CN101109873A - Liquid crystal aligning agent,liquid crystal aligning film and liquid crystal display device - Google Patents
Liquid crystal aligning agent,liquid crystal aligning film and liquid crystal display device Download PDFInfo
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- CN101109873A CN101109873A CNA2007101358292A CN200710135829A CN101109873A CN 101109873 A CN101109873 A CN 101109873A CN A2007101358292 A CNA2007101358292 A CN A2007101358292A CN 200710135829 A CN200710135829 A CN 200710135829A CN 101109873 A CN101109873 A CN 101109873A
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- dicarboxylic anhydride
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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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- 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 relates to a liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display unit. The liquid crystal orientation agent can form liquid crystal orientation film with high voltage conservation rate and good printing property. The said liquid crystal orientation agent contanins benzimalecene repeating unit with 2,7-diamino fluorene as diamino component and the ratio of benzimalecene repeating unit is 50-90weight% relative to summary amount of benzimalecene repeating unit and imide repeating unit.
Description
Technical field
The present invention relates to aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells.More particularly, no matter relate to all good aligning agent for liquid crystal of the how print characteristic of type of electrodes that constitutes liquid crystal display cells, the liquid crystal orientation film that makes by this aligning agent for liquid crystal and liquid crystal display cells with this liquid crystal orientation film.
Background technology
In the past, known TN type liquid crystal display cells with TN (Twisted Nematic) type liquid crystal cell, this element 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 twists 90 degree from a substrate continuously to another piece substrate.
In addition, also have STN (Super Twisted Nematic) type liquid crystal display cells, it makes the major axis of this liquid crystal molecule be in 180 states of spending with upper span that twist continuously between substrate by adding the chirality agent, thereby utilizes consequent birefringence effect.And, recently also at the reflection type liquid crystal display element of developing a kind of guest-principal mode, it forms the cholesteric liquid crystal layers of nematic liquid crystal layer or the screw axis and the substrate normal parastate of the vertical orientated state with negative dielectric anisotropic between opposing substrates, and adds pigment in these liquid crystal layers.The orientation of liquid crystal in these liquid crystal display cells usually shows by carrying out the liquid crystal orientation film that grinding process crosses.Here, as the material of the liquid crystal orientation film that constitutes liquid crystal display cells, according to the known polyimide of prior art, polyamide and polyester etc.Polyimide particularly is owing to thermotolerance, the aspect is good is used in most of liquid crystal display cells with the compatibility of liquid crystal, physical strength etc.
Up to now, carried out with the high-accuracy raising display quality that turns to representative of liquid crystal display cells, reduced the research of power consumption etc., realized the high development of high-performance display element, developed as patent documentation 1 disclosed liquid crystal display cells with high voltage holding ratio, high reliability.But in recent years, except former transmission-type, the range of application of the liquid crystal display cells of reflection-type, Semitransmissive and so on is also enlarging.So, to the performance requirement of liquid crystal orientation film also increasingly stringent.Be that the low voltage drive type liquid crystal display cells of purpose becomes strict more to the requirement of print characteristic to reduce power consumption particularly, the former performance that liquid crystal display cells possessed can't be said enough good.By up to now as the polyamic acid of polyimide precursor and have make its dehydration closed-loop and the liquid crystal orientation film made of the acid imide polymkeric substance etc. of structure in, when adopting this liquid crystal orientation film to make liquid crystal display cells, though the liquid crystal aligning ability is good, and obtained sufficiently high voltage retention, but great majority are having problems all aspect the print characteristic.
[patent documentation 1] TOHKEMY 2001-228481 communique
Summary of the invention
The purpose of this invention is to provide a kind ofly can be used as liquid crystal orientation film, by the polyimide precursor polyamic acid and/or polyimide is formed and can form the aligning agent for liquid crystal that can show the good liquid crystal orientation film of high voltage holding ratio and print characteristic.
Another object of the present invention provides by what above-mentioned aligning agent for liquid crystal made has a liquid crystal orientation film of premium properties as mentioned above.
Still a further object of the present invention provides the liquid crystal display cells with liquid crystal orientation film of the present invention.
Other purpose of the present invention and advantage can be found out by the following description.
Above-mentioned purpose of the present invention and advantage, according to the present invention, the 1st, reach by a kind of aligning agent for liquid crystal, it is characterized in that comprising the polymkeric substance of the acid imide repetitive of amic acid repetitive with following formula (A) expression and following formula (B) expression, total amount with respect to the acid imide repetitive of the amic acid repetitive of formula (A) expression and formula (B) expression, the ratio of the amic acid repetitive of formula (A) expression is 50～90 weight %, and amic acid repetitive at least a portion of formula (A) expression is represented by following formula (A-1).
In the formula, P
1Be the organic group of 4 valencys, and Q
1Organic group for divalent.
In the formula, P
2Be the organic group of 4 valencys, and Q
2Organic group for divalent.
In the formula, P
0Be the aromatic group of 4 valencys, and R
01And R
02Be the organic group of hydrogen atom or 1 valency independently of each other.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 2nd, reach by the liquid crystal orientation film that aligning agent for liquid crystal of the present invention forms.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 3rd, reach by a kind of liquid crystal display cells with liquid crystal orientation film of the present invention.
The liquid crystal orientation film that forms by aligning agent for liquid crystal of the present invention, compared with former alignment films, the print characteristic is better, can be suitable for constituting various liquid crystal display cells such as TN type liquid crystal display cells, STN type liquid crystal display cells, reflection type liquid crystal display element and liquid crystal display element of semi-transmission type.
Liquid crystal display cells of the present invention can be used for various devices effectively, and the display device that for example can be suitable as desk-top calculator, wrist-watch, table clock, mobile phone, counting display screen, word processor, personal computer, liquid crystal TV set etc. is used.
Description of drawings
Fig. 1 is the electrode configuration instruction figure of the box of made in the print experiment.
Embodiment
Below, the present invention will be described in detail.
Aligning agent for liquid crystal of the present invention comprises the polymkeric substance of the acid imide repetitive of amic acid repetitive with above-mentioned formula (A) expression and above-mentioned formula (B) expression.This polymkeric substance can be the polymeric blends of polyamic acid and the polyimide of the acid imide repetitive that comprises above-mentioned formula (B) expression that comprises the amic acid repetitive of above-mentioned formula (A) expression, also can be multipolymer with acid imide repetitive of the amic acid repetitive of above-mentioned formula (A) expression and above-mentioned formula (B) expression (below be also referred to as " part imide amination polymer ").
Above-mentioned polyamic acid can make by making tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound open loop addition polymerization, and polyimide can make by making the polyamic acid dehydration closed-loop usually.Above-mentioned multipolymer can make with the method for synthetic segmented copolymer by making amic acid prepolymer and imide prepolymer bonding usually.
＜polyamic acid and polyimide 〉
[tetrabasic carboxylic acid dicarboxylic anhydride]
P in the repetitive (amic acid unit) of above-mentioned formula (A) expression
1P in the repetitive (acid imide unit) of 4 valency organic groups of expression and above-mentioned formula (B) expression
24 valency organic groups of expression all are the groups that derives from the tetrabasic carboxylic acid dicarboxylic anhydride.Their P
1With P
24 valency organic groups be not identical, preferred different.In other words, preferably derive from 4 valency organic group (P of the tetrabasic carboxylic acid dicarboxylic anhydride that constitutes the amic acid key unit
1) with the 4 valency organic group (P that derive from the tetrabasic carboxylic acid dicarboxylic anhydride that constitutes the imide bond unit
2) inequality.P in the above-mentioned formula (A)
1Wish to contain the organic group that derives from the pyromellitic acid dicarboxylic anhydride of following formula (i) expression.
Except that formula (i),, for example can enumerate 1 as the tetrabasic carboxylic acid dicarboxylic anhydride that constitutes amic acid unit or acid imide unit, 2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride and 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 2,3,6,7-naphthalene tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid dicarboxylic anhydride, the BTCA 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, 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-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, 1,3,3 a, 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-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]-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), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 3,5,6-three carbonyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8,10-tetraketone, following formula (I) and aliphatics and the ester ring type tetrabasic carboxylic acid dicarboxylic anhydrides such as compound (II) represented;
(in the formula, R
1And R
3Expression has the divalent organic group of aromatic rings, R
2And R
4Expression hydrogen atom or alkyl, the R of a plurality of existence
2And R
4Separately can be identical, also can be different);
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, 2,3 ', 2,3 '-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 separately or be used in combination more than 2 kinds.
Wherein, 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, 5-(2,5-dioxo tetrahydrofuran methylene)-and 3-methyl-3-cyclohexene-1,2-dicarboxylic 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, 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), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 3,5,6-three carbonyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8,10-tetraketone, pyromellitic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 2,3 ', 2,3 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, 1,4,5, the compound of following formula (8) expression in the compound that following formula (5)～(7) in the compound of 8-naphthalene tetracarboxylic acid dicarboxylic anhydride, above-mentioned formula (I) expression are represented separately and the compound of above-mentioned formula (II) expression is preferred owing to can make its good liquid crystal aligning of performance.
[diamine compound]
Q in the repetitive (amic acid unit) of above-mentioned formula (A) expression
1Q in the repetitive (acid imide unit) of the divalent organic group of expression and above-mentioned formula (B) expression
2The divalent organic group of expression all is the group that derives from diamine compound.Their Q
1With Q
2The divalent organic group be not identical, preferred different.In other words, preferably derive from the divalent organic group (Q of the diamine compound that constitutes the amic acid key unit
1) with the divalent organic group (Q that derives from the diamine compound that constitutes the imide bond unit
2) inequality.Q in the above-mentioned formula (A)
1At least a portion is (ii) represented by following formula.
(wherein, R
01And R
02Be the organic group of hydrogen atom or 1 valency independently of each other).
As the organic group (Q that is used for divalent
1) the object lesson of diamine compound, can enumerate 2,7-diamino-fluorene, 9,9-dimethyl-2,7-diamino-fluorene, 9,9-dihexyl-2,7-diamino-fluorene, 9,9-dioctyl-2, diamino-fluorenes, 9 such as 7-diamino-fluorene, 9-diphenyl-2,7-diamino-fluorene etc. (below be also referred to as " 2,7-diamino-fluorene etc. ").
2,7-diamino-fluorene etc. can with the following Q that is used for
2Diamines use together, 2, preferred consumption such as 7-diamino-fluorene is at Q
1In account for 5～100%.
As the organic group (Q that is used for divalent
2) diamine compound, can enumerate for example p-phenylenediamine, between-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamido diphenylethane, 4,4 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formailide, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamido benzophenone, 3,4 '-diamido benzophenone, 4,4 '-diamido benzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2 '-trifluoromethyl-4,4 '-benzidine, 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, 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]-octafluoro biphenyl, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3, aromatic diamines such as 5-diaminobenzoic acid ester;
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 bicyclopentadiene diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0
2,7]-undecylene dimethyl diamines, 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, two (4-aminophenyl) phenyl amine, 3,6-diamido carbazole, N-methyl-3,6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole, N has the diamines of the nitrogen-atoms beyond 2 primary amino radicals and this primary amino radical in the compound equimolecular that N '-two (4-aminophenyl)-benzidine and following formula (III)～(IV) 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, X
1The organic group of expression divalent).
(in the formula, X
2Expression is selected from the divalent organic group with nitrogen atom ring texture of pyridine, pyrimidine, triazine, piperidines and piperazine, R
6The organic group of expression divalent, the X of a plurality of existence
2Can be the same or different);
The single-substituted diamines 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).
(in the formula, R
9The expression carbon number is 1～12 alkyl, the R of a plurality of existence
9Separately can be identical, also can be different, p is 1～3 integer, q is 1～20 integer).
The compound that following formula (9)～(13) are represented separately etc.These diamine compounds can be used in combination separately or more than 2 kinds.
(in the formula, y is 2～12 integer, and z is 1～5 integer).
Wherein, preferred p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 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, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, the compound that above-mentioned formula (9)～(13) are represented separately, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 3,6-diamido carbazole, N-methyl-3,6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole, N, N '-two (4-aminophenyl)-benzidine, the compound of following formula (14) expression in the compound of above-mentioned formula (III) expression, the compound that following formula (16)～(21) 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 are represented separately.
[synthesizing 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 equivalent, more preferably is the ratio of 0.8～1.2 equivalent.
The synthetic reaction of polyamic acid in organic solvent, is preferable over-20～150 ℃, more preferably carries out under 0～100 ℃ temperature conditions.Here, as organic solvent, as long as can dissolve synthetic polyamic acid, then it is had no particular limits, can illustration for example 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 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, the poor solvent alcohols of all right coupling 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, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether 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, by this precipitate of drying under reduced pressure or with evaporator the reaction solution decompression is distillated and to obtain polyamic acid.Again, the operation of be dissolved in this polyamic acid in the organic solvent once more, separating out with poor solvent then or carry out once or for several times, can make with extra care polyamic acid thus with the operation that the evaporator decompression distillates.
[imide amination polymer]
The imide amination polymer that constitutes aligning agent for liquid crystal of the present invention can be by preparing aforesaid polyamic acid dehydration closed-loop.Used imide amination polymer can also be imide amination polymer imidizate rate less than 100%, the partial dehydration closed loop among the present invention.Here so-called " imidizate rate " be meant in whole repetitives of polymkeric substance, has the value that the ratio of the repetitive of imide ring or different imide ring is represented with percent.By the imidizate rate is the alignment films that 20～100% imide amination polymer makes, and particularly when being used for TFT type element, can obtain the high evaluation of print and reliability.The dehydration closed-loop of polyamic acid can (i) by the method for heating polyamic acid, perhaps (ii) by polyamic acid is dissolved in the organic solvent, in this solution, adds the method for dewatering agent and dehydration closed-loop catalyzer and heating as required and carry out.
The temperature of reaction of the method for the heating polyamic acid of above-mentioned (i) is preferably 50～200 ℃, more preferably 60～170 ℃.When 50 ℃ of temperature of reaction less thaies, then the dehydration closed-loop reaction is difficult to carry out fully, 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 the above-mentioned method of in polyamic acid solution, adding dewatering agent and dehydration closed-loop catalyzer (ii),, can use for example acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride as dewatering agent.The consumption of dewatering agent preferably with respect to the repetitive of 1 mole of polyamic acid, is 0.01～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, collidine, 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 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.
Used imide amination polymer among the present invention can also be the low polymkeric substance of imidizate rate of partial dehydration closed loop.The imidizate rate of used imide amination polymer is preferably more than 80% among the present invention, more preferably more than 85%.Here so-called " imidizate rate " is meant the sum with respect to polymer repeat unit, the value that the quantity ratios of the repetitive of formation imide ring is represented with %.At this moment, the part of imide ring can also be different imide ring.
[end modified]
Polyamic acid and as atactic polymers imide amination polymer, part imidizate block polymer and part imidizate 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 prerequisite of not damaging effect of the present invention, improve the coating characteristic 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.
[solution viscosity]
The polymkeric substance that alignment agent of the present invention uses when the solution that is 10%, preferably has the viscosity of 20～800mPas, more preferably has the viscosity of 30～500mPas.
Again, the solution viscosity of polymkeric substance (mPas) is adopting specified solvent, is being diluted in the solution of regulation solid portion concentration, adopts E type rotational viscosimeter to carry out the mensuration of viscosity under 25 ℃.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention is contained in above-mentioned polymer dissolution in the organic solvent and constitutes.In constituting the polymkeric substance of aligning agent for liquid crystal of the present invention, the repetitive of above-mentioned formula (A) expression: the ratio of the repetitive of above-mentioned formula (B) expression is preferably 9: 1～and 5: 5.
As the organic solvent that constitutes aligning agent for liquid crystal of the present invention, can enumerate with as the illustrated identical solvent of the solvent that uses in the polyamic acid synthetic reaction.In addition, can also suitably select with as can coupling when the polyamic acid synthetic reaction and the identical solvent of illustrative poor solvent carries out coupling.
Solids content concn 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, aligning agent for liquid crystal of the present invention is coated on substrate surface, formation is filmed as liquid crystal orientation film, and when solids content concn less than 1 weight %, the thickness that will cause this to film is too small, thereby is difficult to obtain good liquid crystal orientation film; When solids content concn surpasses 10 weight %, will cause coating thickness blocked up, thereby be difficult to obtain good liquid crystal orientation film, and the viscosity of aligning agent for liquid crystal increases, the easy variation of coating characteristic.
In addition, particularly preferred solids content concn scope is according to the method that is adopted when the coating of substrates aligning agent for liquid crystal and difference.For example, when being spin-coating method, the scope of preferred especially 1.5～4.5 weight %.When adopting print process, special preferable solids content concentration is 3～9 weight %, like this, can make solution viscosity drop on the scope of 12～50mPas.When adopting ink-jet method, special preferable solids content concentration is the scope of 1～5 weight %, can make solution viscosity drop on the scope of 3～15mPas like this.
Particularly preferred organic solvent as aligning agent for liquid crystal use of the present invention, can exemplify the N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolacton, butyrolactam, N, dinethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2 pentanone, glycol monoethyl ether, butyl lactate, butyl acetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-just-propyl ether, ethylene glycol-different-propyl ether, ethylene glycol-just-butyl ether (butyl cellosolve), 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, diisobutyl ketone (DIBK), isoamyl propionate, isoamyl isobutyrate, isoamyl ether etc.These can use separately, or mix more than 2 kinds and use.
In addition, the temperature when preparing aligning agent for liquid crystal of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
From improving the fusible angle of substrate surface is considered, formed the aligning agent for liquid crystal of liquid crystal orientation film of the present invention, preferably contain the compound that has an epoxy radicals in the molecule at least (below be also referred to as " compound that contains epoxy radicals ").As this epoxy compounds that contains, as preferably enumerating 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-xylylenediamine, 1,3-two (N, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-amino methyl cyclohexane etc.These contain the proportioning of epoxy compounds, with respect to 100 parts by weight polymer, are preferably below 40 weight portions, more preferably 0.1～15 weight portion.
In addition, aligning agent for liquid crystal of the present invention can also contain the compound of functional silanes.As this compound that contains 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-tri-ethoxy silylpropyl diethylenetriamine, N-trimethoxy silane base propyl group diethylenetriamine, 10-trimethoxy silane-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 etc.
These contain the proportioning of functional silanes compound, with respect to 100 parts by weight polymer, are preferably below 40 weight portions.
＜liquid crystal display cells 〉
With liquid crystal orientation film and the liquid crystal display cells that aligning agent for liquid crystal of the present invention makes, can be by for example following method manufacturing.
(1) adopt for example methods such as rolling method, spin-coating method, print process, ink-jet method, aligning agent for liquid crystal of the present invention is coated on the substrate one side, this substrate is provided with the conducting film that forms pattern, then, films by applicator surface is 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, alicyclic polyolefin.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 formation pattern of these nesa coatings adopts photoetch method or uses 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 this surface of substrate coating in advance contain functional silanes compound, contain the compound of functionality titanium etc.Behind the coated with liquid crystal alignment agent, the purpose for the sagging grade of alignment agent liquid that prevents to apply preferably preheats (prebake).The prebake temperature is preferably 30～300 ℃, and more preferably 40～200 ℃, preferred especially 50～150 ℃.Then, remove fully and desolvate,, carry out roasting (afterwards curing) operation in order to make the purpose of polyamic acid hot-imide.This roasting (afterwards curing) temperature is preferably 80～300 ℃, more preferably 120～250 ℃.Like this, 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, can also make its dehydration closed-loop by further heating, forms 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 film coated surface is carried out grinding process with the certain orientation friction with being tied with the roller of fibrous cloth such as nylon, regenerated fiber, cotton for example.Like this, be formed in produced on filming liquid crystal molecular orientation can liquid crystal orientation film.
In addition; to the liquid crystal orientation film that forms by aligning agent for liquid crystal of the present invention; carry out for example special open flat 6-222366 communique or special opening shown in the flat 6-281937 communique; part irradiation ultraviolet radiation and processing that tilt angle is changed; perhaps carry out the spy and open the liquid crystal orientation film upper surface branch ground formation diaphragm after implementing grinding process shown in the flat 5-107544 communique; after carrying out grinding process with the direction different with previous grinding process; remove diaphragm; the processing that the liquid crystal aligning of liquid crystal orientation film can be changed can improve the visual field characteristic of liquid crystal display cells like this.
(3) make 2 substrates that as above form liquid crystal orientation film, 2 substrates are staggered relatively by gap (box gap), make the vertical mutually or antiparallel of polishing direction of liquid crystal orientation film separately, fitted with sealant in 2 substrate periphery positions, in the box gap that is partitioned into by substrate surface and sealant, annotate the topping up crystalline substance, the sealing filling orifice constitutes liquid crystal cell.Then,, promptly constitute the transparency carrier one side configuration polaroid of liquid crystal cell, make liquid crystal display cells at the outside surface of liquid crystal cell.
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 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, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal and the chirality agent of selling with trade name " C-15 ", " CB-15 " (manufacturing of メ Le Network company) etc. and using.And, can also use oxygen base benzylidene-right-ferroelectric liquid crystals such as amino-2-methyl butyl cinnamate in the last of the ten Heavenly stems.
In addition, as the polaroid of fitting on the liquid crystal cell outside surface, can enumerate that the polarizing coating that is referred to as the H film that absorbs the iodine gained when polyvinyl alcohol (PVA) extended orientation is clipped in the acetate fiber diaphragm and the polaroid that polaroid of making or H film self are made.
[embodiment]
Below, by embodiment the present invention is carried out more specific description, but the present invention is not limited to these embodiment.The imidizate rate of the imide amination polymer in embodiment and the comparative example, voltage retention are estimated by the following method.
[imidizate rate]
By the 1381cm in the FT-IR mensuration
-1Neighbouring absorption (absorption of C-N-C flexural vibrations=imide bond) and 1503cm
-1Near the peak area ratio of absorption (absorption of amic acid key) calculates the imidizate rate according to the following equation,
Imidizate rate={ α
1/ (α
1+ α
2) * 100 (%)
α
1: 1381cm
-1Near absorption peak area
α
2: 1503cm
-1Near absorption peak area
In addition, α
2Be with filming after heating 10 minutes on 300 ℃ the heating plate at 1503cm
-1The value of peak area is obtained near absorption as 0.
[solution viscosity]
The value of the solution viscosity of polymkeric substance (mPas) is adopting specified solvent, is being diluted in the solution of regulation solid portion concentration, adopts E type rotational viscosimeter to carry out the mensuration of viscosity under 25 ℃.
[voltage retention]
Apply the voltage of 5V to liquid crystal display cells, the voltage application time is 60 microseconds, and the application time span is 167 milliseconds, then, measures from voltage and removes voltage retention after 167 milliseconds.Determinator adopts the (VHR-1 that strain) East Yang テ Network ニ カ makes.
[print experiment]
Make the box that has the ITO electrode as shown in Figure 1.At room temperature apply 72 hours 6.0V DC voltage, apply 72 hours 0.5V DC voltage to electrode B to electrode A.After discharging stress, apply 0.1～5.0V DC voltage with the gradient of 0.1V to electrode A, B.Luminance difference by each voltage bottom electrode A, B is judged the print characteristic.When luminance difference was big, it is poor that the print characteristic is judged as.
Synthesis example 1
Will be as 2 of tetrabasic carboxylic acid dicarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride 112g (0.50 mole) and 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c] furans-1,3-diketone 157g (0.50 mole) is as the p-phenylenediamine 96g (0.89 mole) of diamine compound, 3,3 '-(tetramethyl disiloxane-1,3-two bases) two (propylamine) 25g (0.10 mole) and 3,6-two (4-aminobenzoic acyl-oxygen base) cholestane 13g (0.02 mole), n-octadecane base amine 8.1g (0.03 mole) as monoamine is dissolved in the 960gN-N-methyl-2-2-pyrrolidone N-, and it was reacted 6 hours down at 60 ℃.The polyamic acid solution branch that obtains is taken a morsel, add NMP, under the solution of solid portion concentration 10%, measure viscosity, be 60mPas.Then, in the gained polyamic acid solution, add 2700g N-N-methyl-2-2-pyrrolidone N-, 396g pyridine and 409g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours.After the imidization reaction, solvent in system carries out solvent exchange (in this operation with new gamma-butyrolacton, outside system, remove the pyridine, the acetic anhydride that use in the imidization reaction), obtain imide amination polymer (its as " polyimide (A-1) ") solution of about 2000g solid component concentration 15wt%.
Synthesis example 2
Will be as 2 of tetrabasic carboxylic acid dicarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride 224g (1.0 moles), p-phenylenediamine 108g (1.0 moles) and 3 as diamine compound, 5-diaminobenzoic acid cholestane base ester 7.8g (0.015 mole) is dissolved in the 4500g N-N-methyl-2-2-pyrrolidone N-, and it was reacted 6 hours down at 60 ℃.In gained polyamic acid solution 427g, append 173g N-N-methyl-2-2-pyrrolidone N-, add 23.4g pyridine and 18.1g acetic anhydride, make it 110 ℃ of following dehydration closed-loops 4 hours, after the imidization reaction, solvent in system carries out solvent exchange (in this operation with new gamma-butyrolacton, outside system, remove the pyridine, the acetic anhydride that use in the imidization reaction), obtain imide amination polymer (its as " polyimide A-2 ") the about 150g of solution of solid component concentration 15wt%.
Synthesis example 3
Will be as 1 of tetrabasic carboxylic acid dicarboxylic anhydride, 2,4,5-benzene tertacarbonic acid dicarboxylic anhydride 218g (1.0 moles), as 2 of diamine compound, 7-diamino-fluorene 196g (1.0 moles) is dissolved in the 4500g N-N-methyl-2-2-pyrrolidone N-, and it was reacted 3 hours down at 40 ℃, obtains polyamic acid (it is as " polyamic acid (B-1) ") the about 4800g of solution.
Synthesis example 4
Will be as 1 of tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride 196g (1.0 moles), as 2 of diamine compound, 2 '-dimethyl-4,4 '-benzidine 212g (1.0 moles) is dissolved in 370g N-N-methyl-2-2-pyrrolidone N-, the 3300g gamma-butyrolacton, it was reacted 3 hours down at 40 ℃, obtain polyamic acid (it is as " polyamic acid (B-2) ") the about 3700g of solution.
Embodiment 1
With the polyamic acid (B-1) that makes in the polyimide (A-1) that makes in the synthesis example 1 and the synthesis example 3 with polyimide: polyamic acid=20: 80 (weight ratio) is dissolved in gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/butyl cellosolve mixed solvent (weight ratio 71/17/12), dissolve 2 weight portion N with respect to 100 parts by weight polymer, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane is made the solution that solids content concn is 3.5 weight %.After fully stirring, be the filter filtration of 1 μ m with the aperture, prepare aligning agent for liquid crystal of the present invention this solution.Adopt spin coater that above-mentioned aligning agent for liquid crystal is coated on (rotating speed: 2500rpm on the nesa coating that thickness is ITO film system set on the one side of glass substrate of 1mm, the coating time: 1 minute), drying is 1 hour under 200 ℃, and forming dry film thickness is the overlay film of 0.08 μ m.Measure the imidizate rate of this overlay film, the imidizate rate is 53%.The sander of the roller that twines Artificial Fibers cloth is equipped with in employing, is that 400rpm, operator's console translational speed are 3cm/ second at the roller rotating speed, and fine hair is clamp-oned under the condition that length is 0.4mm, and this overlay film is carried out grinding process.Above-mentioned liquid crystal orientation film coated substrate was washed in ultrapure water 1 minute, 100 ℃ cleaning oven inner dryings 10 minutes.Then, on each outer rim of the above-mentioned liquid crystal orientation film coated substrate of a pair of transparency electrode/transparent electrode substrate with liquid crystal orientation film, it is the epoxy adhesive of the alumina balls of 5.5 μ m that coating has added diameter, then, the liquid crystal aligning face is relatively overlapped and pressing, bonding agent is solidified.Then, (メ Le Network company makes, and MLC-6221), with the acrylic compounds Photocurable adhesive liquid crystal injecting port is sealed then, makes liquid crystal display cells to fill nematic crystal by liquid crystal injecting port between substrate.Voltage retention to the gained liquid crystal display cells is estimated.The voltage retention of the aligning agent for liquid crystal that obtains among the present invention shows the high numerical value more than 99%.In addition, carry out the print experiment, demonstrate good result.
Comparative example 1～2
With polyamic acid (B-2) and the N that makes in the polyimide (A-2) that makes in the synthesis example 1～2, the synthesis example 4, N, N ', N '-four glycidyl group-4, it is in the mixed solvent of principal ingredient that 4 '-diaminodiphenyl-methane is dissolved in the gamma-butyrolacton, making solids content concn and be 3.5% solution, is that the filtrator of 1 μ m filters with this solution with the aperture, modulates aligning agent for liquid crystal of the present invention.Adopt so each aligning agent for liquid crystal of modulation, on substrate surface, form overlay film similarly to Example 1, adopt the substrate manufacture liquid crystal display cells that forms this liquid crystal orientation film.Then, estimate voltage retention, print characteristic.The results are shown in table 1.
Comparative example 3
With the polyamic acid (B-2) that makes in the polyimide (A-1) that makes in the synthesis example 1, the synthesis example 4 with polyimide: it is in the mixed solvent of principal ingredient that the ratio of polyamic acid=20: 80 (weight ratio) is dissolved in the gamma-butyrolacton, with respect to 100 parts by weight polymer, dissolve 2 weight portion N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, make the solution that solids content concn is 3.5 weight %, is the filtrator filtration of 1 μ m with this solution with the aperture, modulates aligning agent for liquid crystal of the present invention.Adopt so aligning agent for liquid crystal of modulation, on substrate surface, form overlay film similarly to Example 1, adopt the substrate manufacture liquid crystal display cells that forms this liquid crystal orientation film.Then, estimate voltage retention, print characteristic.The results are shown in table 1.
Table 1
| Embodiment | Polymkeric substance | The imidizate rate | Epoxy compounds introducing amount * | Voltage retention | |
| 1 | A-1、B-1 | 53 | 2 | ＞99 | ○ |
| Comparative example | |||||
| 1 | A-2 | 100 | 2 | ＞99 | × |
| 2 | B-2 | 21 | 0 | ＜99 | × |
| 3 | A-1、B-2 | 53 | 2 | ＞99 | △ |
*Introducing amount (weight portion) with respect to 100 parts by weight polymer.
Claims (4)
1. aligning agent for liquid crystal, it is characterized in that comprising the polymkeric substance of the acid imide repetitive of amic acid repetitive with following formula (A) expression and following formula (B) expression, total amount with respect to the acid imide repetitive of the amic acid repetitive of formula (A) expression and formula (B) expression, the ratio of the amic acid repetitive of formula (A) expression is 50～90 weight %, and amic acid repetitive at least a portion of formula (A) expression is represented by following formula (A-1)
In the formula, P
1Be the organic group of 4 valencys, and Q
1Be the organic group of divalent,
In the formula, P
2Be the organic group of 4 valencys, and Q
2Be the organic group of divalent,
In the formula, P
0Be the aromatic group of 4 valencys, and R
01And R
02Be the organic group of hydrogen atom or 1 valency independently of each other.
2. the described aligning agent for liquid crystal of claim 1, the amic acid repetitive of its Chinese style (A-1) expression be by following formula (A-2) expression,
In the formula, R
01And R
02Definition and above-mentioned formula (A-1) in identical.
3. liquid crystal orientation film, it is formed by claim 1 or the described aligning agent for liquid crystal of claim 2.
4. a liquid crystal display cells is characterized in that having the liquid crystal orientation film that is formed by claim 1 or the described aligning agent for liquid crystal of claim 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006197124 | 2006-07-19 | ||
| JP2006197124 | 2006-07-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101109873A true CN101109873A (en) | 2008-01-23 |
Family
ID=39042005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101358292A Pending CN101109873A (en) | 2006-07-19 | 2007-07-16 | Liquid crystal aligning agent,liquid crystal aligning film and liquid crystal display device |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20080008273A (en) |
| CN (1) | CN101109873A (en) |
| TW (1) | TW200811552A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102165364A (en) * | 2008-07-25 | 2011-08-24 | 内莫普蒂公司 | Method for making bistable nematic liquid-crystal devices |
| CN102276835A (en) * | 2010-05-12 | 2011-12-14 | 奇美实业股份有限公司 | Treated polymer for liquid crystal aligning agent, and preparation method and application thereof |
| CN102453486A (en) * | 2010-10-26 | 2012-05-16 | 奇美实业股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| CN103459466A (en) * | 2011-03-30 | 2013-12-18 | 日东电工株式会社 | Polyimide, polyimide polymer electrolyte membrane, membrane-electrode assembly, and solid polymer fuel cell |
| CN103476832A (en) * | 2011-03-30 | 2013-12-25 | 日东电工株式会社 | Polyimide, polyimide polymer electrolyte membrane, membrane electrode assembly, and solid polymer fuel cell |
| CN109073935A (en) * | 2016-01-07 | 2018-12-21 | 日产化学工业株式会社 | Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal expression element using it |
| CN112457866A (en) * | 2020-10-29 | 2021-03-09 | 深圳清荷科技有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100943147B1 (en) * | 2007-12-21 | 2010-02-18 | 주식회사 엘지화학 | Composition for liquid crystal aligning, liquid crystal aligning film manufactured by the same, and liquid crystal display comprising the same |
-
2007
- 2007-07-16 CN CNA2007101358292A patent/CN101109873A/en active Pending
- 2007-07-18 KR KR1020070071640A patent/KR20080008273A/en not_active Application Discontinuation
- 2007-07-18 TW TW096126084A patent/TW200811552A/en unknown
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102165364A (en) * | 2008-07-25 | 2011-08-24 | 内莫普蒂公司 | Method for making bistable nematic liquid-crystal devices |
| CN102276835A (en) * | 2010-05-12 | 2011-12-14 | 奇美实业股份有限公司 | Treated polymer for liquid crystal aligning agent, and preparation method and application thereof |
| CN102276835B (en) * | 2010-05-12 | 2013-05-01 | 奇美实业股份有限公司 | Treated polymer for liquid crystal aligning agent, and preparation method and application thereof |
| CN102453486A (en) * | 2010-10-26 | 2012-05-16 | 奇美实业股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| CN103459466A (en) * | 2011-03-30 | 2013-12-18 | 日东电工株式会社 | Polyimide, polyimide polymer electrolyte membrane, membrane-electrode assembly, and solid polymer fuel cell |
| CN103476832A (en) * | 2011-03-30 | 2013-12-25 | 日东电工株式会社 | Polyimide, polyimide polymer electrolyte membrane, membrane electrode assembly, and solid polymer fuel cell |
| CN109073935A (en) * | 2016-01-07 | 2018-12-21 | 日产化学工业株式会社 | Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal expression element using it |
| CN109073935B (en) * | 2016-01-07 | 2021-06-25 | 日产化学工业株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same |
| CN112457866A (en) * | 2020-10-29 | 2021-03-09 | 深圳清荷科技有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN112457866B (en) * | 2020-10-29 | 2021-07-27 | 深圳清荷科技有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200811552A (en) | 2008-03-01 |
| KR20080008273A (en) | 2008-01-23 |
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