tetrabasic carboxylic acid diester diacid chloride and the total concentration of two amine components in reaction solution are better 1～30 quality %, are more preferably 5～20 quality %.
Reaction is better to carry out in nitrogen atmosphere, prevents sneaking into of external gas.
<polyamide >
Polyamide also can be similarly synthetic with poly amic acid ester.
The recovery of<polymkeric substance >
When the polyamic acid reclaim generated from the reaction solution of polyamic acid, poly amic acid ester, polyimide etc., poly amic acid ester, polyimide etc., reaction solution can be put into to Weak solvent and make the polymkeric substance precipitation.Weak solvent as for precipitation, can exemplify methyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water etc.Put in Weak solvent and the polymkeric substance of precipitation can, after filtered and recycled, carry out drying in normal temperature or heating under normal pressure or decompression.In addition, if the polymkeric substance that repeats precipitation is reclaimed is dissolved in the organic solvent operation that also precipitation reclaims again 2～10 times again, can reduce the impurity in polymkeric substance.As Weak solvent now, can exemplify such as alcohols, ketone, hydro carbons etc., if use the Weak solvent more than 3 kinds that is selected from these solvents, purification efficiency further improves, therefore desirable.
Contained polyamic acid and the molecular weight of polyimide in aligning agent for liquid crystal of the present invention, considering intensity that gained is filmed, in the operability while forming of filming and the inhomogeneity situation of filming, the weight-average molecular weight of 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 that is used to form liquid crystal orientation film, is that the resinous principle that is used to form resin coating is dissolved in organic solvent and the solution formed.Here, the resinous principle that above-mentioned resinous principle is at least one polymkeric substance of comprising the polymkeric substance that is selected from the invention described above.Now, the content of resinous principle is 1～20 quality % preferably, 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 in polymkeric substance of the present invention, mix polymkeric substance of the present invention other polymkeric substance in addition.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 for example can exemplify as two amine components that reacts with tetracarboxylic dianhydride's composition, uses diamine compound in addition of specific diamine compound and the polyamic acid that obtains or polyimide etc.
The organic solvent used in aligning agent for liquid crystal of the present invention, so long as the organic solvent of energy dissolving resin composition gets final product, is not particularly limited.Below exemplify its object lesson:
Can exemplify N, dinethylformamide, N, the N-dimethyl acetamide, METHYLPYRROLIDONE, the N-methyl caprolactam, 2-Pyrrolidone, the N-ethyl pyrrolidone, NVP, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, the pregnancy sulfoxide, gamma-butyrolacton, 3-methoxyl-N, N-dimethyl propylene acid amides, 3-ethoxy-N, N-dimethyl propylene acid amides, 3-butoxy-N, N-dimethyl propylene acid amides, 1, the 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, but also also mix together.
Aligning agent for liquid crystal of the present invention can comprise above-mentioned composition in addition.Its example has, the compound of the adaptation of the film thickness uniformity while improving the coating of liquid crystalline aligning agent or the solvent of surface smoothness or compound, raising liquid crystal orientation film and substrate etc.
Concrete example as the solvent (Weak solvent) of the homogeneity that can improve thickness or surface smoothness, can exemplify following material.
For example, can exemplify isopropyl alcohol, the methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, the ethyl carbitol acetic acid esters, ethylene glycol, ethylene glycol acetate, the glycol monomethyl isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, the propylene glycol monoacetate, propylene glycol monomethyl ether, the glycol tertiary butyl ether, DPGME, diethylene glycol, the diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethylether, the single propyl ether of dipropylene glycol, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxyl butylacetic acid ester, the tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, the ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, the 1-hexanol, normal hexane, n-pentane, normal octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid propylene glycol ester list ethylether, methyl pyruvate, ethyl pyruvate, the 3-methoxy methyl propionate, 3-ethoxy-propionic acid methyl ethyl ester, 3-methoxy propyl acetoacetic ester, the 3-ethoxy-propionic acid, the 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, the 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, the propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, the mono-ethylether of propylene glycol-1--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 of low surface tension etc.
These Weak solvents can one or more mix use.While using solvent as above, be better 5～80 quality % of the solvent total amount that comprises in aligning agent for liquid crystal, be more preferably 20～60 quality %.
As the homogeneity that improves thickness or the compound of surface smoothness, can exemplify fluorine class surfactant, siloxane type surfactants, nonionic surfactant etc.
More specifically, such as exemplifying エ Off ト Star プ EF301, EF303, EF352 (illuminating product Co., Ltd. (ト mono-ケ system プ mouth ダ Network Star 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, with respect to resinous principle 100 mass parts that comprise 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 the compound of the adaptation that improves liquid crystal orientation film and substrate, can exemplify the compound containing functional silanes shown below, containing the compound of epoxy radicals etc.
For example, can exemplify the 3-TSL 8330, APTES, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, 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 8330s of N-, two (the oxyethylene group)-APTESs 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, the 4-hexanediol, N, N, N ', N ' ,-four glycidyl group-m-xylene diamine, two (N, the N-diglycidyl amino methyl) cyclohexanes of 1,3-, N, N, N ', N ' ,-four glycidyl group-4, 4 '-diaminodiphenyl-methane etc.
Except the adaptation that improves substrate and film, for degradation under the electrical characteristics that prevent from being caused by backlight, also can contain phenoplast class adjuvant as follows in aligning agent for liquid crystal.Concrete phenoplast class adjuvant is as follows, but is not limited to this structure.
[changing 54]
While use improving the compound with the adaptation of substrate, with respect to resinous principle 100 mass parts that contain in aligning agent for liquid crystal, its consumption is better 0.1～30 mass parts, is more preferably 1～20 mass parts.If consumption less than 0.1 mass parts, can't expect the effect that adaptation improves, if more than 30 mass parts, the orientation variation of liquid crystal sometimes.
In aligning agent for liquid crystal of the present invention, except above-mentioned, in the scope of not damaging effect of the present invention, dielectric or conductive materials that the electrical characteristics such as the specific inductive capacity of liquid crystal orientation film or electric conductivity are purpose can be added to change, the hardness of the film while forming liquid crystal orientation film or the cross-linked compound that density is purpose etc. can also be added to improve.
<liquid crystal orientation film and liquid crystal display cells >
Aligning agent for liquid crystal of the present invention is being coated on substrate and, after burning till, can carried out the orientation process such as friction treatment or irradiation, or in vertical orientated purposes etc. without orientation process and as liquid crystal orientation film.Now, the substrate of use, so long as the high substrate of the transparency gets final product, is not particularly limited, and can use glass substrate or the plastic bases such as acrylic acid substrate and polycarbonate substrate etc.In addition, from the viewpoint of work simplification, preferably use the substrate be formed with for the ITO electrode of liquid crystal drive etc.In addition, in reflection type liquid crystal display element, can use the opaque materials such as silicon wafer, but only limit to the substrate of a side, electrode now can be used the reflectorized materials such as aluminium.
The coating process of aligning agent for liquid crystal is not particularly limited, industrial common 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., can use these methods according to purpose.
After coating on substrate by aligning agent for liquid crystal burn till can by the heating arrangements such as heating plate 50～300 ℃, better be to carry out under 80～250 ℃, so that the solvent evaporation is filmed thereby form.If it is blocked up to burn till the thickness of filming of rear formation, unfavorable aspect the power consumption of liquid crystal display cells, if excessively thin, the reliability of liquid crystal display cells reduces sometimes, therefore preferably 5～300nm, more preferably 10～100nm.While making liquid crystal horizontal alignment or tilted alignment, by friction or polarisation ultraviolet ray irradiation etc., filming after burning till processed.
Liquid crystal display cells of the present invention is, after obtaining the substrate with liquid crystal orientation film by said method by aligning agent for liquid crystal of the present invention, by known method, to manufacture the liquid crystal display cells that liquid crystal cells forms.
If exemplify an example of manufacturing liquid crystal cells, but the following method of illustration: a pair of substrate of preparing to be formed with liquid crystal orientation film, scatter sept on the liquid crystal orientation film of a substrate, make the liquid crystal aligning face become interior rear flank another baseplate-laminating, the method for liquid crystal sealing is injected in decompression; Or drip liquid crystal on being scattered with the liquid crystal aligning face of sept after, the method that baseplate-laminating is sealed etc.Now, the thickness of sept is 1～30 μ m preferably, more preferably 2～10 μ m.
As mentioned above, use aligning agent for liquid crystal of the present invention and the reliability of the liquid crystal display cells that makes is good, can perform well in the LCD TV of large picture and high-resolution etc.
