CN103361081B - Crystal aligning agent, liquid crystal orienting film, liquid crystal display device, polymkeric substance and compound - Google Patents

Crystal aligning agent, liquid crystal orienting film, liquid crystal display device, polymkeric substance and compound Download PDF

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CN103361081B
CN103361081B CN201310102105.3A CN201310102105A CN103361081B CN 103361081 B CN103361081 B CN 103361081B CN 201310102105 A CN201310102105 A CN 201310102105A CN 103361081 B CN103361081 B CN 103361081B
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liquid crystal
aligning agent
polymkeric substance
compound
crystal aligning
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CN103361081A (en
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秋池利之
内山克博
菅野尚基
野口峻一
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JSR Corp
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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    • 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
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Abstract

The invention provides a kind of crystal aligning agent, liquid crystal orienting film, liquid crystal display device, polymkeric substance and compound, this crystal aligning agent can show excellent LCD alignment and photostabilization, and can form the film good to the separability of substrate.Crystal aligning agent of the present invention comprise to be selected from by polyamic acid, poly amic acid ester, polyimide and organopolysiloxane form at least one polymkeric substance in cohort, and the polymkeric substance (P1) containing the group had represented by following formula (0) is as this polymkeric substance.

Description

Crystal aligning agent, liquid crystal orienting film, liquid crystal display device, polymkeric substance and compound
Technical field
The present invention relates to a kind of crystal aligning agent, liquid crystal orienting film, liquid crystal display device, polymkeric substance and compound, particularly relate to a kind of crystal aligning agent etc. that can be suitable for manufacturing vertical orientation type liquid crystal display device.
Background technology
In the past, liquid crystal display device has developed the different multiple type of drive such as electrode structure or physical property of liquid crystal molecule of using, such as there will be a known twisted nematic (twistednematic, TN) type or STN Super TN (supertwistednematic, STN) type, vertical orientation (verticalalignment, VA) type, many quadrants vertical orientation (multi-domainverticalalignment, MVA) type, coplanar switching (in-planeswitching, IPS) type, fringing field switches (fringefieldswitching, FFS) type, optical compensation curved (opticallycompensatedbend, OCB) the various liquid crystal display device such as type.These liquid crystal display device have the liquid crystal orienting film for making liquid crystal alignment.The material of liquid crystal orienting film uses the polymkeric substance such as polyamic acid (polyamicacid), polyimide (polyimide), poly amic acid ester (polyamicacidester), polyester (polyester), organopolysiloxane (polyorganosiloxane), wherein, with regard to thermotolerance, physical strength, the aspect good with the various characteristic such as the affinity of liquid crystal, usually use polyamic acid or polyimide.
To liquid crystal orienting film require characteristic can enumerate can show corresponding with type of drive needed for tilt angle as one of its characteristic, such as when being applied to the vertical orientation type liquid crystal display device of VA type or MVA type etc., requirement can show high tilt angle (such as the tilt angle of more than 87 degree).In addition, liquid crystal orienting film was utilized to have to the method proposition controlling the orientation of liquid crystal molecule in the past: the side chain of component of polymer contained in crystal aligning agent imports chain alkyl or steroid skeleton, or import the multiple structure (for example, referring to patent documentation 1 ~ patent documentation 3) linked of the cyclic group such as phenylene or cyclohexyl.
But in recent years, liquid crystal display device is used for the small-sized display terminal such as PC (personalcomputer) not only as beforely, and for the large-scale display unit such as the LCD TV of such as large picture or information display.In addition, due to the expansion of purposes, maximize with substrate, liquid crystal drop under type (instil (OneDropFill, ODF) mode) as liquid crystal display device manufacturing technology and receive publicity.ODF mode is by liquid crystal molecule that the wherein one piece of substrate in a pair substrate being formed with liquid crystal orienting film drips, another block substrate of fitting in a vacuum, thus on whole of panel the method for filling liquid crystal molecule.According to the method, compared with the vacuum injection mode used in the past, there is the advantage that significantly can shorten the processing time of liquid crystal filling step.
[prior art document]
[patent documentation]
No. 2008/117759th, [patent documentation 1] International Publication
No. 2008/117760th, [patent documentation 2] International Publication
[patent documentation 3] Japanese Patent Laid-Open 2001-305549 publication
In ODF mode, there is above-mentioned advantage, but then, when manufacturing vertical orientation type liquid crystal display device, there is easily generation and being called that the display of " ODF is uneven " is uneven, causing the situation that the display quality of liquid crystal display device declines.A reason of this display inequality is considered to the orientation performance deficiency of the liquid crystal molecule being to utilize liquid crystal orienting film.Therefore, in order to also make the display quality of liquid crystal display device good when adopting ODF mode, and requirement can show the liquid crystal orienting film of the more excellent LCD alignment of liquid crystal orienting film than before.
In addition, in the manufacturing step of liquid crystal orienting film, have at use crystal aligning agent and be formed at the situation film on substrate producing pin hole (pinhole) or the unequal defect of film.Film produces defect, there is release coated film from substrate and situation about being recycled by substrate, but in this reprocessing, requirement can easily from release coated film substrate (separability be good).
In addition, the operation principles of various liquid crystal display device roughly divides into penetrating type and reflection-type.Wherein, in penetrating type liquid crystal display device, show, so liquid crystal orienting film can be exposed in the light from back light for a long time owing to utilizing the back light from the element back side.On the other hand, in reflection type liquid crystal display element, owing to not using backlight light source, but utilize sunlight etc. to show from the reflected light of the light of outside, so there is the advantage that power consumption is few compared with penetrating type liquid crystal display device, can be exposed to but then in strong ultraviolet.Therefore, photostabilization all excellent under any one operation principles is required in liquid crystal display device.
Summary of the invention
The present invention is formed in view of above-mentioned problem, and main purpose is to provide a kind of crystal aligning agent, and it can show excellent LCD alignment, and can be formed the separability of substrate and the good film of photostabilization.In addition, another object of the present invention is to provide and a kind ofly has excellent LCD alignment, photostabilization and to the liquid crystal orienting film of the good separability of substrate and the liquid crystal display device comprising this liquid crystal orienting film concurrently.
The present inventors carry out active research to reach the problem of prior art as above, found that by solving above-mentioned problem containing polymkeric substance side chain with ad hoc structure at least partially as polymkeric substance contained in crystal aligning agent, thus complete the present invention.Specifically, following crystal aligning agent, liquid crystal orienting film and liquid crystal display device is provided by the present invention and for the manufacture of their compound and polymkeric substance.
An aspect of of the present present invention is to provide a kind of crystal aligning agent, its comprise to be selected from by polyamic acid, poly amic acid ester, polyimide and organopolysiloxane form at least one polymkeric substance in cohort, and the polymkeric substance (P1) containing the group had represented by following formula (0) is as above-mentioned polymkeric substance.
[changing 1]
(in formula (0), Ac 1and Ac 2be separately cyclohexane ring or phenyl ring, these rings can have substituting group; R 1for the alkyl of hydrogen atom or carbon number 1 ~ 20; X is Sauerstoffatom ,+-CO-O-,+-O-CO-,+-O-CH 2-,+-CH 2-O-,+-CO-S-,+-S-CO-,+-CONH-or+-NHCO-(wherein, "+" represents the associative key with phenylene); n 1be 1 or 2, n 2be 0 or 1; Wherein, at n 1when being 2, multiple Ac 1separately there is above-mentioned definition; M is the integer of 1 ~ 3; " * " represents associative key.)
According to crystal aligning agent of the present invention, by containing above-mentioned polymkeric substance (P1) as component of polymer at least partially, the liquid crystal orienting film that can show excellent LCD alignment can be formed.In addition, according to crystal aligning agent of the present invention, can be formed and can easily peel off and the good liquid crystal orienting film of photostabilization from substrate.
In crystal aligning agent of the present invention, polymkeric substance (P1) to be preferably selected from by polyamic acid, poly amic acid ester and polyimide form at least one in cohort, this polyamic acid, poly amic acid ester and polyimide be to make to be selected from by tetracarboxylic dianhydride and tetracarboxylic acid diester compound form at least one compound in cohort, carry out reacting with the diamines of the compound comprised represented by following formula (1) and obtain.By making the diamines of the group had represented by above-mentioned formula (0), reacting with tetracarboxylic dianhydride, polymkeric substance side chain with the group represented by above-mentioned formula (0) can be synthesized with comparalive ease.
[changing 2]
(in formula (1), Ac 1, Ac 2, R 1, X, n 1, n 2, n 1and m is identical with above-mentioned formula (0) implication.)
In crystal aligning agent of the present invention, polymkeric substance (P1) is preferably said n 1with said n 2and be 2 or 3, be more preferably said n 1with said n 2and be 2.In addition, above-mentioned X is preferably Sauerstoffatom ,+-COO-or+-O-CO-(wherein, "+" represents the associative key with phenylene).In this case, the voltage retention of liquid crystal display device can be improved further.
Another aspect of the present invention is to provide and a kind ofly uses above-mentioned described crystal aligning agent and the liquid crystal orienting film that formed.And then another aspect of the present invention is to provide a kind of liquid crystal display device comprising above-mentioned liquid crystal orienting film.
Other aspects of the present invention are to provide a kind of polymkeric substance, this polymkeric substance be to make to be selected from by tetracarboxylic dianhydride and tetracarboxylic acid diester compound form at least one compound in cohort, carry out reacting with the diamines of the compound comprised represented by above-mentioned formula (1) and obtain.In addition, the invention provides the compound represented by above-mentioned formula (1).
Embodiment
Below, crystal aligning agent of the present invention is described in detail.
< crystal aligning agent >
Crystal aligning agent of the present invention contain to be selected from by polyamic acid, poly amic acid ester, polyimide and organopolysiloxane form at least one polymkeric substance in cohort as component of polymer.In addition, the polymkeric substance (P1) of the group had represented by following formula (0) is especially comprised as this polymkeric substance.
[changing 3]
(in formula (0), Ac 1, Ac 2, R 1, X, n 1, n 2, n 1, m and " * " identical with above-mentioned implication.)
In above-mentioned formula (0), R 1in the alkyl of carbon number 1 ~ 20 can be straight-chain, also can be branch-like, specifically, include, for example: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base etc.
As R 1, be wherein preferably the straight-chain alkyl of carbon number 3 ~ 12, be more preferably the straight-chain alkyl of carbon number 3 ~ 7.
With regard to can improving the aspect of the voltage retention of liquid crystal display device, X is preferably Sauerstoffatom ,+-CO-O-or+-O-CO-, is particularly preferably Sauerstoffatom.
Ac 1and Ac 2can cyclohexane ring be, also can be phenyl ring, or also can be the combination of cyclohexane ring and phenyl ring.Wherein, with regard to LCD alignment or to regard to the viewpoints such as the solvability of solvent, Ac is preferably 1and Ac 2be cyclohexane ring.In addition, at Ac 1and Ac 2when for cyclohexane ring, the Sys-trans isomerism of Isosorbide-5-Nitrae-cyclohexylidene (Isosorbide-5-Nitrae-cyclohexylene) is preferably trans-isomer(ide) respectively.
Ac 1and Ac 2substituting group can be had respectively.This substituting group include, for example: the halogen atoms such as fluorine atom, chlorine atom, bromine atoms, atomic iodine, or the alkyl of carbon number 1 ~ 5, fluoroalkyl or alkoxyl group, hydroxyl, cyano group, nitro etc.
As n 1and n 2if, n 1be 1 or 2 and n 2be 0 or 1, then its combination is not particularly limited.Wherein, n is preferably 1with n 2and (n 1+ n 2) be 2 or 3, be more preferably (n 1+ n 2) be 2.That is, n 1and n 2combination be preferably n 1=1 and n 2=2, n 1=1 and n 2=1 or n 1=2 and n 2=0, be more preferably n 1=1 and n 2=1 or n 1=2 and n 2=0.
Group represented by above-mentioned formula (0) is at ring Ac 1with ring Ac 2between there is the alkylidene group (alkylene) of carbon number 2,4 or 6.On the side chain of polymkeric substance, by ring Ac 1with ring Ac 2between (at n 2at ring Ac when=0 1and between phenyl ring) there is this alkylidene group, and can improve further the regiospecific of the liquid crystal molecule of liquid crystal orienting film in preferred.This alkylidene group is preferably the alkylidene group of carbon number 2 or 4, is particularly preferably the alkylidene group of carbon number 2.
The concrete example of the group represented by above-mentioned formula (0) include, for example the group etc. represented by following formula (0-1) ~ formula (0-10) difference, in these groups, be preferably the group represented by following formula (0-1) ~ formula (0-6) difference.
[changing 4]
(in formula, R 1and " * " is identical with above-mentioned formula (0) implication.)
< polymkeric substance (P1): polyamic acid >
One of polymkeric substance of the present invention (P1) can enumerate the polyamic acid of the group had represented by above-mentioned formula (0).This polyamic acid such as can utilize following methods to obtain: [I] makes the tetracarboxylic dianhydride of the group had represented by above-mentioned formula (0), carries out the method for reacting with diamines; [II] makes tetracarboxylic dianhydride, carries out the method for reacting with the diamines of group had represented by above-mentioned formula (0).In these methods, with regard to aspect easy to manufacture, be preferably using method [II].Below, to the polyamic acid of the group had represented by above-mentioned formula (0), enumerate the situation that using method [II] synthesizes and be described as an example.
[tetracarboxylic dianhydride]
Tetracarboxylic dianhydride for the synthesis of polyamic acid of the present invention include, for example: aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.The concrete example of these tetracarboxylic dianhydrides can be enumerated respectively:
Aliphatics tetracarboxylic dianhydride include, for example: 1,2,3,4-butane tetracarboxylic acid dianhydride (1,2,3,4-butanetetracarboxylicdianhydride) etc.;
Ester ring type tetracarboxylic dianhydride include, for example: 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride (1, 2, 3, 4-cyclobutanetetracarboxylicdianhydride), 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride (2, 3, 5-tricarboxycyclopentylaceticdianhydride), 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone (1, 3, 3a, 4, 5, 9b-hexahydro-5-(tetrahydro-2, 5-dioxo-3-furanyl)-naphtho [1, 2-c] furan-1, 3-dione), 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone (1, 3, 3a, 4, 5, 9b-hexahydro-8-methyl-5-(tetrahydro-2, 5-dioxo-3-furanyl)-naphtho [1, 2-c] furan-1, 3-dione), 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-volution-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone) (3-oxabicyclo [3.2.1] octane-2, 4-dione-6-spiro-3 '-(tetrahydrofuran-2 ', 5 '-dione)), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride (5-(2, 5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1, 2-dicarboxylicanhydride), 3, 5, 6-tri-carboxyl-2-carboxymethyl group norcamphane-2:3, 5:6-dianhydride (3, 5, 6-tricarboxy-2-carboxymethylnorbornane-2:3, 5:6-dianhydride), 2, 4, 6, 8-tetracarboxylic dicyclo [3.3.0] octane-2:4, 6:8-dianhydride (2, 4, 6, 8-tetracarboxybicyclo [3.3.0] octane-2:4, 6:8-dianhydride), 4, 9-dioxa three ring [5.3.1.0 2,6] undecane-3,5,8,10-tetraketone 4,9-dioxatricyclo [5.3.1.0 2,6] undecane-3,5,8,10-tetraone), cyclopentanetetracarboxylic's dianhydride cyclohexanetetracarboxylicdianhydride) etc.,
Aromatic tetracarboxylic acid's dianhydride include, for example: pyromellitic acid anhydride (pyromelliticdianhydride) etc.;
In addition, the tetracarboxylic dianhydride etc. described in Japanese Patent Laid-Open 2010-97188 publication can be used.In addition, above-mentioned tetracarboxylic dianhydride can be used alone a kind or two or more combinationally used.
With regard to regard to the solvability of solvent or the good aspect of the transparency, the tetracarboxylic dianhydride for the synthesis of polyamic acid preferably comprises ester ring type tetracarboxylic dianhydride person.Wherein, being more preferably to comprise is selected from by 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 2, 4, 6, 8-tetracarboxylic dicyclo [3.3.0] octane-2:4, 6:8-dianhydride and 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride form at least one (hereinafter also referred to " specific tetracarboxylic dianhydride ") in cohort, especially preferably comprise and be selected from by 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 2, 4, 6, 8-tetracarboxylic dicyclo [3.3.0] octane-2:4, 6:8-dianhydride and 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride form at least one in cohort.
Tetracarboxylic dianhydride for the synthesis of polyamic acid be preferably relative to for the synthesis of tetracarboxylic dianhydride total amount and comprise the above-mentioned specific tetracarboxylic dianhydride person of more than 20 % by mole, be more preferably and comprise more than 50 % by mole, especially preferably comprise more than 80 % by mole.
[diamines]
Specific diamines (D)
Diamines for the synthesis of polyamic acid of the present invention comprises the diamines (hereinafter also referred to specific diamines (D)) of the group had represented by above-mentioned formula (0).Specific diamines (D) can be any one in aliphatie diamine, ester ring type diamines, aromatic diamine, diamino organo-siloxane etc.Specific diamines (D) is preferably aromatic diamine wherein, specifically can enumerate the compound represented by following formula (1).
[changing 5]
(in formula (1), Ac 1, Ac 2, R 1, X, n 1, n 2and m is identical with above-mentioned formula (0) implication.)
In formula (1), Ac 1, Ac 2, R 1, X, n 1, n 2and m preferred concrete example separately directly can apply the explanation of above-mentioned formula (0).
2 one-level amino in diamino-phenyl are preferably positioned at 2,4-position or 3,5-position relative to X.Which one in these binding sites more preferably, according to being incorporated into the kind of the X on diamino-phenyl and different, such as when X is Sauerstoffatom, preferably be positioned at 2 relative to X, 4-position or 3,5-position, when X is "+-O-CO-" or "+-CO-O-", preferably be positioned at 3,5-position relative to X.
The concrete example of above-mentioned specific diamines (D) include, for example the compound etc. represented by following formula (1-1) ~ formula (1-10) difference.
[changing 6]
(in formula, R 1identical with above-mentioned formula (0) implication.)
Above-mentioned specific diamines (D) is preferably the compound represented by above-mentioned formula (1-1) ~ formula (1-6) difference in these compounds, is more preferably the compound represented by above-mentioned formula (1-1) ~ formula (1-4) difference.
The synthesis of specific diamines
Above-mentioned specific diamines (D) can by synthesizing appropriately combined for vitochemical ordinary method.As one example, such as, there is by synthesis the dinitrobenzene of the group represented by above-mentioned formula (0), then use suitable restoring system, the nitro of the dinitro matrix of gained is carried out hydrogenation, form amino and synthesize.
Herein, such as when " X " is for Sauerstoffatom, above-mentioned dinitro matrix, by under the alkali existence such as such as sodium bicarbonate, salt of wormwood, Quilonum Retard, makes corresponding cyclohexyl phenol class, carries out reacting to synthesize with the halogenide containing dinitrobenzene such as dinitrochlorobenzene or dinitrofluorobenzene.Or also can by the presence of a base, make the corresponding halogenide with alkyl based structures, carry out reacting to synthesize with the hydroxy derivatives containing dinitrobenzene such as dinitrophenol(DNP).
Be "+-O-CH at " X " 2-" when, by the presence of a base, make corresponding cyclohexyl phenol class, carry out reacting to synthesize with the halogenide containing dinitrobenzene such as dinitrobenzene benzyl chlorine (dinitrobenzylchloride).
Be "+-CH at " X " 2-O-" when, by the presence of a base, make the corresponding halogenide with alkyl based structures, carry out reacting to synthesize with the hydroxy derivatives containing dinitrobenzene such as dinitrophenol(DNP).
When " X " is "+-O-CO-", by under the existence of the suitable alkali such as such as triethylamine, make corresponding cyclohexyl phenol class, carry out reacting to synthesize with the carboxylic acid halide containing dinitrobenzene such as dinitrobenzoyl chloride (dinitrobenzoylchloride) or dinitro benzoyl bromine (dinitrobenzoylbromide).
When " X " is "+-CO-O-", by under the existence of suitable alkali, make the corresponding carboxylic acid halide with alkyl based structures, carry out reacting to synthesize with the hydroxy derivatives containing dinitrobenzene such as dinitrophenol(DNP).
When " X " is "+-S-CO-", by under the existence of the suitable alkali such as such as triethylamine, make the corresponding mercaptan compound with alkyl based structures, carry out reacting to synthesize with the carboxylic acid halide containing dinitrobenzene such as dinitrobenzoyl chloride.
When " X " is "+-CO-S-", by under the existence of suitable alkali, make the corresponding carboxylic acid halide with alkyl based structures, carry out reacting to synthesize with the thiol derivative containing dinitrobenzene such as dinitrobenzene thiophenol (dinitrothiophenol).
When " X " is "+-NHCO-", by under the existence of suitable alkali, make the corresponding amino substituents with alkyl based structures, carry out reacting to synthesize with the carboxylic acid halide containing dinitrobenzene such as dinitrobenzoyl chloride.
When " X " is "+-CONH-", by under the existence of suitable alkali, make the corresponding carboxylic acid halide with alkyl based structures, replace body with dinitraniline etc. containing the amino of dinitrobenzene and carry out reacting to synthesize.
Reaction for obtaining above-mentioned dinitro matrix is preferably carried out in organic solvent.Temperature of reaction is now preferably-20 DEG C ~ 180 DEG C, is more preferably 0 DEG C ~ 120 DEG C.In addition, the reaction times is preferably 0.1 hour ~ 24 hours, is more preferably 0.5 hour ~ 12 hours.Normally used compound when organic solvent can use substitution reaction, specifically, include, for example: alcohol, tetrahydrofuran (THF), toluene, dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE, 1-Methyl-2-Pyrrolidone etc.
The reduction reaction of above-mentioned dinitro matrix can in organic solvent, such as, use zinc, aluminium hydroxide lithium, palladium catalyst-hydrogen system etc. to implement.Normally used compound when organic solvent can use reduction reaction, specifically, include, for example tetrahydrofuran (THF), alcohol etc.Temperature of reaction is preferably-20 DEG C ~ 180 DEG C, is more preferably 10 DEG C ~ 120 DEG C.In addition, the reaction times, for being preferably 0.1 hour ~ 72 hours, is more preferably 0.5 hour ~ 48 hours.But the synthetic method of specific diamines (D) is not limited to aforesaid method.
Other diamines
The diamines used to synthesize polyamic acid of the present invention only can use above-mentioned specific diamines (D), also other diamines and specific diamines (D) can be used simultaneously.
Other diamines spendable include, for example aliphatie diamine, ester ring type diamines, aromatic diamine, diamino organo-siloxane etc. herein.The concrete example of these diamines can be enumerated respectively: aliphatie diamine include, for example: m-xylene diamine (metaxylylenediamine), 1,3-propylene diamine (1,3-propanediamine), tetramethylene-diamine (tetramethylenediamine), five methylene diamine (pentamethylenediamine), hexamethylene-diamine (hexamethylenediamine) etc.;
Ester ring type diamines include, for example: 1,4-diamino-cyclohexane (1,4-diaminocyclohexane), 4,4 '-methylene-bis (hexahydroaniline) (4,4 '-methylenebis (cyclohexylamine)), 1, two (amino methyl) hexanaphthenes (1,3-bis (aminomethyl) cyclohexane) of 3-etc.;
Aromatic diamine include, for example: Ursol D (p-phenylenediamine), 4, 4 '-diaminodiphenyl-methane (4, 4 '-diaminodiphenylmethane), 4, 4 '-diaminodiphenyl sulfide (4, 4 '-diaminodiphenylsulfide), 1, 5-diaminonaphthalene (1, 5-diaminonaphthalene), 2, 2 '-dimethyl-4, 4 '-benzidine (2, 2 '-dimethyl-4, 4 '-diaminobiphenyl), 2, 2 '-bis-(trifluoromethyl)-4, 4 '-benzidine (2, 2 '-bis (trifluoromethyl)-4, 4 '-diaminobipenyl), 2, 7-diamino-fluorene (2, 7-diaminofluorene), 4, 4 '-diaminodiphenyl oxide (4, 4 '-diaminodiphenylether), 2, two [4-(4-amino-benzene oxygen) phenyl] propane (2 of 2-, 2-bis [4-(4-aminophenoxy) phenyl] propane), 9, two (4-aminophenyl) fluorenes 9 of 9-, 9-bis (4-aminophenyl) fluorene), 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa (2 of 2-, 2-bis [4-(4-aminophenoxy) phenyl] hexafluoropropane), 2, two (4-aminophenyl) HFC-236fa (2 of 2-, 2-bis (4-aminophenyl) hexafluoropropane), 4, 4 '-(to phenylene diisopropylidene) dianiline (4, 4 '-(p-phenylenediisopropylidene) bisaniline), 4, 4 '-(metaphenylene diisopropylidene) dianiline (4, 4 '-(m-phenylenediisopropylidene) bisaniline), 1, two (4-amino-benzene oxygen) benzene (1 of 4-, 4-bis (4-aminophenoxy) benzene), 4, 4 '-bis-(4-amino-benzene oxygen) biphenyl (1, 4-bis (4-aminophenoxy) biphenyl), 2, 6-diamino-pyridine (2, 6-diaminopyridine), 3, 4-diamino-pyridine (3, 4-diaminopyridine), 2, 4-di-amino-pyrimidine (2, 4-diaminopyrimidine), 3, 6-proflavin (3, 6-diaminoacridine), 3, 6-diaminocarbazole (3, 6-diaminocarbazole), N-methyl-3, 6-diaminocarbazole (N-methyl-3, 6-diaminocarbazole), N-ethyl-3, 6-diaminocarbazole (N-ethyl-3, 6-diaminocarbazole), N-phenyl-3, 6-diaminocarbazole (N-phenyl-3, 6-diaminocarbazole), N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl (N, N '-bis (4-aminophenyl)-benzidine), N, N '-bis-(4-aminophenyl)-N, N '-tolidine (N, N '-bis (4-aminophenyl)-N, N '-dimethylbenzidine), 1, 4-pair-(4-aminophenyl)-piperazine (1, 4-bis-(4-aminophenyl)-piperazine), 1-(4-aminophenyl)-2, 3-dihydro-1, 3, 3-trimethylammonium-1H-indenes-5-amine (1-(4-aminophenyl)-2, 3-dihydro-1, 3, 3-trimethyl-1H-indene-5-amine), 1-(4-aminophenyl)-2, 3-dihydro-1, 3, 3-trimethylammonium-1H-indenes-6-amine (1-(4-aminophenyl)-2, 3-dihydro-1, 3, 3-trimethyl-1H-indene-6-amine), 3, 5-diaminobenzoic acid (3, 5-diaminobenzoicacid), cholestane base oxygen base-3, 5-diaminobenzene (cholestanyloxy-3, 5-diaminobenzene), cholesteryl oxygen base-3, 5-diaminobenzene (cholestenyloxy-3, 5-diaminobenzene), cholestane base oxygen base-2, 4-diaminobenzene (cholestanyloxy-2, 4-diaminobenzene), cholesteryl oxygen base-2, 4-diaminobenzene (cholestenyloxy-2, 4-diaminobenzene), 3, 5-diaminobenzoic acid cholestane base ester (cholestanyl3, 5-diaminobenzoate), 3, 5-diaminobenzoic acid cholesteryl ester (cholestenyl3, 5-diaminobenzoate), 3, 5-diaminobenzoic acid lanostane base ester (lanostanyl3, 5-diaminobenzoate), 3, two (the 4-aminobenzoic acyl-oxygen base) cholestane (3 of 6-, 6-bis (4-aminobenzoyloxy) cholestane), 3, two (4-amino-benzene oxygen) cholestane (3 of 6-, 6-bis (4-aminophenoxy) cholestane), 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3, 5-diaminobenzoic acid ester (4-(4 '-trifluoromethoxybenzoyloxy) cyclohexyl-3, 5-diaminobenzoate), 4-(4 '-trifluoromethylbenzoyl oxygen base) cyclohexyl-3, 5-diaminobenzoic acid ester (4-(4 '-trifluoromethylbenzoyloxy) cyclohexyl-3, 5-diaminobenzoate), 1, two (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexane (1 of 1-, 1-bis (4-((aminophenyl) methyl) phenyl)-4-butylcyclohexane), 1, two (4-((aminophenyl) methyl) the phenyl)-4-heptylcyclohexane (1 of 1-, 1-bis (4-((aminophenyl) methyl) phenyl)-4-heptylcyclohexane), 1, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptylcyclohexane (1 of 1-, 1-bis (4-((aminophenoxy) methyl) phenyl)-4-heptylcyclohexane), 1, two (4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) hexanaphthene (1 of 1-, 1-bis (4-((aminophenyl) methyl) phenyl)-4-(4-heptylcyclohexyl) cyclohexane), 2, 4-diamino-N, N-diallyl aniline (2, 4-diamino-N, N-diallylaniline), 4-aminobenzyl amine (4-aminobenzylamine), 3-aminobenzyl amine (3-aminobenzylamine), and following formula (A-1)
[changing 7]
(in formula, X iand X iIbe respectively singly-bound ,-O-,-COO-or-OCO-, R ifor alkane two base of carbon number 1 ~ 3, a be 0 or 1, b be the integer of 0 ~ 2, c is the integer of 1 ~ 20, and n is 0 or 1; Wherein, a and b can not be 0 simultaneously)
Represented compound etc.;
Diamino organo-siloxane include, for example two (3-aminopropyl)-tetramethyl disiloxanes (1,3-bis (3-aminopropyl)-tetramethyldisiloxane) of 1,3-etc.;
In addition, the diamines recorded in Japanese Patent Laid-Open 2010-97188 publication can be used.As other diamines, these diamines can be used alone a kind or two or more combinationally used.
"-X in above-mentioned formula (A-1) i-(R i-X iI) n-" represented by divalent group be preferably alkane two base of carbon number 1 ~ 3, *-O-, *-COO-or *-O-C 2h 4-O-(associative key wherein, marking " * " is combined with diamino-phenyl).Group "-C ch 2c+1" concrete example can enumerate R as above-mentioned formula (0) 1in the alkyl of carbon number 1 ~ 20 and illustrative group.2 amino in diamino-phenyl are preferably positioned at 2 relative to other groups, 4-position or 3,5-position.
The concrete example of the compound represented by above-mentioned formula (A-1) include, for example the compound etc. represented by following formula (A-1-1) ~ formula (A-1-3) difference.
[changing 8]
Relative to the total amount of the diamines for the synthesis of polyamic acid, the ratio that contains of specific diamines (D) is preferably more than 1 % by mole, is more preferably 1 % by mole ~ 50 % by mole.Being set to more than 1 % by mole by this being contained ratio, can improving further and using this crystal aligning agent and the tilt angle of liquid crystal orienting film that formed.5 % by mole ~ 30 % by mole should be particularly preferably containing ratio.
[molecular weight regulator]
During synthesizing polyamides acid, suitable molecular weight regulator can be used, synthesize end modified type polymkeric substance together with tetracarboxylic dianhydride as above and diamines.By making this end modified type polymkeric substance, the coating (printing) of crystal aligning agent can be improved further when not undermining effect of the present invention.
Molecular weight regulator include, for example: monoester anhydride (monoanhydride), monoamine compound (monoaminecompound), monoisocyanate compound (monoisocyanatecompound) etc.The concrete example of these molecular weight regulators can be enumerated respectively: monoester anhydride include, for example: MALEIC ANHYDRIDE (maleicanhydride), Tetra hydro Phthalic anhydride (phthalicanhydride), itaconic anhydride (itaconicanhydride), positive decyl Succinic anhydried (n-decylsuccinicanhydride), dodecyl Succinic anhydried (n-dodecylsuccinicanhydride), n-tetradecane base Succinic anhydried (n-tetradecylsuccinicanhydride), n-hexadecyl Succinic anhydried (n-hexadecylsuccinicanhydride) etc.,
Monoamine compound include, for example: aniline (aniline), hexahydroaniline (cyclohexylamine), n-Butyl Amine 99 (n-butylamine), n-amylamine (n-pentylamine), normal hexyl Amine (n-hexylamine), positive heptyl amice (n-heptylamine), n-octyl amine (n-octylamine) etc.; Monoisocyanate compound include, for example: phenylcarbimide (phenylisocyanate), naphthyl isocyanate (naphthylisocyanate) etc.
Relative to total 100 weight part of used tetracarboxylic dianhydride and diamines, the usage ratio of molecular weight regulator is preferably set to below 20 weight parts, is more preferably and is set to below 10 weight parts.
The synthesis > of < polyamic acid
The usage ratio of the tetracarboxylic dianhydride and diamines that are supplied to the building-up reactions of polyamic acid of the present invention is preferably, relative to amino 1 equivalent of diamines, the anhydride group of tetracarboxylic dianhydride becomes the ratio of 0.2 equivalent ~ 2 equivalent, is more preferably the ratio becoming 0.3 equivalent ~ 1.2 equivalent.
The building-up reactions of polyamic acid is preferably carried out in organic solvent.Temperature of reaction is now preferably-20 DEG C ~ 150 DEG C, is more preferably 0 DEG C ~ 100 DEG C.In addition, the reaction times is preferably 0.1 hour ~ 24 hours, is more preferably 0.5 hour ~ 12 hours.
Herein, organic solvent include, for example: aprotic polar solvent, phenol series solvent, alcohol, ketone, ester, ether, halohydrocarbon, hydrocarbon etc.
The concrete example of these organic solvents can be enumerated respectively: above-mentioned aprotic polar solvent include, for example: METHYLPYRROLIDONE (N-methyl-2-pyrrolidone), 1, 3-dimethyl-2-imidazolidone (1, 3-dimethyl-2-imidazolidinone), N-ethyl-2-pyrrolidone (N-ethyl-2-pyrrolidone), N, N-N,N-DIMETHYLACETAMIDE (N, N-dimethylacetamide), N, dinethylformamide (N, N-dimethylformamide), dimethyl sulfoxide (DMSO) (dimethylsulfoxide), gamma-butyrolactone (γ-butyrolactone), tetramethyl-urea (tetramethylurea), HMPA (hexamethylphosphortriamide) etc., above-mentioned phenol series solvent include, for example: phenol (phenol), meta-cresol (m-cresol), xylenol (xylenol), halogenated phenol (halogenatedphenol) etc.,
Above-mentioned alcohol include, for example: methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, BDO, triethylene glycol, ethylene glycol monomethyl ether etc.; Above-mentioned ketone include, for example: acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.; Above-mentioned ester include, for example: ethyl lactate, n-Butyl lactate, methyl acetate, ethyl acetate, butylacetate, methoxy methyl propionate, ethoxyl ethyl propionate, diethyl oxalate, diethyl malonate, isoamyl propionate, isoamyl isobutyrate etc.;
Above-mentioned ether include, for example: diethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether, glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, tetrahydrofuran (THF), isoamyl ether etc.;
Above-mentioned halohydrocarbon include, for example: methylene dichloride, 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene etc.; Above-mentioned hydrocarbon include, for example: hexane, heptane, octane, benzene,toluene,xylene etc.
In these organic solvents, be preferably use to be selected from and to form more than one organic solvents in cohort (organic solvent of the first cohort) by aprotic polar solvent and phenol and its derivatives institute, or more than the a kind organic solvent be selected from the organic solvent of the first cohort and to be selected from by alcohol, ketone, ester, ether, halohydrocarbon and hydrocarbon form the mixture of more than one organic solvents in cohort (organic solvent of the second cohort).In the case of the latter, relative to the total amount of the organic solvent of the first cohort and the organic solvent of the second cohort, the usage ratio of the organic solvent of the second cohort is preferably less than 50 % by weight, is more preferably less than 40 % by weight, is especially preferably less than 30 % by weight.
The usage quantity (a) of organic solvent is preferably set to the total amount (a+b) relative to reaction soln, and the total amount (b) of tetracarboxylic dianhydride and diamines becomes the amount of 0.1 % by weight ~ 50 % by weight.
Obtain the reaction soln dissolved by polyamic acid in the above described manner.This reaction soln directly can be supplied to the preparation of crystal aligning agent, also can reoffer after polyamic acid contained in reaction soln segregation to the preparation of crystal aligning agent, or also can reoffer after the polyamic acid purifying of segregation to the preparation of crystal aligning agent.When polyamic acid dehydration closed-loop is made polyimide, above-mentioned reaction soln directly can be supplied to dehydration closed-loop reaction, also can reoffer after polyamic acid contained in reaction soln segregation to dehydration closed-loop reaction, or also can react reoffering after the polyamic acid purifying of segregation to dehydration closed-loop.The segregation of polyamic acid and purifying can carry out according to well-known method.
< polymkeric substance (P1): poly amic acid ester >
Polymkeric substance (P1) contained in crystal aligning agent of the present invention can enumerate the poly amic acid ester of the group had represented by above-mentioned formula (0).This poly amic acid ester such as can utilize following methods to obtain: [I] is by using compound or the ether compound of hydroxyl, the method that the polyamic acid obtained utilizing above-mentioned building-up reactions carries out esterification to synthesize; [II] makes tetracarboxylic acid diester compound, carries out the method for reacting with the diamine compound that comprises above-mentioned specific diamines (D).Herein, the tetracarboxylic acid diester compound in method [II] can enumerate the precursor of above-mentioned tetracarboxylic dianhydride and the diester compound of tetracarboxylic acid, specifically, include, for example tetracarboxylic acid diester dichloride, has the tetracarboxylic acid diester etc. of 2 carboxyls.In addition, other diamines above-mentioned can use by the diamines used in method [II] together with above-mentioned specific diamines (D).In addition, the poly amic acid ester as polymkeric substance (P1) can only have amic acid esters structure, also can be amido acid structure and amic acid esters structure and the partial esterification thing deposited.
< polymkeric substance (P1): polyimide >
Other forms of polymkeric substance (P1) contained in crystal aligning agent of the present invention can enumerate the polyimide of the group had represented by above-mentioned formula (0).This polyimide can by carrying out dehydration closed-loop by the polyamic acid of the group had represented by above-mentioned formula (0) synthesized in the above described manner, in addition imidization and obtaining.
Above-mentioned polyimide can be using the amido acid structure fully dehydrating closed loop that has as the polyamic acid of its precursor and the complete imide compound obtained, also can be only by a part of dehydration closed-loop of amido acid structure, amido acid structure and imide ring structure the part imide compound of depositing.The imide rate of polyimide of the present invention is preferably more than 30%, is more preferably 50% ~ 99%, is especially preferably 60% ~ 99%.This imide rate is the ratio representing for the amido acid number of structures of polyimide and the total of imide ring number of structures shared by imide ring number of structures with percentage.Herein, a part for imide ring can be different imide ring.
The dehydration closed-loop of polyamic acid, preferably by the method heated polyamic acid, or by being dissolved in organic solvent by polyamic acid, adds the method that dewatering agent and dehydration closed-loop catalyzer optionally carry out heating in this solution.Wherein, a kind of rear method of utilization is preferably.
Add in the solution of above-mentioned polyamic acid in the method for dewatering agent and dehydration closed-loop catalyzer, dewatering agent such as can use the acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.Relative to 1 mole of the amido acid structure of polyamic acid, the usage quantity of dewatering agent is preferably 0.01 mole ~ 20 moles.Dehydration closed-loop catalyzer such as can use: the tertiary amines such as pyridine (pyridine), collidine (collidine), two picolins (lutidine), triethylamine (triethylamine).Relative to used dewatering agent 1 mole, the usage quantity of dehydration closed-loop catalyzer is preferably set to 0.01 mole ~ 10 moles.The organic solvent used in dehydration closed-loop reaction can enumerate the illustrative organic solvent as the organic solvent for the synthesis of polyamic acid.The temperature of reaction of dehydration closed-loop reaction is preferably 0 DEG C ~ 180 DEG C, is more preferably 10 DEG C ~ 150 DEG C.Reaction times is preferably 1.0 hours ~ 120 hours, is more preferably 2.0 hours ~ 30 hours.
Obtain the reaction soln containing polyimide in the above described manner.This reaction soln directly can be supplied to the preparation of crystal aligning agent, also reoffer after can removing dewatering agent and dehydration closed-loop catalyzer from reaction soln to the preparation of crystal aligning agent, also reoffer to the preparation of crystal aligning agent after polyimide can being emanated, or also can reoffer after the polyimide purifying of segregation to the preparation of crystal aligning agent.These purification process can be carried out according to well-known method.
The polyamic acid obtained in the above described manner, poly amic acid ester and polyimide preferably have the soltion viscosity person of 10mPas ~ 800mPas when being made into concentration and being the solution of 10 % by weight, be more preferably the soltion viscosity person with 15mPas ~ 500mPas.In addition, the soltion viscosity (mPas) of above-mentioned polymkeric substance be to the concentration using the good solvent (such as gamma-butyrolactone, METHYLPYRROLIDONE etc.) of this polymkeric substance to prepare be 10 % by weight polymers soln, use the value that E type rotational viscosimeter measures at 25 DEG C.
To polyamic acid, poly amic acid ester and polyimide, the weight average molecular weight of the polystyrene conversion utilizing gel permeation chromatography to measure is preferably 1,000 ~ 500,000, is more preferably 2,000 ~ 300,000.
< polymkeric substance (P1): organopolysiloxane >
Other forms of polymkeric substance (P1) contained in crystal aligning agent of the present invention can enumerate the organopolysiloxane of the group had represented by above-mentioned formula (0).This organopolysiloxane such as can utilize following methods to obtain: (I) to be hydrolyzed making to have the hydrolysable silanes compound (s1) of epoxy group(ing) or this silane compound (s1) and the mixture of other silane compounds condensation and the polymkeric substance that obtains, carries out the method for reacting with the carboxylic acid of the group had represented by above-mentioned formula (0); (II) make to have the hydrolysable silanes compound (s2) of the group represented by above-mentioned formula (0) or this silane compound (s2) and the mixture of other silane compounds to be hydrolyzed the method etc. of condensation.In addition, in the method for above-mentioned (I) and (II), as long as by being undertaken appropriately combined for vitochemical ordinary method.
To organopolysiloxane, the weight average molecular weight of the polystyrene conversion utilizing gel permeation chromatography to measure is preferably 500 ~ 1,000,000, is more preferably 1,000 ~ 100,000, is especially preferably 1,000 ~ 50,000.
Crystal aligning agent of the present invention separately containing a kind or combination containing of more than two kinds above-mentioned to be selected from by polyamic acid, poly amic acid ester, polyimide and organopolysiloxane form polymkeric substance in cohort as polymkeric substance (P1).In crystal aligning agent of the present invention, each polymer phase is for suitably can the selecting according to used purposes or environment containing proportional of total amount of polymkeric substance (P1), with regard to the viewpoint of acquisition preferably effect of the present invention, preferably comprise and be selected from by polyamic acid, poly amic acid ester and polyimide form at least one in cohort as polymkeric substance (P1), be more preferably comprise to be selected from by polyamic acid and polyimide form at least one in cohort as polymkeric substance (P1), especially be preferably polymkeric substance (P1) for be selected from by polyamic acid and polyimide form at least one in cohort.
When comprise polyamic acid and polyimide at least any one is as polymkeric substance (P1), relative to the total amount of polymkeric substance (P1) contained in crystal aligning agent, its content added up to is preferably 1 % by weight ~ 100 % by weight, is more preferably 5 % by weight ~ 100 % by weight.In addition, polymkeric substance (P1) can be used alone above-mentioned shown in a kind of polymkeric substance, also two or more can be combinationally used.In addition, when two or more being combinationally used, can be the combination of the polymkeric substance that main framing is identical, also can be the combination of the different polymkeric substance of main framing.
< solvent >
In crystal aligning agent of the present invention, above-mentioned polymkeric substance is preferably dissolved in organic solvent and forms.
Solvent for the preparation of crystal aligning agent of the present invention is different according to the kind of polymkeric substance contained in crystal aligning agent.Specifically, comprise separately at crystal aligning agent of the present invention and be selected from by polyamic acid, poly amic acid ester and polyimide form at least any one polymkeric substance in cohort, or comprise the polymkeric substance such as this polyamic acid and organopolysiloxane when being used as polymkeric substance, include, for example: METHYLPYRROLIDONE, gamma-butyrolactone, butyrolactam, DMF, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, methoxy methyl propionate, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (ethylene glycol butyl ether), glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, dipropylene glycol monomethyl ether (dipropyleneglycolmonomethylether, DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, ethylene carbonate, propylene carbonate etc.These solvents can be used alone or two or more is used in combination.
On the other hand, when crystal aligning agent of the present invention only comprises organopolysiloxane as polymkeric substance, include, for example: the alcohol such as 1-oxyethyl group-2-propyl alcohol, dihydroxypropane single-ether, ethylene glycol butyl ether; The ethers such as diethylene glycol ethyl methyl ether; The esters etc. such as n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, Isoamyl Acetate FCC.
Other compositions of < >
Crystal aligning agent of the present invention optionally can contain other compositions.These other compositions include, for example: the compound (hereinafter referred to as " compound containing epoxy group(ing) "), functional silanes compound etc. in other polymkeric substance beyond above-mentioned particular polymers, molecule with at least one epoxy group(ing).
[other polymkeric substance]
Other polymkeric substance above-mentioned can be used in improving solution properties or electrical specification.These other polymkeric substance include, for example: do not have the polymkeric substance of the group represented by above-mentioned formula (0), polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenylmaleimide) derivative, poly-(methyl) acrylate etc. in polyamic acid, poly amic acid ester, polyimide and organopolysiloxane.When other polymkeric substance are made an addition in crystal aligning agent, relative to the total polymer amount in said composition, the allotment ratio of these other polymkeric substance is preferably less than 50 % by weight, is more preferably 0.1 % by weight ~ 40 % by weight, is especially preferably 0.1 % by weight ~ 30 % by weight.
[compound containing epoxy group(ing)]
Compound containing epoxy group(ing) can be used for improving liquid crystal orienting film with the tackiness of substrate surface or electrical specification.Herein, compound containing epoxy group(ing) include, for example following compound as preferred compound: ethylene glycol bisthioglycolate glycidyl ethers, polyoxyethylene glycol Diglycidyl, propylene glycol Diglycidyl, tripropylene glycol Diglycidyl, polypropylene glycol Diglycidyl, neopentyl glycol Diglycidyl, 1, 6-hexylene glycol Diglycidyl, glycerol Diglycidyl, trimethylolpropane tris glycidyl ethers, 2, 2-dibromoneopentyl glycol Diglycidyl, N, N, N ', N '-four epoxypropyl-m-xylene diamine, 1, two (the N of 3-, N-diepoxy propylcarbamic methyl) hexanaphthene, N, N, N ', N '-four epoxypropyl-4, 4 '-diaminodiphenyl-methane, N, N-diepoxy propyl group-benzyl amine, N, N-diepoxy propyl-amino methylcyclohexane, N, N-diepoxy propyl-cyclohexyl amine etc.
In addition, containing the organopolysiloxane containing epoxy group(ing) that the example of the compound of epoxy group(ing) can also use No. 2009/096598th, International Publication to record.
When these epoxy compoundss are made an addition in crystal aligning agent, relative to total 100 weight part of polymkeric substance contained in crystal aligning agent, the allotment ratio of this epoxy compounds is preferably below 40 weight parts, is more preferably 0.1 weight part ~ 30 weight part.
[functional silanes compound]
Above-mentioned functional silanes compound can use for the object of the printing improving crystal aligning agent.This functional silanes compound include, for example: 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl Trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-tri-ethoxy silylpropyl diethylenetriamine, 10-Trimethoxy silane base-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-Trimethoxy silane base-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-phenyl-3-TSL 8330, glycidyl oxy methyl Trimethoxy silane, 2-glycidoxyethyl Trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane etc.
When being made an addition in crystal aligning agent by these functional silanes compounds, relative to total 100 weight part of polymkeric substance, the allotment ratio of this functional silanes compound is preferably below 2 weight parts, is more preferably 0.02 weight part ~ 0.2 weight part.
In addition, other compositions in addition to the foregoing, can also use in molecule the compound or antioxidant etc. with at least one oxetanylmethoxy (oxetanyl).
Solid component concentration (ratio of total weight shared by the gross weight of crystal aligning agent of the composition beyond the solvent of crystal aligning agent) in crystal aligning agent of the present invention considers that viscosity, volatility etc. are suitably selected, and is preferably the scope of 1 % by weight ~ 10 % by weight.Namely, crystal aligning agent of the present invention is by coating substrate surface in aftermentioned mode, preferably heat, formed as liquid crystal orienting film film or become the film of liquid crystal orienting film, now, when solid component concentration is less than 1 % by weight, the thickness of this film becomes too small and cannot obtain good liquid crystal orienting film.On the other hand, when solid component concentration is more than 10 % by weight, the thickness of film becomes excessive and cannot obtain good liquid crystal orienting film, and in addition, the viscosity of crystal aligning agent increases and forms the liquid crystal orienting film of coating characteristics difference.
The scope of particularly preferred solid component concentration is different according to the method used during coating of liquid crystalline orientation agent on substrate.Such as when utilizing turner (spinner) method, solid component concentration is particularly preferably the scope of 1.5 % by weight ~ 4.5 % by weight.When utilizing print process, being particularly preferably scope solid component concentration being set to 3 % by weight ~ 9 % by weight, thus soltion viscosity being set to the scope of 12mPas ~ 50mPas.When utilizing ink jet method, being particularly preferably scope solid component concentration being set to 1 % by weight ~ 5 % by weight, thus soltion viscosity being set to the scope of 3mPas ~ 15mPas.
Temperature when preparing crystal aligning agent of the present invention is preferably 10 DEG C ~ 50 DEG C, is more preferably 20 DEG C ~ 30 DEG C.
< liquid crystal orienting film and liquid crystal display device >
Liquid crystal orienting film of the present invention utilizes the crystal aligning agent prepared in the above described manner to be formed.In addition, liquid crystal display device of the present invention comprises and uses this crystal aligning agent and the liquid crystal orienting film that formed.The operating mode of this liquid crystal display device is not particularly limited, and is particularly preferably the vertical orientation type such as VA type or MVA type.
Below, the manufacture method of liquid crystal display device of the present invention is described, also the manufacture method of liquid crystal orienting film of the present invention is described in this explanation simultaneously.In addition, the manufacture method below enumerating VA type liquid crystal display device is described as an example.
[step (1): the formation of film]
First, substrate is coated with crystal aligning agent of the present invention, then heats coated face, on substrate, form film thus.
First, to be provided with two pieces of substrates of patterned nesa coating as a pair, the forming surface of the nesa coating in these substrates is coated with crystal aligning agent of the present invention respectively, is preferably and utilizes: flexographic printing process (offsetprintingmethod), method of spin coating (spincoatingmethod), roll-coater method (rollcoatermethod) or ink jet printing method (inkjetprintingmethod).Wherein, substrate such as can use: the glass such as float glass (floatglass), soda glass (sodaglass); Comprise the transparency carrier of the plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-(ester ring type alkene).The nesa coating being arranged at the wherein one side of substrate can use: comprise stannic oxide (SnO 2) NESA film (PPG register of company of U.S. trade mark), comprise indium oxide-tin oxide (In 2o 3-SnO 2) ito film etc.In order to obtain patterned nesa coating, such as, can utilize following methods: after forming patternless nesa coating, being formed the method for pattern by photoetch (photoetching); The method etc. with the shade of required pattern is used when forming nesa coating.During coating of liquid crystalline orientation agent, in order to make the tackiness of substrate surface and nesa coating and film better, also the pre-treatment being coated with functional silanes compound, functionality titanium compound etc. in advance can be implemented to the face that should form film in substrate surface.
After coating of liquid crystalline orientation agent, for the object such as sagging preventing be coated with crystal aligning agent, be preferably enforcement and preheat (prebake conditions (prebake)).Prebake conditions temperature is preferably 30 DEG C ~ 200 DEG C, is more preferably 40 DEG C ~ 150 DEG C, is particularly preferably 40 DEG C ~ 100 DEG C.The prebake conditions time is preferably 0.25 minute ~ 10 minutes, is more preferably 0.5 minute ~ 5 minutes.Then, solvent is removed completely, optionally implement calcining (rear baking (postbake)) step for the object of the amido acid existed in polymkeric substance structure being carried out hot-imide.Rear storing temperature is preferably 80 DEG C ~ 300 DEG C, is more preferably 120 DEG C ~ 250 DEG C.Post-bake times is preferably 5 minutes ~ 200 minutes, is more preferably 10 minutes ~ 100 minutes.So, the thickness of the film formed is preferably 0.001 μm ~ 1 μm, is more preferably 0.005 μm ~ 0.5 μm.
Remove organic solvent by the heating after coating of liquid crystalline orientation agent, be formed into the film of alignment film thus.Now, polymkeric substance contained in crystal aligning agent of the present invention be polyamic acid or poly amic acid ester or the imide amination polymer with imide ring structure and amido acid structure, also can carry out dehydration closed-loop reaction by heating further after film is formed, making further through the film of imidization.
[step (2): constructing of liquid crystal cells]
By preparing the substrate that two pieces are formed with liquid crystal orienting film in the above described manner, between two pieces of substrates of subtend configuration, configuring liquid crystal, manufacture liquid crystal cells.
In order to manufacture liquid crystal cells, include, for example following two kinds of methods.
The method (vacuum injection mode) that first method is known before being.First, in the mode of each liquid crystal orienting film subtend, across gap (cell gap), two pieces of substrate subtends are configured, sealing agent is used to be fitted by the periphery of two pieces of substrates, inject filling liquid crystal in the cell gap divided by substrate surface and sealing agent after, filling orifice is sealed, manufactures liquid crystal cells thus.Second method is the method being called instillation (OneDropFill, ODF) mode.Predetermined portion on wherein one piece of substrate in the two pieces of substrates being formed with liquid crystal orienting film is coated with the sealing material of such as ultraviolet light photopolymerization, and then several positions of regulation on LCD alignment face are dripped after liquid crystal, to fit another block substrate in the mode of liquid crystal orienting film subtend, and liquid crystal is spread out on whole of substrate, then to whole irradiating ultraviolet light of substrate, cure the sealant, manufacture liquid crystal cells thus.When utilizing any one method, it is desirable to by the liquid crystal cells manufactured in the above described manner, and then be heated to after used liquid crystal becomes the temperature of isotropic phase, slowly be cooled to room temperature, remove flowing orientation when liquid crystal is filled.Then, liquid crystal display device of the present invention is obtained by the outer surface laminating Polarizer at liquid crystal cells.
Sealing agent such as can use the epoxy resin etc. containing stiffening agent and the alumina balls as spacer.
Liquid crystal can enumerate nematic liquid crystal (nematicliquidcrystal) and smectic liquid crystal (smecticliquidcrystal), wherein be preferably nematic liquid crystal, such as can use: schiff bases (Schiffbase) is liquid crystal, azoxy (azoxy) is liquid crystal, biphenyl (biphenyl) is liquid crystal, Santosol 360 (phenylcyclohexane) is liquid crystal, ester (ester) is liquid crystal, terphenyl (terphenyl) is liquid crystal, xenyl hexanaphthene (biphenylcyclohexane) is liquid crystal, pyrimidine (pyrimidine) is liquid crystal, dioxan system liquid crystal, double-octane (bicyclooctane) is liquid crystal, cubane (cubane) is liquid crystal etc.In addition, also can add following material to use in these liquid crystal: the cholesteric liquid crystals (cholestericliquidcrystal) such as such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate (cholesterylcarbonate); As the chiral agent (chiralagent) that trade(brand)name " C-15 ", " CB-15 " (manufacture of Merck (Merck) company) are sold; To oxygen base α-tolylene-to ferroelectric liquid crystals (ferroelectricliquidcrystal) etc. such as amino-2-methyl butyl laurates (p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate) in the last of the ten Heavenly stems.
The Polarizer fitting in the outside surface of liquid crystal cells can be enumerated: be called as the Polarizer of the light polarizing film (described H film makes polyvinyl alcohol extension orientation make it absorb the light polarizing film of iodine) of " H film " with the clamping of rhodia protective membrane or comprise itself Polarizer of H film.
Liquid crystal display device of the present invention can be effectively applied to multiple device, such as can be used in: clock and watch, portable game machine (portablegameconsole), word processor (wordprocessor), notes type PC (notetypepersonalcomputer), auto-navigation system (carnavigationsystem), video camera (camcorder), personal digital assistant (PersonalDigitalAssistant, PDA), digital camera (digitalcamera), mobile phone, smart mobile phone (smartphone), various watch-dog, LCD TV, the various display unit such as information display (informationdisplay).
[embodiment]
Below, utilize embodiment to be specifically described further the present invention, but the present invention is not by the restriction of these embodiments.
The soltion viscosity of each polymers soln in synthesis example and the imide rate of polyimide utilize following methods to measure.
[soltion viscosity of polymers soln]
The soltion viscosity [mPas] of polymers soln uses E type rotational viscosimeter, being prepared into the solution that polymer concentration is 10 % by weight, measuring at 25 DEG C using the solvent of regulation.
[the imide rate of polyimide]
The solution of polyimide is fed in pure water, at room temperature by after the precipitation of gained fully drying under reduced pressure, is dissolved in deuterodimethylsulfoxide, using tetramethylsilane as primary standard, at room temperature measures 1h-nucleus magnetic resonance ( 1h-Nuclearmagneticresonance, 1h-NMR).According to gained 1h-NMR spectrum, obtains imide rate [%] by the formula shown in following mathematical expression (1a).
Imide rate [%]=(1-A 1/ A 2× α) × 100... (1a)
(in mathematical expression (1a), A 1for the peak area being derived from the proton of NH base occurred near chemical shift 10ppm, A 2for being derived from the peak area of other protons, α is the number ratios of other protons relative to 1 proton of the NH base in the precursor (polyamic acid) of polymkeric substance.)
The synthesis > of the specific diamines of < (D)
[synthesis example 1: the synthesis of compound (D-1)]
Synthetic compound (D-1) is carried out according to following flow process 1.
[changing 9]
Take into account in the 500mL there-necked flask of nitrogen ingress pipe in possessing temperature, add compound represented by above-mentioned formula (1-1-1A) (wherein, 1, the Sys-trans isomerism of 4-cyclohexylidene is respectively trans-isomer(ide)) 35.7g, 2,4-dinitrochlorobenzene 20.3g, salt of wormwood 15.2g and N, N-N,N-DIMETHYLACETAMIDE 300mL, reacts 4 hours at 100 DEG C.After completion of the reaction, add ethyl acetate 1L, tetrahydrofuran (THF) 500mL, 1M hydrochloric acid water 1L and remove water layer, clean 3 times with water.Then, in organic layer, add magnesium sulfate and after making its drying, concentrate, the crystallization of separating out is reclaimed, dry, obtain the pale yellow crystals 36.6g of the compound represented by above-mentioned formula (1-1-1B) thus.
Then, take into account in the 1L there-necked flask of nitrogen ingress pipe in possessing temperature, add the compound 36.6g represented by above-mentioned formula (1-1-1B), palladium carbon 1.83g, tetrahydrofuran (THF) 350mL, ethanol 350mL and 80% hydrazine monohydrate aqueous solution 39.4g, at room temperature react 20 hours.After completion of the reaction, add ethyl acetate 1L, after cleaning 3 times with water, organic layer is concentrated, by the crystallization of precipitation filtration, drying, obtain the filbert crystallization 25.9g of the compound (D-1) represented by above-mentioned formula (1-1-1) thus.
[synthesis example 2: the synthesis of compound (D-2)]
Synthetic compound (D-2) is carried out according to following flow process 2.
[changing 10]
In possessing dropping funnel, temperature takes into account in the 500mL there-necked flask of nitrogen ingress pipe, add compound represented by above-mentioned formula (1-1-1A) (wherein, 1, the Sys-trans isomerism of 4-cyclohexylidene is respectively trans-isomer(ide)) 35.7g, tetrahydrofuran (THF) 200mL and triethylamine 11.13g, ice bath is cooled to less than 5 DEG C.Then, spending slowly drips for 30 minutes to be dissolved in solution in tetrahydrofuran (THF) 100mL by 3,5 dinitrobenzoylchloride 23.0g, return to room temperature, react 1 hour.After completion of the reaction, add ethyl acetate 500mL and 1M aqueous hydrochloric acid 500mL and carry out separatory, and then after 3 separatory cleanings being carried out to organic layer with water, make organic layer dry with magnesium sulfate, concentrate, by the crystallization of precipitation filtration, drying, obtain the pale yellow crystals 49.6g of the compound represented by above-mentioned formula (1-2-1B) thus.
Then, take into account in the 2L there-necked flask of nitrogen ingress pipe in possessing temperature, after adding above-mentioned formula (1-2-1B) 49.6g, 5% palladium carbon dust 2.48g, tetrahydrofuran (THF) 300mL and ethanol 300mL, slow interpolation 80% hydrazine monohydrate aqueous solution 51g, at room temperature stir 1 hour, be heated to 70 DEG C, and then react 2 hours.After completion of the reaction, will by filtering the palladium removing carbon and the filtrate that obtains is concentrated into about 200mL of making a return journey, add ethyl acetate 500mL, after carrying out 3 separatory cleanings with water, organic layer is concentrated, by the crystallization of precipitation filtration, drying, obtain the white crystals 39.8g of the compound (D-2) represented by above-mentioned formula (1-2-1) thus.
[synthesis example 3: the synthesis of compound (D-3)]
Synthetic compound (D-3) is carried out according to following flow process 3.
[changing 11]
Take into account in the 500mL there-necked flask of nitrogen ingress pipe in possessing temperature, add compound represented by above-mentioned formula (1-3-1A) (wherein, 1, the Sys-trans isomerism of 4-cyclohexylidene is respectively trans-isomer(ide)) 35.7g, 2,4-dinitrochlorobenzene 20.3g, salt of wormwood 15.2g and N, N-N,N-DIMETHYLACETAMIDE 300mL, reacts 4 hours at 100 DEG C.After completion of the reaction, add ethyl acetate 1L, tetrahydrofuran (THF) 500mL, 1M hydrochloric acid water 1L and remove water layer, clean 3 times with water.Then, in organic layer, add magnesium sulfate and after making its drying, concentrate, the crystallization of separating out is reclaimed, dry, obtain the pale yellow crystals 35.8g of the compound represented by above-mentioned formula (1-3-1B) thus.
Then, take into account in the there-necked flask of the 1L of nitrogen ingress pipe in possessing temperature, add the compound 35.8g represented by above-mentioned formula (1-3-1B), palladium carbon 1.83g, tetrahydrofuran (THF) 350mL, ethanol 350mL and 80% hydrazine monohydrate aqueous solution 39.4g, at room temperature react 20 hours.After completion of the reaction, add ethyl acetate 1L, after cleaning 3 times with water, organic layer is concentrated, by the crystallization of precipitation filtration, drying, obtain the filbert crystallization 25.0g of the compound (D-3) represented by above-mentioned formula (1-3-1) thus.
[synthesis example 4: the synthesis of compound (D-4)]
Synthetic compound (D-4) is carried out according to following flow process 4.
[changing 12]
In possessing dropping funnel, temperature takes into account in the 500mL there-necked flask of nitrogen ingress pipe, add compound represented by above-mentioned formula (1-3-1A) (wherein, 1, the Sys-trans isomerism of 4-cyclohexylidene is respectively trans-isomer(ide)) 35.7g, tetrahydrofuran (THF) 200mL and triethylamine 11.13g, ice bath is cooled to less than 5 DEG C.Then, spending slowly drips for 30 minutes to be dissolved in solution in tetrahydrofuran (THF) 100mL by 3,5 dinitrobenzoylchloride 23.0g, return to room temperature, react 1 hour.After completion of the reaction, add ethyl acetate 500mL and 1M aqueous hydrochloric acid 500mL and carry out separatory, and then after 3 separatory cleanings being carried out to organic layer with water, make organic layer dry with magnesium sulfate, concentrate, by the crystallization of precipitation filtration, drying, obtain the pale yellow crystals 49.0g of the compound represented by above-mentioned formula (1-4-1B) thus.
Then, take into account in the there-necked flask of the 2L of nitrogen ingress pipe in possessing temperature, after adding the compound 49.0g represented by above-mentioned formula (1-4-1B), 5% palladium carbon dust 2.48g, tetrahydrofuran (THF) 300mL and ethanol 300mL, slow interpolation 80% hydrazine monohydrate aqueous solution 51g, at room temperature stir 1 hour, be heated to 70 DEG C, and then react 2 hours.After completion of the reaction, will by filtering the palladium removing carbon and the filtrate that obtains is concentrated into about 200mL of making a return journey, add ethyl acetate 500mL, after carrying out 3 separatory cleanings with water, organic layer is concentrated, by the crystallization of precipitation filtration, drying, obtain the white crystals 38.8g of the compound (D-4) represented by above-mentioned formula (1-4-1) thus.
The synthesis > of < polymkeric substance (P1)
[polymerization example 1: the synthesis of polyimide (PI-1)]
Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride (TCA) 22.4g (0.1 mole), be dissolved in METHYLPYRROLIDONE (NMP) 175g as Ursol D (PDA) 7.5g (0.07 mole), compound (D-1) 13.8g (0.03 mole) of diamines, at 60 DEG C, carry out reaction in 6 hours, obtain the solution of the polyamic acid containing 20 % by weight.Divide the gained polyamic acid solution taken a morsel, add NMP and make the solution that polyamic acid concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 78mPas.
Then, in the polyamic acid solution of gained, add NMP406g, add pyridine 11.8g and diacetyl oxide 15.3g, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, with new NMP, solvent exchange is carried out to intrasystem solvent and (by this operation, the pyridine and diacetyl oxide that are used for dehydration closed-loop reaction are removed to outside system; Identical below), the imide rate obtained thus containing 22 % by weight is about the solution of the polyimide (PI-1) of 62%.Divide the gained polyimide solution taken a morsel, add NMP and make the solution that polyimide concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 44mPas.
[polymerization example 2: the synthesis of polyimide (PI-2)]
TCA22.5g (0.1 mole) as tetracarboxylic dianhydride, the PDA7.6g (0.07 mole) as diamines, compound (D-2) 14.8g (0.03 mole) are dissolved in NMP179g, at 60 DEG C, carry out reaction in 6 hours, obtain the solution of the polyamic acid containing 20 % by weight.Divide the gained polyamic acid solution taken a morsel, add NMP and make the solution that polyamic acid concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 88mPas.
Then, in the polyamic acid solution of gained, add NMP416g, add pyridine 11.9g and diacetyl oxide 15.3g, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, carry out solvent exchange with new NMP to intrasystem solvent, the imide rate obtained thus containing 22 % by weight is about the solution of the polyimide (PI-2) of 65%.Divide the gained polyimide solution taken a morsel, add NMP and make the solution that polyimide concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 49mPas.
[polymerization example 3: the synthesis of polyimide (PI-3)]
TCA22.4g (0.1 mole) as tetracarboxylic dianhydride, the PDA7.5g (0.07 mole) as diamines, compound (D-3) 13.8g (0.03 mole) are dissolved in NMP175g, at 60 DEG C, carry out reaction in 6 hours, obtain the solution of the polyamic acid containing 20 % by weight.Divide the gained polyamic acid solution taken a morsel, add NMP and make the solution that polyamic acid concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 89mPas.
Then, in the polyamic acid solution of gained, add NMP406g, add pyridine 11.8g and diacetyl oxide 15.3g, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, carry out solvent exchange with new NMP to intrasystem solvent, the imide rate obtained thus containing 22 % by weight is about the solution of the polyimide (PI-3) of 67%.Divide the gained polyimide solution taken a morsel, add NMP and make the solution that polyimide concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 49mPas.
[polymerization example 4: the synthesis of polyimide (PI-4)]
TCA22.5g (0.1 mole) as tetracarboxylic dianhydride, the PDA7.6g (0.07 mole) as diamines, compound (D-4) 14.8g (0.03 mole) are dissolved in NMP179g, at 60 DEG C, carry out reaction in 6 hours, obtain the solution of the polyamic acid containing 20 % by weight.Divide the gained polyamic acid solution taken a morsel, add NMP and make the solution that polyamic acid concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 70mPas.
Then, in the polyamic acid solution of gained, add NMP416g, add pyridine 11.9g and diacetyl oxide 15.3g, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, carry out solvent exchange with new NMP to intrasystem solvent, the imide rate obtained thus containing 22 % by weight is about the solution of the polyimide (PI-4) of 63%.Divide the gained polyimide solution taken a morsel, add NMP and make the solution that polyimide concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 45mPas.
[polymerization example 5: the synthesis of polyimide (PI-5)]
Utilize the composition identical with above-mentioned polymerization example 1 and identical condition, obtain the solution of the polyamic acid containing 20 % by weight.Divide the gained polyamic acid solution taken a morsel, add NMP and make the solution that polyamic acid concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 75mPas.
Then, in the polyamic acid solution of gained, add NMP406g, add pyridine 13.4g and diacetyl oxide 17.3g, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, carry out solvent exchange with new NMP to intrasystem solvent, the imide rate obtained thus containing 22 % by weight is about the solution of the polyimide (PI-5) of 76%.Divide the gained polyimide solution taken a morsel, add NMP and make the solution that polyimide concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 55mPas.
[polymerization example 6: the synthesis of polyimide (PI-6)]
Using as tetracarboxylic dianhydride's 2,4,6,8-tetracarboxylic dicyclo [3.3.0] octane-2:4,6:8-dianhydride (BODA) 25.0g (0.1 mole), be dissolved in NMP189g as PDA7.6g (0.07 mole), compound (D-2) 14.7g (0.03 mole) of diamines, at 60 DEG C, carry out reaction in 8 hours, obtain the solution of the polyamic acid containing 20 % by weight.Divide the gained polyamic acid solution taken a morsel, add NMP and make the solution that polyamic acid concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 36mPas.
Then, in the polyamic acid solution of gained, add NMP439g, add pyridine 11.9g and diacetyl oxide 15.3g, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, carry out solvent exchange with new NMP to intrasystem solvent, the imide rate obtained thus containing 22 % by weight is about the solution of the polyimide (PI-6) of 64%.Divide the gained polyimide solution taken a morsel, add NMP and make the solution that polyimide concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 30mPas.
[polymerization example 7: the synthesis of polyimide (PI-7)]
Using the BODA18.9g (0.075 mole) and 1 as tetracarboxylic dianhydride, 2,3,4-tetramethylene tetracarboxylic dianhydride (CB) 4.9g (0.025 mole), be dissolved in NMP185g as PDA7.6g (0.07 mole), compound (D-2) 14.8g (0.03 mole) of diamines, at 60 DEG C, carry out reaction in 8 hours, obtain the solution of the polyamic acid containing 20 % by weight.Divide the gained polyamic acid solution taken a morsel, add NMP and make the solution that polyamic acid concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 40mPas.
Then, in the polyamic acid solution of gained, add NMP429g, add pyridine 11.9g and diacetyl oxide 15.4g, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, carry out solvent exchange with new NMP to intrasystem solvent, the imide rate obtained thus containing 22 % by weight is about the solution of the polyimide (PI-7) of 66%.Divide the gained polyimide solution taken a morsel, add NMP and make the solution that polyimide concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 29mPas.
[polymerization example 8: the synthesis of polyimide (PI-8)]
TCA22.3g (0.1 mole) as tetracarboxylic dianhydride, the PDA5.4g (0.05 mole) as diamines, compound (D-2) 24.4g (0.05 mole) are dissolved in NMP209g, at 60 DEG C, carry out reaction in 6 hours, obtain the solution of the polyamic acid containing 20 % by weight.Divide the gained polyamic acid solution taken a morsel, add NMP and make the solution that polyamic acid concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 55mPas.
Then, in the polyamic acid solution of gained, add NMP484g, add pyridine 7.9g and diacetyl oxide 10.2g, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, carry out solvent exchange with new NMP to intrasystem solvent, the imide rate obtained thus containing 22 % by weight is about the solution of the polyimide (PI-8) of 50%.Divide the gained polyimide solution taken a morsel, add NMP and make the solution that polyimide concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 36mPas.
[comparing polymerization example 1: the synthesis of polyimide (PI-9)]
Using the TCA22.4g (0.1 mole) as tetracarboxylic dianhydride, PDA7.6g (0.07 mole), the 4-octadecane Oxy-1 as diamines, 3-diaminobenzene 11.3g (0.03 mole) is dissolved in NMP165g, at 60 DEG C, carry out reaction in 6 hours, obtain the solution of the polyamic acid containing 20 % by weight.Divide the gained polyamic acid solution taken a morsel, add NMP and make the solution that polyamic acid concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 99mPas.
Then, in the polyamic acid solution of gained, add NMP384g, add pyridine 11.9g and diacetyl oxide 15.3g, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, carry out solvent exchange with new NMP to intrasystem solvent, the imide rate obtained thus containing 22 % by weight is about the solution of the polyimide (PI-9) of 69%.Divide the gained polyimide solution taken a morsel, add NMP and make the solution that polyimide concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 67mPas.
[comparing polymerization example 2: the synthesis of polyimide (PI-10)]
Using the TCA22.4g (0.1 mole) as tetracarboxylic dianhydride, the PDA7.6g (0.07 mole), 1 as diamines, 3-diamino-4-{4-[trans-4-(trans-4-n-pentyl cyclohexyl) cyclohexyl] phenoxy group } benzene 13.0g (0.03 mole) is dissolved in NMP172g, at 60 DEG C, carry out reaction in 6 hours, obtain the solution of the polyamic acid containing 20 % by weight.Divide the gained polyamic acid solution taken a morsel, add NMP and make the solution that polyamic acid concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 59mPas.
Then, in the polyamic acid solution of gained, add NMP400g, add pyridine 11.9g and diacetyl oxide 15.3g, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, carry out solvent exchange with new NMP to intrasystem solvent, the imide rate obtained thus containing 22 % by weight is about the solution of the polyimide (PI-10) of 62%.Divide the gained polyimide solution taken a morsel, add NMP and make the solution that polyimide concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 40mPas.
[comparing polymerization example 3: the synthesis of polyimide (PI-11)]
Utilize and be polymerized the identical composition of example 10 and identical condition with above-mentioned comparison, obtain the solution of the polyamic acid containing 20 % by weight.Divide the gained polyamic acid solution taken a morsel, add NMP and make the solution that polyamic acid concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 62mPas.
Then, in the polyamic acid solution of gained, add NMP400g, add pyridine 13.5g and diacetyl oxide 17.4g, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, carry out solvent exchange with new NMP to intrasystem solvent, the imide rate obtained thus containing 22 % by weight is about the solution of the polyimide (PI-11) of 74%.Divide the gained polyimide solution taken a morsel, add NMP and make the solution that polyimide concentration is 10 % by weight, the soltion viscosity gone out this measured in solution is 42mPas.
The preparation of < crystal aligning agent and evaluation >
[embodiment 1]
(1) preparation of crystal aligning agent
In containing polyimide (PI-1) as in the solution of polymkeric substance, N is added relative to polyimide (PI-1) 100 weight part contained in above-mentioned solution, N, N ', N '-four epoxypropyl-4,4 '-diaminodiphenyl-methane (E-1) 5 weight part is as epoxy compounds, and then add NMP and ethylene glycol list-n-butyl ether (BC) as solvent, make solvent composition be NMP: BC=60: 40 (weight ratios) and solid component concentration be 3.5 % by weight solution.The strainer being 1 μm by use aperture carries out filtration to this solution and prepares crystal aligning agent (S-1).
(2) manufacture of the liquid crystal display device of vertical orientation evaluation
Utilize turner, be arranged at coating of liquid crystalline orientation agent (S-1) on the nesa coating comprising ito film that thickness is the wherein one side of the glass substrate of 1mm, the prebake conditions of 1 minute is carried out on hot plate with 80 DEG C, heat 60 minutes at 200 DEG C, form the film that thickness is 0.08 μm thus.
To this film, utilize and there is the friction machine of the roller being wound with artificial silk cloth, carry out friction treatment with roller rotating speed 400rpm, platform movement speed 3em/ second, hair press-in length 0.4mm.Then, in ultrapure water, carry out 1 minute ultrasonic washer, then in 200 DEG C of cleaning ovens (cleanoven) dry 10 minutes, obtain the substrate with the liquid crystal orienting film implementing friction treatment thus.Repeat this operation, obtain the substrate that a pair (two pieces) have liquid crystal orienting film.
Then, at each outward flange with liquid crystal orienting film of above-mentioned a pair substrate, after coating adds the epoxy adhesive of the alumina balls having diameter 3.5 μm, become the mode overlap crimping of antiparallel (antiparallel) with LCD alignment face, tackiness agent is hardened.Then, (Merck & Co., Inc. manufactures to fill nematic liquid crystal between from liquid crystal injecting port to a pair substrate, MLC-6608) after, encapsulated liquid crystals inlet is carried out with acrylic acid series photo-hardening tackiness agent, make liquid crystal cells, and then in the two sides, outside of this liquid crystal cells laminating Polarizer, manufacture the liquid crystal display device of vertical orientation evaluation thus.
(3) evaluation of vertical orientation
To the liquid crystal display device of above-mentioned vertical orientation evaluation, crystallization is utilized to rotate horn cupping to measure tilt angle.Evaluation carries out as follows: be that the situation of more than 87 ° is denoted as vertical orientation " well " by tilt angle, situation tilt angle being less than 87 ° is denoted as vertical orientation " bad ".Its evaluation result is shown in following table 1.
In addition, when manufacturing the liquid crystal display device of vertical orientation evaluation, friction treatment is carried out to the film be formed on substrate, but this friction treatment known has the effect of the vertical orientation control weakening liquid crystal orienting film.Therefore, even if when implementing friction treatment and also showing the tilt angle of more than 87 °, this liquid crystal orienting film can say that the vertical orientation of liquid crystal molecule is extremely excellent.In addition, clear and definite by experience, providing the crystal aligning agent of this result when for utilizing ODF mode to manufacture vertical orientation type liquid crystal display device, also substantially can not produce display uneven (ODF is uneven).
(4) manufacture of the liquid crystal display device of voltage retention evaluation
Except not implementing friction treatment to formed film and except the cleaning after it and drying treatment, utilizing the method identical with the situation of the liquid crystal display device manufacturing vertical orientation evaluation to manufacture the liquid crystal display device of voltage retention evaluation.
(5) evaluation of voltage retention
To the liquid crystal display device of above-mentioned manufactured voltage retention evaluation, apply the voltage of 1V with the interval (span) of the application time of 60 microseconds, 1670 microseconds at 60 DEG C after, measure the voltage retention VHR [%] after 1670 milliseconds from releasing voltage applies.Mensuration is that the VHR-1 using Dongyang technology (ToyoCorporation) to manufacture carries out.Its measurement result is shown in following table 1.
(6) evaluation of the re-workability of liquid crystal orienting film
Utilize turner, being arranged at coating of liquid crystalline orientation agent (S-1) on the nesa coating comprising ITO that thickness is the wherein one side of the glass substrate of 1mm, carrying out the prebake conditions of 90 seconds on hot plate with 100 DEG C, forming the film that thickness is about 80nm.Repeat this operation, make two pieces of substrates with film.Then, two of gained pieces of substrates are taken care of in the darkroom of 25 DEG C in a nitrogen environment.From keeping starts after 12 hours and after 48 hours, removing 1 piece of substrate respectively, being added with in the beaker of the NMP of temperature adjustment to 40 DEG C dipping 2 minutes, then with ultrapure water cleaning for several times, being removed the water droplet on surface by air blast.For this substrate, utilize opticmicroscope to carry out observation to find out that film is with or without residue, evaluate the stripping easiness (re-workability) on substrate of liquid crystal orienting film thus.Evaluation carries out as follows: even if the substrate will taken out after 48 hours starting from keeping, the average evaluation also not observing the residue of film after NMP dipping is re-workability " Gifted is good "; Though substrate after 48 hrs will be observed the residue of film, situation substrate after 12h not being observed the residue of film is denoted as re-workability " well "; The situation of the residue observing film in substrate is after 12h denoted as re-workability " bad ".Its evaluation result is shown in following table 1.
(7) sunproof evaluation
To above-mentioned manufactured liquid crystal display device, measure initial voltage retention with the condition identical with the evaluation of voltage retention.Then, under 100 watts of type white fluorescent lamps, be configured at the distance of 5em, after irradiating the light of 500 hours, again measure voltage retention with condition same as described above.By the rate of descent of the voltage retention compared with initial value be less than 1% situation be denoted as photostabilization " A ", by more than 1% and be less than 2% situation be denoted as " B ", the situation more than 2% is denoted as photostabilization " C ".
[embodiment 2 ~ embodiment 10, comparative example 1 ~ comparative example 4]
Except the content of the kind of polymkeric substance and epoxy compounds is changed to as described in Table 1 respectively, prepare crystal aligning agent (S-2) ~ crystal aligning agent (S-14) in the same manner as example 1 respectively, and carry out vertical orientation, voltage retention, re-workability and sunproof each evaluation.These results evaluated are shown in following table 1.
[table 1]
As shown in table 1, in the liquid crystal orienting film that the crystal aligning agent of embodiment is formed, tilt angle all shows the high value to more than 87 °, and the vertical orientation of liquid crystal molecule is excellent.In addition, in the crystal aligning agent of embodiment, even if implement friction treatment to the film be formed on substrate, tilt angle is also high, therefore can saying when utilizing ODF mode to manufacture vertical orientation type liquid crystal display device, also can suitably suppress to show uneven generation.In addition, in the crystal aligning agent of embodiment, not only photostabilization is good, and when contain epoxy compounds in crystal aligning agent, re-workability is also good.
In addition, in the crystal aligning agent of embodiment, voltage retention is also good, wherein, comprise polyimide (PI-1), polyimide (PI-3) or polyimide (PI-5) as in the embodiment 1 of component of polymer, embodiment 3, embodiment 5, embodiment 10, the high voltage holding ratio of display more than 98.0%.
On the other hand, in comparative example 1 ~ comparative example 3, though re-workability is good, vertical orientation and photostabilization bad.In addition, in comparative example 4, though vertical orientation and photostabilization are well, re-workability is bad.

Claims (9)

1. a crystal aligning agent, its contain to be selected from by polyamic acid, poly amic acid ester, polyimide and organopolysiloxane form at least one polymkeric substance in cohort, and the feature of described crystal aligning agent is: the polymkeric substance (P1) containing the group had represented by following formula (0) is as above-mentioned polymkeric substance:
In formula (0), Ac 1and Ac 2be separately cyclohexane ring or phenyl ring, these rings can have substituting group; R 1for the alkyl of hydrogen atom or carbon number 1 ~ 20; X is Sauerstoffatom; n 1be 1 or 2, n 2be 0 or 1; Wherein, at n 1when being 2, multiple Ac 1separately there is above-mentioned definition; M is the integer of 1 ~ 3; " * " represents associative key.
2. crystal aligning agent according to claim 1, it is characterized in that, above-mentioned polymkeric substance (P1) for be selected from by polyamic acid, poly amic acid ester and polyimide form at least one in cohort, described polyamic acid, poly amic acid ester and polyimide be to make to be selected from by tetracarboxylic dianhydride and tetracarboxylic acid diester compound form at least one compound in cohort, carry out reacting with the diamines of the compound comprised represented by following formula (1) and obtain:
In formula (1), Ac 1and Ac 2be separately cyclohexane ring or phenyl ring, these rings can have substituting group; R 1for the alkyl of hydrogen atom or carbon number 1 ~ 20; X is Sauerstoffatom; n 1be 1 or 2, n 2be 0 or 1; Wherein, at n 1when being 2, multiple Ac 1separately there is above-mentioned definition; M is the integer of 1 ~ 3.
3. crystal aligning agent according to claim 1 and 2, is characterized in that, said n 1with said n 2and be 2 or 3.
4. crystal aligning agent according to claim 1 and 2, is characterized in that, said n 1with said n 2and be 2.
5. crystal aligning agent according to claim 1 and 2, is characterized in that, above-mentioned X is Sauerstoffatom ,+-CO-O-or+-O-CO-, and wherein, "+" represents the associative key with phenylene.
6. a liquid crystal orienting film, is characterized in that, uses the crystal aligning agent according to any one of claim 1 to 5 to be formed.
7. a liquid crystal display device, is characterized in that, comprises liquid crystal orienting film as claimed in claim 6.
8. a polymkeric substance, is characterized in that, to make to be selected from by tetracarboxylic dianhydride and tetracarboxylic acid diester compound form at least one compound in cohort, carry out reacting with the diamines of the compound comprised represented by following formula (1) and obtain:
In formula (1), Ac 1and Ac 2be separately cyclohexane ring or phenyl ring, these rings can have substituting group; R 1for the alkyl of hydrogen atom or carbon number 1 ~ 20; X is Sauerstoffatom; n 1be 1 or 2, n 2be 0 or 1; Wherein, at n 1when being 2, multiple Ac 1separately there is above-mentioned definition; M is the integer of 1 ~ 3.
9. the compound represented by a following formula (1):
In formula (1), Ac 1and Ac 2be separately cyclohexane ring or phenyl ring, these rings can have substituting group; R 1for the alkyl of hydrogen atom or carbon number 1 ~ 20; X is Sauerstoffatom; n 1be 1 or 2, n 2be 0 or 1; Wherein, at n 1when being 2, multiple Ac 1separately there is above-mentioned definition; M is the integer of 1 ~ 3.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101470302A (en) * 2007-12-27 2009-07-01 智索株式会社 Liquid crystal tropism agent, liquid crystal tropism film and liquid crystal display element
CN101570636A (en) * 2008-04-30 2009-11-04 Jsr株式会社 Liquid crystal aligning agent, liquid crystal display element, polyamic acid and imide amination polymer and compound thereof
CN101606100A (en) * 2007-03-26 2009-12-16 夏普株式会社 Liquid crystal indicator and polymer for aligning film material
CN101735826A (en) * 2008-11-25 2010-06-16 智索株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
CN102604652A (en) * 2011-01-13 2012-07-25 Jsr株式会社 Liquid crystal aligning agent,liquid crystal display element and manufacture method thereof
CN102618299A (en) * 2011-01-11 2012-08-01 Jsr株式会社 Liquid crystal aligning agent, liquid crystal display device, liquid crystal alignment film and polyorganosiloxane compound

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05216046A (en) * 1992-02-06 1993-08-27 Fuji Photo Film Co Ltd Oriented film
JP3432584B2 (en) * 1994-04-27 2003-08-04 住友化学工業株式会社 Optical anisotropic film, method of manufacturing the same, retardation plate and liquid crystal display
JP4433113B2 (en) 2000-04-24 2010-03-17 Ｊｓｒ株式会社 Liquid crystal alignment agent
JP4569145B2 (en) * 2004-03-25 2010-10-27 チッソ株式会社 Polyimide copolymer, liquid crystal aligning agent and liquid crystal display element using the same
JP5273035B2 (en) 2007-03-23 2013-08-28 日産化学工業株式会社 Liquid crystal alignment treatment agent
WO2008117760A1 (en) 2007-03-23 2008-10-02 Nissan Chemical Industries, Ltd. Diamine compound, polyamic acid, polyimide and liquid crystal aligning agent
JP5407394B2 (en) * 2008-03-21 2014-02-05 Ｊｎｃ株式会社 Photo-alignment agent, alignment film, and liquid crystal display device using the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101606100A (en) * 2007-03-26 2009-12-16 夏普株式会社 Liquid crystal indicator and polymer for aligning film material
CN101470302A (en) * 2007-12-27 2009-07-01 智索株式会社 Liquid crystal tropism agent, liquid crystal tropism film and liquid crystal display element
CN101570636A (en) * 2008-04-30 2009-11-04 Jsr株式会社 Liquid crystal aligning agent, liquid crystal display element, polyamic acid and imide amination polymer and compound thereof
CN101735826A (en) * 2008-11-25 2010-06-16 智索株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
CN102618299A (en) * 2011-01-11 2012-08-01 Jsr株式会社 Liquid crystal aligning agent, liquid crystal display device, liquid crystal alignment film and polyorganosiloxane compound
CN102604652A (en) * 2011-01-13 2012-07-25 Jsr株式会社 Liquid crystal aligning agent,liquid crystal display element and manufacture method thereof

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