CN104364296A - Polymer, liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, and diamine - Google Patents

Polymer, liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, and diamine Download PDF

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CN104364296A
CN104364296A CN201380031830.4A CN201380031830A CN104364296A CN 104364296 A CN104364296 A CN 104364296A CN 201380031830 A CN201380031830 A CN 201380031830A CN 104364296 A CN104364296 A CN 104364296A
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liquid crystal
acid
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bound
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CN104364296B (en
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芦泽亮一
南悟志
星野稔
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/32—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and esterified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • 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
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    • 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
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K19/2014—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -(CH2)m-COO-(CH2)n-
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
    • C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Liquid Crystal (AREA)
  • Polyamides (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

The present invention is at least one type of polymer selected from a polyimide precursor containing a structure expressed by the following formula [I] as a side chain and polyimide and polyamide that are obtained through the imidization of the polyimide precursor (In the formula, Y1 is an unsubstituted or substituted and carbocyclic or heterocyclic divalent aromatic group selected from a monocyclic ring with a number of atoms of 5 or 6, two adjacent monocyclic rings with a number of atoms of 5 or 6, a bicyclic ring system with a number of atoms of between 8 and 10, and a tricyclic ring system with a number of atoms of 13 or 14, Y2 is a divalent linking group selected from a group consisting of single bond or ether bond, ester bond, amide bond, and urethane bond, and Y3 is a monovalent organic group containing a straight-chain alkyl group with a carbon number of between 3 and 20 in which the hydrogen atom may be substituted with a fluorine atom, or an alicyclic skeleton with a carbon number of between 4 and 40).

Description

Polymkeric substance, liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device and diamines
Technical field
The present invention relates to polyimide precursor, polyimide and polymeric amide, liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device and diamines.
Background technology
In liquid crystal display device, liquid crystal orientation film carries the effect making liquid crystal orientation on certain direction.Now, the main liquid crystal orientation film of industrial use is by substrate carrying out film forming using being coated on by the liquid crystal aligning agent of the polyimide formed as the solution of the polyamic acid of polyimide precursor, poly amic acid ester or polyimide and obtaining.In addition, make mesomorphic phase for real estate during parallel-oriented or tilted alignment, after film forming, carry out further adopting the surface of friction prolonged treatment.In addition, propose and utilize the method for the anisotropy photochemical reaction of employing polarisation uviolizing etc. to be used as substituting of friction treatment, carried out in recent years towards industrialized research.
In order to improve the display characteristic of this liquid crystal display device, by changing the structure of polyamic acid, poly amic acid ester and polyimide, polyamic acid, poly amic acid ester and polyimide that blending rating is different, or add the method for additive etc., carry out the improvement of liquid crystal aligning and electrical characteristic etc., the control etc. of tilt angle.Such as, even if in order to obtain the liquid crystal aligning agent that the printing of the liquid crystal orientation film using liquid crystal aligning performance also not deteriorated under the high temperature conditions for a long time of good electric performance can be provided excellent, propose the polymkeric substance (with reference to patent documentation 1 etc.) using and there is the group of ad hoc structure.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2011-100099 publication
Summary of the invention
Invent technical problem to be solved
But, along with the energy-saving technology etc. of the high performance of liquid crystal display device, big area, display device, the characteristic required by liquid crystal orientation film is also become harsh, also requires the patience that liquid crystal display device exposes to the open air backlight.Especially use liquid crystal aligning agent in the past, utilize the method for the anisotropy photochemical reaction by polarized UV rays irradiation etc., the liquid crystal orientation film that the method for namely carrying out orientation process with rayed is formed, owing to there is unreacted photoreactive group in liquid crystal orientation film, the problem of the liquid crystal aligning performance degradation therefore having liquid crystal display device to be exposed to cause in backlight.
The object of the invention is the problem points solving above-mentioned prior art, the liquid crystal orientation film of the liquid crystal aligning performance degradation that inhibit backlight to cause is provided.That is, the object of the present invention is to provide polyimide precursor, polyimide or the polymeric amide with above-mentioned characteristic, the liquid crystal aligning agent and liquid crystal display device and diamines that use these compounds are provided further.
The technical scheme that technical solution problem adopts
Present inventor has performed and conscientiously study, found that, comprising side chain, to have the liquid crystal aligning agent of the polyimide precursor of the structure represented by following formula [I], polyimide or polymeric amide very effective to realizing above-mentioned purpose, thus complete the present invention.
That is, the present invention has following technology contents.
1. a polymkeric substance, is characterized in that, for being selected from least one as side chain with the polyimide precursor of the structure represented by following formula [I], the polyimide obtained by this polyimide precursor imidization and polymeric amide.
(in formula, Y 1for be selected from atomicity be 5 or 6 monocyclic ring, atomicity be 5 or 62 adjacent monocyclic rings, atomicity be the lopps of the dicyclic of 8 ~ 10 or atomicity be the lopps of the three-ring type of 13 or 14, non-substituted or replace, the divalent aromatic group of carbon-ring type or hetero ring type; Y 2for singly-bound or the divalent linking group being selected from ehter bond, ester bond, amido linkage and amino-formate bond; Y 3straight-chain alkyl that can be replaced by fluorine atoms for hydrogen atom, carbon number 3 ~ 20 or there is the 1 valency organic group of alicyclic skeleton of carbon number 4 ~ 40.)
2. the polymkeric substance as described in 1, is characterized in that, uses the diamines represented by following formula (1) and obtains.
(in formula, Y 1for be selected from atomicity be 5 or 6 monocyclic ring, atomicity be 5 or 62 adjacent monocyclic rings, atomicity be the lopps of the dicyclic of 8 ~ 10 or atomicity be the lopps of the three-ring type of 13 or 14, non-substituted or replace, the divalent aromatic group of carbon-ring type or hetero ring type; Y 2for singly-bound or the divalent linking group being selected from ehter bond, ester bond, amido linkage and amino-formate bond; Y 3straight-chain alkyl that can be replaced by fluorine atoms for hydrogen atom, carbon number 3 ~ 20 or there is the 1 valency organic group of alicyclic skeleton of carbon number 4 ~ 40; Y 4for the alkylidene group of singly-bound, methylene radical or carbon number 2 ~ 6; Y 5for singly-bound, Sauerstoffatom, *-OCO-or-CH 2o-* is (wherein, with key and the Y of " * " 4in conjunction with.)。Wherein, Y is worked as 4for Y during singly-bound 5for singly-bound.)
3. a liquid crystal aligning agent, is characterized in that, containing the polymkeric substance described in 1 or 2.
4. a liquid crystal orientation film, is characterized in that, uses the liquid crystal aligning agent described in 3 and obtains.
5. a liquid crystal display device, is characterized in that, possesses the liquid crystal orientation film described in 4.
6. a diamines, is characterized in that, represents with following formula (1).
(in formula, Y 1for be selected from atomicity be 5 or 6 monocyclic ring, atomicity be 5 or 62 adjacent monocyclic rings, atomicity be the lopps of the dicyclic of 8 ~ 10 or atomicity be the lopps of the three-ring type of 13 or 14, non-substituted or replace, the divalent aromatic group of carbon-ring type or hetero ring type; Y 2for singly-bound or the divalent linking group being selected from ehter bond, ester bond, amido linkage and amino-formate bond; Y 3straight-chain alkyl that can be replaced by fluorine atoms for hydrogen atom, carbon number 3 ~ 20 or there is the 1 valency organic group of alicyclic skeleton of carbon number 4 ~ 40; Y 4for the alkylidene group of singly-bound, methylene radical or carbon number 2 ~ 6; Y 5for singly-bound, Sauerstoffatom, *-OCO-or-CH 2o-* is (wherein, with key and the Y of " * " 4in conjunction with.)。Wherein, Y is worked as 4for Y during singly-bound 5for singly-bound.)
Invention effect
If employing the present invention, then the novel polyimide precursor of the liquid crystal orientation film of the liquid crystal aligning performance degradation that the backlight that can be inhibited can be provided to cause, polyimide and polymeric amide.And even if be also difficult to liquid crystal aligning performance degradation occurs because this liquid crystal orientation film is exposed to backlight, the liquid crystal display device thus with this liquid crystal orientation film achieves the excellent effect of long-time display characteristic.In addition, this liquid crystal orientation film further suppress the deterioration that AC drives the liquid crystal aligning performance caused, and sintering attachment not easily occurs.
Embodiment
Below, the present invention is described in detail.
Polymkeric substance of the present invention be as side chain have the structure represented by above formula [I] polyimide precursor, there is as side chain the polyimide of the structure represented by above formula [I] and there is as side chain the polymeric amide of the structure represented by above formula [I].In addition, polyimide precursor refers to polyamic acid or poly amic acid ester etc.Structure represented by above formula [I] can with the main chain of the polyimide precursor such as polyamic acid or poly amic acid ester, polyimide or polymeric amide, namely polyamic acid skeleton, polyimide backbone or polyimide backbone directly combine, in addition, also can be combined by suitable linking group.
In formula [I], Y 1as mentioned above for be selected from atomicity be 5 or 6 monocyclic ring, atomicity be 5 or 62 adjacent monocyclic rings, atomicity be 8 ~ 10 dicyclic lopps, or atomicity be the non-substituted of the lopps of the three-ring type of 13 or 14 or replace, the divalent aromatic group of carbon-ring type or hetero ring type.As the monocyclic ring that atomicity is 5 or 6, phenyl ring or pyridine ring etc. can be exemplified.Be 5 or 62 adjacent monocyclic rings as atomicity, can biphenyl etc. be exemplified.As the dicyclic lopps that atomicity is 8 ~ 10, naphthalene etc. can be exemplified.In addition, be the three-ring type lopps of 13 or 14 as atomicity, can anthracene or fluorenes etc. be exemplified.And as mentioned above, the hydrogen atom of these compounds can by the replacement such as alkyl, alkoxy or halogen of such as carbon number 1 ~ 4.Y 2singly-bound or the divalent linking group being selected from ehter bond (-O-), ester bond (-COO-or-OCO-), amido linkage (-CONH-or-NHCO-) and amino-formate bond (-NHCOO-or-OCONH-).Y 3it is 1 valency organic group of straight-chain alkyl that hydrogen atom can be replaced by fluorine atoms, carbon number 3 ~ 20 or the alicyclic skeleton with carbon number 4 ~ 40.Y 1be preferably phenylene or divalent naphthalene (-C 10h 6-), Y 2be preferably singly-bound or ehter bond, Y 3be preferably cyclohexyl or dicyclohexyl.
Use and as side chain, there is the liquid crystal aligning agent of the polyimide precursor such as polyamic acid, poly amic acid ester of the structure represented by above formula [I], polyimide or polymeric amide and the deterioration of liquid crystal aligning performance that the liquid crystal orientation film that formed inhibits the irradiation of backlight to cause containing such.Specifically, use containing such as side chain, there is the liquid crystal aligning agent of the polyimide precursor such as polyamic acid, poly amic acid ester of the structure represented by formula [I], polyimide or polymeric amide and utilize by the method for the anisotropy photochemical reaction of polarized UV rays irradiation etc., namely, the liquid crystal orientation film (also referred to as " optical alignment film ") that uses the method for carrying out orientation process with rayed the to be formed liquid crystal aligning performance degradation that inhibits the irradiation of backlight to cause.Therefore, even if the liquid crystal display device with this liquid crystal orientation film is also good due to the long-time liquid crystal aligning performance that uses, the effect that long-time display characteristic is excellent is thus achieved.In addition, even if there is the polyimide precursor of the structure represented by above formula [I], polyimide or polymeric amide to being used as side chain and the liquid crystal orientation film formed applies long-time AC (interchange) drives, the deterioration of liquid crystal aligning performance also can be suppressed.Therefore, even if drive the liquid crystal display device with this liquid crystal orientation film with long-time AC, also not easily produce sintering attachment.
Infer that the effect of the liquid crystal aligning performance degradation that the irradiation of such suppression backlight causes is that structure represented by above formula of the present invention [I] has oxo acrylate-based and not there is the group that the cinnamoyl etc. near 313nm with maximum absorption has maximum absorption in the ultra-violet region of longer wavelength.On the other hand; if use the liquid crystal aligning agent with the structure of cinnamoyl of liquid crystal aligning agent in the past, the such as patent documentation 1 that replacement oxo is acrylate-based; the unreacted photoreactive group cinnamoyl then had due to liquid crystal orientation film can react in liquid crystal orientation film due to the light from backlight; upset the orientation of liquid crystal, the deterioration of the liquid crystal aligning performance thus making the irradiation of backlight cause is serious.
In addition, the effect of the deterioration of liquid crystal aligning performance also can be suppressed to be that structure represented by above formula [I] has longer chain alkyl or ring structure, has the reason of high vertical orientated performance even if infer that long-time AC drives.
Of the present invention have the polyimide precursor of the structure represented by above formula [I] such as by making diamine component and tetracarboxylic acid composition containing having the diamines of the structure represented by above formula [I] as side chain carry out reacting and obtain as side chain.In addition, poly amic acid ester obtains by the carboxyl of polyamic acid is converted to the method for ester.In addition, polyimide precursor of the present invention is also by making to have the tetracarboxylic acid composition of the structure represented by above formula [I] as side chain and diamine component carries out reacting and obtains.Then, by carrying out imidization to these polyimide precursors such as polyamic acid or poly amic acid ester, the polyimide as side chain with the structure represented by above formula [I] of the present invention can be obtained.In addition, the polymeric amide as side chain with the structure represented by above formula [I] of the present invention reacts in the presence of base by making the diamine component of diamines and the halogenide of dicarboxylic acid containing having the structure represented by above formula [I] as side chain, or makes diamine component and dicarboxylic acid containing having the diamines of the structure represented by above formula [I] as side chain carry out reacting under the existence of suitable condensing agent, alkali and obtain.In addition, polymeric amide of the present invention also by making to have the halogenide of the dicarboxylic acid of the structure represented by above formula [I] as side chain and diamine component reacts in the presence of base, or makes to have the dicarboxylic acid of the structure represented by above formula [I] as side chain and diamine component carries out reacting and obtains under the existence of suitable condensing agent, alkali.Any one of polyimide precursor, polyimide and the polymeric amide such as described polyamic acid, poly amic acid ester is all useful as the polymkeric substance for obtaining liquid crystal orientation film.In addition, the diamines of the structure had represented by formula [I] as side chain contained by diamine component can be a kind, also can be two or more; In addition, diamine component also can containing other diamines beyond the one kind or two or more diamines as side chain with the structure represented by formula [I].In addition, the tetracarboxylic acid composition or dicarboxylic acid etc. as side chain with the structure represented by formula [I] can be a kind, also can be two or more; In addition, also other tetracarboxylic acid beyond the tetracarboxylic acid composition of the structure represented by formula [I] or dicarboxylic acid etc. or dicarboxylic acid can be had containing one kind or two or more as side chain.
The diamines of the structure had represented by above formula [I] as side chain can exemplify the diamines represented by above formula (1).In addition, the diamines represented by above formula (1) is the novel cpd that document is not yet recorded.In formula (1), Y 1, Y 2, Y 3respectively with the Y in formula [I] 1, Y 2, Y 3identical.In addition, Y 4for the alkylidene group of singly-bound, methylene radical or carbon number 2 ~ 6.Further, Y 5for singly-bound, Sauerstoffatom, *-OCO-or-CH 2o-* is (wherein, with key and the Y of " * " 4in conjunction with).In addition, Y 4for Y during singly-bound 5for singly-bound.In formula (1), Y 1be preferably phenylene or divalent naphthalene (-C 10h 6-), Y 2be preferably singly-bound or ehter bond, Y 3be preferably cyclohexyl or dicyclohexyl, Y 4be preferably singly-bound, Y 5be preferably singly-bound or-CH 2o-.
In addition, in formula (1), there is no particular limitation in amino position, although as long as then there is no particular limitation for diamines, but the viewpoint of the difficulty from liquid crystal aligning or synthesis, such as acrylate-based relative to oxo respectively, 2 on phenyl ring can be exemplified by, 3,2,4,2,5,2,6,3,4 or 3,5.Wherein, consider from reactive viewpoint during synthetic polymer, preferably 2,4,2,5 or 3,5.
As the concrete example of the diamines represented by formula (1), following diamines can be exemplified.
The synthetic method of the diamine compound that above formula as above (1) represents is not particularly limited, such as, can manufacture according to synthesis example described later.Such as, the diamines represented by formula (1) obtains by restoring nitro after synthesizing the dinitro compound represented by corresponding following formula (1 ') and making it convert amino to.The method of reduction dinitro compound is had no particular limits, usually palladium-carbon, platinum oxide, Raney nickel, iron, tin chloride, platinum black, rhodium-aluminum oxide, platinum sulfide carbon etc. can be used as catalyzer, but never reduce alkene and retain and optionally only reduce the viewpoint of nitro with high yield and consider, utilize the chemical reduction method using iron or tin chloride to be effective.Have and use ethyl acetate, toluene, tetrahydrofuran (THF), two the alcoholic solvent such as alkane, methyl alcohol, as solvent, uses hydrogen, hydrazine, hydrogenchloride, ammonium chloride etc. to carry out the method for reacting as reductive agent.
(in formula, Y 1, Y 2, Y 3, Y 4, Y 5respectively with the Y in formula (1) 1, Y 2, Y 3, Y 4, Y 5identical)
The synthetic method of the dinitro compound represented by formula (1 ') is not particularly limited, and by any means synthesis, as its object lesson, such as, synthesizes by the method shown in following reaction.
In the reaction, by making dinitro compound A and there is the compd B of hydroxyl at such as ethyl acetate, toluene, tetrahydrofuran (THF), two in the organic solvents such as alkane, chloroform, methylene dichloride, the basic catalysts such as DABCO (Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane) or DMAP (DMAP) are used to carry out reacting to synthesize.
In above-mentioned dinitro compound A, Y 4, Y 5respectively with the Y in formula (1) 4, Y 5identical, as long as have alkynes structure in side chain terminal, then there is no particular limitation in structure.In addition, above-mentioned have in the compd B of hydroxyl, Y 1, Y 2, Y 3respectively with the Y in formula (1) 1, Y 2, Y 3identical, such as can exemplify phenol and its derivatives, be not particularly limited.
By making diamines represented by above formula (1) relative to diamine component total amount more than 10 % by mole, effect of the present invention can be realized, preferably 30 ~ 100 % by mole, preferably 50 ~ 100 % by mole further.In addition, in this specification sheets, if do not recorded especially, ratio refers to mole number to be the ratio of benchmark.
In addition, as other diamines beyond the diamines represented by formula (1), the diamines represented by following formula (2) can be exemplified.
(in formula (2), R 2for singly-bound ,-O-or divalent organic group, X 2, X 3, X 4be separately divalent phenyl ring or cyclohexane ring, p, q, r are separately the integer of 0 or 1, R 3for hydrogen atom, carbon number 1 ~ 22 alkyl or there is the 1 valency organic group of carbon number 12 ~ 25 of steroid skeleton.)
In formula (2), R 2be preferably ehter bond, ester bond, amido linkage or amino-formate bond.R 3be preferably the alkyl of carbon number 12 ~ 18.The alkyl of carbon number 1 ~ 22 can be straight-chain, also can be branched.
Diamines represented by formula (2) is the compound contributing to the tilt angle (angle of inclination relative to the liquid crystal of liquid crystal orientation film) increasing liquid crystal, preferably has the diamines of the substituting group of chain alkyl, perfluoroalkyl, aromatic cyclic base, aliphatic cyclic base and these moiety combinations, steroid skeleton base etc.
Diamines represented by formula (2) relative to diamine component total amount, preferably 5 ~ 50 % by mole, preferably 10 ~ 30 % by mole further.
In addition, as other diamines beyond the diamines represented by above formula (1), Ursol D can be exemplified, 2,3,5,6-tetramethyl-para-phenylene diamine, 2,5-dimethyl-p-phenylenediamine, mphenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diamino benzylalcohol, 2,4-diamino benzylalcohol, 4,6-diaminoresorcinol, 4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxyl-4,4 '-benzidine, 3,3 '-dicarboxyl-4,4 '-benzidine, 3,3 '-two fluoro-4,4 '-biphenyl, 3,3 '-trifluoromethyl-4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-benzidine, 2,3 '-benzidine, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methane, 2,3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 2,2 '-diamino-diphenyl ether, 2,3 '-diamino-diphenyl ether, 4,4 '-alkylsulfonyl dianiline, 3,3 '-alkylsulfonyl dianiline, two (4-aminophenyl) silane, two (3-aminophenyl) silane, dimethyl-bis-(4-aminophenyl) silane, dimethyl-bis-(3-aminophenyl) silane, 4,4 '-thiobis aniline, 3,3 '-thiobis aniline, 4,4 '-diamino-diphenylamine, 3,3 '-diamino-diphenylamine, 3,4 '-diamino-diphenylamine, 2,2 '-diamino-diphenylamine, 2,3 '-diamino-diphenylamine, N-methyl (4,4 '-diamino-diphenyl) amine, N-methyl (3,3 '-diamino-diphenyl) amine, N-methyl (3,4 '-diamino-diphenyl) amine, N-methyl (2,2 '-diamino-diphenyl) amine, N-methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, Isosorbide-5-Nitrae-diaminonaphthalene, 2,2 '-diaminobenzophenone, 2,3 '-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, two (4-aminophenyl) ethane of 1,2-, two (3-aminophenyl) ethane of 1,2-, two (4-aminophenyl) propane of 1,3-, two (3-aminophenyl) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) butane, Isosorbide-5-Nitrae-bis-(3-aminophenyl) butane, two (3,5-diethyl-4-aminophenyl) methane, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) benzene, two (4-aminophenyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminobenzyl) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, 4,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene radical)] dianiline, 4,4 '-[1,3-phenylene two (methylene radical)] dianiline, 3,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene radical)] dianiline, 3,4 '-[1,3-phenylene two (methylene radical)] dianiline, 3,3 '-[Isosorbide-5-Nitrae-phenylene two (methylene radical)] dianiline, 3,3 '-[1,3-phenylene two (methylene radical)] dianiline, Isosorbide-5-Nitrae-phenylene two [(4-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two [(3-aminophenyl) ketone], 1,3-phenylene two [(4-aminophenyl) ketone], 1,3-phenylene two [(3-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two (PABA ester), Isosorbide-5-Nitrae-phenylene two (3-Aminobenzoate), 1,3-phenylene two (PABA ester), 1,3-phenylene two (3-Aminobenzoate), two (4-aminophenyl) terephthalate, two (3-aminophenyl) terephthalate, two (4-aminophenyl) isophthalic acid ester, two (3-aminophenyl) isophthalic acid ester, N, N '-(Isosorbide-5-Nitrae-phenylene) two (4-aminobenzamide), N, N '-(1,3-phenylene) two (4-aminobenzamide), N, N '-(Isosorbide-5-Nitrae-phenylene) two (3-AB), N, N '-(1,3-phenylene) two (3-AB), N, N '-bis-(4-aminophenyl) terephthalamide, N, N '-bis-(3-aminophenyl) terephthalamide, N, N '-bis-(4-aminophenyl) isophtalamide, N, N '-bis-(3-aminophenyl) isophtalamide, two (4-aminophenyl) anthracene of 9,10-, 4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2 '-bis-(4-aminophenyl) HFC-236fa, 2,2 '-bis-(3-aminophenyl) HFC-236fa, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) HFC-236fa, 2,2 '-bis-(4-aminophenyl) propane, 2,2 '-bis-(3-aminophenyl) propane, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) propane, two (4-amino-benzene oxygen) propane of 1,3-, two (3-amino-benzene oxygen) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) butane, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) butane, two (4-amino-benzene oxygen) pentane of 1,5-, two (3-amino-benzene oxygen) pentane of 1,5-, two (4-amino-benzene oxygen) hexane of 1,6-, two (3-amino-benzene oxygen) hexane of 1,6-, two (4-amino-benzene oxygen) heptane of 1,7-, 1,7-(3-amino-benzene oxygen) heptane, two (4-amino-benzene oxygen) octane of 1,8-, two (3-amino-benzene oxygen) octane of 1,8-, two (4-amino-benzene oxygen) nonane of 1,9-, two (3-amino-benzene oxygen) nonane of 1,9-, 1,10-(4-amino-benzene oxygen) decane, 1,10-(3-amino-benzene oxygen) decane, 1,11-(4-amino-benzene oxygen) undecane, 1,11-(3-amino-benzene oxygen) undecane, 1,12-(4-amino-benzene oxygen) dodecane, 1,12-(3-amino-benzene oxygen) dodecane, 4-(amino methyl) aniline, 3-(amino methyl) aniline, 3-((amino methyl) methyl) aniline, the aromatic diamines such as 4-(2-amino-ethyl) aniline or 3-(2-amino-ethyl aniline), the ester ring type diamines such as two (4-aminocyclohexyl) methane or two (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropanes, 1,4-Diaminobutane, 1,5-1,5-DAP, 1,6-diamino hexane, 1,7-diaminoheptane, 1,8-diamino-octane, 1,9-diamino nonane, 1, the aliphatie diamines such as 10-diamino decane, 1,11-diamino undecane or 1,12-diamino dodecane.
Other diamines above-mentioned according to the characteristic such as liquid crystal aligning, voltage retention, accumulated charge when making liquid crystal orientation film, can be used alone, or mixing two or more.
Tetracarboxylic acid composition refers at least one being selected from tetracarboxylic acid and tetracarboxylic acid derivatives.As tetracarboxylic acid derivatives, tetracarboxylic acid two carboxylic acid halides, tetracarboxylic dianhydride, tetracarboxylic acid diester diacid chloride, tetracarboxylic acid diester etc. can be exemplified.Such as, by making tetracarboxylic acid two carboxylic acid halides, tetracarboxylic dianhydride etc. react with diamine component, polyamic acid is obtained.In addition, by tetracarboxylic acid diester diacid chloride and diamine component reaction or tetracarboxylic acid diester and diamine component are reacted under the existence of suitable condensing agent, alkali, obtain poly amic acid ester.In addition, tetracarboxylic acid composition can be a kind, also can be two or more.
As tetracarboxylic acid composition, the tetracarboxylic dianhydride shown in following formula (3) can be exemplified.
(in formula (3), Z 14 valency organic groups of the carbon number 4 ~ 13 of the non aromatic cyclic alkyl containing carbon number 4 ~ 6.)
In formula (3), as Z 1concrete example, the 4 valency organic groups that following formula (3a) ~ formula (3j) represents can be exemplified.
(in formula (3a), Z 2~ Z 5be hydrogen atom, methyl, chlorine atom or phenyl ring, they each other can be identical or different; In formula (3g), Z 6and Z 7be hydrogen atom or methyl, they each other can be identical or different.)
In formula (3), consider from the easness of polymerisation reactivity and synthesis, Z 1particularly preferred structure be formula (3a), formula (3c), formula (3d), formula (3e), formula (3f) or formula (3g).Wherein, preferred formula (3a), formula (3e), formula (3f) or formula (3g).
In addition, relative to tetracarboxylic acid composition total amount, the ratio of the tetracarboxylic dianhydride shown in above formula (3) is not particularly limited, and such as, tetracarboxylic acid composition can be only the tetracarboxylic dianhydride represented with above formula (3).Certainly, in the scope not damaging effect of the present invention, tetracarboxylic acid composition also can comprise tetracarboxylic acid beyond the tetracarboxylic dianhydride shown in above formula (3) and tetracarboxylic acid derivatives.Now, more than 1 % by mole of preferred tetracarboxylic acid composition total amount is the tetracarboxylic dianhydride shown in above formula (3), more preferably more than 5 % by mole, preferably more than 10 % by mole further.
As other tetracarboxylic dianhydride except the tetracarboxylic dianhydride that above-mentioned formula (3) represents, Pyromellitic Acid can be exemplified, 2, 3, 6, 7-naphthalenetetracarbacidic acidic, 1, 2, 5, 6-naphthalenetetracarbacidic acidic, 1, 4, 5, 8-naphthalenetetracarbacidic acidic, 2, 3, 6, 7-anthracene tetracarboxylic acid, 1, 2, 5, 6-anthracene tetracarboxylic acid, 3, 3 ', 4, 4 '-bibenzene tetracarboxylic, 2, 3, 3 ', 4-bibenzene tetracarboxylic, two (3, 4-dicarboxyphenyi) ether, 3, 3 ', 4, 4 '-benzophenone tetracarboxylic, two (3, 4-dicarboxyphenyi) sulfone, two (3, 4-dicarboxyphenyi) methane, 2, 2-two (3, 4-dicarboxyphenyi) propane, 1, 1, 1, 3, 3, 3-hexafluoro-2, 2-two (3, 4-dicarboxyphenyi) propane, two (3, 4-dicarboxyphenyi) dimethylsilane, two (3, 4-dicarboxyphenyi) diphenyl silane, 2, 3, 4, 5-pyridine tetracarboxylic acid, 2, 6-two (3, 4-dicarboxyphenyi) pyridine, 3, 3 ', 4, 4 '-diphenyl sulfone tetraformic acid, 3, 4, 9, 10-perylene tetracarboxylic acid, or 1, 3-phenylbenzene-1, 2, 3, 4-cyclobutanetetracarboxylic.
Tetracarboxylic acid diester is also not particularly limited.Exemplify its concrete example below.
As the object lesson of aliphatics tetracarboxylic acid diester, can 1 be exemplified, 2, 3, 4-tetramethylene tetracarboxylic acid dialkyl, 1, 2-dimethyl-1, 2, 3, 4-tetramethylene tetracarboxylic acid dialkyl, 1, 3-dimethyl-1, 2, 3, 4-tetramethylene tetracarboxylic acid dialkyl, 1, 2, 3, 4-tetramethyl--1, 2, 3, 4-tetramethylene tetracarboxylic acid dialkyl, 1, 2, 3, 4-pentamethylene tetracarboxylic acid dialkyl, 2, 3, 4, 5-tetrahydrofuran (THF) tetracarboxylic acid dialkyl, 1, 2, 4, 5-cyclopentanetetracarboxylic dialkyl, 3, 4-dicarboxyl-1-cyclohexyl dialkyl succinate, 3, 4-dicarboxyl-1, 2, 3, 4-tetrahydrochysene-1-naphthalene succinic dialkyl, 1, 2, 3, 4-butane tetracarboxylic acid dialkyl ester, two rings [3, 3, 0] octane-2, 4, 6, 8-tetracarboxylic acid dialkyl, 3, 3 ', 4, 4 ' dicyclohexyl tetracarboxylic acid dialkyl, 2, 3, 5-tricarboxylic cyclopentyl dialkyl acetates, cis-3, 7-dibutyl ring pungent-1, 5-diene-1, 2, 5, 6-tetracarboxylic acid dialkyl, three ring [4.2.1.0 2,5] nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dialkyl, six ring [6.6.0.1 2,7.0 3,6.1 9,14.0 10,13] n-Hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dialkyl, 4-(2,5-dioxotetrahydro furans-3-base)-1,2,3,4-tetralin-1,2-dicarboxylic acid dialkyl esters etc.
As aromatic tetracarboxylic acid's dialkyl, Pyromellitic Acid dialkyl, 3 can be exemplified, 3 ', 4,4 '-biphenyltetracarboxyacid acid dialkyl, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid dialkyl, 2,3,3 ', 4-biphenyltetracarboxyacid acid dialkyl, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dialkyl, 2,3,3 ', 4-benzophenone tetracarboxylic acid dialkyl, two (3,4-dicarboxyphenyi) ether dialkyl, two (3,4-dicarboxyphenyi) sulfone dialkyl, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl etc.
Be not particularly limited with the dicarboxylic acid etc. that diamine component reacts for for obtaining polymeric amide of the present invention.As in order to obtain polymeric amide and the concrete example of the aliphatic dicarboxylic acid of the dicarboxylic acid or derivatives thereof reacted with diamine component, propanedioic acid, oxalic acid, dimethyl malonic acid, succsinic acid, fumaric acid, pentanedioic acid, hexanodioic acid, muconic acid, 2-methyl hexanodioic acid, trimethyladipic acid, pimelic acid, 2 can be exemplified, the dicarboxylic acid such as 2-dimethylated pentanedioic acid, 3,3-diethyl succsinic acids, nonane diacid, sebacic acid and suberic acid.
As the dicarboxylic acid of ester ring type class, 1,1-cyclopropane dicarboxylic acid can be exemplified, 1,2-cyclopropane dicarboxylic acid, 1,1-cyclobutane dicarboxylic acid, 1,2-cyclobutane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 3,4-phenylbenzene-1,2-cyclobutane dicarboxylic acid, 2,4-phenylbenzene-1,3-cyclobutane dicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,1-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-(2-norbornylene) dicarboxylic acid, norbornylene-2,3-dicarboxylic acid, two rings [2.2.2] octane-Isosorbide-5-Nitrae-dicarboxylic acid, two rings [2.2.2] octane-2,3-dicarboxylic acid, 2,5-dioxo-Isosorbide-5-Nitrae-two ring [2.2.2] octane dicarboxylic acid, 1,3-diamantane dicarboxylic acid, 4,8-dioxo-1,3-diamantane dicarboxylic acid, 2,6-spiral shell [3.3] heptane dicarboxylic acid, 1,3-diamantane oxalic acid, dextrocamphoric acid etc.
As aromatic dicarboxylic acid, phthalic acid can be exemplified, m-phthalic acid, terephthalic acid, oreinol dioctyl phthalate, 5-tert-butyl isophthalic acid, 5-amino isophthalic acid, 5-Hydroxy M Phthalic Acid, 2, 5-dimethyl terephthalic acid, tetramethyl-terephthalic acid, 1, 4-naphthalene dicarboxylic acids, 2, 5-naphthalene dicarboxylic acids, 2, 6-naphthalene dicarboxylic acids, 2, 7-naphthalene dicarboxylic acids, 1, 4-anthracene dicarboxylic acid, 1, 4-anthraquinone dicarboxylic acid, 2, 5-diphenyl dicarboxylic acid, 4, 4 '-diphenyl dicarboxylic acid, 1, 5-diphenylene dicarboxylic acids, 4, 4 "-terphenyl dicarboxylic acid, 4, 4 '-ditan dicarboxylic acid, 4, 4 '-diphenylethane dicarboxylic acid, 4, 4 '-diphenyl propane dicarboxylic acid, 4, 4 '-phenylbenzene HFC-236fa dicarboxylic acid, 4, 4 '-diphenyl ether dicarboxylic acid, 4, 4 '-dibenzyl dicarboxylic acid, 4, 4 '- dicarboxylic acid, 4, 4 '-tolane dioctyl phthalate, 4, 4 '-carbonyl diurethane phenylformic acid, 4, 4 '-sulfonyl dibenzoic acid, 4, 4 '-dithiodibenzoic acid, to phenylene-diacetic acid, 3, 3 '-to benzene dipropionic acid, 4-o-carboxy cinnamic acid, to benzene diacrylate, 3, 3 '-[4, 4 '-(methylene radical two pairs of phenylenes)] dipropionic acid, 4, 4 '-[4, 4 '-(oxo two pairs of phenylenes)] dipropionic acid, 4, 4 '-[4, 4 '-(oxo two pairs of phenylenes)] two butyric acid, (isopropylidene two pairs of phenylene dioxies) two butyric acid, the dicarboxylic acid such as two (to carboxyl phenyl) dimethylsilane.
As the dicarboxylic acid containing heterocycle, 1,5-(9-oxo fluorenes) dicarboxylic acid, 3,4-furans dicarboxylic acid, 4,5-thiazole dicarboxylic acid, 2-phenyl-4,5-thiazole dicarboxylic acid, 1,2,5-thiadiazoles-3,4-dicarboxylic acid, 1,2,5-can be exemplified diazole-3,4-dicarboxylic acid, 2,3-pyridine dicarboxylic acids, 2,4-pyridine dicarboxylic acids, 2,5-Pyridinedicarboxylic acid, 2, dipicolimic acid 2,3,4-pyridine dicarboxylic acids, 3,5-pyridine dicarboxylic acids etc.
Above-mentioned various dicarboxylic acid also can be the structure of sour two carboxylic acid halides or acid anhydrides.Wherein, preferred use terephthalic acid, m-phthalic acid, 1,4-cyclohexane dicarboxylic acid, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-ditan dicarboxylic acid, 4,4 '-diphenylethane dicarboxylic acid, 4,4 '-diphenyl propane dicarboxylic acid, 4,4 '-phenylbenzene HFC-236fa dicarboxylic acid, 2,2-bis-(phenyl) propane dicarboxylic acid, 4,4 "-terphenyl dicarboxylic acid, 2; 6-naphthalene dicarboxylic acids, 2,5-Pyridinedicarboxylic acid or their acid two carboxylic acid halides etc.Sometimes also there is isomer in these compounds, also can be the mixture comprising isomer.In addition, the compound that also two or more kinds may be used.
Tetracarboxylic dianhydride shown in above formula (3), other tetracarboxylic acid and tetracarboxylic acid derivatives, dicarboxylic acid etc., characteristic that also can be required according to liquid crystal aligning, voltage retention and the accumulated charge etc. when making liquid crystal orientation film uses a kind or two or more is used in combination.
The reaction of diamine component and tetracarboxylic acid composition is carried out usually in organic solvent.As the organic solvent now used, as long as can dissolve the polyimide precursors such as the polyamic acid of generation, there is no particular limitation.As object lesson, DMF can be exemplified, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-methyl caprolactam, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolactone, Virahol, methoxymethyl amylalcohol, limonene, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methylcyclohexane, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monobutyl ether, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, DPGME, Diethylene Glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethyl ether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, tetrahydrotoluene, propyl ether, two hexyl ethers, two alkane, normal hexane, normal heptane, octane, diethyl ether, pimelinketone, ethylene carbonate, Texacar PC, methyl lactate, lactic acid ethyl, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethyl ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, 3-methoxy methyl propionate, 3-ethoxy-propionic acid methyl ethyl ester, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diglyme or 4-hydroxy-4-methyl-2-pentanone etc.These solvents can be used alone, also can be used in combination.Further, even the solvent of polyimide precursor can not be dissolved, in the scope also can not separated out at the polyimide precursor generated, be blended in above-mentioned solvent and use.In addition, because the moisture in organic solvent hinders polyreaction, and then become the reason that the polyimide precursor of generation is hydrolyzed, so it is desirable to use the organic solvent through dehydrating.
When diamine component and tetracarboxylic acid composition are reacted in organic solvent, following method can be exemplified: the solution that stirring makes diamine component be dispersed or dissolved in organic solvent and obtains, the method for then directly adding tetracarboxylic acid composition or adding again after making tetracarboxylic acid composition be dispersed or dissolved in organic solvent; The method of diamine component is added in the solution obtained tetracarboxylic dianhydride is dispersed or dissolved in organic solvent on the contrary; Alternately add the method etc. of tetracarboxylic acid composition and diamine component, any one method wherein can be used.In addition, when diamine component or tetracarboxylic acid composition use multiple reaction respectively, it can be made to react under the state be pre-mixed, it also can be made to react successively respectively, then the low-molecular weight hybrid reaction making to react respectively and obtain.Polymerization temperature now can select the arbitrary temp of-20 DEG C ~ 150 DEG C, preferably the scope of-5 DEG C ~ 100 DEG C.In addition, reaction can be carried out with arbitrary concentration, if but concentration is too low, and be difficult to the polyimide precursor (and then polyimide) obtaining high molecular, if excessive concentration, the viscosity of reaction solution is too high, is difficult to stir uniformly.Therefore, the concentration of the total amount of diamine component and tetracarboxylic acid composition is preferably 1 ~ 50 quality %, more preferably 5 ~ 30 quality % in reaction solution.Initial reaction stage is carried out in higher concentrations, can add organic solvent afterwards.
In the polyreaction of the polyimide precursors such as polyamic acid, the total mole number of diamine component is preferably 0.8 ~ 1.2 with the ratio of the total mole number of tetracarboxylic acid composition.Identical with common polycondensation, this mol ratio is more close to 1.0, and the molecular weight of the polyimide precursor of generation is larger.
In addition, poly amic acid ester by above-mentioned tetracarboxylic acid diester diacid chloride and diamine component reaction or make tetracarboxylic acid diester and diamine component carry out reacting obtaining under the existence of suitable condensing agent, alkali.Or also can use the pre-synthesis polyamic acid of aforesaid method, recycling high molecular weight reactive carries out esterification to obtain to the carboxyl in polyamic acid.
Specifically, can by such as making tetracarboxylic acid diester diacid chloride and diamine component under the existence of alkali and organic solvent, and-20 DEG C ~ 150 DEG C, preferably 0 DEG C ~ 50 DEG C at reaction 30 minutes ~ 24 hours, preferably 1 hour ~ 4 hours, carry out synthesizing polyamides acid esters.
As alkali, pyridine, triethylamine, 4-dimethylaminopyridine can be used, in order to carry out with making reacting balance, preferred pyridine.The addition of alkali is from the viewpoint of the amount of easily removing and easily obtain high molecular body, relative to tetracarboxylic acid diester diacid chloride, and preferably 2 ~ 4 times moles.
In addition, when making to carry out polycondensation under tetracarboxylic acid diester and the existence of diamine component at condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride, N can be used as alkali, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazine methylmorpholine , O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylurea (TMU) Tetrafluoroboric acid ester, O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylurea (TMU) phosphofluoric acid ester, (2,3-dihydro-2-sulfo--3-benzo azoles base) phosphonic acid diphenyl ester, chlorination 4-(4,6-dimethoxy-1,3,5-triazines-2-base) 4-methoxyl group morpholine n hydrate etc.
In addition, in the method using above-mentioned condensing agent, by adding Lewis acid as additive, reaction can be carried out efficiently.As Lewis acid, the lithium halides such as preferred lithium chloride, lithiumbromide.Lewis acidic addition is relative to the diamines carrying out reacting or tetracarboxylic acid diester preferably 0.1 ~ 1.0 times of molar weight.
As the solvent used in above-mentioned reaction, the solvent same with the solvent phase used when the above-mentioned synthesizing polyamides illustrated is sour can be used, consider from monomer and structure adaptability, preferred METHYLPYRROLIDONE, gamma-butyrolactone, can use in them a kind or two or more is used in combination.From the viewpoint of be difficult to occur polymkeric substance precipitation and easily obtain high molecular body, total concn in the reaction soln of the tetracarboxylic acid derivatives such as concentration during synthesis, tetracarboxylic acid diester diacid chloride or tetracarboxylic acid diester and diamine component is preferably 1 ~ 30 quality %, more preferably 5 ~ 20 quality %.In addition, in order to prevent tetracarboxylic acid diester diacid chloride to be hydrolyzed, the solvent for the synthesis of poly amic acid ester can be the state of dewatering as far as possible, preferably in nitrogen atmosphere, prevents being mixed into of foreign gas.
To be polymerized thus and the polyimide precursor obtained is such as the polymkeric substance with the repeating unit shown in following formula [a].
(in formula [a], R 114 valency organic groups of the tetracarboxylic acid composition deriving from raw material; R 12it is the divalent organic group of the diamine component deriving from raw material; A 11and A 12be the alkyl of hydrogen atom or carbon number 1 ~ 4, they each other can be identical or different; J represents positive integer.)
Can be that there is R in above formula [a] 11and R 12a kind of polymkeric substance of identical repeating unit respectively, in addition, also can for having R 11and R 12it is the polymkeric substance of the repeating unit of multiple different structure.
In above formula [a], R 11it is the group deriving from the tetracarboxylic acid composition that the following formula [c] etc. as raw material represents.In addition, R 12derive from the group as the diamine component shown in the following formula [b] etc. of raw material, such as, if R 12for deriving from the group of the diamine compound represented by above formula (1), be then the C on phenyl ring with 2 keys 6h 3-Y 5-Y 4-OCO-CH=CH-O-Y 1-Y 2-Y 3.
(in formula [b] and formula [c], R 11and R 12identical with the definition in formula [a].)
Then, by by these polyimide precursor dehydration closed-loops, polyimide is obtained.
As the method making polyimide precursor carry out imidization, the hot-imide of the solution of direct heating polyimide precursor can be exemplified, or in the solution of polyimide precursor, add the catalysis imidization of catalyzer.
Make temperature during polyimide precursor hot-imide be 100 DEG C ~ 400 DEG C in the solution, preferably 120 DEG C ~ 250 DEG C, preferably carry out while the water will generated by imidization reaction is got rid of to system.
The catalysis imidization of polyimide precursor by adding basic catalyst and acid anhydrides in polyimide precursor solution, and-20 ~ 250 DEG C, preferably at 0 ~ 180 DEG C stir and carry out.The amount of basic catalyst is 0.5 ~ 30 mole times of acid amides acidic group, preferably 2 ~ 20 moles times, and the amount of acid anhydrides is 1 ~ 50 mole times of acid amides acidic group, preferably 3 ~ 30 moles times.As basic catalyst, pyridine, triethylamine, Trimethylamine 99, Tributylamine or trioctylamine etc. can be exemplified, wherein pyridine have for make reaction carry out for appropriateness alkalescence, therefore preferably.As acid anhydrides, diacetyl oxide, trimellitic acid 1,2-anhydride or pyromellitic dianhydride etc. can be exemplified, wherein, use during diacetyl oxide and be easy to carry out reacting the purifying after terminating, therefore preferably.Adopt the imide rate of catalysis imidization can be controlled by adjustment catalytic amount and temperature of reaction, reaction times.
In addition, when reclaiming from the reaction soln of the polyimide precursor such as polyamic acid, poly amic acid ester or polyimide the polyimide precursor or polyimide that generate, reaction soln can be poured into solvent and make it precipitate.As the solvent for precipitating, methyl alcohol, acetone, hexane, ethylene glycol butyl ether, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene or water etc. can be exemplified.Putting in solvent the polyimide precursor of precipitation or polyimide can after filtered and recycled, under normal or reduced pressure, at normal temperature or heat and carry out drying.In addition, if the polyimide precursor making precipitation reclaim or polyimide repeat to be dissolved in organic solvent again 2 ~ 10 times and the operation of redeposition recovery, then the impurity in polyimide precursor or polyimide can be reduced.As solvent now, can exemplify such as alcohols, ketone or hydro carbons etc., if use the solvent of more than 3 kinds be selected from these solvents, then purification efficiency improves further, therefore preferably.
The dehydration closed-loop rate (imide rate) of the acid amides acidic group of polyimide need not be 100%, can select arbitrarily in the scope of 0% to 100% according to purposes and object, and preferably 30% ~ 80%.
Polymeric amide can synthesize in the mode identical with poly amic acid ester.
For the molecular weight of polyimide precursor of the present invention, polyimide or polymeric amide, consider the homogeneity of the operability when intensity of the polymkeric substance tunicle (liquid crystal orientation film) of gained, polymkeric substance tunicle are formed, polymkeric substance tunicle, 5000 ~ 1000000 are preferably, more preferably 10000 ~ 150000 with the Weight-average molecular gauge utilizing GPC (gel permeation chromatography) method to record.
Liquid crystal aligning agent of the present invention comprises polyimide precursor, polyimide or the polymeric amide such as polyamic acid of the present invention, poly amic acid ester as side chain with the structure represented by above formula [I].Liquid crystal aligning agent refers to the solution for the formation of liquid crystal orientation film, is the solution component of polymer for the formation of liquid crystal orientation film being dispersed or dissolved in organic solvent and being formed.In addition, liquid crystal orientation film refers to for making liquid crystal along the film of the direction orientation of regulation.And, in the present invention, as above-mentioned component of polymer, containing at least one being selected from above-mentioned polyimide precursor of the present invention, polyimide and polymeric amide.
Component of polymer contained in liquid crystal aligning agent of the present invention can be all above-mentioned polyimide precursor of the present invention, polyimide or polymeric amide, also can mix other polymkeric substance in above-mentioned polyimide precursor of the present invention, polyimide or polymeric amide in addition.When component of polymer contains other polymkeric substance, the content of other the polymkeric substance in component of polymer total amount is 0.5 quality % ~ 80 quality %, preferably 40 quality % ~ 80 quality %.
As other such polymkeric substance, can exemplify and such as carry out as with tetracarboxylic dianhydride's composition or dicarboxylic acid etc. the diamine component that reacts, only use the diamines beyond the diamines as side chain with the structure represented by above formula [I] of the present invention and polyimide precursor, polyimide or the polymeric amide etc. that obtain.Further, the polymkeric substance beyond polyimide precursor, polyimide or polymeric amide, specifically can exemplified by acrylic polymkeric substance, methacrylate polymer, polysiloxane, polystyrene etc.
In liquid crystal aligning agent of the present invention, the at least one being selected from polyimide precursor of the present invention, polyimide and polymeric amide and other polymkeric substance of mixing as required in component of polymer total amount, be preferably 1 quality % ~ 20 quality % containing proportional, more preferably 3 quality % ~ 15 quality %, particularly preferably 3 ~ 10 quality %.
As long as the organic solvent of the component of polymer such as solvent solubilized polyimide precursor of the present invention, polyimide or polymeric amide that liquid crystal aligning agent of the present invention contains, is not particularly limited.As its concrete example, N can be exemplified, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrolidone, NVP, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolactone, 3-methoxyl group-N, N-dimethylpropionamide, 3-oxyethyl group-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1, 3-dimethyl-2-imidazolidinone, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, pimelinketone, ethylene carbonate, Texacar PC, diglyme, 4-hydroxy-4-methyl-2-pentanone etc.These solvents can be used alone, also can be used in combination.
In liquid crystal aligning agent of the present invention, in the scope not damaging effect of the present invention, can containing the film uniformity of polymkeric substance tunicle when can improve coating of liquid crystalline alignment agent and the organic solvent (also referred to as poor solvent) of surface smoothness or compound.Further, the compound etc. of the adaptation that can improve liquid crystal orientation film and substrate can also be contained.
As the concrete example of the poor solvent of the homogeneity and surface smoothness that can improve thickness, Virahol can be exemplified, methoxymethyl amylalcohol, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monobutyl ether, ethyl carbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, DPGME, Diethylene Glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethyl ether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, tetrahydrotoluene, propyl ether, two hexyl ethers, normal hexane, Skellysolve A, octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethyl ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, 3-methoxy methyl propionate, 3-ethoxy-propionic acid methylethyl ester, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 1-methoxy-2-propanol, 1-oxyethyl group-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 ester, propylene glycol-1-single ethyl ether-2-acetic ester, dipropylene glycol, 2-(2-oxyethyl group propoxy-) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate or isoamyl lactate etc. have the organic solvent etc. of low surface tension.
These poor solvents can use a kind, or by multiple used in combination.When using solvent as above, preferably account for 5 ~ 80 quality % of solvent total amount contained in liquid crystal aligning agent, more preferably 20 ~ 60 quality %.
As the compound improving film uniformity or surface smoothness, fluorine class tensio-active agent, siloxane type surfactants, nonionic surface active agent etc. can be exemplified.More specifically, such as エ Off ト ッ プ EF301 can be exemplified, EF303, EF352 (Tuo Kaimu product Co., Ltd. (ト ー ケ system プ ロ ダ Network Star) system), メ ガ Off ァ ッ Network F171, F173, R-30 (large Japanese ink Co., Ltd. (large Japanese イ Application キ) system), Off ロ ラ ー De FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo ス リ ー エ system) system), ア サ ヒ ガ ー De AG710, サ ー Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd's (Asahi Glass) system) etc.The usage ratio of these tensio-active agents relative to component of polymer 100 mass parts contained in liquid crystal aligning agent, preferably 0.01 ~ 2 mass parts, more preferably 0.01 ~ 1 mass parts.
As the compound of adaptation improving liquid crystal orientation film and substrate, the compound containing functional silanes or the compound containing epoxy group(ing) can be exemplified, such as, 3-TSL 8330 can be exemplified, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl Trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (the oxyethylene group)-3-TSL 8330 of N-, two (the oxyethylene group)-APTES of N-, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidylether, 1,3,5,6-four glycidyl group-2,4-hexylene glycol, N, N, N ', N ' ,-four glycidyl group-m-xylene diamine, two (N, the N-diglycidyl amino methyl) hexanaphthene of 1,3-or N, N, N ', N ' ,-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.
When use can improve the compound with the adaptation of substrate, its usage quantity, relative to component of polymer 100 mass parts contained in liquid crystal aligning agent, is preferably 0.1 ~ 30 mass parts, more preferably 1 ~ 20 mass parts.If usage quantity is less than 0.1 mass parts, then cannot expect the effect that adaptation improves, if more than 30 mass parts, then the orientation of liquid crystal is deteriorated sometimes.
In liquid crystal aligning agent of the present invention, in addition to the foregoing, in the scope not damaging effect of the present invention, the dielectric medium for the purpose of the electrical characteristic such as the specific inductivity that is changed liquid crystal orientation film or electroconductibility or conducting material can be added, the cross-linked compound for the purpose of the hardness improving film when forming liquid crystal orientation film or density can also be added.
Liquid crystal aligning agent of the present invention can coated on substrate and after burning till, carry out orientation process with rayed etc., thus is used as liquid crystal orientation film.Liquid crystal orientation film of the present invention like this has the polyimide precursor of the structure represented by above formula [I], polyimide or polymeric amide owing to comprising as side chain, therefore be difficult to the liquid crystal aligning performance degradation that generation backlight causes, be difficult to that AC occurs in addition and drive the liquid crystal aligning performance degradation caused.In addition, liquid crystal aligning agent of the present invention also may be used for above-mentionedly carrying out orientation process with rayed and forming purposes beyond liquid crystal orientation film (optical alignment film).Specifically, may be used for burning till after the liquid crystal orientation film that carries out friction treatment or do not carry out orientation process and formed in vertical orientated purposes etc.
As substrate, as long as the substrate that the transparency is high, be not particularly limited, except glass substrate, also can use the plastic bases etc. such as vinylformic acid substrate, polycarbonate substrate.From the viewpoint of work simplification, preferably use the substrate of ITO (the Indium Tin Oxide) electrode etc. defined for liquid crystal drive.In addition, in reflection type liquid crystal display element, also can use the opaque substrates such as silicon wafer, but be only limitted to one-sided substrate, electrode now also can use the material of the reflected light such as aluminium.In addition, in the contour performance components of TFT type element, the component for being formed with the elements such as transistor between the electrode of liquid crystal drive and substrate can be used in.
Be not particularly limited the coating process of liquid crystal aligning agent, the method be coated with is carried out in industrial usual employing by silk screen printing, offset printing, flexographic printing or ink jet method etc.As other coating process, also have dip coating, rolling method, slot coated method, spin-coating method or spraying method etc., these methods can be used according to object.
Liquid crystal aligning agent is coated after on substrate, can pass through the heating units such as hot-plate, heat-circulation type stove or IR (infrared rays) type stove 50 ~ 300 DEG C, preferably at 80 ~ 250 DEG C, solvent is evaporated, thus formed liquid crystal orientation film (polymkeric substance tunicle).If the thickness of the liquid crystal orientation film after burning till is blocked up, then unfavorable in the power consumption of liquid crystal display device, if excessively thin, then the reliability of liquid crystal display device reduces sometimes, therefore preferably 5 ~ 300nm, more preferably 10 ~ 100nm.When making liquid crystal vertical-tropism, horizontal alignment or tilted alignment, can the radioactive rays such as polarized UV rays be irradiated the liquid crystal orientation film after burning till or carry out friction treatment.
Liquid crystal display device of the present invention is after being with the substrate of liquid crystal orientation film by aforesaid method by liquid crystal aligning agent acquisition of the present invention, the liquid crystal display device formed by known method manufacture liquid crystal cell.If exemplify an example, then there is the liquid crystal display device possessing following liquid crystal cell: this liquid crystal cell possesses the 2 pieces of substrates configured in opposite directions, be arranged on the liquid crystal layer between substrate, and be arranged on the above-mentioned liquid crystal orientation film formed by liquid crystal aligning agent of the present invention between substrate and liquid crystal layer.As such liquid crystal display device of the present invention, vertical orientated (VA:Vertical Alignment) mode, stable twisted nematic (TN:Twisted Nematic) mode and horizontal alignment (IPS:In-PlaneSwitching can be exemplified, switch in face) the various liquid crystal display device such as mode, OCB orientation (OCB:Optically Compensated Bend, optical compensation curved).In addition, at least one piece that liquid crystal orientation film can be arranged in 2 pieces of substrates.
As the substrate that liquid crystal display device of the present invention uses, as long as the substrate that the transparency is high, be not particularly limited, on substrate, be normally formed with the substrate of the transparency electrode for driving liquid crystal.As concrete example, the substrate same with the substrate recorded in above-mentioned liquid crystal orientation film can be exemplified.
In addition, liquid crystal orientation film burns till after being coated with liquid crystal aligning agent of the present invention on the substrate, then irradiate the radioactive rays such as polarized UV rays as required and formed, and detailed content is described above.
The liquid crystal material of the liquid crystal layer forming liquid crystal display device of the present invention is not particularly limited, the positive type liquid crystal with positive dielectric anisotropy or the negative type liquid crystal with negative dielectric anisotropy can be used.As concrete example, the liquid crystal material that vertical orientation mode in the past uses can be used, MLC-6608, MLC-6609 etc. that such as Merck & Co., Inc. (メ ルク society) makes.
An example of liquid crystal cell is manufactured if exemplify, following method can be illustrated: a pair substrate preparing to be formed with liquid crystal orientation film, the liquid crystal orientation film of a plate base scatters pearl thing at equal intervals, make liquid crystal aligning face become interior rear flank the laminating of another plate base, decompression injects liquid crystal and the method for sealing; Or drip liquid crystal on the liquid crystal aligning face being scattered with spacer after, baseplate-laminating is carried out the method etc. sealed.Now, the thickness of spacer preferably 1 ~ 30 μm, more preferably 2 ~ 10 μm.
As above the liquid crystal display device using liquid crystal aligning agent of the present invention to be made is owing to having the liquid crystal orientation film of the deterioration of the liquid crystal aligning performance that inhibit the irradiation of backlight to cause, and thus long-time display characteristic is excellent.In addition, even if carry out driving the liquid crystal orientation film of the deterioration that also can suppress liquid crystal aligning performance owing to having long-time applying AC, even if be therefore carry out driving with AC the liquid crystal display device also not easily producing sintering attachment for a long time.
Embodiment
Below, be described in further detail based on embodiment, but the present invention is not by any restriction of this embodiment.
The breviary symbol used in the present embodiment is as follows:
(tetracarboxylic dianhydride)
CBDA:1,2,3,4-tetramethylene tetracarboxylic dianhydride
(diamines)
DA-1: (E) represented by following formula-3,5-diamino benzyl 3-(4-(trans-4-heptyl cyclohexyl) phenoxy group) acrylate
DA-2: (E) represented by following formula-3,5-diamino benzyl 3-(4-(trans-4 '-amyl group-[1,1 '-bis-(hexanaphthene)]-4-base) phenoxy group) acrylate
PCH:1,3-diamino-4-[4-(4-heptyl cyclohexyl) phenoxy group] benzene
(organic solvent)
NMP:N-N-methyl-2-2-pyrrolidone N-
BCS: ethylene glycol butyl ether
< polymer molecule flow measurement >
Normal temperature gel permeation chromatography (GPC) device (SSC-7200) that the molecular weight of polymkeric substance (polyamic acid etc.) uses Sen Xiu science Co., Ltd. (セ Application シ ュ ー science society) to make, the post (KD-803, KD-805) of Showa electrician (Shodex) Co., Ltd. measure as follows.
Column temperature: 50 DEG C
Elutriant: N, N'-dimethyl formamide (as additive, lithiumbromide hydrate (LiBrH 2o) be 30 mM/ls, phosphoric anhydride crystallization (o-phosphoric acid) is 30 mM/ls, tetrahydrofuran (THF) (THF) is 10 milliliters/liter)
Flow velocity: 1.0ml/ minute
Calibration curve making standard test specimen: Dong Cao company (East ソ ー society) TSK standard polyethylene oxide (molecular weight is about 900000,150000,100000,30000) processed and Polymer Laboratory company (Port リ マ ー ラ ボ ラ ト リ ー society) polyoxyethylene glycol processed (molecular weight is about 12000,4000,1000).
The synthesis of < synthesis example 1>DA-1 ((E)-3,5-diamino benzyl 3-(4-(trans-4-heptyl cyclohexyl) phenoxy group) acrylate)
(in above-mentioned reaction formula, the cis-trans isomerization of cyclohexylidene is respectively trans-isomer(ide).)
Compound [A] (11.00g is added in the four-hole boiling flask of 1L, 55.5mmol), triphenylphosphine (16.02g, 61.1mmol), tetrahydrofuran (THF) (80g) (being also denoted as THF below), after carrying out nitrogen displacement, reaction soln is cooled to 0 DEG C.Slowly drip the mixing solutions of propynoic acid [B] (4.67g, 66.6mmol), azodicarboxy isopropyl propionate (12.34g, 61.1mmol), THF (120g) wherein.After dropping terminates, reaction soln is returned to 23 DEG C, stir further.Carry out reactive tracing by high performance liquid chromatography (HPLC), after confirming that reaction terminates, remove with vaporizer distillation the crude product that solvent obtains compound [C].
Then, compound [D] (15.23g is added in compound obtained above [C], 55.5mmol) with THF (140g), add 1 again, 4-diazabicyclo [2.2.2] octane (being also denoted as DABCO below) (622mg, 5.55mmol), stir at 23 DEG C.Carry out reactive tracing with HPLC, after confirming that reaction terminates, add 10wt% aqueous sodium hydroxide solution 200g, extract with ethyl acetate (200mL)/hexane (600mL) mixing solutions.After removing water layer, clean 3 times with saturated aqueous common salt (500g), after making its drying with magnesium sulfate, remove solvent with vaporizer distillation, obtain the crude product of compound [E].Then, 2-propyl alcohol (being also denoted as IPA below) (200g) is added and after carrying out 30 minutes heated and stirred in the crude product of the compound obtained [E], placement is cooled to 30 DEG C, carry out filtering, drying under reduced pressure, obtain compound [E] (15.4g, yield 53%).The result measuring the compound [E] obtained with NMR is as follows.
1H-NMR(400MHz，CDCl 3，δppm)：9.01(1H，t)，8.57-8.56(2H，m)，7.88(1H，d)，7.23-7.01(2H，m)，7.01-6.98(2H，m)，5.58(1H，d)，5.35(2H，s)，2.53-2.44(1H，m)，1.88-1.85(4H，m)，1.49-1.00(17m)，0.89(3H，t)。
Compound [E] (14.81g is added in the four-hole boiling flask of 500mL, 28.2mmol), ferrous components (9.46g, 169mmol), 10wt% aqueous ammonium chloride solution (45g), ethyl acetate (130g), at 70 DEG C, carry out heated and stirred.Use HPLC following response, reaction is removed solids component with diatomite filtration, is cleaned with ethyl acetate and distilled water after terminating confirmation.Analyze filtrate, after removing water layer, clean organic layer 3 times with distilled water (500g), after making its drying with magnesium sulfate, remove solvent with vaporizer distillation, obtain the crude product of Compound D A-1.In this crude product, add methyl alcohol (30g), stirring at room temperature was filtered after 30 minutes, carried out washed with methanol and drying under reduced pressure, obtained Compound D A-1 (9.9g, yield 76%).The result measuring the Compound D A-1 obtained with NMR is as follows.
1H-NMR(400MHz，CDCl 3，δppm)：7.81(1H，d)，7.20-7.18(2H，m)，6.98-6.96(2H，m)，6.11(2H，d)，5.98(1H，t)，5.54(1H，m)，4.99(2H，s)，3.60(4H，brs)，2.48-2.42(1H，m)，1.87-1.85(4H，m)，1.42-1.20(14H，m)，1.08-0.99(3H，m)，0.89-0.87(3H，m)。
< synthesis example 2>DA-2 ((E)-3,5-diamino benzyl 3-(4-(trans-4 '-amyl group-[1,1 '-bis-(hexanaphthene)]-4-base) phenoxy group) acrylate) synthesis
(in above-mentioned reaction formula, the cis-trans isomerization of cyclohexylidene is respectively trans-isomer(ide).)
Propynoic acid [B] (3.23g is added in the four-hole boiling flask of 200mL, 46.2mmol) and N, N '-dimethyl methane amide (40g) (being also denoted as DMF below), stir while successively add sodium bicarbonate (7.76g on a small quantity at 23 DEG C, 92.4mmol) powder, at room temperature stirs 30 minutes.Then, solution is heated to 50 DEG C, slowly drips DMF (60g) solution of 3,5-dinitrobenzyl chlorine [F] (10.00g, 46.2mmol).Carry out reactive tracing with HPLC, after reaction terminates, add ethyl acetate (600g), hexane (200g) and distilled water (600g), carry out separatory operation, remove water layer.Clean organic layer 3 times with distilled water (500g), after making its drying with magnesium sulfate, remove solvent with vaporizer distillation, obtain compound [C] (11.05g, yield 96%).The result measuring the compound [C] obtained with NMR is as follows.
1H-NMR(400MHz，CDCl 3，δppm)：9.06-9.05(1H，m)，8.60-8.59(2H，m)，5.41(2H，s)，3.04(1H，s)。
Compound [C] (11.05g is added in the four-hole boiling flask of 200mL, 44.2mmol), compound [G] (14.51g, 44.2mmol), 1,4-diazabicyclo [2.2.2] octane (495mg, 4.42mmol) with tetrahydrofuran (THF) (140g), stir at 23 DEG C.Carry out reactive tracing with HPLC, after reaction terminates, add 10wt% aqueous sodium hydroxide solution (100g), add ethyl acetate (200g) further, remove water layer by separatory operation.Clean organic layer 3 times with saturated aqueous common salt (500g), after making its drying with magnesium sulfate, remove solvent with vaporizer distillation, obtain the crude product of compound [H].In this crude product, add 2-propyl alcohol (180g), carry out after 30 minutes reflux stir, being cooled to 40 DEG C, filter and after carrying out IPA cleaning, carry out drying under reduced pressure, obtain compound [H] (25.3g, yield 98%).The result measuring the compound [H] obtained with NMR is as follows.
1H-NMR(400MHz，CDCl 3，δppm)：9.00(1H，t)，8.57-8.56(2H，m)，7.88(1H，d)，7.22-7.21(2H，m)，7.00-6.98(2H，m)，5.58(1H，d)，5.36(2H，s)，2.50-2.37(1H，m)，1.94-0.84(30H，m)。
Compound [H] (25.3g is added in the four-hole boiling flask of 500mL, 44.2mmol), ferrous components (14.80g, 265mmol), 10wt% aqueous ammonium chloride solution (71g), ethyl acetate (230g), at 70 DEG C, carry out heated and stirred.Use HPLC following response, reaction is removed solids component with diatomite filtration, is cleaned with ethyl acetate and distilled water after terminating confirmation.Analyze filtrate, after removing water layer, clean organic layer 3 times with distilled water (500g), after making its drying with magnesium sulfate, remove solvent with vaporizer distillation, obtain the crude product of Compound D A-2.In this crude product, add methyl alcohol (50g), stirring at room temperature was filtered after 30 minutes, carried out washed with methanol and drying under reduced pressure, obtained Compound D A-2
(14.7g, yield 64%).The result measuring the Compound D A-2 obtained with NMR is as follows.
1H-NMR(400MHz，CDCl 3，δppm)：7.81(1H，d)，7.20-7.18(2H，m)，6.98-6.96(2H，m)，6.11(2H，d)，5.98(1H，t)，5.54(1H，m)，4.99(2H，s)，3.59(4H，brs)，2.53-2.38(1H，m)，1.87-0.90(30H，m)。
The synthesis of < synthesis example 3>DA-3
Synthesis example 1-1 according to patent documentation 1 synthesizes DA-3.
The synthesis of < synthesis example 4>DA-4
Embodiment 1 according to Japanese Patent spy table 2001-517719 publication synthesizes DA-4.
The making > of < liquid crystal aligning agent A1
By CBDA (0.288g, 1.50mmol) and DA-1 (0.697g, 1.5mmol) mixing in NMP (5.58g), at room temperature reaction obtains polyamic acid solution in 10 hours.In this polyamic acid solution, add BCS (4.93g) and NMP (4.93g), be 6 quality % by polyamic acid concentration dilution, obtains liquid crystal aligning agent A1 by room temperature stirring 5 hours.The number-average molecular weight of this polyamic acid is 14000, and weight-average molecular weight is 74000.
The making > of < liquid crystal aligning agent A2
By CBDA (0.485g, 2.50mmol) and DA-2 (1.297g, 2.5mmol) mixing in NMP (10.1g), at room temperature reaction obtains polyamic acid solution in 10 hours.In this polyamic acid solution, add BCS (8.91g) and NMP (8.91g), be 6 quality % by polyamic acid concentration dilution, obtains liquid crystal aligning agent A2 by room temperature stirring 5 hours.The number-average molecular weight of this polyamic acid is 3500, and weight-average molecular weight is 5300.
The making > of < liquid crystal aligning agent A3
By CBDA (0.485g, 2.50mmol) and DA-3 (1.052g, 2.5mmol) mixing in NMP (8.71g), at room temperature reaction obtains polyamic acid solution in 10 hours.In this polyamic acid solution, add BCS (7.68g) and NMP (7.68g), be 6 quality % by polyamic acid concentration dilution, obtains liquid crystal aligning agent A3 by room temperature stirring 5 hours.The number-average molecular weight of this polyamic acid is 5500, and weight-average molecular weight is 13000.
The synthesis > of < liquid crystal aligning agent A4
By CBDA (1.537g, 7.8mmol), DA-4 (2.832g, 6.4mmol), PCH (0.609g, 1.6mmol) mixing in NMP (19.91g), at room temperature reaction obtains polyamic acid solution in 10 hours.In this polyamic acid solution, add NMP (33.19g) and BCS (24.89g), be 6 quality % by polyamic acid concentration dilution, obtains liquid crystal aligning agent A4 by room temperature stirring 5 hours.The number-average molecular weight of this polyamic acid is 12000, and weight-average molecular weight is 24000.
< embodiment 1>
Use liquid crystal aligning agent A1, make liquid crystal orientation film according to step shown below, measure UV (ultraviolet) absorption spectrum.In addition, use liquid crystal aligning agent A1, make liquid crystal cell by step shown below, and carry out the evaluation of the evaluation of tilt angle, evaluation that AC (interchanges) sintering adheres to and backlight patience.
[mensuration of UV absorption spectrum]
Liquid crystal aligning agent A1 is spun on quartz base plate, after dry 90 seconds, burns till 30 minute with the heated air circulation type stove of 200 DEG C with the hot-plates of 80 DEG C, form the liquid crystal orientation film of thickness 100nm.Shimadzu Seisakusho Ltd. (Island Jin System is used to do institute to the substrate being formed with this liquid crystal orientation film) UV-3600 mensuration UV absorption spectrum processed, obtain maximum absorption wavelength (λ max).Result is shown in table 1.
[making of liquid crystal cell]
Liquid crystal aligning agent A1 is spun on the face being formed with ito film of the glass substrate with the transparency electrode be made up of ito film, on the hot plate of 80 DEG C after dry 90 seconds, in the heated air circulation type stove of 200 DEG C, burn till 30 minutes, forming thickness is the liquid crystal orientation film of 100nm.To the substrate being formed with this liquid crystal orientation film, use exposure intensity 2.0mW/cm -2the linear polarization UV of 254nm, irradiate in the mode that exposure changes between 0 ~ 1000mJ.The direction of incident beam is 40 ° of inclinations relative to substrate normal direction.Linear polarization UV is in the UV-light of high voltage mercury lamp after the bandpass filter of 254nm, makes through the polarization plates of 254nm.
Prepare 2 pieces of aforesaid substrates, after the liquid crystal orientation film of the substrate of a side scatters the pearl spacer of 4 μm, printing and sealing agent thereon (Xie Li KCC (the vertical chemistry of Association) XN-1500T processed).Then, making the liquid crystal aligning face of 2 pieces of substrates relative, is that antiparallel condition crimps with the projecting direction of the optical axis of the linear polarization UV to each substrate, keep 150 DEG C 105 minutes, make sealing agent thermofixation.In this negative crystal born of the same parents, inject negative type liquid crystal (Merck & Co., Inc.'s system, MLC-6608) by decompression injection method, in the stove of 120 DEG C, carry out isotropic process (adopting the reorientation process of the liquid crystal of heating), obtained liquid crystal cell.
[evaluation of tilt angle]
" AxoScan " that the tilt angle of liquid crystal cell uses Acker Suo Mei tex company (Axo Metrix society) to make is measured by Muller matrix method.Result is shown in table 1.
[evaluation of AC sintering attachment]
After making liquid crystal cell, after 240 hours are driven under the voltage of alternating current of 16Vpp to the liquid crystal cell determining tilt angle, drive the tilt angle stopping beginning again measuring liquid crystal cell after 1 hour, evaluate the change of the tilt angle before and after AC driving.It is good for judging that AC sinters attachment characteristic when the change (tilt angle after the tilt angle-AC driving before AC Δ angle=AC driving) of the tilt angle before and after AC drives is less than 0.2 °.AC Δ angle is shown in table 1.
[evaluation of backlight patience]
After making liquid crystal cell, the liquid crystal cell determining tilt angle is placed (slaking) uses (wavelength 400 ~ 800nm) backlight (BL) after upper 240 hour at 40 inch type liquid crystal TVs, after leaving 1 hour from BL, again measure the tilt angle of liquid crystal cell, evaluate the change of the tilt angle before and after slaking.Judge that BL patience is good when the change (the postradiation tilt angle of tilt angle-BL of BL Δ angle=BL pre-irradiation) of the tilt angle before and after slaking is less than 0.1 °.BL Δ angle is shown in table 1.
< embodiment 2>
Make liquid crystal orientation film in the mode identical with embodiment 1 except using liquid crystal aligning agent A2 replacement liquid crystal aligning agent A1, measure the UV absorption spectrum of the liquid crystal orientation film obtained.
In addition, with except use liquid crystal aligning agent A2 replace liquid crystal aligning agent A1 except the mode identical with embodiment 1 make liquid crystal cell, the evaluation of tilt angle, the evaluation of AC sintering attachment and the evaluation of backlight patience are carried out to the liquid crystal cell obtained.Result is shown in table 1.
< comparative example 1>
Make liquid crystal orientation film in the mode identical with embodiment 1 except using liquid crystal aligning agent A3 replacement liquid crystal aligning agent A1, measure the UV absorption spectrum of the liquid crystal orientation film obtained.
In addition, with except using liquid crystal aligning agent A3 to replace liquid crystal aligning agent A1 and the illumination wavelength of linear polarization UV is changed to mode identical with embodiment 1 except 313nm making liquid crystal cell, the evaluation of tilt angle, the evaluation of AC sintering attachment and the evaluation of backlight patience are carried out to the liquid crystal cell obtained.Result is shown in table 1.
< comparative example 2>
Make liquid crystal orientation film in the mode identical with embodiment 1 except using liquid crystal aligning agent A4 replacement liquid crystal aligning agent A1, measure the UV absorption spectrum of the liquid crystal orientation film obtained.
In addition, with except using liquid crystal aligning agent A4 to replace liquid crystal aligning agent A1 and the illumination wavelength of linear polarization UV is changed to mode identical with embodiment 1 except 313nm making liquid crystal cell, the evaluation of tilt angle, the evaluation of AC sintering attachment and the evaluation of backlight patience are carried out to the liquid crystal cell obtained.Result is shown in table 1.
[table 1]
By the results verification of above-mentioned table 1, employ side chain of the present invention and there is the embodiment 1 of the polymkeric substance of the structure represented by formula [I] and the liquid crystal display device of embodiment 2 because tilt angle is high, namely have high vertical orientated ability, thus AC drives the change of the tilt angle of front and back little, demonstrates good AC and sinters attachment characteristic.In addition, the structure confirmed represented by formula of the present invention [I] has UV absorption band near the 254nm as low wavelength region may, thus the liquid crystal display device of embodiment 1 and embodiment 2 is not subject to the impact of backlight, even if be exposed to the change that tilt angle also occurs backlight hardly for a long time.On the other hand, owing to having absorption near 300nm, thus easily by the impact of backlight, if be exposed to backlight for a long time, slowly can there is the change of tilt angle in the known use comparative example 1 with the diamines of cinnamoyl in the past and comparative example 2.

Claims (6)

1. a polymkeric substance, is characterized in that, for being selected from least one as side chain with the polyimide precursor of the structure represented by following formula [I], the polyimide obtained by this polyimide precursor imidization and polymeric amide;
In formula, Y 1for be selected from atomicity be 5 or 6 monocyclic ring, atomicity be 5 or 62 adjacent monocyclic rings, atomicity be the lopps of the dicyclic of 8 ~ 10 or atomicity be the lopps of the three-ring type of 13 or 14, non-substituted or replace, the divalent aromatic group of carbon-ring type or hetero ring type; Y 2for singly-bound or the divalent linking group being selected from ehter bond, ester bond, amido linkage and amino-formate bond; Y 3straight-chain alkyl that can be replaced by fluorine atoms for hydrogen atom, carbon number 3 ~ 20 or there is the 1 valency organic group of alicyclic skeleton of carbon number 4 ~ 40.
2. polymkeric substance as claimed in claim 1, is characterized in that, uses the diamines represented by following formula (1) and obtains;
In formula, Y 1for be selected from atomicity be 5 or 6 monocyclic ring, atomicity be 5 or 62 adjacent monocyclic rings, atomicity be the lopps of the dicyclic of 8 ~ 10 or atomicity be the lopps of the three-ring type of 13 or 14, non-substituted or replace, the divalent aromatic group of carbon-ring type or hetero ring type; Y 2for singly-bound or the divalent linking group being selected from ehter bond, ester bond, amido linkage and amino-formate bond; Y 3straight-chain alkyl that can be replaced by fluorine atoms for hydrogen atom, carbon number 3 ~ 20 or there is the 1 valency organic group of alicyclic skeleton of carbon number 4 ~ 40; Y 4for the alkylidene group of singly-bound, methylene radical or carbon number 2 ~ 6; Y 5for singly-bound, Sauerstoffatom, *-OCO-or-CH 2o-*, wherein, with key and the Y of " * " 4in conjunction with; Work as Y 4for Y during singly-bound 5for singly-bound.
3. a liquid crystal aligning agent, is characterized in that, containing the polymkeric substance described in claim 1 or 2.
4. a liquid crystal orientation film, is characterized in that, uses the liquid crystal aligning agent described in claim 3 and obtains.
5. a liquid crystal display device, is characterized in that, possesses liquid crystal orientation film according to claim 4.
6. a diamines, is characterized in that, represents with following formula (1);
In formula, Y 1for be selected from atomicity be 5 or 6 monocyclic ring, atomicity be 5 or 62 adjacent monocyclic rings, atomicity be the lopps of the dicyclic of 8 ~ 10 or atomicity be the lopps of the three-ring type of 13 or 14, non-substituted or replace, the divalent aromatic group of carbon-ring type or hetero ring type; Y 2for singly-bound or the divalent linking group being selected from ehter bond, ester bond, amido linkage and amino-formate bond; Y 3straight-chain alkyl that can be replaced by fluorine atoms for hydrogen atom, carbon number 3 ~ 20 or there is the 1 valency organic group of alicyclic skeleton of carbon number 4 ~ 40; Y 4for the alkylidene group of singly-bound, methylene radical or carbon number 2 ~ 6; Y 5for singly-bound, Sauerstoffatom, *-OCO-or-CH 2o-*, wherein, with key and the Y of " * " 4in conjunction with; Work as Y 4for Y during singly-bound 5for singly-bound.
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JP2003167139A (en) * 2001-11-30 2003-06-13 Kanegafuchi Chem Ind Co Ltd Optical waveguide and polyimide precursor and polyimide having cinnamic acid structure to be used for the same
JP2011100099A (en) * 2009-10-06 2011-05-19 Jsr Corp Liquid crystal aligning agent, method of producing liquid crystal aligning film, and liquid crystal display element
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