CN100529917C - Liquid crystal tropism agent and LCD member - Google Patents
Liquid crystal tropism agent and LCD member Download PDFInfo
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- CN100529917C CN100529917C CNB200610083462XA CN200610083462A CN100529917C CN 100529917 C CN100529917 C CN 100529917C CN B200610083462X A CNB200610083462X A CN B200610083462XA CN 200610083462 A CN200610083462 A CN 200610083462A CN 100529917 C CN100529917 C CN 100529917C
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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
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- 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
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- 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
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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
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
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- 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
The invention provides the liquid crystal orientation agent. The vertical liquid crystal orientation agent comprises polyamic acid or polyimide, the polyamic acid is the reaction product of 1, 3-diamino-benzene and aromatic tetracarboxylic acid dianhydride.
Description
Technical field
The present invention relates to vertical alignment-type liquid crystal aligning agent and liquid crystal display cells.More particularly, relate to the good novel liquid crystal alignment agent of printing, vertical orientated property, voltage retention performance and sealer adhesion and have graceful picture and solid liquid crystal display cells.
Background technology
So far, known liquid crystal display cells with TN (twisted-nematic) type or STN (supertwist is to row) type liquid crystal cell, described liquid crystal cell by nesa coating between 2 substrates that formed the liquid crystal orientation film that constitutes by polyamic acid or polyimide on the surface, formation has the nematic crystal layer of positive dielectric anisotropy, constitute sandwich construction, the major axis of above-mentioned liquid crystal molecule twist continuously between the substrate 90 degree or more than.Drive this TN type liquid crystal display cells work that makes by TFT, the cathode-ray tube (CRT) before so-called TFT LCDs substitutes popularizes widely.Liquid crystal aligning in these liquid crystal display cells usually by given through grinding process etc. liquid crystal molecular orientation can liquid crystal orientation film realize.In addition, as the liquid crystal display cells beyond above-mentioned, known liquid crystal display cells with vertical orientated (Vertical Alignment) type liquid crystal cell, described liquid crystal cell make the liquid crystal molecule with negative dielectric anisotropic vertical orientated on substrate (giving 90 degree tilt angles).In this liquid crystal display cells, the control of the orientation of liquid crystal also realizes by the liquid crystal orientation film that is formed by the aligning agent for liquid crystal that contains polymkeric substance such as polyamic acid, polyimide usually.
Tilt angle can be by introducing in polymkeric substance as having 1-octadecane oxygen base-2 on the disclosed side chain in the patent documentation 1, the substituent monomer of the such large volume of 4-diaminobenzene and show (below, be called the monomer that shows tilt angle).In addition, patent documentation 2, patent documentation 3 disclose 3,5-diaminobenzoic acid cholesteryl ester, lithocholic acid octadecyl (3,5-diaminobenzoic acid ester), 3,5-diaminobenzoic acid cholestane base ester etc., and patent documentation 4 discloses and has comprised cholestene oxygen base-2, and the 4-diaminobenzene is at the monomer of interior multiple performance tilt angle.By adopting their polymkeric substance, can prepare the aligning agent for liquid crystal that possesses stable tilt angle.
The necessary fundamental characteristics of liquid crystal orientation film as the liquid crystal display cells that is used for having the vertical alignment-type liquid crystal box, can enumerate printing, vertical orientated property, voltage retention performance etc., and in recent years, development along with big pictureization, for the sealant that makes bonding two substrates can reach the liquid crystal orientation film dispensing area, also require to improve the cohesive between liquid crystal orientation film and the bonding agent.
The flat 6-136122 communique of [patent documentation 1] TOHKEMY
No. 2893671 communique of [patent documentation 2] patent
[patent documentation 3] TOHKEMY 2004-331937 communique
[patent documentation 4] TOHKEMY 2004-262921 communique
Summary of the invention
The present invention is based on above-mentioned situation proposition, and therefore first purpose of the present invention provides a kind of vertical orientated property, the voltage retention performance is good, has higher fusible aligning agent for liquid crystal by sealant simultaneously.
Second purpose of the present invention provides a kind of solid and liquid crystal display cells with high image quality.
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 vertical alignment-type liquid crystal aligning agent, it is characterized in that containing polyamic acid and make this polyamic acid dehydration closed-loop and at least a in the imide amination polymer that generates, described polyamic acid is the 1st diamines that makes following formula (1) expression
Wherein, R
1The group of representing separately for following formula (1-1)～(1～4),
With the 1st diamines the 2nd diamines in addition of following formula (2) expression,
H
2N-R
2-NH
2 …(2)
Wherein, R
2Be the organic group of divalent,
And the tetrabasic carboxylic acid dicarboxylic anhydride of following formula (3) expression,
Wherein, R
3For aliphatic series contains 4 valency organic groups of ring texture,
Reaction and generate.
And, according to the present invention, above-mentioned purpose of the present invention and advantage, the second, reach by a kind of vertical alignment-type liquid crystal display device with the liquid crystal orientation film that forms by above-mentioned aligning agent for liquid crystal.
By aligning agent for liquid crystal of the present invention, can obtain vertical orientated property, voltage retention and the good liquid crystal orientation film of sealer adhesion.
Embodiment
[polyamic acid and imide amination polymer]
Below, the present invention is described in detail.The polyamic acid that uses among the present invention can carry out addition polymerization by the tetrabasic carboxylic acid dicarboxylic anhydride that the diamines and the above-mentioned formula (3) that make the expression of above-mentioned formula (1) and above-mentioned formula (2) are represented and make.And the imide amination polymer that uses among the present invention can make by making above-mentioned polyamic acid dehydration closed-loop.
[diamines]
Aligning agent for liquid crystal of the present invention is owing to the diamines that uses above-mentioned formula (1) and above-mentioned formula (2) to represent separately has vertical orientated property, voltage retention performance and the good performance of sealer adhesion.
The ratio that the 1st diamine compound of preferred above-mentioned formula (1) expression accounts for the diamine compound total amount of above-mentioned formula (1) and (2) representing separately is 5～80 moles of %, is preferably 5～50 moles of % especially.
The 2nd diamine compound as above-mentioned formula (2) expression, can enumerate for example p-phenylenediamine, between-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diamido diphenylethane, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino diphenyl sulfone, 2,2 '-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 '-diaminodiphenyl ether, 3,3 '-diamido benzophenone, 3,4 '-diamido benzophenone, 4,4 '-diamido benzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two [4-aminophenyl] HFC-236fa, 2,2-two [4-(1-amino-benzene oxygen) phenyl] sulfone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 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 '-diamido-2,2 '-dimethyl diphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-aromatic diamines such as octafluoro biphenyl;
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 that two (4-aminophenyl) aniline and following formula (4) and (5) are represented separately
(in the formula, R
5Expression is selected from the 1 valency organic group with nitrogen atom ring texture of pyridine, pyrimidine, triazine, piperidines and piperazine, and X represents the divalent organic group),
(in the formula, R
6Expression is selected from the divalent organic group with nitrogen atom ring texture of pyridine, pyrimidine, triazine, piperidines and piperazine);
Single-substituted two amines of following formula (6) expression (wherein, except the 1st diamines of above-mentioned (1) 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 1 valency organic group of at least a group in the steroid backbone of being selected from, trifluoromethyl, trifluoromethoxy and the fluorin radical or carbon number),
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 alicyclic diamines such as (cyclohexylamine);
The diamido organosiloxane of following formula (7) expression,
(in the formula, R
9The expression carbon number is 1～12 alkyl, a plurality of R of existence
9Separately can be identical, also can be different, p is 1～3 integer, q is 1～20 integer); They can independent or multiple being used in combination.
Wherein, preferred p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl ether, 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, 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-diamido-2,2 '-dimethyl diphenyl, 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 (8) expression in the compound of above-mentioned formula (4) expression, the compound of following formula (9) expression in the compound of above-mentioned formula (5) expression, and the following formula (10) in the compound of above-mentioned formula (6) expression, (11) compound of representing separately, 1, the 4-cyclohexane diamine, 4,4 '-methylene two (cyclohexylamine), the compound of following formula (12) expression in the compound of above-mentioned formula (7) expression
Further particularly preferredly can enumerate p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 2,2 '-dimethyl-4,4 '-benzidine, 1,3 '-two (4-amino-benzene oxygens)-2,2-dimethylpropane.
＜tetrabasic carboxylic acid dicarboxylic anhydride 〉
In the above-mentioned formula (3), R
3The 4 valency organic groups that contain ring texture for aliphatic series.Wherein, be combined in R
3On 2 anhydride groups be aliphatics.As the object lesson of the tetrabasic carboxylic acid dicarboxylic anhydride of above-mentioned formula (3) expression, can enumerate 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)-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)-and 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, 5-(2,5-dioxo tetrahydrofuran methylene)-and 3-methyl-3-cyclohexene-1,2-dicarboxylic acid dicarboxylic anhydride, dicyclo [2,2,2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride and following formula (13), (14), (15) and (16) tetrabasic carboxylic acid dicarboxylic anhydrides such as tetrabasic carboxylic acid dicarboxylic anhydride of representing separately.They can independent or multiple being used in combination.
Wherein, preferred 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, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrofuran methylene)-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, the tetrabasic carboxylic acid dicarboxylic anhydride of 6-tetrabasic carboxylic acid dicarboxylic anhydride and above-mentioned formula (13) expression, wherein, preferred especially 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, 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.
In addition, as tetrabasic carboxylic acid dicarboxylic anhydride for obtaining above-mentioned polyamic acid and using by the imide amination polymer that this polyamic acid dehydration closed-loop is generated, in the scope of not damaging effect of the present invention, other tetrabasic carboxylic acid dicarboxylic anhydride beyond the tetrabasic carboxylic acid dicarboxylic anhydride of all right above-mentioned formula of coupling (3) expression.At this moment, the ratio that the tetrabasic carboxylic acid dicarboxylic anhydride of above-mentioned formula (3) expression accounts for the tetrabasic carboxylic acid dicarboxylic anhydride total amount of supply response preferably is at least 30 moles of %, more preferably is at least 50 moles of %, especially preferably is at least 80 moles of %.
But other tetrabasic carboxylic acid dicarboxylic anhydride as coupling, for example can enumerate 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 ' diphenyl methane 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), 2,3,4,5-pyridine tetrabasic carboxylic acid dicarboxylic anhydride, 2,6-two (3,4-dicarboxyl phenyl) cinchomeronic acid acid anhydride.They can independent or multiple being used in combination.
Synthesizing of＜polyamic acid 〉
The tetrabasic carboxylic acid dicarboxylic anhydride of the synthetic reaction of supply polyamic acid of the present invention and the usage rate of diamine compound, with respect to contained amino in the 1 equivalent diamine compound, the anhydride group that preferably makes the tetrabasic carboxylic acid dicarboxylic anhydride is the ratio of 0.2～2 equivalent, more preferably is the ratio of 0.3～1.2 equivalent.
The synthetic reaction of polyamic acid is preferable over-20～150 ℃, more preferably carries out under 0～100 ℃ temperature conditions in organic solvent.Here, as organic solvent,, then it is had no particular limits so long as can dissolve synthetic polyamic acid.Can illustration for example N-N-methyl-2-2-pyrrolidone N-, N,N-dimethylacetamide, 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 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).
In addition, in the scope that the polyamic acid that does not make generation is separated out, poor solvent alcohols, ketone, ester class, ethers, halogenated hydrocarbon and the hydro carbons etc. of all right coupling polyamic acid 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, diacetone alcohol, 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, propylene carbonate, diethy-aceto oxalate, diethyl malonate, ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), 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.These poor solvents can independent or multiple being used in combination.
As mentioned above, obtained dissolving the reaction solution of polyamic acid.Then, this reaction solution put in a large amount of poor solvents obtain precipitate, can get polyamic acid by this precipitate of drying under reduced pressure then.And, once more this polyamic acid is dissolved in the organic solvent, separate out with poor solvent then, by carrying out once or this operation several times, can make with extra care polyamic acid.
＜imide amination polymer 〉
Imide amination polymer of the present invention can be by preparing above-mentioned polyamic acid dehydration closed-loop.The dehydration closed-loop of polyamic acid can (I) by the method for heating polyamic acid, perhaps (II) by being dissolved in polyamic acid in the organic solvent, adds dewatering agent and dehydration closed-loop catalyzer and the method that heats is as required carried out in this solution.
Temperature of reaction is preferably 50～200 ℃, more preferably 60～170 ℃ in the method for above-mentioned (I) heating polyamic acid.When 50 ℃ of temperature of reaction less thaies, the dehydration closed-loop reaction can not fully be carried out, if temperature of reaction surpasses 200 ℃, the situation of the molecular weight and molecular weight of gained imide amination polymer then can occur.
On the other hand, in polyamic acid solution, adding in the method for dewatering agent and dehydration closed-loop catalyzer of above-mentioned (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, collidine, 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 the identical solvent of illustrative organic solvent with synthesize middle solvent for use as polyamic acid.And the temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, more 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.
Preferred imidizate rate is 1～100% in the imide amination polymer when constituting aligning agent for liquid crystal of the present invention, more preferably 10～98%.Here, so-called " imidizate rate " is meant the sum with respect to repetitive in the polymkeric substance, the value that the ratio of the repetitive quantity of formation imide ring is represented with %.At this moment, the part of imide ring can also be different imide ring.The acid imide rate can be controlled by the reaction conditions of regulating above-mentioned dehydration closed-loop reaction.
＜end modified type polymkeric substance 〉
The polyamic acid and the imide amination polymer that constitute 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.By using this end modified type polymkeric substance, can under the situation 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.Here, 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.And, as monoamine compound, can enumerate for example aniline, cyclo-hexylamine, 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.
In addition, aligning agent for liquid crystal of the present invention can also be opened the method for polyimide block and polyamic acid block being carried out copolymerization shown in the 2002-204250 communique and makes by for example special.At this moment preferred imidizate rate is 10～100% in the polyimide block, more preferably 30～98%.
The logarithm viscosity of＜polymkeric substance 〉
Constitute the polyamic acid and the imide amination polymer of aligning agent for liquid crystal of the present invention, its logarithm viscosity (η ln) value is preferably 0.05～10dl/g, more preferably 0.1～5dl/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).
The imidizate rate of＜polymkeric substance 〉
Polyimide at room temperature behind the drying under reduced pressure, is dissolved in the deuterated dimethyl sulfoxide, is primary standard substance with the tetramethylsilane, at room temperature measures
1H-NMR is tried to achieve by the formula shown in the following formula (II).
Imidizate rate (%)=(1-A
1/ A
2* α) * 100 (II)
A
1: the peak area (10ppm) that comes from NH matrix
A
2: the peak area that comes from other proton
α: in the precursor of polymkeric substance (polyamic acid), with respect to 1 NH matrix, the individual percentage of other proton.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention preferably is dissolved in organic solvent with the polyamic acid that constitutes and imide amination polymer and constitutes.
Temperature when preparing aligning agent for liquid crystal of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
As the organic solvent that constitutes aligning agent for liquid crystal of the present invention, can enumerate as the solvent that uses in the polyamic acid synthetic reaction and illustrative solvent.Wherein consider from the angle of printing, preferred boiling point is 160 ℃ or above solvent, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, N, the N-dimethyl acetamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, HMPA, between sylvan, xylenols, phenol, cyclohexanol, ethylene glycol, propylene glycol, 1, the 4-butylene glycol, triethylene glycol, diacetone alcohol, butyl lactate, butyl acetate, ethoxyl ethyl propionate, propylene carbonate, diethy-aceto oxalate, diethyl malonate, ethylene glycol monobutyl ether, 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, 1, the 4-dichloroetane, o-dichlorobenzene etc., wherein, preferred especially N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolacton, diacetone alcohol, ethylene glycol monobutyl ether, propylene carbonate, diethyl carbitol.
The concentration of solid constituent is considered viscosity, volatility etc. and is selected in the aligning agent for liquid crystal of the present invention, is preferably the scope of 1～10 weight %.That is to say that aligning agent for liquid crystal of the present invention is coated substrate surface, form that when solid component concentration less than 1 weight %, then this thickness of filming is too small and can not obtain good liquid crystal orientation film as the filming of liquid crystal orientation film.When solid component concentration surpassed 10 weight %, then coating thickness was blocked up and can not obtain good liquid crystal orientation film, and the viscosity of aligning agent for liquid crystal increases, the coating characteristics variation.
From improving, can also contain compound with functional silanes or compound in the aligning agent for liquid crystal of the present invention with epoxy radicals to the fusible angle of substrate surface.As this compound with functional silanes, 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-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, N-two (oxyethylene group)-3-TSL 8330, N-two (oxyethylene group)-3-aminopropyltriethoxywerene werene etc.
In addition, as compound with epoxy radicals, preferably can enumerate for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2, the 4-hexanediol, N, N, N ', N '-four glycidyl group-m-benzene dimethylamine, 1,3-two (N, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.The mixture ratio that these have the compound of functional silanes and have the compound of epoxy radicals with respect to 100 parts by weight polymer, is preferably 60 weight portions or following, more preferably 50 weight portions or following.
＜liquid crystal display cells 〉
Liquid crystal display cells of the present invention 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 substrate one side that is provided with the nesa coating that forms pattern, then,, coated face films by being added thermosetting.Here, as substrate, can use for example glass such as float glass, soda-lime glass; Plastics system transparency carriers such as polyethylene terephthalate, polybutylene terephthalate, 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 the method that adopts photoetch method and use mask in advance.Can use metals such as Al or Ag in the reflecting electrode, perhaps contain the alloy of these metals etc.As long as have enough reflectivity, then it had no particular limits.When the coating of aligning agent for liquid crystal, for the cohesive of further improving substrate surface and nesa coating and reflecting electrode and filming, can also be on this surface of substrate coating in advance contain functional silanes compound, contain the compound of functionality titanium etc.Heating-up temperature behind the coating of liquid crystalline alignment agent is preferably 80～300 ℃, more preferably 120～250 ℃.The aligning agent for liquid crystal of the present invention that contains 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 also 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.
(2) formed coated surface is opened shown in the 2002-327058 communique as the spy on substrate, formed structure like that, form the vertical liquid crystal tropism film thereon with photoresist.
(3) make 2 substrates that as above form the vertical liquid crystal tropism film, 2 substrates are staggered relatively by gap (box gap), fitted with sealant in 2 substrate periphery positions, in the box gap that is partitioned into by substrate surface and sealant, inject filling liquid crystal, the sealing filling orifice constitutes liquid crystal cell.Then, at the outside surface of liquid crystal cell, this side of transparency carrier that promptly constitutes liquid crystal cell is provided with polaroid, makes liquid crystal display cells.
Here, 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 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, also can add cholesteryl liquid crystal such as for example cholesteryl chloride, cholesteryl nonanoate, carbonic acid cholesteryl ester 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 the strong dielectricity liquid crystal of oxygen base benzylidene-p-amino-2-methyl butyl cinnamate etc. in the last of the ten Heavenly stems.
In addition,, can enumerate polyvinyl alcohol (PVA) is extended that polarizing coating that orientation absorbs the resulting H of the being referred to as film of iodine simultaneously is clipped in the acetate fiber diaphragm and the polaroid of making, perhaps the polaroid made of H film self as the polaroid of fitting on the liquid crystal cell outside surface.
[embodiment]
By the following examples the present invention is carried out more specific description, but the present invention is not limited to these embodiment.Sealer adhesion in embodiment and the comparative example, vertical orientated property and voltage retention are estimated by following method.
[vertical orientated property]
Under the crossed nicols (crossed nicols) abnormal area of liquid crystal display cells when voltage open to cut off observed, being evaluated as of no abnormal zone " well " has be evaluated as " bad " of abnormal area.
[voltage retention performance]
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.
[cohesive of sealant]
Using spin coater coats aligning agent for liquid crystal of the present invention on the glass substrate that has the transparency electrode that has formed the thick ITO film of 200nm, behind baking formation liquid crystal orientation film,, the cohesive of sealant is estimated 2 same base plate bondings that have liquid crystal orientation film with the epoxy resin sealant with tension tester.
[printing test]
With liquid crystal orientation film printing machine (Japanese photographic printer (strain) manufacturing) aligning agent for liquid crystal of the present invention is coated on the transparency electrode face of glass substrate, described glass substrate has that to form thickness at interval with 100 μ m be that 200nm, width are the transparency electrode of the striated ITO film of 20 μ m, behind baking formation liquid crystal orientation film, the peripheral position of this liquid crystal orientation film, the microscope that the central part multiplying power is 20 times are observed, the situation of not having the coating speckle is judged to be " well ", has the situation of coating speckle to be judged to be " bad ".
Synthesis example 1
Will be as 2,3 of tetrabasic carboxylic acid dicarboxylic anhydride, 5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride 224g (1.0 moles) is as the p-phenylenediamine 99g (0.8 mole) and the middle R of above-mentioned formula (1) of diamine compound
1For the represented diamine compound 87g of formula (1-1) (0.2 mole) is dissolved in the 4500gN-N-methyl-2-2-pyrrolidone N-, reacted 4 hours down at 60 ℃.Then, reaction solution is injected in the big excessive methyl alcohol, makes the reaction product precipitation.Then, use methanol wash, in 40 ℃ of dryings 24 hours, obtaining 370g logarithm viscosity was the polyamic acid of 0.55dl/g by under reduced pressure.30g gained polyamic acid is dissolved in the 570g N-N-methyl-2-2-pyrrolidone N-, add 5.8g pyridine and 7.5g acetic anhydride (pyridine, acetic anhydride are 1 equivalent with respect to the polyamic acid repetitive), 110 ℃ of following dehydration closed-loops 4 hours, similarly precipitate, wash, reduce pressure with above-mentioned, obtaining 18g logarithm viscosity is that 0.51dl/g, imidizate rate are 51% imide amination polymer (it is represented as " (P-1) ").
Synthesis example 2～3 and comparison synthesis example 1～3
Except tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound are replaced with table 1 listed, similarly operate with synthesis example 1, obtain the polymkeric substance (these are represented as " P-2 "～" P-7 ") of logarithm viscosity shown in the table 1 and imidizate rate.In addition, " P-4 " and " P-7 " is polyamic acid, not by imidizate.
Table 1
Acid anhydrides and diamine compound in the table 1 are as follows:
Acid anhydrides A:2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride
Acid anhydrides B: pyromellitic acid dicarboxylic anhydride
Diamines A: R in the above-mentioned formula (1)
1Be the represented diamine compound of formula (1-1)
Diamines B: R in the above-mentioned formula (1)
1Be the represented diamine compound of formula (1-2)
Diamines C: p-phenylenediamine (PPD)
Diamines D:4,4 '-diaminodiphenyl-methane
Diamines E:3,5-diaminobenzoic acid cholestane base ester
Diamines F:2,2 '-two [4-(4-amino-benzene oxygen) phenyl] propane
Embodiment 1
Vertical orientated property, voltage retention and sealer adhesion among the embodiment are estimated by the following method.
(vertical orientated property)
The imide amination polymer (P-1) that makes in the synthesis example 1 is dissolved in N-N-methyl-2-2-pyrrolidone N-/ethylene glycol monobutyl ether mixed solvent (weight ratio 50/50), with respect to P-1, the N that adds 20 weight %, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, make the solution that solid component concentration is 3.5 weight %, after fully stirring, with this solution is the filter filtration of 1 μ m with the aperture, use spin coater to coat then to be arranged on the ITO film system nesa coating on the glass substrate one side, under 80 ℃, carrying out 1 minute predrying on the heating plate, then in dustless formula baking oven in 200 ℃ dry 1 hour down, make and have the transparent electrode substrate that dry film thickness is the liquid crystal orientation film of 50nm.Then, on each outer rim of a pair of transparency electrode/transparent electrode substrate with above-mentioned liquid crystal orientation film of configuration in opposite directions, it is the epoxy adhesive of the alumina balls of 5.5 μ m that coating adds diameter, then, the liquid crystal aligning face is relatively overlapped and carry out pressing, bonding agent is solidified.Then, (メ Le Network society system MLC-2038), is sealed liquid crystal injecting port with the acrylic compounds Photocurable adhesive then, produces liquid crystal display cells to fill negative type liquid crystal by liquid crystal injecting port between substrate.Observe at the abnormal area of under the crossed nicols (crossed nicols) liquid crystal display cells of made being opened when cutting off at voltage, being evaluated as of no abnormal zone " well " has be evaluated as " bad " of abnormal area.The results are shown in table 2.
(voltage retention)
In 167 milliseconds time span, apply the voltage of 5V for the liquid crystal display cells of made, 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.The results are shown in table 2.
(cohesive of sealant)
Similarly operate with above-mentioned liquid crystal display cells facture, make transparent electrode substrate with P-1 liquid crystal orientation film.Then, in a pair of each centre of the transparency electrode/transparent electrode substrate with above-mentioned liquid crystal orientation film of configuration in opposite directions, it is the epoxy adhesive of the alumina balls of 5.5 μ m that coating adds diameter, the liquid crystal aligning face is relatively overlapped and carries out pressing, and bonding agent is solidified.With tension tester the cohesive of sealant is estimated.What do not break away from when applying 2Kgf pressure is evaluated as " well ", being evaluated as of disengaging " bad ".The results are shown in table 2.
(printing test)
The imide amination polymer (P-1) that makes in the synthesis example 1 is dissolved in N-N-methyl-2-2-pyrrolidone N-/ethylene glycol monobutyl ether mixed solvent (weight ratio 50/50), with respect to P-1, the N that adds 20 weight %, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane is made the solution that solid component concentration is 3.5 weight %, after fully stirring, is the filter filtration of 1 μ m with this solution with the aperture, prepares aligning agent for liquid crystal of the present invention.Using liquid crystal orientation film printing machine (Japanese photographic printer (strain) manufacturing) coats above-mentioned aligning agent for liquid crystal on the ITO film system nesa coating that is arranged on the glass substrate one side, under 80 ℃, carrying out 1 minute predrying on the heating plate, then in dustless formula baking oven in 200 ℃ dry 1 hour down, forming dry film thickness is the liquid crystal orientation film of 50nm.This liquid crystal orientation film is not observed the coating speckle, so the printing of the aligning agent for liquid crystal of preparation is judged as " well " among the embodiment 1.
Embodiment 2～3 and comparative example 1～3
At " P-2 "～" P-7 ", except the amount that adopts solvent composition shown in the table 2 and adjuvant, prepare aligning agent for liquid crystal similarly to Example 1, and similarly to Example 1 vertical orientated property, voltage retention, sealer adhesion, printing are estimated.The results are shown in table 2.
Table 2
| Polymkeric substance | Solvent (weight %) | The amount of adjuvant (weight %) | Vertical orientated property | Voltage retention (%) | Sealer adhesion | Printing | |
| Embodiment 1 | P-1 | NMP(50) BC(50) | 20 | Well | 99 | Well | Well |
| Embodiment 2 | P-2 | NMP(70) BC(30) | 20 | Well | 99 | Well | Well |
| Embodiment 3 | P-3 | BL(40) NMP(30) BC(30) | 20 | Well | 99 | Well | Well |
| Embodiment 4 | P | NMP(50) BC(50) | 0 | Well | 98 | Well | Well |
| Embodiment 5 | P-4 | NMP(50) BC(50) | 20 | Well | 98 | Well | Well |
| Comparative example 1 | P-5 | NMP(50) BC(50) | 20 | Well | 99 | Bad | Bad |
| Comparative example 2 | P-6 | NMP(70) BC(30) | 20 | Well | 98 | Bad | Bad |
| Comparative example 3 | P-7 | NMP(50) BC(50) | 0 | Bad | 88 | Well | Well |
Mark is as follows in the table 2:
Adjuvant: N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane
BL: gamma-butyrolacton
The NMP:N-N-methyl-2-2-pyrrolidone N-
BC: ethylene glycol monobutyl ether
Claims (3)
1. vertical alignment-type liquid crystal aligning agent, it is characterized in that containing from the imide amination polymer that polyamic acid generates with making this polyamic acid dehydration closed-loop, select at least a, described polyamic acid is to make the tetrabasic carboxylic acid dicarboxylic anhydride reaction of the 2nd diamines beyond the 1st diamines of the 1st diamines of following formula (1) expression and following formula (2) expression and following formula (3) expression and generate
Wherein, R
1The group of representing separately for following formula (1-1)～(1～4),
H
2N-R
2-NH
2…(2)
Wherein, R
2Be the organic group of divalent,
Wherein, R
3The 4 valency organic groups that contain ring texture for aliphatic series.
2. vertical alignment-type liquid crystal aligning agent according to claim 1, the tetrabasic carboxylic acid dicarboxylic anhydride of wherein above-mentioned formula (3) expression is 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 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c] furans-1, the 3-diketone.
3. a vertical alignment-type liquid crystal display device is characterized in that having the liquid crystal orientation film that is formed by the described aligning agent for liquid crystal of claim 1.
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| JP2005166047A JP4605376B2 (en) | 2005-06-06 | 2005-06-06 | Liquid crystal aligning agent and liquid crystal display element |
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| KR101397294B1 (en) | 2006-12-27 | 2014-05-22 | 닛산 가가쿠 고교 가부시키 가이샤 | Liquid crystal aligning agent, liquid crystal alignment film using the same, and liquid crystal display element |
| JP5041157B2 (en) * | 2007-01-10 | 2012-10-03 | Ｊｓｒ株式会社 | Vertical alignment type liquid crystal aligning agent and vertical alignment type liquid crystal display element |
| JP5158314B2 (en) * | 2007-02-02 | 2013-03-06 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| KR101435690B1 (en) * | 2007-03-08 | 2014-09-01 | 제이에스알 가부시끼가이샤 | Liquid crystal aligning agent and in-plane switching mode liquid crystal display |
| JP5013106B2 (en) * | 2007-03-16 | 2012-08-29 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| JP5224034B2 (en) * | 2008-01-31 | 2013-07-03 | Ｊｓｒ株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| JP5360376B2 (en) * | 2008-03-07 | 2013-12-04 | 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 |
| JP5844094B2 (en) * | 2011-09-05 | 2016-01-13 | スタンレー電気株式会社 | Liquid crystal element, liquid crystal display device |
| KR101987373B1 (en) * | 2015-02-16 | 2019-06-10 | 주식회사 엘지화학 | Liquid crystal device |
| KR101959468B1 (en) * | 2015-03-26 | 2019-03-18 | 주식회사 엘지화학 | Liquid crystal device and the use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6103322A (en) * | 1998-12-23 | 2000-08-15 | Elsicon Inc. | Materials for inducing alignment of liquid crystals and liquid crystal optical elements |
| TW556029B (en) * | 2000-10-16 | 2003-10-01 | Nissan Chemical Ind Ltd | Aligning agent for liquid crystal for in-plane switching, liquid-crystal alignment film, and liquid-crystal display element |
| JP4050487B2 (en) * | 2001-03-02 | 2008-02-20 | Ｊｓｒ株式会社 | Vertical alignment type liquid crystal aligning agent and liquid crystal display element |
| JP2003073471A (en) * | 2001-08-31 | 2003-03-12 | Jsr Corp | Vertically aligning-type liquid crystal aligner and liquid crystal display element using the same |
| JP4172200B2 (en) * | 2002-04-25 | 2008-10-29 | Ｊｓｒ株式会社 | Ether compound and process for producing the same |
| KR100882706B1 (en) * | 2002-07-29 | 2009-02-06 | 제이에스알 가부시끼가이샤 | Diamine Compound, Polyamic Acid, Imide Polymer, Liquid Crystal Alignment Agent and Liquid Crystal Display |
| JP4215603B2 (en) * | 2002-09-11 | 2009-01-28 | 達興材料股▲ふん▼有限公司 | Aromatic diamine derivatives, methods for their preparation, and alignment film materials containing the derivatives for liquid crystal display cells |
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2005
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107430301A (en) * | 2015-06-12 | 2017-12-01 | 株式会社Lg化学 | Display element |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200700856A (en) | 2007-01-01 |
| JP4605376B2 (en) | 2011-01-05 |
| CN1877426A (en) | 2006-12-13 |
| KR20060127782A (en) | 2006-12-13 |
| JP2006337958A (en) | 2006-12-14 |
| TWI399596B (en) | 2013-06-21 |
| KR100794075B1 (en) | 2008-01-10 |
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