CN101597498B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element Download PDF

Info

Publication number
CN101597498B
CN101597498B CN200910142627.XA CN200910142627A CN101597498B CN 101597498 B CN101597498 B CN 101597498B CN 200910142627 A CN200910142627 A CN 200910142627A CN 101597498 B CN101597498 B CN 101597498B
Authority
CN
China
Prior art keywords
liquid crystal
bis
polyamic acid
tetracarboxylic dianhydride
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN200910142627.XA
Other languages
Chinese (zh)
Other versions
CN101597498A (en
Inventor
黑田美彦
吉尾浩平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JSR Corp
Original Assignee
JSR Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JSR Corp filed Critical JSR Corp
Publication of CN101597498A publication Critical patent/CN101597498A/en
Application granted granted Critical
Publication of CN101597498B publication Critical patent/CN101597498B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • 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
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Landscapes

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

Abstract

The invention relates to a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display element. The liquid crystal alignment agent is capable of having high voltage retaining quality, inhabiting after image after releasing stress and having excellent attenuating property of after image. The liquid crystal alignment agent comprises (A) polyamic acid for enabling tetracarboxylic dianhydride containing 1,2, 3, 4-cyclobutance tetracarboxylic dianhydride to react with diamine containing compound shown in formula (1), and (B) polyamic acid polymer for enabling tetracarboxylic dianhydride to react with diamine. In formula (1), R<I> and R <II> are alkyl with 1-4 of hydrogen atom number or carbon number, respectively. And, average imidation ratio of (A) polyamic acid and (B) polyamic acid polymer is 10-50%.

Description

Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device
Technical field
The present invention relates to liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device.
Background technology
At present, as liquid crystal display device, the known TN type liquid crystal display device with so-called TN type (twisted-nematic) liquid crystal cell, it forms liquid crystal orientation film being provided with on the substrate surface of nesa coating, as the substrate of used for liquid crystal display element, by two these substrate subtends arrange, form betwixt the nematic liquid crystal layer with positive dielectric anisotropy in gap, the box that forms sandwich structure, the major axis of liquid crystal molecule is turned round and is turn 90 degrees continuously to another piece substrate from a substrate; And compare with TN type liquid crystal display device and can realize the more STN of high-contrast (supertwist is to row) type liquid crystal display device, IPS (switching in face) the type liquid crystal display device that view angle dependency is little, optical compensation curved (optical compensation birefringence=OCB) type liquid crystal display device that video pictures high-speed response of little while of view angle dependency is good, (patent documentations 1～6) such as VA (vertical orientated) type liquid crystal display device that employing has the nematic liquid crystal of negative dielectric anisotropic.
As the material of the liquid crystal orientation film in these liquid crystal display device, known polyimide, polymeric amide, polyester etc.Polyimide wherein, due to its thermotolerance, good with the various aspects of performance such as the affinity of liquid crystal, physical strength, so be used to (non-patent literature 1 and 2) in a lot of liquid crystal display device.
But, in liquid crystal display device, the increasingly stringent that requires to raising display qualities such as high-precision refinements.Particularly in recent years, along with the development of the universal and motion picture technique for fixing of large-scale LCD TV, even in liquid crystal display device, for can be fast and show subtly and require the performance of the picture of high degree of motion all improving all the time.From this angle, for liquid crystal orientation film, require to have high-voltage retention and good image retention performance.Here, so-called image retention, refer to the image showing by applying electric charge on picture, remaining phenomenon still after electric charge is removed, the remaining degree of image (the image retention performance after stress has just discharged) and self charge de-stressing to the required time length of fade down (image retention Decay Rate) two aspects after just having been removed by electric charge stress show.In other words, if the image retention degree after stress has just discharged is large, can be only bad by image retention performance evaluation whereby, even if the image retention degree after stress has just discharged is little, for example, if its long-time (several days time) does not disappear, and can be still bad by image retention performance evaluation.
Except possessing as liquid crystal orientation film desired various performance all the time, be thermotolerance, with the affinity of liquid crystal, physical strength etc. beyond, also having all good liquid crystal aligning mould materials of image retention after high-voltage retention and stress have just discharged and image retention Decay Rate, was unknown in the past.
[patent documentation 1] TOHKEMY 2002-62537 communique;
[patent documentation 2] Japanese kokai publication hei 7-261181 communique;
[patent documentation 3] TOHKEMY 2003-107486 communique;
[patent documentation 4] Japanese kokai publication hei 11-258605 communique;
[patent documentation 5] TOHKEMY 2007-9031 communique;
[patent documentation 6] Japanese kokai publication hei 4-153622 communique;
[patent documentation 7] TOHKEMY 2002-327058 communique;
[patent documentation 8] Japanese kokai publication hei 6-222366 communique;
[patent documentation 9] Japanese kokai publication hei 6-281937 communique;
[patent documentation 10] Japanese kokai publication hei 5-107544 communique;
[non-patent literature 1] electronic material (12), p52 (1988);
[non-patent literature 2] デ イ ス プ レ イ ア Application De イ メ mono-ジ Application グ, the 4th volume, p213 (1996).
Summary of the invention
The present invention In view of the foregoing makes, and its objective is the various performances that have as liquid crystal orientation film are provided, and meanwhile, has high-voltage retention, can suppress the image retention performance after stress has just discharged, and the liquid crystal orientation film of image retention excellent attenuating property; Can produce the liquid crystal aligning agent of this liquid crystal orientation film; And can be fast and show subtly liquid crystal display device picture, that display quality is good of high degree of motion.
Other objects of the present invention and advantage can be learned by the following description.
According to the present invention, above object and advantages of the present invention, first, by a kind of liquid crystal aligning agent, reached, it comprises (A) makes to contain 1,2,3,4-tetramethylene tetracarboxylic dianhydride's tetracarboxylic dianhydride and the prepared polyamic acid of diamine reactant of the compound that contains following formula (1) expression and the imide amination polymer that (B) makes tetracarboxylic dianhydride and the prepared polyamic acid of diamine reactant
Figure G200910142627XD00031
(in formula (1), R iand R iIrespectively do for oneself hydrogen atom or carbonatoms is 1～4 alkyl),
And, the amido acid structure number having with respect to (A) polyamic acid and imide number of rings that (B) imide amination polymer has and the total quantity of amido acid structure number, the ratio of the imide number of rings that (B) imide amination polymer has is 10～50%;
The second, the liquid crystal orientation film being formed by above-mentioned liquid crystal aligning agent is reached;
The 3rd, by the liquid crystal display device with above-mentioned liquid crystal orientation film, reached.
The liquid crystal orientation film being formed by liquid crystal aligning agent of the present invention, has the various performances as liquid crystal orientation film, meanwhile, and image retention and image retention excellent attenuating property after high-voltage retention, stress have just discharged.Liquid crystal aligning agent of the present invention is applicable to various liquid crystal display device such as TN type, STN type, VA type, IPS type, OCB type, ferroelectricity, anti-ferroelectricities.
The liquid crystal display device of the present invention with the liquid crystal orientation film being formed by liquid crystal aligning agent of the present invention, can be fast and show subtly the picture of high degree of motion, and display quality is good.Liquid crystal display device of the present invention is applicable to various devices, such as the display unit for counter, wrist-watch, table clock, counting display screen, word processor, Personal Computer, liquid crystal TV set etc.
Accompanying drawing explanation
Fig. 1 is for showing the brief description figure of the pattern of transparency electrode used in image retention performance evaluation.
Embodiment
Liquid crystal aligning agent of the present invention comprises (A) makes to contain 1,2,3,4-tetramethylene tetracarboxylic dianhydride's tetracarboxylic dianhydride and the prepared polyamic acid of diamine reactant of the compound that contains above-mentioned formula (1) expression and the imide amination polymer that (B) makes tetracarboxylic dianhydride and the prepared polyamic acid of diamine reactant.
< (A) polyamic acid >
[tetracarboxylic dianhydride]
As the tetracarboxylic dianhydride for the synthesis of (A) polyamic acid, can only use 1,2,3,4-tetramethylene tetracarboxylic dianhydride, also can be by 1,2,3,4-tetramethylene tetracarboxylic dianhydride and other tetracarboxylic dianhydride's coupling.As operable other tetracarboxylic dianhydrides here, can enumerate for example butane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-bis-is chloro-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 3,5,6-, tri-carboxyl norbornane-2-acetic acid dianhydrides, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-, six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride, dicyclo [2.2.2]-Xin-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride, 3,5,6-, tri-carboxyls-2-carboxyl norbornane-2:3,5:6-dianhydride, 4,9-dioxa, three ring [5.3.1.0 2,6] undecane-3,5,8,10-tetraketone, following formula (T-I) and the aliphatics such as compound or the ester ring type tetracarboxylic dianhydride that (T-II) represent separately,
Figure G200910142627XD00061
(formula (T-I) and (T-II) in, R 1and R 3respectively do for oneself and there is the divalent organic group of aromatic nucleus, R 2and R 4respectively do for oneself hydrogen atom or alkyl, a plurality of R of existence 2and R 4separately can be identical, also can be different);
Pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) sulfobenzide dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two O-phthalic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) phosphniline oxide compound dicarboxylic anhydride, to phenylene-bis-(triphenyl phthalic acid) dicarboxylic anhydride, metaphenylene-bis-(triphenyl phthalic acid) dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-phenyl ether dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-ditan dicarboxylic anhydride, ethylene glycol-bis-(dehydration trimellitate), propylene glycol-bis-(dehydration trimellitate), BDO-bis-(dehydration trimellitate), 1,6-hexylene glycol-bis-(dehydration trimellitate), 1,8-ethohexadiol-bis-(dehydration trimellitate), 2,2-bis-(4-hydroxyphenyl) propane-bis-(dehydration trimellitate), aromatic tetracarboxylic acid's dianhydrides such as compound that following formula (T-1)～(T-4) represents separately.They can a kind ofly be used alone or in combination of two or more.
Figure G200910142627XD00071
As can be for the synthesis of other tetracarboxylic dianhydrides of (A) polyamic acid, from making formed liquid crystal orientation film show the angle of better liquid crystal aligning, in the middle of above-mentioned, be preferably selected from butane tetracarboxylic acid dianhydride, 1, 3-dimethyl-1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 1, 2, 3, 4-pentamethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic basic ring amyl group acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-5, 8-dimethyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2, 3, 5, 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyls-2-carboxyl norbornane-2:3, 5:6-dianhydride, 4, 9-dioxa three ring [5.3.1.0 2,6] undecane-3,5,8,10-tetraketone, pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1, at least one in the compound that following formula (T-8) in following formula (T-5) in the compound that 4,5,8-naphthalene tetracarboxylic acid dianhydride, above-mentioned formula (T-I) represent～compound (T-7) representing separately and the compound of above-mentioned formula (T-II) expression represents.
Figure G200910142627XD00081
Figure G200910142627XD00091
Particularly preferred other tetracarboxylic dianhydrides are 2, 3, 5-tricarboxylic basic ring amyl group acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyls-2-carboxyl norbornane-2:3, 5:6-dianhydride, 4, 9-dioxa three ring [5.3.1.0 2,6] undecane-3, at least one in the group that the compound that 5,8,10-tetraketone, pyromellitic acid dianhydride and above-mentioned formula (T-5) represent forms.
For the synthesis of the tetracarboxylic dianhydride of (A) polyamic acid, preferably with respect to whole tetracarboxylic dianhydrides, contain 40 % by mole of above 1,2,3,4-tetramethylene tetracarboxylic dianhydrides, more preferably contain more than 50 % by mole, particularly preferably contain more than 80 % by mole.
[diamines]
The diamines that is the compound that contains above-mentioned formula (1) and represent for the synthesis of the diamines of (A) polyamic acid.
As the R in above-mentioned formula (1) iand R iIthe carbonatoms alkyl that is 1～4, can enumerate for example methyl, ethyl, propyl group.As R iand R iI, preferably hydrogen atom or methyl separately.Work as R iand R iIduring for the carbonatoms alkyl that is 1～4, its link position be preferably separately amido linkage between position.
In above-mentioned formula (1), 2 amino link positions that connect on phenyl ring are preferably the contraposition of amido linkage separately.
The preferred concrete example of the compound representing as above-mentioned formula (1), can enumerate such as the compound of following formula (1-1)～(1-3) represent etc.
Figure G200910142627XD00101
As the diamines for the synthesis of (A) polyamic acid, the compound that can only use above-mentioned formula (1) to represent, compound and other diamines couplings that also above-mentioned formula (1) can be represented.As operable other diamines here, can enumerate for example Ursol D, mphenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminodiphenyl oxide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 3,3 '-bis-(trifluoromethyl)-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamino benzophenone, 3,4 '-diamino benzophenone, 4,4 '-diamino benzophenone, 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-[4-(4-amino-benzene oxygen) phenyl] sulfone, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, 1,3-bis-(4-amino-benzene oxygen) benzene, 1,3-bis-(3-amino-benzene oxygen) benzene, 9,9-bis-(4-aminophenyl)-10-hydrogen anthracene, 2,7 diamin of luorene, 9,9-dimethyl-2,7 diamin of luorene, 9,9-bis-(4-aminophenyl) fluorenes, 4,4 '-methylene radical-bis-(2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-bis-is chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 '-(to phenylene diisopropylidene) pentanoic, 4,4 '-(metaphenylene diisopropylidene) pentanoic, 2,2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-bis-(trifluoromethyl) biphenyl, 4,4 '-bis-[(4-amino-2-trifluoromethyl) phenoxy group]-aromatic diamines such as octafluoro biphenyl,
1,1-m-xylene diamine, 1,3-propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 4,4-diamino heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene Dicyclopentadiene (DCPD) diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0 2,7]-hendecene dimethyl two amidos, 4,4 '-methylene radical two (hexahydroaniline), 1, aliphatics or the ester ring type diamines such as 3-bis-(amino methyl) hexanaphthene, Isosorbide-5-Nitrae-bis-(amino methyl) hexanaphthene;
2,3 diamino pyridine, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 5,6-diamino-2,3-dicyano pyrazine, 5,6-diamino-2,4-dihydroxy-pyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazines, Isosorbide-5-Nitrae-bis-(3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazines, 2,4-diamino-6-methoxyl group-1,3,5-triazines, 2,4-diamino-6-phenyl-1,3,5-triazines, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazines, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenyl thiazole, 2,6-diaminopurine, 5,6-diaminostilbene, 3-dimethyl uracil, 3,5-diaminostilbene, 2,4-triazole, 6,9-diamino-2-oxyethyl group acridine lactate, 3,8-diamino-6-phenylphenanthridineand, Isosorbide-5-Nitrae-diamino piperazine, 3,6-proflavin, two (4-aminophenyl) phenyl amine, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-bis-(4-aminophenyl) p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-dimethyl-p-diaminodiphenyl, the compound that following formula (D-I) represents,
Figure G200910142627XD00111
(in formula (D-I), R 5represent to have 1 valency organic group of the nitrogen atom ring texture of the group that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine formation, X 1the organic group that represents divalent, R 6represent the alkyl that carbonatoms is 1～4, a1 represents 0～3 integer), there is the diamines of the nitrogen-atoms beyond 2 primary aminos and this primary amino in the compound equimolecular that represents of following formula (D-II),
(in formula (D-II), R 7represent to have the divalent organic group of the nitrogen atom ring texture that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, X 2the organic group that represents separately divalent, a plurality of X of existence 2can be identical, also can be different, R 8represent that separately carbonatoms is 1～4 alkyl, a2 represents 0～3 integer separately); The single-substituted diamines such as compound that following formula (D-III) represents,
(in formula (D-III), R 9represent be selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent key group of CO-, R 10represent to have skeleton in the steroid backbone of being selected from, trifluoromethyl, Trifluoromethoxyphen-l and difluorophenyl or 1 valency organic group of group, or carbonatoms be 6～30 alkyl, R 11represent the alkyl that carbonatoms is 1～4, a3 represents 0～3 integer); The diamino organo-siloxanes such as compound that following formula (D-IV) represents,
Figure G200910142627XD00123
(in formula (D-IV), R 12represent that separately carbonatoms is 1～12 alkyl, a plurality of R of existence 12separately can be identical, also can be different, respectively do for oneself 1～3 integer of p, the integer that q is 1～20); The compound that following formula (D-1)～(D-5) represents separately etc.,
Figure G200910142627XD00131
(integer that the y in formula (D-4) is 2～12, the integer that the z in formula (D-5) is 1～5).These other diamines can be used alone or in combination of two or more.
The alkyl (preferable methyl) that the phenyl ring of above-mentioned aromatic diamine can be optionally 1～4 by one or more carbonatoms replaces.Above-mentioned formula (D-I), (D-II) and (D-III) in R 6, R 8and R 11be preferably separately methyl, a1, a2 and a3 are preferably 0 or 1 separately, and more preferably 0.
As can be for the synthesis of other diamines of (A) polyamic acid, above-mentioned in the middle of, preferably use and be selected from Ursol D, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 9,9-bis-(4-aminophenyl) fluorenes, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-bis-(4-aminophenyl) HFC-236fa, 4,4 '-(to phenylene diisopropylidene) pentanoic, 4,4 '-(metaphenylene diisopropylidene) pentanoic, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, Isosorbide-5-Nitrae-cyclohexane diamine, 4,4 '-methylene radical two (hexahydroaniline), 1,3-bis-(amino methyl) hexanaphthene, the compound that above-mentioned formula (D-1)～(D-5) represents separately, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-bis-(4-aminophenyl) p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-dimethyl-p-diaminodiphenyl, the compound that following formula (D-6) in the compound that above-mentioned formula (D-I) represents represents, the compound that following formula (D-7) in the compound that above-mentioned formula (D-II) represents represents,
Figure G200910142627XD00141
Dodecyloxy-2 in the compound that above-mentioned formula (D-III) represents, 4-diaminobenzene, pentadecane oxygen base-2, 4-diaminobenzene, n-Hexadecane oxygen base-2, 4-diaminobenzene, octadecane oxygen base-2, 4-diaminobenzene, dodecyloxy-2, 5-diaminobenzene, pentadecane oxygen base-2, 5-diaminobenzene, n-Hexadecane oxygen base-2, 5-diaminobenzene, octadecane oxygen base-2, 5-diaminobenzene, in following formula (D-8)～compound (D-16) representing separately and the compound of above-mentioned formula (D-IV) expression 1, at least one in the group that 3-bis-(3-aminopropyl)-tetramethyl disiloxane forms.
Figure G200910142627XD00151
Figure G200910142627XD00161
Can preferably with respect to whole diamines, contain the compound that 5 % by mole of above above-mentioned formulas (1) represent for the synthesis of the diamines of (A) polyamic acid, more preferably contain more than 10 % by mole, further contain more than 20 % by mole.
[(A) polyamic acid is synthetic]
(A) polyamic acid contained in liquid crystal aligning agent of the present invention can be by making the tetracarboxylic acid that contains 1,2,3,4-tetramethylene tetracarboxylic dianhydride as above make with the diamine reactant of the compound that contains above-mentioned formula (1) expression.
Supply with the tetracarboxylic dianhydride of building-up reactions and the usage rate of diamines of (A) polyamic acid, preferably amino with respect to 1 equivalent contained in diamine compound, the anhydride group that makes tetracarboxylic dianhydride is the ratio of 0.5～2 equivalent, is more preferably the ratio of 0.7～1.2 equivalent.
The building-up reactions of polyamic acid, in organic solvent, is preferable over-20～150 ℃, more preferably under the temperature condition of 0～100 ℃, carries out.Reaction times is preferably 0.5～48 hour, more preferably 1～24 hour.As organic solvent, so long as can dissolve the solvent of synthetic polyamic acid, it is had no particular limits, can enumerate for example METHYLPYRROLIDONE, N, the non-proton class polar solvents such as N-N,N-DIMETHYLACETAMIDE, DMF, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA; Between the phenol solvent such as sylvan, xylenol, phenol, halogenated phenol.In addition, to be preferably the total amount (b) that makes tetracarboxylic dianhydride and diamines be the amount of 0.1～30 % by weight with respect to the total amount (a+b) of reaction soln to the consumption of organic solvent (a).In addition, when the poor solvent coupling of organic solvent and the following stated, the consumption of above-mentioned organic solvent (a), should be understood to the total consumption of organic solvent and poor solvent.
In above-mentioned organic solvent, in the scope of separating out at the polyamic acid that does not make to generate, the poor solvent alcohols of all right coupling polyamic acid, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc.As the object lesson of this poor solvent, can enumerate for example methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, BDO, triglycol, ethylene glycol monomethyl ether, ethyl lactate, n-Butyl lactate, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, ritalin, vinyl acetic monomer, N-BUTYL ACETATE, methoxy methyl propionate, ethoxyl ethyl propionate, oxalic acid diethyl ester, diethyl malonate, ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethyl cellosolve acetate, diglyme, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, tetrahydrofuran (THF), methylene dichloride, 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene, isoamyl propionate, isoamyl isobutyrate, isoamyl ether etc.
When by organic solvent and poor solvent coupling, as the usage rate of poor solvent, with respect to the total amount of organic solvent and poor solvent, be preferably below 10 % by weight, more preferably below 5 % by weight.
As mentioned above, obtained dissolving the reaction soln of (A) polyamic acid.This reaction soln directly can be supplied with to liquid crystal aligning agent modulates, also polyamic acid contained in reaction soln can be separated to rear supply liquid crystal aligning agent and modulate, or after also can isolated polyamic acid is refining, resupply liquid crystal aligning agent and modulate.The separation of polyamic acid, can obtain precipitate by above-mentioned reaction soln is put in a large amount of poor solvents, then the method for this precipitate of drying under reduced pressure, or reaction soln is undertaken by the method that vaporizer decompression distillates.In addition, by this polyamic acid is dissolved in organic solvent again, then with poor solvent, make its method of separating out, or carry out once or several times the method for the operation that distillates with vaporizer decompression, can refine polyamic acid.
< (B) imide amination polymer >
(B) imide amination polymer containing in liquid crystal aligning agent of the present invention, can be by obtaining the polyamic acid dehydration closed-loop of tetracarboxylic dianhydride and diamine reactant gained.
[tetracarboxylic dianhydride]
As the tetracarboxylic dianhydride for the synthesis of (B) imide amination polymer, can enumerate with above conduct for the synthesis of the tetracarboxylic dianhydride of (A) polyamic acid illustrative identical tetracarboxylic dianhydride.Tetracarboxylic dianhydride for the synthesis of (B) imide amination polymer, in the middle of preferably containing above-mentioned illustrative tetracarboxylic dianhydride, be selected from 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic basic ring amyl group acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyls-2-carboxyl norbornane-2:3, 5:6-dianhydride and 4, 9-dioxa three ring [5.3.1.0 2,6] undecane-3, the tetracarboxylic dianhydride of at least one (hereinafter referred to as " specific tetracarboxylic dianhydride ") in the group that 5,8,10-tetraketone forms.
Particularly preferred specific tetracarboxylic dianhydride is for being selected from 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride and 1,3,3a, 4,5,9b-, six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, at least one in the group that 3-diketone forms.
For the synthesis of the tetracarboxylic dianhydride of (B) imide amination polymer, preferably with respect to whole tetracarboxylic dianhydrides, contain 30 % by mole of above specific tetracarboxylic dianhydrides as above, more preferably contain more than 50 % by mole, particularly preferably contain more than 80 % by mole.
[diamines]
As the diamines for the synthesis of (B) imide amination polymer, can enumerate with above conduct can be for the synthesis of other diamines of (A) polyamic acid illustrative identical diamines.
For the synthesis of the diamines of (B) imide amination polymer, can enumerate the compound that the central above-mentioned formula (D-III) of above illustrative diamines represents, Ursol D, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 9,9-bis-(4-aminophenyl) fluorenes, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-bis-(4-aminophenyl) HFC-236fa, 4,4 '-(to phenylene diisopropylidene) pentanoic, 4,4 '-(metaphenylene diisopropylidene) pentanoic, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene radical two (hexahydroaniline), 1,3-bis-(amino methyl) hexanaphthene, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, N, N '-bis-(4-aminophenyl) p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-dimethyl-p-diaminodiphenyl, the compound that above-mentioned formula (D-1)～(D-5) represents separately, the compound that above-mentioned formula (D-6) in the compound that above-mentioned formula (D-I) represents represents, the compound that above-mentioned formula (D-7) in the compound that above-mentioned formula (D-II) represents represents, in the compound that above-mentioned formula (D-IV) represents 1,3-bis-(3-aminopropyl)-tetramethyl disiloxane etc., more preferably with respect to whole diamines, contain 20 % by mole of above at least one in the middle of them, further preferably contain more than 50 % by mole, particularly preferably contain more than 70 % by mole.
The compound representing as above-mentioned formula (D-III), the compound of preferred above-mentioned formula (D-8)～(D-16) represent separately.
For the synthesis of the diamines of (B) imide amination polymer, be preferably the diamines of the compound not representing containing above-mentioned formula (1).
As the diamines for the synthesis of (B) imide amination polymer, the compound particularly preferably being represented by above-mentioned formula (D-III) be selected from Ursol D, 1,3-bis-(3-aminopropyl)-tetramethyl disiloxane, 4,4 '-diaminodiphenylmethane, 2,2 '-dimethyl-4,4 '-benzidine and 4, the diamines of at least one composition in the group that 4 '-diaminodiphenyl oxide forms, preferably wherein with respect to whole diamines, contain the compound that 0.5～40 % by mole of above-mentioned formula (D-III) represents, more preferably contain 1～15 % by mole.
[(B) imide amination polymer is synthetic]
(B) imide amination polymer can be by making the prepared polyamic acid dehydration closed-loop of tetracarboxylic dianhydride as above and diamine reactant make.Here, tetracarboxylic dianhydride reacts with diamines, can similarly carry out with the described method of synthetic method of above conduct (A) polyamic acid.
The dehydration closed-loop of polyamic acid, can be dissolved in polyamic acid in organic solvent by method, (ii) of for example (i) heating polyamic acid, to adding the method etc. of dewatering agent and dehydration closed-loop catalyzer heating as required in this solution, carries out.
Temperature of reaction in the method for the heating polyamic acid of above-mentioned (i), is preferably 50～200 ℃, more preferably 60～170 ℃.When 50 ℃ of temperature of reaction less thaies, dehydration closed-loop reaction can not be carried out fully, if temperature of reaction surpasses 200 ℃, there will be the situation of the molecular weight and molecular weight of gained imide amination polymer.Reaction times is preferably 0.5～24 hour, more preferably 1～12 hour.
In addition, in the method for adding dewatering agent and dehydration closed-loop catalyzer in polyamic acid solution of above-mentioned (ii), as dewatering agent, can use acid anhydrides such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride.The consumption of dewatering agent, is preferably 0.01～20 mole with respect to 1 mole of repeating unit of polyamic acid.In addition, as dehydration closed-loop catalyzer, can use tertiary amines such as pyridine, collidine, two picolins, triethylamine.But, be not limited to these.The consumption of dehydration closed-loop catalyzer, with respect to 1 mole of dewatering agent used, is preferably 0.01～10 mole.In addition, as organic solvent used in dehydration closed-loop reaction, can enumerate as solvent for use in polyamic acid synthetic and illustrative organic solvent.And the temperature of reaction of dehydration closed-loop reaction, is preferably 0～180 ℃, more preferably 10～150 ℃, the reaction times is preferably 0.5～24 hour, more preferably 1～12 hour.
(B) imide amination polymer making in aforesaid method (i), can directly supply with liquid crystal aligning agent by it and modulate, or after also can the imide amination polymer making is refining, resupplies liquid crystal aligning agent and modulate.In addition, in aforesaid method (ii), obtain the reaction soln containing imide amination polymer.This reaction soln, it directly can be supplied with to liquid crystal aligning agent modulates, also can from reaction soln, remove and supply with liquid crystal aligning agent after dewatering agent and dehydration closed-loop catalyzer and modulate, imide amination polymer can also be separated to rear supply liquid crystal aligning agent and modulate, or after also can separated imide amination polymer is refining, resupply liquid crystal aligning agent and modulate.From reaction soln, remove dewatering agent and dehydration closed-loop catalyzer, can adopt such as methods such as solvent exchanges.(B) separation of imide amination polymer, refining, can take to carry out with separated, the described same operation of process for purification of above conduct (A) polyamic acid.
Contained (B) imide amination polymer in liquid crystal aligning agent of the present invention, can be the complete imide compound of the amido acid structure fully dehydrating closed loop that has of raw material polyamic acid, can be also only part amido acid structure dehydration closed-loop, amido acid structure and imide ring structure the part imide compound of depositing.
Contained (B) imide amination polymer in liquid crystal aligning agent of the present invention, its imide rate is preferably more than 40%, more preferably more than 80%.Here, so-called " imide rate ", refers to the total quantity with respect to amido acid structure number and the imide ring structure number of imide amination polymer, the value that the shared ratio of imide ring structure number represents with percentage.Now, a part for imide ring can also be different imide ring.
[polymkeric substance of end modified type]
Above-mentioned (A) polyamic acid and (B) imide amination polymer can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting separately.This end modified type polymkeric substance can be by (referring to (A) polyamic acid at polyamic acid, or during the polyamic acid as the precursor of (B) imide amination polymer) synthetic, in reaction system, add single acid anhydride, monoamine compound, monoisocyanates compound etc. and synthesize.Here, as single acid anhydride, can enumerate such as maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc.In addition, as monoamine compound, can enumerate such as aniline, hexahydroaniline, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, Pentadecane amine, n-hexadecane amine, n-heptadecane amine, Octadecane amine, NSC 62789 amine etc.In addition, as monoisocyanates compound, can enumerate such as phenylcarbimide, isocyanic acid naphthyl ester etc.The usage rate of molecular weight regulator as above, the tetracarboxylic dianhydride who uses during with respect to 100 weight part synthesizing polyamides acid and the total amount of diamines, be preferably below 10 weight parts, more preferably below 5 weight parts.
[soltion viscosity]
Above-mentioned (A) polyamic acid and (B) imide amination polymer, preferably when being made into concentration and being the solution of 10 % by weight, have the soltion viscosity of 20～800mPas separately, more preferably has the soltion viscosity of 30～500mPas.
The soltion viscosity of above-mentioned polymkeric substance (mPas), the polymers soln of 10 % by weight concentration of good solvent (such as gamma-butyrolactone, the METHYLPYRROLIDONE etc.) modulation to adopting this polymkeric substance, the value of measuring at 25 ℃ with E type rotational viscosimeter.
[(A) polyamic acid and (B) usage rate of imide amination polymer]
Liquid crystal aligning agent of the present invention contains (A) as above polyamic acid and (B) imide amination polymer, their usage rate is: the amido acid structure number having with respect to (A) polyamic acid and imide number of rings that (B) imide amination polymer has and the total quantity of amido acid structure number, making the ratio of the imide number of rings that (B) imide amination polymer has is that 10～50% (hereinafter referred to as " average imide rates ") are 10～50% ratio.Average imide rate more preferably 10～40%.
By make (A) polyamic acid and (B) usage rate of imide amination polymer in above-mentioned scope, can make to form and there is good image retention performance, can suppress the liquid crystal aligning agent of the liquid crystal orientation film of image retention after electric charge stress has just been removed and image retention excellent attenuating property.
Other compositions of < >
Liquid crystal aligning agent of the present invention, as mentioned above, contains (A) polyamic acid and (B) imide amination polymer with above-mentioned ratio, and in the situation that not damaging effect of the present invention and advantage, can also contain other compositions beyond their.As this other compositions, can enumerate such as the compound in molecule with at least one epoxy group(ing) (hereinafter referred to as " epoxy compounds "), functional silanes compound etc.
Above-mentioned epoxy compounds, the fusible angle from the formed liquid crystal orientation film of further raising to substrate surface, can be included in liquid crystal aligning agent of the present invention.As this epoxy compounds, preferably can enumerate for example 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, 1, 3-bis-(N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-amino methyl hexanaphthene etc.The cooperation ratio of these epoxy compounds, with respect to 100 parts by weight polymer (refer to (A) polyamic acid and (B) total amount of imide amination polymer, lower with), is preferably below 40 weight parts, more preferably 0.1～30 weight part.
As above-mentioned functional silanes compound, can enumerate for example 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxycarbonyl-3-TSL 8330, N-ethoxycarbonyl-APTES, N-tri-ethoxy silylpropyl diethylenetriamine, N-Trimethoxy silane base propyl group diethylenetriamine, 10-Trimethoxy silane base-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilicane alkyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, N-bis-(oxyethylene group)-3-TSL 8330, N-bis-(oxyethylene group)-APTES etc.
The cooperation ratio of these functional silanes compounds, with respect to 100 parts by weight polymer total amounts, is preferably below 2 weight parts, more preferably below 0.2 weight part.
< liquid crystal aligning agent >
Liquid crystal aligning agent of the present invention contain (A) as above polyamic acid and (B) imide amination polymer as essential composition, can also according to circumstances contain other compositions, preferably by each composition, dissolve and be contained in organic solvent and form.
As operable organic solvent in liquid crystal aligning agent of the present invention, can enumerate as solvent used in the building-up reactions of (A) polyamic acid and illustrative solvent.And, can coupling in the time of can also suitably selecting coupling as the building-up reactions of (A) polyamic acid and illustrative poor solvent.
As the preferred organic solvent using in liquid crystal aligning agent of the present invention, can enumerate for example METHYLPYRROLIDONE, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, methoxy methyl propionate, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl ether (ethylene glycol butyl ether), ethylene glycol dimethyl ether, ethyl cellosolve acetate, diglyme, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, isoamyl propionate, isoamyl isobutyrate, isoamyl ether etc.They can use separately, or also can two or more mixing use.
Particularly preferred solvent composition, is by the solvent composition of above-mentioned solvent combination gained, is surface tension that in liquid crystal aligning agent, liquid crystal aligning agent can not separated out and make to each composition solvent composition in 25～40mN/m scope.
The solids content concn of liquid crystal aligning agent of the present invention, the total weight of the composition beyond the organic solvent of liquid crystal aligning agent accounts for the ratio of liquid crystal aligning agent gross weight, considers viscosity, volatility etc. and suitably selection, is preferably the scope of 1～10 % by weight.That is to say, liquid crystal aligning agent of the present invention, by being coated on substrate surface, remove organic solvent, formation is filmed as liquid crystal orientation film, when solids content concn less than 1 % by weight, the thickness that there will be this to film is too small and be difficult to obtain the situation of good liquid crystal orientation film, on the other hand, when solids content concn surpasses 10 % by weight, there will be coating thickness blocked up and be difficult to equally obtain the situation of good liquid crystal orientation film, and, also there will be the viscosity of liquid crystal aligning agent to increase, cause the situation of coating property variation.
Particularly preferred solids content concn scope, the method adopting when liquid crystal aligning agent is coated on to substrate and difference.For example, when adopting spin-coating method, the scope of 1.5～4.5 % by weight particularly preferably.When adopting print process, particularly preferably making solids content concn is the scope of 3～9 % by weight, like this, can make the scope of soltion viscosity in 12～50mPas.When adopting ink jet method, particularly preferably making solids content concn is the scope of 1～5 % by weight, like this, can make the scope of soltion viscosity in 3～15mPas.
Temperature during modulation liquid crystal aligning agent of the present invention, is preferably 0 ℃～100 ℃, more preferably 20 ℃～60 ℃.
< liquid crystal display device >
Liquid crystal display device of the present invention has the liquid crystal orientation film being formed by liquid crystal aligning agent of the present invention as above.
Liquid crystal display device of the present invention can be manufactured by for example following method.
(1) first, apply liquid crystal aligning agent of the present invention on a pair of substrate, except desolventizing, formation is filmed.Here, when the display format of the liquid crystal display device that will manufacture is the vertical electric field modes such as TN type, STN type, VA type, two substrates that are provided with the nesa coating that forms pattern on one side of usining use as a pair of substrate.On the other hand, when the display format of the liquid crystal display device that will manufacture is lateral electric field type, the substrate that is provided with the nesa coating with comb teeth-shaped pattern is used as a pair of substrate with the substrate without nesa coating.
In above-mentioned arbitrary situation, equal coated with liquid crystal alignment agents (while thering is nesa coating on substrate, being coated in the one side with nesa coating of substrate) on substrate.As substrate, can use glass such as float glass, soda-lime glass; The plastics transparency carriers such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-(ester ring type alkene).The nesa coating simultaneously above arranging as substrate, can be used stannic oxide (SnO 2) system NESA film (U.S. PPG register of company trade mark), Indium sesquioxide-stannic oxide (In 2o 3-SnO 2) the ITO film etc. of system.In addition, the acquisition that these form the nesa coating of patterns, can adopt after forming patternless nesa coating by the mask etc. that photoetch method forms the method for pattern, apparatus has required pattern when nesa coating forms and be undertaken and directly form the method etc. of the nesa coating of patterning.
To coated with liquid crystal alignment agent on substrate, can adopt the suitable coating methods such as rolling method, spin-coating method, print process, ink jet method to carry out.When the coating of liquid crystal aligning agent, for the binding property of further improving substrate surface and nesa coating and filming, can also on coated of substrate, apply in advance functional silanes compound, functionality titanium compound etc.
After coating, in order to prevent the object of the sagging grade of alignment agent liquid of coating, preferably preheat (prebake).Prebake temperature is preferably 30～200 ℃, and more preferably 40～150 ℃, particularly preferably 40～100 ℃.The prebake time, should suitably set according to the kind of used well heater, for example, when using hot-plate, be preferably 45 seconds～30 minutes, more preferably 45 seconds～20 minutes.Then, for completely, except the object of desolventizing etc., toast (curing afterwards) operation.After this, cure, except from film completely except the object of desolventizing, can also be in order to make the amido acid structure of polymkeric substance contained in liquid crystal aligning agent of the present invention further carry out dehydration closed-loop by heating, thus further improve the object of the average imide rate of filming and carry out.After the temperature of curing be preferably 80～300 ℃, more preferably 120～250 ℃.After cure the time, should be according to the kind of used well heater and suitably set, for example, when using hot-plate, be preferably 3～60 minutes, more preferably 7～30 minutes.
Like this, can form filming as liquid crystal orientation film.Formed thickness of filming, is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
When the liquid crystal display device of application liquid crystal aligning agent of the present invention is VA type liquid crystal display device, can also be described in for example patent documentation 7 (TOHKEMY 2002-327058 communique), on substrate, form coated with liquid crystal alignment agent after overshooting shape structure, to reach the object of improving viewing angle properties.
(2), when the display format of the liquid crystal display device that will manufacture is VA type, filming of as above forming can directly be used as liquid crystal orientation film, also can carry out as required following grinding process.On the other hand, when the vertical electric field mode beyond the display format of the liquid crystal display device that will manufacture is VA type and lateral electric field type, formed coated surface is carried out to grinding process.
The roller that grinding process can be tied with fibrous cloth such as nylon, regenerated fiber, cotton by employing carries out with the method for certain orientation friction.Like this, give and filming with liquid crystal molecular orientation energy, make liquid crystal orientation film.In addition, by to filming after grinding process, carry out shown in patent documentation 8 (Japanese kokai publication hei 6-222366 communique) for example or patent documentation 9 (Japanese kokai publication hei 6-281937 communique), the processing that makes the tilt angle of the subregion of liquid crystal orientation film change to a part of irradiation ultraviolet radiation of liquid crystal orientation film, or carry out shown in patent documentation 10 (Japanese kokai publication hei 5-107544 communique), in the part on liquid crystal orientation film surface, form after etchant resist, with the direction different from previous grinding process, carry out the processing of removing etchant resist after grinding process, make each region of liquid crystal orientation film there is different liquid crystal aligning energy, can improve like this visual field performance of gained liquid crystal display device.
(3) prefabricated two substrates that as above form liquid crystal orientation film, by arrange liquid crystal between two substrates that are oppositely arranged, manufacture liquid crystal cell.Here, when having carried out grinding process to filming, two substrates are in the angle of regulation with the polishing direction of respectively filming, vertical or antiparallel for example, and relatively arrange.
The manufacture of liquid crystal cell, can enumerate two kinds of for example following methods.
First method is previously known method.First, by two substrates are passed through to gap (box gap) relatively to ground setting, make liquid crystal orientation film separately relatively to, fitted with sealing agent in the periphery position of two substrates, in the box gap being surrounded by substrate surface and sealing agent, note after topping up crystalline substance, sealing filling orifice, can make liquid crystal cell.
Second method is the method that is called ODF (One Drop Fill) mode.Regulation position on a substrate in two substrates that form liquid crystal orientation film, coating is ultra-violet solidified sealant material for example, on liquid crystal aligning face, drip after liquid crystal again, another piece substrate of fitting, make liquid crystal orientation film relatively to, then to whole irradiation ultraviolet radiation of substrate, make sealant cures, can manufacture liquid crystal cell.
In the situation that adopting either method, all need by the liquid crystal cell of as above manufacturing being further heated to, after temperature that liquid crystal used is isotropic phase, slowly cool to room temperature, the flow orientation while eliminating Liquid crystal pour.
Then, by the polaroid of fitting, can make liquid crystal display device of the present invention on the outer surface of liquid crystal cell.
Here, as sealing agent, can use such as the epoxy resin containing as the alumina balls of solidifying agent and separator etc.
As above-mentioned liquid crystal, can use such as nematic liquid crystal, dish shape type liquid crystal etc., wherein preferred nematic liquid crystal.When being VA type liquid crystal cell, preferably there is the nematic liquid crystal of negative dielectric anisotropic, can use such as dicyanobenzenes class liquid crystal, pyridazine class liquid crystal, schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal etc.When being TN type liquid crystal cell or STN type liquid crystal cell, the nematic liquid crystal preferably with positive dielectric anisotropy, can be used such as biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cubane-like liquid crystal etc.In these liquid crystal, can also further add cholesteryl liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate; The chirality agent of selling with trade(brand)name C-15, CB-15 (production of メル Network society); To oxygen base α-tolylene-to ferroelectric liquid crystals such as amino-2-methyl butyl laurate etc. and using in the last of the ten Heavenly stems.
As the polaroid of fitting on liquid crystal cell outside surface, can enumerate polyvinyl alcohol is extended to the light polarizing film that is referred to as " H film " that orientation absorbs iodine gained is simultaneously clipped in cellulose acetate protective membrane and the polaroid of making, or the polaroid self made of H film.
[embodiment]
Below, by embodiment, the present invention is carried out to more specific description, but the present invention is not limited to these embodiment.
The soltion viscosity of the polymkeric substance in following synthesis example is the value that adopts E type viscometer to measure at 25 ℃ to the polymers soln shown in each synthesis example.
The imide rate of imide amination polymer, by imide amination polymer at room temperature after drying under reduced pressure, is dissolved in deuterated dimethyl sulfoxide, take tetramethylsilane as standard substance, by what measure under room temperature 1h-NMR, adopts following formula (i) and obtains.
Imide rate (%)=(1-A 1/ A 2* α) * 100 (i)
(in formula (i), A 1for near the peak area that comes from NH matrix occurring 10ppm, A 2for coming from the peak area of other protons, α is with respect to 1 NH matrix in imide amination polymer precursor (polyamic acid), the individual percentage of other protons).
The synthetic > of < (A) polyamic acid
Synthesis example 1
Using as tetracarboxylic dianhydride's 1,2,3,4-tetramethylene tetracarboxylic dianhydride 200g (1.0 moles), as 2 of diamines, 2 '-dimethyl-4,4 '-benzidine 150g (0.7 mole) and 4,4 '-diaminobenzene formylaniline 68g (0.3 mole) is dissolved in the mixed solvent being comprised of 3300g gamma-butyrolactone and 370g METHYLPYRROLIDONE, by carry out reaction in 3 hours at 40 ℃, makes the solution that about 4000g contains 10 % by weight polyamic acids (A-1).The soltion viscosity of this solution is 190mPas.
The comparison synthesis example > of < polyamic acid
Synthesis example 2
Using as tetracarboxylic dianhydride's 1,2,3,4-tetramethylene first carboxylic acid dianhydride 200g (1.0 moles), as 2 of diamines, 2 '-dimethyl-4,4 '-benzidine 210g (1.0 moles) is dissolved in the mixed solvent being comprised of 370g METHYLPYRROLIDONE and 3300g gamma-butyrolactone, by carry out reaction in 3 hours at 40 ℃, make the solution that about 3700g contains 10 % by weight polyamic acids (A-2).The soltion viscosity of this solution is 160mPas.
Synthesis example 3
Using as tetracarboxylic dianhydride's 1,2,3,4-tetramethylene tetracarboxylic dianhydride 98g (0.50 mole) and pyromellitic acid dianhydride 110g (0.50 mole), as 4 of diamines, 4 '-diaminodiphenyl-methane 200g (1.0 moles) is dissolved in the mixed solvent being comprised of 230g METHYLPYRROLIDONE and 2100g gamma-butyrolactone, carries out after reaction in 3 hours at 40 ℃, append 1350g gamma-butyrolactone, make the solution that about 3800g contains 10 % by weight polyamic acids (A-3).The soltion viscosity of this solution is 125mPas.
The synthetic > of < (B) imide amination polymer
Synthesis example 4
Using as tetracarboxylic dianhydride's 2, 3, 5-tricarboxylic basic ring amyl group acetic acid dianhydride 110g (0.5 mole) and 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone 160g (0.5 mole), Ursol D 94g (0.87 mole) as diamines, 1, 3-bis-(3-aminopropyl) tetramethyl disiloxane 25g (0.1 mole) and 3, 6-bis-(4-aminobenzoic acyl-oxygen base) cholestane 9.6g (0.015 mole), and be dissolved in 960g METHYLPYRROLIDONE as the octadecylamine 8.1g (0.030 mole) of monoamine, at 60 ℃, carry out reaction in 6 hours, obtain the solution that contains polyamic acid.The gained polyamic acid solution that takes a morsel, adds METHYLPYRROLIDONE, is made into the solution that polyamic acid concentration is 10 % by weight, and the soltion viscosity of mensuration is 60mPas.
Then, in gained polyamic acid solution, append 2700g METHYLPYRROLIDONE, then add 400g pyridine and 410g acetic anhydride, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, by being carried out to solvent exchange with new gamma-butyrolactone, the solvent in system (by this solvent exchange, operates, the pyridine and the acetic anhydride that in dehydration closed-loop reaction, use are removed to system, lower with), obtain containing the about 2400g of solution that 15 % by weight imide rates are about 95% imide amination polymer (B-1).This imide amination polymer solution takes a morsel, add gamma-butyrolactone, be made into the solution that imide amination polymer content is 10 % by weight, the soltion viscosity of mensuration is 70mPas, be made into the solution that imide amination polymer content is 6.0 % by weight, the soltion viscosity of mensuration is 16.0mPas.
Synthesis example 5
Using as tetracarboxylic dianhydride's 2, 3, 5-tricarboxylic basic ring amyl group acetic acid dianhydride 112g (0.50 mole) and 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone 157g (0.50 mole), Ursol D 88g (0.81 mole) as diamines, two (aminopropyl) tetramethyl disiloxane 25g (0.10 mole) and 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3, 5-diaminobenzoic acid ester 35g (0.080 mole), and be dissolved in 1250gN-N-methyl-2-2-pyrrolidone N-as the aniline 1.4g (0.015 mole) of monoamine, at 60 ℃, carry out reaction in 6 hours, obtain the solution that contains polyamic acid.This solution that takes a morsel, adds METHYLPYRROLIDONE, is made into the solution that polyamic acid concentration is 10 % by weight, and the soltion viscosity of mensuration is 55mPas.
In gained polyamic acid solution, append 2500g METHYLPYRROLIDONE, then add 400g pyridine and 408g acetic anhydride, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, by the solvent in system is carried out to solvent exchange with new METHYLPYRROLIDONE, obtain the about 1800g of solution that contains the imide amination polymer (B-2) that 17 % by weight imide rates are 95%.This solution that takes a morsel, adds METHYLPYRROLIDONE, is made into the solution that imide amination polymer concentration is 6.0 % by weight, and the soltion viscosity of mensuration is 13.0mPas.
Synthesis example 6
Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 224g (1.0 moles), Ursol D 106g (0.99 mole) and 3 as diamines, 5-diaminobenzoic acid cholestane base ester 7.8g (0.015 mole) is dissolved in 3050g METHYLPYRROLIDONE, it is at room temperature reacted 3 hours, obtain the polyamic acid solution that soltion viscosity is 210mPas.
Then, in gained polyamic acid solution, append 3400g METHYLPYRROLIDONE, then add 400g pyridine and 300g acetic anhydride, at 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, by the solvent in system is carried out to solvent exchange with new gamma-butyrolactone, obtain the solution 3100g that contains the polyimide (B-4) that 9 % by weight imide rates are 90%.This solution that takes a morsel, adds gamma-butyrolactone, is made into the solution that polyimide concentration is 3.1 % by weight, and the soltion viscosity of mensuration is 15.0mPas.
Embodiment 1
The modulation > of < liquid crystal aligning agent
The solution containing polyimide (B-1) making in the solution containing polyamic acid (A-1) making in above-mentioned synthesis example 1 and above-mentioned synthesis example 3 is mixed, make to be converted into the amount (A-1) of contained separately polymkeric substance: (B-1)=80: 20 (weight ratios), add wherein gamma-butyrolactone (BL), METHYLPYRROLIDONE (NMP) and ethylene glycol butyl ether (BC), again with respect to the total amount of 100 parts by weight polymer, add 2 weight parts as the N of epoxy compounds, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, being made into solvent composition is BL: NMP: BC=71: 17: 12 (weight ratio), solids content concn is the solution of 6 % by weight.This solution is filtered with the filter that aperture is 1 μ m, make liquid crystal aligning agent (S-1).
In addition, the average imide rate of the polymkeric substance in liquid crystal aligning agent (S-1) is 19%.
The manufacture > of < liquid crystal cell
Adopt spin coater that the liquid crystal aligning agent (S-1) of modulation is above coated on the transparent electrical pole-face with the glass substrate of the transparency electrode of ITO film system, then at 80 ℃, carry out 1 minute prebake, at 210 ℃, carry out curing after 10 minutes, what formation thickness was 60nm films again.The sander of the roller that is wound around Artificial Fibers cloth is equipped with in employing, at roller rotating speed, is that 400rpm, operator's console translational speed are 3cm/ second, and fine hair is clamp-oned under the condition that length is 0.4mm, and this is filmed and carries out grinding process.Then, this substrate is used in ultrapure water to ultrasonic washing 1 minute, then be dried 10 minutes in the cleaning oven of 100 ℃, on the transparent electrical pole-face of glass substrate, form liquid crystal orientation film.Repeat this operation, make the glass substrate that a pair of (2) have liquid crystal orientation film on transparent electrical pole-face.
At each of above-mentioned a pair of substrate, have in the outer rim of face of liquid crystal orientation film, after coating has added diameter to be the epoxy resin binder of alumina balls of 5.5 μ m, liquid crystal aligning face polishing the direction relative and liquid crystal orientation film that two substrates has is vertically overlapped and pressing, tackiness agent is solidified.Then, by liquid crystal injecting port between a pair of substrate, fill nematic liquid crystal (メル Network society produces, MLC-6221) after, with acrylic acid or the like Photocurable adhesive, liquid crystal injecting port is sealed, produce liquid crystal cell.
The evaluation > of < voltage retention
At 60 ℃, in the time span of 167 milliseconds, the liquid crystal cell of above manufacture is applied to the voltage of 5V, application time is 60 microseconds, then measures from voltage and removes to the voltage retention 167 milliseconds.Determinator adopts the (VHR-1 of strain) East Yang テ Network ニ カ system.
In addition, in table 1, " > 99 " represent that the measured value of voltage retention surpasses 99% and be below 100%.
The evaluation > of < image retention performance
Except adopting the substrate of the transparency electrode with pattern shown in Fig. 1, with the above-mentioned liquid crystal cell of similarly manufacturing.
[evaluation of the image retention performance after electric charge stress has just discharged]
To this liquid crystal cell, at 25 ℃, to electrode A, apply the volts DS of 17V, to electrode B, apply the volts DS of 0V, apply 20 hours.Remove after the applying of voltage, to electrode A and B, with the gradient of 0.1V, apply 0.1～3.0V volts DS immediately.Now, investigate two interelectrode luminance differences under each voltage, under the voltage when interelectrode luminance difference is maximum, evaluate the image retention performance after electric charge stress has just discharged.That is, do not observe the situation of luminance difference between two electrodes, the image retention performance evaluation after stress has just discharged is " excellent ", only observe the situation of small luminance difference, image retention performance evaluation is " good ", observes significantly the situation of luminance difference, and image retention performance evaluation is " bad ".
[evaluation of image retention Decay Rate]
To supply with the liquid crystal cell of above-mentioned image retention performance evaluation, self charge stress relief plays at 25 ℃ standing 2 days (48 hours).Then, the voltage while applying in the image retention performance evaluation after above-mentioned electric charge stress has just discharged to electrode A and B that between two electrodes, luminance difference is maximum, investigation two interelectrode luminance differences.To this luminance difference, will similarly using result that Three Estate the evaluates evaluation result as image retention Decay Rate with said reference.The results are shown in table 1.
Embodiment 2 and comparative example 1～5
As the solution containing polymkeric substance, only use the solution that contains the polymkeric substance shown in table 1, the weight that its consumption is converted into wherein contained polymkeric substance is respectively the value of being recorded as in table 1, in addition, operation similarly to Example 1, modulate respectively liquid crystal aligning agent (S-2) and (R-1)～(R-5), and evaluate.Evaluation result is listed in table 1.
Figure G200910142627XD00351

Claims (5)

1. a liquid crystal aligning agent, it is characterized in that comprising (A) and make to contain 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride's tetracarboxylic dianhydride and the prepared polyamic acid of diamine reactant that contains the compound that following formula (1) represents, and (B) make with respect to whole tetracarboxylic dianhydrides contain 30 % by mole above from 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic basic ring amyl group acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphthalene [1, 2-c]-furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyls-2-carboxyl norbornane-2:3, 5:6-dianhydride and 4, 9-dioxa three ring [5.3.1.0 2,6] undecane-3, the tetracarboxylic dianhydride of at least one that select in the group that 5,8,10-tetraketone forms with respect to whole diamines, contain 20 % by mole of above compounds that represent from following formula (D-III), Ursol D, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 9,9-bis-(4-aminophenyl) fluorenes, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-bis-(4-aminophenyl) HFC-236fa, 4,4 '-(to phenylene diisopropylidene) pentanoic, 4,4 '-(metaphenylene diisopropylidene) pentanoic, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene radical two (hexahydroaniline), 1,3-bis-(amino methyl) hexanaphthene, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, N, N '-bis-(4-aminophenyl) p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-dimethyl-p-diaminodiphenyl, the compound that following formula (D-1)～(D-5) represents separately, the compound that following formula (D-6) represents, the imide amination polymer of the prepared polyamic acid of diamine reactant of at least one that select in the compound that following formula (D-7) represents and 1,3-bis-(3-aminopropyl)-tetramethyl disiloxane,
Figure FDA00003017061100021
In formula (1), R iand R iIrespectively do for oneself hydrogen atom or carbonatoms is 1～4 alkyl, and, the amido acid structure number having with respect to (A) polyamic acid and imide number of rings that (B) imide amination polymer has and the total quantity of amido acid structure number, (B) ratio of the imide number of rings that imide amination polymer has is 10～50%
In formula (D-III), R 9represent be selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent key group of CO-, R 10represent to have skeleton in the steroid backbone of being selected from, trifluoromethyl, Trifluoromethoxyphen-l and difluorophenyl or 1 valency organic group of group, or carbonatoms be 6～30 alkyl, R 11represent the alkyl that carbonatoms is 1～4, a3 represents 0～3 integer,
Figure FDA00003017061100031
The integer that y in formula (D-4) is 2～12, the integer that the z in formula (D-5) is 1～5,
Figure FDA00003017061100041
2. liquid crystal aligning agent claimed in claim 1, wherein for the synthesis of the tetracarboxylic dianhydride of (B) imide amination polymer, containing with respect to whole tetracarboxylic dianhydrides is 30 % by mole of above 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride and 1 of being selected from, 3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, at least one in the group that 3-diketone forms.
3. the liquid crystal aligning agent described in claim 1 or 2, wherein, with respect to 100 weight parts (A) polyamic acid and (B) total amount of imide amination polymer, further contains the compound in 0.1～30 weight part molecule with at least one epoxy group(ing).
4. the liquid crystal orientation film being formed by the liquid crystal aligning agent described in claim 1～3 any one.
5. a liquid crystal display device, is characterized in that having liquid crystal orientation film claimed in claim 4.
CN200910142627.XA 2008-06-03 2009-06-02 Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element Active CN101597498B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2008-145270 2008-06-03
JP2008145270 2008-06-03
JP2008145270A JP5158356B2 (en) 2008-06-03 2008-06-03 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Publications (2)

Publication Number Publication Date
CN101597498A CN101597498A (en) 2009-12-09
CN101597498B true CN101597498B (en) 2014-03-19

Family

ID=41419099

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200910142627.XA Active CN101597498B (en) 2008-06-03 2009-06-02 Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

Country Status (4)

Country Link
JP (1) JP5158356B2 (en)
KR (1) KR101543796B1 (en)
CN (1) CN101597498B (en)
TW (1) TWI445736B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102947755B (en) * 2010-04-30 2015-08-26 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells
JP5983936B2 (en) * 2012-11-19 2016-09-06 Jsr株式会社 Liquid crystal alignment agent
JP6269098B2 (en) * 2013-04-26 2018-01-31 Jsr株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
US20160137787A1 (en) * 2013-06-27 2016-05-19 Ube Industries, Ltd. Polymide precursor and polymide
CN109415379A (en) * 2016-05-31 2019-03-01 宇部兴产株式会社 The method for generating Alicyclic tetracarboxylic acid dianhydride
KR101959515B1 (en) * 2016-08-19 2019-03-18 주식회사 엘지화학 Method for preparation of liquid crystal alignment
CN115210638A (en) * 2020-03-06 2022-10-18 日产化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101085921A (en) * 2006-06-05 2007-12-12 Jsr株式会社 Liquid crystal aligning agent and lateral field style liquid crystal display element

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI276899B (en) * 2002-08-29 2007-03-21 Nissan Chemical Ind Ltd Material for liquid crystal alignment and liquid crystal displays using the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101085921A (en) * 2006-06-05 2007-12-12 Jsr株式会社 Liquid crystal aligning agent and lateral field style liquid crystal display element

Also Published As

Publication number Publication date
KR20090126198A (en) 2009-12-08
JP5158356B2 (en) 2013-03-06
KR101543796B1 (en) 2015-08-11
TWI445736B (en) 2014-07-21
JP2009294274A (en) 2009-12-17
TW201005004A (en) 2010-02-01
CN101597498A (en) 2009-12-09

Similar Documents

Publication Publication Date Title
CN101676363B (en) Liquid crystal aligning agent, liquid crystal display element and compound
CN101608124B (en) Liquid crystal aligning agent and liquid crystal display element
CN101382703B (en) Liquid crystal aligning agent and liquid crystal display element
CN101024773B (en) Liquid crystal aligning agent and liquid crystal display device
CN101602949B (en) Liquid crystal alignment agent and liquid crystal display element
CN101452153B (en) Liquid crystal oriented agent and liquid crystal display element
CN101597498B (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
CN101241272B (en) Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element
CN102086400B (en) Liquid crystal orientation agent and liquid crystal display element
CN102051186B (en) Liquid crystal aligning agent, liquid crystal display element, polyamide acids, polyimide and compound
CN101671566B (en) Liquid crystal alignment agent and liquid crystal display element
CN101539687B (en) Liquid crystal alignment agent and liquid crystal display element
CN101515092B (en) Aligning agent for liquid crystal and liquid crystal display element
CN101921597B (en) Liquid crystal alignment agent and liquid crystal display element
CN101526700A (en) Liquid crystal aligning agent and liquid crystal display device
CN101735824B (en) Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device
CN101114085A (en) Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device
CN101539688A (en) Liquid crystal alignment agent and liquid crystal display element
CN101608122B (en) Liquid crystal aligning agent and liquid crystal display element
CN101109873A (en) Liquid crystal aligning agent,liquid crystal aligning film and liquid crystal display device
CN101544829A (en) Alignment agent for liquid crystal and liquid crystal display element
CN101570636B (en) Liquid crystal aligning agent, liquid crystal display element, polyamic acid and imide amination polymer and compound thereof
CN101570635A (en) Liquid crystal orientation agent, liquid crystal display element, poly-amic acid, polyimide and compound
CN101458427B (en) Liquid crystal oriented agent and liquid crystal display element
CN101857804B (en) Liquid crystal aligning agent, liquid crystal display element, polyimide and compound thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant