CN102859426B - Liquid crystal aligning agent, liquid crystal alignment film produced using same, and liquid crystal display element - Google Patents
Liquid crystal aligning agent, liquid crystal alignment film produced using same, and liquid crystal display element Download PDFInfo
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- CN102859426B CN102859426B CN201180019165.8A CN201180019165A CN102859426B CN 102859426 B CN102859426 B CN 102859426B CN 201180019165 A CN201180019165 A CN 201180019165A CN 102859426 B CN102859426 B CN 102859426B
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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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
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
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Abstract
Disclosed is a liquid crystal aligning agent which can prevent the occurrence of a whitening phenomenon and a phenomenon of generating a foreign matter on a substrate, enables the production of a liquid crystal alignment film prevented from the reduction in a pretilt angle, and has a good aligning property. Specifically disclosed are: a liquid crystal aligning agent which is characterized by comprising a polyimide that is produced by imidizing a polyamic acid produced by reacting a diamine component with a tetracarboxylic acid dianhydride and a polyol compound that has a tertiary nitrogen atom and a quaternary carbon atom and contains 3 to 15 carbon atoms; a liquid crystal alignment film produced using the composition; and a liquid crystal display element.
Description
Technical field
The present invention relates to and a kind ofly inhibit albefaction, the generation of foreign matter and the aligning agent for liquid crystal that tilt angle is not reduced, use liquid crystal orientation film and the liquid crystal display cells of this aligning agent for liquid crystal.
Background technology
Liquid crystal display cells has liquid crystal molecule to be formed on the structure clamped by liquid crystal orientation film on substrate, to utilize the display element of the response produced by voltage via liquid crystal orientation film towards the liquid crystal molecule of certain orientation orientation.This liquid crystal orientation film uses the aligning agent for liquid crystal (also referred to as aligning agent for liquid crystal) being formed and have the polyimide film of high reliability usually.
As the method forming polyimide film on electroded substrate, have the film making the aligning agent for liquid crystal be made up of the solution of the polyimide precursors such as polyamic acid, the method making its imidizate on substrate, and use contains in advance through the method for the solution of the polyimide of imidizate.
Wherein, even use the burning till of method lower temperature of the solution containing polyimide also can be formed as the good polyimide film of characteristic during liquid crystal orientation film, but then, the film strength formed is low, easily causes the damage to film surface and film stripping with orientation process such as friction treatment.The damage on liquid crystal orientation film surface and stripping can cause as display during liquid crystal display cells bad, are therefore major issues.
On the other hand, the method of the solution containing polyimide is used also to there is following problem, namely, general in organic solvent poorly soluble compared with polyimide and polyamic acid etc., therefore be sometimes difficult to form uniform film, even also can not dissolve the solvent being usually used in aligning agent for liquid crystal and be difficult to be included in aligning agent for liquid crystal.Therefore, the dissolubility of contained in aligning agent for liquid crystal polyimide is also very important.
In addition, if use the aligning agent for liquid crystal containing polyimide, then when being printed on substrate, polyimide can be separated out because of moisture absorption, varnish generation albinism, makes gained film produce rough surface.
Moreover, under the occasion of the aligning agent for liquid crystal containing polyimide, polyimide and APR(morning sun photosensitive resin (Asahi Photosensitive Resin)) etc. the adaptation of galley poor, in printing process, film can be peeled off from galley, owing to being transferred on substrate with this state, easily causing that the polyimide peeled off to remain on substrate as foreign matter, it produces aggegation and cause the problem of gap inequality.
For above-mentioned technical matters, propose for the purpose of the dissolubility of the rub resistance and polyimide that improve liquid crystal orientation film containing the aligning agent for liquid crystal (see patent documentation 1) of diamine component with ad hoc structure.In addition, as the method for the albinism of the varnish suppressed containing polyimide, propose more than 50% of solvent and use NVP or N-cyclohexyl pyrrolidone etc. can suppress the technical scheme (see patent documentation 2) of the high boiling solvent of drying time.
Prior art document
Patent documentation
Patent documentation 1: International Publication No. 2006/126555 text
Patent documentation 2: Japanese Patent Laid-Open 05-117587 publication
Summary of the invention
Invent technical matters to be solved
But, the existing scheme of above-mentioned proposition might not be abundant, such as, in the scheme of the use high boiling solvent of patent documentation 2, the usual hydroscopicity of these solvents is high, if therefore use quantitative change large, then notify and caused making the above-mentioned albinism of the varnish of aligning agent for liquid crystal to increase and the spinoff of the tilt angle of the liquid crystal orientation film of gained reduction.
In recent years, along with maximization and the high resolving power of liquid crystal display cells, to the requirement increasingly stringent of quality, the problem albinism of the above-mentioned aligning agent for liquid crystal containing polyimide, substrate producing the tilt angle reduction of phenomenon, the also rewarding liquid crystal orientation film of foreign matter becomes the important topic that should solve.
The object of this invention is to provide a kind of aligning agent for liquid crystal that tilt angle reduces, orientation is also good that inhibit the phenomenon albinism of the aligning agent for liquid crystal containing polyimide, substrate producing foreign matter, the liquid crystal orientation film that further suppress gained.
The technical scheme that technical solution problem adopts
The present inventor conducts in-depth research for achieving the above object, and result completes the present invention.That is, the present invention has following main points.
1. aligning agent for liquid crystal, is characterized in that, the polyimide obtained through imidizate containing the polyamic acid be obtained by reacting by diamine component and tetracarboxylic dianhydride and the carbon number with tertiary N atom and quaternary carbon atom are the polyol compound of 3 ~ 15.
2. the aligning agent for liquid crystal as described in above-mentioned 1, wherein, polyol compound is represented by following formula (A),
[changing 1]
(in formula, R
1, R
2separately represent the hydroxyalkyl of carbon number 1 ~ 5, R
3, R
4, R
5separately represent the alkyl of carbon number 1 ~ 5 or the hydroxyalkyl of carbon number 1 ~ 5).
3. the aligning agent for liquid crystal as described in above-mentioned 1 or 2, wherein, polyol compound has 2 ~ 8 hydroxyls.
4., as the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 3, wherein, the content of polyimide is 1 ~ 10 quality %, and the content of polyol compound is 0.1 ~ 10 mass parts relative to 100 mass parts polyimide.
5., as the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 4, wherein, diamine component is have the diaminobenzene being replaced the disubstituted amido obtained by the alkenyl of carbon number 2 or 3.
6. the aligning agent for liquid crystal as described in above-mentioned 5, wherein, diaminobenzene is the diamines represented by following formula [1],
[changing 2]
7. the aligning agent for liquid crystal as described in above-mentioned 6, wherein, diamine component also contains the diamines that following formula [32] represents,
[changing 3]
(in above formula, k represents the integer of 1 ~ 20).
8. the aligning agent for liquid crystal as described in above-mentioned 6 or 7, wherein, the content of the diamines that formula [1] represents in whole diamine component is 20 ~ 90 % by mole.
9. the aligning agent for liquid crystal as described in above-mentioned 7 or 8, wherein, the content of the diamines that formula [32] represents in whole diamine component is 5 ~ 40 % by mole.
10. liquid crystal orientation film, to coat the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 9 on electroded substrate and to obtain through burning till.
11. liquid crystal display cells, have the liquid crystal orientation film described in above-mentioned 10.
Invention effect
The aligning agent for liquid crystal of the application of the invention, the albinism that can be inhibited and substrate produce foreign matter, this foreign matter aggegation and the phenomenon of gap inequality occurs, the tilt angle that further suppress the liquid crystal orientation film of gained reduces, the liquid crystal orientation film that orientation is also good; And by using this liquid crystal orientation film, large-scale, also have high reliability under high-resolution occasion liquid crystal display cells can be produced with good productivity.
Why the mechanism that the aligning agent for liquid crystal of the application of the invention inhibits the tilt angle of phenomenon albinism and substrate producing foreign matter, the liquid crystal orientation film that further suppress gained to reduce it be unclear that, but thinks that reason is roughly as follows.
Think that the carboxylic acid group in the tertiary amine that the polyol compound contained by aligning agent for liquid crystal of the present invention has and polymkeric substance forms salt, thus improve the dissolubility of the polymkeric substance containing polyimide to water, result improves the patience of whitening.Also think the existence of the multiple hydroxyls had due to polyol compound, adaptation between polymkeric substance containing polyimide and APR version promotes, thus because the foreign matter caused by film stripping during printing produces and the gap inequality of consequential liquid crystal display cells is suppressed.
Embodiment
Aligning agent for liquid crystal of the present invention contains the polyimide that the polyamic acid be obtained by reacting by diamine component and tetracarboxylic dianhydride as polymkeric substance obtains through imidizate.The polyimide used in the present invention is not particularly limited, and can obtain as follows.
[diamine component]
Diamine component (also referred to as diamines) for obtaining polyimide is not particularly limited.This diamines can use one, also can multiple and use, does not limit kind.As the kind of diamines, ester ring type diamines, aromatic diamines, hetero ring type Diamines or aliphatic diamine can be illustrated.Below provide its concrete example.
As the example of ester ring type diamines, Isosorbide-5-Nitrae-diamino-cyclohexane, 1,3-diamino-cyclohexane, 4 can be exemplified, 4 '-diamino-dicyclohexyl methane, 4,4 '-diamido-3,3 '-dimethyidicyclohexyl amine and isophorone diamine etc.
As the example of aromatic diamines, o-phenylenediamine can be exemplified, m-phenylene diamine, p-phenylenediamine (PPD), 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, Isosorbide-5-Nitrae-diamido-2-methoxybenzene, 2,5-diamido-P-xylene, 1,3-diamido-4-chlorobenzene, 3,5-diaminobenzoic acid, Isosorbide-5-Nitrae-diamido-2,5-dichloro-benzenes, 4,4 '-diaminostilbene, 2-diphenylethane, 4,4 '-diamido-2,2 '-dimethyl bibenzyl, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diamido-3,3 '-dimethyl diphenylmethane, 2,2 '-diamido Stilbene, 4,4 '-diamido Stilbene, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diamino diphenyl sulfide, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diaminobenzophenone, two (3-amino-benzene oxygen) benzene of 1,3-, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzoic acid of 3,5-, 4,4 '-bis-(4-amino-benzene oxygen) bibenzyl, two [(4-amino-benzene oxygen) methyl] propane of 2,2-, 2,2-pair [4-(4-amino-benzene oxygen) phenyl)] HFC-236fa, 2,2-pair [4-(4-amino-benzene oxygen) phenyl)] propane, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two (4-aminophenyl) cyclohexane of 1,1-, α, α '-bis-(4-aminophenyl)-Isosorbide-5-Nitrae-diisopropyl benzene, two (4-aminophenyl) fluorenes of 9,9-, two (3-aminophenyl) HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-diamino-diphenyl amine, 2,4-diamino-diphenyl amine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diamino-anthraquinone, 1,3-diamido pyrene, 1,6-diamido pyrene, 1,8-diamido pyrene, 2,7-diamino-fluorene, two (4-aminophenyl) tetramethyl disiloxane of 1,3-, biphenylamine, 2,2 '-dimethylbenzidine, two (4-aminophenyl) ethane of 1,2-, two (4-aminophenyl) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) butane, two (4-aminophenyl) pentane of 1,5-, two (4-aminophenyl) hexane of 1,6-, two (4-aminophenyl) heptane of 1,7-, two (4-aminophenyl) octane of 1,8-, two (4-aminophenyl) nonane of 1,9-, two (4-aminophenyl) decane of 1,10-, two (4-amino-benzene oxygen) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) butane, two (4-amino-benzene oxygen) pentane of 1,5-, two (4-amino-benzene oxygen) hexane of 1,6-, two (4-amino-benzene oxygen) heptane of 1,7-, two (4-amino-benzene oxygen) octane of 1,8-, two (4-amino-benzene oxygen) nonane of 1,9-, two (4-amino-benzene oxygen) decane of 1,10-, two (4-aminophenyl)-1,3-malonate, two (4-aminophenyl)-1, 4-succinic acid esters, two (4-aminophenyl)-1,5-glutarate, two (4-aminophenyl)-1,6-adipate, two (4-aminophenyl)-1,7-pimelate, two (4-aminophenyl)-1,8-suberate, two (4-aminophenyl)-1,9-azelate, two (4-aminophenyl)-1,10-sebacate, two [4-(4-amino-benzene oxygen) phenoxy group] propane of 1,3-, Isosorbide-5-Nitrae-bis-[4-(4-amino-benzene oxygen) phenoxy group] butane, two [4-(4-amino-benzene oxygen) phenoxy group] pentane of 1,5-, two [4-(4-amino-benzene oxygen) phenoxy group] hexane of 1,6-, two [4-(4-amino-benzene oxygen) phenoxy group] heptane of 1,7-, two [4-(4-amino-benzene oxygen) phenoxy group] octane of 1,8-, two [4-(4-amino-benzene oxygen) phenoxy group] nonane of 1,9-, two [4-(4-amino-benzene oxygen) phenoxy group] decane of 1,10-etc.
As the example of hetero ring type Diamines, DAP, 2 can be exemplified, 4-diamino-pyridine, 2,4-diaminostilbenes, 3,5-triazine, 2,7-diamido dibenzofurans, 3,6-diaminocarbazole, 2,4-diamido-6-isopropyl-1,3,5-triazine, 2,5-two (4-aminophenyls)-1,3,4-
diazole etc.
As the example of aliphatic diamine, can 1 be exemplified, 2-diaminoethanes, 1, 3-diaminopropanes, 1, 4-diaminobutane, 1, 5-1,5-DAP, 1, 6-diamino hexane, 1, 7-diaminoheptane, 1, 8-diamino-octane, 1, 9-diamino nonane, 1, 10-diamino decane, 1, 3-diamido-2, 2-dimethylpropane, 1, 6-diamido-2, 5-dimethylhexane, 1, 7-diamido-2, 5-dimethyl heptane, 1, 7-diamido-4, 4-dimethyl heptane, 1, 7-diamido-3-methylheptane, 1, 9-diamido-5-methylheptane, 1, 12-diamino dodecane, 1, 18-diamido octadecane, 1, 2-two (the amino propoxyl group of 3-) ethane etc.
In the present invention, as diamines, preferably use the diaminobenzene (hereinafter also referred to specific diamines) with the disubstituted amido obtained by the replacement of the alkenyl of carbon number 2 or 3.Under the occasion using specific diamines, structure adaptability raises, and more effectively can suppress the generation of foreign matter.As specific diamines, what particularly preferably following formula [1] represented have is replaced by 2-propenyl (hereinafter also referred to allyl) and the diaminobenzene of disubstituted amido that obtains.
[changing 4]
In the diamines that formula [1] represents, each substituent position on phenyl ring is not particularly limited, but preferably 2 amino position relationships be between position or contraposition.Below exemplify the preferred concrete example of this diamines.
[changing 5]
Above formula [2] is 2,4-diamino-N, N-diallyl aniline, and above formula [3] is 3,5-diamino-N, N-diallyl aniline, and above formula [4] is 2,5-diamino-N, N-diallyl aniline.Described diaminobenzene is more preferably at least one being selected from above-mentioned [2], [3] and [4].Wherein, described diaminobenzene is particularly preferably 2,4-diamino-N, N-diallyl aniline.
In the present invention, the diamine component as the raw material of polyimide can be only specific diamines, or also can be the combination of specific diamines and other one kind or two or more diamines.Contain specific diamines by being used in the diamine component obtaining polyimide, polyimide raises the dissolubility of organic solvent.Peel off these problems to the damage on film surface and film when also making to carry out friction treatment to film to improve.
In diamine component, the content of specific diamines is preferably at 20 moles of (mol) more than %, more preferably more than 40 % by mole, particularly preferably in more than 50 % by mole.In diamine component specific diamines containing proportional higher, the effect suppressing the damage of alignment layer surface during friction treatment and film to be peeled off is higher.In addition, the polyimide of gained is also higher to the dissolubility of organic solvent.On the other hand, diamine component can be only specific diamines, but and other characteristics needed for liquid crystal orientation film can be given with the diamines beyond specific diamines, therefore preferably.So the content of specific diamines is more preferably below 90 % by mole.Particularly, if use specific diamines and 4-amino-benzylamine, 3-amino-benzylamine or 4-aminophenethyl amine, then polyimide raises the dissolubility of organic solvent, obtains the aligning agent for liquid crystal that liquid crystal aligning is more excellent, therefore particularly preferably.4-amino-benzylamine, 3-amino-benzylamine or the preferred content of 4-aminophenethyl amine in diamine component are 10 % by mole ~ 50 % by mole.
In addition, in order to improve the tilt angle of liquid crystal, the diamines with specified substituent can also be combinationally used.As the substituting group of tilt angle that can increase liquid crystal, preferably chain alkyl, perfluoroalkyl, aromatic cyclic base, aliphatic cyclic base and the substituting group be combined into by them or steroid backbone group etc.Below, exemplify the object lesson with this substituent diamines, but be not limited to this.In addition, in illustrative structure, j represents the integer of 5 ~ 20, more preferably 9 ~ 17 below, and k represents the integer of 1 ~ 20, more preferably 4 ~ 15.
[changing 6]
[changing 7]
[changing 8]
[changing 9]
In above-mentioned diamines, the diamines of formula [5], formula [32] because liquid crystal aligning is excellent preferably.The diamines of formula [12] ~ [19] because of the presentation capability of tilt angle very high and be suitable for OCB(optical compensation curved (OpticallyCompensated Bend)) with alignment films, VA(vertical orientated (Vertical Alignment)) use alignment films.As preference, can exemplify: for TN(twisted-nematic (Twisted nematic)) be 5 ~ 40 % by mole with the content of diamines in diamine component of alignment films (tilt angle is 3 ~ 5 °) then formula [5] or [32], be more preferably 10 ~ 30 % by mole, the content of diamines in diamine component for OCB, VA alignment films (tilt angle is 10 ~ 90 °) then formula [12] ~ [19] is 5 ~ 60 % by mole, is more preferably 10 ~ 40 % by mole.
In above-mentioned diamines, formula [32] even if diamines because of tilt angle high and when combinationally using with described specific diamines when friction condition is weak liquid crystal aligning also excellent and particularly preferably.Moreover, the effect of the tilt angle of the raising liquid crystal of above-mentioned this diamines has containing when more N-ethyl-2-pyrrolidone or CHP the tendency weakened in aligning agent for liquid crystal, but the diamines of formula [32] has the feature not being subject to this impact, and the diamine component as the polyimide contained by aligning agent for liquid crystal of the present invention is fit closely.
[tetracarboxylic dianhydride's composition]
In the present invention, the tetracarboxylic dianhydride's composition as the raw material of polyimide can be a kind of tetracarboxylic dianhydride, the tetracarboxylic dianhydride that also can be mixed with two or more.
But, even also easily obtain the higher polyimide of dissolubility from the polyimide of high acid imide rate and the angle etc. of voltage retention of liquid crystal cell can be improved, preferably use the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure.
As the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure, can 1 be exemplified, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 2-dimethyl-1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 3-dimethyl-1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 2, 3, 4-tetramethyl-1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentane tetracarboxylic dianhydride, 2, 3, 4, 5-tetrahydrofuran tetracarboxylic dianhydride, 1, 2, 4, 5-cyclopentanetetracarboxylic dianhydride, 3, 4-dicarboxyl-1-cyclohexyl succinic acid dianhydride, 3, 4-dicarboxyl-1, 2, 3, 4-tetrahydrochysene-1-naphthalene succinic dianhydride, 1, 2, 3, 4-butane tetracarboxylic acid dianhydride, two rings [3, 3, 0] octane-2, 4, 6, 8-tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-dicyclohexyl tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, cis-3, 7-dibutyl ring pungent-1, 5-diene-1, 2, 5, 6-tetracarboxylic dianhydride, three ring [4.2.1.0
2.5] nonane-3,4,7,8-tetrabasic carboxylic acid-3,4:7,8-dianhydride, six ring [6.6.0.1
2.7.0
3.6.1
9.14.0
10.13] hexadecane-4,5,11,12-tetrabasic carboxylic acid-4,5:11,12-dianhydride etc.
As the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure, if use 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 3,4-dicarboxyls-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride or 1,2,3,4-butane tetracarboxylic acid dianhydride, then because of can obtain liquid crystal aligning excellence alignment films and particularly preferably.
Moreover, if outer again and use aromatic tetracarboxylic acid's dianhydride the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure, then because can liquid crystal aligning be improved and reduce the accumulated charge of liquid crystal cell and preferred.As aromatic tetracarboxylic acid's dianhydride, pyromellitic acid anhydride, 3 can be exemplified, 3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyphenyi) ether dianhydride, two (3,4-dicarboxyphenyi) sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride etc.
As aromatic tetracarboxylic acid's dianhydride, wherein particularly preferably pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, two (3,4-dicarboxyphenyi) ether dianhydride or Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid dianhydride.
If consider the equilibrium between each characteristics such as the orientation of the dissolubility of polyimide, liquid crystal, voltage retention, accumulated charge, have the tetracarboxylic dianhydride of ester ring type structure or aliphatic structure and the ratio of aromatic tetracarboxylic acid's dianhydride with the former/molar ratio computing of the latter is preferably 90/10 ~ 50/50, is more preferably 80/20 ~ 60 ~ 40.
[polyimide and manufacture method thereof]
Aligning agent for liquid crystal of the present invention polyimide used is the polyimide that the polyamic acid being reacted by above-mentioned diamine component and tetracarboxylic dianhydride's composition and obtained obtains through imidizate.Here, polyamic acid can be undertaken reacting by making tetracarboxylic dianhydride's composition and diamine component mix in organic solvent and obtain.
As the method making tetracarboxylic dianhydride's composition and diamine component mix in organic solvent, can exemplify to stir makes diamine component be dispersed or dissolved in organic solvent and the solution, wherein directly interpolation tetracarboxylic dianhydride's composition or the method for adding again after making tetracarboxylic dianhydride's composition be dispersed or dissolved in organic solvent that obtain, add the method for diamine component in the solution obtained tetracarboxylic dianhydride's composition is dispersed or dissolved in organic solvent on the contrary, alternately add the method etc. of tetracarboxylic dianhydride's composition and diamine component.In addition, at tetracarboxylic dianhydride's composition or diamine component by under the occasion that multiple compounds is formed, carry out polyreaction under the state that can be pre-mixed at these Multiple components, also can carry out polyreaction successively respectively.
Temperature when tetracarboxylic dianhydride's composition and diamine component carry out polyreaction is in organic solvent generally 0 ~ 150 DEG C, is preferably 5 ~ 100 DEG C, is more preferably 10 ~ 80 DEG C.Temperature is higher, and polyreaction completes sooner, if but too high, sometimes cannot obtain the polymkeric substance of high molecular.
In addition, polyreaction can be carried out with arbitrary concentration, if but concentration is too low, then be difficult to the polymkeric substance obtaining high molecular, if excessive concentration, the viscosity of reactant liquor is too high and be difficult to stir uniformly, therefore the concentration of the total amount of tetracarboxylic dianhydride's composition and diamine component is preferably 1 ~ 50 quality %, is more preferably 5 ~ 30 quality %.Can carry out with high concentration at the polyreaction initial stage, and then additional organic solvent.
As long as the organic solvent used during above-mentioned reaction can dissolve the solvent of the polyamic acid of generation, then there is no particular limitation, but can use N-ethyl-2-pyrrolidone or CHP or other solvent.Its concrete example can exemplify N, dinethylformamide, N, N-dimethyl acetamide, METHYLPYRROLIDONE, N-methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, pregnancy phosphoric triamide, gamma-butyrolacton, 1,3-dimethyl-imidazolinone etc.These solvents can be used alone, also can be used in combination.Further, even the solvent of insoluble solution polyamic acid, as long as in the scope that the polyamic acid generated can not be separated out, also can be used in combination with above-mentioned solvent.In addition, the moisture in organic solvent hinders polyreaction, and is make the acid-hydrolyzed origin cause of formation of the polyamide of generation, and therefore organic solvent preferably uses the organic solvent as much as possible dehydrated.
The ratio of tetracarboxylic dianhydride's composition that the polyreaction of polyamic acid is used and diamine component is preferably 1:0.8 ~ 1:1.2 with molar ratio computing, and this mol ratio is more close to 1:1, and the molecular weight of the polyamic acid of gained is larger.By controlling the molecular weight of this polyamic acid, the molecular weight of the polyimide obtained after can adjusting imidizate.
There is no particular limitation for the molecular weight of polyimide contained in aligning agent for liquid crystal of the present invention, from the angle being coated with film strength and the tractability as aligning agent for liquid crystal, be preferably 2000 ~ 200000 with Weight-average molecular gauge, be more preferably 5000 ~ 50000.
As above the polyamic acid of gained imidizate can by organic solvent, under the existence of base catalyst and acid anhydrides stirring within 1 ~ 100 hour, carry out.
As base catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be exemplified.Wherein pyridine has appropriate alkaline that reaction is carried out and preferably because of it.In addition, as acid anhydrides, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc. can be exemplified.Wherein acetic anhydride because of after imidizate terminates the polyimide of gained easily refining and preferably.As organic solvent, solvent used when can use above-mentioned polyamic acid polyreaction.
The acid imide rate of polyimide can control by regulating catalytic amount and temperature of reaction, reaction time.The amount of base catalyst is now preferably 0.2 ~ 10 times mole of the acid amides acidic group contained by base polyamide acid, is more preferably 0.5 ~ 5 times mole.In addition, the amount of acid anhydrides is preferably 1 ~ 30 times mole of the acid amides acidic group contained by base polyamide acid, is more preferably 1 ~ 10 times mole.Temperature of reaction preferably-20 ~ 250 DEG C, is more preferably 0 ~ 180 DEG C.
There is no particular limitation for the acid imide rate of the polyimide contained by aligning agent for liquid crystal of the present invention, but consider electrical characteristics preferably more than 40%, in order to obtain higher voltage retention more preferably more than 60%, preferred more than 80% further.
The remaining catalyzer etc. having interpolation in the solution of the polyimide so obtained, therefore preferred by polyimide reclaim, cleaning after be used further to aligning agent for liquid crystal of the present invention.
Solution after imidizate can be dropped into the Weak solvent that stirred by the recovery of polyimide, filters after polyimide is separated out.Weak solvent now can exemplify methyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene etc.The cleaning of the polyimide after recovery also can be carried out with this Weak solvent.
After recovery like this, cleaning, the polyimide that obtains can carry out normal temperature or heat drying and form powder under normal pressure or decompression.
[there is the polyol compound of tertiary nitrogen and quaternary carbon]
Aligning agent for liquid crystal of the present invention contains the polyol compound with tertiary nitrogen and quaternary carbon.Described polyol compound must have tertiary nitrogen and quaternary carbon, under the occasion both do not had, cannot reach above-mentioned purpose of the present invention, or the degree reached diminishes.Such as, as shown in comparative example described later, even there is multiple hydroxyl and tertiary N atom but under there is no the occasion of the triethanolamine of quaternary carbon atom, also cannot reach above-mentioned purpose of the present invention.
Total carbon number that polyol compound has must be 3 ~ 15, is preferably 3 ~ 13, is more preferably 6 ~ 12.The number of the hydroxyl that polyol compound has is important, and hydroxyl is preferably 2 ~ 8, is more preferably 2 ~ 7, is particularly preferably 2 ~ 5.If hydroxyl is too much, then the display characteristic of liquid crystal display cells is deteriorated; If very few conversely, then the adaptation and between APR version is deteriorated, thus bad.The number of tertiary N atom and quaternary carbon atom is that any one all contains more than 1, preferably less than 5, more preferably less than 3.In addition, polyol compound preferably has aliphatic saturated hydrocarbon structure, but under the occasion that total carbon number is large, also a part can have unsaturated link, a part can also have ring texture.
Described polyol compound is preferably the compound that following formula (A) represents.
[changing 10]
In formula, R
1, R
2separately represent carbon number 1 ~ 5, preferably 1 ~ 3 hydroxyalkyl, R
3, R
4, R
5separately represent carbon number 1 ~ 5, preferably 1 ~ 3 alkyl, or the hydroxyalkyl of carbon number 1 ~ 5, preferably 1 ~ 3.
As the preference of the compound that described formula (A) represents, following compound can be exemplified.
[changing 11]
[aligning agent for liquid crystal]
Aligning agent for liquid crystal of the present invention be with described polyimide be component of polymer, there is the polyol compound of tertiary nitrogen and quaternary carbon as adding ingredient, the aligning agent for liquid crystal they being dissolved in solvent.In aligning agent for liquid crystal, polyol compound is relative to 100 mass parts polyimide preferably 0.1 ~ 10 mass parts, more preferably 0.5 ~ 5 mass parts relative to the content of polyimide.Under the occasion that polyol compound content is too much, the properties deteriorate of the liquid crystal display cells of gained; Conversely under very few occasion, target effect of the present invention is little.
In aligning agent for liquid crystal, the content (concentration) of polyimide suitably can change according to the thickness setting of formed liquid crystal orientation film, but solvent is relative to 1 mass parts polyimide preferably 9 ~ 99 mass parts, more preferably 11.5 ~ 49 mass parts.If solvent is more than 99 mass parts, be then difficult to form homogeneous and flawless film; If conversely less than 9 mass parts, then the storage stability of solution is poor sometimes.In addition, in aligning agent for liquid crystal of the present invention, the content of solvent is preferably 90 ~ 99 quality % of aligning agent for liquid crystal entirety, is more preferably 92 ~ 98 quality %.
As the solvent used in aligning agent for liquid crystal of the present invention, N can be exemplified, dinethylformamide, N, N-dimethyl acetamide, METHYLPYRROLIDONE, N-methyl caprolactam, 2-Pyrrolidone, NVP, dimethyl sulfoxide, tetramethylurea, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton, 1,3-dimethyl-imidazolinone etc.Wherein METHYLPYRROLIDONE, 1,3-dimethyl-imidazolinone, gamma-butyrolacton are suitable for because of high to the dissolubility of polyimide using.In addition, gamma-butyrolacton is suitable for because suppressing albefaction using.
In addition, when containing N-ethyl-2-pyrrolidone or CHP as the solvent used in aligning agent for liquid crystal of the present invention, the thickness near the albefaction of film and printed edge can be suppressed uneven, thus preferably.The amount of these solvents, relative to when the polymkeric substance of 1 mass parts is more than 0.5 mass parts, can presents the improvement effect suppressing agglutinator to produce, be preferably 1 ~ 80 weight portion, is more preferably 2 ~ 70 weight portions.
Polyimide contained in aligning agent for liquid crystal of the present invention can be the potpourri of the polyimide of more than two kinds that structure is different.In addition, also can not damaging electrical characteristics, do not reduce the storage stability of varnish, do not produce when printing cause the agglutinator of liquid crystal panel gap inequality extent and scope in and with the polymkeric substance of polyamic acid or other kinds.Should and the consumption of polymkeric substance be preferably 0.05 ~ 7 mass parts relative to 1 mass parts polyimide, be more preferably 0.1 ~ 4 mass parts.The content of the polymkeric substance containing polyimide in aligning agent for liquid crystal of the present invention is preferably 1 ~ 10 quality %, more preferably 2 ~ 8 quality % of aligning agent for liquid crystal entirety.
As the solvent for aligning agent for liquid crystal of the present invention, can partly containing the solvent with low surface tension.By appropriateness mixing in solvent composition, there is the solvent of low surface tension, can make to improve film homogeneity during base plate coating.
As the solvent with low surface tension, ethyl cellosolve can be exemplified, butyl cellosolve, ethyl carbitol, butyl carbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, diethyl carbitol, propylene-glycol monoacetate, propylene-glycol diacetate, dipropylene glycol monomethyl ether, propylene glycol-1-monomethyl ether-2-acetic acid esters, propylene glycol-1-monoethyl ether-2-acetic acid esters, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc.Wherein from the viewpoint of the coating to substrate, butyl cellosolve, ethyl carbitol, dipropylene glycol monomethyl ether or diethylene glycol diethyl ether are particularly preferably.
There is the coating of solvent improvement to substrate of low surface tension, if but consumption crosses the precipitation that polymkeric substance occurs at most, and therefore its content is preferably at below the 60 quality % of solvent composition, more preferably below 50 quality %.By when being used for guaranteeing that the deliquescent solvent of resinous principle combinationally uses with the solvent with low surface tension, more preferably the content of each solvent is the deliquescent solvent for guaranteeing resinous principle is 5 ~ 70 quality %, have the solvent of low surface tension is 10 ~ 60 quality %, further preferably for guaranteeing that the deliquescent solvent of resinous principle is 10 ~ 45 quality %, to have the solvent of low surface tension be 20 ~ 50 quality %.
In aligning agent for liquid crystal of the present invention, the silane coupling agents such as 3-amino propyl methyl diethoxy silane, 3-phenyl amino propyl trimethoxy silane, APTES, (aminoethylaminomethyl) phenethyl trimethoxy silane can be added.By the interpolation of these silane coupling agents, can further improve the adaptation of film to substrate.The content of silane coupling agent is preferably 0.1 ~ 20 mass parts relative to 100 mass parts polymkeric substance, is more preferably 0.2 ~ 10 mass parts.
[modulator approach of aligning agent for liquid crystal]
As long as the modulator approach of aligning agent for liquid crystal of the present invention is based on each composition of above-mentioned polyimide, in aligning agent for liquid crystal, in uniform state, then there is no particular limitation.One example makes the powder dissolution of polyimide form polyimide solution in solvent, then add the method etc. of solvent dilution to required concentration.In this dilution operation, the adjustment of the solvent composition for controlling the coating on substrate and adding for the additive that improves coating characteristic can be carried out.As above the aligning agent for liquid crystal obtained preferably filtered before coating substrate.
Aligning agent for liquid crystal of the present invention can by coating substrate and drying, burning till rear formation film, and by carrying out friction treatment to this coated surface, the liquid crystal orientation film as friction is used.In addition, also can be used as and used without the VA liquid crystal orientation film of friction treatment or optical alignment film.
Now, as long as the substrate that the substrate transparency used is high then limits without special, the plastic bases etc. such as glass substrate, acrylic acid substrate or polycarbonate substrate can be used, use the substrate be formed for the ITO electrode etc. of liquid crystal drive to consider it is preferred from the angle simplifying production technology.In addition, for the liquid crystal display cells of reflection-type, can use the opaque materials such as silicon wafer by the substrate only in side, the electrode under this occasion also can use the material of the reflected light such as metallic aluminium.
As the coating process of aligning agent for liquid crystal, spin-coating method, print process, ink-jet method etc. can be exemplified, but from the viewpoint of productivity, flexographic printing process is widely adopted in commercial production, aligning agent for liquid crystal of the present invention is also applicable to adopting.
Although the drying process after coating of liquid crystalline alignment agent is not required, when each block substrate not being burnt till after fixing and coating immediately to the time before burning till after coating, preferably comprise drying process.The degree that film shape is not out of shape because of substrate transport etc. as long as this drying makes solvent be evaporated to both can, to this drying means, there is no particular limitation.Specifically can exemplify and make its dry 0.5 ~ 30 minute, more preferably method of 1 ~ 5 minute on the hot plate of 50 ~ 150 DEG C, more preferably 80 ~ 120 DEG C.
Be coated with burning till of the substrate of aligning agent for liquid crystal to carry out under the arbitrary temp in 100 ~ 350 DEG C, but preferably 150 ~ 300 DEG C, be more preferably 180 DEG C ~ 250 DEG C.Time in aligning agent for liquid crystal containing acid amides acidic group, transform to acid imide from amic acid according to firing temperature, but in that case without the need to 100% imidizate.
If the thickness of the film after burning till is blocked up, undesirable in the energy consumption of liquid crystal display cells, if cross thin, the reliability decrease of liquid crystal display cells sometimes, is therefore preferably 10 ~ 200nm, is more preferably 50 ~ 100nm.
The friction treatment being formed at the coated surface on substrate as mentioned above can use existing rubbing device.The material of friction cloth now can exemplify cotton, rayon, nylon etc.
Liquid crystal display cells of the present invention is after to be obtained being with the substrate of liquid crystal orientation film by aligning agent for liquid crystal of the present invention by said method, adopts known method to manufacture liquid crystal cell and the liquid crystal display cells that obtains.If exemplify the example manufacturing liquid crystal cell, then normally following method: the 1 pair of substrate being formed with liquid crystal orientation film is clipped preferably 1 ~ 30 μm, the more preferably sept of 2 ~ 10 μm, the mode at any angle of 0 ~ 270 ° is become to arrange to make orientation process direction, with sealant, periphery is fixed, seal after injecting liquid crystal.To enclosing the method for liquid crystal, there is no particular limitation, can exemplify to the method etc. of dripping sealed after injecting the vacuum method of liquid crystal, the liquid crystal that drips after reducing pressure in obtained liquid crystal cell.
The liquid crystal display cells obtained thus is suitable for the display element of TN liquid crystal display cells, stn liquid crystal display element, TFT liquid crystal display cells, OCB liquid crystal display cells, the in addition various mode such as liquid crystal display cells, VA liquid crystal display cells of lateral electric-field type.
Embodiment
The present invention will be described in more detail below to exemplify embodiment, but the present invention is not limited by this.
The breviary that uses in embodiment and comparative example is number as follows.
< tetracarboxylic dianhydride >
A-1:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
A-2: pyromellitic acid anhydride
< diamine component >
B-1:2,4-diamino-N, N-diallyl aniline
[changing 12]
B-2:3-amino-benzylamine
The trans-4-pentylcyclohexyl of B-3:4-() benzamido-2', 4 '-phenylenediamine
[changing 13]
B-4:4-tetradecyloxyaniline-1,3-diaminobenzene
< additive >
Amino three (methylol) methane of compound-1: two (2-hydroxyethyl)
[changing 14]
Compound-2:N-tertiarybutyldiethanolamine
[changing 15]
Compound-3: triethanolamine
[changing 16]
Compound-4: propylamine
[changing 17]
< organic solvent >
NMP:N-N-methyl-2-2-pyrrolidone N-
NEP:N-ethyl-2-pyrrolidone
GBL: gamma-butyrolacton
DMI:1,3-dimethyl-imidazolinone
BS: butyl cellosolve
The mensuration > of < molecular weight
Measured the molecular weight of polyimide by GPC (normal temperature gel permeation chromatography) device, calculate number-average molecular weight and weight-average molecular weight as polyglycol, polyethylene oxide scaled value.
GPC device: Showa Denko K. K (Shodex society) system (GPC-101)
Post: Showa Denko K. K's system (series connection of KD803, KD805)
Column temperature: 50 DEG C
Eluent: DMF (as adjuvant, lithium bromide monohydrate (LiBrH
20) for 30mmol/l, phosphoric acid anhydrous crystal (o-phosphoric acid) be 30mmol/L, tetrahydrofuran (THF) is 10ml/l)
Flow velocity: 1.0ml/ minute
Calibration curve making standard sample: (East ソ ー society of TOSOH Co., Ltd) TSK standard polyethylene oxide processed (weight-average molecular weight about 900000,150000,100000,30000) and Polymer Laboratory company (Port リ マ ー ラ ボ ラ ト リ ー society) polyglycol processed (weight-average molecular weight about 12000,4000,1000).
The mensuration > of < acid imide rate
The acid imide rate of polyimide measures as follows.20mg polyimide powder is put into NMR coupon, adds 0.53ml deuterated dimethyl sulfoxide (DMSO-d
6, 0.05%TMS melange), make it dissolve completely.The proton N MR of the 500MHz of this solution is measured with NEC De Temu company (Japanese Electricity デ ー タ system society) NMR analyzer (JNM-ECA500) processed.Acid imide rate is tried to achieve as follows: the proton coming from unconverted structure before and after imidizate is decided to be reference proton, uses the peak integrated value of this proton and the proton peak integrated value of the NH base from amic acid that occurs near 9.5 ~ 10.0ppm to be tried to achieve by following formula.
Acid imide rate (%)=(1-α x/y) × 100
In above formula, x is the proton peak integrated value of the NH base from amic acid, and y is the peak integrated value of reference proton, and when α is polyamic acid (acid imide rate is 0%), reference proton is relative to the number ratio of NH matrix of an amic acid.
(embodiment 1)
With 13.53g (0.069mol) A-1,6.54g (0.030mol) A-2 as tetracarboxylic dianhydride's composition, with 6.10g (0.030mol) B-1,4.89g (0.040mol) B-2,9.62g (0.030mol) B-4 as diamine component, react 24 hours under room temperature in 162.7g NMP, obtain polyamic acid solution.
In this polyamic acid solution of 142.8g, add 255.64g NMP dilute, add 20.64g acetic anhydride and 8.8g pyridine, at the temperature of 50 DEG C, react 3 hours with imidizate.
After this reaction solution is cooled to room temperature, be fed in 1498.8ml methyl alcohol, reclaim the solid matter of precipitation.Then, by this solid matter with after washed with methanol several, drying under reduced pressure at the temperature of 100 DEG C, obtains the white powder of polyimide (SPI-1).The number-average molecular weight of this polyimide is 13653, and weight-average molecular weight is 33847.In addition, acid imide rate is 90%.
In the polyimide SPI-1 powder of 5g gained, add 65g GBL makes it dissolve completely, then adds 30gBS, stirs 24 hours at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.After being cooled back room temperature, add 0.25g compound-1, stir 3 hours, obtain aligning agent for liquid crystal.
(embodiment 2)
In 5g polyimide SPI-1 powder, add 65g NMP makes it dissolve completely, then adds 30g BS, stirs 24 hours at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.After being cooled back room temperature, add 0.25g compound-1, stir 3 hours, obtain aligning agent for liquid crystal.
(embodiment 3)
In 5g polyimide SPI-1 powder, add 65g NEP makes it dissolve completely, then adds 30g BS, stirs 24 hours at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.After being cooled back room temperature, add 0.25g compound-1, stir 3 hours, obtain aligning agent for liquid crystal.
(embodiment 4)
With 8.18g (42mmol) A-1,1.63g (7.5mmol) A-2 as tetracarboxylic dianhydride's composition, with 1.22g (10mmol) B-2,5.08g (25mmol) B-1,6.11g (15mmol) B-3 as diamine component, react 24 hours under room temperature in 88.96g NMP, obtain polyamic acid solution.In this polyamic acid solution of 95.8g, add 228.5gNMP dilute, add 15.1g acetic anhydride and 6.4g pyridine, at the temperature of 50 DEG C, react 3 hours with imidizate.
After this reaction solution is cooled to room temperature, be fed in 1259.1ml methyl alcohol, reclaim the solid matter of precipitation.Then, by this solid matter with after washed with methanol several, drying under reduced pressure at the temperature of 100 DEG C, obtains the white powder of soluble polyimide (SPI-2).The number-average molecular weight of this polyimide is 18195, and weight-average molecular weight is 57063.In addition, acid imide rate is 93%.
In the polyimide SPI-2 powder of 5g gained, add 65g GBL makes it dissolve completely, then adds 30gBS, stirs 24 hours at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.After being cooled back room temperature, add 0.25g compound-1, stir 3 hours, obtain aligning agent for liquid crystal.
(embodiment 5)
In 5g polyimide SPI-2 powder, add 65g NMP makes it dissolve completely, then adds 30g BS, stirs 24 hours at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.After being cooled back room temperature, add 0.25g compound-1, stir 3 hours, obtain aligning agent for liquid crystal.
(embodiment 6)
In 5g polyimide SPI-2 powder, add 65g NEP makes it dissolve completely, then adds 30g BS, stirs 24 hours at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.After being cooled back room temperature, add 0.25g compound-1, stir 3 hours, obtain aligning agent for liquid crystal.
(embodiment 7)
In 5g polyimide SPI-1 powder, add 65g GBL makes it dissolve completely, then adds 30g BS, stirs 24 hours at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.After being cooled back room temperature, add 0.25g compound-2, stir 3 hours.
(embodiment 8)
In 5g polyimide SPI-1 powder, add 65g NMP makes it dissolve completely, then adds 30g BS, stirs 24 hours at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.After being cooled back room temperature, add 0.25g compound-2, stir 3 hours.
(comparative example 1)
In 5g polyimide SPI-1 powder, add 65g GBL makes it dissolve completely, then adds 30g BS, stirs 24 hours, obtain aligning agent for liquid crystal at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.
(comparative example 2)
In 5g polyimide SPI-1 powder, add 65g NMP makes it dissolve completely, then adds 30g BS, stirs 24 hours, obtain aligning agent for liquid crystal at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.
(comparative example 3)
In 5g polyimide SPI-1 powder, add 65g NEP makes it dissolve completely, then adds 30g BS, stirs 24 hours, obtain aligning agent for liquid crystal at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.
(comparative example 4)
In 5g polyimide SPI-1 powder, add 65g GBL makes it dissolve completely, then adds 30g BS, stirs 24 hours, obtain aligning agent for liquid crystal at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.After being cooled back room temperature, add 0.25g compound-3, stir 3 hours, obtain aligning agent for liquid crystal.
(comparative example 5)
In 5g polyimide SPI-1 powder, add 65g NMP makes it dissolve completely, then adds 30g BS, stirs 24 hours at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.After being cooled back room temperature, add 0.25g compound-3, stir 3 hours.
(comparative example 6)
In 5g polyimide SPI-2 powder, add 65g GBL makes it dissolve completely, then adds 30g BS, stirs 24 hours, obtain aligning agent for liquid crystal at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.
(comparative example 7)
In 5g polyimide SPI-2 powder, add 65g NEP makes it dissolve completely, then adds 30g BS, stirs 24 hours, obtain aligning agent for liquid crystal at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.
(comparative example 8)
In 5g polyimide SPI-2 powder, add 65g GBL makes it dissolve completely, then adds 30g BS, stirs 24 hours at the temperature of 50 DEG C.At the end of stirring, polyimide dissolves completely.After being cooled back room temperature, add 0.25g compound-4, stir 3 hours, obtain aligning agent for liquid crystal.
The embodiment 1 ~ 8 of above-mentioned gained and the aligning agent for liquid crystal of comparative example 1 ~ 8 are carried out that following tilt angle measures, the evaluation of weighting characteristics and printing time foreign matter evaluation.The results are shown in table 1 and table 2.
The mensuration > of < tilt angle
Aligning agent for liquid crystal is spun on the glass substrate of band transparency electrode, makes it after dry 70 seconds, the heating plate of 210 DEG C to carry out within 10 minutes, burn till on the heating plate that temperature is 70 DEG C, form the film of thickness 100nm.With rayon cloth, this face is rubbed under the condition of roller rotating speed 1000rpm, roller gait of march 50mm/ second, intrusion 0.3mm with the rubbing device of roller footpath 120mm, obtain the substrate being with liquid crystal orientation film.Prepare 2 pieces of these substrates, the liquid crystal aligning face of one piece of substrate scatters the sept of 6 μm, printing and sealing agent it on, by another block substrate to make liquid crystal aligning face relative and after frictional direction is orthogonal mode fits, make sealant cures and make negative crystal born of the same parents.In this negative crystal born of the same parents, inject liquid crystal MLC-2003(Merck Japanese firm (メ Le Network ジ ャ パ Application society) system by decompression injection method), sealing inlet, obtains twisted nematic liquid crystals structure cell.
Use the liquid crystal cell obtained by said method, carry out the mensuration of tilt angle.Measure the TBA107 using Ao Chu Nico company (autronic society) to make.
The evaluation > of < weighting characteristics
Drip above-mentioned aligning agent for liquid crystal about 0.1ml respectively on Cr substrate, is placed in the environment of temperature 23 DEG C, humidity 70%.Every 1 hour with near the end of this drop of microscopic examination and near central authorities.Observe by the multiplying power with 50 times near the central authorities of the multiplying power of 100 times, drop near the end of drop.6 hours with find near the end of inherent drop and central authorities the situation of agglutinator be ×, even if do not find that through 6 hours the situation of agglutinator is that only find a little agglutinator in zero, 6 hours in the end of drop is △ yet.Result is recorded in table 2.
Foreign matter during < printing evaluates >
Device similar to the above is used to implement printing.After implementing 10 dry runnings, printing machine is shut down 10 minutes, make galley dry.Then, print 1 piece of Cr substrate, burn till as described above.Substrate after burning till confocal some laser microscope (laser Te Ke Co., Ltd. (レ ー ザ ー テ ッ Network society) system, trade name: VL2000) is observed near printed edge, what near printed edge, do not produce foreign matter is zero, that produce the foreign matter of 0.1 ~ 3 μm is △, produce the foreign matter of more than 0.3 μm be ×.Result is recorded in table 2.
[table 1]
[table 2]
| Polymkeric substance | Additive | Tilt angle | Albefaction | Foreign matter | |
| Embodiment 1 | SPI-1 | Compound-1 | 3.1 | ○ | ○ |
| Embodiment 2 | SPI-1 | Compound-1 | 3.1 | ○ | ○ |
| Embodiment 3 | SPI-1 | Compound-1 | 3.1 | ○ | ○ |
| Embodiment 4 | SPI-2 | Compound-1 | 6.8 | ○ | ○ |
| Embodiment 5 | SPI-2 | Compound-1 | 6.7 | ○ | ○ |
| Embodiment 6 | SPI-2 | Compound-1 | 6.7 | ○ | ○ |
| Embodiment 7 | SPI-1 | Compound-2 | 3.1 | ○ | △ |
| Embodiment 8 | SPI-1 | Compound-2 | 3.1 | ○ | ○ |
| Comparative example 1 | SPI-1 | Nothing | 3.0 | △ | × |
| Comparative example 2 | SPI-1 | Nothing | 2.3(0.7) | × | △ |
| Comparative example 3 | SPI-1 | Nothing | 2.2(0.8) | △ | △ |
| Comparative example 4 | SPI-1 | Compound-3 | 3.1 | ○ | × |
| Comparative example 5 | SPI-1 | Compound-3 | 2.7(0.4) | ○ | △ |
| Comparative example 6 | SPI-2 | Nothing | 6.7 | × | × |
| Comparative example 7 | SPI-2 | Nothing | 5.4(1.3) | × | △ |
| Comparative example 8 | SPI-2 | Compound-4 | 6.7 | × | × |
Value in table bracket represents tilt angle decreasing value when comparing with GBL main solvent system.
The feasibility that industry utilizes
The liquid crystal display cells using aligning agent for liquid crystal of the present invention to make as the high liquid crystal display device of reliability, can be suitable for the display element of the various modes such as TN liquid crystal display cells, stn liquid crystal display element, TFT liquid crystal display cells, OCB liquid crystal display cells.
Claims (14)
1. aligning agent for liquid crystal, is characterized in that, the polyimide obtained through imidizate containing the polyamic acid be obtained by reacting by diamine component and tetracarboxylic dianhydride and the carbon number with tertiary N atom and quaternary carbon atom are the polyol compound of 3 ~ 15.
2. aligning agent for liquid crystal as claimed in claim 1, is characterized in that, polyol compound is represented by following formula (A),
In formula, R
1, R
2separately represent the hydroxyalkyl of carbon number 1 ~ 5, R
3, R
4, R
5separately represent the alkyl of carbon number 1 ~ 5 or the hydroxyalkyl of carbon number 1 ~ 5.
3. aligning agent for liquid crystal as claimed in claim 1 or 2, it is characterized in that, polyol compound is the compound with 2 ~ 8 hydroxyls.
4. aligning agent for liquid crystal as claimed in claim 1, it is characterized in that, polyol compound is any one following compound,
5. aligning agent for liquid crystal as claimed in claim 1, it is characterized in that, the content of polyol compound is 0.1 ~ 10 mass parts relative to 100 mass parts polyimide.
6. aligning agent for liquid crystal as claimed in claim 1, it is characterized in that, diamine component is have the diaminobenzene being replaced the disubstituted amido obtained by the alkenyl of carbon number 2 or 3.
7. aligning agent for liquid crystal as claimed in claim 6, it is characterized in that, diaminobenzene is the diamines represented by following formula [1],
8. aligning agent for liquid crystal as claimed in claim 7, is characterized in that, diamine component also contains the diamines that following formula [32] represents,
In above formula, k represents the integer of 1 ~ 20.
9. aligning agent for liquid crystal as claimed in claim 7 or 8, it is characterized in that, the content of the diamines that formula [1] represents in whole diamine component is 20 ~ 90 % by mole.
10. aligning agent for liquid crystal as claimed in claim 8, it is characterized in that, the content of the diamines that formula [32] represents in whole diamine component is 5 ~ 40 % by mole.
11. aligning agent for liquid crystal as claimed in claim 9, is characterized in that, the content of the diamines that formula [32] represents in whole diamine component is 5 ~ 40 % by mole.
12. aligning agent for liquid crystal as claimed in claim 1, is characterized in that, the polymkeric substance containing polyimide is being 1 ~ 10 quality % containing the content in the aligning agent for liquid crystal of solvent.
13. liquid crystal orientation films, is characterized in that, to be coated by the aligning agent for liquid crystal according to any one of claim 1 ~ 12 on electroded substrate and to obtain through burning till.
14. liquid crystal display cells, is characterized in that, have liquid crystal orientation film according to claim 13.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2010095417 | 2010-04-16 | ||
| JP2010-095417 | 2010-04-16 | ||
| PCT/JP2011/059309 WO2011129414A1 (en) | 2010-04-16 | 2011-04-14 | Liquid crystal aligning agent, liquid crystal alignment film produced using same, and liquid crystal display element |
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| CN102859426A CN102859426A (en) | 2013-01-02 |
| CN102859426B true CN102859426B (en) | 2015-04-01 |
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|---|---|
| JP (1) | JP5713008B2 (en) |
| KR (1) | KR101759756B1 (en) |
| CN (1) | CN102859426B (en) |
| TW (1) | TWI507447B (en) |
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| CN103782231B (en) * | 2011-09-08 | 2017-05-10 | 日产化学工业株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| TWI706028B (en) * | 2014-04-09 | 2020-10-01 | 日商日產化學工業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| CN105087018B (en) * | 2014-07-21 | 2018-01-19 | 中节能万润股份有限公司 | Aligning agent for liquid crystal, liquid crystal orientation film and its liquid crystal display cells |
| KR101973192B1 (en) * | 2017-06-29 | 2019-04-26 | 주식회사 엘지화학 | Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film using the same |
| KR20220147083A (en) | 2020-02-26 | 2022-11-02 | 닛산 가가쿠 가부시키가이샤 | polyimide varnish |
| CN111647412A (en) * | 2020-06-12 | 2020-09-11 | 江苏三月科技股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN111575023B (en) * | 2020-06-12 | 2022-03-01 | 江苏三月科技股份有限公司 | Compound additive, liquid crystal aligning agent prepared from compound additive and liquid crystal aligning film |
| CN118696267A (en) | 2022-02-17 | 2024-09-24 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
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| EP0683418A2 (en) * | 1994-05-17 | 1995-11-22 | Japan Synthetic Rubber Co., Ltd. | Liquid crystal aligning agent and liquid crystal display device |
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| JP2008266421A (en) * | 2007-04-18 | 2008-11-06 | Jsr Corp | Liquid crystal aligning agent, liquid crystal display element, polymer therefor and raw material diamine |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2009040984A (en) | 2007-08-13 | 2009-02-26 | Dainippon Printing Co Ltd | Liquid crystal composition, retardation-controlling members using the same, and liquid crystal display |
| KR101488265B1 (en) * | 2007-09-28 | 2015-02-02 | 삼성디스플레이 주식회사 | Composition for stripping and stripping method |
| JP2009104065A (en) | 2007-10-25 | 2009-05-14 | Nippon Zeon Co Ltd | Luminance enhancing film and liquid crystal display device |
| WO2010117223A2 (en) | 2009-04-09 | 2010-10-14 | 주식회사 엘지화학 | Alignment layer composition, alignment layer prepared with the same, preparation method of alignment layer, optical film containing the same, and display device including the optical film |
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- 2011-04-14 JP JP2012510696A patent/JP5713008B2/en active Active
- 2011-04-14 KR KR1020127029199A patent/KR101759756B1/en active IP Right Grant
- 2011-04-14 WO PCT/JP2011/059309 patent/WO2011129414A1/en active Application Filing
- 2011-04-14 CN CN201180019165.8A patent/CN102859426B/en active Active
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| JPS62283153A (en) * | 1986-06-02 | 1987-12-09 | Toray Ind Inc | Polyimide coating agent composition |
| EP0683418A2 (en) * | 1994-05-17 | 1995-11-22 | Japan Synthetic Rubber Co., Ltd. | Liquid crystal aligning agent and liquid crystal display device |
| CN1274345A (en) * | 1998-07-29 | 2000-11-22 | 智索股份有限公司 | Novel diamino compounds, polyamic acid, polyimide, liquid-crystal alignment film made from film of polyimide, and liquid-crystal display element containing same |
| JP2008266421A (en) * | 2007-04-18 | 2008-11-06 | Jsr Corp | Liquid crystal aligning agent, liquid crystal display element, polymer therefor and raw material diamine |
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| JPWO2011129414A1 (en) | 2013-07-18 |
| WO2011129414A1 (en) | 2011-10-20 |
| TWI507447B (en) | 2015-11-11 |
| KR20130101440A (en) | 2013-09-13 |
| JP5713008B2 (en) | 2015-05-07 |
| KR101759756B1 (en) | 2017-07-19 |
| CN102859426A (en) | 2013-01-02 |
| TW201211108A (en) | 2012-03-16 |
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