CN102203662A - Liquid crystal aligning agent - Google Patents

Liquid crystal aligning agent Download PDF

Info

Publication number
CN102203662A
CN102203662A CN2009801446214A CN200980144621A CN102203662A CN 102203662 A CN102203662 A CN 102203662A CN 2009801446214 A CN2009801446214 A CN 2009801446214A CN 200980144621 A CN200980144621 A CN 200980144621A CN 102203662 A CN102203662 A CN 102203662A
Authority
CN
China
Prior art keywords
liquid crystal
formula
aligning agent
add
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2009801446214A
Other languages
Chinese (zh)
Other versions
CN102203662B (en
Inventor
中原翔一
南悟志
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Priority to CN201310611123.4A priority Critical patent/CN103739523B/en
Priority to CN201510089713.4A priority patent/CN104761471B/en
Publication of CN102203662A publication Critical patent/CN102203662A/en
Application granted granted Critical
Publication of CN102203662B publication Critical patent/CN102203662B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/06—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
    • C07C275/10—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton being further substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/20—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
    • C07C275/24—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Provided is a liquid crystal aligning agent capable of forming a liquid crystal alignment film the surface of which is rarely scratched or abraded when rubbed, and which exhibits excellent liquid crystal aligning properties and enables the production of liquid crystal cells having high voltage holding ratios and low ion densities. The liquid crystal aligning agent contains either a polyimide precursor or a polyimide, said polyimide precursor and polyimide being substances obtained by reacting a diamine component with a tetracarboxylic acid derivative. The liquid crystal aligning agent is characterized in that the diamine component contains a diamine represented by formula (1) [wherein X is an oxygen atom or a sulfur atom; Y1 and Y2 are each independently a single bond, -O-, -S-, -OCO-, or -COO-; and R1 and R2 are each independently a C1-3 alkylene group].

Description

Aligning agent for liquid crystal
Technical field
The present invention relates to be used to make the aligning agent for liquid crystal of liquid crystal orientation film.Be particularly related to the aligning agent for liquid crystal that uses in the liquid crystal orientation film of making through the friction treatment operation.
Background technology
Liquid crystal orientation film is that the direction of orientation that is used to control liquid crystal molecule in liquid crystal display cells or the polarizer that uses polymerizable liquid crystal etc. makes its constant film.
As the method for making liquid crystal orientation film easily, polymeric membranes such as forming polyimide is arranged on substrate and implements nowadays still to be extensive use of at industrial circle with the rub method of so-called friction treatment on this surface of cloth.
The problem that friction treatment exists dust that the wearing and tearing by liquid crystal orientation film produce and the scar that results from liquid crystal orientation film that display quality is descended, so one of the desired characteristic of liquid crystal orientation film is exactly a rub resistance.
As the method that obtains to be difficult for producing the frictional dissipation and the liquid crystal orientation film of friction scar, known method (for example with reference to patent documentation 1,2) of in polyimide or polyimide precursor, adding various adjuvants.The good polyimide structures of wear-resisting wiping (for example with reference to patent documentation 3,4) has in addition also been proposed.
In recent years, in the part purposes of liquid crystal display cells, there is the trend of carrying out friction treatment by stronger friction.This is because by implementing strong friction treatment, can make the state of orientation of liquid crystal more even, and can obtain more strong product.Therefore, also more and more higher to the requirement of the wear-resisting wiping of liquid crystal orientation film.
Patent documentation 1: Japanese patent laid-open 7-120769 communique
Patent documentation 2: Japanese patent laid-open 9-146100 communique
Patent documentation 3: the Jap.P. spy opens the 2008-90297 communique
Patent documentation 4: Japanese patent laid-open 9-258229 communique
The announcement of invention
The aligning agent for liquid crystal that the purpose of this invention is to provide the good liquid crystal orientation film of the wear-resisting wiping that can obtain be difficult for to produce frictional dissipation and friction scar.
The inventor has carried out conscientiously research for achieving the above object, found that the novel liquid crystal aligning agent that can obtain the good liquid crystal orientation film of wear-resisting wiping, and the present invention is based on the invention of this discovery, has following technology contents.
1. aligning agent for liquid crystal, this treating agent comprise make two amine components and tetracarboxylic acid derivatives reaction and polyimide precursor or in the polyimide any, it is characterized in that described two amine components comprise the diamines of following formula (1) expression;
In the formula (1), X is oxygen atom or sulphur atom, Y 1And Y 2Respectively be independently singly-bound ,-O-,-S-,-OCO-or-COO-, R 1And R 2Be the alkylidene of carbon number 1～3 independently respectively.
2. the aligning agent for liquid crystal of record in above-mentioned 1, wherein, in the formula (1)-R 1-Y 1-and-R 2-Y 2-structure identical.
3. the aligning agent for liquid crystal of record in above-mentioned 1 or 2, wherein, the Y in the formula (1) 1And Y 2Be singly-bound.
4. the aligning agent for liquid crystal of each record in above-mentioned 1～3, wherein, the X in the formula (1) is an oxygen atom.
5. the aligning agent for liquid crystal of each record in above-mentioned 1～4, wherein, described tetracarboxylic acid derivatives is tetracarboxylic dianhydride, tetrabasic carboxylic acid list acid anhydride, tetrabasic carboxylic acid, dicarboxylic acid dialkyl esters or dicarboxylic acid acyl chlorides dialkyl.
6. the aligning agent for liquid crystal of each record in above-mentioned 1～5 wherein, also wraps fluorinated surfactant, silicone surfactant or nonionic surfactant.
7. the aligning agent for liquid crystal of each record in above-mentioned 1～6 wherein, also comprises compound that contains functional silanes or the compound that contains epoxy radicals.
8. the aligning agent for liquid crystal of each record in above-mentioned 1～7, wherein, the solid component concentration in the aligning agent for liquid crystal is 1～20 quality % with respect to aligning agent for liquid crystal total amount 100 quality %.
9. liquid crystal orientation film is characterized in that, is obtained by the aligning agent for liquid crystal of each record in above-mentioned 1～8.
10. liquid crystal display cells is characterized in that, has the liquid crystal orientation film of above-mentioned 9 records.
11. two aminophenyls or two amino-benzene oxygen ureine of following formula (1-7), formula (1-8), formula (1-b) or formula (1-c) expression;
Figure BPA00001368916700031
In the formula (1-b), R 12And R 22The alkylidene of the carbon number 1～3 that the expression carbon number differs from one another, in the formula (1-c), R 13And R 23Be the alkylidene of carbon number 1～3 independently respectively.
12. two aminophenyls or two amino-benzene oxygen ureine of following formula (1-9)～formula (1-11) expression.
Figure BPA00001368916700041
The aligning agent for liquid crystal of the application of the invention, the scar on the film surface in the time of can obtaining friction treatment and wearing and tearing less, the good liquid crystal orientation film of orientation of liquid crystal.In addition, in the liquid crystal orientation film that obtains with aligning agent for liquid crystal of the present invention, because the voltage retention height of liquid crystal structure cell, ion concentration is also low, so can make high-quality liquid crystal display cells.
The best mode that carries out an invention
＜specific diamine compound 〉
Aligning agent for liquid crystal of the present invention is characterised in that, comprises polyimide precursor or polyimide such as polyamic acid, poly amic acid ester, as two amine components of its synthesis material, uses the specific diamines of following formula (1) expression.
In the formula (1), X is oxygen atom or sulphur atom, Y 1And Y 2Respectively be independently singly-bound ,-O-,-S-,-OCO-or-COO-, R 1And R 2Be the alkylidene of carbon number 1～3 independently respectively.
In the formula (1), X is a urea groups during for oxygen atom, is ghiourea group (following (sulphur) urea groups that sometimes urea groups and ghiourea group is referred to as) during for sulphur atom.
Oxygen atom and sulphur atom are the high atom of electronegativity.In addition, there are two on the nitrogen-atoms and give the high hydrogen atom of electronics.Therefore, two hydrogen atoms in oxygen in (sulphur) urea groups or sulphur atom and other (sulphur) urea groups pass through non-covalent bond self aggregation comparatively securely.Among the present invention, the X preferred oxygen atom in the formula (1).Think that its reason is, if oxygen atom and sulphur atom are compared, then because be that oxygen atom is higher, so compare the easier self aggregation securely of urea structure with the thiocarbamide structure aspect electronegativity.
In the aligning agent for liquid crystal, in macromolecular chain, have (sulphur) urea groups among the present invention, should (sulphur) urea groups derive from the have following formula specific diamines of ad hoc structure of (1).Therefore, the electrostatic interaction by between (sulphur) urea groups that exists in the macromolecular chain with ad hoc structure can improve wear-resisting wiping.In this, the present invention and passing through of usually in the liquid crystal orientation film field, adopting to link the method that improves wear-resisting wiping with crosslinking chemical between with macromolecular chain different.
In the formula (1), R 1And R 2The alkylidene of representing carbon number 1～3 respectively independently, its structure can be any in the straight or branched.
As its object lesson, can exemplify methylene, ethylidene, 1,3-propylidene, 1-methyl ethylidene, 2-methyl ethylidene.Wherein,, preferably have the position and the sterically hindered little structure that rotate freely as much as possible from the orientation of liquid crystal and the angle of wear-resisting wiping, particularly, preferred methylene, ethylidene, 1,3-propylidene.
In the formula (1), Y 1And Y 2Respectively be independently singly-bound ,-O-,-S-,-OCO-or-COO-.About Y 1And Y 2Structure, from the orientation of liquid crystal and the angle of wear-resisting wiping, also preferred soft as far as possible and sterically hindered little structure, preferred singly-bound ,-O-or-S-.
Aspect forming the high film of film density, forming more firm liquid crystal orientation film, the structure between (sulphur) urea groups and the phenyl ring better is to be the center symmetry with (sulphur) urea groups, is more preferably-R 1-Y 1-and-R 2-Y 2-structure identical.
In the specific diamines of formula (1) expression, the compound of preferred following formula (1-a)～formula (1-c) expression.
In the formula (1-a), R 11And R 21Be the alkylidene of the equal carbon number 1～3 of carbon number.
Figure BPA00001368916700052
In the formula (1-b), R 12And R 22The alkylidene of the carbon number 1～3 that differs from one another for carbon number.
In the formula (1-c), R 13And R 23Be the alkylidene of carbon number 1～3 independently respectively.
In the formula (1), the binding site of the amino on the phenyl ring is not particularly limited, from the angle of the orientation of liquid crystal, and preferred 3-aminophenyl structure or 4-aminophenyl structure, special preferred 4-aminophenyl structure.Particularly, as the example of formula (1), any in preferred following formula (1-1), formula (1-2) or the formula (1-3), special preferred formula (1-1).
Figure BPA00001368916700062
In formula (1-1), formula (1-2) and the formula (1-3), Y 1, Y 2, R 1And R 2Definition identical with the definition in the formula (1).
Below, as the object lesson of formula (1), announcement formula (1-4)～formula (1-15).
Figure BPA00001368916700071
The compound of formula (1-7)～(1-11) is the new compound that is provided first by the present invention, and obviously, using the polyimide precursor of this compound or polyimide also is new compound.Formula (1-7)～(1-11) diamine compound in addition is a compound known, is new compound but use the polyimide precursor of these diamine compounds or polyimide.
The synthetic method of＜diamines 〉
The diamines of formula (1) expression for example can as described belowly synthesize.The diamine compound of formula of the present invention (1) expression is by aniline skeleton, interval base section (R 1, R 2), linking group (Y 1, Y 2) and (sulphur) urea groups formation, its synthetic method is not particularly limited, for example can be synthetic by method as described below.
Figure BPA00001368916700081
In the formula (1), X is oxygen atom or sulphur atom, Y 1And Y 2Respectively be independently singly-bound ,-O-,-S-,-OCO-or-COO-, R 1And R 2Be the alkylidene of carbon number 1～3 independently respectively.In addition, the binding site of the amino on the phenyl ring is not particularly limited.
Figure BPA00001368916700082
The diamine compound of formula of the present invention (1) expression can obtain by the following method: and the dinitro compound that synthetic corresponding formula (2) is represented (in the following formula (2), R 1, R 2, Y 1, Y 2And identical in the definition of X and the formula (1)), then nitroreduction is converted into amino.The method of reduction dinitro compound is not particularly limited, and use palladium-carbon, platinum oxide, Raney nickel, iron, tin chloride, platinum black, rhodium-aluminium oxide or platinum sulfide carbon etc. is arranged usually as catalyzer, at ethyl acetate, toluene, tetrahydrofuran, two
Figure BPA00001368916700083
Alkane, alcohol are in the equal solvent, the method for reducing by the reaction of using hydrogen, hydrazine, hydrogen chloride or ammonium chloride etc.
The synthetic method of the dinitro compound of formula (2) expression is not particularly limited, can be synthetic by any means, and as its object lesson, for example can be synthetic by the method shown in the following reacting flow chart (3).
Figure BPA00001368916700084
In the reacting flow chart (3), the dinitro compound of formula (2) expression can by make nitrobenzene compound (α), (α ') and (sulfo-) carbonyls (general designation of carbonyls and thiocarbonyl compound) (β) in organic solvent in the presence of alkali reaction come synthetic.
Above-mentioned nitrobenzene compound (α), (α ') in, R 1, R 2, Y 1And Y 2Cotype (1) is with NH 2The amino of expression can form hydrochloride (NH 2Salt such as HCl).As its object lesson, can exemplify nitro-benzylamine or its hydrochloride, 2-(nitrobenzophenone) ethamine or its hydrochloride, 3-(nitrobenzophenone) propylamine or its hydrochloride etc.In addition, the position of substitution of the nitro on the phenyl ring can suitably select to obtain the position of substitution of targeted diamine compound.Also have, the compound shown in is an example here, is not particularly limited.
In (sulfo-) carbonyls (β), X cotype (1), Z are 1～divalent organic group.As (sulfo-) carbonyls (β), can exemplify for example phosgene, thiophosgene, diphenyl carbonate, thiocarbonic acid diphenyl ester, two (nitrobenzophenone) esters of carbonic acid, two (nitrobenzophenone) esters of thiocarbonic acid, dimethyl carbonate, thiocarbonic acid dimethyl ester, diethyl carbonate, thiocarbonic acid diethylester, ethylene carbonate, thiocarbonic acid ethyl, 1,1 '-carbonyl is two-1H-imidazoles, 1, and 1 '-thiocarbonyl is two-the 1H-imidazoles etc.In addition, also can use oxycarbide (carbon monoxide or carbon dioxide) to replace carbonyls (β).Also have, the compound shown in is an example here, is not particularly limited.
In the above-mentioned reacting flow chart (3), is centrosymmetric compound for obtaining structure with (sulphur) urea groups, can adopt identical nitrobenzene compound (α) and (α '), for obtaining asymmetrical compound, can after making nitrobenzene compound (α) and (sulfo-) carbonyls (β), add the nitrobenzene compound different (α ') again with nitrobenzene compound (α) structure with reaction with same mole.
As alkali, can exemplify for example triethylamine, diisopropylethylamine, DMAP alkaline organic compounds such as (4-N, N-dimethyl aminopyridines), inorganic alkali compounds such as NaOH, sal tartari, metal hydrides such as sodium hydride etc.Also have, the compound shown in is an example here, is not particularly limited.
As organic solvent, can use not the solvent that can impact reaction separately, aromatic series kind solvents such as toluene, dimethylbenzene are particularly arranged, aliphatic hydrocarbon such as hexane, heptane kind solvent, methylene chloride, 1, halogen solvents such as 2-ethylene dichloride, tetrahydrofuran, 1,4-two
Figure BPA00001368916700091
Ether solvents such as alkane, N, non-proton property polar solvents such as dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide perhaps also can use multiple above-mentioned solvent.Their consumption is an any amount.
He Cheng diamines also can be used as the raw material of polyamide or polyureas except the raw material that can be used as polyimide precursors such as polyamic acid described later, poly amic acid ester or polyimide as mentioned above, and these polymkeric substance can be used as various electronic material starting material.
＜polyimide precursor or polyimide 〉
The polyimide precursor that aligning agent for liquid crystal of the present invention comprised can obtain as two amine components that must composition and the reaction of tetracarboxylic acid derivatives by comprising above-mentioned specific diamines.
Two amine components that are used to obtain polyimide precursor both can also can and be used with other diamines only for the specific diamines of formula (1) expression.
With other diamines and time spent, the ratio of the specific diamines of formula (1) expression can be to be worth arbitrarily, in order to obtain enough wear-resisting wipings, in whole two amine components (100 moles of %), preferred 10 moles more than the % of this ratio is preferably 30 moles more than the %, more preferably 50 moles more than the %.On the other hand, from the optimization of tilt angle with accumulate the angle of the minimizing etc. of electric charge, in whole two amine components, preferred 90 moles below the % of specific diamines components in proportions.
Be not particularly limited available following formula (4) expression with the specific diamines of formula (1) expression and the diamines of usefulness.
In the following formula (4), R 5Expression divalent organic group, R 3And R 4The organic group of representing hydrogen atom or 1 valency respectively independently.
As R 5Object lesson, can exemplify following divalent organic group.
Figure BPA00001368916700102
Figure BPA00001368916700111
Figure BPA00001368916700121
Figure BPA00001368916700131
Figure BPA00001368916700141
Figure BPA00001368916700151
Figure BPA00001368916700171
Two Q in formula [B-112] and the formula [B-113] respectively independently expression-COO-,-OCO-,-CONH-,-NHCO-,-CH 2-,-O-,-CO-or-among the NH-any.
In the following formula (4), R 5Part or all when being formula [B-80]～formula [B-101] etc., can increase the tilt angle of liquid crystal.
When making liquid crystal vertical-tropism, better be and with the diamines that satisfies following condition: and the following formula (4) of usefulness in R 5Has any one structure in formula [B-80]～formula [B-101].The content of this diamines when using such diamines is preferably 5～90 moles of % in whole diamines, more preferably 10～80 moles of %.On the other hand, when tilt angle is reduced, better be and with the diamines that satisfies following condition: the R in the following formula (4) 5Has any one structure in formula [B-1]～formula [B-79] and [the B-102]～formula [B-118].In addition, better be R in the formula (4) 3And R 4In at least one side be 1 valency organic group, be more preferably methyl.
With specific two amine components of formula (1) expression or comprise the tetracarboxylic acid derivatives that specific two amine components of formula (1) expression of the diamines of following formula (4) expression react and be not particularly limited.Tetracarboxylic acid derivatives of the present invention can exemplify tetracarboxylic dianhydride, tetrabasic carboxylic acid list acid anhydride, tetrabasic carboxylic acid, dicarboxylic acid dialkyl esters (with following formula (5-d) expression), dicarboxylic acid acyl chlorides dialkyl (with following formula (5-e) expression) etc., so long as can get final product, be not limited to this with the compound that diamines reacts.
Tetracarboxylic acid derivatives is with following formula (5-a)～(5-e) expression, R 7The expression alkyl.As R 6Object lesson, can exemplify following [A-1]～[A-47].
Figure BPA00001368916700181
Wherein, R 6For formula [A-6], formula [A-16], formula [A-18]～formula [A-22], formula [A-25], formula [A-37] and formula [A-38] even the high polyimide of tetracarboxylic acid derivatives imidizate rate, the dissolubility in organic solvent is also high, so preferred.In addition, 10 moles of % of used tetracarboxylic acid derivatives are above, to be preferably 20 moles be to have the such alicyclic structure of formula [A-1]～formula [A-25] or the R of aliphatic structure more than the % 6The time, voltage retention improves, and is therefore preferred.Use R 6When being selected from the tetracarboxylic acid derivatives of formula [A-1], formula [A-16] and formula [A-19] in these alicyclic structures or the aliphatic structure, the relaxation that can obtain electric charge is liquid crystal orientation film faster.
On the other hand,, then can improve liquid crystal aligning, and can reduce and accumulate electric charge if 10 moles of % of the total amount of used tetracarboxylic acid derivatives are above, to be preferably 20 moles be aromatic tetracarboxylic acid's derivant more than the %, therefore preferred.
Obtain the method for polyimide precursor or polyimide as making above-mentioned two amine components (below abbreviate diamines as) and tetracarboxylic acid derivatives composition (below abbreviate tetracarboxylic acid derivatives as) reaction, can obtain by known method.Below, describe as example with the situation of using the tetracarboxylic dianhydride.
The tetracarboxylic acid derivatives that uses in the manufacturing of aligning agent for liquid crystal of the present invention and the polymerisation process of diamines are not particularly limited.Generally can be by in organic solvent, mixing and carrying out polyreaction and make polyamic acid.In addition, by make the hydroxy-acid group esterification of polyamic acid with known esterifying agent, can obtain poly amic acid ester.By making thus obtained polyamic acid and poly amic acid ester cyclodehydration, can be made into polyimide.
The method that tetracarboxylic acid derivatives and two amine components are mixed in organic solvent can exemplify and stir the solution that makes diamines be dispersed or dissolved in organic solvent and get, and directly adds the tetracarboxylic acid derivatives composition therein or makes the tetracarboxylic acid derivatives composition be dispersed or dissolved in the method for adding again behind the organic solvent; Add the method for diamines in the solution that gets in that tetracarboxylic acid derivatives is dispersed or dissolved in organic solvent; Alternately add the method for tetracarboxylic acid derivatives and diamines etc.In addition, when at least one side in tetracarboxylic acid derivatives composition and the diamines was made up of multiple compound, the state that can in advance these multiple compositions be mixed carried out polyreaction, also can carry out polyreaction respectively successively.
Temperature when tetracarboxylic acid derivatives and diamines carry out polyreaction in organic solvent is generally 0～150 ℃, is preferably 5～100 ℃, more preferably 10～80 ℃.The high more polyreaction of temperature is finished more soon, if but too high then can't obtain high molecular weight polymers sometimes.In addition, polyreaction can be carried out with blanking concentration arbitrarily, if but blanking concentration is low excessively, then be difficult to obtain high molecular weight polymers, if blanking excessive concentration then the viscosity of reactant liquor is too high is difficult to stir uniformly, therefore better be 1～50 quality %, be more preferably 5～30 quality %.Can carry out at the polyreaction initial stage, and then append organic solvent with high concentration.Here said blanking concentration is meant the concentration of the gross mass of tetracarboxylic dianhydride's composition and two amine components.
Used organic solvent is not particularly limited as long as can dissolve polyamic acid and the poly amic acid ester (the following polyamic acid (ester) that is called sometimes) that is generated when carrying out above-mentioned reaction.As object lesson, can exemplify N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton etc.These solvents can be used alone, but also also mix together.Also have, even the insoluble solvent of separating polyamic acid (ester), so long as in the scope that the polyamic acid (ester) that generates can not be separated out, also can use with above-mentioned solvent.
In addition, the moisture in the organic solvent hinders polyreaction, and can make polyamic acid (ester) hydrolysis of generation, so organic solvent preferably uses the organic solvent through farthest dehydrating.
The ratio that is used to obtain used tetracarboxylic acid derivatives of the polyreaction of polyamic acid and diamines with molar ratio computing be preferably 1: 0.8～1: 1.2, this mol ratio molecular weight near 1: 1 resulting polyamic acid more is big more.If the molecular weight of polyamic acid (ester) is too small, the intensity of filming that then obtains thus may be not enough, on the contrary, if the molecular weight of polyamic acid (ester) is excessive, the viscosity of the aligning agent for liquid crystal that then makes thus may be too high, film operability when forming and the lack of homogeneity of filming.Therefore, the weight-average molecular weight of used polyamic acid (ester) is preferably 2000～500000 in the aligning agent for liquid crystal of the present invention, and more preferably 5000～300000.
Among the present invention, use tetracarboxylic acid derivatives and diamines for obtaining polyamic acid, as diamines, the diamines that the specific diamines of use following formula (1) expression and the following formula (4) that uses are as required represented.During the diamines of use formula (4) expression, in the preferred tetracarboxylic acid derivatives that uses, the R in following formula (5-a)～formula (5-e) 6Be formula [A-1], formula [A-2], formula [A-16], formula [A-18], formula [A-19], formula [A-25], formula [A-26], formula [A-27], formula [A-32], formula [A-35], formula [A-38] or formula [A-47], as with the diamines of the following formula (4) of specific diamines and usefulness, the preferred R that uses wherein 5Be formula [B-6], formula [B-7], formula [B-8], formula [B-16], formula [B-17], formula [B-20], formula [B-21], formula [B-29], formula [B-30], formula [B-32], formula [B-33], formula [B-40], formula [B-44], formula [B-45], formula [B-48], formula [B-56], formula [B-57], formula [B-58], formula [B-61], formula [B-62], formula [B-63], formula [B-76], formula [B-80], formula [B-82], formula [B-83], formula [B-84], formula [B-85], formula [B-86], formula [B-87], formula [B-93], formula [B-104], formula [B-114], the diamines of formula [B-115] or formula [B-118].Wherein, as tetracarboxylic acid derivatives, the R in the following formula (5-a) 6Preferred formula [A-1], formula [A-2], formula [A-16], formula [A-18], formula [A-19], formula [A-25], formula [A-26], formula [A-27] or formula [A-32], as the diamines of formula (4), R wherein 5Preferred formula [B-7], formula [B-8], formula [B-17], formula [B-20], formula [B-21], formula [B-29], formula [B-30], formula [B-32], formula [B-61], formula [B-76], formula [B-80], formula [B-82], formula [B-83], formula [B-84], formula [B-85], formula [B-104], formula [B-114], formula [B-115] or formula [B-118].
The polyamic acid that obtains as mentioned above can represent that also poly amic acid ester also can be represented with following formula (7) with the repetitive of following formula (6).
In following formula (6), (7), R a, R b, R cFor deriving from the group of diamines of following formula (1) or formula (4) expression, during the diamines of use formula (1) expression, R aAnd R bBe hydrogen, R cFor-phenylene-Y 1-NH-CX-HN-R 2-Y 2-phenylene-, during the diamines of use formula (4) expression, R aBe R 3, R bBe R 4, R cBe R 5R 6With the R in the tetracarboxylic acid derivatives of following formula (5-a)～(5-e) expression 6Implication identical.R in the formula (7) is the group that derives from employed esterifying agent.
Polyamic acid that obtains as mentioned above or poly amic acid ester both can be directly used in aligning agent for liquid crystal of the present invention, also can make its cyclodehydration and used after becoming polyimide.But, according to the difference of the structure of polyamic acid (ester), become insolublely because of imidization reaction sometimes, be difficult to use in aligning agent for liquid crystal.At this moment, can not make the whole imidizates of amic acid (ester) base in the polyamic acid (ester), but in the scope that can keep appropriate solubility, carry out imidizate.
The imidization reaction that makes polyamic acid (ester) cyclodehydration is normally directly to the hot-imide of the solution heating of polyamic acid or add the chemical imidizate of catalyzer in the solution of polyamic acid (ester), the chemical imidizate that carries out imidization reaction under lower temperature is difficult for taking place the molecular weight reduction of gained polyimide, and is therefore preferred.
The chemistry imidizate can be undertaken by stir polyamic acid (ester) in the presence of base catalyst and acid anhydrides in organic solvent.The temperature of reaction of this moment is-20～250 ℃, is preferably 0～180 ℃, and the reaction time can carry out 1～100 hour.The amount of base catalyst is 0.5～30 mole a times of polyamic acid (ester), better is 2～20 moles times, and the amount of acid anhydrides is 1～50 mole a times of polyamic acid (ester), better is 3～30 moles times.If the amount of base catalyst and acid anhydrides is less, then reaction can't fully be carried out, if too much, then reaction is difficult to remove fully after finishing.
The used base catalyst of imidizate can exemplify pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc.Wherein preferred pyridine is because it has the suitable alkalescence that the reaction of making is carried out.
In addition,, can exemplify acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc., wherein, be easy to react the purifying after the end when using acetic anhydride as acid anhydrides, therefore preferred.Used solvent when organic solvent can use above-mentioned polyamic acid polyreaction.Imidizate rate based on chemical imidizate can be controlled by regulating catalytic amount and temperature of reaction, reaction time.
In the polyimide solution that obtains as mentioned above, because the catalyzer that adds remains in the solution, therefore in order to be used for aligning agent for liquid crystal of the present invention, better be that this polyimide solution is put in the Weak solvent in the stirring, the polyimide precipitation is reclaimed the back use.Used Weak solvent was not particularly limited during the precipitation of polyimide reclaimed, and can exemplify methyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene etc.Can filter, clean and reclaim the back and under normal pressure or reduced pressure, carry out normal temperature or heat drying by putting into the polyimide that precipitates in the Weak solvent, thereby make powder.If again with this powder dissolution in good solvent and repeat the operation of 2～10 reprecipitations, but also purifying polyimide then.In the time of can't thoroughly removing impurity by the primary sedimentation reclaimer operation, better be to carry out this purification procedures repeatedly.Weak solvent when carrying out purification procedures repeatedly is because purification efficiency further improves, so better be that for example Weak solvent more than 3 kinds such as alcohols, ketone, hydro carbons is mixed or uses successively.
In addition, polyamic acid (ester) also can precipitate by same operation and reclaim and purifying.When not wanting to make the used solvent of the polymerization that contains polyamic acid in the aligning agent for liquid crystal, when perhaps wanting to remove unreacted monomer component in the reaction solution and impurity, can carry out this precipitation and reclaim and purifying.
The imidizate rate of the polyimide that aligning agent for liquid crystal of the present invention comprised is not particularly limited.The dissolubility that can consider polyimide is set at arbitrary value.The molecular weight of the polyimide that aligning agent for liquid crystal of the present invention comprised is not particularly limited, if but the molecular weight of polyimide is too small, then the gained intensity of filming may be not enough, on the contrary, if the molecular weight of polyimide is excessive, the viscosity of the aligning agent for liquid crystal that then makes may be too high, film operability when forming and the lack of homogeneity of filming.Therefore, the weight-average molecular weight of used polyimide is preferably 2000～500000 in the aligning agent for liquid crystal of the present invention, and more preferably 5000～300000.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention comprises the polyimide precursor that obtains as mentioned above or in the polyimide any, makes these polymer dissolution make coating fluid in organic solvent usually.The polymkeric substance that aligning agent for liquid crystal of the present invention comprised also can comprise the polymkeric substance with other structure except described polyimide precursor or polyimide.The organic solvent that aligning agent for liquid crystal of the present invention comprised is not particularly limited as long as can dissolve the polymkeric substance that is comprised.
Object lesson as organic solvent, can exemplify N, dinethylformamide, N, N-dimethyl acetamide, N-N-methyl-2-2-pyrrolidone N-, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrolidone, N-vinyl pyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton, 1,3-dimethyl-imidazolinone etc.These can use to mix more than a kind or 2 kinds and use.
In addition, even solvent that can't dissolve polymer when using separately as long as in the scope that polymkeric substance can not be separated out, then can mix with aligning agent for liquid crystal of the present invention.Particularly known to mixing ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, the ethyl carbitol acetic acid esters, ethylene glycol, 1-methoxyl-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, propylene-glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, propylene glycol-1-monoethyl ether-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, and the film uniformity that is coated with on the substrate improves.Therefore, these solvents can one or more mix use.
The also preferred solvent with low surface tension that uses in the aligning agent for liquid crystal of the present invention, its consumption better is 5～80 quality % of whole solvents that aligning agent for liquid crystal comprised, and is more preferably 20～60 quality %.
In the aligning agent for liquid crystal of the present invention, except that above-mentioned polymkeric substance and organic solvent, also can comprise various adjuvants.
As the homogeneity that improves thickness or the adjuvant of surface smoothing, can exemplify fluorine class surfactant, silicone surfactant, nonionic surfactant etc.
More specifically, for example can exemplify エ Off ト Star プ EF301, EF303, EF352 (illuminating product Co., Ltd. (ト one ケ system プ ロ ダ Network Star society) system), メ ガ Off ア Star Network F171, F173, R-30 (big Japanese ink Co., Ltd. (big Japanese イ Application キ society) system), Off ロ ラ one De FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo ス リ one エ system society) system), ア サ ヒ ガ one De AG710, サ one Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd (Asahi Glass society) system) etc.The usage ratio of these surfactants better is 0.01～2 mass parts with respect to component of polymer 100 mass parts that comprise in the aligning agent for liquid crystal, is more preferably 0.01～1 mass parts.
Adjuvant as the adaptation that improves liquid crystal orientation film and substrate can exemplify the compound that contains functional silanes, the compound that contains epoxy radicals etc.
For example, can exemplify the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 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-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three 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-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, two (the oxyethylene group)-3-TSL 8330s of N-, two (the oxyethylene group)-3-aminopropyltriethoxywerene werene of N-, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 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, 1, two (the N of 3-, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N ' ,-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.
When adding these compounds, with respect to component of polymer 100 mass parts that comprise in the aligning agent for liquid crystal, its content better is 0.1～30 mass parts, is more preferably 1～20 mass parts.If less than 0.1 mass parts then can't be expected the effect that adaptation improves, if more than 30 mass parts, the orientation variation of liquid crystal sometimes then.
In the aligning agent for liquid crystal of the present invention, except above-mentioned, in the scope of not damaging effect of the present invention, can add with electrical characteristics such as the specific inductive capacity that changes liquid crystal orientation film or electric conductivity is the dielectric or the conductive materials of purpose, can also add with hardness that improves the film when forming liquid crystal orientation film or the cross-linked compound that density is purpose etc.
The concentration of the solid constituent in the aligning agent for liquid crystal of the present invention can be according to the target film thickness appropriate change of liquid crystal orientation film, owing to can form flawless filming, and can obtain the suitable thickness as liquid crystal orientation film, better be 1～20 quality % therefore, is more preferably 2～10 quality %.
Aligning agent for liquid crystal of the present invention is being coated on the substrate and after burning till, can carried out orientation process such as friction treatment or rayed, perhaps in vertical orientated purposes etc. without orientation process and as liquid crystal orientation film.At this moment, used substrate is not so long as the high substrate of the transparency then has special qualification, can use plastic bases such as glass substrate and acrylic acid substrate, polycarbonate substrate etc., from the angle that production technology is simplified, the preferred substrate that is formed with the ITO electrode that is used for liquid crystal drive etc. that uses.In addition, in the reflection type liquid crystal display element, can use opaque materials such as silicon wafer, but only limit to one-sided substrate, the electrode of this moment also can use reflectorized materials such as aluminium.
The coating process of aligning agent for liquid crystal is not particularly limited, and industrial circle adopts the method that is coated with by serigraphy, hectographic printing, aniline printing, ink-jet etc. usually.As other coating process, also have dip coating, rolling method, slot coated, spin-coating method etc., can use these methods according to purpose.
The burning till of substrate that has been coated with aligning agent for liquid crystal can be carried out under the arbitrary temp of 100～350 ℃ of temperature, and preferred temperature is 150～300 ℃, and preferred temperature is 180～250 ℃.When comprising polyamic acid or poly amic acid ester in the aligning agent for liquid crystal, the conversion ratio that transforms to acid imide changes with this firing temperature, but aligning agent for liquid crystal of the present invention need not 100% imidizate.Therefore, firing time can be set at random time, if but firing time is too short, then show badly because of the influence of remaining solvent sometimes, and better be 5～60 minutes therefore, be more preferably 10～40 minutes.
When the thickness of filming after burning till is blocked up, unfavorable at the consumption concerned power of liquid crystal display cells, cross when approaching, the reliability of liquid crystal display cells reduces sometimes, better is 5～300nm therefore, is more preferably 10～100nm.When making liquid crystal horizontal alignment or tilted alignment, filming after burning till handled by friction or polarisation ultraviolet ray irradiation etc.
Liquid crystal display cells of the present invention is after obtaining the substrate of band liquid crystal orientation film by said method by aligning agent for liquid crystal of the present invention, to make the liquid crystal display cells that the liquid crystal structure cell forms by known method.
If exemplify an example of making the liquid crystal structure cell, 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 and sealing is injected in decompression; Or on being scattered with the liquid crystal aligning face of sept, drip after the liquid crystal method that baseplate-laminating is sealed etc.The thickness of the sept of this moment better is 1～30 μ m, is 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 giant-screen and high-resolution etc.
Embodiment
The present invention will be described in more detail below to exemplify embodiment, but the present invention is not limited by this.
Abbreviation used in following embodiment and the comparative example is as described below.
BABU:1, two (4-aminobenzyl) ureas of 3-
BAPU:1, two (the 4-aminobenzene ethyl) ureas of 3-
DA-3:1, two (3-aminobenzyl) ureas of 3-
DA-4:1-(4-aminobenzyl)-3-(4-aminobenzene ethyl) urea
DA-5:1, two (2-(4-amino-benzene oxygen) ethyl) ureas of 3-
DA-6:1, two (3-(4-amino-benzene oxygen) propyl group) ureas of 3-
DA-7:1,5 '-two (4-amino-benzene oxygen) pentane
CBDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
PMDA: pyromellitic acid anhydride
BODA: dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride.
CA-4:1,3-dicarbapentaborane methoxyl-2, two (chloroformyl base) cyclo-butane of 4-
CA-5:2,5-dicarbapentaborane methoxyl terephthalic acid (TPA) diacid chloride
P-PDA: p-phenylenediamine (PPD)
In the synthesis example, 1H-NMR is meant the nuclear magnetic resoance spectrum of hydrogen atom in the molecule.
[synthesis example 1]
1, two (the 4-aminobenzene ethyl) ureas [BAPU] of 3-synthetic
Figure BPA00001368916700281
In the four-hole boiling flask of nitrogen replacement, adding 2-(4-nitrobenzophenone) ethylamine hydrochloride [C] (52.50g, 259mmol), two (4-nitrobenzophenone) esters [D] (37.53g, 123mmol) of carbonic acid and THF (tetrahydrofuran) (1877g) under the room temperature, add triethylamine (74.90g, 740mmol) and 4-N therein, N-dimethyl aminopyridine (3.01g, 24.7mmol) stirs with mechanical stirrer.Follow the tracks of reaction by HPLC (high performance liquid chromatography), reaction joins reaction solution in the pure water (9L) after finishing, and carries out 30 minutes stirring.Filter then, clean, obtain the crude product of white solid with pure water (1L).After this gained white solid disperse cleaned with ultrasonic unit in methyl alcohol (488g), filter, drying, obtain the dinitro compound [E] (must measure 42.3g, yield 96%) of white solid.
1H-NMR(400MHz，DMSO-d6，δppm)：8.11-8.08(4H，m)，7.43-7.40(4H，m)，5.89(2H，t)，3.24-3.19(4H，q)，2.76(4H，t).
(4.23g) with 1,4-two with compound [E] (42.32g, 118mmol), 5% palladium carbon (5%Pd/C)
Figure BPA00001368916700282
The potpourri of alkane (2031g) with nitrogen replacement after, replace again with hydrogen, in the presence of hydrogen, under room temperature, stir.Follow the tracks of reaction by HPLC, after reaction finishes, with zeyssatite (Celite) filtering catalyst.Under reduced pressure steam the solvent that removes filtrate then, obtain the crude product of white solid.In the gained crude product, add 2-propyl alcohol (85g), after disperseing to clean with ultrasonic unit, filter, drying, obtain the diamino compounds [BAPU] (must measure 31.9g, yield 91%) of white solid.
1H-NMR(400MHz，DMSO-d6，δppm)：6.85-6.82(4H，m)，6.51-6.48(4H，m)，5.78(2H，t)，4.83(4H，s)，3.14-3.09(4H，m)，2.50-2.45(4H，m).
[synthesis example 2]
1, two (4-aminobenzyl) ureas [BABU] of 3-synthetic
Figure BPA00001368916700291
In the four-hole boiling flask of nitrogen replacement, adding 4-nitro benzyl amine hydrochlorate [F] (25.00g, 133mmol), two (4-nitrobenzophenone) esters [D] (19.20g, 63.1mmol) of carbonic acid and THF (750g) under the room temperature, add triethylamine (38.32g, 379mmol) and 4-N therein, N-dimethyl aminopyridine (1.54g, 12.6mmol) stirs with mechanical stirrer.Follow the tracks of reaction by HPLC, reaction joins reaction solution in the pure water (4.5L) after finishing, and carries out 30 minutes stirring.Filter then, clean, obtain the crude product of ivory buff solid shape with pure water (500mL).After this gained ivory buff solid disperse cleaned with ultrasonic unit in methyl alcohol (300g), filter, drying, obtain the dinitro compound [G] (must measure 19.01g, yield 91%) of ivory buff solid shape.
1H-NMR(400MHz，DMSO-d6，δppm)：8.22-8.19(4H，m)，7.53-7.50(4H，m)，6.82(2H，t)，4.36(4H，d).
(1.60g) with 1,4-two with compound [G] (16.00g, 48.4mmol), 5% palladium carbon (5%Pd/C)
Figure BPA00001368916700292
The potpourri of alkane (800g) with nitrogen replacement after, replace again with hydrogen, in the presence of hydrogen, under room temperature, stir.Follow the tracks of reaction by HPLC, reaction is used the diatomite filtration catalyzer after finishing.Under reduced pressure steam the solvent that removes filtrate then, obtain the crude product of white solid.In the gained crude product, add 2-propyl alcohol (128g), after disperseing to clean with ultrasonic unit, filter, drying, obtain the diamino compounds [BABU] (must measure 12.19g, yield 93%) of white-yellowish solid shape.
1H-NMR(400MHz，DMSO-d6，δppm)：6.92-6.88(4H，m)，6.51-6.48(4H，m)，6.03(2H，t)，4.91(4H，s)，4.02(4H，d).
[synthesis example 3]
1, two (3-aminobenzyl) ureas [DA-3] of 3-synthetic
Figure BPA00001368916700301
In the four-hole boiling flask of nitrogen replacement, adding 3-nitro benzyl amine hydrochlorate [H] (10.00g, 53.0mmol), two (4-nitrobenzophenone) esters [D] (7.68g, 25.3mmol) of carbonic acid and THF (384g) under the room temperature, add triethylamine (15.33g, 152mmol) and 4-N therein, N-dimethyl aminopyridine (0.62g, 5.05mmol) stirs.Follow the tracks of reaction by HPLC, reaction joins reaction solution in the pure water (2.3L) after finishing, and carries out 30 minutes stirring.Filter then, clean, obtain the crude product of tea white solid with pure water (500mL).After this gained white solid disperse cleaned with ultrasonic unit in 2-propyl alcohol (50g), filter, drying, obtain the dinitro compound [I] (must measure 7.04g, yield 84%) of white solid.
1H-NMR(400MHz，DMSO-d6，δppm)：8.06-8.05(4H，m)，7.68(2H，d)，7.56-7.55(2H，m)，6.84(2H，t)，4.32(4H，d).
(0.7g) with 1,4-two with compound [I] (7.04g, 21.3mmol), 5% palladium carbon (5%Pd/C)
Figure BPA00001368916700302
The potpourri of alkane (350g) with nitrogen replacement after, replace again with hydrogen, in the presence of hydrogen, under room temperature, stir.Follow the tracks of reaction by HPLC, reaction is used the diatomite filtration catalyzer after finishing.Under reduced pressure filtrate is carried out the solvent steaming then and remove, obtain the crude product of tea white solid.In the gained crude product, add 2-propyl alcohol (60g), after disperseing to clean with ultrasonic unit, filter, drying, obtain the diamino compounds [DA-3] (must measure 4.04g, yield 81%) of tea white solid.
1H-NMR(400MHz，DMSO-d6，δppm)：6.93(2H，t)，6.46-6.45(2H，m)，6.42-6.34(4H，m)，6.20(2H，t)，5.01(4H，s)，4.07(4H，d).
[synthesis example 4]
Synthesizing of 1-(4-aminobenzyl)-3-(4-aminobenzene ethyl) urea [DA-4]
Figure BPA00001368916700311
In the four-hole boiling flask of nitrogen replacement, adding 4-nitro benzyl amine hydrochlorate [F] (50.00g, 265mmol), pyridine (20.97g, 265mmol) and methylene chloride (750g), solution is cooled to below 10 degree under the room temperature.After adding methylene chloride (150g) solution of chloro-carbonic acid 4-nitro phenyl ester [J] (53.43g, 265mmol) therein, temperature of reaction is risen to 23 ℃, stir and carry out reflux after 1 hour.After reaction finishes, reaction solution is cooled to room temperature, adds methylene chloride (500g) and be diluted to the aqueous hydrochloric acid solution (1000g) of 10 quality %, filter.Stir filtrate under the room temperature, with the solid filtering of separating out.(200g) cleans this solid with methyl alcohol, and drying obtains the compound [K] (must measure 33.26g, yield 40%) of white solid.On the other hand, in filtrate, add after saturated sodium bicarbonate aqueous solution (500g) cleans, use saturated aqueous common salt (500g) to clean organic layer again, use dried over mgso.Filter then, steaming desolventizes, and obtains the crude product of white.With this crude product methyl alcohol (200g) recrystallization, obtain the compound [K] (must measure 16.6g, yield 20%) of white solid.
1H-NMR(400MHz，CDCl 3，δppm)：8.8.28-8.24(4H，m)，7.55-7.53(2H，m)，7.37-7.34(2H，m)，5.64(1H，t)，4.59(2H，d).
In the four-hole boiling flask of nitrogen replacement, adding 2-(4-nitrobenzophenone) ethylamine hydrochloride [C] (30.29g, 150mmol), compound [K] (45.18g, 142mmol) and THF (2260g) under the room temperature, add triethylamine (43.23g, 427mmol) and 4-N therein, N-dimethyl aminopyridine (1.74g, 14.2mmol) reacts.Follow the tracks of reaction by HPLC, reaction joins reaction solution in the pure water (10L) after finishing, and carries out 30 minutes stirring.Filter then, clean, obtain the crude product of white solid with pure water (2L).After this gained white solid cleaned with 2-propyl alcohol (300g), filter, drying, obtain the dinitro compound [L] (must measure 43.9g, yield 90%) of white solid.
1H-NMR(400MHz，DMSO-d6，δppm)：8.19-8.14(4H，m)，7.52-7.44(4H，m)，6.62(1H，t)，6.12(1H，t)，4.31(2H，d)，3.33(2H，m)，2.86(2H，t).
(5.0g) with 1,4-two with compound [L] (50.00g, 145mmol), 5% palladium carbon (5%Pd/C)
Figure BPA00001368916700321
The potpourri of alkane (1000g) with nitrogen replacement after, replace again with hydrogen, in the presence of hydrogen, under room temperature, stir.Follow the tracks of reaction by HPLC, reaction is used the diatomite filtration catalyzer after finishing.Under reduced pressure filtrate is carried out the solvent steaming then and remove, obtain the crude product of tea white solid.In this crude product, add 2-propyl alcohol (330g), after disperseing to clean with ultrasonic unit, filter, drying, obtain the diamino compounds [DA-4] (must measure 37.0g, yield 90%) of peach white solid.
1H-NMR(400MHz，DMSO-d6，δppm)：6.90-6.87(2H，m)，6.84-6.82(2H，m)，6.51-6.47(4H，m)，6.08(1H，t)，5.73(1H，t)，4.9(2H，s)，4.84(2H，s)，3.99(2H，d)，3.15-3.10(2H，m)，2.51-2.46(2H，m).
[synthesis example 5]
1, two (2-(4-amino-benzene oxygen) ethyl) ureas [DA-5] of 3-synthetic
Synthesizing of the compound [P] of employing reaction process A
Add 4-nitrophenol (27.69g, 199mmol), sal tartari (55.01g, 398mmol) and N under room temperature, nitrogen atmosphere in four-hole boiling flask, dinethylformamide (following note is made DMF) (140g) is heated to 65 ℃.Drip DMF (140g) solution of N-(2-bromoethyl) phthalimide (50.57g, 199mmol) therein.Reaction joins reaction solution in the frozen water (2240g) after finishing, and obtains yellow solid.After its filtration, washing, make white-yellowish solid by drying, obtain compound [O] (must measure 44.2g, yield 71%).
1H-NMR(400MHz，CDCl 3，δppm)：8.19-8.16(2H，m)，7.90-7.87(2H，m)，7.77-7.74(2H，m)，6.96-6.94(2H，m)，4.33(2H，t)，4.14(2H，t).
Add hydrazine monohydrate (81.00g, 1.28mol) in ethanol (930g) solution of the compound under room temperature, nitrogen atmosphere in four-hole boiling flask [O] (40.00g, 128mmol), carry out reflux then.After reaction finished, behind the solid of separating out with distilled water (930g) dissolving, with 1,2-ethylene dichloride (500g) carried out 4 times and extracts.After merging organic layer, carry out 2 washings (500g), after dried over mgso, filter, steaming desolventizes, and obtains compound [P] (must measure 16.5g, yield 51%) with the form of yellow solid.
1H-NMR(400MHz，CDCl 3，δppm)：8.22-8.20(2H，m)，6.99-6.96(2H，m)，4.09(2H，t)，3.15(2H，t)，1.26(2H，brs).
Synthesizing of the compound [P] of employing reaction process B
Add 1 in room temperature, stream of nitrogen gas in four-hole boiling flask, 2-dimethoxy-ethane (following note is made DME) (150g) adds 60% sodium hydride (16.24g, 372mmol) therein.Slowly drip DME (50g) solution of 2-monoethanolamine (22.73g, 372mmol) then.Drip DME (50g) solution of 1-fluoro-4-nitrobenzene (50.00g, 354mmol) then.Reaction joins reaction solution in the distilled water (1250g) after finishing, and carries out 3 extractions with methylene chloride (400g).Merge organic layer, after dried over mgso, filter, steaming desolventizes, and obtains compound [P] (must measure 46.1g, yield 71%) with the form of yellow solid.
1H-NMR(400MHz，CDCl 3，δppm)：8.22-8.20(2H，m)，6.99-6.96(2H，m)，4.09(2H，t)，3.15(2H，t)，1.26(2H，brs).
Adding two (4-nitrobenzophenone) esters [D] (7.95g, 26.1mmol) of carbonic acid, triethylamine (15.87g, 157mmol), 4-N under the room temperature in the four-hole boiling flask of nitrogen replacement, N-dimethyl aminopyridine (0.64g, 5.23mmol) and THF (280g) also stir.Add THF (40g) solution of compound [P] (10.00g, 54.9mmol) therein, react then.Follow the tracks of reaction by HPLC, reaction joins reaction solution in the pure water (1.9L) after finishing, and carries out 30 minutes stirring.Filter then, clean, obtain the crude product of yellow solid shape with pure water (500mL).After gained crude product usefulness 2-propyl alcohol (60g) cleaning, carry out drying, obtain the dinitro compound [Q] (must measure 6.98g, yield 68%) of yellow solid shape.
1H-NMR(400MHz，CDCl 3，δppm)：8.21-8.18(4H，m)，6.97-6.93(4H，m)，4.83(2H，t)，4.15(4H，q)，3.68(4H，q).
Adding is had compound [Q] (6.73g, 17.2mmol), 5% palladium carbon (5%Pd/C) (0.67g) with 1, and 4-two
Figure BPA00001368916700341
With behind the nitrogen replacement, replace again in the four-hole boiling flask of the potpourri of alkane (337g), in the presence of hydrogen, under room temperature, stir with hydrogen.Follow the tracks of reaction by HPLC, reaction is used the diatomite filtration catalyzer after finishing.Under reduced pressure filtrate is carried out the solvent steaming then and remove, obtain the crude product of light yellow solid shape.In this crude product, add 2-propyl alcohol (48g), after disperseing to clean with ultrasonic unit, filter, drying, obtain the diamino compounds [DA-5] (must measure 3.43g, yield 60%) of peach white solid.
1H-NMR(400MHz，DMSO-d6，δppm)：6.67-6.63(4H，m)，6.51-6.48(4H，m)，6.18(2H，t)，4.60(4H，brs)，3.79(4H，t)，3.30(4H，q).
[synthesis example 6]
Synthesizing of two (3-(4-amino-benzene oxygen) propyl group) ureas [DA-6] of 3-
Figure BPA00001368916700342
Synthesizing of the compound [T] of employing reaction process C
Under room temperature, nitrogen atmosphere, in four-hole boiling flask, add 4-nitrophenol (25.79g, 185mmol), sal tartari (49.70g, 185mmol) and DMF (130g), be heated to 65 ℃.Drip DMF (130g) solution of N-(3-bromopropyl) phthalimide (49.7g, 185mmol) therein.Reaction joins reaction solution in the frozen water (2080g) after finishing, and obtains yellow solid.After its filtration, washing, make white-yellowish solid by drying, obtain compound [S] (must measure 59.5g, yield 98%).
1H-NMR(400MHz，CDCl 3，δppm)：8.8.17-8.15(2H，m)，7.89-7.84(2H，m)，7.76-7.73(2H，m)，6.86-6.84(2H，m)，4.13(2H，t)，3.93(2H，t)，2.27-2.20(2H，m).
Add hydrazine monohydrate (116.0g, 1.85mol) in ethanol (908g) solution of the compound under room temperature, nitrogen atmosphere in four-hole boiling flask [S] (60.50g, 185mmol), carry out reflux then.After reaction finished, behind the solid of separating out with distilled water (908g) dissolving, with 1,2-ethylene dichloride (500g) carried out 4 times and extracts.After merging organic layer, carry out 2 washings (500g), use dried over mgso.Filter then, steaming desolventizes, and obtains compound [T] (must measure 36.0g, yield 99%) with the form of glassy yellow grease.
1H-NMR(400MHz，CDCl 3，δppm)：8.20-8.17(2H，m)，6.98-6.94(2H，m)，4.18-4.15(2H，m)，3.40-3.37(2H，m)，2.20-2.14(2H，m)，2.03-2.20(2H，m).
Synthesizing of the compound [T] of employing reaction process D
Add 1 in room temperature, stream of nitrogen gas in four-hole boiling flask, 2-dimethoxy-ethane (following note is made DME) (188g) adds 60% sodium hydride (14.52g, 333mmol) therein.Slowly drip DME (94g) solution of 3-amino-1-propyl alcohol (25.00g, 333mmol) then.Drip DME (94g) solution of 1-fluoro-4-nitrobenzene (46.96g, 333mmol) then.Reaction joins reaction solution in the distilled water (564g) after finishing, and carries out 3 extractions with methylene chloride (500g).Merge organic layer, with filtering after the dried over mgso, steaming desolventizes, and obtains compound [T] (must measure 60.72g, yield 93%) with the form of yellow oil.
1H-NMR(400MHz，CDCl 3，δppm)：8.20-8.17(2H，m)，6.98-6.94(2H，m)，4.18-4.15(2H，m)，3.40-3.37(2H，m)，2.20-2.14(2H，m)，2.03-2.20(2H，m).
Adding compound [T] (60.72g, 310mmol), two (4-nitrobenzophenone) esters [D] (35.87g, 118mmol) of carbonic acid, triethylamine (47.72g, 472mmol), 4-N under the room temperature in the four-hole boiling flask of nitrogen replacement, N-dimethyl aminopyridine (1.44g, 11.8mmol) and THF (720g) also stir.Follow the tracks of reaction by HPLC, reaction joins reaction solution in the pure water (4.3L) after finishing, and carries out 30 minutes stirring.Filter then, clean, obtain the crude product of yellow solid shape with pure water (1L).After gained crude product usefulness 2-propyl alcohol (400g) cleaning, carry out drying, obtain the dinitro compound [U] (must measure 38.1g, yield 77%) of yellow solid shape.
1H-NMR(400MHz，DMSO-d6，δppm)：8.18-8.14(4H，m)，7.11-7.08(4H，m)，5.96(2H，t)，4.07(4H，5)，3.11(4H，q)，1.84-1.78(4H，m).
Adding is had compound [U] (26.00g, 62.1mmol), 5% palladium carbon (5%Pd/C) (2.6g) with 1, and 4-two With behind the nitrogen replacement, replace again in the four-hole boiling flask of the potpourri of alkane (160g)/ethanol (160g), in the presence of hydrogen, under room temperature, stir with hydrogen.Follow the tracks of reaction by HPLC, after reaction finishes, the solid of separating out in order to dissolve, carry out nitrogen replacement after, add acetonitrile (1500g) and DMF (150g), heat it dissolved fully.Use the diatomite filtration catalyzer then.Under reduced pressure filtrate is carried out the solvent steaming then and remove, obtain the crude product of tea white solid.In this crude product, add 2-propyl alcohol (160g), disperse to clean with ultrasonic unit.Filter then, drying, obtain the diamino compounds [DA-6] (must measure 17.7g, yield 79%) of tea white solid.
1H-NMR(400MHz，DMSO-d6，δppm)：6.65-6.61(4H，m)，6.51-6.47(4H，m)，5.90(2H，t)，4.58(4H，s)，3.81(4H，t)，3.13-3.08(4H，m)，1.77-1.70(4H，m).
[embodiment 1]
In the 50ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the BAPU of 0.60g (2.0mmol) and the p-PDA of 1.95g (18.0mmol), add the N-N-methyl-2-2-pyrrolidone N-of 30g, on one side supplying nitrogen stir on one side and make its dissolving.While stirring the CBDA that this two amine aqueous solution adds 3.70g (18.9mmol), add the N-N-methyl-2-2-pyrrolidone N-again, make solid component concentration reach 12 quality %, under nitrogen atmosphere,, obtain polyamic acid (P1) solution in stirring at room 4 hours.With E type viscosity meter ((East Machine industry society of Toki Sangyo Co., Ltd.) system) confirmed the viscosity of this polyamic acid solution under 25 ℃, the result is 316mPas.
Add the N-N-methyl-2-2-pyrrolidone N-of 9.94g and the butyl cellosolve of 6.54g in this polyamic acid solution of 16.24g, the concentration that obtains P1 is the aligning agent for liquid crystal of 6.0 quality %.
(wear-resisting wiping)
Be spun on the glass substrate of band transparency electrode after the above-mentioned aligning agent for liquid crystal that obtains filtered with 1.0 μ m filters, after on 80 ℃ the heating plate dry 5 minutes, burnt till 30 minutes in 230 ℃, obtain the polyimide film of thickness 100nm.With rayon cloth to this polyimide film rub (roller footpath 120mm, rotating speed 1000rpm, translational speed 20mm/sec, the amount of being pressed into 0.4mm).With the surface state on this film surface of confocal laser microscopic examination, have or not abrasive dust and scar with 10 times multiples observations.It the results are shown in table 2.
(manufacturing of liquid crystal structure cell)
Be spun on the glass substrate of band transparency electrode after the above-mentioned aligning agent for liquid crystal that obtains filtered with 1.0 μ m filters, after on 80 ℃ the heating plate dry 5 minutes, burnt till 30 minutes in 230 ℃, obtain the polyimide film of thickness 100nm.With rayon cloth this polyimide film is rubbed after (roller footpath 120mm, rotating speed 300rpm, translational speed 20mm/sec, the amount of being pressed into 0.2mm), in pure water, carry out 1 minute ultrasonic irradiation, in 80 ℃ of dryings 10 minutes.Prepare 2 substrates that have above-mentioned liquid crystal orientation film, after on the liquid crystal aligning face of a substrate, the sept of 6 μ m being set, with the antiparallel condition of the frictional direction of 2 substrates with 2 substrate in combination, sealing on every side, but stay liquid crystal injecting port, making structure cell interval (cell gap) is the negative crystal born of the same parents of 6 μ m.Vacuum is injected liquid crystal (MLC-2041, Merck ﹠ Co., Inc.'s system) in this structure cell at normal temperatures, with the inlet sealing, makes antiparallel type liquid crystal structure cell.
(liquid crystal aligning)
With the state of orientation of the above-mentioned liquid crystal structure cell of polarized light microscope observing, results verification is flawless uniform orientation.
(tilt angle)
For above-mentioned liquid crystal structure cell, use determinator (TBA107, autroNic-MELCHERS GmbH corporate system) to measure in the tilt angle of the liquid crystal of 110 ℃ of heating after 30 minutes based on rotating crystal method.
(voltage retention)
The liquid crystal structure cell that similarly makes with above-mentioned (manufacturing of liquid crystal structure cell) is applied the voltage 60 μ s of 4V, measures the voltage behind the 16.67ms, calculate variation by this with respect to initial value, with it as voltage retention.During mensuration, the temperature of liquid crystal structure cell is made as 90 ℃, under different temperatures, measures respectively.
(ion concentration)
Using the liquid crystal structure cell that similarly makes with above-mentioned (manufacturing of liquid crystal structure cell), with the (East Yang テ of Toyo Corp. Network ニ カ society) the 6254 type liquid crystal evaluation of physical property devices of making carry out the mensuration of ion concentration.During mensuration, apply the triangular wave of 10V, 0.01Hz, calculate the area suitable of gained waveform with ion concentration by the triangle method of approximation, with it as ion concentration.During mensuration, the temperature of liquid crystal structure cell is made as 60 ℃ measures.
[embodiment 2]
In the 50ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the BAPU of 2.39g (8.0mmol) and the p-PDA of 0.87g (8.0mmol), add the N-N-methyl-2-2-pyrrolidone N-of 30g, on one side supplying nitrogen stir on one side and make its dissolving.While stirring the CBDA that this two amine aqueous solution adds 2.92g (14.9mmol), add the N-N-methyl-2-2-pyrrolidone N-again, make solid component concentration reach 12 quality %, under nitrogen atmosphere,, obtain polyamic acid (P2) solution in stirring at room 2 hours.Confirmed the viscosity of this polyamic acid solution under 25 ℃ with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), the result is 281mPas.
Add the N-N-methyl-2-2-pyrrolidone N-of 9.61g and the butyl cellosolve of 6.43g in this polyamic acid solution of 16.12g, the concentration that obtains P2 is the aligning agent for liquid crystal of 6.0 quality %.
[embodiment 3]
In the 50ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the BAPU of 2.68g (9.0mmol) and the N-N-methyl-2-2-pyrrolidone N-of 30g, on one side supplying nitrogen stir on one side and make its dissolving.While stirring the CBDA that this two amine aqueous solution adds 1.69g (8.6mmol), add the N-N-methyl-2-2-pyrrolidone N-again, make solid component concentration reach 12 quality %, under nitrogen atmosphere,, obtain polyamic acid (P3) solution in stirring at room 6 hours.Confirmed the viscosity of this polyamic acid solution under 25 ℃ with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), the result is 206mPas.
Add the N-N-methyl-2-2-pyrrolidone N-of 5.10g and the butyl cellosolve of 4.94g in this polyamic acid solution of 14.65g, the concentration that obtains P3 is the aligning agent for liquid crystal of 6.0 quality %.
[embodiment 4]
In the 50ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the BABU of 2.62g (9.7mmol) and the N-N-methyl-2-2-pyrrolidone N-of 25g, on one side supplying nitrogen stir on one side and make its dissolving.While stirring the CBDA that this two amine aqueous solution adds 1.85g (9.4mmol), add the N-N-methyl-2-2-pyrrolidone N-again, make solid component concentration reach 10 quality %, under nitrogen atmosphere,, obtain polyamic acid (P4) solution in stirring at room 2 hours.Confirmed the viscosity of this polyamic acid solution under 25 ℃ with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), the result is 173mPas.
Add the N-N-methyl-2-2-pyrrolidone N-of 5.10g and the butyl cellosolve of 4.75g in this polyamic acid solution of 13.90g, the concentration that obtains P4 is the aligning agent for liquid crystal of 6.0 quality %.
[embodiment 5]
In the 50ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the BAPU of 2.54g (8.5mmol) and the N-N-methyl-2-2-pyrrolidone N-of 30g, on one side supplying nitrogen stir on one side and make its dissolving.While stirring the PMDA that this two amine aqueous solution adds 1.69g (7.7mmol), add the N-N-methyl-2-2-pyrrolidone N-again, make solid component concentration reach 10 quality %, under nitrogen atmosphere,, obtain polyamic acid (P5) solution in stirring at room 4 hours.Confirmed the viscosity of this polyamic acid solution under 25 ℃ with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), the result is 138.6mPas.
Add the N-N-methyl-2-2-pyrrolidone N-of 5.64g and the butyl cellosolve of 4.94g in this polyamic acid solution of 15.13g, the concentration that obtains P5 is the aligning agent for liquid crystal of 6.0 quality %.
[embodiment 6]
In the 50ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the BABU of 2.43g (9.0mmol) and the N-N-methyl-2-2-pyrrolidone N-of 30g, on one side supplying nitrogen stir on one side and make its dissolving.While stirring the PMDA that this two amine aqueous solution adds 1.88g (8.6mmol), add the N-N-methyl-2-2-pyrrolidone N-again, make solid component concentration reach 10 quality %, under nitrogen atmosphere,, obtain polyamic acid (P6) solution in stirring at room 3 hours.Confirmed the viscosity of this polyamic acid solution under 25 ℃ with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), the result is 276mPas.
Add the N-N-methyl-2-2-pyrrolidone N-of 8.56g and the butyl cellosolve of 4.83g in this polyamic acid solution of 10.75g, the concentration that obtains P6 is the aligning agent for liquid crystal of 4.5 quality %.
[embodiment 7]
In the 50ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the BAPU of 3.58g (12.0mmol) and the N-N-methyl-2-2-pyrrolidone N-of 30g, on one side supplying nitrogen stir on one side and make its dissolving.While stirring the BODA that this two amine aqueous solution adds 2.86g (11.4mmol), add the N-N-methyl-2-2-pyrrolidone N-again, make solid component concentration reach 12 quality %, under nitrogen atmosphere,, obtain polyamic acid (P7) solution in 50 ℃ of stirrings 28 hours.Confirmed the viscosity of this polyamic acid solution under 25 ℃ with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), the result is 630mPas.
Add the N-N-methyl-2-2-pyrrolidone N-of 12.80g and the butyl cellosolve of 6.32g in this polyamic acid solution of 12.22g, the concentration that obtains P7 is the aligning agent for liquid crystal of 6.0 quality %.
[embodiment 8]
In the 50ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the BABU of 3.24g (12.0mmol) and the N-N-methyl-2-2-pyrrolidone N-of 25g, on one side supplying nitrogen stir on one side and make its dissolving.While stirring the BODA that this two amine aqueous solution adds 2.99g (11.9mmol), add the N-N-methyl-2-2-pyrrolidone N-again, make solid component concentration reach 15 quality %, under nitrogen atmosphere,, obtain polyamic acid (P8) solution in 50 ℃ of stirrings 24 hours.Confirmed the viscosity of this polyamic acid solution under 25 ℃ with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), the result is 498mPas.
Add the N-N-methyl-2-2-pyrrolidone N-of 12.0g and the butyl cellosolve of 5.50g in this polyamic acid solution of 9.95g, the concentration that obtains P8 is the aligning agent for liquid crystal of 6.0 quality %.
[embodiment 9]
In the 50ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the DA-3 of 2.31g (8.54mmol) and the N-N-methyl-2-2-pyrrolidone N-of 24.3g, on one side supplying nitrogen stir on one side and make its dissolving.While stirring the CBDA that this two amine aqueous solution adds 1.66g (8.46mmol), add the N-N-methyl-2-2-pyrrolidone N-again, make solid component concentration reach 10 quality %, under nitrogen atmosphere,, obtain polyamic acid (P9) solution in stirring at room 4 hours.Confirmed the viscosity of this polyamic acid solution under 25 ℃ with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), the result is 155mPas.
Add the N-N-methyl-2-2-pyrrolidone N-of 7.57g and the butyl cellosolve of 6.09g in this polyamic acid solution of 16.80g, the concentration that obtains P9 is the aligning agent for liquid crystal of 6.0 quality %.
[embodiment 10]
In the 50ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the DA-4 of 2.84g (9.98mmol) and the N-N-methyl-2-2-pyrrolidone N-of 29.5g, on one side supplying nitrogen stir on one side and make its dissolving.While stirring the CBDA that this two amine aqueous solution adds 1.66g (9.53mmol), add the N-N-methyl-2-2-pyrrolidone N-again, make solid component concentration reach 10 quality %, under nitrogen atmosphere,, obtain polyamic acid (P10) solution in stirring at room 4 hours.Confirmed the viscosity of this polyamic acid solution under 25 ℃ with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), the result is 206mPas.
Add the N-N-methyl-2-2-pyrrolidone N-of 7.75g and the butyl cellosolve of 6.22g in this polyamic acid solution of 17.12g, the concentration that obtains P10 is the aligning agent for liquid crystal of 5.5 quality %.
[embodiment 11]
In the 50ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the DA-6 of 3.40g (9.48mmol) and the N-N-methyl-2-2-pyrrolidone N-of 29.5g, on one side supplying nitrogen stir on one side and make its dissolving.While stirring the CBDA that this two amine aqueous solution adds 1.76g (8.97mmol), add the N-N-methyl-2-2-pyrrolidone N-again, make solid component concentration reach 10 quality %, under nitrogen atmosphere,, obtain polyamic acid (P11) solution in stirring at room 4 hours.Confirmed the viscosity of this polyamic acid solution under 25 ℃ with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), the result is 150mPas.
Add the N-N-methyl-2-2-pyrrolidone N-of 5.26g and the butyl cellosolve of 6.03g in this polyamic acid solution of 18.88g, the concentration that obtains P11 is the aligning agent for liquid crystal of 6.0 quality %.
[embodiment 12]
In the 50ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the DA-5 of 0.53g (1.6mmol) and the p-PDA of 1.56g (14.4mmol), add the N-N-methyl-2-2-pyrrolidone N-of 30.9g again, on one side supplying nitrogen stir on one side and make its dissolving.While stirring the CBDA that this two amine aqueous solution adds 2.82g (15.4mmol), add the N-N-methyl-2-2-pyrrolidone N-again, make solid component concentration reach 10 quality %, under nitrogen atmosphere,, obtain polyamic acid (P12) solution in stirring at room 4 hours.Confirmed the viscosity of this polyamic acid solution under 25 ℃ with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), the result is 160mPas.
Add the N-N-methyl-2-2-pyrrolidone N-of 6.03g and the butyl cellosolve of 6.11g in this polyamic acid solution of 18.41g, the concentration that obtains P12 is the aligning agent for liquid crystal of 6.0 quality %.
[embodiment 13]
In the 1000ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the DA-7 of 7.00g (24.44mmol) and the BAPU of 3.13g (10.48mmol), will use nitrogen replacement in the flask.Then, add 359.90g dehydration N-N-methyl-2-2-pyrrolidone N-and 6.63g pyridine, use magnetic stirrer in 25 ℃, BAPU and DA-7 are dissolved fully with syringe.Then with the reactant liquor water-cooled, with magnetic stirrer on one side add the CA-4 of 9.34g (31.44mmol) on one side.Use funnel to add with 30 seconds time.Then, add used funnel,, under water-cooled, continue to stir 3 hours carrying out nitrogen replacement in the reaction vessel with the dehydration N-N-methyl-2-2-pyrrolidone N-cleaning of 10.00g.Then, carry out under the stirring condition to wherein injecting reaction solution on a small quantity one by one, continuation stirring 1 hour at methyl alcohol 5 times of weight of reaction solution.Then, with filtration and precipitate after the methyl alcohol of 5 times of weight stirs 1 hour, the filtered and recycled precipitate.Then, carry out same operation with the methyl alcohol of 5 times of weight, in 100 ℃ under reduced pressure with dry 24 hours of gained precipitate, obtain the poly amic acid ester (P13) of 14.59g.2.26g in the gained solid matter is dissolved in fully the N-N-methyl-2-2-pyrrolidone N-of 20.36g.Then, add the N-N-methyl-2-2-pyrrolidone N-of 2.12g and the butyl cellosolve of 10.60g in this solution, the concentration that obtains P13 is the aligning agent for liquid crystal of 6.0 quality %.
[embodiment 14]
In the 300ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the DA-7 of 4.00g (13.97mmol) and the BAPU of 1.78g (5.99mmol), will use nitrogen replacement in the flask.Then, add 202.93g dehydration N-N-methyl-2-2-pyrrolidone N-and 3.79g pyridine, use magnetic stirrer in 25 ℃, BAPU and DA-7 are dissolved fully with syringe.Then with the reactant liquor water-cooled, with magnetic stirrer on one side add the CA-5 of 1.27g (3.99mmol) and the CA-4 of 4.15g (13.96mmol) on one side.Use funnel to add with 30 seconds time.Then, add used funnel,, under water-cooled, continue to stir 3 hours carrying out nitrogen replacement in the reaction vessel with the dehydration N-N-methyl-2-2-pyrrolidone N-cleaning of 10.00g.Then, carry out under the stirring condition to wherein injecting reaction solution on a small quantity one by one, continuation stirring 1 hour at methyl alcohol 5 times of weight of reaction solution.Then, with filtration and precipitate after the methyl alcohol of 5 times of weight stirs 1 hour, the filtered and recycled precipitate.Then, the methyl alcohol with 5 times of weight carries out same operation again, in 100 ℃ under reduced pressure with dry 24 hours of gained precipitate, obtain the poly amic acid ester (P14) of 8.87g.2.27g in the gained solid matter is dissolved in fully the N-N-methyl-2-2-pyrrolidone N-of 20.45g.Then, add the N-N-methyl-2-2-pyrrolidone N-of 2.13g and the butyl cellosolve of 10.65g in this solution, the concentration that obtains P14 is the aligning agent for liquid crystal of 6.0 quality %.
[comparative example 1]
The p-PDA that adds 2.17g (20.0mmol) in the 50ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe adds the N-N-methyl-2-2-pyrrolidone N-of 25g again, on one side supplying nitrogen stir on one side and make its dissolving.Add 1,2,3 of 3.77g (19.2mmol) while stirring this two amine aqueous solution, 4-cyclo-butane tetracarboxylic dianhydride adds the N-N-methyl-2-2-pyrrolidone N-again, makes solid component concentration reach 12 quality %, in stirring at room 4 hours, obtains polyamic acid solution.Confirmed the viscosity of this polyamic acid solution under 25 ℃ with E type viscosity meter (Toki Sangyo Co., Ltd.'s system), the result is 602.3mPas.
The gained polyamic acid solution of 7.89g is sub-packed in the 50ml Erlenmeyer flask that stirrer is housed, add the N-N-methyl-2-2-pyrrolidone N-of 6.29g and the butyl cellosolve of 3.55g, with magnetic stirrer 30 minutes, obtain the aligning agent for liquid crystal of polyamic acid concentration 5.5 quality %.
[comparative example 2]
In the 1000ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the DA-7 of 10.00g (34.92mmol), will use nitrogen replacement in the flask.Then, add 304g dehydration N-N-methyl-2-2-pyrrolidone N-and 6.1g pyridine, use magnetic stirrer in 25 ℃, DA-7 is dissolved fully with syringe.Then with the reactant liquor water-cooled, with magnetic stirrer on one side add the CA-4 of 9.34g (31.43mmol) on one side.Use funnel to add with 30 seconds time.Then, add used funnel,, under water-cooled, continue to stir 3 hours carrying out nitrogen replacement in the reaction vessel with the dehydration N-N-methyl-2-2-pyrrolidone N-cleaning of 20g.Then, carry out under the stirring condition to wherein injecting reaction solution on a small quantity one by one, continuation stirring 1 hour at distilled water 5 times of weight of reaction solution.Then, with filtration and precipitate after the distilled water of 5 times of weight stirs 1 hour, the filtered and recycled precipitate.Then, the ethanol with 5 times of weight carries out same operation again, in 100 ℃ under reduced pressure with dry 24 hours of gained precipitate, obtain the solid matter of 14.82g.3.99g in the gained solid matter is dissolved in fully the N-N-methyl-2-2-pyrrolidone N-of 35.90g.Then, add the N-N-methyl-2-2-pyrrolidone N-of 6.91g and the butyl cellosolve of 19.36g in this solution, the concentration that obtains poly amic acid ester is the aligning agent for liquid crystal of 5.5 quality %.
[comparative example 3]
In the 1000ml four-hole boiling flask of band stirring apparatus and nitrogen ingress pipe, add the DA-7 of 7.00g (24.44mmol), will use nitrogen replacement in the flask.Then, add 249.3g dehydration N-N-methyl-2-2-pyrrolidone N-and 4.6g than pyridine, use magnetic stirrer in 25 ℃, DA-7 is dissolved fully with syringe.Then with the reactant liquor water-cooled, with magnetic stirrer on one side add the CA-5 of 1.56g (4.88mmol) and the CA-4 of 6.08g (17.12mmol) on one side.Use funnel to add with 30 seconds time.Then, add used funnel,, under water-cooled, continue to stir 3 hours carrying out nitrogen replacement in the reaction vessel with the dehydration N-N-methyl-2-2-pyrrolidone N-cleaning of 10g.Then, carry out under the stirring condition to wherein injecting reaction solution on a small quantity one by one, continuation stirring 1 hour at methyl alcohol 5 times of weight of reaction solution.Then, with filtration and precipitate after the methyl alcohol of 5 times of weight stirs 1 hour, the filtered and recycled precipitate.Then, the methyl alcohol with 5 times of weight carries out same operation again, in 100 ℃ under reduced pressure with dry 24 hours of gained precipitate, obtain the solid matter of 11.15g.10.06g in the gained solid matter is dissolved in fully the N-N-methyl-2-2-pyrrolidone N-of 90.54g.Then, add the N-N-methyl-2-2-pyrrolidone N-of 5.63g and the butyl cellosolve of 44.97g in this solution, the concentration that obtains poly amic acid ester is the aligning agent for liquid crystal of 6.0 quality %.
The viscosity that gathers the N-N-methyl-2-2-pyrrolidone N-solution of the contracted notation that contracts (P1 etc.) of the consumption that shows starting material (diamines etc.) used in embodiment 1～14 and the comparative example 1～3, gained polyamic acid and this polyamic acid in the table 1.The unmarked contracted notation that contracts of the polyamic acid of comparative example 1～3 and poly amic acid ester (representing with blank column in the table 1).
In the table 1, "-" expression viscosity undetermined.
Make the liquid crystal structure cell with the aligning agent for liquid crystal that obtains in embodiment 2～embodiment 4, embodiment 7～embodiment 13, comparative example 1 and the comparative example 2 similarly to Example 1, measure wear-resisting wiping, liquid crystal aligning, tilt angle, voltage retention and ion concentration.For embodiment 5, embodiment 6, embodiment 14 and comparative example 3, measure wear-resisting wiping and liquid crystal aligning with method similarly to Example 1.Gained the results are shown in table 2.
[table 1]
Figure BPA00001368916700441
[table 2]
Figure BPA00001368916700451
The possibility of utilizing on the industry
The liquid crystal of the application of the invention orientation inorganic agent can obtain that wear-resisting wiping is good, the also good and liquid crystal orientation film that needs strong friction to process of the orientation of liquid crystal. In addition, the voltage retention height of the liquid crystal structure cell of liquid crystal of the present invention orientation film, ion concentration is also low, therefore can be used as to need not the vertical orientated liquid crystal display element that rubs and process, also can be used as the liquid crystal display element of light orientation.
Here quote of the announcement of the full content of Japanese patent application 2008-285860 number instructions, claims and the specification digest of filing an application on November 6th, 2008 as instructions of the present invention.

Claims (12)

1. aligning agent for liquid crystal, this treating agent comprise make two amine components and tetracarboxylic acid derivatives reaction and polyimide precursor or in the polyimide any, it is characterized in that described two amine components comprise the diamines of following formula (1) expression;
Figure FPA00001368916600011
In the formula (1), X is oxygen atom or sulphur atom, Y 1And Y 2Respectively be independently singly-bound ,-O-,-S-,-OCO-or-COO-, R 1And R 2Be the alkylidene of carbon number 1～3 independently respectively.
2. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, in the formula (1)-R 1-Y 1-and-R 2-Y 2-structure identical.
3. aligning agent for liquid crystal as claimed in claim 1 or 2 is characterized in that, the Y in the formula (1) 1And Y 2Be singly-bound.
4. as each described aligning agent for liquid crystal in the claim 1～3, it is characterized in that the X in the formula (1) is an oxygen atom.
5. as each described aligning agent for liquid crystal in the claim 1～4, it is characterized in that described tetracarboxylic acid derivatives is tetracarboxylic dianhydride, tetrabasic carboxylic acid list acid anhydride, tetrabasic carboxylic acid, dicarboxylic acid dialkyl esters or dicarboxylic acid acyl chlorides dialkyl.
6. as each described aligning agent for liquid crystal in the claim 1～5, it is characterized in that, also wrap fluorinated surfactant, silicone surfactant or nonionic surfactant.
7. as each described aligning agent for liquid crystal in the claim 1～6, it is characterized in that, also comprise compound that contains functional silanes or the compound that contains epoxy radicals.
8. as each described aligning agent for liquid crystal in the claim 1～7, it is characterized in that the solid component concentration in the aligning agent for liquid crystal is 1～20 quality % with respect to aligning agent for liquid crystal total amount 100 quality %.
9. liquid crystal orientation film is characterized in that, is obtained by each described aligning agent for liquid crystal in the claim 1～8.
10. liquid crystal display cells is characterized in that, has the described liquid crystal orientation film of claim 9.
11. two aminophenyls or two amino-benzene oxygen ureine of following formula (1-7), formula (1-8), formula (1-b) or formula (1-c) expression;
Figure FPA00001368916600021
In the formula (1-b), R 12And R 22The alkylidene of the carbon number 1～3 that the expression carbon number differs from one another, in the formula (1-c), R 13And R 23Be the alkylidene of carbon number 1～3 independently respectively.
12. two aminophenyls or two amino-benzene oxygen ureine of following formula (1-9)～formula (1-11) expression.
Figure FPA00001368916600031
CN200980144621.4A 2008-11-06 2009-11-05 Liquid crystal aligning agent Active CN102203662B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201310611123.4A CN103739523B (en) 2008-11-06 2009-11-05 Aligning agent for liquid crystal
CN201510089713.4A CN104761471B (en) 2008-11-06 2009-11-05 Aligning agent for liquid crystal

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2008-285860 2008-11-06
JP2008285860 2008-11-06
PCT/JP2009/068915 WO2010053128A1 (en) 2008-11-06 2009-11-05 Liquid crystal aligning agent

Related Child Applications (2)

Application Number Title Priority Date Filing Date
CN201510089713.4A Division CN104761471B (en) 2008-11-06 2009-11-05 Aligning agent for liquid crystal
CN201310611123.4A Division CN103739523B (en) 2008-11-06 2009-11-05 Aligning agent for liquid crystal

Publications (2)

Publication Number Publication Date
CN102203662A true CN102203662A (en) 2011-09-28
CN102203662B CN102203662B (en) 2014-04-16

Family

ID=42152935

Family Applications (3)

Application Number Title Priority Date Filing Date
CN201310611123.4A Active CN103739523B (en) 2008-11-06 2009-11-05 Aligning agent for liquid crystal
CN200980144621.4A Active CN102203662B (en) 2008-11-06 2009-11-05 Liquid crystal aligning agent
CN201510089713.4A Active CN104761471B (en) 2008-11-06 2009-11-05 Aligning agent for liquid crystal

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201310611123.4A Active CN103739523B (en) 2008-11-06 2009-11-05 Aligning agent for liquid crystal

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201510089713.4A Active CN104761471B (en) 2008-11-06 2009-11-05 Aligning agent for liquid crystal

Country Status (5)

Country Link
JP (2) JP5333454B2 (en)
KR (2) KR101671659B1 (en)
CN (3) CN103739523B (en)
TW (1) TWI477533B (en)
WO (1) WO2010053128A1 (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102947755A (en) * 2010-04-30 2013-02-27 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
CN103773391A (en) * 2012-10-17 2014-05-07 Jsr株式会社 Liquid crystal orientation agent, liquid crystal orientation film, liquid crystal display element, polymer and compound
CN103849406A (en) * 2012-12-03 2014-06-11 Jsr株式会社 Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, phase difference film, manufacturing method for the phase difference film, polymer, and compound
CN104024932A (en) * 2011-10-27 2014-09-03 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
CN104109538A (en) * 2013-04-18 2014-10-22 Jsr株式会社 Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, phase different film, method of making phase difference film, polymer, and compound
CN104335112A (en) * 2012-03-30 2015-02-04 日产化学工业株式会社 Liquid crystal display element and manufacturing method therefor
CN104380188A (en) * 2012-03-29 2015-02-25 日产化学工业株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
CN104685412A (en) * 2012-08-06 2015-06-03 日产化学工业株式会社 Liquid crystal aligning agent, and liquid crystal alignment film produced using same
CN105385454A (en) * 2014-08-25 2016-03-09 Jsr株式会社 Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element
CN107022358A (en) * 2016-01-29 2017-08-08 Jsr株式会社 Aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal cell, polymer and diamines
CN108604027A (en) * 2015-11-25 2018-09-28 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
CN109716222A (en) * 2016-09-16 2019-05-03 日产化学株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
CN113956475A (en) * 2021-11-05 2022-01-21 深圳市道尔顿电子材料有限公司 Polyimide liquid crystal aligning agent chelated with metal ions, liquid crystal alignment film and preparation method of liquid crystal alignment film

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102971288B (en) * 2010-04-30 2015-01-21 日产化学工业株式会社 Novel process for producing bisaminophenylalkylurea
CN102559205B (en) 2010-12-29 2014-07-30 第一毛织株式会社 Liquid crystal alignment agent, liquid crystal alignment film manufactured using the same, and liquid crystal display device
CN103797409B (en) * 2011-07-14 2017-05-24 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
KR101444190B1 (en) 2011-12-19 2014-09-26 제일모직 주식회사 Liquid crystal alignment agent, liquid crystal alignment film using the same, and liquid crystal display device including the liquid crystal alignment film
JP6328484B2 (en) * 2014-02-27 2018-05-23 四国化成工業株式会社 Imidazolesilane compound, method for synthesizing the compound and use thereof
JP7425537B2 (en) * 2016-10-06 2024-01-31 日産化学株式会社 Diamine, polymer, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
CN110692166B (en) * 2017-05-31 2022-02-25 日产化学株式会社 Functional resin composition for phase shift modulation element using liquid crystal
CN111095091B (en) 2017-09-13 2022-08-26 日产化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
WO2020054797A1 (en) 2018-09-14 2020-03-19 日産化学株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element, and diamine and production method therefor, and polymer
TW202402732A (en) * 2022-07-08 2024-01-16 星歐光學股份有限公司 Plasticizer, plastic composition, and plastic product
KR102550865B1 (en) * 2022-11-28 2023-07-04 주식회사 피엔에스테크놀로지 Polyamic acid ester, method for its production and photosensitive resin composition comprising the polyamic acid ester.

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2635400A1 (en) * 1976-08-06 1978-02-09 Bayer Ag Polyurethane elastomer prepd. by solvent-free process - from poly:isocyanate, poly:hydroxy cpd. and solid aromatic di:amine
US4202987A (en) * 1977-12-09 1980-05-13 Ciba-Geigy Corporation Bis-anthranilates
US5011753A (en) * 1987-11-24 1991-04-30 Hoechst Celanese Corporation Photoresist compositions containing polyamides polybenzoxa from bis((aminohydroxyphenyl)hexafluoroisopropyl)diphenyl ethers
JP3191535B2 (en) 1993-10-21 2001-07-23 ジェイエスアール株式会社 Liquid crystal alignment agent and liquid crystal display device
FR2731223A1 (en) * 1995-03-02 1996-09-06 Pf Medicament NOVEL BI-TRYPTAMINE DERIVATIVES, PROCESS FOR THEIR PREPARATION AND THEIR USE AS MEDICAMENTS
JP3206401B2 (en) 1995-11-20 2001-09-10 ジェイエスアール株式会社 Liquid crystal alignment agent and liquid crystal display device
JP3603460B2 (en) 1996-03-25 2004-12-22 Ｊｓｒ株式会社 Liquid crystal alignment agent and liquid crystal display device
US6808766B1 (en) * 1998-08-26 2004-10-26 Nissan Chemical Industries, Ltd. Liquid crystal alignment agent and liquid crystal device using the liquid crystal alignment and method for alignment of liquid crystal molecules
CN100537638C (en) * 2004-04-28 2009-09-09 日产化学工业株式会社 Liquid-crystal aligning agent, liquid-crystal alignment film comprising the same, and liquid-crystal element
ES2475728T3 (en) * 2005-02-09 2014-07-11 3M Innovative Properties Company Thiazoloquinolines and alkoxy substituted thiazolonaphthyridines
CU23431B6 (en) * 2005-05-12 2009-10-16 Ct Ingenieria Genetica Biotech METHOD FOR INHIBITION OF PROLIFERATION OF TUMOR CELLS AND TREATMENT OF CANCER
JP2009538270A (en) * 2006-03-21 2009-11-05 ヨーロピアン モレキュラー バイオロジー ラボラトリー Cell replication disruptors and their use in preventing pathological conditions
KR101426102B1 (en) * 2006-07-28 2014-08-05 닛산 가가쿠 고교 가부시키 가이샤 Liquid crystal aligning agent and liquid crystal displays made by using the same
TWI371635B (en) * 2006-09-08 2012-09-01 Jsr Corp Liquid crystal alignment agent and liquid crystal display element
JP2008090297A (en) 2006-09-08 2008-04-17 Jsr Corp Liquid crystal aligning agent and liquid crystal display element

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102947755B (en) * 2010-04-30 2015-08-26 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells
CN102947755A (en) * 2010-04-30 2013-02-27 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
CN104024932A (en) * 2011-10-27 2014-09-03 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
CN104380188B (en) * 2012-03-29 2017-05-31 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells
CN104380188A (en) * 2012-03-29 2015-02-25 日产化学工业株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
CN104335112A (en) * 2012-03-30 2015-02-04 日产化学工业株式会社 Liquid crystal display element and manufacturing method therefor
CN104685412B (en) * 2012-08-06 2018-02-13 日产化学工业株式会社 Aligning agent for liquid crystal and the liquid crystal orientation film for having used the aligning agent for liquid crystal
CN104685412A (en) * 2012-08-06 2015-06-03 日产化学工业株式会社 Liquid crystal aligning agent, and liquid crystal alignment film produced using same
CN103773391B (en) * 2012-10-17 2016-11-02 Jsr株式会社 Aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal display cells, polymer and compound
CN103773391A (en) * 2012-10-17 2014-05-07 Jsr株式会社 Liquid crystal orientation agent, liquid crystal orientation film, liquid crystal display element, polymer and compound
CN103849406A (en) * 2012-12-03 2014-06-11 Jsr株式会社 Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, phase difference film, manufacturing method for the phase difference film, polymer, and compound
TWI567109B (en) * 2012-12-03 2017-01-21 Jsr股份有限公司 Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display device, phase difference film and manufacturing method thereof, polymer and compound
CN103849406B (en) * 2012-12-03 2017-03-22 Jsr株式会社 Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, phase difference film, manufacturing method for the phase difference film, polymer, and compound
CN104109538B (en) * 2013-04-18 2018-01-16 Jsr株式会社 Aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal display cells, phase retardation film and its manufacture method, polymer and compound
CN104109538A (en) * 2013-04-18 2014-10-22 Jsr株式会社 Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, phase different film, method of making phase difference film, polymer, and compound
CN105385454A (en) * 2014-08-25 2016-03-09 Jsr株式会社 Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element
CN108604027A (en) * 2015-11-25 2018-09-28 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
CN107022358A (en) * 2016-01-29 2017-08-08 Jsr株式会社 Aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal cell, polymer and diamines
CN107022358B (en) * 2016-01-29 2021-09-07 Jsr株式会社 Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, polymer, and diamine
CN109716222A (en) * 2016-09-16 2019-05-03 日产化学株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
CN109716222B (en) * 2016-09-16 2022-07-26 日产化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
CN113956475A (en) * 2021-11-05 2022-01-21 深圳市道尔顿电子材料有限公司 Polyimide liquid crystal aligning agent chelated with metal ions, liquid crystal alignment film and preparation method of liquid crystal alignment film
CN113956475B (en) * 2021-11-05 2022-07-29 深圳市道尔顿电子材料有限公司 Polyimide liquid crystal aligning agent chelated with metal ions, liquid crystal alignment film and preparation method of liquid crystal alignment film

Also Published As

Publication number Publication date
CN104761471A (en) 2015-07-08
WO2010053128A1 (en) 2010-05-14
JPWO2010053128A1 (en) 2012-04-05
KR20150138410A (en) 2015-12-09
CN104761471B (en) 2017-01-04
JP2013241412A (en) 2013-12-05
TW201030059A (en) 2010-08-16
JP5333454B2 (en) 2013-11-06
KR20110082589A (en) 2011-07-19
CN102203662B (en) 2014-04-16
KR101671659B1 (en) 2016-11-01
CN103739523B (en) 2015-08-05
KR101613757B1 (en) 2016-04-19
TWI477533B (en) 2015-03-21
CN103739523A (en) 2014-04-23
JP5733340B2 (en) 2015-06-10

Similar Documents

Publication Publication Date Title
CN102203662B (en) Liquid crystal aligning agent
TWI540154B (en) A liquid crystal alignment agent for a light alignment treatment, and a liquid crystal alignment film using the same
TWI449727B (en) A liquid crystal alignment agent, and a liquid crystal display device using the liquid crystal display device
CN101910929B (en) Liquid crystal aligning agent and liquid crystal display device using the same
TW201118062A (en) Diamine compound, polyamic acid, polyimide, and liquid crystal aligning agent
KR101742838B1 (en) Liquid crystal aligning agent and liquid crystal display element using same
CN102428121A (en) Polyimide precursor, polyimide, and liquid crystal aligning agent
TWI649362B (en) Composition, liquid crystal alignment treatment agent, liquid crystal alignment film and liquid crystal display element
CN104106001A (en) Liquid crystal alignment film, method for producing liquid crystal alignment film, and liquid crystal display element
TWI758513B (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element using the same
CN103827740A (en) Method for producing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element
KR102009543B1 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
US10982147B2 (en) Liquid crystal aligning agent composition, method for preparing liquid crystal alignment film using same, and liquid crystal alignment film using same
JP6278216B2 (en) Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element using the same
JPWO2020080477A1 (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element using it
CN107003574B (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same
TW202202605A (en) Liquid crystal aligning agent, liquid crystal alignment layer, and liquid crystal display element
JPWO2018051923A1 (en) Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device
TW202130704A (en) Liquid crystal aligning agent, radical generation film and method for producing in-plane switching liquid crystal cell
TW202328292A (en) Liquid crystal aligning agent, liquid crystal aligned film, liquid crystal display element, and compound

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant