CN101730862B - Liquid crystal aligning agent, liquid crystal alignment film, method for producing the same, and liquid crystal display device - Google Patents

Liquid crystal aligning agent, liquid crystal alignment film, method for producing the same, and liquid crystal display device Download PDF

Info

Publication number
CN101730862B
CN101730862B CN2008800238690A CN200880023869A CN101730862B CN 101730862 B CN101730862 B CN 101730862B CN 2008800238690 A CN2008800238690 A CN 2008800238690A CN 200880023869 A CN200880023869 A CN 200880023869A CN 101730862 B CN101730862 B CN 101730862B
Authority
CN
China
Prior art keywords
liquid crystal
alkyl
compound
expression
carbon number
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
CN2008800238690A
Other languages
Chinese (zh)
Other versions
CN101730862A (en
Inventor
秋池利之
熊谷勉
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 CN101730862A publication Critical patent/CN101730862A/en
Application granted granted Critical
Publication of CN101730862B publication Critical patent/CN101730862B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation

Landscapes

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

Abstract

Disclosed is a liquid crystal aligning agent containing at least one polymer (A) selected from the group consisting of polyamic acids and polyimides, and a compound (B) having a photosensitive group which is crosslinked or isomerized by light having a wavelength of 200-400 nm and an epoxy group. The liquid crystal aligning agent is used for forming a liquid crystal alignment film which is capable of aligning liquid crystals through irradiation of polarized or unpolarized radiation without performing a rubbing process.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and forming method thereof and liquid crystal display cells
Technical field
The present invention relates to aligning agent for liquid crystal, liquid crystal orientation film and forming method thereof and liquid crystal display cells.More particularly, relate to can not carry out grinding process and by irradiation polarisation or non-polarisation ray produce liquid crystal aligning can the formation of liquid crystal orientation film in operable aligning agent for liquid crystal; Under the situation that does not have dust and generation of static electricity, form the method for liquid crystal orientation film by this aligning agent for liquid crystal, and the display quality liquid crystal display device with excellent.
Background technology
So far, known have the nematic crystal that will have positive dielectric anisotropy form sandwich construction in the substrate that has the transparency electrode with liquid crystal orientation film, and the major axis that makes liquid crystal molecule is as required reversing 0～360 ° and the liquid crystal display cells (with reference to Japanese kokai publication sho 56-91277 communique and Japanese kokai publication hei 1-120528 communique) of liquid crystal cells such as TN (twisted-nematic) type made, STN (supertwist is to row) type, IPS (switching face in) type continuously between substrate.
In this liquid crystal cell, be orientated with certain orientation for substrate surface in order to make liquid crystal phase, liquid crystal orientation film must be set on substrate surface.This liquid crystal orientation film is usually by forming with the method (polishing method) of clothes such as regenerated fiber with formed organic membrane surface on the certain orientation rubbed substrate surface.But, if the formation of liquid crystal orientation film undertaken by grinding process, then exist owing to be easy to generate dust in the technology, produce static, cause alignment layer surface to adhere to dust and become the problem of the reason that shows bad generation.Particularly for the situation of substrate, also exist the static that produces to cause the TFT element circuitry to be damaged and become the problem of the reason of decrease in yield with TFT (thin film transistor (TFT)) element.And,,, thereby make and carry out the grinding process difficulty that becomes equably because along with the densification of pixel, substrate surface produces uneven from now on day by day in the liquid crystal display cells of high-precisionization.
As other means that make the liquid crystal aligning in the liquid crystal cell, known by the ray to the photosensitive film irradiation polarisation of the polyvinyl cinnamate that forms on the substrate surface, polyimide, azobenzene derivatives etc. or non-polarisation make its produce liquid crystal aligning can optical alignment method.If this method of employing, then can not produce static and dust, can realize that uniform liquid crystal aligning is (with reference to Japanese kokai publication hei 6-287453 communique, Japanese kokai publication hei 10-251646 communique, Japanese kokai publication hei 11-2815 communique, Japanese kokai publication hei 11-152475 communique, TOHKEMY 2000-144136 communique, TOHKEMY 2000-319510 communique, TOHKEMY 2000-281724 communique, Japanese kokai publication hei 9-297313 communique, TOHKEMY 2003-307736 communique, TOHKEMY 2004-163646 communique and TOHKEMY 2002-250924 communique).
But, in the liquid crystal cell of TN (twisted-nematic) type, STN (supertwist is to row) type etc., liquid crystal orientation film must have makes liquid crystal molecule with respect to the tilt angle characteristic of real estate with predetermined angle tilt orientation.Adopting optical alignment method to form under the situation of liquid crystal orientation film, tilt angle is usually by making irradiated ray produce from the substrate normal run-off the straight to the incident direction of real estate.
In addition, as the mode of operation of the liquid crystal display cells beyond above-mentioned, also known VA (vertical orientated) the type liquid crystal cell that makes liquid crystal molecule vertical orientated vertical (homeotrophic) alignment mode on substrate with negative dielectric anisotropic.In this mode of operation, make liquid crystal molecule when the direction parallel with substrate tilts to applying voltage between substrate, liquid crystal molecule is tilted from the direction of substrate normal direction in real estate.As the means that reach this purpose, for example proposed in the method that projection is set on the substrate surface, made method that band is set on the transparency electrode, adopted the polishing alignment films to make liquid crystal molecule from the method for the direction slight inclination (make its pre-tilt) of substrate normal direction in real estate etc.
Above-mentioned optical alignment method, known in the liquid crystal cell of vertical alignment mode the method as control liquid crystal molecules tilt direction also be of great use.That is to say, known to using the vertical alignment layer that produces orientation control force and tilt angle by optical alignment method, can control the method for tilting (with reference to TOHKEMY 2003-307736 communique, TOHKEMY 2004-163646 communique, TOHKEMY 2004-83810 communique, Japanese kokai publication hei 9-211468 communique and TOHKEMY 2003-114437 communique) of the liquid crystal molecule when applying voltage equably.
Like this, the liquid crystal orientation film that adopts above-mentioned optical alignment method to make can be effectively applied to various liquid crystal display cells.But though can obtain bigger tilt angle, there is the very big problem of required radiation exposure in optical alignment film in the past.For example, existing report is in containing the optical alignment film of azobenzene derivatives, in order to obtain enough big tilt angle, essential irradiation 10000J/m 2The ray that above optical axis tilts from substrate normal is (with reference to TOHKEMY 2002-250924 communique, TOHKEMY 2004-83810 communique and J.of the SID 11/3,2003, p.579).
Summary of the invention
The present invention In view of the foregoing makes, its objective is provide can not carry out grinding process and by irradiation polarisation or non-polarisation ray produce liquid crystal aligning can the formation of liquid crystal orientation film in operable aligning agent for liquid crystal.
Another object of the present invention provides a kind of method that is formed liquid crystal orientation film under the situation that does not have dust and generation of static electricity by aligning agent for liquid crystal.
Further aim of the present invention provides good liquid crystal orientation film of liquid crystal aligning and display quality liquid crystal display device with excellent.
The present invention is other purposes and advantage further, can be learned by the following description.
According to the present invention, above-mentioned purpose of the present invention and advantage, the first, to reach by a kind of aligning agent for liquid crystal, it contains:
(A) be selected from the group that polyamic acid and polyimide constitute at least a polymkeric substance and
(B) having by wavelength is light generation cross-linking reaction or the photosensitive group of isomerization reaction and the compound of epoxy radicals of 200～400nm.
Above-mentioned purpose of the present invention and advantage, the second, reach by the formed liquid crystal orientation film of above-mentioned aligning agent for liquid crystal.The 3rd, to reach by a kind of method that forms of liquid crystal orientation film, it has on substrate the above-mentioned aligning agent for liquid crystal of coating and forms and film, and to the operation of this film irradiation polarisation or non-polarisation ray.
And, above-mentioned purpose of the present invention and advantage, the 4th, reach by liquid crystal display cells with above-mentioned liquid crystal orientation film.
Below, the present invention is described in detail.
Aligning agent for liquid crystal of the present invention contains (A) and is selected from least a polymkeric substance in the group that polyamic acid and polyimide constitute.
＜(A) polymkeric substance 〉
Above-mentioned polyamic acid can be by tetracarboxylic dianhydride and diamine reactant and is synthesized.Above-mentioned polyimide can synthesize by above-mentioned polyamic acid is carried out dehydration closed-loop.
[tetracarboxylic dianhydride]
As operable tetracarboxylic dianhydride in above-mentioned polyamic acid synthetic, can enumerate for example butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 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, the 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, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 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, the 3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-ethyloic norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0 2,6] undecane-3,5,8,10-tetraketone, following formula (T-I) and aliphatics or the ester ring type tetracarboxylic dianhydrides such as compound that (T-II) represent separately,
Figure G2008800238690D00051
(formula (T-I) and (T-II) in, R 1And R 3The divalent organic group of respectively doing for oneself and having aromatic rings, 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 '-diphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-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 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3, the 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 dianhydride, to phenylene-two (triphenyl phthalic acid) dianhydride, metaphenylene-two (triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl methane dianhydride, ethylene glycol-two (dehydration trimellitate), propylene glycol-two (dehydration trimellitate), 1,4-butylene glycol-two (dehydration trimellitate), 1,6-hexanediol-two (dehydration trimellitate), 1,8-ethohexadiol-two (dehydration trimellitate), 2,2-two (4-hydroxyphenyl) propane-two (dehydration trimellitate), following formula (T-1)～(T-4)
Figure G2008800238690D00071
Figure G2008800238690D00081
Biao Shi aromatic tetracarboxylic acid's dianhydrides such as compound separately.They can a kind ofly be used alone or in combination of two or more.The phenyl ring of these aromatic tetracarboxylic acid's dianhydrides can be 1～4 alkyl (preferable methyl) replacement by one or more carbon number.
Operable tetracarboxylic dianhydride in above-mentioned polyamic acid synthetic shows the angle of good liquid crystal aligning from making formed liquid crystal orientation film, preferred use to contain be selected from the butane tetracarboxylic acid dianhydride in the middle of above-mentioned, 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane 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, the 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, the 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, the 3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-ethyloic norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [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 '-diphenyl sulfone tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1,4,5, the tetracarboxylic dianhydride of at least a (hereinafter referred to as " specific tetracarboxylic dianhydride ") in the group that the compound of following formula (8) expression in the compound that the following formula (T-5)～(T-7) in the compound of 8-naphthalene tetracarboxylic acid dianhydride, above-mentioned formula (T-I) expression is represented separately and the compound of above-mentioned formula (T-II) expression constitutes.
Figure G2008800238690D00101
Particularly preferred specific tetracarboxylic dianhydride is for being selected from 1,2,3,4-cyclo-butane 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, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-ethyloic norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0 2,6] undecane-3,5,8, at least a in the group that the compound of 10-tetraketone, pyromellitic acid dianhydride and above-mentioned formula (T-5) expression constitutes.
Operable tetracarboxylic dianhydride in above-mentioned polyamic acid synthetic preferably with respect to whole tetracarboxylic dianhydrides, is contained the above aforesaid specific tetracarboxylic dianhydride of 20 moles of %, more preferably contains 50 moles more than the %, especially preferably contains 80 moles more than the %.
[diamines]
As operable diamines in above-mentioned polyamic acid synthetic, can enumerate for example p-phenylenediamine (PPD), m-phenylene diamine, 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 '-diaminobenzene formailide, 4,4 '-diaminodiphenyl ether, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamido benzophenone, 3,4 '-diamido benzophenone, 4,4 '-diamido benzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogen anthracene, 2, the 7-diamino-fluorene, 9,9-dimethyl-2, the 7-diamino-fluorene, 9,9-two (4-aminophenyl) fluorenes, two (4-amino-2-chlorphenyl) methane, 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamido-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 '-(to the phenylene diisopropylidene) diphenylamine, 4,4 '-(metaphenylene diisopropylidene) diphenylamine, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamido-3,3 '-two (trifluoromethyl) biphenyl, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl, the aromatic diamines such as compound that following formula (D-1)～(D-5) is represented separately
Figure G2008800238690D00121
(y in the formula (D-4) is 2～12 integer, and the z in the formula (D-5) is 1～5 integer.)
1,1-m-xylene diamine, 1,3-propane diamine, butanediamine, pentanediamine, hexane diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene bicyclopentadiene diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0 2,7] 11 alkylidene dimethyl diamines, 4,4 '-methylene two (cyclohexylamine), 1,3-two (amino methyl) cyclohexane, 1, aliphatics or ester ring type diamines such as 4-two (amino methyl) cyclohexane;
2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamido-2,3-dicyano pyrazine, 5,6-diamido-2, the 4-dihydroxy-pyrimidine, 2,4-diamido-6-dimethylamino-1,3, the 5-triazine, 1,4-two (3-aminopropyl) piperazine, 2,4-diamido-6-isopropoxy-1,3, the 5-triazine, 2,4-diamido-6-methoxyl-1,3, the 5-triazine, 2,4-diamido-6-phenyl-1,3,5-triazines, 2,4-diamido-6-methyl-s-triazine, 2, the 4-diamino-1,3,5-triazines, 4,6-diamido-2-vinyl-s-triazine, 2,4-diamido-5-phenyl thiazole, 2, the 6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3, the 5-diaminostilbene, 2, the 4-triazole, 3,8-diamido-6-phenylphenanthridineand, 1,4-diamido piperazine, 3, the 6-proflavin, N, N '-two (4-aminophenyl) aniline, 3,6-diamido carbazole, N-methyl-3,6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole, N, N '-two (4-aminophenyl) biphenylamine, N, N '-two (4-aminophenyl)-N, N '-dimethyl-biphenylamine, the compound of following formula (D-I) expression
Figure G2008800238690D00131
(in the formula (D-I), R 5For having 1 valency organic group of the nitrogen atom ring texture that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, X IBe the organic group of divalent, R 6For carbon number is 1～4 alkyl, a1 is 0～3 integer), have the diamines of the nitrogen-atoms beyond 2 primary amino radicals and this primary amino radical in the compound equimolecular of following formula (D-II) expression,
Figure G2008800238690D00141
(in the formula (D-II), R 7For having the divalent organic group of the nitrogen atom ring texture that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, X IIRespectively the do for oneself organic group of divalent, a plurality of X of existence IISeparately can be identical, also can be different, R 8The carbon number of respectively doing for oneself is 1～4 alkyl, respectively do for oneself 0～3 integer of a2); The single-substituted diamines such as compound of following formula (D-III) expression,
Figure G2008800238690D00142
(in the formula (D-III), X 9For-O-,-COO-,-OCO-,-NHCO-,-CONH-or-CO-, R 10For having skeleton in the steroid backbone of being selected from, trifluoromethyl, Trifluoromethoxyphen-l and the fluoro phenyl or 1 valency organic group of group, perhaps carbon number is 6～30 alkyl, R 11For carbon number is 1～4 alkyl, a3 is 0～3 integer); The diamido organosiloxanes such as compound of following formula (D-IV) expression etc.,
Figure G2008800238690D00151
(in the formula (D-IV), R 12The carbon number of respectively doing for oneself 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, q is 1～20 integer).These diamines can be used alone or in combination of two or more.
The phenyl ring of above-mentioned aromatic diamine can also be that 1～4 alkyl (preferable methyl) replaces by one or more carbon number.Above-mentioned formula (D-I), (D-II) and (D-III) in R 6, R 8And R 11Be preferably methyl separately, a1, a2 and a3 are preferably 0 or 1 separately, and more preferably 0.
The R of above-mentioned formula (D-III) 10Steroid backbone, be meant by structure that cyclopentane-the perhydro phenanthrene nucleus constitutes or in its carbon-carbon bond one or more to change the skeleton of two keys into.As R with this steroid backbone 101 valency organic group, preferred carbon number is 17～51 group, more preferably carbon number is 17～29 group.As R with steroid backbone 10Object lesson, can enumerate for example cholestane-3-base, courage steroid-5-alkene-3-base, courage steroid-24-alkene-3-base, courage steroid-5,24-diene-3-base, lanostane-3-base etc.
As the diamines that can be used for synthetic above-mentioned polyamic acid, preferably contain and be selected from p-phenylenediamine (PPD) in the middle of above-mentioned, 4,4 '-diaminodiphenylmethane, 4,4 '-diamino-diphenyl thioether, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(to the phenylene diisopropylidene) diphenylamine, 4,4 '-(metaphenylene diisopropylidene) diphenylamine, 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 1, the 4-diamino-cyclohexane, 4,4 '-methylene two (cyclohexylamine), 1,3-two (amino methyl) cyclohexane, the compound that above-mentioned formula (D-1)～(D-5) is represented separately, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 3,6-diamido carbazole, N-methyl-3,6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole, N, N '-two (4-aminophenyl) biphenylamine, N, N '-two (4-aminophenyl)-N, N '-dimethylbenzidine, the compound of following formula (D-6) expression in the compound of above-mentioned formula (D-I) expression, the compound of following formula (D-7) expression in the compound of above-mentioned formula (D-II) expression;
Dodecyloxy-2 in the compound of above-mentioned formula (D-III) expression, the 4-diaminobenzene, pentadecane oxygen base-2, the 4-diaminobenzene, hexadecane oxygen base-2, the 4-diaminobenzene, octadecane oxygen base-2, the 4-diaminobenzene, dodecyloxy-2, the 5-diaminobenzene, pentadecane oxygen base-2, the 5-diaminobenzene, hexadecane oxygen base-2, the 5-diaminobenzene, octadecane oxygen base-2, the 5-diaminobenzene, in the compound of compound that following formula (D-8)～(D-15) is represented separately and above-mentioned formula (D-IV) expression 1, the diamines of at least a (hereinafter referred to as " specific diamines ") in the group that 3-two (3-aminopropyl)-tetramethyl disiloxane constitutes.
Figure G2008800238690D00171
The diamines that can be used for synthetic above-mentioned polyamic acid preferably with respect to whole diamines, contains the above aforesaid specific diamines of 20 moles of %, more preferably contains 50 moles more than the %, especially preferably contains 80 moles more than the %.
Synthesizing of＜polyamic acid 〉
Polyamic acid in the aligning agent for liquid crystal of the present invention can make by making aforesaid tetracarboxylic dianhydride and diamine reactant.
Supply with the tetracarboxylic dianhydride of polyamic acid synthetic reaction and the usage rate of diamines, preferably with respect to 1 equivalent amino of diamines, the anhydride group that makes the tetracarboxylic dianhydride is the ratio of 0.2～2 equivalent, more preferably is the ratio of 0.8～1.2 equivalent.
The synthetic reaction of polyamic acid preferably in organic solvent, is preferable over-20～150 ℃, more preferably under 0～100 ℃ temperature conditions, preferably carries out 0.1～24 hour, more preferably carries out 0.5～12 hour.Here, as organic solvent, so long as can dissolve the solvent of the polyamic acid of generation, then have no particular limits, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, N, N-dimethyl acetamide, N, non-proton property polar solvents such as dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, HMPA; Between phenol solvent such as sylvan, xylenols, phenol, halogenated phenol.The consumption of organic solvent (a), being preferably the total amount (b) that makes tetracarboxylic dianhydride and diamine compound is the amount of 0.1～30 weight % with respect to the total amount (a+b) of reaction solution.In addition, when organic solvent and following poor solvent coupling, the consumption of above-mentioned organic solvent (a) should be understood to the implication of the total consumption of organic solvent and poor solvent.
In the above-mentioned organic solvent, in the scope that the polyamic acid that does not make generation is separated out, the poor solvent alcohols of all right coupling polyamic acid, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc.Object lesson as this poor solvent, can enumerate for example methyl alcohol, ethanol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1, the 4-butylene glycol, triethylene glycol, glycol monoethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, diethy-aceto oxalate, diethyl malonate, ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, the ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic acid esters, the diethylene glycol monoethyl ether acetic acid esters, tetrahydrofuran, methylene chloride, 1, the 2-ethylene dichloride, 1, the 4-dichloroetane, trichloroethanes, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene, isoamyl propionate, isoamyl isobutyrate, isoamyl ether etc.
When with organic solvent and poor solvent coupling, the usage rate of poor solvent can suitably be set in the scope that the polyamic acid that does not make generation is separated out, and preferably the total amount with respect to solvent is below the 50 weight %, more preferably below the 40 weight %, more preferably below the 30 weight %.
As mentioned above, obtained dissolving the reaction solution of polyamic acid.This reaction solution, it directly can be supplied with the modulation of aligning agent for liquid crystal, also polyamic acid contained in the reaction solution can be separated the back and supply with the modulation of aligning agent for liquid crystal, resupply the modulation of aligning agent for liquid crystal after perhaps also isolated polyamic acid can being made with extra care.The separation of polyamic acid can obtain precipitate by above-mentioned reaction solution is put in a large amount of poor solvents, and the method for this precipitate of drying under reduced pressure perhaps distillates the method for reaction solution with the evaporator decompression and carries out.In addition, be dissolved in once more in the organic solvent, make its method of separating out with poor solvent then, perhaps carry out once or the method for the operation that distillates with evaporator decompression several times, can make with extra care polyamic acid by making this polyamic acid.
＜polyimide 〉
Preferred polyimide in the aligning agent for liquid crystal of the present invention can make by aforesaid polyamic acid is carried out the dehydration closed-loop imidizate.
Contained polyimide in the aligning agent for liquid crystal of the present invention, can be the complete imidizate thing of the amic acid structure fully dehydrating closed loop that has of its precursor polyamic acid, also can be a part of dehydration closed-loop, amic acid structure and the imide ring structure of only amic acid structure and the part imidizate thing of depositing.
Polyimide in the aligning agent for liquid crystal of the present invention, its imidizate rate is preferably more than 30%, more preferably more than 50%, is preferably more than 80% especially.Above-mentioned imidizate rate is the total quantity with respect to the amic acid structure number and the imide ring structure number of polyimide, the value that the shared ratio of imide ring structure number is represented with percent.At this moment, the part of imide ring can also be different imide ring.This imidizate rate can be by polyimide 1H-NMR learns.
The dehydration closed-loop of polyamic acid, preferred (i) are by the method for heating polyamic acid, and perhaps (ii) by polyamic acid is dissolved in the organic solvent, the method that adds dewatering agent and dehydration closed-loop catalyzer and heating as required in this solution is carried 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, then the dehydration closed-loop reaction can not be carried out fully, if temperature of reaction surpasses 200 ℃, the situation of the molecular weight and molecular weight of gained polyimide then can occur.Reaction time is preferably 1.0～24 hours, more preferably 1.0～12 hours.
On the other hand, in the above-mentioned method of in polyamic acid solution, adding dewatering agent and dehydration closed-loop catalyzer (ii),, can use for example acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride as dewatering agent.The consumption of dewatering agent is decided according to required imidizate rate, and preferably 1 mole of amic acid structure with respect to polyamic acid is 0.01～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, collidine, two picolins, triethylamine.But, be not limited to these.The dehydration closed-loop catalyst consumption is 0.01～10 mole with respect to 1 mole of used dewatering agent preferably.The consumption of above-mentioned dewatering agent and dehydration closed-loop agent is many more, can make the imidizate rate high more.As used organic solvent in the dehydration closed-loop reaction, can enumerate as operable organic solvent in polyamic acid synthetic and illustrative organic solvent.The temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 10～150 ℃.Reaction time is preferably 1.0～120 hours, more preferably 2.0～30 hours.
Modulation of aligning agent for liquid crystal can directly be supplied with it by the polyimide that makes in the said method (i), resupplies the modulation of aligning agent for liquid crystal after perhaps also the polyimide that makes can being made with extra care.In addition, said method (ii) in, obtain containing the reaction solution of polyimide.This reaction solution, it directly can be supplied with the modulation of aligning agent for liquid crystal, also can from reaction solution, remove dewatering agent and dehydration closed-loop catalyzer and supply with the modulation of aligning agent for liquid crystal afterwards, polyimide can also be separated the back and supply with the modulation of aligning agent for liquid crystal, resupply the modulation of aligning agent for liquid crystal after perhaps also the polyimide that separates can being made with extra care.From reaction solution, remove dewatering agent and dehydration closed-loop catalyzer, can adopt for example method such as solvent exchange.The separation of polyimide, refining can be taked to carry out as the separating of polyamic acid, the described same operation of process for purification with above.
The polymkeric substance of-end modified type-
Contained polyamic acid and polyimide in the aligning agent for liquid crystal of the present invention can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting separately.By using the polymkeric substance of end modified type, can under the prerequisite of not damaging effect of the present invention, further improve the coating performance of aligning agent for liquid crystal etc.This end modified type polymkeric substance can be by when polyamic acid synthetic, adds molecular weight regulator and carry out in polymerization reaction system.As molecular weight regulator, can enumerate for example single acid anhydride, monoamine compound, monoisocyanates compound etc.
As above-mentioned single acid anhydride, can enumerate for example maleic anhydride, phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinic anhydride, n-tetradecane base succinic anhydride, n-hexadecyl succinic anhydride etc.As above-mentioned monoamine compound, can enumerate for example aniline, cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, n-pentadecane amine, n-hexadecane amine, n-heptadecane amine, n-octadecane amine, n-eicosane amine etc.As above-mentioned monoisocyanates compound, can enumerate for example phenyl isocyanate, isocyanic acid naphthyl ester etc.
The usage rate of molecular weight regulator, the total amount of employed tetracarboxylic dianhydride and diamines is preferably below 20 weight portions, more preferably below 10 weight portions when synthetic with respect to the acid of 100 weight parts of polyamide.
-solution viscosity-
Polyamic acid that as above makes and polyimide preferably when it being made into concentration respectively when being the solution of 10 weight %, have the solution viscosity of 20～800mPas, more preferably have the solution viscosity of 30～500mPas.
The solution viscosity of above-mentioned polymkeric substance (mPas) is that the concentration that the good solvent (for example gamma-butyrolacton, N-N-methyl-2-2-pyrrolidone N-etc.) that adopts this polymkeric substance is modulated is the polymer solution of 10 weight %, with the values of E type rotational viscosimeter mensuration under 25 ℃.
＜(B) compound 〉
Contained (B) compound in the aligning agent for liquid crystal of the present invention is that to have by wavelength be light generation cross-linking reaction or the photosensitive group of isomerization reaction and the compound of epoxy radicals of 200～400nm.
Above-mentioned (B) compound, as long as have above-mentioned character, then it is had no particular limits, for example, compound can be that to have carbon number be 4～20 alkyl, carbon number is 1～20 fluoro-alkyl, cyclohexyl, has carbon number and is the alkyl-cyclohexyl or the alkyl phenyl of 1～20 alkyl, has carbon number and is the fluoro-alkyl cyclohexyl or the fluoro-alkyl phenyl of 1～20 fluoro-alkyl, 4～20 alkoxy, carbon number is 1～20 fluoroalkyl, cyclohexyloxy, has carbon number and is the alkoxy cyclohexyl or the alkoxyl phenyl of 1～20 alkoxy, has carbon number and is the fluoro-alkyl cyclohexyl or the fluoroalkyl phenyl of 1～20 fluoro-alkyl, or the carbon number with steroid backbone is 17～51 group, and epoxy radicals, and following formula (1)
Figure G2008800238690D00241
The compound of the group of expression.
As this (B) compound, be preferably the compound of following formula (1-1) expression,
(A-W) m-X-(Ep) n (1-1)
(in the formula (1-1), A is the group of any one expression of following formula (A-1)～(A-8), W is the group of any one expression of following formula (W-1)～(W-4), X is 4 valency groups of any one expression of following formula (X-1)～(X-5), Ep be following formula (Ep-1) or (Ep-2) expression group, m is 1～3 integer, and n is 4-m.)
(in the formula (A-1), R IBe that 4～20 alkyl, carbon number are 1～20 fluoro-alkyl, cyclohexyl, to have alkyl-cyclohexyl or alkyl phenyl that carbon number is 1～20 alkyl, have carbon number be that the fluoro-alkyl cyclohexyl or the fluoro-alkyl phenyl of 1～20 fluoro-alkyl or the carbon number with steroid backbone are 17～51 group for carbon number independently of one another
X 1For singly-bound, oxygen atom, sulphur atom ,-COO-,-NHCO-,-CONH-or-CO-, X 2Be singly-bound or following formula (X 2-1)～(X 2-3) group of any one expression,
Figure G2008800238690D00251
(in the above-mentioned formula, the connecting key that " * " expression has it is positioned at X1 one side)
X 3Be singly-bound, *-O-(CH 2) a-, *-O-(CH 2) a-CO-,-(CH 2) a-OCO-(CH 2) a-or following formula
Figure G2008800238690D00252
The group of expression (wherein, a is 1～6 integer independently of one another, and the connecting key that " * " expression has it is positioned at-CH=CH-CO-one side), wherein, when two adjacent keys were singly-bound, they were together as a singly-bound.)
Figure G2008800238690D00253
(in the formula (A-2), R IWith the R in the above-mentioned formula (A-1) IDefinition identical,
X 4For singly-bound, oxygen atom, sulphur atom ,-COO-,-OCO-,-NHCO-,-CONH-or-CO-,
X 5Be singly-bound or phenylene,
X 6Be singly-bound or following formula (X 6-1) Biao Shi group,
Figure G2008800238690D00261
(formula (X 6-1) in, the connecting key that " * " expression has it is positioned at X 7One side)
X 7Be singly-bound, *-OCO-(CH 2) a-, *-OCO-(CH 2) a-CO-or following formula (X 7-1)
Figure G2008800238690D00262
(in the middle of above-mentioned, a is 1～6 integer to the group of expression, and the connecting key that " * " expression has it is positioned at X 6One side), wherein, when two adjacent keys were singly-bound, they were together as a singly-bound.)
Figure G2008800238690D00263
(in the formula (A-3), R IWith the R in the above-mentioned formula (A-1) IDefinition identical.)
Figure G2008800238690D00271
(in the formula (A-4)～(A-6), R ISeparately with above-mentioned formula (A-1) in R IDefinition identical, X 8Respectively do for oneself singly-bound, oxygen atom, sulphur atom ,-COO-,-OCO-,-NHCO-,-CONH-or-CO-.)
(formula (A-7) and (A-8) in, R 1Separately with above-mentioned formula (A-1) in R IDefinition identical, X 9Singly-bound or *-(CH respectively does for oneself 2) a-COO-(wherein, a is 1～6 integer, and the connecting key that " * " expression has it is positioned at-CO-one side).)
(in the above-mentioned formula, the connecting key that " * " expression has it is positioned at X one side.)
Figure G2008800238690D00291
(in the above-mentioned formula, Y be singly-bound ,-O-,-S-,-CH 2-,-C (CH 3) 2-or the group of following formula (Y-1) expression,
Figure G2008800238690D00292
R IIThe optional carbon number that can be replaced by fluorine atom of respectively doing for oneself is 1～6 alkyl or fluorine atom, respectively do for oneself 0～4 integer of b.)
Figure G2008800238690D00301
Wherein, in the above-mentioned formula (A-1)～(A-8), do not allow to form the such substituting group combination of O-O key.
As the R in the above-mentioned formula (A-1)～(A-8) ICarbon number be 4～20 alkyl, can enumerate for example normal-butyl, n-pentyl, n-hexyl, n-octyl, positive decyl, dodecyl, n-hexadecyl, n-octadecane base, n-eicosane base etc.;
As carbon number is 1～20 fluoro-alkyl, can enumerate for example trifluoromethyl, perfluor ethyl, 3,3,3-trifluoro propyl, 4,4,4-trifluoro butyl, 4,4,5,5,5-five fluorine amyl groups, 4,4,5,5,6,6,6-seven fluorine hexyls etc.;
As having the alkyl-cyclohexyl that carbon number is 1～20 alkyl, can enumerate for example 4-methylcyclohexyl, 4-normal-butyl cyclohexyl, 4-n-pentyl cyclohexyl, 4-n-hexyl cyclohexyl etc.;
As having the alkyl phenyl that carbon number is 1～20 alkyl, can enumerate for example 4-n-butylphenyl, 4-n-pentyl phenyl etc.;
As having the fluoro-alkyl cyclohexyl that carbon number is 1～20 fluoro-alkyl, can enumerate for example 4-trifluoromethyl cyclohexyl etc.;
As having the fluoro-alkyl phenyl that carbon number is 1～20 fluoro-alkyl, can enumerate for example 4-trifluoromethyl etc.;
R IIn steroid backbone, be meant by skeleton that cyclopentane-the perhydro phenanthrene nucleus constitutes or in its carbon-carbon bond one or more to change the skeleton of two keys into.As R with this steroid backbone I1 valency organic group, preferred carbon number is 17～29 group.As R with steroid backbone IObject lesson, can enumerate for example cholestane-3-base, courage steroid-5-alkene-3-base, courage steroid-24-alkene-3-base, courage steroid-5,24-diene-3-base, lanostane-3-base etc.
Preferred respectively:
Position or contraposition between two nitrogen-atoms in the above-mentioned formula (X-1) are positioned at separately;
Two nitrogen-atoms in the above-mentioned formula (X-2) are positioned at 4,4 '-position separately;
Two nitrogen-atoms in the above-mentioned formula (X-3) are positioned at 1 separately, 3-position or 1,4-position;
Two nitrogen substituted methylenes in the above-mentioned formula (X-4) are positioned at 1 separately, 3-position or 1,4-position;
Position or contraposition between two nitrogen substituted methylenes in the above-mentioned formula (X-5) are positioned at separately.
Aforesaid (B) compound can be by for example with compounds X-(Ep) 4(wherein, X is identical with the definition in the above-mentioned formula (1-1) separately with Ep) and compd A-OH is (wherein, A is identical with the definition in the above-mentioned formula (1-1)) potpourri, preferably in suitable organic solvent, in the presence of catalyzer, heat as required and synthesize.
As compounds X-(Ep) 4Object lesson, radicals X is the group of above-mentioned formula (X-1) expression, can enumerate for example following formula (X-1-1) and the compound (X-1-2) represented separately etc.;
Radicals X is the group of above-mentioned formula (X-2) expression, can enumerate compound that for example following formula (X-2-1)～(X-2-6) represents separately etc.;
Radicals X is the group of above-mentioned formula (X-3) expression, can enumerate for example following formula (X-3-1) and the compound (X-3-2) represented separately etc.;
Radicals X is the group of above-mentioned formula (X-4) expression, can enumerate for example following formula (X-4-1) and the compound (X-4-2) represented separately etc.;
Radicals X is the group of above-mentioned formula (X-5) expression, can enumerate for example following formula (X-5-1) and the compound (X-5-2) represented separately etc.
Figure G2008800238690D00321
Figure G2008800238690D00331
As the example of compd A-OH, group A is the group of above-mentioned formula (A-1) expression, can enumerate compound that for example following formula (A-1-1)～(A-1-30) represents separately etc.;
Group A is the group of above-mentioned formula (A-2) expression, can enumerate compound that for example following formula (A-2-1)～(A-1-15) represents separately etc.;
Group A is the group of above-mentioned formula (A-3) expression, can enumerate compound that for example following formula (A-3-1)～(A-3-42) represents separately etc.;
Group A is the group of above-mentioned formula (A-4) expression, can enumerate compound that for example following formula (A-4-1)～(A-4-3) represents separately etc.;
Group A is the group of above-mentioned formula (A-5) expression, can enumerate the compound of for example following formula (A-5-1) expression etc.;
Group A is the group of above-mentioned formula (A-6) expression, can enumerate the compound of for example following formula (A-6-1) expression etc.;
Group A is the group of above-mentioned formula (A-7) expression, can enumerate the compound of for example following formula (A-7-1) expression etc.;
Group A is the group of above-mentioned formula (A-8) expression, can enumerate for example following formula (A-8-1) and the compound (A-8-2) represented separately etc.
Figure G2008800238690D00341
Figure G2008800238690D00361
Figure G2008800238690D00371
Figure G2008800238690D00381
Figure G2008800238690D00391
Figure G2008800238690D00401
Figure G2008800238690D00411
Figure G2008800238690D00421
Figure G2008800238690D00431
Figure G2008800238690D00441
(in the above-mentioned formula, R ISeparately with above-mentioned formula (1-1) in R IDefinition identical, a separately with above-mentioned formula (A-1) in X 3, the X in (A-2) 7Or the X (A-8) 9In definition in the definition of a that occurs identical.)
In above-mentioned formula (A-3-1)～(A-3-42), two keys of phenyl ring both sides are respectively with trans forms record, but should be understood to equally also disclose both be the cis form a compound and a side be trans forms and opposite side is the compound of cis form.
Wherein, from the liquid crystal aligning and the UV absorbability angle of yield-power and formed liquid crystal orientation film, preferred above-mentioned formula (A-1-1), (A-1-2), (A-1-3), (A-1-4), (A-1-27), (A-3-1)～(A-3-7), (A-3-12)～(A-3-18), (A-3-26)～(A-3-29), (A-3-36)～(A-3-39) and the compound of (A-4-1) representing separately.
Aforesaid compd A-OH can synthesize by vitochemical conventional method is made up.
For example, the compound of above-mentioned formula (A-1-1) expression, can by for example with malonic acid with have the R of being equivalent to IThe benzaldehyde of alkyl in the presence of suitable alkali such as piperazine, heat and make its reaction and make.
The compound of above-mentioned formula (A-1-2) expression, can by for example with hydroxycinnamic acid with have the R of being equivalent to IAlkyl alkyl halide heat in the presence of the suitable alkali such as sal tartari make its reaction after, be hydrolyzed and make with the aqueous alkali that contains suitable alkali such as NaOH.
The compound of above-mentioned formula (A-1-3) expression can be by for example having the R of being equivalent to IThe benzoic acid derivative of alkyl make acyl chlorides with thionyl chloride after, it made its reaction with hydroxycinnamic acid and make in the presence of suitable alkali such as sal tartari under the temperature of 0 ℃～room temperature.
The compound of above-mentioned formula (A-1-4) expression, can by for example with methyl hydroxybenzoate with have the R of being equivalent to IThe alkyl halide of alkyl or tosylation alkane in the presence of the suitable alkali such as sal tartari after making its reaction under the temperature of room temperature～100 ℃; be hydrolyzed with the aqueous alkali that contains suitable alkali such as NaOH; after again it being made acyl chlorides with thionyl chloride, in the presence of suitable alkali such as sal tartari, under the temperature of 0 ℃～room temperature, make its reaction and make with hydroxycinnamic acid.
The compound of above-mentioned formula (A-1-27) expression can be by for example having the R of being equivalent to IThe 4-alkyl-cyclohexyl carboxylic acid of alkyl make acyl chlorides with thionyl chloride, it made its reaction with hydroxycinnamic acid and make in the presence of suitable alkali such as sal tartari under the temperature of 0 ℃～room temperature.
The compound of above-mentioned formula (A-2-1) expression, can by for example with iodo phenol with have the R of being equivalent to IThe alkyl acrylate of alkyl use the coupling reaction (this reaction is commonly called " Heck reaction ") of palladium catalyst and make.
The compound of above-mentioned formula (A-2-6) expression can make by the compound that the following formula of compound addition that makes above-mentioned formula (A-2-1) expression is represented.
Figure G2008800238690D00451
(in the above-mentioned formula, a is identical with the definition in the above-mentioned formula (A-2-6).)
The compound of above-mentioned formula (A-3-1)～(A-3-42) expression, can be respectively by after 4-bromo-cinnamic acid or 4-cinnamyl bromide acyl chlorides and alkanol, phenol, alkyl halide, halogenated aryl hydrocarbon or alkyl amine with required group being reacted make 4-cinnamyl bromide acid esters, make it pass through He Ke (Heck) reaction addition acrylic acid and synthesize.
The compound of above-mentioned formula (A-4-1) expression can have required radicals R by for example making ISuccinic anhydride derivant and 4-amino-cinnamic acid in acetic acid, reflux the perhaps method that in toluene or dimethylbenzene, in the presence of suitable catalyzer such as sulfuric acid, triethylamine, refluxes and synthesizing.
The compound of above-mentioned formula (A-4-2) expression can have required radicals R by for example making IIdoalkane or the methyl esters of bromoalkane and malic acid or ethyl ester react in the presence of the suitable catalyzer such as silver oxide make ether after, it is hydrolyzed with alkali, carry out dehydration closed-loop with acetic anhydride again, make and have R IBehind the anhydride ester derivs of-O-, be raw material, adopt the synthetic same quadrat method of the compound of representing with above-mentioned formula (A-4-1) to synthesize with it.
The compound of above-mentioned formula (A-4-3) expression can be by for example making maleimide and having required radicals R IAlkanethiol carry out Michael (Michael) addition after, maleimide is hydrolyzed, carry out dehydration closed-loop then after, be raw material with it, adopt with the synthetic same quadrat method of the compound of above-mentioned formula (A-4-1) expression and synthesize.
The compound of above-mentioned formula (A-5-1) expression can make it and have required radicals R by after for example the hydrogenation thing of trimellitic acid acid anhydrides being made acyl chlorides with thionyl chloride IAlcohol after ester is made in reaction in the presence of the suitable alkali such as for example triethylamine, be raw material with it, adopt with the synthetic same quadrat method of the compound of above-mentioned formula (A-4-1) expression and synthesize.
The compound of above-mentioned formula (A-6-1) expression, can be by after for example hydroxyl phthalic anhydride being carried out dehydration closed-loop, by itself and 4-amino-cinnamic acid are refluxed in acetic acid, perhaps in toluene or dimethylbenzene after the method that refluxes in the presence of the suitable catalyzer such as sulfuric acid, triethylamine synthesizes imide compound, make it and have a R of being equivalent to IThe halogenide of alkyl in the presence of alkali such as sal tartari, react and make.
The compound of above-mentioned formula (A-7-1) expression can be by for example making the 4-nitrocinnamic and having required radicals R IAlkyl halide react in the presence of the suitable alkali such as sal tartari make ester after, it is reduced with tin chloride etc., make nitro change into amino, after making intermediate, by this intermediate is refluxed simultaneously at cyclohexane tricarboxylic acid anhydride and acetic acid, perhaps the method that refluxes in the presence of suitable catalyzer such as triethylamine in toluene or dimethylbenzene is synthesized.
The compound of above-mentioned formula (A-8-1) expression, can be by in the compound of above-mentioned formula (A-7-1) expression synthetic, except replace cyclohexane tricarboxylic acids acid anhydrides with the trimellitic acid acid anhydrides, similarly synthesize with the synthetic of compound of above-mentioned formula (A-7-1) expression.
The compound of above-mentioned formula (A-8-2) expression can be by for example making the 4-nitrocinnamic and having required radicals R IAlkyl halide react in the presence of the suitable alkali such as sal tartari make ester after, it is reduced with tin chloride etc., make nitro change into amino, after making intermediate, by this intermediate is refluxed simultaneously at hydroxyl phthalic anhydride and acetic acid, perhaps in toluene or dimethylbenzene, in the presence of suitable catalyzer such as triethylamine, reflux, the method for this product addition succinic anhydride is synthesized.
At compounds X-(Ep) 4When reacting, with respect to 1 mole compound X-(Ep) with compd A-OH 4, compd A-OH preferably uses 1～3 mole, more preferably uses 1～2 mole.
As compounds X-(Ep) 4Operable organic solvent when reacting with compd A-OH, can preferably use non-proton organic solvent, as its object lesson, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolacton, N, N-dimethyl acetamide, N, dinethylformamide, dimethyl sulfoxide (DMSO), tetramethylurea, HMPA etc., from the angle cheaply of aligning agent for liquid crystal modulation, the preferred use and the identical organic solvent of organic solvent as the solvent use of aligning agent for liquid crystal.When using mixed solvent as the organic solvent of aligning agent for liquid crystal, a kind of in the preferred organic solvent of selecting to constitute mixed solvent as organic solvent.
The usage rate of organic solvent preferably makes solids content concn (compounds X-(Ep) 4With the total weight of compd A-OH shared ratio in reaction solution) be the ratio more than the 1 weight %, more preferably making this value is the ratio of 5～50 weight %.
As compounds X-(Ep) 4Operable catalyzer when reacting with compd A-OH can be enumerated for example alkali, specifically, can enumerate imidazoles, Tetrabutylammonium bromide etc.The usage rate of catalyzer is with respect to 100 weight portion compounds Xs-(Ep) 4, be preferably below 20 weight portions, more preferably below 5 weight portions.
Temperature of reaction is preferably 20～250 ℃, more preferably 50～180 ℃.Reaction time is preferably 0.1～24 hour, more preferably 1～6 hour.
The compound of above-mentioned formula (1-1) expression that so makes, can be used as the simplification compound and only use a kind ofly, also the two or more compounds inequality more than in the value of the kind of A, D, X and Ep in the above-mentioned formula (1-1) and m and n can be mixed and use.
The usage rate of (B) compound in the aligning agent for liquid crystal of the present invention with respect to 100 weight portions (A) polymkeric substance, is preferably 1～200 weight portion, more preferably 5～100 weight portions.
＜other compositions 〉
Aligning agent for liquid crystal of the present invention contain aforesaid (A) polymkeric substance and (B) compound and can contain other compositions as required as essential composition.As this other compositions, can enumerate for example thermal sensitivity crosslinking chemical, functional silanes compound etc.
As above-mentioned thermal sensitivity crosslinking chemical, can be contained in the aligning agent for liquid crystal of the present invention for the stability of the tilt angle that further improves formed liquid crystal orientation film and film strength, as this thermal sensitivity crosslinking chemical, can enumerate the compound that has 2 above epoxy radicals in a part for example (wherein, belong to (B) compound except.Hereinafter referred to as " epoxy compounds ") etc.As its object lesson, preferably can enumerate for example above-mentioned formula (X-1-1), (X-1-2), (X-2-1)～(X-2-6), (X-3-1), (X-3-2), (X-4-1), (X-4-2), (X-5-1) and (X-5-2) compound of expression separately, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N-diglycidyl-benzyl amine, N, N-diglycidyl-amino methyl cyclohexane, N, N-diglycidyl-cyclo-hexylamine etc.The usage rate of the epoxy compounds in the aligning agent for liquid crystal of the present invention with respect to 100 weight portions (A) polymkeric substance, is preferably below 40 weight portions, more preferably below 25 weight portions.
Above-mentioned functional silanes compound can be contained in the aligning agent for liquid crystal in order further to improve the fusible purpose of formed liquid crystal orientation film and substrate.As this functional silanes compound, can enumerate for example 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-carbethoxyl group-3-TSL 8330, N-carbethoxyl group-3-aminopropyltriethoxywerene werene, N-tri-ethoxy silylpropyl diethylenetriamine, N-trimethoxy silane base propyl group diethylenetriamine, 10-trimethoxy silane base-1,4,7-three azepine decane, 10-triethoxysilicane alkyl-1,4,7-three azepine decane, 9-trimethoxy silane base-3,6-diaza nonyl acetic acid esters, 9-trimethoxy silane base-3,6-diaza nonyl acetic acid esters, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic acid esters, 9-trimethoxy silane base-3,6-diaza methyl pelargonate, 9-triethoxysilicane alkyl-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, the glycidoxy methyltrimethoxy silane, the glycidoxy methyl triethoxysilane, 2-glycidoxy ethyl trimethoxy silane, 2-glycidoxy ethyl triethoxysilane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane etc.The usage rate of the functional silanes compound in the aligning agent for liquid crystal of the present invention with respect to 100 weight portions (A) polymkeric substance, is preferably below 2 weight portions, more preferably below 0.2 weight portion.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention, contain aforesaid (A) polymkeric substance and (B) compound and can choose wantonly and contain above-mentioned other compositions as essential composition, preferably these compositions are modulated into the state that is dissolved in solvent.
As operable solvent in the aligning agent for liquid crystal of the present invention, preferably can dissolve above-mentioned each composition and not with their the reaction organic solvent, as its example, for example can enumerate above as spendable solvent in polyamic acid synthetic and illustrative organic solvent etc.Can also coupling as operable poor solvent in polyamic acid synthetic and illustrative solvent.These organic solvents can be used alone or in combination of two or more.Preferred solvent composition is the composition that makes above-mentioned solvent combination gained, is that each composition in the aligning agent for liquid crystal can not separated out, and makes the surface tension of aligning agent for liquid crystal drop on the composition of 25～40mN/m scope.
Solids content concn in the aligning agent for liquid crystal of the present invention (the total weight of the composition in the aligning agent for liquid crystal beyond the solvent accounts for the ratio of aligning agent for liquid crystal general assembly (TW)) should be considered viscosity, volatility etc. and suitably selection, is preferably the scope of 1～10 weight %.That is to say that aligning agent for liquid crystal of the present invention is coated on substrate surface, form that when solids content concn less than 1 weight %, it is too small and be difficult to obtain the situation of good liquid crystal orientation film this thickness of filming then can to occur as the filming of liquid crystal orientation film.On the other hand, when solids content concn surpassed 10 weight %, it was blocked up and be difficult to obtain have the situation of the liquid crystal orientation film of superperformance coating thickness then can to occur, and the viscosity that aligning agent for liquid crystal can occur is excessive, causes the imperfect situation of screening characteristics.
Particularly preferred solids content concn scope, the coating method that is adopted when aligning agent for liquid crystal is coated on substrate and difference.For example, when adopting spin-coating method, the scope of preferred especially 1.5～4.5 weight %.When adopting print process, especially preferably making solids content concn is the scope of 3～9 weight %, like this, can make solution viscosity drop on the scope of 12～50mPas.When adopting ink-jet method, especially preferably making solids content concn is the scope of 1～5 weight %, like this, can make solution viscosity drop on the scope of 3～15mPas.
Temperature when modulating aligning agent for liquid crystal of the present invention is preferably 0 ℃～100 ℃, more preferably 10 ℃～40 ℃.
＜liquid crystal orientation film 〉
Next, the formation method to liquid crystal orientation film of the present invention describes.
The formation method of liquid crystal orientation film of the present invention is included on the substrate the above-mentioned aligning agent for liquid crystal of coating and forms and film, and to the operation of this film irradiation polarisation or non-polarisation ray.
At first, by coating aligning agent for liquid crystal of the present invention on substrate, then heat applicator surface and on substrate, form and film.
When making TN type, STN type or VA type liquid crystal display cells, with two substrates that are provided with the nesa coating that forms pattern as a pair of, preferred hectographic printing method, spin-coating method or the ink jet printing method of adopting, form its each on face of nesa coating and apply aligning agent for liquid crystal of the present invention respectively, then, form and film by heating each applicator surface.Here, as substrate, can use for example glass such as float glass, soda-lime glass; Polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-plastics system transparency carriers such as (ester ring type alkene).Simultaneously go up the nesa coating that is provided with as substrate, can use tin oxide (SnO 2) system NESA film (U.S. PPG register of company trade mark), indium oxide-tin oxide (In 2O 3-SnO 2) the ITO film etc. of system, form the acquisition of the nesa coating of pattern, for example can adopt after forming patternless nesa coating method etc. by photoengraving forms method of patterning, employing has the mask of required pattern when nesa coating forms.When the coating of aligning agent for liquid crystal, for the cohesive of further improving substrate surface and nesa coating and filming, can also will form on the face of filming in substrate surface, apply the pre-treatment of functional silanes compound, functionality titanium compound etc. in advance.
Behind the coated with liquid crystal alignment agent, the purpose for the sagging grade of alignment agent liquid that prevents to apply preferably preheats (prebake).The prebake temperature is preferably 30～200 ℃, and more preferably 40～150 ℃, preferred especially 40～100 ℃.The prebake time is preferably 0.25～10 minute, more preferably 0.5～5 minute.Then, in order to remove the purpose desolvate etc. fully, burn till (afterwards curing) operation.This burns till (afterwards curing) temperature and is preferably 80～300 ℃, more preferably 120～250 ℃.After the time of curing be preferably 5～200 minutes, more preferably 10～100 minutes.When (A) polymkeric substance contained in the aligning agent for liquid crystal of the present invention is when having the polymkeric substance of amic acid structure, can also make the amic acid structure carry out dehydration closed-loop by above-mentioned heating and form filming of further imidizate.
The thickness of filming that forms is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
On the other hand, when making IPS type liquid crystal display cells, preferred hectographic printing method, spin-coating method or the ink jet printing method of adopting, on the conducting film formation face of the substrate that is provided with the nesa coating that forms the comb teeth shape pattern, and be not provided with on the one side of subtend substrate of conducting film, apply aligning agent for liquid crystal of the present invention respectively, heat each applicator surface then and form and film.
The preferred thickness of filming of pre-treatment, the heating means behind the coated with liquid crystal alignment agent and the formation of the formation method of the material of employed substrate and nesa coating, electrically conducting transparent film figure, substrate is identical during with above-mentioned manufacturing TN type, STN type or VA type liquid crystal display cells at this moment.
Then by filming of as above forming being shone the ray or the non-polarisation ray of linear polarization or part polarisation, and according to circumstances further under 150～250 ℃ temperature, preferably carry out 1～120 minute heat treated, making films produces the liquid crystal aligning energy and makes liquid crystal orientation film.Here, as ray, can use for example to have 150nm～ultraviolet ray and the luminous ray of 800nm wavelength light, preferably contain the ultraviolet ray of 300nm～400nm wavelength light.When used ray was linear polarization or part polarisation, irradiation can be carried out from the direction perpendicular to real estate, also can carry out from oblique direction in order to produce pre-tilt angle, and, they combinations can also be carried out.When the non-polarisation ray of irradiation, direction of illumination must be a tilted direction.As the irradiating angle when tilted direction shines, be 20～70 ° preferably with respect to the normal of filming, more preferably 30～60 °.
As used light source, can use for example low pressure mercury lamp, high-pressure sodium lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer laser etc.The ultraviolet ray of above-mentioned preferred wavelength range can be by obtaining the means of above-mentioned light source and for example coupling such as light filter, diffraction grating etc.
Exposure as ray is preferably 1J/m 2More than, and not enough 10000J/m 2, 100～3000J/m more preferably 2In addition, when make by optical alignment method by filming of forming of previously known aligning agent for liquid crystal produce liquid crystal aligning can the time, need 10000J/m 2Above radiation exposure.But, if use aligning agent for liquid crystal of the present invention, even the radiation exposure when then adopting optical alignment method is 3000J/m 2Below in addition 1000J/m 2When following, also can produce good liquid crystal aligning energy, help reducing the manufacturing cost of liquid crystal display cells.
Like this liquid crystal orientation film that forms when for example using it for vertical alignment-type liquid crystal display device, is compared with previously known liquid crystal orientation film, has liquid crystal response speed advantage faster.
＜liquid crystal display cells 〉
Next liquid crystal display cells of the present invention is described.
Liquid crystal display cells of the present invention has the liquid crystal orientation film that is formed by aligning agent for liquid crystal of the present invention.
Liquid crystal display cells of the present invention can be arranged liquid crystal and make liquid crystal cell at it relatively by preparing the substrate that a pair of (two) as above form liquid crystal orientation film in formed gap is set, on two lateral surfaces polaroid is set again and makes.
The manufacturing of liquid crystal cell can be enumerated two kinds of for example following methods.
First method is previously known method.At first, two substrates are oppositely arranged by gap (box gap), make separately liquid crystal orientation film relatively to, with sealant fitted in the peripheral position of two substrates, annotate the topping up crystalline substance in the box gap that is surrounded by substrate surface and sealant after, the sealing filling orifice can make liquid crystal cell.
Second method is the method that is called ODF (One Drop Fill) mode.Regulation position on the substrate in two substrates that form liquid crystal orientation film, apply for example ultra-violet solidified sealant material, again behind the liquid crystal that drips on the liquid crystal aligning face, another piece substrate of fitting, make liquid crystal orientation film relatively to, to whole irradiation ultraviolet radiation of substrate, make sealant cures then, can make liquid crystal cell.
When adopting arbitrary method, all need the liquid crystal cell of as above making further is heated to after used liquid crystal is the temperature of isotropic phase, slowly cool to room temperature, the flow orientation when eliminating liquid crystal and injecting.
Then, by the polaroid of on the outer surface of liquid crystal cell, fitting, can make liquid crystal display cells of the present invention.
Here, as sealant, can use epoxy resin that for example contains as the alumina balls of hardening agent and separator etc.
As above-mentioned liquid crystal, can use for example nematic crystal, dish shape type liquid crystal etc., wherein preferred nematic crystal.When being VA type liquid crystal cell, preferably have the nematic crystal of negative dielectric anisotropic, can use for example diaminobenzene class liquid crystal, pyridazine class liquid crystal, schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal etc.When being TN type liquid crystal cell or STN type liquid crystal cell, the nematic crystal that preferably has positive dielectric anisotropy can use for example biphenyls liquid crystal, cyclohexylbenzene class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.Can also further add for example cholesteryl liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal; Chirality agent with trade name C-15, CB-15 (production of メ Le Network society) sale; To oxygen base benzylidene-to ferroelectric liquid crystals such as amino-2-methyl butyl cinnamate etc. and using in the last of the ten Heavenly stems.
As the polaroid of fitting on the liquid crystal cell outside surface, can enumerate polyvinyl alcohol (PVA) is extended that the light polarizing film that is referred to as " H film " that orientation absorbs iodine simultaneously is clipped in the acetate fiber diaphragm and the polaroid of making, perhaps the polaroid made of H film self.
Embodiment
Below, by embodiment the present invention is carried out more specific description, but the present invention is not limited to these embodiment.
Synthesis example 1 (synthesizing of compound (A-1-2-1))
Synthesized compound (A-1-2-1) according to following synthetic route 1.
Figure G2008800238690D00551
Synthetic route 1
In the eggplant type flask of 1L, add 82g p-Coumaric Acid, 304g sal tartari and 400ml N-N-methyl-2-2-pyrrolidone N-, after at room temperature carrying out stirring in 1 hour, add the 166g1-bromo pentane silane, stirred 5 hours down at 100 ℃.Then, under reduced pressure distillate solvent.To wherein adding 48g NaOH and 400ml water, the reaction that is hydrolyzed in 3 hours refluxes again.Reaction neutralizes reaction system after finishing with hydrochloric acid, reclaim the precipitation that generates, and carries out recrystallization with ethanol, obtains the white crystal of the compound of the following formula of 80g (A-1-2-1) expression.
Synthesis example 2 (synthesizing of compound (A-1-2-2))
In above-mentioned synthesis example 1, except with 262g 1-iodo-4,4, beyond the alternative 1-bromo pentane silane of 4-trifluoro butane, similarly carry out with synthesis example 2, obtain the white powder of the compound (compound (A-1-2-2)) of the following formula of 85g (A-1-2-2) expression.
Figure G2008800238690D00561
Synthesis example 3 (synthesizing of compound (A-1-4-1))
Synthesized compound (A-1-4-1) according to following synthetic route 2.
Figure G2008800238690D00571
Synthetic route 2
(synthesizing of compound (A-1-4-1A))
In the eggplant type flask of 1L, add 91.3g 4-Para Hydroxy Benzoic Acid methyl esters, 182.4g sal tartari and 320ml N-N-methyl-2-2-pyrrolidone N-, after at room temperature carrying out stirring in 1 hour, add 99.7g 1-bromo pentane silane, stir down at 100 ℃ and reacted in 5 hours.After reaction finished, water precipitated again.Then, add 48g NaOH and 400ml water in this precipitation, the reaction that is hydrolyzed in 3 hours refluxes.Reaction neutralizes with hydrochloric acid after finishing, and the precipitation that generates is carried out recrystallization with ethanol, obtains the white crystal of 102g compound (A-1-4-1A).
(synthesizing of compound (A-1-4-1))
Get 52g in this compound (A-1-4-1A) to reaction vessel, to wherein adding 200ml thionyl chloride and 0.2ml N, dinethylformamide stirred 1 hour down at 80 ℃.Then, under reduced pressure distillate and remove thionyl chloride, add methylene chloride, wash,, after concentrating, add the tetrahydrofuran wiring solution-forming the organic layer dried over mgso with sodium bicarbonate aqueous solution.
Then, add 37g 4-hydroxycinnamic acid, 69g sal tartari, 2.4g TBuA, 250ml tetrahydrofuran and 500ml water in the 500ml three-neck flask beyond above-mentioned.This aqueous solution with ice-cooled, is slowly dripped the above-mentioned tetrahydrofuran solution of the reaction product that contains compound (A-1-4-1A) and thionyl chloride, further stirred 2 hours.After reaction finishes, add hydrochloric acid and neutralize, after extracting with ethyl acetate, use dried over mgso, after concentrating, carry out recrystallization, obtain the white crystal of 45g compound (A-1-4-1) with ethanol.
Synthesis example 4 (synthesizing of compound (A-1-4-2))
Synthesized compound (A-1-4-2) according to following synthetic route 3.
Figure G2008800238690D00591
Synthetic route 3
(synthesizing of compound (A-1-4-2A))
Add 82g 4-Para Hydroxy Benzoic Acid methyl esters, 166g sal tartari and 400ml N,N-dimethylacetamide in the eggplant type flask of 1L, after at room temperature carrying out stirring in 1 hour, add 95g 1,1,1-three fluoro-4-iodobutanes at room temperature stir and reacted in 5 hours.After reaction finished, water precipitated again.Then, add 32g NaOH and 400ml water in this precipitation, the reaction that is hydrolyzed in 4 hours refluxes.Reaction neutralizes with hydrochloric acid after finishing, and the precipitation that generates is carried out recrystallization with ethanol, obtains the white crystal of 80g compound (A-1-4-2A).
(synthesizing of compound (A-1-4-2))
Get 46.4g in this compound (A-1-4-2A) to reaction vessel, to wherein adding 200ml thionyl chloride and 0.2ml N, dinethylformamide stirred 1 hour down at 80 ℃.Then, under reduced pressure distillate and remove thionyl chloride, add methylene chloride, wash, use dried over mgso again, after concentrating, add the tetrahydrofuran wiring solution-forming with sodium bicarbonate aqueous solution.
Then, add 36g 4-hydroxycinnamic acid, 55g sal tartari, 2.4g TBuA, 200ml tetrahydrofuran and 400ml water in the 2L three-neck flask beyond above-mentioned.This aqueous solution with ice-cooled, is slowly dripped the above-mentioned tetrahydrofuran solution of the reaction product that contains compound (A-1-4-2A) and thionyl chloride, further stirred 2 hours.After reaction finishes, add hydrochloric acid and neutralize, after extracting with ethyl acetate, use dried over mgso, after concentrating, carry out recrystallization, obtain the white crystal of 39g cinnamic acid derivative (A-1-4-2) with ethanol.
Synthesis example 5
Synthesized compound (A-4-1-1) according to following synthetic route 4.
Figure G2008800238690D00601
Synthetic route 4
In the 1L eggplant type flask that recirculatory pipe, nitrogen ingress pipe and Dean-Stark (Dean-Stark) pipe is housed, add 72g decyl succinic anhydride, 49g 4-amino-cinnamic acid, 70ml triethylamine, 500ml toluene and 200ml tetrahydrofuran, under refluxing, carry out reaction in 36 hours.After reaction finishes, after reaction mixture washed with watery hydrochloric acid and water successively, use dried over mgso, after concentrating, the mixed solvent with ethanol and tetrahydrofuran carries out recrystallization again, obtains the white crystal of 72g compound (A-4-1-1).
Synthesis example 6
Synthesized compound (A-5-1-1) according to following synthetic route 5.
Synthetic route 5
(synthesizing of compound (A-5-1-1a))
In the 2L eggplant type flask that recirculatory pipe is housed, add 198g 1,2,4-cyclohexane tricarboxylic acid anhydride, 500ml thionyl chloride and 2ml N, dinethylformamide refluxes under 80 ℃ and reacted in 1 hour.After reaction finishes, under reduced pressure remove thionyl chloride, in residue, add methylene chloride, after organic layer is washed with saturated sodium bicarbonate aqueous solution and water successively, use dried over mgso, after concentrated, the drying, adding 500ml tetrahydrofuran.
In addition, in the 3L three-neck flask that addition funnel, thermometer and nitrogen ingress pipe are housed, add 178g 4,4,5,5,5-Pentafluorobenzyl pentanol, 160ml pyridine and 1.5L tetrahydrofuran cool off in ice bath.Contain above-mentionedly 1,2 to wherein slowly dripping, behind the tetrahydrofuran solution of the reaction product of 4-cyclohexane tricarboxylic acid anhydride and thionyl chloride, at room temperature further stir and reacted in 4 hours.Reaction extracts with ethyl acetate after finishing.The organic layer water is washed, with after the dried over mgso, make with extra care again, obtain 268g compound (A-5-1-1a) with silicagel column.
(synthesizing of compound (A-5-1-1))
In the 200ml eggplant type flask that Dean-Stark pipe is housed, add the above-mentioned compound that makes of 241g (A-5-1-1a), 109g 4-amino-cinnamic acid, 190ml triethylamine, 16g 4-dimethylamino naphthyridine, 1L toluene and 2L tetrahydrofuran, under refluxing, carry out reaction in 24 hours.Reaction is washed reaction mixture after finishing with watery hydrochloric acid and water.With organic layer with dried over mgso after, carry out recrystallization with methyl alcohol, obtain 78g compound (A-5-1-1).
Synthesis example 7
Synthesized compound (A-6-1-1) according to following synthetic route 6.
Synthetic route 6
(synthesizing of compound (A-6-1-1a))
In the 2L three-neck flask that recirculatory pipe, Dean-Stark pipe and nitrogen ingress pipe are housed, add 90g 5-hydroxyl phthalic and 500ml diethylbenzene, refluxed 1 hour.Then, to wherein adding 80g 4-amino-cinnamic acid and 500ml tetrahydrofuran, under refluxing, reacted 12 hours.After reaction finishes, reaction mixture is washed with watery hydrochloric acid and water successively, carries out drying with magnesium sulphate again, concentrated after, carry out recrystallization with the mixed solvent of ethyl acetate and tetrahydrofuran, obtain 95g compound (A-6-1-1a).
(synthesizing of compound (A-6-1-1))
In the eggplant type flask of 500ml, add the above-mentioned compound that makes of 75g (A-6-1-1a), 70g sal tartari and 150ml N-N-methyl-2-2-pyrrolidone N-, at room temperature stir 1 hour after, add 59g 4,4,4-three fluoro-1-iodobutanes at room temperature stirred 24 hours.After reaction finishes, add 1L water, reclaim precipitation.,, remove and desolvate after by silicagel column this precipitation being made with extra care as eluent with ethyl acetate and hexane, obtain 50g compound (A-6-1-1).
Synthesis example 8
Synthesized compound (A-7-1-1) according to following synthetic route 7.
Synthetic route 7
(synthesizing of compound (A-7-1-1a))
In the 300ml three-neck flask that thermometer and nitrogen ingress pipe are housed, add 9.7g 4-nitrocinnamic, 12g 4,4,4-three fluoro-1-iodobutanes, 14g sal tartari and 150ml 1-Methyl-2-Pyrrolidone stir under 50 ℃ and reacted in 1 hour.After reaction finishes, in reaction mixture, add ethyl acetate and extract.Organic layer is washed with water,, concentrate, remove again and desolvate, obtain 14g compound (A-7-1-1a) again with after the dried over mgso.
(synthesizing of compound (A-7-1-1b))
In the 300ml three-neck flask that thermometer and nitrogen ingress pipe are housed, add the above-mentioned compound that makes of 14g (A-7-1-1a), 53g tin chloride dihydrate and 150ml ethanol, stir at 70 ℃ and reacted in 1 hour.After reaction finishes, reaction mixture is poured in the frozen water, neutralized, behind the adding ethyl acetate, remove sediment with the sodium hydrate aqueous solution of 2M.In filtrate, add ethyl acetate and extract, obtain organic layer.This organic layer is washed, used dried over mgso, and concentrate, remove again and desolvate, obtain 12g compound (A-7-1-1b).
(synthesizing of compound (A-7-1-1))
In the 200ml eggplant type flask that recirculatory pipe and nitrogen ingress pipe are housed, add the above-mentioned compound that makes of 12g (A-7-1-1b), 8.7g 1,2,4-cyclohexane tricarboxylic acid anhydride and 100ml acetic acid reacted 1 hour under refluxing.Reaction extracts reaction mixture after finishing with ethyl acetate, obtain organic layer.This organic layer is washed, after dried over mgso, concentrated to remove and desolvate, use the mixed solvent of forming by ethyl acetate and hexane to carry out recrystallization again, obtain the white crystal of 11g compound (A-7-1-1).
Synthesis example 9
Synthesized compound (A-3-26) according to following synthetic route 8.
Synthetic route 8
(synthesizing of compound (i) (4-cinnamyl bromide acyl chlorides))
107g (0.47 mole) 4-bromo-cinnamic acid was refluxed 4 hours in the 83g thionyl chloride, obtain red clear solution.Then, distillate remove unreacted thionyl chloride after, residue is carried out recrystallization from toluene, wash with normal hexane again, obtain the white crystal (yield rate 74%) of 85g compound (i).
Compound is (synthesizing of 4-bromo-cinnamic acid (4-amyl group cyclohexyl ester)) (ii)
25.0g (0.147 mole) 4-amyl group cyclohexanol is dissolved in the 25ml pyridine.Be maintained at about under 3 ℃ in the temperature with this solution, the compound (i) that makes more than wherein dripping 43.3g (0.176 mole) simultaneously is suspended in the liquid in the 350ml pyridine, carries out reaction in 3 hours again.The reaction mixture (suspension) of gained is joined in the acid frozen water of 1.3kg hydrochloric acid, leaches the precipitation of generation, and wash, drying, obtain 50g compound crude product (cream-coloured) (yield rate 85%) (ii).
(synthesizing of compound (A-3-26))
Under nitrogen environment, in the potpourri of the compound that more than 50g, makes crude product, 0.28g (1.25 mM) palladium and 1.52g (5 mM) three (o-tolyl) phosphine (ii), add 125ml (0.9 mole) dry triethylamine and react.After compound crude product (ii) dissolves fully, inject 10.8g (0.15 mole) acrylic acid, continue reaction 2 hours down at 95 ℃ again with syringe.The dirty-green reaction mixture of gained is joined in the acid frozen water of 1.3kg hydrochloric acid, reclaim by filtering the precipitation that generates.This precipitation is dissolved in the 500ml ethyl acetate, after washing with the sodium bicarbonate solution of the hydrochloric acid of 1N and 5 weight % successively, reclaims organic layer, use dried over mgso, distillate solvent, obtain the crude product (yellow solid) of 56g compound (A-3-26).This crude product is carried out recrystallization from ethanol, obtain the yellow powder (yield rate 55%) of 30g compound (A-3-26).
Synthesis example 10～16
In above-mentioned synthesis example 9, except distinguishing each with the replacement of the compound shown in the 0.147mol table 1 4-aminocyclohexanol, similarly carry out with the foregoing description 5, (wherein, two keys of phenyl ring both sides are trans forms to have synthesized the compound that above-mentioned formula (A-3-1)～(A-3-7) represents separately.Below, these compounds are called compound (A-3-1)～(A-3-7)).
Table 1
Classes of compounds Product
Synthesis example 10 N-amyl alcohol Compound (A-3-1)
Synthesis example 11 N-hexyl alcohol Compound (A-3-2)
Synthesis example 12 N-octyl alcohol Compound (A-3-3)
Synthesis example 13 Decanol Compound (A-3-4)
Synthesis example 14 N-dodecane alcohol Compound (A-3-5)
Synthesis example 15 Cetyl alcohol Compound (A-3-6)
Synthesis example 16 N-octadecane alcohol Compound (A-3-7)
Synthesis example 17～24
In above-mentioned synthesis example 9～16, except respectively using the alternative 4-bromo-cinnamic acid of 0.47mol 2-fluoro-4-bromo-cinnamic acid respectively, similarly carry out with the foregoing description 5～12, (wherein, two keys of phenyl ring both sides are trans forms respectively to the compound that has synthesized above-mentioned formula (A-3-36) and (A-3-12)～(A-3-18) represented separately.Below, these compounds are called compound (A-3-36) or (A-3-12)～(A-3-18)).
Synthesis example 25
Synthesized compound (A-2-14-1) according to following synthetic route 9.
Figure G2008800238690D00681
Synthetic route 9
In the three-neck flask of 1L, add 27.2g 4-hydroxy acetophenone, 27.6g sal tartari, 1.0g potassium iodide and 500ml acetone, at room temperature stir 30 minutes after, add 30.2g 1-bromo pentane silane, under nitrogen environment, reflux and reacted in 5 hours.Reaction after finishing is added to the water reaction solution, makes the product precipitation.Reclaim the precipitation that generates, carry out recrystallization, obtain 35g 4-amyl phenyl ether ethyl ketone (white crystal of compound (A-2-14-1A)) with acetone.
Get the three-neck flask that 20.6g, 4-formoxyl benzoic acid 15.0g, NaOH 8.0g and ethanol 150ml in the above 4-amyl phenyl ether ethyl ketone that makes places 500ml, under refluxing, reacted 6 hours.After reaction finishes, place be cooled to room temperature after, add 200ml water, obtain solution after being stirred to evenly.The solution of getting the 1L gained places beaker, it is stirred, and meanwhile drip concentrated hydrochloric acid to pH be below 7.Reclaim the precipitation that generates, carry out recrystallization, obtain the white crystal of 25g 4-carboxyl-4 '-amoxy chalcone (compound (A-2-14-1)) with ethanol.
Synthesis example 26
In above-mentioned synthesis example 25, except with 47.6g 1-iodo-4,4, beyond the alternative 1-bromo pentane silane of 4-trifluoro butane, similarly carry out with synthesis example 1, obtain the white powder of the compound (compound (A-2-14-2)) of the following formula of 28g (A-2-14-2) expression.
Synthesis example 27
Synthesized compound (A-1-29-1) according to following synthetic route 10.
Figure G2008800238690D00701
Synthetic route 10
In the three-neck flask of 1L, add 24.4g 4-hydroxy benzaldehyde, 27.6g sal tartari, 1.0g potassium iodide and 500ml acetone, at room temperature stir 30 minutes after, add 30.2g 1-bromo pentane silane, under nitrogen environment, reflux and reacted in 5 hours.Reaction after finishing is added to the water reaction solution, makes the product precipitation.Reclaim the precipitation that generates, carry out recrystallization, obtain 33g 4-amyl phenyl ether formaldehyde (white crystal of compound (A-1-29-1A)) with acetone.
Get the three-neck flask that 19.2g, 4-acetyl group benzoic acid 16.4g, NaOH 8.0g and ethanol 150ml in the above 4-amyl phenyl ether formaldehyde that makes places 500ml, under refluxing, reacted 6 hours.After reaction finishes, place be cooled to room temperature after, add 200ml water, obtain solution after being stirred to it evenly.The solution of getting the 1L gained places beaker, under it is stirred, drip concentrated hydrochloric acid to pH be below 7.Reclaim the precipitation that generates, carry out recrystallization, obtain the white crystal of 29g 4-amoxy-4 '-carboxyl chalcone (compound (A-1-29-1)) with ethanol.
Synthesis example 28
In above-mentioned synthesis example 27, except with 47.6g 1-iodo-4,4, beyond the alternative 1-bromo pentane silane of 4-trifluoro butane, similarly carry out with synthesis example 27, obtain the white powder of the compound (compound (A-2-29-2)) of the following formula of 30g (A-1-29-2) expression.
Figure G2008800238690D00711
Synthesizing of the compound of＜above-mentioned formula (B) expression 〉
Embodiment 1
In the 500ml three-neck flask that thermometer, stirrer and nitrogen ingress pipe are housed, add compound (A-1-2-1) 23.4g (0.10 mole) that makes in the above-mentioned synthesis example 1 as compd A-OH, as compounds X-(Ep) 4The compound 47.1g (0.10 mole) and the 188.4g N-N-methyl-2-2-pyrrolidone N-(solids content concn 27 weight %) of above-mentioned formula (X-2-4) expression, flow down at nitrogen, under 140 ℃, reacted 5 hours, obtain containing the solution of compound (B-1).
In addition, above-mentioned solution is adopted liquid chromatography (ODS post, acetonitrile: water=80: 20) measure, confirmed that used compound (A-1-2-1) all is consumed.
Embodiment 2～40
Except compd A-OH and compounds X-(Ep) 4Use kind shown in the table 2 and consumption respectively, and adjust beyond the consumption of N-N-methyl-2-2-pyrrolidone N-, similarly make solids content concn be made into 27 weight % with the foregoing description 1 and react, contained the solution of compound (B-2)～(B-40) respectively.
Each solution is adopted liquid chromatography (ODS post, acetonitrile: water=80: 20) measure, confirm that employed compd A-OH all is consumed among all embodiment 2～40 respectively.
Table 2
Figure G2008800238690D00721
Table 2 (continuing)
Figure G2008800238690D00731
In above-mentioned table 2, compd A-OH and compounds X-(Ep) 4Abbreviation be respectively following implication.
(compd A-OH)
A-1-2-1: the compound (A-1-2-1) that makes in the above-mentioned synthesis example 1
A-1-2-2: the compound (A-1-2-2) that makes in the above-mentioned synthesis example 2
A-1-4-1: the compound (A-1-4-1) that makes in the above-mentioned synthesis example 3
A-1-4-2: the compound (A-1-4-2) that makes in the above-mentioned synthesis example 4
A-7-1-1: the compound (A-7-1-1) that makes in the above-mentioned synthesis example 5
A-5-1-1: the compound (A-5-1-1) that makes in the above-mentioned synthesis example 6
A-6-1-1: the compound (A-6-1-1) that makes in the above-mentioned synthesis example 7
A-7-1-1: the compound (A-7-1-1) that makes in the above-mentioned synthesis example 8
A-3-26: the compound (A-3-26) that makes in the above-mentioned synthesis example 9
A-3-1: the compound (A-3-1) that makes in the above-mentioned synthesis example 10
A-3-2: the compound (A-3-2) that makes in the above-mentioned synthesis example 11
A-3-3: the compound (A-3-3) that makes in the above-mentioned synthesis example 12
A-3-4: the compound (A-3-4) that makes in the above-mentioned synthesis example 13
A-3-5: the compound (A-3-5) that makes in the above-mentioned synthesis example 14
A-3-6: the compound (A-3-6) that makes in the above-mentioned synthesis example 15
A-3-7: the compound (A-3-7) that makes in the above-mentioned synthesis example 16
A-3-36: the compound (A-3-36) that makes in the above-mentioned synthesis example 17
A-3-12: the compound (A-3-12) that makes in the above-mentioned synthesis example 18
A-3-13: the compound (A-3-13) that makes in the above-mentioned synthesis example 19
A-3-14: the compound (A-3-14) that makes in the above-mentioned synthesis example 20
A-3-15: the compound (A-3-15) that makes in the above-mentioned synthesis example 21
A-3-16: the compound (A-3-16) that makes in the above-mentioned synthesis example 22
A-3-17: the compound (A-3-17) that makes in the above-mentioned synthesis example 23
A-3-18: the compound (A-3-18) that makes in the above-mentioned synthesis example 24
A-2-14-1: the compound (A-2-14-1) that makes in the above-mentioned synthesis example 25
A-2-14-2: the compound (A-2-14-2) that makes in the above-mentioned synthesis example 26
A-1-29-1: the compound (A-1-29-1) that makes in the above-mentioned synthesis example 27
A-1-29-2: the compound (A-1-29-2) that makes in the above-mentioned synthesis example 28
(compounds X-(Ep) 4)
X-2-4: the compound of above-mentioned formula (X-2-4) expression
X-4-2: the compound of above-mentioned formula (X-4-2) expression
X-5-2: the compound of above-mentioned formula (X-5-2) expression
X-1-1: the compound of above-mentioned formula (X-1-1) expression
X-2-1: the compound of above-mentioned formula (X-2-1) expression
X-2-2: the compound of above-mentioned formula (X-2-2) expression
Synthesizing of＜polyamic acid 〉
Synthesis example 29
Will be as tetracarboxylic dianhydride's 1,2,3,4-cyclo-butane tetracarboxylic dianhydride 19.6g (0.1 mole), as 2 of diamines, 2 '-dimethyl-4,4 '-benzidine 21.2g (0.1 mole) is dissolved in the 367g N-N-methyl-2-2-pyrrolidone N-, by under 40 ℃, carrying out reaction in 3 hours, obtain the solution that 407g contains 10 weight % polyamic acids (PA-1).The solution viscosity of this polyamic acid solution is 170mPas.
Synthesis example 30
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 22.4g (0.1 mole), cyclohexane two-1 as diamines, 3-(methyl amine) 14.23g (0.1 mole) is dissolved in the 329.3g N-N-methyl-2-2-pyrrolidone N-, by under 60 ℃, carrying out reaction in 6 hours, obtain the solution that 365g contains 10 weight % polyamic acids (PA-2).The solution viscosity of this polyamic acid solution is 110mPas.
Synthesizing of＜polyimide 〉
Synthesis example 31
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 22.4g (0.1 mole), be dissolved in the 336.2g N-N-methyl-2-2-pyrrolidone N-as the p-phenylenediamine (PPD) 9.73g (0.09 mole) of diamines and the represented diamines 5.23g (0.01 mole) of compound of above-mentioned formula (D-10) expression, by under 60 ℃, carrying out reaction in 4 hours, obtain containing the solution of 10 weight % polyamic acids.The solution viscosity of this polyamic acid solution is 126mPas.
Then, in the gained polyamic acid solution, append 348g N-N-methyl-2-2-pyrrolidone N-, add 7.9g pyridine and 10.2g acetic anhydride again, under 110 ℃, carry out 4 hours dehydration closed-loops.After the dehydration closed-loop reaction, by being carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-, (in this operation, the pyridine and the acetic anhydride that use in the dehydration closed-loop reaction are removed to system by the solvent in the system, down with), obtain about 230g and contain the solution that 16.1 weight % imidizate rates are about 54% polyimide (PI-1).This polyimide solution that takes a morsel adds the N-N-methyl-2-2-pyrrolidone N-, is made into the solution that polymer concentration is 10 weight %, and the solution viscosity of mensuration is 75mPas.
Synthesis example 32
Only get and be converted into polyamic acid (PA-2) and be equivalent to the solution that contains polyamic acid (PA-2) that makes in the above-mentioned synthesis example 30 of amount of 17.5g, to wherein adding 232.5g N-N-methyl-2-2-pyrrolidone N-, 3.8g pyridine and 4.9g acetic anhydride, under 110 ℃, carry out 4 hours dehydration closed-loops.After the dehydration closed-loop reaction,, obtain about 81g and contain the solution that 14.8 weight % imidizate rates are about 50% polyimide (PI-2) by the solvent in the system is carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-.This polyimide solution that takes a morsel adds the N-N-methyl-2-2-pyrrolidone N-, is made into the solution that polymer concentration is 10 weight %, and the solution viscosity of mensuration is 69mPas.
Embodiment 41
The modulation of＜aligning agent for liquid crystal 〉
Only get and be converted into the solution that contains polyamic acid (PA-1) that polyamic acid (PA-1) is equivalent to make in the above-mentioned synthesis example 25 of amount of 100 weight portions as (A) polymkeric substance, be converted into the solution that contains compound (B-1) that compound (B-1) is equivalent to make in the foregoing description 1 of amount of 50 weight portions as compound (B) to wherein adding, add N-N-methyl-2-2-pyrrolidone N-and butyl cellosolve again, being made into solvent composition is the N-N-methyl-2-2-pyrrolidone N-: butyl cellosolve=50: 50 (weight ratio), solids content concn are the solution of 2.5 weight %.Is the filter filtration of 1 μ m with this solution with the aperture, modulates aligning agent for liquid crystal (S-1).
Embodiment 42～89
As (A) polymkeric substance and (B) compound, only use the material of the kind shown in this table of amount shown in the table 3 respectively, in addition, similarly modulate aligning agent for liquid crystal (S-2)～(S-49) respectively with the foregoing description 41.
In addition, (A) polymkeric substance and (B) compound supply with the modulation of aligning agent for liquid crystal respectively with the solution that makes in above-mentioned synthesis example or the foregoing description.Amount in the table 3 is to be converted into (A) polymkeric substance contained in each solution or (B) value of the amount of compound.
Table 3
Figure G2008800238690D00781
Table 3 (continuing)
Figure G2008800238690D00791
Embodiment 90
Adopt the aligning agent for liquid crystal S-1 of modulation in the foregoing description 41, following manufacturing VA type liquid crystal display cells, and carry out the evaluation of liquid crystal aligning and voltage retention.
The manufacturing of＜VA type liquid crystal display cells 〉
Adopt spin-coating method to be coated on the transparency electrode face of the glass substrate that has ITO film system transparency electrode the aligning agent for liquid crystal S-1 of above modulation, after carrying out 1 minute prebake on 80 ℃ the heating plate, cure after carrying out 1 hour under 200 ℃ in the baking oven by the nitrogen ventilation, forming thickness is filming of 0.1 μ m.By with Hg-Xe lamp and Glan-Taylor prism to the direction irradiation 1000J/m of this film surface with 40 ° of the normal slopes of filming certainly 2Contain the polarisation ultraviolet ray of 313nm bright line, make liquid crystal orientation film.
Repeat this operation, make a pair of (two) have liquid crystal orientation film on the transparency electrode face substrate.
Each of this a pair of substrate formed the periphery of the face of liquid crystal orientation film, after having added the epoxy adhesive of alumina balls that diameter is 5.5 μ m by serigraphy coating, make the mutual antiparallel of the projecting direction of ultraviolet optical axis on real estate and substrate is carried out overlapping and pressing, heating made bonding agent carry out heat curing in 1 hour under 150 ℃ again.Then, by liquid crystal injecting port between a pair of substrate, fill negative type liquid crystal (メ Le Network society produces, MLC-6608) after, with epoxy base class adhesive closure liquid crystal injecting port.And the flow orientation when injecting in order to eliminate liquid crystal after heating under 150 ℃, slowly cools to room temperature with it.Then, outside substrate, survey the polaroid of fitting on the two sides, make its polarization direction vertical mutually, and with the projecting direction of ultraviolet optical axis on the real estate angle at 45 of liquid crystal orientation film, promptly made VA type liquid crystal display cells.
The evaluation of＜liquid crystal aligning 〉
To the VA type liquid crystal display cells of above manufacturing, have or not abnormal area when opening cut-out (applying releasing) 5V DC voltage by observation by light microscope, do not observe abnormal area in the above-mentioned liquid crystal display cells this moment, and liquid crystal aligning is " well ".
The evaluation of＜voltage retention 〉
Under 60 ℃, in 167 milliseconds span, the VA type liquid crystal display cells of above manufacturing is applied the voltage of 5V, application time is 60 microseconds, measures then from voltage and removes voltage retention after 167 milliseconds.Determinator adopts the (VHR-1 of strain) East Yang テ Network ニ カ system.
When this voltage retention is 90% when above, voltage retention is evaluated as " well ", and average evaluation in addition is " bad ", and this moment, the voltage retention of above-mentioned liquid crystal display cells was " well ".
Embodiment 91～114,116,118～135,138 and 139
As aligning agent for liquid crystal, use the alignment agent shown in the table 4 respectively, polarisation ultraviolet irradiation amount is as shown in table 4 respectively during the manufacturing of liquid crystal display cells, in addition, similarly make VA type liquid crystal display cells with the foregoing description 90, and carry out the evaluation of liquid crystal aligning and voltage retention.Evaluation result is listed in table 4.
Embodiment 115
Adopt the aligning agent for liquid crystal S-26 of modulation in the foregoing description 66, following manufacturing TN type liquid crystal display cells, and carry out the evaluation of aligning agent for liquid crystal and voltage retention.
The manufacturing of＜TN type liquid crystal display cells 〉
Adopt spin-coating method to be coated on the transparency electrode face of the glass substrate that has ITO film system transparency electrode the aligning agent for liquid crystal S-26 of above modulation, after carrying out 1 minute prebake on 80 ℃ the heating plate, heated 1 hour down in 200 ℃ in by the baking oven of nitrogen ventilation, forming thickness is filming of 0.1 μ m.By with Hg-Xe lamp and Glan-Taylor prism to this film surface to tilt 40 ° direction irradiation 1000J/m from substrate normal 2Contain the polarisation ultraviolet ray of 313nm bright line, make it produce the liquid crystal aligning energy, form liquid crystal orientation film.
Repeat above-mentioned same operation, make a pair of (two) have liquid crystal orientation film on the electrically conducting transparent face glass substrate.
Each of this a pair of substrate formed the peripheral position of the face of liquid crystal orientation film, after having added the epoxy adhesive of alumina balls that diameter is 5.5 μ m by serigraphy coating, make polarisation ultraviolet ray direction of illumination vertically substrate be carried out overlapping and pressing mutually, heating made bonding agent carry out heat curing in 1 hour under 150 ℃ again.Then, by liquid crystal injecting port in substrate gap, annotate fill eurymeric nematic crystal (メ Le Network society produce, MLC-6221 has added the chirality agent) after, with epoxy base class adhesive closure liquid crystal injecting port.And the flow orientation when injecting in order to eliminate liquid crystal slowly cools to room temperature in heating under 150 ℃ after 10 minutes with it.Then, outside substrate, survey the polaroid of fitting on the two sides, make its polarization direction vertical mutually, and parallel with the polarization direction of liquid crystal orientation film, promptly made TN type liquid crystal display cells.
The evaluation of＜liquid crystal aligning 〉
To the TN type liquid crystal display cells of above manufacturing, have or not abnormal area when opening cut-out (applying releasing) 5V DC voltage by observation by light microscope, do not observe abnormal area in the above-mentioned liquid crystal display cells this moment, and liquid crystal aligning is " well ".
The evaluation of＜voltage retention 〉
Under 60 ℃, in 167 milliseconds span, the TN type liquid crystal display cells of above manufacturing is applied the voltage of 5V, application time is 60 microseconds, measures then from voltage and removes voltage retention after 167 milliseconds.Determinator adopts the (VHR-1 of strain) East Yang テ Network ニ カ system.
When this voltage retention is 90% when above, voltage retention is evaluated as " well ", and average evaluation in addition is " bad ", and this moment, the voltage retention of above-mentioned liquid crystal display cells was " well ".
Embodiment 117,136 and 137
As aligning agent for liquid crystal, use the alignment agent shown in the table 4 respectively, polarisation ultraviolet irradiation amount is as shown in table 4 respectively during the manufacturing of liquid crystal display cells, in addition, similarly make TN type liquid crystal display cells with the foregoing description 90, and carry out the evaluation of liquid crystal aligning and voltage retention.Evaluation result is listed in table 4.
Table 4
The aligning agent for liquid crystal title Polarisation radiation exposure (J/m 2) Display mode Liquid crystal aligning Voltage retention
Embodiment 90 S-1 1000 VA Well Well
Embodiment 91 S-2 1000 VA Well Well
Embodiment 92 S-3 1000 VA Well Well
Embodiment 93 S-4 1000 VA Well Well
Embodiment 94 S-5 1000 VA Well Well
Embodiment 95 S-6 1000 VA Well Well
Embodiment 96 S-7 1000 VA Well Well
Embodiment 97 S-8 1000 VA Well Well
Embodiment 98 S-9 1000 VA Well Well
Embodiment 99 S-10 1000 VA Well Well
Embodiment 100 S-11 1000 VA Well Well
Embodiment 101 S-12 1000 VA Well Well
Embodiment 102 S-13 1000 VA Well Well
Embodiment 103 S-14 1000 VA Well Well
Embodiment 104 S-15 1000 VA Well Well
Embodiment 105 S-16 1000 VA Well Well
Embodiment 106 S-17 1000 VA Well Well
Embodiment 107 S-18 1000 VA Well Well
Embodiment 108 S-19 1000 VA Well Well
Embodiment 109 S-20 1000 VA Well Well
Embodiment 110 S-21 1000 VA Well Well
Embodiment 111 S-22 1000 VA Well Well
Embodiment 112 S-23 1000 VA Well Well
Embodiment 113 S-24 1000 VA Well Well
Embodiment 114 S-25 1000 VA Well Well
Table 4 (continuing)
The aligning agent for liquid crystal title Polarisation radiation exposure (J/m 2) Display mode Liquid crystal aligning Voltage retention
Embodiment 115 S-26 1000 TN Well Well
Embodiment 116 S-27 1000 VA Well Well
Embodiment 117 S-28 1000 TN Well Well
Embodiment 118 S-29 1000 VA Well Well
Embodiment 119 S-30 1000 VA Well Well
Embodiment 120 S-31 1000 VA Well Well
Embodiment 121 S-32 1000 VA Well Well
Embodiment 122 S-33 1000 VA Well Well
Embodiment 123 S-34 1000 VA Well Well
Embodiment 124 S-35 1000 VA Well Well
Embodiment 125 S-36 1000 VA Well Well
Embodiment 126 S-37 1000 VA Well Well
Embodiment 127 S-38 1000 VA Well Well
Embodiment 128 S-39 1000 VA Well Well
Embodiment 129 S-40 1000 VA Well Well
Embodiment 130 S-41 1000 VA Well Well
Embodiment 131 S-42 1000 VA Well Well
Embodiment 132 S-43 1000 VA Well Well
Embodiment 133 S-44 1000 VA Well Well
Embodiment 134 S-21 200 VA Well Well
Embodiment 135 S-45 1000 VA Well Well
Embodiment 136 S-46 3000 TN Well Well
Embodiment 137 S-47 3000 TN Well Well
Embodiment 138 S-48 3000 VA Well Well
Embodiment 139 S-49 3000 VA Well Well
The invention effect
Show particularly in the foregoing description, aligning agent for liquid crystal of the present invention, as aligning agent for liquid crystal applicable to optical alignment method, compare with previously known, can form the good liquid crystal aligning of demonstration and the liquid crystal orientation film of high voltage holding ratio with radiation exposure still less.Therefore, when this liquid crystal orientation film is applied to liquid crystal display cells, can be to make the display quality liquid crystal display device with excellent than lower in the past cost.
Have the liquid crystal display cells of the present invention of this liquid crystal orientation film that forms by aligning agent for liquid crystal of the present invention, have good display quality.Therefore, liquid crystal display cells of the present invention can be effectively applied to various devices, for example applicable to devices such as desk-top calculator, wrist-watch, table clock, counting display screen, word processor, personal computer or liquid crystal TV sets.

Claims (9)

1. aligning agent for liquid crystal is characterized in that containing:
(A) be selected from the group that polyamic acid and polyimide constitute at least a polymkeric substance and
(B) having by wavelength is light generation cross-linking reaction or the photosensitive group of isomerization reaction and the compound of epoxy radicals of 200～400nm,
Wherein (B) compound is for having:
Carbon number is 4～20 alkyl, carbon number is 1～20 fluoro-alkyl, cyclohexyl, has carbon number and is the alkyl-cyclohexyl or the alkyl phenyl of 1～20 alkyl, has carbon number and is the fluoro-alkyl cyclohexyl or the fluoro-alkyl phenyl of 1～20 fluoro-alkyl, carbon number is 4～20 alkoxy, carbon number is 1～20 fluoroalkyl, cyclohexyloxy, has carbon number and is the alkoxy cyclohexyl or the alkoxyl phenyl of 1～20 alkoxy, has carbon number and is the fluoro-alkyl cyclohexyl or the fluoroalkyl phenyl of 1～20 fluoro-alkyl, or the carbon number with steroid backbone be 17～51 group and
Epoxy radicals, and
Following formula (1)
Figure FSB00000570160500011
The compound of the group of expression.
2. the described aligning agent for liquid crystal of claim 1, wherein above-mentioned (B) compound are the compound of following formula (1-1) expression,
Figure FSB00000570160500012
In the formula (1-1), A is the group of any one expression of following formula (A-1)～(A-8), W is the group of any one expression of following formula (W-1)～(W-4), X is 4 valency groups of any one expression of following formula (X-1)～(X-5), Ep be following formula (Ep-1) or (Ep-2) expression group, m is 1～3 integer, and n is 4-m
Figure FSB00000570160500021
In the formula (A-1), R IBe that 4～20 alkyl, carbon number are 1～20 fluoro-alkyl, cyclohexyl, to have alkyl-cyclohexyl or alkyl phenyl that carbon number is 1～20 alkyl, have carbon number be that the fluoro-alkyl cyclohexyl or the fluoro-alkyl phenyl of 1～20 fluoro-alkyl or the carbon number with steroid backbone are 17～51 group for carbon number independently of one another
X 1For singly-bound, oxygen atom, sulphur atom ,-COO-,-NHCO-,-CONH-or-CO-, X 2Be singly-bound or following formula (X 2-1)～(X 2-3) group of any one expression,
Figure FSB00000570160500022
In the above-mentioned formula, the connecting key that " * " expression has it is positioned at X 1One side,
X 3Be singly-bound, *-O-(CH 2) a-, *-O-(CH 2) a-CO-, *-(CH 2) a-OCO-(CH 2) a-or following formula
Figure FSB00000570160500031
The group of expression, wherein, a is 1～6 integer independently of one another, and the connecting key that " * " expression has it is positioned at-CH=CH-CO-one side, and wherein, when two adjacent keys were singly-bound, they were together as a singly-bound;
Figure FSB00000570160500032
In the formula (A-2), R IWith the R in the above-mentioned formula (A-1) IDefinition identical,
X 4For singly-bound, oxygen atom, sulphur atom ,-COO-,-OCO-,-NHCO-,-CONH-or-CO-,
X 5Be singly-bound or phenylene,
X 6Be singly-bound or following formula (X 6-1) Biao Shi group,
Figure FSB00000570160500033
Formula (X 6-1) in, the connecting key that " * " expression has it is positioned at X 7One side,
X 7Be singly-bound, *-OCO-(CH 2) a-, *-OCO-(CH 2) a-CO-or following formula (X 7-1)
Figure FSB00000570160500034
The group of expression, above-mentioned in the middle of, a is 1～6 integer, the connecting key that " * " expression has it is positioned at X 6One side, wherein, when two adjacent keys were singly-bound, they were together as a singly-bound;
Figure FSB00000570160500041
In the formula (A-3), R IWith the R in the above-mentioned formula (A-1) IDefinition identical;
Figure FSB00000570160500042
In the formula (A-4)～(A-6), R ISeparately with above-mentioned formula (A-1) in R IDefinition identical, X 8Respectively do for oneself singly-bound, oxygen atom, sulphur atom ,-COO-,-OCO-,-NHCO-,-CONH-or-CO-;
Figure FSB00000570160500051
Formula (A-7) and (A-8) in, R ISeparately with above-mentioned formula (A-1) in R IDefinition identical, X 9Singly-bound or *-(CH respectively does for oneself 2) a-COO-, wherein, a is 1～10 integer, the connecting key that " * " expression has it is positioned at-CO-one side;
Figure FSB00000570160500052
In the above-mentioned formula, the connecting key that " * " expression has it is positioned at X one side;
Figure FSB00000570160500061
In the above-mentioned formula, Y be singly-bound ,-O-,-S-,-CH 2-,-C (CH 3) 2-or the group of following formula (Y-1) expression,
R IIThe optional carbon number that can be replaced by fluorine atom of respectively doing for oneself is 1～6 alkyl or fluorine atom, and b is 0～4 integer;
Figure FSB00000570160500072
3. the described aligning agent for liquid crystal of claim 1, wherein (B) compound is for by to compounds X-(Ep) 4Heat with the potpourri of compd A-OH and to make, wherein, X is identical with the definition in the above-mentioned formula (1-1) separately with Ep, and A is identical with the definition in the above-mentioned formula (1-1).
4. liquid crystal orientation film, it is formed by each described aligning agent for liquid crystal of claim 1～3.
5. the formation method of liquid crystal orientation film is characterized in that having coating each described aligning agent for liquid crystal of claim 1～3 on substrate and forms and film, and to the operation of this film irradiation polarisation or non-polarisation ray.
6. liquid crystal display cells, it has the described liquid crystal orientation film of claim 4.
7. the described liquid crystal display cells of claim 6, it adopts negative type liquid crystal.
8. compound, it is characterized in that having by wavelength is the light generation cross-linking reaction of 200～400nm or the photosensitive group and the epoxy radicals of isomerization reaction,
Described compound has:
Carbon number is 1～20 alkyl, carbon number is 1～20 fluoro-alkyl, cyclohexyl, has carbon number and is the alkyl-cyclohexyl or the alkyl phenyl of 1～20 alkyl, has carbon number and is the fluoro-alkyl cyclohexyl or the fluoro-alkyl phenyl of 1～20 fluoro-alkyl, carbon number is 4～20 alkoxy, carbon number is 1～20 fluoroalkyl, cyclohexyloxy, has carbon number and is the alkoxy cyclohexyl or the alkoxyl phenyl of 1～20 alkoxy, has carbon number and is the fluoro-alkyl cyclohexyl or the fluoroalkyl phenyl of 1～20 fluoro-alkyl, or the carbon number with steroid backbone be 17～51 group and
Epoxy radicals, and
The group of above-mentioned formula (1) expression.
9. the preparation method of the described compound of claim 8 is characterized in that compounds X-(Ep) 4Heat with the potpourri of compd A-OH, wherein, X is identical with the definition in the above-mentioned formula (1-1) separately with Ep, and A is identical with the definition in the above-mentioned formula (1-1).
CN2008800238690A 2007-08-02 2008-07-31 Liquid crystal aligning agent, liquid crystal alignment film, method for producing the same, and liquid crystal display device Active CN101730862B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2007201881 2007-08-02
JP201881/2007 2007-08-02
PCT/JP2008/064166 WO2009017252A1 (en) 2007-08-02 2008-07-31 Liquid crystal aligning agent, liquid crystal alignment film, method for producing the same, and liquid crystal display device

Publications (2)

Publication Number Publication Date
CN101730862A CN101730862A (en) 2010-06-09
CN101730862B true CN101730862B (en) 2011-12-07

Family

ID=40304472

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008800238690A Active CN101730862B (en) 2007-08-02 2008-07-31 Liquid crystal aligning agent, liquid crystal alignment film, method for producing the same, and liquid crystal display device

Country Status (5)

Country Link
JP (1) JP5170468B2 (en)
KR (1) KR101143129B1 (en)
CN (1) CN101730862B (en)
TW (1) TWI482799B (en)
WO (1) WO2009017252A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103320146A (en) * 2012-03-22 2013-09-25 Jsr株式会社 Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element and method of making liquid crystal display element

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5370646B2 (en) * 2009-02-12 2013-12-18 Ｊｓｒ株式会社 Method for producing radiation-sensitive polyorganosiloxane
JP5483005B2 (en) * 2009-03-31 2014-05-07 Ｊｓｒ株式会社 Liquid crystal aligning agent and liquid crystal display element
JP5776152B2 (en) * 2009-10-14 2015-09-09 Jsr株式会社 Liquid crystal aligning agent, liquid crystal display element, and polyorganosiloxane compound
KR20130001144A (en) * 2011-06-23 2013-01-03 (주)켐넥스 Photoactive crosslinking compound, method for preparing the same, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device
CN102786488A (en) * 2012-08-06 2012-11-21 天津信汇制药股份有限公司 Preparation method of intermediate for synthesis of micafungin and derivative thereof
EP3495424B1 (en) 2012-09-10 2020-09-09 LG Chem, Ltd. Composition for photo-alignment layer and photo-alignment layer
KR102069288B1 (en) 2013-08-28 2020-01-23 삼성디스플레이 주식회사 Liquid crystal aligning agent and liquid crystal display
CN104020609A (en) * 2014-05-16 2014-09-03 京东方科技集团股份有限公司 Liquid crystal coating method and display panel manufacturing method
TWI560242B (en) 2014-11-05 2016-12-01 Chi Mei Corp Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
TWI560241B (en) * 2014-11-05 2016-12-01 Chi Mei Corp Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
JP6701661B2 (en) * 2014-12-25 2020-05-27 Jsr株式会社 Liquid crystal aligning agent, method for producing liquid crystal element, liquid crystal aligning film and liquid crystal element
CN105647548B (en) 2016-02-23 2018-10-16 京东方科技集团股份有限公司 Orientation agent, the production method of alignment film, display panel and display device
JP7039166B2 (en) * 2016-09-30 2022-03-22 東京応化工業株式会社 Resin composition, method for producing cured product, and cured product
WO2020111198A1 (en) * 2018-11-29 2020-06-04 日産化学株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and retardation material
CN110526923A (en) * 2019-08-09 2019-12-03 南京邮电大学 A kind of Porphyrin Molecule of side chain modification and its application
CN113861416A (en) * 2021-09-30 2021-12-31 Tcl华星光电技术有限公司 Liquid crystal alignment agent, liquid crystal display panel and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1408817A (en) * 2001-10-03 2003-04-09 捷时雅株式会社 Liquid crystal oriented agent and liquid crystal display element
WO2003100510A1 (en) * 2002-05-23 2003-12-04 Nissan Chemical Industries, Ltd. Liquid crystal aligning agent, liquid crystal aligning films and liquid crystal display devices
CN1707336A (en) * 2004-06-08 2005-12-14 株式会社日立显示器 Liquid crystal display
JP2006171304A (en) * 2004-12-15 2006-06-29 Jsr Corp Liquid crystal aligning agent, liquid crystal alignment layer, liquid crystal display element and optical member

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61275325A (en) * 1985-05-31 1986-12-05 Toshiba Corp Resin composition for sealing electronic element
JP2001290155A (en) * 2000-04-10 2001-10-19 Agency Of Ind Science & Technol Method for forming liquid crystal alignment layer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1408817A (en) * 2001-10-03 2003-04-09 捷时雅株式会社 Liquid crystal oriented agent and liquid crystal display element
WO2003100510A1 (en) * 2002-05-23 2003-12-04 Nissan Chemical Industries, Ltd. Liquid crystal aligning agent, liquid crystal aligning films and liquid crystal display devices
CN1707336A (en) * 2004-06-08 2005-12-14 株式会社日立显示器 Liquid crystal display
JP2006171304A (en) * 2004-12-15 2006-06-29 Jsr Corp Liquid crystal aligning agent, liquid crystal alignment layer, liquid crystal display element and optical member

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103320146A (en) * 2012-03-22 2013-09-25 Jsr株式会社 Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element and method of making liquid crystal display element
CN103320146B (en) * 2012-03-22 2016-06-15 Jsr株式会社 The manufacture method of crystal aligning agent, liquid crystal orienting film, liquid crystal display device and liquid crystal display device

Also Published As

Publication number Publication date
WO2009017252A1 (en) 2009-02-05
TWI482799B (en) 2015-05-01
KR101143129B1 (en) 2012-05-08
TW200911884A (en) 2009-03-16
JPWO2009017252A1 (en) 2010-10-28
CN101730862A (en) 2010-06-09
JP5170468B2 (en) 2013-03-27
KR20100029144A (en) 2010-03-15

Similar Documents

Publication Publication Date Title
CN101730862B (en) Liquid crystal aligning agent, liquid crystal alignment film, method for producing the same, and liquid crystal display device
CN101452153B (en) Liquid crystal oriented agent and liquid crystal display element
CN101602949B (en) Liquid crystal alignment agent and liquid crystal display element
CN101990650B (en) Liquid crystal aligning agent and method for forming liquid crystal alignment films
CN101809066A (en) Liquid crystal-aligning agent, and method for production of liquid crystal alignment film
CN100529917C (en) Liquid crystal tropism agent and LCD member
CN101836155B (en) Liquid crystal aligning agent, method for forming liquid crystal alignment film and liquid crystal display device
CN101591544B (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
CN101042505B (en) Vertical liquid crystal aligning agent and vertical liquid crystal display
CN101544828B (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
CN102629030A (en) Liquid crystal display element and manufacturing method thereof, and liquid crystal orientation agent
CN102108300B (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
TW201533158A (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
CN101539688B (en) Liquid crystal alignment agent and liquid crystal display element
CN101526700A (en) Liquid crystal aligning agent and liquid crystal display device
CN101539687A (en) Liquid crystal alignment agent and liquid crystal display element
CN101735824A (en) Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device
CN101802692B (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display device
CN101261403A (en) Liquid crystal oriented agent and liquid crystal display element
CN100520537C (en) Vertical liquid crystal tropism agent
CN101458425A (en) Liquid crystal oriented agent and liquid crystal display element
CN101220279B (en) Vertical orientation type aligning agent for liquid crystal and vertical orientation type liquid crystal display device
CN101458427B (en) Liquid crystal oriented agent and liquid crystal display element
CN101256314B (en) Liquid crystal aligning agent and liquid crystal display element
CN101487955B (en) Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element

Legal Events

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