CN1896843A - Liquid crystal tropism agent and liquid crystal display element - Google Patents

Liquid crystal tropism agent and liquid crystal display element Download PDF

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CN1896843A
CN1896843A CNA200610098724XA CN200610098724A CN1896843A CN 1896843 A CN1896843 A CN 1896843A CN A200610098724X A CNA200610098724X A CN A200610098724XA CN 200610098724 A CN200610098724 A CN 200610098724A CN 1896843 A CN1896843 A CN 1896843A
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liquid crystal
dicarboxylic anhydride
expression
compound
crystal display
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川口贵之
熊谷勉
西川通则
高桥敦也
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • 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

Abstract

Providing a liquid crystal aligning film having high voltage retention and good printability on an organic film, and a transverse electric field system liquid crystal display device having the liquid crystal aligning film. The liquid crystal aligning agent contains a polymer having a polyamic acid repeating unit and a repeating unit of imidated polyamic acid, a compound having four epoxy groups in a molecule and a silane coupling agent. The liquid crystal display device has the liquid crystal aligning film formed of the liquid crystal aligning agent.

Description

Aligning agent for liquid crystal and liquid crystal display cells
Technical field
The present invention relates to aligning agent for liquid crystal and liquid crystal display cells.More particularly, relate to the electrical characteristics excellence, and the aligning agent for liquid crystal of printing excellence and by its lateral electric field type liquid crystal display element aligning agent for liquid crystal that makes.
Background technology
All the time, known TN type liquid crystal display cells with TN (twisted-nematic) type liquid crystal cell, its by nesa coating between 2 substrates that form liquid crystal orientation film on the surface, formation has the nematic crystal layer of positive dielectric anisotropy, constitute the box of sandwich construction, the major axis of above-mentioned liquid crystal molecule is turned round continuously to another piece substrate from a substrate and is turn 90 degrees.
And, also there is STN (supertwist to row) type liquid crystal display cells, it is by adding the chirality agent, the major axis of this liquid crystal molecule is reached be between substrate to turn round turnback continuously or with the state of upper span, and utilizes consequent birefringence effect.
Under comparing therewith, in lateral electric field type liquid crystal display element, 2 electrodes that drive liquid crystal are broach shape ground and are provided with on substrate one side, produce the electric field parallel with real estate, the control liquid crystal molecule.Its maximum feature is not use optical compensating film, just can obtain the wide view angle that is equal to mutually with the cathode-ray tube (CRT) that does not have GTG counter-rotating and tonal variation.The orientation of liquid crystal is manifested by the liquid crystal orientation film of implementing grinding process usually in these liquid crystal display cells.
As the material of the liquid crystal orientation film of these liquid crystal display cells, according to the known polyimide of conventional art, polyamide and polyester etc.Polyimide particularly is because it is used in most liquid crystal display cells in thermotolerance, and aspect excellences such as the compatibility of liquid crystal, physical strength.
Recently, carried out the research with the high-accuracy raising display quality that turns to the beginning of liquid crystal display cells, low consumption electrification etc., the range of application of liquid crystal display cells also constantly enlarges.In recent years, except former transmission-type, the range of application of the liquid crystal display cells that reflection-type, Semitransmissive are so is also enlarging.And, keep flatness on the nesa coating in order to make, first organic membrane such as coating diaphragm, and then coating of liquid crystalline alignment films thereon.But; lack compatibility between the organic membrane such as liquid crystal orientation film of making by polyimide in the past and diaphragm; be easy to generate repulsion during coating, and be easy to generate pore, the problem that these electrical characteristics that can produce the orientation that makes liquid crystal and gained liquid crystal display cells descend.
Summary of the invention
The purpose of this invention is to provide a kind of liquid crystal orientation film; make by precursor-polyamic acid and polyimide as the useful polyimide of liquid crystal orientation film; and voltage retention height; and the printing to organic membrane such as diaphragms is good, and the lateral electric field type liquid crystal display element with this liquid crystal orientation film is provided.
Other purpose of the present invention and advantage can be found out by the following description.
According to the present invention, above-mentioned purpose of the present invention and advantage, first, reach by a kind of aligning agent for liquid crystal, it is characterized in that containing the compound and the silane coupling agent that have 4 epoxy radicals in polymkeric substance (hereinafter referred to as " particular polymers ") that (A) have the repetitive of the repetitive of following formula (I-1) expression and following formula (I-2) expression, the molecule.
Figure A20061009872400051
(in the formula, P 1Be 4 valency organic groups, Q 1Be the divalent organic group).
(in the formula, P 2For with P 14 different valency organic groups, Q 2Be the divalent organic group).
According to the present invention, above-mentioned purpose of the present invention and advantage, the second, reach by a kind of lateral electric field type liquid crystal display element, it is characterized in that having the liquid crystal orientation film that forms by above-mentioned aligning agent for liquid crystal of the present invention.
According to aligning agent for liquid crystal of the present invention, when printing coating on organic membranoid substances such as diaphragm, do not print inequality and pore, printing is good, and can make the liquid crystal orientation film that is applicable to lateral electric field type liquid crystal display element of voltage retention excellence.
And, liquid crystal display cells with the alignment films that adopts aligning agent for liquid crystal formation of the present invention, the orientation of its liquid crystal and reliability excellence, can be used for various devices effectively, for example can be used for the display device of desk-top computer, wrist-watch, table clock, counting display screen, word processor, personal computer, liquid crystal TV set etc.
Embodiment
Below, the present invention is described in detail.
Aligning agent for liquid crystal of the present invention contains the polymkeric substance of the repetitive of repetitive with above-mentioned formula (I-1) expression and above-mentioned formula (I-2) expression.This polymkeric substance can be the polyamic acid of (1) repetitive with above-mentioned formula (I-1) expression and the potpourri of the repetitive polyimide with above-mentioned formula (I-2) expression, also can be the polymkeric substance (hereinafter referred to as " part imide amination polymer ") of the repetitive of the repetitive of (2) above-mentioned formula (I-1) expression and above-mentioned formula (I-2) expression random or block-wise bonding in a part.
Above-mentioned polyamic acid can make by making tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound open loop addition polymerization, and polyimide is made by the polyamic acid dehydration closed-loop usually.The part imide amination polymer usually can be by polyamic acid partial dehydration closed loop method or make amic acid give the method that polymers and acid imide give polymers bonding, synthetic segmented copolymer to make.
＜polyamic acid 〉
[tetrabasic carboxylic acid dicarboxylic anhydride]
As the tetrabasic carboxylic acid dicarboxylic anhydride, for example, can enumerate the BTCA dicarboxylic anhydride, 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 3,5,6-three carboxyls norbornane-2-acetic acid dicarboxylic anhydride, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acid dicarboxylic anhydride, 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)-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-8-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-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 5-(2,5-dioxo tetrahydrofuran methylene)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dicarboxylic anhydride, dicyclo [2,2,2]-and Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), following formula (I) and aliphatics and the ester ring type tetrabasic carboxylic acid dicarboxylic anhydrides such as compound (II) represented
Figure A20061009872400081
(in the formula, R 1And R 3Representative has the divalent organic group of aromatic rings, R 2And R 4Represent hydrogen atom or alkyl, the R of a plurality of existence 2And R 4Separately can be identical, also can be different);
Pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-tetraphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-furans tetrabasic carboxylic acid dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dicarboxylic anhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two phthalic acid dicarboxylic anhydrides, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, two (phthalic acid) phosphniline oxide dicarboxylic anhydride, right-phenylene-two (triphenyl phthalic acid) dicarboxylic anhydride, between-phenylene-two (triphenyl phthalic acid) dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl ether dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl methane dicarboxylic anhydride, 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), aromatic tetracarboxylic acid's dicarboxylic anhydrides such as compound of following formula (1)～(4) expression.They can a kind of independent or multiple being used in combination.
Figure A20061009872400091
Wherein, from showing the angle of good liquid crystal aligning, preferred BTCA dicarboxylic anhydride, 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrofuran methylene)-and 3-methyl-3-cyclohexene-1,2-dicarboxylic acid dicarboxylic anhydride, 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-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride, the compound of following formula (8) representative in the compound of following formula (5)～(7) expression in the compound of above-mentioned formula (I) expression and the compound of above-mentioned formula (II) expression.As particularly preferred, can enumerate 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 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, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), the compound of pyromellitic acid dianhydride and following formula (5) expression.
P in the repetitive (amic acid unit) of above-mentioned formula (I-1) expression 1P in the repetitive (acid imide unit) of 4 valency organic groups of representative and above-mentioned formula (I-2) expression 24 valency organic groups of representative all are the groups that derive from the tetrabasic carboxylic acid dicarboxylic anhydride.They can be identical, also can be different, and as the P in the above-mentioned formula (I-1) 1, preferably can enumerate following formula (i) and (the i ') group of expression separately.P 2Preferably group can be enumerated, particularly preferredly following formula can be enumerated (ii) and (ii ') group of expression separately with alicyclic ring skeleton.
Figure A20061009872400111
(in the formula, R is halogen atom, methyl or ethyl, and a is 0 or 1 integer, and b is 0～6 integer, and c is 0～4 integer, and d is 0～5 integer).
If want the object lesson of preferred tetrabasic carboxylic acid dicarboxylic anhydride in each repetitive of illustration,, can enumerate 1 as the tetrabasic carboxylic acid dicarboxylic anhydride that constitutes the amic acid unit, 2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, pyromellitic acid dianhydride etc.Can enumerate ester ring type tetrabasic carboxylic acid dicarboxylic anhydride as the tetrabasic carboxylic acid dicarboxylic anhydride that constitutes the acid imide unit, particularly 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 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-7-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-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-1,3-diketone etc., wherein, more preferably 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone and 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.
[diamine compound]
As the synthetic middle diamine compound that uses of above-mentioned polyamic acid, can enumerate for example p-phenylenediamine, between-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamido diphenylethane, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formailide, 4,4 '-diaminodiphenyl ether, 1, the 5-diaminonaphthalene, 3,3-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, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 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-two (4-aminophenyl) fluorenes, 4,4 '-methylene-two (2-chloroaniline), 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, 1,4,4 '-(right-the phenylene isopropylidene) diphenylamine, 4,4 '-(-the phenylene isopropylidene) diphenylamine, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-aromatic diamines such as octafluoro biphenyl;
1,1-m-xylene diamine, 1,3-propane diamine, butanediamine, pentanediamine, hexane diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 4,4-diamido heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene two rings penta inferior diene diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0 2,7]-undecylene two methanediamines, 4,4 '-methylene two aliphatics and ester ring type diamines such as (cyclohexylamine);
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-2,4-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, the 5-triazine, 2,4-diamido-6-methyl-s-triazine, 2,4-diaminostilbene, 3, the 5-triazine, 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, 3,5-diaminostilbene, 2, the 4-triazole, 6,9-diamido-2-ethoxy acridine lactate, 3,8-diamido-6-phenylphenanthridineand, 1,4-diamido piperazine, 3, the 6-proflavin, the diamines that has 2 primary amino radicals and this primary amino radical nitrogen-atoms in addition in the compound equimolecular of two (4-aminophenyl) phenyl amine and following formula (III)～(IV) expression
Figure A20061009872400131
(in the formula, R 5Representative is selected from the 1 valency organic group with nitrogen atom ring texture of pyridine, pyrimidine, triazine, piperidines and piperazine, and X represents the organic group of divalent).
Figure A20061009872400132
(in the formula, R 6Representative is selected from the divalent organic group with nitrogen atom ring texture of pyridine, pyrimidine, triazine, piperidines and piperazine, and X represents the organic group of divalent, and the X of a plurality of existence can be the same or different);
Single-substituted two amines of following formula (V) expression; The diamido organosiloxane of following formula (VI) expression;
(in the formula, R 7Expression is selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R 8It is 6～30 alkyl that expression has the 1 valency organic group of group of the steroid backbone of being selected from, trifluoromethyl and fluorine or carbon number).
Figure A20061009872400141
(in the formula, R 9The expression carbon number is 1～12 alkyl, the R of a plurality of existence 9Can be the same or different separately, p is 1～3 integer, and q is 1～20 integer);
The compound of following formula (9)～(13) expression etc.These diamine compounds can independent or multiple being used in combination.
Figure A20061009872400142
(in the formula, y is 2～12 integer, and z is 1～5 integer).
Wherein, preferred p-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl 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 '-(right-the phenylene diisopropylidene) diphenylamine, 4,4 '-(-the phenylene diisopropylidene) diphenylamine, 1, the 4-cyclohexane diamine, 4,4 '-methylene two (cyclohexylamine), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, the compound of above-mentioned formula (9)～(13) expression, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, the compound of following formula (14) expression in the compound of above-mentioned formula (III) expression, the compound of following formula (16)～(21) expression in the compound of following formula (15) expression in the compound of above-mentioned formula (IV) expression and the compound of above-mentioned formula (V) expression.
Figure A20061009872400151
[synthetic reaction of polyamic acid]
Supply with the tetrabasic carboxylic acid dicarboxylic anhydride of polyamic acid synthetic reaction and the usage rate of diamine compound, preferably with respect to contained amino in the 1 equivalent diamine compound, the anhydride group that makes the tetrabasic carboxylic acid dicarboxylic anhydride is the ratio of 0.2～2.0 equivalent, more preferably the ratio of 0.3～1.2 equivalent.
The synthetic reaction of polyamic acid, in organic solvent usually in-20～150 ℃, more preferably under 0～100 ℃ temperature conditions, carry out.Here, as organic solvent, as long as can dissolve synthetic polyamic acid, then it is had no particular limits, for example can illustration N-N-methyl-2-2-pyrrolidone N-, N, N-dimethyl acetamide, N, aprotic polar solvents such as dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, HMPA; Between phenol solvent such as sylvan, xylenols, phenol, halogenated phenol.In addition, to be preferably the total amount (b) that makes tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound usually be the amount of 0.1～30 weight % with respect to the total amount (a+b) of reaction solution to the consumption of organic solvent (a).
[poor solvent]
In addition, in the scope that the polyamic acid that does not make generation is separated out, can also unite the poor solvent alcohols that uses polyamic acid, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc. in the above-mentioned organic solvent.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 etc.
As mentioned above, obtained dissolving the reaction solution of polyamic acid.Then, this reaction solution is put in a large amount of poor solvents, obtained precipitate.Can get polyamic acid by this precipitate of drying under reduced pressure.And, once more this polyamic acid is dissolved in the organic solvent, with poor solvent it is separated out then, by carrying out once or this operation several times, can make with extra care polyamic acid.
[imide amination polymer]
The imide amination polymer that constitutes aligning agent for liquid crystal of the present invention can be by making above-mentioned polyamic acid dehydration closed-loop.The dehydration closed-loop of polyamic acid can perhaps (ii) be dissolved in polyamic acid in the organic solvent by the method for (i) heating polyamic acid, and the method that adds dewatering agent and dehydration closed-loop catalyzer and heating as required in this solution is carried out.
Temperature of reaction is generally 50～200 ℃ in the method for the heating polyamic acid of above-mentioned (i), is preferably 60～170 ℃.When 50 ℃ of temperature of reaction less thaies, 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 imide amination polymer can occur.
On the other hand, in the above-mentioned method that in polyamic acid solution, adds 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 with respect to 1 mole of polyamic acid repetitive, is preferably 0.01～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, trimethylpyridine, lutidines, triethylamine.But, be not limited to these.The dehydration closed-loop catalyst consumption with respect to 1 mole of used dewatering agent, is preferably 0.01～10 mole.In addition, as the organic solvent that uses in the dehydration closed-loop reaction, can enumerate as polyamic acid and synthesize middle solvent for use and illustrative organic solvent.And the temperature of reaction of dehydration closed-loop reaction is generally 0～180 ℃, is preferably 10～150 ℃.In addition, by the reaction solution that so obtains is carried out the operation same with the polyamic acid process for purification, can make with extra care imide amination polymer.
[part acid imide]
＜contain the polyamic acid of imide 〉
The used polyamic acid that contains imide is to have the structure that above-mentioned polyamic acid part imidizate obtains among the present invention, among the present invention in the used polyamic acid that contains imide preferred imidizate rate be 30% or more than, more preferably 50% or more than.Here, so-called " imidizate rate " is meant the sum with respect to repetitive in the polymkeric substance, the value that the ratio of the number of repeat unit of formation imide ring is represented with number percent.At this moment, the part of imide ring can also be different imide ring.
As the synthetic method that contains the polyamic acid of imide, can use (i) by heat above-mentioned polyamic acid partly dehydration closed-loop and synthetic method, (ii) by above-mentioned polyamic acid is dissolved in the organic solvent, in this solution, add dewatering agent and dehydration closed-loop catalyzer and as required heating carry out partly dehydration closed-loop and synthetic method, perhaps (iii) pass through tetracarboxylic dianhydride, diamine compound and diisocyanate cpd are mixed, and heating is carried out condensation and synthetic method as required.
In the method for above-mentioned (i), temperature of reaction is generally 300 ℃ or following, is preferably 100～250 ℃.If temperature of reaction surpasses 300 ℃, the situation that molecular weight that gained contains the polyamic acid of imide reduces can appear.
On the other hand, as used dewatering agent in above-mentioned method (ii), can use for example acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride.The consumption of dewatering agent with respect to 1 mole of polyamic acid repetitive, is preferably 0.2～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, trimethylpyridine, lutidines, triethylamine.But, be not limited to these.And the consumption of imidization catalyst with respect to 1 mole of used dewatering agent, is preferably 0.1～10 mole.In addition, as the organic solvent that uses in the dehydration closed-loop reaction, can enumerate as polyamic acid and synthesize middle solvent for use and illustrative organic solvent.And the temperature of reaction of dehydration closed-loop is generally 0～180 ℃, is preferably 60～150 ℃.In addition, by the reaction solution that so obtains is carried out the operation same with the polyamic acid process for purification, can make with extra care the polyamic acid that contains imide.
As the object lesson of diisocyanate cpd used in the above-mentioned reaction (iii), can enumerate aliphatic diisocyanates such as hexamethylene diisocyanate; Cyclohexane-1,2-diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, 1,2-dimethyl cyclohexane-ω, ω '-diisocyanate, 1,4-dimethyl cyclohexane-ω, ω '-diisocyanate, isophorone diisocyanate, 1,3,5-trimethyl-2-propyl cyclohexane-1 ω, 2 ω-diisocyanate, dicyclohexyl methyl hydride-4, ester ring type diisocyanate such as 4 '-diisocyanate; Diphenyl methane-4,4 '-diisocyanate, 1,3-phenylene vulcabond, 1,4-phenylene vulcabond, 1-methyl-2,4-phenylene vulcabond, 1-methyl-2, the aromatic diisocyanates such as diisocyanate of 6-phenylene vulcabond, following formula (22)～(26) expression.
Figure A20061009872400191
Wherein, as preferably enumerating dicyclohexyl methyl hydride-4,4 '-diisocyanate, diphenyl methane-4,4 '-diisocyanate, 1-methyl-2,4-phenylene vulcabond, 1-methyl-2,6-phenylene vulcabond.They can independent or multiple being used in combination.In addition, the unessential especially catalyzer of above-mentioned reaction (iii), temperature of reaction is generally 50～200 ℃, is preferably 100～160 ℃.
[end modified]
＜end modified type polymkeric substance 〉
Above-mentioned polyamic acid can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting with the polyamic acid that contains imide.By using this end modified type polymkeric substance, can under the prerequisite of not damaging effect of the present invention, improve the coating characteristics of aligning agent for liquid crystal etc.This end modified type polymkeric substance can be by when polyamic acid synthetic, adds monobasic acid anhydrides, monoamine compound, monoisocyanates compound etc. and synthesize in reaction system.Wherein, as the monobasic acid anhydrides, 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.In addition, as 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.In addition, as the monoisocyanates compound, can enumerate for example phenyl isocyanate, isocyanic acid naphthyl ester etc.
[logarithm viscosity]
The logarithm viscosity of＜polymkeric substance 〉
The as above polyamic acid of gained and contain the polyamic acid of imide, its logarithm viscosity (η ln) value is generally 0.05～10dl/g, is preferably 0.05～5dl/g.
Logarithm viscosity among the present invention (η ln) value is by using the N-N-methyl-2-2-pyrrolidone N-as solvent, is that the solution of 0.5g/100ml carries out viscosimetric analysis to concentration under 30 ℃, the value of being tried to achieve by following formula (i).
Figure A20061009872400201
[aligning agent for liquid crystal]
Aligning agent for liquid crystal of the present invention usually by above-mentioned polymer dissolution in organic solvent and constitute.In addition, in constituting the polymkeric substance of aligning agent for liquid crystal of the present invention, as the repetitive of above-mentioned formula (I-1) expression: the ratio of the repetitive of above-mentioned formula (I-2) expression is preferably 1: 9～5: 5.
As the organic solvent that constitutes aligning agent for liquid crystal of the present invention, can enumerate as solvent for use in the polyamic acid synthetic reaction and illustrative solvent.In addition, can also suitably select as solvent that can coupling when the polyamic acid synthetic reaction and illustrative poor solvent is united use.
Solid component concentration is considered viscosity, volatility etc. and is selected the scope of preferred 1～10 weight % in the aligning agent for liquid crystal of the present invention.That is to say that aligning agent for liquid crystal of the present invention is coated substrate surface, formation is filmed as liquid crystal orientation film, and when solid component concentration less than 1 weight %, the thickness that causes this to film is too small, is difficult to obtain good liquid crystal orientation film.When solid component concentration surpasses 10 weight %, cause coating thickness blocked up, be difficult to obtain good liquid crystal orientation film, and the viscosity of aligning agent for liquid crystal increases, then the easy variation of coating characteristics.Temperature when in addition, preparing aligning agent for liquid crystal of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
Aligning agent for liquid crystal of the present invention with respect to 100 weight portion particular polymers, contains the compound that has 4 epoxy radicals in the 2 weight portion molecules (below, be also referred to as " compound that contains epoxy radicals ") at least.
As the compound that contains epoxy radicals, for example preferably can enumerate 1,3,5,6-four glycidyl group-2,4-hexanediol, N, N, N ', N '-four glycidyl group-m-xylylenediamine, 1,3-two (N, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N, N ', N '-four glycidyl group-4,4 '-diamino-diphenyl ether, N, N, N ', N '-four glycidyl group-right-benzene dimethylamine, N, N, N ', N '-four glycidyl group-3,4 '-diaminodiphenyl-methane, N, N, N ', N '-four glycidyl group-1,3-propanediamine, N, N, N ', N '-four glycidyl group-4,4 '-diamido heptamethylene diamine, 1,3-two (N, N-diglycidyl amino-ethyl) cyclohexane, N, N, N ', N '-four glycidyl group-2,2 '-dimethyl-4,4 '-benzidine etc.As the content of this epoxy compound,, be preferably 2～40 weight portions, more preferably 5～30 weight portions with respect to contained particular polymers in the 100 weight portion alignment agents.
And aligning agent for liquid crystal of the present invention can also contain compound with functional silanes (below, be also referred to as " silane coupling agent ").As silane coupling agent, the silane coupling agent of preferred following formula (I-4) expression,
YR 3SiR 3-mX m (I-4)
(in the formula, Y has amino organic group, R 3Be that carbon number is 1～10 divalent alkyl, R is that carbon number is 1～5 alkyl, and X represents OR 4The alkoxy or the OCOR of expression 5The alkoxy carbonyl group of expression (R wherein 4And R 5Be that carbon number is 1～10 alkyl), m represents 1～3 integer).
As this silane coupling agent, 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-triethoxysilicane alkyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, N-two (oxyethylene group)-3-TSL 8330, N-two (oxyethylene group)-3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, 3-[2-(3-trimethoxy silane base propyl group amino) ethylamino] methyl propionate etc.
The mixture ratio of these silane coupling agents with respect to 100 weight portion particular polymers, is generally 0.01～5 weight portion, is preferably 0.1～3 weight portion, more preferably 0.5～2 weight portion.If less than 0.01 weight portion printing then can occur and improve the not enough situation of effect, if surpass 5 weight portions, the situation that viscosity increases can appear then.
＜liquid crystal display cells 〉
The liquid crystal display cells that uses aligning agent for liquid crystal of the present invention and obtain can be by for example following method manufacturing.
(1) by for example methods such as roll coater method, spin coater method, print process, ink-jet method, aligning agent for liquid crystal of the present invention is coated on the one side of the substrate that is provided with the nesa coating that forms pattern, then,, coated face films by being added thermosetting.Wherein, as substrate, can use for example glass such as float glass, soda-lime glass; Plastics system transparency carriers such as polyethylene terephthalate, polybutyleneterephthalate, polyethersulfone, polycarbonate.Simultaneously go up set nesa coating 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.The pattern of these nesa coatings forms, and can adopt photoetch method and use the method for mask in advance.When the coating of aligning agent for liquid crystal, for the cohesive of further improving substrate surface and nesa coating and filming, can also be on the surface of substrate coating in advance contain the compound of functional silanes or contain the compound etc. of functionality titanium.Heating-up temperature behind the coating of liquid crystalline alignment agent is preferably 80～300 ℃, more preferably 120～250 ℃.In addition, contain the aligning agent for liquid crystal of the present invention of polyamic acid, by removing organic solvent after the coating, formation is filmed as alignment films, or carries out dehydration closed-loop by further heating, can form filming of further imidizate.The thickness of filming that forms is generally 0.001～1 μ m, is preferably 0.005～0.5 μ m.
(2) roller of fibrous cloth such as nylon, regenerated fiber, cotton carries out grinding process with certain direction friction with for example being tied with to formed film coated surface.Like this, make give film with liquid crystal molecular orientation can liquid crystal orientation film.
In addition; by the processing of the liquid crystal orientation film that is formed by aligning agent for liquid crystal of the present invention being carried out pre-tilt angle is changed through the part irradiation ultraviolet radiation shown in flat 6-222366 communique of for example open patent or the flat 6-281937 communique of open patent; perhaps carry out the branch ground, liquid crystal orientation film upper surface shown in the flat 5-107544 communique of open patent and form diaphragm having carried out grinding process; with with after the direction that grinding process is different is before carried out grinding process; remove diaphragm; the processing that the liquid crystal aligning of liquid crystal orientation film can be changed can improve the field-of-view characteristics of liquid crystal display cells thus.
(3) make 2 substrates that form liquid crystal orientation film as mentioned above, 2 substrates are staggered relatively by gap (box gap), make the vertical mutually or antiparallel of polishing direction in the liquid crystal orientation film separately, fitted with sealant in 2 substrate periphery positions.Annotate the topping up crystalline substance in the box gap that is partitioned into by substrate surface and sealant, the sealing filling orifice forms liquid crystal cell.Then,, promptly constitute the transparent substrate side applying polaroid of liquid crystal cell, make liquid crystal display cells at the outside surface of liquid crystal cell.
Wherein, as sealant, for example can use epoxy resin as the salic ball of hardening agent and separator etc.
As liquid crystal, can enumerate nematic crystal and dish shape type liquid crystal.Wherein preferred nematic crystal can use for example schiff base class liquid crystal, azoxy base class liquid crystal, 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.In addition, can also add cholesteryl liquid crystal such as for example cholesteryl chloride, cholesterol n-nonanoic acid fat, cholesteryl carbonate in these liquid crystal and the chirality agent of selling with trade name " C-15 ", " CB-15 " (メ Le Network corporate system) etc. and using.And, can also use right-strong dielectricity liquid crystal of oxygen base benzylidene-right-amino-2-methyl butyl cinnamate etc. in the last of the ten Heavenly stems.
In addition, as the polaroid of fitting on the liquid crystal cell outside surface, on one side polyvinyl alcohol (PVA) is extended that the polarizing coating that is referred to as the H film that orientation absorbs the iodine gained is clipped in the acetate fiber diaphragm and the polaroid that polaroid of making or H film itself are made Yi Bian can enumerate.
[embodiment]
By the following examples the present invention is carried out more specific description, but the present invention is not limited to these embodiment.Voltage retention is estimated according to following method in embodiment and the comparative example.
[voltage retention]
In 167 milliseconds time span, apply the voltage of 5V to liquid crystal display cells, the voltage application time is 60 microseconds, measures from voltage and removes voltage retention after 167 milliseconds.Determinator adopts the (VHR-1 of strain) East Yang テ Network ニ カ system.Voltage retention is 95% or is evaluated as " good " when above that average evaluation in addition is " bad ".
Synthesis example 1
Will be as 2,3 of tetrabasic carboxylic acid dicarboxylic anhydride, 5-tricarboxylic basic ring amyl group acetic acid dianhydride 224.17g (1.0 moles) and be dissolved in the 4500g N-N-methyl-2-2-pyrrolidone N-as the p-phenylenediamine 108.14g (1.0 moles) of diamine compound is 60 ℃ of reactions 6 hours down.Then, reaction solution is poured into to big excessive methyl alcohol, made the reaction product precipitation.Then, use methanol wash, in 40 ℃ of dryings 15 hours, obtaining 380g logarithm viscosity thus was the polyamic acid of 0.75dl/g by under reduced pressure.30g gained polyamic acid is dissolved in the 570g N-N-methyl-2-2-pyrrolidone N-, add 23.4g pyridine and 18.1g acetic anhydride, under 110 ℃, make its dehydration closed-loop 4 hours, similarly precipitate, wash, reduce pressure with above-mentioned, obtain the polyimide that 18.2g logarithm viscosity is 0.68dl/g (it is as " polyimide (A-1) ").
Synthesis example 2
In synthesis example 1, except using 198.27g (1.0 moles) 4,4 '-diaminodiphenyl-methane is similarly operated with synthesis example 1 as beyond the diamine compound, and obtaining 390g logarithm viscosity is the polyamic acid of 0.55dl/g.30g gained polyamic acid is dissolved in the 570g N-N-methyl-2-2-pyrrolidone N-, add 5.7g pyridine and 7.4g acetic anhydride, under 110 ℃, make its dehydration closed-loop 4 hours, similarly precipitate, wash, reduce pressure with above-mentioned, obtain the polyimide that 20.5g logarithm viscosity is 0.49dl/g (it is as " polyimide (A-2) ").
Synthesis example 3
In synthesis example 1, except using 200.24g (1.0 moles) 4,4 '-diamino-diphenyl ether is similarly operated with synthesis example 1 as beyond the diamine compound, and obtaining 390g logarithm viscosity is the polyamic acid of 0.52dl/g.30g gained polyamic acid is dissolved in the 570g N-N-methyl-2-2-pyrrolidone N-, add 5.7g pyridine and 7.4g acetic anhydride, under 110 ℃, make its dehydration closed-loop 4 hours, similarly precipitate, wash, reduce pressure with above-mentioned, obtain the polyimide that 18.5g logarithm viscosity is 0.48dl/g (it is as " polyimide (A-3) ").
Synthesis example 4
In synthesis example 1, except using 75.69g (0.7 mole) p-phenylenediamine and 59.48g (0.3 mole) 4,4 '-diaminodiphenyl-methane is similarly operated with synthesis example 1 as beyond the diamine compound, and obtaining 390g logarithm viscosity is the polyamic acid of 0.56dl/g.30g gained polyamic acid is dissolved in the 570g N-N-methyl-2-2-pyrrolidone N-, add 5.7g pyridine and 7.4g acetic anhydride, under 110 ℃, make its dehydration closed-loop 4 hours, similarly precipitate, wash, reduce pressure with above-mentioned, obtain the polyimide that 17.5g logarithm viscosity is 0.50dl/g (it is as " polyimide (A-4) ").
Synthesis example 5
In synthesis example 1, except using 86.51g (0.8 mole) p-phenylenediamine and 40.04g (0.2 mole) 4,4 '-diamino-diphenyl ether is similarly operated with synthesis example 1 as beyond the diamine compound, and obtaining 390g logarithm viscosity is the polyamic acid of 0.70dl/g.30g gained polyamic acid is dissolved in the 570g N-N-methyl-2-2-pyrrolidone N-, add 5.7g pyridine and 7.4g acetic anhydride, under 110 ℃, make its dehydration closed-loop 4 hours, similarly precipitate, wash, reduce pressure with above-mentioned, obtain the polyimide that 19.8g logarithm viscosity is 0.61dl/g (it is as " polyimide (A-5) ").
Synthesis example 6
In synthesis example 1, except using 112.08g (0.5 mole) 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride and 157.14g (0.5 mole) 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 is as the tetrabasic carboxylic acid dicarboxylic anhydride, and 108.14g (1.0 moles) p-phenylenediamine is as beyond the diamine compound, similarly operate with synthesis example 1, obtaining 390g logarithm viscosity is the polyamic acid of 0.8dl/g.30g gained polyamic acid is dissolved in the 570g N-N-methyl-2-2-pyrrolidone N-, add 5.7g pyridine and 7.4g acetic anhydride, under 110 ℃, make its dehydration closed-loop 4 hours, similarly precipitate, wash, reduce pressure with above-mentioned, obtain the polyimide that 18.3g logarithm viscosity is 0.68dl/g (it is as " polyimide (A-6) ").
Synthesis example 7
In synthesis example 1, except using 86.51g (0.8 mole) p-phenylenediamine and 82.1g (0.2 mole) 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane is similarly operated with synthesis example 1 as beyond the diamine compound, and obtaining 390g logarithm viscosity is the polyamic acid of 0.61dl/g.30g gained polyamic acid is dissolved in the 570g N-N-methyl-2-2-pyrrolidone N-, add 5.7g pyridine and 7.4g acetic anhydride, under 110 ℃, make its dehydration closed-loop 4 hours, similarly precipitate, wash, reduce pressure with above-mentioned, obtain the polyimide that 19.2g logarithm viscosity is 0.53dl/g (it is as " polyimide (A-7) ").
Synthesis example 8
In synthesis example 1, except using 112.08g (0.5 mole) 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride and 157.14g (0.5 mole) 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone is as the tetrabasic carboxylic acid dicarboxylic anhydride, 95.71g (0.885 mole) p-phenylenediamine and 24.85g (0.1 mole) diamido propyl group tetramethyl disiloxane is as diamine compound, 2.793g (0.03 mole) aniline as beyond the monoamine, is similarly operated with synthesis example 1, obtaining 390g logarithm viscosity is the polyamic acid of 0.85dl/g.30g gained polyamic acid is dissolved in the 570g N-N-methyl-2-2-pyrrolidone N-, add 5.7g pyridine and 7.4g acetic anhydride, under 110 ℃, make its dehydration closed-loop 4 hours, similarly precipitate, wash, reduce pressure with above-mentioned, obtain the polyimide that 18.5g logarithm viscosity is 0.70dl/g (it is as " polyimide (A-8 ").
Embodiment 1
With polyimide (A-1), the 10 weight portion N that make in the 100 weight portion synthesis examples 1, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane and 0.75 weight portion 3-[2-(3-trimethoxy silane base propyl group amino) ethylamino] methyl propionate is dissolved in gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-mixed solvent (weight ratio 90/10), make the solution that solid component concentration is 4 weight %, after fully stirring, is the filter filtration of 1 μ m with this solution with the aperture, makes aligning agent for liquid crystal of the present invention.The aligning agent for liquid crystal of the present invention of as above preparation is arranged on the ITO film system nesa coating on the glass substrate one side that thickness is 1mm with spin coater with coating the broach shape, and 180 ℃ of dryings 1 hour down, the formation dry film thickness is the overlay film of 0.08 μ m.Adopt the sander that the roller that twines nylon cloth is housed to carry out grinding process to the coated surface that forms, make liquid crystal orientation film.Wherein, the grinding process condition is: the roller rotating speed is that 400rpm, operator's console (ス テ one ジ) translational speed are 3cm/ second, and it is 0.4mm that fine hair is clamp-oned length.(this substrate is as " substrate A ").
The aligning agent for liquid crystal of the present invention of as above preparation is coated on the glass substrate one side that thickness is 1mm with spin coater, and drying is 1 hour under 180 ℃, and forming dry film thickness is the overlay film of 0.08 μ m.Is 20 times microscopically when observing with this substrate in multiplying power, finds printing inequality and eyelet, and printing is good.
Adopt the sander that the roller that twines nylon cloth is housed to carry out grinding process formed coated surface, make liquid crystal orientation film.Wherein, the grinding process condition is: the roller rotating speed is that 400rpm, operator's console translational speed are 3cm/ second, and it is 0.4mm that fine hair is clamp-oned length.(this substrate is as " substrate B ").
Coated surface outer rim position at substrate A and B, after containing the epoxy adhesive of alumina balls that diameter is 17 μ m by silk screen print method coating, make the mutual antiparallel of polishing direction in the liquid crystal orientation film separately and 2 substrates relatively are provided with by the gap, make between the outer rim position and contact pressing, and bonding agent is solidified.
Then, between a pair of substrate, fill nematic crystal (メ Le Network society system by liquid crystal injecting port, MLC-2019) after, with epoxy adhesive liquid crystal injecting port is sealed, the polaroid of on the two sides in the substrate outside, fitting, make the polarization direction of polaroid consistent, make liquid crystal display cells with the polishing direction of the liquid crystal orientation film of substrate separately.
Voltage retention to the gained liquid crystal display cells is estimated.Voltage retention demonstrates 95% or above good numerical value, does not have to find to apply the uneven and display defect of contrast behind the voltage etc.
Embodiment 2～8 and comparative example 1～3
Will be in synthesis example 2～8 prepared polyimide (A-2)～(A-8), the various compound that contains epoxy radicals and silane coupling agent to be dissolved in the gamma-butyrolacton be in the mixed solvent of principal ingredient, make solid component concentration and be 4.0% solution, with this solution is the filter filtration of 1 μ m with the aperture, make aligning agent for liquid crystal of the present invention, on substrate, form overlay film similarly to Example 1, observation has or not printing inequality and eyelet, further make liquid crystal display cells, voltage retention is estimated.The results are shown in table 1.
Table 1
Polymkeric substance Contain epoxy compounds (10 parts) Silane coupling agent (0.75 part) Printing Voltage retention
Embodiment 2 A-2 N, N, N ', N '-four glycidyl group-3,4 '-diaminodiphenyl-methane 3-[2-(3-trimethoxy silane base propyl group amino) ethylamino] methyl propionate Well Well
Embodiment 3 A-3 N, N, N ', N '-four glycidyl group-3,4 '-diaminodiphenyl-methane 3-[2-(3-trimethoxy silane base propyl group amino) ethylamino] methyl propionate Well Well
Embodiment 4 A-4 1,3,5,6-four glycidyl group-2,4-hexanediol The 2-TSL 8330 Well Well
Embodiment 5 A-5 1,3,5,6-four glycidyl group-2,4-hexanediol The 2-TSL 8330 Well Well
Embodiment 6 A-6 N, N, N ', N '-four glycidyl group-m-xylylenediamine N-(2-amino-ethyl)-3-TSL 8330 Well Well
Embodiment 7 A-7 N, N, N ', N '-four glycidyl group-m-xylylenediamine N-carbethoxyl group-3-aminopropyltriethoxywerene werene Well Well
Embodiment 8 A-8 1,3-two (N, N-diglycidyl amino methyl) cyclohexane 10-trimethoxy silane base-1,4,7-three azepine decane Well Well
Comparative example 1 A-2 - 10-trimethoxy silane base-1,4,7-three azepine decane Well Bad
Comparative example 2 A-2 1,3-two (N, N-diglycidyl amino methyl) cyclohexane - Bad Well
Comparative example 3 A-2 - - Bad Bad

Claims (5)

1. lateral electric field type liquid crystal display element aligning agent for liquid crystal, it is characterized in that containing the compound and the functional silanes compound that have 4 epoxy radicals in polymkeric substance that (A) have the repetitive of the repetitive of following formula (I-1) expression and following formula (I-2) expression, the molecule
Figure A2006100987240002C1
In the formula, P 1Be the organic group of 4 valencys, Q 1Be the organic group of divalent,
In the formula, P 2For with P 14 different valency organic groups, Q 2Be the divalent organic group.
2. the described lateral electric field type liquid crystal display element aligning agent for liquid crystal of claim 1, the compound that wherein has 4 epoxy radicals in the molecule contains epoxy compounds at least a kind of selecting the group who forms from the compound of following formula (I-3) expression,
In the formula, R 2Represent the organic group of divalent.
3. the described lateral electric field type liquid crystal display element aligning agent for liquid crystal of claim 1, the silane coupling agent of functional silanes compound wherein for selecting the group who forms from the compound of following formula (I-4) expression,
YR 3SiR 3-mX m (I-4)
In the formula, Y has amino organic group, R 3Be that carbon number is 1～10 divalent alkyl, R is that carbon number is 1～5 alkyl, and X represents OR 4The alkoxy or the OCOR of expression 5The alkoxy carbonyl group of expression, wherein R 4And R 5Be that carbon number is 1～10 alkyl, m represents 1～3 integer.
4. any described lateral electric field type liquid crystal display element aligning agent for liquid crystal of claim 1～3, the tetrabasic carboxylic acid dicarboxylic anhydride that wherein produces polymkeric substance (A) comprises 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone or 1,3,3 a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, in the pyromellitic acid acid anhydride any one.
5. a lateral electric field type liquid crystal display element is characterized in that having by any liquid crystal orientation film that described aligning agent for liquid crystal forms of claim 1～4.
CNA200610098724XA 2005-07-12 2006-07-10 Liquid crystal tropism agent and liquid crystal display element Pending CN1896843A (en)

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