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 >
Add 4-iodophenol 1 (22.0g, 0.100mol), sal tartari (20.7g, 0.150mol), dimethyl formamide 130ml (mM) in four-hole boiling flask, after stirring, be warming up to 80 ℃ under nitrogen atmosphere.After arriving 80 ℃, with the times dropping 1-bromo-decane (17.9g, 0.0809mol) of 30 minutes, dropping was stirred 1 hour after finishing again.After confirming that by GC (vapor-phase chromatography) the 1-bromo-decane disappears, steaming desolventizes, and adds toluene 120ml and pure water 150g to be extracted, and removes water layer.Then in organic layer, add 1N NaOH100ml to be extracted, remove water layer.By the organic layer anhydrous magnesium sulfate drying of gained, then filtering magnesium sulphate, under reduced pressure steam the organic layer of gained to desolventize, and obtains compound 2 (must measure 26.9g, 0.0747mol, yield 92.3%).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 ℃ of stirring, drips the solution mixed by acryloyl chloride (21.7g, 0.240mol) and tetrahydrofuran 40ml under nitrogen atmosphere in this solution with the times of 30 minutes.After dropping, then stir 4 hours, after reaction finishes, steaming desolventizes, and adds water 300g in the crude product of gained, under slurry form, in 25 ℃, stirs 30 minutes.Then filtering reacting liquid, under reduced pressure in 70 ℃ of dryings 3 hours, obtain compound 4 (must measure 48.7g, 0.193mol, yield 96.5%) by solid constituent.The structure of compound 4 is passed through
1h-NMR analyzes to confirm.
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, recover pressure with nitrogen, repeat above action 10 times, remove in reactor and contained oxygen in dimethyl acetamide.Then heated up, stirred 3 hours in 110 ℃ under nitrogen atmosphere.After reaction finishes, steaming desolventizes, water 200g and chloroform 250g extraction.The water layer that separatory goes out is again with chloroform 250g extraction 2 times, by the organic layer anhydrous magnesium sulfate drying of gained.Filtering magnesium sulphate, under reduced pressure steam the organic layer of gained to desolventize, with the crude product of acetonitrile 170g washing gained.Then filtering for crystallizing, by the solid constituent drying under reduced pressure of gained, thereby obtain compound 5 (must measure 32.5g, 0.0671mol, yield 95.6%).The structure of compound 5 is passed through
1h-NMR analyzes to confirm.
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 to pure water 90.0g, the solution of gained is heated to 55 ℃, stir.After arriving 55 ℃, add iron powder (51.1g, 0.915mol), further be warming up to 80 ℃.After arriving 80 ℃, drip and to be dissolved in the compound 5 (29.0g, 0.0599mol) of heating to the toluene of the 145g of 80 ℃.After dripping end, stir 2 hours, reaction is carried out the thermosol filtration after finishing under the condition of heating of 80 ℃, by the reactant liquor separatory of gained, removes water layer again.Add activated charcoal 1.2g in the organic layer of gained, stir 30 minutes under the condition of heating of 80 ℃.Then, under the condition of heating of 80 ℃, carry out the thermosol filtration, with the organic layer 2 times that is heated in advance the pure water washing gained of 80 ℃.By the organic layer anhydrous magnesium sulfate drying of gained, then filtering magnesium sulphate, under reduced pressure steam the organic layer of gained to desolventize, and obtains compound 6 (must measure 18.7g, 0.0440mol, yield 73.5%).The structure of compound 6 is passed through
1h-NMR analyzes to confirm.
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 borine dimethyl sulphide complex compound (57.0g, 750mmol) in tetrahydrofuran (452g) solution of 4-dinitro benzene guanidine-acetic acid (56.6g, 250mmol), at room temperature stir 22 hours.Then under 0 ℃, the time with 2 hours drips water (112g), after at room temperature stirring 2 hours, with ethyl acetate and water, is extracted, and separates water layer, uses the dried over mgso organic layer.By removing by filter magnesium sulphate, concentrate the organic layer of gained, make crude product recrystallization from ethyl acetate and hexane of gained, obtain 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]
Add dimethyl formamide (90.1g) in iodobutane (30.0g, 163mmol), 4-iodophenol (39.4g, 179mmol) and sal tartari (27.0g, 196mmol), under 85 ℃, stir 2 hours, then by removing by filter sal tartari.Then, with the sodium hydrate aqueous solution of toluene and 1 equivalent, extracted.Separate water layer, with the organic layer of dried over mgso gained, after removing by filter magnesium sulphate, concentrated organic layer, obtain 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]
Add dimethyl acetamide (362g) 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), stir 2 hours under 140 ℃.Then, with ethyl acetate and water, extracted, separated water layer, used the dried over mgso organic layer.By removing by filter magnesium sulphate, concentrate the organic layer of gained, make crude product recrystallization from ethyl acetate and hexane of gained, obtain 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), add 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride (16.2g, 84.5mmol) under 0 ℃, at room temperature stir 15 hours.Then, with ethyl acetate and water, extracted, separated water layer, used the dried over mgso organic layer.By removing by filter magnesium sulphate, the organic layer of concentrated gained, purify the crude product of gained by column chromatography, 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 to ethyl acetate (200g) and water (77.1g), stir 14 hours under 70 ℃.Then remain on 70 ℃, filtered with zeyssatite, use the organic layer of the filtrate of dried over mgso gained.By removing by filter magnesium sulphate, the organic layer of concentrated gained, obtain crude product.The crude product of gained is dissolved in to tetrahydrofuran (200g), adds activated charcoal (2.00g), at room temperature stir 18 hours.By removing by filter activated charcoal, concentrated organic layer, obtain 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).
[synthesizing of polyamic acid]
Abbreviation for the synthetic tetracarboxylic dianhydride of polyamic acid and diamine compound etc. below is 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)
The NMP:N-N-methyl-2-2-pyrrolidone N-
BC: butyl cellosolve
The molecular weight determination of<polyimide >
The molecular weight of polyimide is normal temperature gel permeation chromatography (GPC) device (SSC-7200) and the post (KD-803, KD-805) clear and electrician (Shodex) Co., Ltd. system that uses eternal lasting science Co., Ltd. (セ Application シ ユ mono-science society) system, following mensuration.
Column temperature: 50 ℃
Eluent: N, and the N'-dimethyl formamide (as adjuvant, lithium bromide monohydrate (LiBrH
2o) be that 30mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) are 10ml/L for 30mmol/L, tetrahydrofuran (THF))
Flow velocity: 1.0ml/ minute
Calibration curve is made and to be used standard sample: (East ソ ー society of eastern Cao company) TSK standard polyethylene oxide processed (molecular weight approximately 900000,150000,100000,30000) and polymkeric substance laboratory company (Port リ マ ー ラ ボ ラ ト リ ー society) polyglycol processed (molecular weight approximately 12000,4000,1000).
<embodiment 5 >
DA1 (0.637g, 1.50mmol) and p-PDA (0.162g, 1.50mmol) are mixed in NMP (8.13g), after at room temperature stirring and within 1 hour, making it dissolve, add PMDA (0.635g, 2.91mmol), at room temperature react 12 hours, obtain polyamic acid solution.Add NMP (9.56g) and BC (4.78g) in this polyamic acid solution (9.56g), stir 5 hours, thereby 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 >
DA1 (0.743g, 1.75mmol) and p-PDA (0.081g, 0.75mmol) are mixed in NMP (7.67g), after at room temperature stirring and within 1 hour, making it dissolve, add PMDA (0.529g, 2.43mmol), at room temperature react 12 hours, obtain polyamic acid solution.Add NMP (9.02g) and BC (4.51g) in this polyamic acid solution (9.02g), stir 5 hours, thereby 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 >
DA1 (0.849g, 2.0mmol) is mixed in NMP (7.21g), after at room temperature stirring and within 1 hour, making it dissolve, add PMDA (0.424g, 1.94mmol), at room temperature react 12 hours, obtain polyamic acid solution.Add NMP (8.48g) and BC (4.24g) in this polyamic acid solution (8.48g), stir 5 hours, thereby 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 >
DA1 (0.509g, 1.20mmol) and p-PDA (0.194g, 1.80mmol) are mixed in NMP (7.22g), after at room temperature stirring and within 1 hour, making it dissolve, add CBDA (0.571g, 2.91mmol), at room temperature react 12 hours, obtain polyamic acid solution.Add NMP (9.02g) and BC (4.51g) in this polyamic acid solution (9.02g), stir 5 hours, thereby 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 >
DA1 (0.637g, 1.50mmol) and p-PDA (0.163g, 1.50mmol) are mixed in NMP (7.76g), after at room temperature stirring and within 1 hour, making it dissolve, add CBDA (0.571g, 2.91mmol), at room temperature react 12 hours, obtain polyamic acid solution.Add NMP (9.13g) and BC (4.57g) in this polyamic acid solution (9.13g), stir 5 hours, thereby 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 structure cell with step as follows.
[manufacture of liquid crystal structure cell]
The aligning agent for liquid crystal [A] obtained in embodiment 5 is spun on to the ito surface with the glass substrate of the transparency electrode consisted of the ITO film, on the heating plate of 80 ℃, drying is after 90 seconds, carry out 30 minutes burn till in the heated air circulation type baking oven of 200 ℃, the liquid crystal orientation film that to form thickness be 100nm.
It is 8.0mW/cm that this substrate is irradiated to exposure intensity
2the straight line polarization UV of 313nm, exposure is 100mJ.The direction of incident ray has tilted 40 ° with respect to the substrate normal direction.Straight line polarization UV is adjusted by the following method: make the ultraviolet light of high-pressure sodium lamp by the bandpass filter of 313nm, then make it by the polaroid of 313nm.
Prepare two aforesaid substrates, scatter the pearl sept of 6 μ m on the liquid crystal orientation film of a substrate after, printing and sealing agent thereon.Then, the liquid crystal aligning that makes two substrates, in the face of putting, carries out crimping, makes the projecting direction of optical axis on each substrate of straight line polarization UV be antiparallel, in 150 ℃ of time chien shih sealant heat curings with 105 minutes.(Merck & Co., Inc. (メ Le Network society) system, MLC-6608), make the liquid crystal structure cell to inject negative liquid crystal by the decompression injection method in this negative crystal born of the same parents.
In said method, change the exposure of the polarization UV of irradiation into 0mJ～1000mJ, make same liquid crystal structure cell.
[evaluation of liquid crystal structure cell]
The liquid crystal structure cell is applied/removes the voltage of 8V under 25 ℃, with polarizing microscope, observe and now have or not abnormal farmland, will there is no be evaluated as " liquid crystal aligning is good " on abnormal farmland.The liquid crystal structure cell of making as mentioned above demonstrates good vertical orientated property not executing under alive state, and the liquid crystal aligning while applying voltage is also good.
[evaluation of tilt angle]
The mensuration of the tilt angle of liquid crystal structure cell is to use " the Axo Scan " of Axo Metrix company system to be measured by the Muller matrix method.
<embodiment 11 >
Except aligning agent for liquid crystal (A) being changed into to aligning agent for liquid crystal (B), make similarly to Example 10 the liquid crystal structure cell, carry out the mensuration of orientation and the tilt angle of liquid crystal.
<embodiment 12 >
Except aligning agent for liquid crystal (A) being changed into to aligning agent for liquid crystal (C), make similarly to Example 10 the liquid crystal structure cell, carry out the mensuration of orientation and the tilt angle of liquid crystal.
<embodiment 13 >
Except aligning agent for liquid crystal (A) being changed into to aligning agent for liquid crystal (D), make similarly to Example 10 the liquid crystal structure cell, carry out the mensuration of orientation and the tilt angle of liquid crystal.
<embodiment 14 >
Except aligning agent for liquid crystal (A) being changed into to aligning agent for liquid crystal (E), make similarly to Example 10 the liquid crystal structure cell, carry out the mensuration of orientation and the tilt angle of liquid crystal.
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 () mean in all acid two anhydride components or this acid dianhydride in whole two amine components or diamine compound containing proportional (% by mole).
The tilt angle of the liquid crystal structure cell made in each embodiment is shown in table 2.
[table 1]
[table 2]
Result by table 2 can be confirmed, the liquid crystal display cells that uses novel diamine compound of the present invention and obtain demonstrates good vertical orientated property, and, by irradiating the ultraviolet ray of polarization, even less like this exposure also can make liquid crystal aligning with 100mJ, 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, irrelevant with the ultraviolet irradiation amount.This just means, even, after being exposed to for a long time under the light of backlight etc., also can stably keep tilt angle.
Hence one can see that, and novel diamine compound of the present invention can be used for the liquid crystal orientation film of the used for liquid crystal display element of vertical orientation mode, also is preferred for irradiating by ultraviolet ray the optical alignment method of giving the liquid crystal aligning ability.
<comparative example 1 >
[changing 65]
The DA3 of the DA2 of 1.11g (2.70mmol) and 0.11g (0.30mmol) is mixed in NMP (10.22g), after at room temperature stirring and within 1 hour, making it dissolve, the CBDA that adds 0.58g (2.94mmol), at room temperature react 12 hours, obtains polyamic acid solution.Add NMP (9.0g) and BC (9.0g) in this polyamic acid solution (12.0g), stir 5 hours, thereby 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 aligning agent for liquid crystal (A) being changed into to aligning agent for liquid crystal (F), make similarly to Example 10 the liquid crystal structure cell, carry out the mensuration of orientation and the tilt angle of liquid crystal.
The synthetic middle acid dianhydride used 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 the liquid crystal structure cell made in comparative example 1 is shown in table 4.
[table 3]
[table 4]
The possibility of utilizing on industry
Be exposed to for a long time under the light of backlight etc. and also can stably keep tilt angle even have the liquid crystal display cells of the liquid crystal orientation film obtained by novel diamine compound of the present invention, reliability is good, can be preferred for the LCD TV of large picture and high-resolution etc.
Quote the full content of instructions, claims and specification digest of No. 2010-153075, the Japanese patent application of filing an application on July 5th, 2010 here as the announcement of instructions of the present invention.
Claims (17)
1. an aligning agent for liquid crystal, it is characterized in that at least one polymkeric substance that comprises the polyamic acid that two amine components that are selected from the diamine compound by containing following formula [1] obtain with reacting of tetracarboxylic dianhydride's composition and the polyimide that this polyamic acid imidizate is obtained;
[changing 1]
In formula, X
1the expression singly-bound ,-CH
2o-,-O-,-COO-,-OCO-,-NHCO-or-CONH-, X
2the alkylidene that means carbon number 1～3, X
3expression-O-,-NH-or-N (R
1)-, X
4mean singly-bound ,-O-,-S-or-NH-; X
5mean singly-bound or be selected from following formula [X
5-1]～[X
5-5] carbocyclic ring, X
6mean the straight chain of carbon number 1～18 or the alkyl of branch-like, X
7the expression hydrogen atom ,-R
2,-OR
3,-NHR
4,-N (R
5)
2or-SR
6; Here, R
1～R
6mean independently respectively the alkyl of carbon number 1～5; N means 1 or 2 integer;
[changing 2]
Here, in above-mentioned carbocyclic ring structure, hydrogen atom can be by CH arbitrarily
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 two amine components 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]
3be-O-X
7it is hydrogen atom.
4. aligning agent for liquid crystal as described as any one in claim 1～3, wherein, the X of above-mentioned formula [1]
5it is singly-bound.
5. aligning agent for liquid crystal as described as any one in claim 1～4, wherein, the X of above-mentioned formula [1]
1singly-bound, X
4be-O-.
6. aligning agent for liquid crystal as described as any one in claim 1～5, wherein, the n of above-mentioned formula [1] is 1.
7. aligning agent for liquid crystal as described as any one in claim 1～6, wherein, the X of above-mentioned formula [1]
2be-CH
2-, X
6it is the alkyl of carbon number 8～12.
8. a liquid crystal orientation film, is characterized in that, by the described aligning agent for liquid crystal of any one in claim 1～7, obtained.
9. a liquid crystal orientation film, its be by the described aligning agent for liquid crystal of any one in claim 1～7 liquid crystal orientation film, the liquid crystal aligning ability is given in the irradiation of the radioactive ray by polarized light or nonpolarized light.
10. a liquid crystal display cells, is characterized in that, has the described liquid crystal orientation film of claim 8 or 9.
11. the diamine compound that following formula [1] means;
[changing 3]
In formula, X
1the expression singly-bound ,-CH
2o-,-O-,-COO-,-OCO-,-NHCO-or-CONH-, X
2the alkylidene that means carbon number 1～3, X
3expression-O-,-NH-or-N (R
1)-, X
4mean singly-bound ,-O-,-S-or-NH-; X
5mean singly-bound or be selected from following formula [X
5-1]～[X
5-5] carbocyclic ring, X
6mean the straight chain of carbon number 1～18 or the alkyl of branch-like, X
7the expression hydrogen atom ,-R
2,-OR
3,-NHR
4,-N (R
5)
2or-SR
6; Here, R
1～R
6mean independently respectively the alkyl of carbon number 1～5; N means 1 or 2 integer;
[changing 4]
Here, in above-mentioned carbocyclic ring structure, hydrogen atom can be by CH arbitrarily
3replace.
12. diamine compound as claimed in claim 11, wherein, the X of above-mentioned formula [1]
3be-O-X
7it is hydrogen atom.
13. diamine compound as described as claim 11 or 12, wherein, the X of above-mentioned formula [1]
5it is singly-bound.
14. diamine compound as described as any one in claim 11～13, wherein, the X of above-mentioned formula [1]
1singly-bound, X
4be-O-.
15. diamine compound as described as any one in claim 11～14, wherein, the n of above-mentioned formula [1] is 1.
16. diamine compound as described as any one in claim 11～15, wherein, the X of above-mentioned formula [1]
2be-CH
2-, X
6it is the alkyl of carbon number 8～12.
17. a polyamic acid maybe by this polyamic acid imidizate and polyimide, described polyamic acid reacts and obtains with tetracarboxylic dianhydride's composition by making to contain two amine components of the described diamine compound of any one in claim 11～16.
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| JP2008266421A (en) * | 2007-04-18 | 2008-11-06 | Jsr Corp | Liquid crystal aligning agent, liquid crystal display element, polymer therefor and raw material diamine |
| WO2009054545A1 (en) * | 2007-10-26 | 2009-04-30 | Jsr Corporation | Liquid crystal aligning agent, method for forming liquid crystal alignment film and liquid crystal display device |
| WO2009104468A1 (en) * | 2008-02-22 | 2009-08-27 | 株式会社Adeka | Liquid crystal composition containing polymerizable compound, and liquid crystal display element comprising the liquid crystal composition |
| JP2011100099A (en) * | 2009-10-06 | 2011-05-19 | Jsr Corp | Liquid crystal aligning agent, method of producing liquid crystal aligning film, and liquid crystal display element |
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| JP4094764B2 (en) | 1999-03-30 | 2008-06-04 | Ｊｓｒ株式会社 | Liquid crystal alignment agent |
| JP2000281783A (en) | 1999-03-31 | 2000-10-10 | Kanegafuchi Chem Ind Co Ltd | Novel diamine and novel polyimide composition prepared by using same |
| KR100837788B1 (en) | 2007-06-13 | 2008-06-13 | 한국화학연구원 | Aromatic diamines with a photoreactive aromatic side group, polyamic acid photo-alignment layers with them and method for preparing liquid crystal cells |
| JP5057056B2 (en) | 2007-08-03 | 2012-10-24 | Ｊｓｒ株式会社 | Liquid crystal aligning agent, method for producing liquid crystal aligning film, polyamic acid, polyimide and diamine compound |
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| JP2003520878A (en) * | 2000-01-24 | 2003-07-08 | ロリク アーゲー | Photoactive polyimide, polyamic acid or ester having a photocrosslinkable group in the side chain |
| JP2008266421A (en) * | 2007-04-18 | 2008-11-06 | Jsr Corp | Liquid crystal aligning agent, liquid crystal display element, polymer therefor and raw material diamine |
| WO2009054545A1 (en) * | 2007-10-26 | 2009-04-30 | Jsr Corporation | Liquid crystal aligning agent, method for forming liquid crystal alignment film and liquid crystal display device |
| WO2009104468A1 (en) * | 2008-02-22 | 2009-08-27 | 株式会社Adeka | Liquid crystal composition containing polymerizable compound, and liquid crystal display element comprising the liquid crystal composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107003568A (en) * | 2014-09-18 | 2017-08-01 | 日产化学工业株式会社 | Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element |
| CN107003568B (en) * | 2014-09-18 | 2020-09-15 | 日产化学工业株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
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| KR20130041150A (en) | 2013-04-24 |
| KR101831008B1 (en) | 2018-02-21 |
| JPWO2012005266A1 (en) | 2013-09-05 |
| CN104774157A (en) | 2015-07-15 |
| WO2012005266A1 (en) | 2012-01-12 |
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