CN101114085A - 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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- CN101114085A CN101114085A CNA2007101376411A CN200710137641A CN101114085A CN 101114085 A CN101114085 A CN 101114085A CN A2007101376411 A CNA2007101376411 A CN A2007101376411A CN 200710137641 A CN200710137641 A CN 200710137641A CN 101114085 A CN101114085 A CN 101114085A
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
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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
Abstract
The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display device. The invention provides a liquid crystal aligning agent for forming the liquid crystal aligning film which can represent high pressure-retaining ratio and the print character of the liquid crystal film is excellent. The liquid crystal aligning agent includes the polyamic acid or its imine polymer and the diamine-compounds of diaminocarbazole, diaminofluorene, etc.
Description
Technical field
The present invention relates to aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells.More particularly, and though relate to constitute liquid crystal display cells type of electrodes how, all good aligning agent for liquid crystal of print characteristic, the liquid crystal orientation film that makes by this aligning agent for liquid crystal and liquid crystal display cells with this 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 and a kind ofly 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 containing the compound of polyamic acid and/or its imide amination polymer and following formula (1) expression,
Wherein, X is
Or
R
1～R
4Be the aliphatic group of hydrogen atom or 1 valency independently of each other, and R
5～R
7Be the organic group of hydrogen atom or 1 valency independently of each other.
Above-mentioned purpose of the present invention and advantage, the 2nd, reach by the liquid crystal orientation film that forms with aligning agent for liquid crystal of the present invention.
Above-mentioned purpose of the present invention and advantage, the 3rd, reach by 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 counter, 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 key diagram of box used in the print experiment.
Embodiment
Below, the present invention will be described in detail.
Aligning agent for liquid crystal of the present invention contains compound (below, be also referred to as " specific compound ") and polyamic acid and/or its imide amination polymer of above-mentioned formula (1) expression, preferably it is dissolved in the organic solvent.
[specific compound]
Specific compound is represented by above-mentioned formula (1).In the formula (1), X is
Or
When X is
The time, formula (1) is represented by following formula (1)-1.In addition, as X be
The time, formula (1) is represented by following formula (1)-2.
R
5, R
6And R
7Be the organic group of hydrogen atom or 1 valency independently of each other.As the organic group of 1 valency, can enumerate carbon number for example and be 1～12 alkyl, alkoxy, phenyl etc.They can be substituted, for example R
7It can also be alkyl with epoxy radicals.
In addition, R
1～R
4Be the aliphatic group of hydrogen atom or 1 valency independently of one another.As the aliphatic group of 1 valency, can enumerate carbon number for example and be 1～12 alkyl, cyclohexyl, carbon number and be 1～12 alkoxy, vinyl, allyl, glycidyl etc.
As specific compound, the compound of preferred following formula (1)-1 or (1)-2 expression.
Wherein, R
1～R
6Definition and above-mentioned formula (1) in identical.
Wherein, R
1～R
4, R
7Definition and above-mentioned formula (1) in identical.
Specific compound can use separately or more than 2 kinds together.
Specific compound can be synthesized as starting material by following listed diamine compound.
As diamine compound, can enumerate 2,8-diamido dibenzofurans, 2,8-diamido dibenzothiophene, 3,7-diamido-dibenzothiophene, 3,7-diamido-2,8-dimethyl-dibenzothiophene, 9,9-dimethyl-2,7-diamino-fluorene, 2,7-diamino-fluorene, 9,9-diphenyl-2,7-diamino-fluorene, 3,6-diamido carbazole, 9-methyl-3,6-diamido carbazole, 9-ethyl-3,6-diamido carbazole, 9-phenyl-3,6-diamido carbazole etc.
As the object lesson of specific compound, can enumerate N, N, N, N-tetrapropyl-2, the 7-diamino-fluorene, N, N, N, N-Fourth Ring hexyl-2,7-diamino-fluorene, N, N, N, N-tetraallyl-2,7-diamino-fluorene, N, N, N, N-methoxyl methyl-2,7-diamino-fluorene, N, N, N, N-four glycidyl group-2,7-diamino-fluorene, N, N, N, N-tetrapropyl-3,6-diamido carbazole, N, N, N, N-Fourth Ring hexyl-3,6-diamido carbazole, N, N, N, N-tetraallyl-3,6-diamido carbazole, N, N, N, N-methoxyl methyl-3,6-diamido carbazole, N, N, N, N-four glycidyl group-3,6-diamido carbazole etc.
In addition, specific compound can also contain the substitution product of 1～3 the hydrogen atom that has replaced above-claimed cpd except above-claimed cpd.
The proportioning of these specific compounds with respect to 100 weight parts of polyamide acid or polyimide fluidized polymer, is preferably below 40 weight portions, more preferably 0.1～30 weight portion.
Polymkeric substance
Used polyamic acid and its imide amination polymer among the present invention preferably have the repetitive of following formula (I-1) expression, repetitive or this two kinds of repetitives of following formula (I-2) expression respectively.For example, can enumerate polyamic acid and/or have imide amination polymer by this polyamic acid dehydration closed-loop (imidizate) resulting structures.In addition, " imide amination polymer " among the present invention both comprised the polymkeric substance of the whole imidizates of its repetitive, also comprised the polymkeric substance of part imidizate.And the part of imide ring can also be different imide ring.
Wherein, P
1For removing 4 valency organic groups of 2 anhydride groups from the tetrabasic carboxylic acid dicarboxylic anhydride, and Q
1For remove the divalent organic group of 2 amino from diamine compound.
Wherein, P
2For removing 4 valency organic groups of 2 anhydride groups from the tetrabasic carboxylic acid dicarboxylic anhydride, and Q
2For remove the divalent organic group of 2 amino from diamine compound.
Preferred polymkeric substance is to have the repetitive of above-mentioned formula (I-1) expression and the polymkeric substance of the repetitive that above-mentioned formula (I-2) is represented among the present invention.As aligning agent for liquid crystal, can enumerate the polymkeric substance of for example following (1)～(3) with this polymkeric substance.
(1) contains the aligning agent for liquid crystal of polyamic acid and imide amination polymer.
(2) contain the aligning agent for liquid crystal of the segmented copolymer that makes by prepolymer with amic acid structure and the prepolymer with imide structure.
(3) contain the aligning agent for liquid crystal of the imide amination polymer that makes polyamic acid partial dehydration closed loop gained.
Wherein, preferred (1) and (2), preferred (1) especially.
Polyamic acid
Polyamic acid used among the present invention can make by making tetrabasic carboxylic acid dicarboxylic anhydride and diamine reactant.
[tetrabasic carboxylic acid dicarboxylic anhydride]
As above-mentioned polyamic acid synthetic in used tetrabasic carboxylic acid dicarboxylic anhydride, for example, can enumerate the BTCA dicarboxylic anhydride, 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 3,5,6-three carboxyls norbornane-2-acetic acid dicarboxylic anhydride, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3 a, 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, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 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 separately;
(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);
The 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, 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 that following formula (1)～(4) are represented separately.They can a kind separately or be used in combination more than 2 kinds.
Wherein, from showing the angle of good liquid crystal aligning, preferred BTCA dicarboxylic anhydride, 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrofuran methylene)-and 3-methyl-3-cyclohexene-1,2-dicarboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-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-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 carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 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 of following formula (5)～(7) expression in the compound of 8-naphthalene tetracarboxylic acid dicarboxylic anhydride, above-mentioned formula (I) expression and the compound of above-mentioned formula (II) expression.As particularly preferred, can enumerate 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 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)-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)-naphthalene [1,2-c] furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8, the compound that 10-tetraketone, pyromellitic acid dicarboxylic anhydride and following formula (5) are represented separately.
[diamines]
As above-mentioned polyamic acid synthetic in used diamines, can enumerate for example p-phenylenediamine, between-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diamido diphenylethane, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formailide, 4,4 '-diaminodiphenyl ether, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 3,3 '-two (trifluoromethyl)-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 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogen anthracene, 2, the 7-diamino-fluorene, 9,9-dimethyl-2,7-diamino-fluorene, 9,9-two (4-aminophenyl) fluorenes, 4,4 '-methylene-two (2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamido-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 1,4,4 '-(right-the phenylene isopropylidene) diphenylamine, 4,4 '-(-the phenylene isopropylidene) diphenylamine, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-aromatic diamines such as octafluoro biphenyl;
1,1-m-xylene diamine, 1,3-propane diamine, butanediamine, pentanediamine, hexane diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 4,4-diamido heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene bicyclopentadiene diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0
2,7]-undecylene two methanediamines, 4,4 '-methylene two aliphatics and ester ring type diamines such as (cyclohexylamine);
2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamido-2,3-dicyano pyrazine, 5,6-diamido-2,4-dihydroxy-pyrimidine, 2,4-diamido-6-dimethylamino-1,3, the 5-triazine, 1,4-two (3-aminopropyl) piperazine, 2,4-diamido-6-isopropoxy-1,3, the 5-triazine, 2,4-diamido-6-methoxyl-1,3, the 5-triazine, 2,4-diamido-6-phenyl-1,3, the 5-triazine, 2,4-diamido-6-methyl-s-triazine, 2,4-diaminostilbene, 3, the 5-triazine, 4,6-diamido-2-vinyl-s-triazine, 2,4-diamido-5-phenyl thiazole, 2, the 6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3,5-diaminostilbene, 2, the 4-triazole, 6,9-diamido-2-ethoxy acridine lactate, 3,8-diamido-6-phenylphenanthridineand, 1,4-diamido piperazine, 3, the 6-proflavin, 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, N '-two (4-aminophenyl)-biphenylamine, the diamines that has the nitrogen-atoms beyond 2 primary amino radicals and this primary amino radical in the compound equimolecular of representing separately with following formula (III)～(VI);
(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 organic group of divalent).
(in the formula, X represents to be 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 can be the same or different);
Single-substituted two amines of following formula (V) expression; The diamido organosiloxane of following formula (VI) expression;
(in the formula, R
7Expression is selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R
8It is 6～30 alkyl that expression has the 1 valency organic group of group of the steroid backbone of being selected from, trifluoromethyl and fluorine or carbon number).
(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).
Can enumerate compound of representing separately following formula (9)～(13) etc.These diamines 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 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(right-the phenylene diisopropylidene) diphenylamine, 4,4 '-(-the phenylene diisopropylidene) diphenylamine, 1, the 4-cyclohexane diamine, 4,4 '-methylene two (cyclohexylamine), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, the compound 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)-biphenylamine, the compound of following formula (14) expression in the compound of above-mentioned formula (III) expression, dodecyloxy-2 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, the 4-diaminobenzene, pentadecane oxygen base-2, the 4-diaminobenzene, hexadecane oxygen base-2, the 4-diaminobenzene, dodecyloxy-2, the 5-diaminobenzene, pentadecane oxygen base-2, the 5-diaminobenzene, hexadecane oxygen base-2, the 5-diaminobenzene, octadecane oxygen base-2, the 5-diaminobenzene, the compound of following formula (16)～(23) expression.
[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 0.3～1.2 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, 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).
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, isobutyrone, isoamyl propionate, isoamyl isobutyrate, isoamyl 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, the reaction solution decompression distillation can be got polyamic acid by this precipitate of drying under reduced pressure or with evaporator.And, this polyamic acid is dissolved in the organic solvent once more, with poor solvent it is separated out then, perhaps use the evaporator decompression distillation, by carrying out once or this operation several times, can make with extra care polyamic acid.
Imide amination polymer
Imide amination polymer used among the present invention makes by the polyamic acid dehydration closed-loop that makes tetrabasic carboxylic acid dicarboxylic anhydride and diamine reactant gained.
[tetrabasic carboxylic acid dicarboxylic anhydride]
As above-mentioned imide amination polymer synthetic in used tetrabasic carboxylic acid dicarboxylic anhydride, can enumerate and the used identical compound of tetrabasic carboxylic acid dicarboxylic anhydride during above-mentioned polyamic acid is synthetic.
As imide amination polymer of the present invention synthetic in used tetrabasic carboxylic acid dicarboxylic anhydride, preferred ester ring type tetrabasic carboxylic acid dicarboxylic anhydride.As particularly preferred object lesson, can enumerate 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)-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, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8, the 10-tetraketone.In addition, can also be with ester ring type tetrabasic carboxylic acid dicarboxylic anhydride and other tetrabasic carboxylic acid dicarboxylic anhydride coupling.
[diamines]
As above-mentioned imide amination polymer synthetic in used diamines, can enumerate and the used identical diamines of diamines during above-mentioned polyamic acid is synthetic.
As imide amination polymer of the present invention synthetic in used diamines, the diamines of preferred above-mentioned formula (V) expression.As preferred object lesson, can enumerate dodecyloxy-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, hexadecane oxygen base-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2, the compound of 5-diaminobenzene, above-mentioned formula (16)～(23) expression.
In addition, in the imide amination polymer of the present invention, diamines and other diamines of all right above-mentioned formula of coupling (V) expression.As preferred compound in other diamines, can enumerate p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(right-the phenylene diisopropylidene) diphenylamine, 4,4 '-(-the phenylene diisopropylidene) diphenylamine, 1, the 4-cyclohexane diamine, 4,4 '-methylene two (cyclohexylamine), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, the compound 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, N, N '-two (4-aminophenyl)-biphenylamine, the compound of above-mentioned formula (14) expression in the compound of above-mentioned formula (III) expression, the compound of above-mentioned formula (15) expression in the compound of above-mentioned formula (IV) expression etc.
In imide amination polymer of the present invention, the diamines of above-mentioned formula (V) expression preferably uses more than the 0.5 weight % of whole diamines, especially preferably uses more than the 1 weight %.
[synthesizing of imide amination polymer]
The imide amination polymer that constitutes aligning agent for liquid crystal of the present invention is made by 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) polyamic acid is dissolved in the organic solvent, the method that adds dewatering agent and dehydration closed-loop catalyzer and heating as required in this solution is carried out.
In the method for above-mentioned (i) heating polyamic acid, temperature of reaction is preferably 50～200 ℃, more preferably 60～170 ℃.When 50 ℃ of temperature of reaction less thaies, then the dehydration closed-loop reaction can not be carried out fully, if temperature of reaction surpasses 200 ℃, the situation of the molecular weight and molecular weight of gained 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 with respect to the repetitive of 1 mole of polyamic acid, 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.
The polymkeric substance that used imide amination polymer among the present invention can also be the partial dehydration closed loop, the imidizate rate is low.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.The imidizate rate can be tried to achieve by following method.
[the imidizate rate assay method of imide amination polymer]
At room temperature, be dissolved in the deuterate dimethyl sulfoxide then, at room temperature measure as primary standard substance with tetramethylsilane with the imide amination polymer drying under reduced pressure
1H-NMR can try to achieve by the formula that following formula is (ii) represented.
Imidizate rate (%)=(1-A
1/ A
2* α) * 100------------is (ii)
A
1: the peak area (10ppm) that derives from the proton of NH group
A
2: the peak area that derives from other proton
α: with respect to other the individual percentage of proton of the proton of NH group in the precursor (polyamic acid) of 1 polymkeric substance.
End modified type polymkeric substance
Above-mentioned polyamic acid and imide amination polymer can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting.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 is used, in the time of 10% solution, preferred viscosities is the polymkeric substance of 20～800mPas, more preferably viscosity is the polymkeric substance of 30～500mPas.
In addition, it is the solution of certain solids content concn that the solution viscosity of polymkeric substance (mPas) adopts down certain solvent dilutions at 25 ℃, measures by E type rotational viscosimeter.
Aligning agent for liquid crystal
Aligning agent for liquid crystal of the present invention usually by with above-mentioned (A) polymkeric substance with (B) contain epoxy compounds and dissolve to be contained in the organic solvent and constitute.
Temperature when modulating 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 with as the illustrated identical solvent of the solvent that uses in the polyamic acid synthetic reaction.In addition, can also suitably select as can coupling when the polyamic acid synthetic reaction and 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.Be preferably the scope of 1～10 weight %.That is to say that aligning agent for liquid crystal of the present invention is coated on substrate surface, 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, be difficult to obtain good liquid crystal orientation film equally, and the viscosity of aligning agent for liquid crystal increases, coating characteristic variation.
In addition, the scope of particularly preferred solids content concn is coated on method difference used on the substrate and difference according to aligning agent for liquid crystal.For example, the occasion of spin-coating method, the scope of preferred especially 1.5～4.5 weight %.The occasion of print process, solids content concn are the scope of 3～9 weight %, thus the scope of the preferred especially 12～50mPas of solution viscosity.The occasion of ink-jet method, solids content concn are the scope of 1～5 weight %, thus the scope of the preferred especially 3～15mPas of solution viscosity.
Can enumerate the N-N-methyl-2-2-pyrrolidone N-as the particularly preferred organic solvent that aligning agent for liquid crystal of the present invention is used, 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, the ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl 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, isobutyrone (DIBK), isoamyl propionate, isoamyl isobutyrate, isoamyl ether etc.These can use separately, perhaps can mix use more than 2 kinds.
From improving the fusible angle of substrate surface is considered, can also be contained the compound of epoxy radicals in the aligning agent for liquid crystal of the present invention.As this compound that contains epoxy radicals, as preferably enumerating for example 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.The mixture ratio of their compound that contains epoxy radicals with respect to 100 parts by weight polymer, is preferably below 40 weight portions, more preferably below 30 weight portions.
Liquid crystal display cells
Liquid crystal display cells of the present invention can be by for example following method manufacturing.
(1) aligning agent for liquid crystal of the present invention preferably is coated on the substrate one side that is provided with the nesa coating that forms pattern by methods such as print processes, 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, ester ring type 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.After the aligning agent for liquid crystal coating, be purpose with the sagging grade of the alignment agent liquid that prevents to apply, preferred heating (preliminary drying) in advance, preferred 30～300 ℃ of preliminary drying temperature, more preferably 40～200 ℃, preferred especially 50～150 ℃ implemented.Then, remove solvent fully, so that the polyamic acid hot-imide is implemented roasting (heat baking) operation as purpose.Preferred 80～300 ℃ of this roasting (heat baking) temperature, more preferably 120～250 ℃.Like this, contain the aligning agent for liquid crystal of the present invention of polyamic acid, remove organic solvent by applying the back, formation is filmed as alignment films, can also make its dehydration closed-loop by further heating, forms filming of further imidizate.Formed thickness of filming is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) roller of fibrous cloth such as nylon, regenerated fiber, cotton carries out the grinding process that certain orientation rubs with for example being tied with to formed coated surface.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 opening as shown in the flat 5-107544 communique as the spy; carrying out the liquid crystal orientation film upper surface branch ground formation diaphragm that grinding process is crossed; with with after the direction that grinding process is different is before carried out grinding process; remove diaphragm; the processing that the liquid crystal aligning of liquid crystal orientation film can be changed can improve the 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, at the outside surface of liquid crystal cell, promptly constitute the polaroid of fitting on the another side of each substrate of liquid crystal cell, it is consistent or vertical to make its polarization direction and this substrate simultaneously go up the polishing direction of the liquid crystal orientation film that forms, and 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 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 right-last of the ten Heavenly stems oxygen base benzylidene-right-ferroelectric liquid crystals such as amino-2-methyl butyl cinnamate.
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.Imidizate rate, the voltage retention of imide amination polymer estimated by the following method in embodiment and the comparative example.
[the imidizate rate assay method of imide amination polymer]
At room temperature, be dissolved in the deuterate dimethyl sulfoxide then, at room temperature measure as primary standard substance with tetramethylsilane with the imide amination polymer drying under reduced pressure
1H-NMR can try to achieve by the formula that following formula is (ii) represented.
Imidizate rate (%)=(1-A
1/ A
2* α) * 100-----is (ii)
A
1: the peak area (10ppm) that derives from the proton of NH group
A
2: the peak area that derives from other proton
α: with respect to other the individual percentage of proton of the proton of NH group in the precursor (polyamic acid) of 1 polymkeric substance.
[solution viscosity]
It is the solution of certain solids content concn that the solution viscosity of polymkeric substance (mPas) adopts down certain solvent dilutions at 25 ℃, measures by E type rotational viscosimeter.
[voltage retention]
In 167 milliseconds time span, apply the voltage of 5V to liquid crystal display cells, application time is 60 microseconds, measures then from voltage and removes voltage retention after 167 milliseconds.The VHR-1 that determinator adopts (strain) bundle Yang テ Network ニ カ to make.
[print experiment]
Make the box that has the ITO electrode as shown in Figure 1.At room temperature apply 24 hours 6.0V DC voltage, apply 24 hours 0.5V DC voltage to electrode B to electrode A.After discharging stress, apply 0.1～5.0V DC voltage with the amplification 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), p-phenylenediamine 96g (0.89 mole) as diamine compound, two aminopropyl tetramethyl disiloxane 25g (0.10 mole), and 3,6-two (4-aminobenzoic acyl-oxygen base) cholestane 13g (0.020 mole), n-octadecane base amine 8.1g (0.030 mole) as monoamine is dissolved in the 960g N-N-methyl-2-2-pyrrolidone N-, and it was reacted 6 hours down at 60 ℃.The polyamic acid solution that obtains is separated on a small quantity, and adding NMP solids content concn is 10% measured in solution viscosity, is 60mPaS.Then, in the polyamic acid solution of gained, add the 2700gN-N-methyl-2-2-pyrrolidone N-again, add 396g pyridine and 409g acetic anhydride and 110 ℃ of following dehydration closed-loops 4 hours.After the imidization reaction, with new gamma-butyrolacton the solvent in the system is carried out solvent replacing (it is outer to be removed to system by this operation pyridine that imidization reaction is used, acetic anhydride), the imide amination polymer of the solution viscosity 16mPaS of (gamma-butyrolacton solution), imidizate rate about 95% when obtaining about 2000g solids content concn 15wt%, solids content concn 6.0% (it is as " polyimide (A-1) ") solution.
Synthesis example 2
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, and it was reacted 3 hours down at 40 ℃.The polyamic acid that to obtain about 3700g solution viscosity be 160mPaS (it is as " polyamic acid (B-1) ") solution.
Synthesis example 3
With 2,7-diamino-fluorene 10g (0.051 mole), epichlorokydrin 3.8g (0.041 mole), tetrahydrofuran 100ml, water 4.5ml mixed, 80 ℃ of following heated and stirred 4 hours.After making temperature of reaction drop to 60 ℃, drip the NaOH aqueous solution of 10g 50%.After the heated and stirred 4 hours, unreacted epichlorokydrin is removed in decompression distillation.Residue carries out the separatory washing with toluene, and distillation removes and desolvates, and obtains 13.9g target epoxy matrix (C-1).
Synthesis example 4
By in synthesis example 3 with 3,6-diamido carbazole 10.06g (0.051 mole) replaces 2, the 7-diamino-fluorene obtains 12.9g target epoxy matrix (C-2).
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), in this solution, dissolve 15 weight portion epoxy matrixes (C-1), make the solution that solids content concn is 3.5 weight % with respect to 100 parts by weight polymer.After fully stirring, be the filter filtration of 1 μ m with the aperture, modulate 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.The sander of the roller of the cloth that twines regenerated fiber 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.Ultrasonic cleaning is after 1 minute in ultrapure water with above-mentioned liquid crystal orientation film coated substrate, and drying is 10 minutes in 100 ℃ clean baking box.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 aligning agent for liquid crystal that obtains among the present invention, voltage retention shows the high numerical value more than 99%.In addition, carry out the print experiment, show good result.
Embodiment 2
Except replace epoxy matrix (C-1) with epoxy matrix (C-2), carry out similarly to Example 1.The results are shown in table 1.
Comparative example 1
Except not using epoxy matrix making liquid crystal display cells, carry out similarly to Example 1.Then, estimate voltage retention, print characteristic.The results are shown in table 1.
Table 1
| Embodiment | Epoxy matrix | Epoxy matrix introducing amount * | Voltage retention | |
| 1 | C-1 | 15 | ＞99 | Very |
| 2 | C-2 | 15 | ＞99 | Very |
| Comparative example | ||||
| 1 | Do not have | 0 | ＞99 | Difference |
*Introducing parts by weight with respect to 100 parts by weight polymer
Claims (5)
1. an aligning agent for liquid crystal is characterized in that containing the compound that polyamic acid and/or its imide amination polymer and following formula (1) are represented,
Wherein, X is
Or
R
1～R
4Be the aliphatic group of hydrogen atom or 1 valency independently of each other, and R
5～R
7Be 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 compound of wherein above-mentioned formula (1) expression be by following formula (1)-1 expression,
Wherein, R
1～R
6Definition and above-mentioned formula (1) in identical.
3. the described aligning agent for liquid crystal of claim 1, the compound of wherein above-mentioned formula (1) expression be by following formula (1)-2 expression,
Wherein, R
1～R
4And R
7Definition and above-mentioned formula (1) in identical.
4. liquid crystal orientation film, it is formed by each aligning agent for liquid crystal of claim 1～3.
5. liquid crystal display cells, it has the described liquid crystal orientation film of claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006206964 | 2006-07-28 | ||
| JP2006206964 | 2006-07-28 |
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| Publication Number | Publication Date |
|---|---|
| CN101114085A true CN101114085A (en) | 2008-01-30 |
Family
ID=39022506
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101376411A Pending CN101114085A (en) | 2006-07-28 | 2007-07-27 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20080011118A (en) |
| CN (1) | CN101114085A (en) |
| TW (1) | TW200811553A (en) |
Cited By (8)
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| CN105646260A (en) * | 2016-01-18 | 2016-06-08 | 吉林大学 | Diacid monomer containing diphenylamine-fluorene, preparation method and application thereof for preparing polyamide |
| CN109369613A (en) * | 2018-12-04 | 2019-02-22 | 中节能万润股份有限公司 | A kind of diamine compounds being used to prepare aligning agent for liquid crystal and its application |
| CN109456215A (en) * | 2016-01-12 | 2019-03-12 | 湖南工业大学 | Contain fluorenes or Fluorenone structure function diamine monomer and its synthetic method and application with high flatness |
| CN109880635A (en) * | 2019-03-19 | 2019-06-14 | 西安瑞立电子材料有限公司 | Contain dibenzofurans and oxygen heterocycle class liquid-crystal compounds and composition and application |
| CN110392725A (en) * | 2017-03-03 | 2019-10-29 | 罗利克技术有限公司 | Novel smooth orientation composition for pre-tilt angle in stabilizing solution crystal layer |
| CN112005164A (en) * | 2018-03-30 | 2020-11-27 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| 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 |
| CN113045755A (en) * | 2021-03-19 | 2021-06-29 | 深圳清荷科技有限公司 | Alignment film material, liquid crystal alignment 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
- 2007-07-27 KR KR1020070075685A patent/KR20080011118A/en not_active Application Discontinuation
- 2007-07-27 TW TW096127501A patent/TW200811553A/en unknown
- 2007-07-27 CN CNA2007101376411A patent/CN101114085A/en active Pending
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| CN109456215B (en) * | 2016-01-12 | 2021-10-01 | 湖南工业大学 | Functional diamine monomer with high planarity and containing fluorene or fluorenone structure as well as synthesis method and application thereof |
| CN109456215A (en) * | 2016-01-12 | 2019-03-12 | 湖南工业大学 | Contain fluorenes or Fluorenone structure function diamine monomer and its synthetic method and application with high flatness |
| CN105646260A (en) * | 2016-01-18 | 2016-06-08 | 吉林大学 | Diacid monomer containing diphenylamine-fluorene, preparation method and application thereof for preparing polyamide |
| CN110392725A (en) * | 2017-03-03 | 2019-10-29 | 罗利克技术有限公司 | Novel smooth orientation composition for pre-tilt angle in stabilizing solution crystal layer |
| CN110392725B (en) * | 2017-03-03 | 2023-12-01 | 罗利克技术有限公司 | Photoalignment composition for stabilizing pretilt angle in liquid crystal layer |
| CN112005164A (en) * | 2018-03-30 | 2020-11-27 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN112005164B (en) * | 2018-03-30 | 2023-09-12 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN109369613A (en) * | 2018-12-04 | 2019-02-22 | 中节能万润股份有限公司 | A kind of diamine compounds being used to prepare aligning agent for liquid crystal and its application |
| CN109880635A (en) * | 2019-03-19 | 2019-06-14 | 西安瑞立电子材料有限公司 | Contain dibenzofurans and oxygen heterocycle class liquid-crystal compounds and composition and application |
| 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 |
| 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 |
| CN113045755B (en) * | 2021-03-19 | 2023-03-17 | 深圳清荷科技有限公司 | Alignment film material, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| CN113045755A (en) * | 2021-03-19 | 2021-06-29 | 深圳清荷科技有限公司 | Alignment film material, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080011118A (en) | 2008-01-31 |
| TW200811553A (en) | 2008-03-01 |
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