CN100501532C - Liquid crystal directing agent, liquid crystal oriented film and liquid crystal display element - Google Patents
Liquid crystal directing agent, liquid crystal oriented film and liquid crystal display element Download PDFInfo
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- CN100501532C CN100501532C CNB2005100513395A CN200510051339A CN100501532C CN 100501532 C CN100501532 C CN 100501532C CN B2005100513395 A CNB2005100513395 A CN B2005100513395A CN 200510051339 A CN200510051339 A CN 200510051339A CN 100501532 C CN100501532 C CN 100501532C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
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Abstract
The invention provides a liquid crystal aligning agent capable of forming a liquid crystal alignment film which prevents display defects, has an excellent after-image characteristic even after long-time driving, does not decrease the capability of aligning liquid crystal, and has a small decrease in voltage holding rate against light and heat. Disclosed is a liquid crystal aligning agent composition containing a tetrafunctional silicon composition like tetrachalcoxylan, a trifunctional composition like trialcoxylan, and a product of reaction with 0.8 to 3.0 mol water for a 1 mol functional group like an alxoky group, and a glycol-ether-based solvent.
Description
Technical field
The present invention relates to liquid crystal orientating agent, liquid crystal orientating membrane and liquid crystal display cells, more specifically, relate to a kind of liquid crystal alignment layer, the liquid crystal orientating agent that can form this liquid crystal alignment layer and liquid crystal display cells, wherein the liquid crystal alignment layer liquid crystal aligning is good, and can not damage electrical characteristics such as voltage residual rate under the harsh and unforgiving environments of illumination and high temperature or after long-time the driving yet, under the good liquid crystal aligning state of maintenance, also be difficult to produce the image retention video picture.
Background technology
At present, known liquid crystal display cells has the TN type liquid crystal display cells with TN type (twisted nematic) liquid crystal cell line, this element forms the substrate of liquid crystal orientating membranes such as polyamic acid, polyimide as liquid crystal display cells being provided with on the substrate surface of nesa coating, two substrates are oppositely arranged, form nematic crystal layer betwixt in the crack with positive dielectric anisotropy, form the cell of sandwich construction, the major axis of liquid crystal molecule is turned round continuously to another piece substrate from a substrate and is turn 90 degrees.In addition, developing and to realize IPS (face intort (In-Plane Switching)) the type liquid crystal display cells, VA (Vertical Allignment) the type liquid crystal display cells that lack than higher STN (STN Super TN) the type liquid crystal display cells of TN type liquid crystal display cells contrast and view angle dependency.
The principle of work of various liquid crystal display cells like this is divided into transmission-type and reflection-type.
The transmission-type liquid crystal display element is when element drives, and the back side light that utilizes the element back side shows with the variation of the transmitted intensity of light source.Reflection type liquid crystal display element does not use back side light light source, when element drives, utilizes the variation of the reflection strength of ambient lights such as sunshine to show, because that itself and transmission-type are compared power consumption is less, therefore thinks for outdoor application it is particularly advantageous.
In the transmission-type liquid crystal display element, liquid crystal orientating membrane is always used the rayed from back side light source.Particularly in commercial and in recent years home theater, in the application of the higher liquid crystal projection apparatus of demand, adopt the very large light sources of exposure intensity such as metal halide lamp.Reflection type liquid crystal display element is big in the possibility of outdoor application, in this case with containing the sunshine of strong ultraviolet light as light source.In addition, when using reflection-type, on principle, light is longer than transmission-type by the distance of element internal.
In the manufacturing process of liquid crystal display cells, from shortening the angle of manufacture process and raising productive rate, what first-selection was used is that the liquid crystal mode of splashing into is ODF (One Drop Fill) mode.The ODF mode is different with the existing method of injecting liquid crystal in the prior empty liquid crystal cell line of assembling with the Thermocurable sealant, it is behind the necessary position coating ultraviolet light curable sealant of the one-sided substrate that has been coated with liquid crystal orientating membrane, splash into liquid crystal to necessary position, another piece substrate of fitting again, integral body is carried out UV-irradiation and is made sealant cures then, makes liquid crystal cell line.This moment, the ultraviolet light intensity of irradiation was generally several joules/cm
2Promptly in the manufacturing process of liquid crystal display cells, liquid crystal orientating membrane and liquid crystal shine with this strong ultraviolet light simultaneously.
When using the transmission-type liquid crystal display element, consider to be accompanied by high-intensity rayed that the temperature of liquid crystal display cells system itself raises sometimes during driving.And, along with the liquid crystal display cells multi-usageization, also consider use in outdoor grade, perhaps be arranged on and use and be provided with environment under the temperature that the general room temperature of geometric ratio is high in the private savings automobile in the parking lot.
In this liquid crystal display cells, along with its high performance, multi-usageization etc., need a kind of after standing the harsh and unforgiving environments of light and heat or long-time electrical characteristics such as back liquid crystal aligning and voltage residual rate or the image retention characteristic of driving than existing better element.
As the material of the liquid crystal orientating membrane that constitutes liquid crystal display cells, according to prior art, known have resins such as polyimide, polyamide and polyester.Polyimide particularly and since in resin its thermotolerance, and aspects such as the compatibility of liquid crystal, physical strength show good physical characteristics, be used to many liquid crystal display cells.
But, liquid crystal display cells in recent years is towards high performance and multi-usage development, the probability that use is set in the harsh and unforgiving environments of above-mentioned hot environment and illumination is increasing, and, in manufacturing process, need further to shorten process and improve productive rate, also require the life-span of liquid crystal display cells longer on the other hand.Meanwhile, do not allow owing to the tolerance to the hot environment of allowing and illumination in the past produces surface imperfection or image retention inadequately.
Therefore, polyamic acid that in the past used as liquid crystal orientating membrane and polyimide organic resin are to the tolerance of light and heat not enough.Therefore, need a kind of liquid crystal display cells that can not reduce in face, to make evenly directed ability of liquid crystal and the new material good to the light and heat tolerance.
Open the spy and to disclose a kind of vertical orientation film in the flat 9-281502 communique, it is adding thermal response by the silicon compound (B) that the silicon compound (A) that makes tetraethoxysilane etc. and contain 4 alkoxys and octadecyltriethoxy silane etc. contain 3 alkoxys under 50 ℃～180 ℃ in the presence of oxalic acid catalyzer in alcoholic solvent, generate (A) and (B) cocondensation compound polysiloxane solution, with this solution as coating fluid, it is coated on the electrode base board surface, and gained is filmed and is carried out heat curing and make under 80～400 ℃.This communique further illustrates the straight directionality of described vertical orientation costal fold, reappearance, thermotolerance and excellent in uniform, and the stability of coating fluid is also excellent.
But this vertical orientation film or its formation method be imperfection also.Open the vertical orientation film of record in flat 9-281502 number for above-mentioned spy, probably understand the siloxane group of remained unreacted during gained is filmed.Unreacted siloxane group instability, the moisture that contained micro-moisture or liquid crystal cell line sealant are brought in the liquid crystal make the siloxane group hydrolysis, produce pure molecule, and this alcohol molecular diffusion causes occurring poor display etc. to liquid crystal.
Summary of the invention
The present invention In view of the foregoing makes, the purpose of this invention is to provide a kind of liquid crystal orientating agent, this liquid crystal orientating agent is by the reaction that is hydrolyzed fully, siloxane 99% or above quilt are transformed, prevent this poor display, drive that back image retention characteristic still well, can not reduce the ability that makes liquid crystal aligning and for the few liquid crystal orientating membrane of light and heat voltage residual rate decline through long-time thereby can form.
Another object of the present invention provides a kind of liquid crystal orientating membrane and manufacture method thereof of each premium properties as mentioned above of having of using liquid crystal orientating agent of the present invention.
Another purpose of the present invention provides the liquid crystal display cells with liquid crystal orientating membrane of the present invention.
Other purpose of the present invention and advantage can be learned by following explanation.
According to the present invention, above-mentioned purpose of the present invention and advantage, first, reach by a kind of liquid crystal orientating agent, described liquid crystal orientating agent is characterised in that the reaction product that comprises (I) specific two kinds of siloxane and water and (II) solvent, specifically, comprise the silicon compound of (I) following formula (1) expression, silicon compound and the reaction product (hereinafter referred to as " reaction product (1) ") of water and the solvent of (II) stating formula (3) expression of following formula (2) expression
Si(OR
1)
4..................(1)
R wherein
1Be the organic group of hydrogen atom, fluorine atom or monovalence,
RSi(OR
2)
3..................(2)
Wherein R is the organic group of monovalence, and R
2Be the organic group of hydrogen atom, fluorine atom or monovalence,
Wherein, R
3Be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl or the tert-butyl group, m is 0 or 1, and n is 1,2 or 3.
According to the present invention, above-mentioned purpose of the present invention and advantage, the second, be to reach by the formation method of liquid crystal orientating membrane, this method is characterised in that and comprises that the substrate that liquid crystal orientating membrane of the present invention is coated the operation of substrate and heating coating makes the operation of curing of coating.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 3rd, be to reach by the liquid crystal orientating membrane that adopts the invention described above method to form.
According to the present invention, above-mentioned purpose of the present invention and advantage, last, be to reach by liquid crystal display cells with liquid crystal orientating membrane of the present invention.
According to the present invention, compare with existing material, by using the liquid crystal orientating agent of applying silicon class material, can make a kind of liquid crystal display cells, after even this liquid crystal display cells stands to carry out rayed and heat treated harsh and unforgiving environments, after perhaps long-time the driving, its good liquid crystal aligning, voltage residual rate and image retention characteristic can not reduce largely yet.
The liquid crystal display cells that uses liquid crystal orientating agent of the present invention to make, except can being applicable to TN type and STN type liquid crystal display cells, according to selected liquid crystal, can also be applicable to SH (Super Homeotropic) type, IPS (In-Plane Switching) type, VA (Vertical Allignment) type, strong dielectricity and anti-strong dielectricity liquid crystal display cells etc.
And, liquid crystal display cells liquid crystal aligning and reliability with the oriented film that forms with liquid crystal orientating agent of the present invention are good, can be used for various devices effectively, for example be used for display device such as desk-top computer, wrist-watch, table clock, coefficient display screen, word processor, personal computer, liquid crystal data projector, liquid crystal TV set, electronic newspaper.
Embodiment
Liquid crystal orientating agent
Liquid crystal orientating agent of the present invention comprises (I) reaction product (1) and (II) solvent.(I) reaction product (1) is the silicon compound (hereinafter referred to as " silicon compound (1) ") of following formula (1) expression, the silicon compound (hereinafter referred to as " silicon compound (2) ") of following formula (2) expression and the reaction product of water
Si(OR
1)
4..................(1)
R wherein
1Be the organic group of hydrogen atom, fluorine atom or monovalence,
RSi(OR
2)
3..................(2)
Wherein R is the organic group of monovalence, and R
2Organic group for hydrogen atom, fluorine atom or monovalence.
In the formula (1), as R
1Any monovalent organic radical group, can enumerate for example alkyl, aryl, allyl, acyl group, glycidyl etc.Here, alkyl can be enumerated for example methyl, ethyl, propyl group, butyl etc.Preferred carbon number be 1～5 alkyl, these alkyl can for chain, also can branch, and hydrogen atom can also be by replacements such as fluorine atoms.Aryl can be enumerated for example phenyl, naphthyl, tolyl, ethylbenzene base, chlorophenyl, bromo phenyl, fluoro phenyl etc.
Acyl group can be enumerated for example acetyl group, benzoyl, formoxyl, propiono etc.
The instantiation of compound (1) can be enumerated tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, four sec-butoxy silane, four tert-butoxy silane, tetraphenoxy-silicane alkane, tetrem acyloxy silane, Fourth Ring oxygen propoxyl group silane etc.They can a kind or 2 kinds or above use together.
In the formula (2), R is the organic group of monovalence, and R
2Organic group for hydrogen atom, fluorine atom or monovalence.R
2Any monovalent organic radical group can enumerate and R
1Same group.
In addition, alkyl, vinyl and the phenyl of for example optional C1～4 that can be replaced by amino, glycidoxy or trifluoromethyl preferably can be enumerated by any monovalent organic radical of R group; Carbon number is 16 or above straight chained alkyl; Can be substituted and have any monovalent organic radical group of at least one norbornane ring; Can be substituted and have any monovalent organic radical group of at least one steroid backbone; Have have fluorine atom, trifluoromethyl or a trifluoromethoxy substituting group aromatic rings and carbon number be 8 or above univalent perssad; And has photonasty group of cinnamoyl or chalcone base (カ Le コ ニ Le base) etc.
R can be by amino for choosing wantonly, C1～4 alkyl that glycidoxy or trifluoromethyl replace, the instantiation of the compound of vinyl and phenyl (hereinafter referred to as compound (A)) can be enumerated methyltrimethoxy silane, methyl triethoxysilane, methyl three positive propoxy silane, methyl three isopropoxy silane, methyl three n-butoxy silane, methyl three sec-butoxy silane, the methyl-tert butoxy silane, methyl triple phenoxyl silane, the ethyl methoxy silane, ethyl triethoxysilane, ethyl three positive propoxy silane, ethyl three isopropoxy silane, ethyl three n-butoxy silane, ethyl three sec-butoxy silane, ethyl three tert-butoxy silane, ethyl triple phenoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three positive propoxy silane, the vinyl tri isopropyl silane, vinyl three n-butoxy silane, vinyl three sec-butoxy silane, vinyl three tert-butoxy silane, vinyl triple phenoxyl silane, the n-pro-pyl trimethoxy silane, the n-pro-pyl triethoxysilane, n-pro-pyl three positive propoxy silane, n-pro-pyl three isopropoxy silane, n-pro-pyl three n-butoxy silane, n-pro-pyl three sec-butoxy silane, n-pro-pyl tert-butoxy silane, n-pro-pyl triple phenoxyl silane, the isopropyl trimethoxy silane, the isopropyl triethoxysilane, isopropyl three positive propoxy silane, isopropyl three isopropoxy silane, isopropyl three n-butoxy silane, isopropyl three sec-butoxy silane, isopropyl tert-butoxy silane, isopropyl triple phenoxyl silane, the normal-butyl trimethoxy silane, ne-butyltriethoxysilaneand, normal-butyl three positive propoxy silane, normal-butyl three isopropoxy silane, normal-butyl three n-butoxy silane, normal-butyl three sec-butoxy silane, normal-butyl tert-butoxy silane, normal-butyl triple phenoxyl silane, the sec-butyl trimethoxy silane, sec-butyl-i-triethoxysilane, sec-butyl three positive propoxy silane, sec-butyl three isopropoxy silane, sec-butyl three n-butoxy silane, sec-butyl three sec-butoxy silane, sec-butyl tert-butoxy silane, sec-butyl triple phenoxyl silane, tert-butyl trimethoxy silane, tert-butyl group triethoxysilane, the tert-butyl group three positive propoxy silane, the tert-butyl group three isopropoxy silane, the tert-butyl group three n-butoxy silane, the tert-butyl group three sec-butoxy silane, tert-butyl group tert-butoxy silane, tert-butyl group triple phenoxyl silane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl three positive propoxy silane, phenyl three isopropoxy silane, phenyl three n-butoxy silane, phenyl three sec-butoxy silane, phenyl tert-butoxy silane, phenyl triple phenoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-trifluoro propyl trimethoxy silane, γ-trifluoro propyl triethoxysilane etc.Wherein, preferable methyl trimethoxy silane, methyl triethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane etc.
In addition, in the formula (2), R is
(ア) carbon number is 16 or above straight chained alkyl;
(イ) can be substituted and have any monovalent organic radical group of at least one norbornane ring;
(ウ) can be substituted and have any monovalent organic radical group of at least one steroid backbone;
(エ) have that to have the substituent aromatic rings that is selected from fluorine atom, trifluoromethyl and trifluoromethoxy and carbon number be 8 or above univalent perssad; Perhaps
(オ) has the photonasty group of cinnamoyl or chalcone base
Compound (hereinafter referred to as compound (B)) for example can enumerate cetyl trimethoxy silane, heptadecyl trimethoxy silane, octadecyl trimethoxy silane, nonadecyl trimethoxy silane, cetyl triethoxysilane, heptadecyl triethoxysilane, octadecyltriethoxy silane, nonadecyl triethoxysilane etc. (more than be that R is the compound of (ア));
R is the compound (R is the compound of (イ)) that is selected from the structure of following formula (4)～(16);
R is the compound (R is the compound of (ウ)) that is selected from the structure of following formula (17)～(26);
R is the compound (R is the compound of (エ)) that is selected from the structure of following formula (27)～(30);
4 '-chalcone base trimethoxy silane, 4 '-chalcone ethyl triethoxy silicane alkane, cinnamoyl trimethoxy silane, cinnamoyl triethoxysilane, cinnamoyloxy group trimethoxy silane, cinnamoyloxy group triethoxysilane (more than be that R is the compound of (オ)) etc.
They can a kind or 2 kinds or above use simultaneously.
As compound (2), preferably one or more are used in combination from above-claimed cpd (A) and each group selection of above-claimed cpd (B).
The usage rate of compound (1) and compound (2), with respect to the total amount of compound (1) and (2), preferred compound (2) is 10～99 moles of %, more preferably 50～99 moles of %.
Reaction product (1) can be reacted by making compound (1), compound (2) and water, makes its hydrolyzable moiety condensation and makes.In order to make compound (1) and compound (2) hydrolysis, part condensation, every mole of siloxane key (formula (1)-OR
1With formula (2)-OR
2Summation) preferably use 1.0～1.5 mole of water.When the amount of water reaches 1 mole or when above, the residual possibility of the unreacted former state of siloxane bond descends, and is not coated with possibility that film uniformity descends, and the possibility that the liquid crystal orientating agent storage stability descends also reduces, so is preferred.Water can be intermittently or is joined continuously in the organic solvent that is dissolved with compound (1) and compound (2).At this moment can use catalysts, when using catalyzer, can in advance catalyzer be joined in the organic solvent, also can when adding entry, it be dissolved or dispersed in the water.The temperature of reaction of this moment is preferably 0～100 ℃, more preferably 15～80 ℃.
Organic solvent when making compound (1) and compound (2) hydrolysis, part condensation preferably can use at least a kind of solvent that is selected from alcohols solvent, ketones solvent, amide solvent, esters solvent and non-proton kind solvent.
Here, as alcohols solvent, can enumerate for example methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, sec-butyl alcohol, the tert-butyl alcohol, n-amyl alcohol, isoamylol, the 2-methyl butanol, sec-amyl alcohol, tert-pentyl alcohol, the 3-methoxybutanol, n-hexyl alcohol, the 2-methyl amyl alcohol, secondary hexyl alcohol, the 2-ethyl butanol, secondary enanthol, the 3-enanthol, n-octyl alcohol, 2-Ethylhexyl Alcohol, secondary octanol, n-nonyl alcohol, 2, the 6-2,6-dimethyl-4-heptanol, Decanol, secondary hendecanol, Exxal 12, secondary tetradecanol, secondary heptadecanol, phenol, cyclohexanol, methyl cyclohexanol, 3,3, the 5-cyclonol, benzylalcohol, unary alcohol solvents such as diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1, ammediol, 2,4-pentanediol, 2-methyl 2,4-pentanediol, 2,5-hexanediol, 2,4-heptandiol, 2-ethyl-1, polyalcohols solvents such as 3-hexanediol, diglycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, ethylene glycol mono hexyl ether, the glycol monomethyl phenyl ether, glycol monomethyl-2-second butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diglycol monotertiary propyl ether, the diglycol monotertiary butyl ether, diglycol, single hexyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, the propylene glycol single-butyl ether, the dipropylene glycol monomethyl ether, dipropylene glycol list ether, polyol moiety ether solvents such as dipropylene glycol list propyl ether; Or the like.
These alcohols solvents can a kind or 2 kinds or above use simultaneously.
As ketones solvent, for example except acetone, methyl ethyl ketone, methyl n-pro-pyl ketone, methyl n-butyl ketone, metacetone, methyl isobutyl ketone, methyl-n-amyl ketone, ethyl normal-butyl ketone, methyl n hexyl ketone, diisobutyl ketone, the trimethyl nonanone, cyclohexanone, methyl-n-butyl ketone, methyl cyclohexanone, 2, the 4-pentanedione, acetonyl acetone, acetophenone, beyond the fenchone etc., can also enumerate diacetone, 2, the 4-acetyl butyryl, 2, the 4-heptadione, 3, the 5-heptadione, 2, the 4-acetyl caproyl, 3, the 5-acetyl caproyl, 2,4-diketone in the ninth of the ten Heavenly Stems, 3,5-diketone in the ninth of the ten Heavenly Stems, 5-methyl-2, the 4-acetyl butyryl, 2,2,6,6-tetramethyl-3, the 5-heptadione, 1,1,1,5,5,5-hexafluoro-2, beta-diketon classes such as 4-heptadione etc.
These ketones solvents can a kind or 2 kinds or above use simultaneously.
As amide solvent; can enumerate for example formamide, N-NMF, N; dinethylformamide, N-ethyl-formamide, N; N-diethylformamide, acetamide, N-methylacetamide, N; N-dimethyl acetamide, N-ethyl acetamide, N, N-diethyl acetamide, N-methyl propanamide, N-Methyl pyrrolidone, N-formyl morpholine, N-formyl piperidine, N-carbonyl pyrrolidine, N-acetyl group morpholine, N-acetyl group piperidines, N-acetyl-pyrrolidine etc.
These amide solvents can a kind or 2 kinds or above use simultaneously.
As esters solvent, can enumerate for example diethyl carbonate, ethylene carbonate, carbonic allyl ester, diethyl carbonate, methyl acetate, ethyl acetate, gamma-butyrolacton, gamma-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, 2-butyl acetate, n-Amyl acetate, the secondary pentyl ester of acetic acid, acetic acid 3-methoxyl butyl ester, acetic acid methyl pentyl ester, acetic acid 2-ethyl butyl ester, acetic acid 2-Octyl Nitrite, benzyl acetate, cyclohexyl acetate, acetic acid methyl cyclohexane ester, acetic acid n-nonyl ester, methyl acetoacetate, ethyl acetoacetate, the acetic acid glycol monoethyl ether, the acetic acid ethylene glycol monoethyl ether, the acetic acid diethylene glycol monomethyl ether, the acetic acid diethylene glycol monoethyl ether, acetic acid diglycol monotertiary n-butyl ether, the acetic acid propylene glycol monomethyl ether, the acetic acid dihydroxypropane single-ether, the acetic acid propylene glycol monopropyl ether, acetic acid propylene glycol single-butyl ether, acetic acid dipropylene glycol monomethyl ether, acetic acid dipropylene glycol list ether, ethylene diacetate, methoxyl triethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethy-aceto oxalate, the oxalic acid di-n-butyl, methyl lactate, ethyl lactate, n-butyl lactate, the lactic acid n-pentyl ester, diethyl malonate, dimethyl phthalate, diethyl phthalate etc.
These esters solvents can a kind or 2 kinds or above use simultaneously.
As non-proton kind solvent, can enumerate for example acetonitrile, dimethyl sulfoxide (DMSO), N, N, N ' N '-tetraethyl sulfonamide, hexamethyl phosphoric triamide, N-methylmorpholine (メ チ Le モ Le ホ ロ Application), N-methylpyrrole, N-N-ethyl pyrrole N-, N-methyl-Δ 3-pyrrolin, N-methyl piperidine, N-ethylpiperidine, N, N-lupetazin, N-methylimidazole, N-methyl-4-piperidones, N-methyl-2-piperidones, N-N-methyl-2-2-pyrrolidone N-, 1,3-dimethyl-2-imidazolone, 1,3-dimethyl tetrahydro-2 (1H)-pyrimidone etc.Wherein, special preferred polyol kind solvent, polyol moiety ether solvent, esters solvent.
In addition, in the hydrolysis of compound (1) and compound (2), part condensation reaction, preferably use catalyzer.As this catalyzer, can enumerate following metal complex, organic acid, mineral acid, organic base, inorganic base.
As metal complex, can enumerate for example triethoxy list (diacetone) titanium, three positive propoxy list (diacetone) titaniums, three isopropoxy list (diacetone) titaniums, three n-butoxy list (diacetone) titaniums, three sec-butoxy list (diacetone) titaniums, three tert-butoxy list (diacetone) titaniums, the diethoxy bis(acetylacetonate) titanium, two positive propoxy bis(acetylacetonate) titaniums, the diisopropoxy bis(acetylacetonate) titanium, two n-butoxy bis(acetylacetonate) titaniums, two sec-butoxy bis(acetylacetonate) titaniums, two tert-butoxy bis(acetylacetonate) titaniums, monosubstituted ethoxy tri acetylacetonato titanium, single positive propoxy tri acetylacetonato titanium, single isopropoxy tri acetylacetonato titanium, single n-butoxy tri acetylacetonato titanium, single sec-butoxy tri acetylacetonato titanium, single tert-butoxy tri acetylacetonato titanium, four (diacetone) titanium;
Triethoxy list (ethyl acetoacetate) titanium, three positive propoxy list (ethyl acetoacetate) titaniums, three isopropoxy list (ethyl acetoacetate) titaniums, three n-butoxy list (ethyl acetoacetate) titaniums, three sec-butoxy list (ethyl acetoacetate) titaniums, three tert-butoxy list (ethyl acetoacetate) titaniums, diethoxy two (ethyl acetoacetate) titanium, two positive propoxy two (ethyl acetoacetate) titaniums, diisopropoxy two (ethyl acetoacetate) titanium, two n-butoxy two (ethyl acetoacetate) titaniums, two sec-butoxy two (ethyl acetoacetate) titaniums, two tert-butoxy two (ethyl acetoacetate) titaniums, monosubstituted ethoxy three (ethyl acetoacetate) titanium, single positive propoxy three (ethyl acetoacetate) titanium, single isopropoxy three (ethyl acetoacetate) titanium, single n-butoxy three (ethyl acetoacetate) titanium, single sec-butoxy three (ethyl acetoacetate) titanium, single tert-butoxy three (ethyl acetoacetate) titanium, four (ethyl acetoacetate) titanium, single (diacetone) three (ethyl acetoacetate) titanium, two (diacetone) two (ethyl acetoacetate) titaniums, titanium complexes such as tri acetylacetonato list (ethyl acetoacetate) titanium;
Triethoxy list (diacetone) zirconium, three positive propoxy list (diacetone) zirconiums, three isopropoxy list (diacetone) zirconiums, three n-butoxy list (diacetone) zirconiums, three sec-butoxy list (diacetone) zirconiums, three tert-butoxy list (diacetone) zirconiums, diethoxy two (diacetone) zirconium, two positive propoxy two (diacetone) zirconiums, diisopropoxy two (diacetone) zirconium, two n-butoxy two (diacetone) zirconiums, two sec-butoxy two (diacetone) zirconiums, two tert-butoxy two (diacetone) zirconiums, monosubstituted ethoxy tri acetylacetonato zirconium, single positive propoxy tri acetylacetonato zirconium, single isopropoxy tri acetylacetonato zirconium, single n-butoxy tri acetylacetonato zirconium, single sec-butoxy tri acetylacetonato zirconium, single tert-butoxy tri acetylacetonato zirconium, four (diacetone) zirconium;
Triethoxy list (ethyl acetoacetate) zirconium, three positive propoxy list (ethyl acetoacetate) zirconiums, three isopropoxy list (ethyl acetoacetate) zirconiums, three n-butoxy list (ethyl acetoacetate) zirconiums, three sec-butoxy list (ethyl acetoacetate) zirconiums, three tert-butoxy list (ethyl acetoacetate) zirconiums, diethoxy two (ethyl acetoacetate) zirconium, two positive propoxy two (ethyl acetoacetate) zirconiums, diisopropoxy two (ethyl acetoacetate) zirconium, two n-butoxy two (ethyl acetoacetate) zirconiums, two sec-butoxy two (ethyl acetoacetate) zirconiums, two tert-butoxy two (ethyl acetoacetate) zirconiums, monosubstituted ethoxy three (ethyl acetoacetate) zirconium, single positive propoxy three (ethyl acetoacetate) zirconium, single isopropoxy three (ethyl acetoacetate) zirconium, single n-butoxy three (ethyl acetoacetate) zirconium, single sec-butoxy three (ethyl acetoacetate) zirconium, single tert-butoxy three (ethyl acetoacetate) zirconium, four (ethyl acetoacetate) zirconium, single (diacetone) three (ethyl acetoacetate) zirconium, two (diacetone) two (ethyl acetoacetate) zirconiums, zirconium complexs such as tri acetylacetonato list (ethyl acetoacetate) zirconium;
Aluminum complexes such as aluminium tris(acetylacetonate), three (ethyl acetoacetate) aluminium; Or the like.
Organic acid can be enumerated for example acetate, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, hexanedioic acid, decanedioic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, 2 ethyl hexanoic acid, oleic acid, stearic acid, linoleic acid, leukotrienes, salicylic acid, benzoic acid, para-aminobenzoic acid, p-toluenesulfonic acid, benzene sulfonic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalandione, fumaric acid, citric acid, tartrate etc.
Mineral acid can be enumerated for example hydrochloric acid, nitric acid, sulfuric acid, hydrofluorite, phosphoric acid etc.
Organic base can be enumerated for example pyridine, pyrroles, piperazine, pyrrolidine, piperidines, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine, triethanolamine, diazabicyclooctane (ジ ア ザ PVC シ Network ロ オ Network ラ Application), diazabicyclononane, diazabicylo undecylene, tetramethyl ammonium hydroxide etc.
Inorganic base can be enumerated for example ammonia, NaOH, potassium hydroxide, baryta hydrate, calcium hydroxide etc.
In these catalyzer, preferable alloy complex, organic acid, mineral acid preferredly can be enumerated titanium complex, organic acid.They can a kind or 2 kinds or above use simultaneously.
Above-mentioned catalyst consumption, the combination (converting with the complete hydrolysis condensation product) with respect to 100 weight portion compounds (1) and compound (2) is preferably 0.001～10 weight portion, more preferably 0.001～1 weight portion.
Liquid crystal orientating agent of the present invention is dissolved in or is scattered in the organic solvent by reaction product (1) and forms.
Organic solvent uses the solvent of following formula (3) expression,
Wherein, R
3Be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl or the tert-butyl group, m is 0 or 1, and n is 1,2 or 3.
This organic solvent instantiation can be enumerated glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, dihydroxypropane single-ether, ethylene glycol propyl ether, propylene glycol list positive propyl ether, glycol monomethyl isopropyl ether, propylene glycol list isopropyl ether, glycol monomethyl n-butyl ether, propylene glycol list n-butyl ether, glycol monomethyl tertbutyl ether, propylene glycol list tertbutyl ether.
These solvents can be separately or two kinds or above mixing use.In addition, can also unite the poor solvent that is difficult to dissolve material therefor that use does not cause the amount that solid separates out.
Instantiation as this poor solvent, can enumerate for example n-pentane, isopentane, normal hexane, isohexane, normal heptane, isoheptane, 2,2, varsols such as 4-trimethylpentane, normal octane, isooctane, cyclohexane, methylcyclohexane, decane, dicyclopentadiene, benzene,toluene,xylene, durene, indenes, naphthane, decahydronaphthalene, squalane, ethylbenzene, trimethylbenzene, ethyl methyl benzene, n-propylbenzene, cumene, diethylbenzene, isobutyl-benzene, triethylbenzene, diisopropyl benzene, n-pentyl naphthalene, trimethylbenzene; Methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, sec-butyl alcohol, the tert-butyl alcohol, n-amyl alcohol, isoamylol, the 2-methyl butanol, sec-amyl alcohol, tert-pentyl alcohol, the 3-methoxybutanol, hexanol, the 2-methyl amyl alcohol, secondary hexyl alcohol, the 2-ethyl butanol, secondary enanthol, the 3-enanthol, n-octyl alcohol, 2-Ethylhexyl Alcohol, secondary octanol, secondary nonyl alcohol, 2, the 6-2,6-dimethyl-4-heptanol, Decanol, secondary undecyl alcohol, Exxal 12, secondary myristyl alcohol, secondary pentadecyl alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3,3, the 5-cyclonol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, unary alcohol solvents such as cresols; Ethylene glycol, 1,2-propylene glycol, 1,3 butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-two heptandiols, 2-ethyl-1, polyalcohols solvents such as 3-hexanediol, diglycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerine; Acetone, methyl ethyl ketone, methyl n-pro-pyl ketone, methyl n-butyl ketone, metacetone, methyl isobutyl ketone, methyl-n-amyl ketone, methyl amyl ketone, ethyl normal-butyl ketone, methyl n hexyl ketone, dipropyl ketone, diisopropyl ketone, trimethyl nonanone, cyclopentanone, cyclohexanone, methyl cyclohexanone, cycloheptanone, 2, ketones solvents such as 4-pentanedione, acetonyl acetone, acetophenone, fenchone; Anaesthetie Ether, Di Iso Propyl Ether, di ether, di-n-butyl ether, di-n-hexyl ether, 2-ethylhexyl ether, oxirane, 1, ether solvents such as 2-epoxypropane, two oxa-s, penta ring, 4-methyl dioxolanes, dioxane, dimethyl dioxane, phenetol, diphenyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; Diethyl carbonate, carbonic allyl ester, gamma-butyrolacton, gamma-valerolactone, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, 2-butyl acetate, n-Amyl acetate, the secondary pentyl ester of acetic acid, acetic acid 3-methoxyl butyl ester, acetic acid methyl pentyl ester, acetic acid 2-ethyl butyl ester, acetic acid 2-Octyl Nitrite, benzyl acetate, the just own ester of acetic acid, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate, acetic acid methyl cyclohexane ester, acetic acid n-nonyl ester, methyl acetoacetate, ethyl acetoacetate, the acetic acid glycol monoethyl ether, the acetic acid ethylene glycol monoethyl ether, the acetic acid ethylene glycol ether, the acetic acid ethylene glycol monobutyl ether, the acetic acid diethylene glycol monomethyl ether, the acetic acid diethylene glycol monoethyl ether, acetic acid diglycol monotertiary n-butyl ether, the acetic acid propylene glycol monomethyl ether, the acetic acid dihydroxypropane single-ether, the acetic acid propylene glycol monopropyl ether, acetic acid propylene glycol single-butyl ether, acetic acid dipropylene glycol monomethyl ether, acetic acid dipropylene glycol list ether, ethylene diacetate, methoxyl triethylene glycol acetate, phenylacetic acid second fat, 3-methoxypropionic acid methyl esters, the triethoxy ethyl propionate, methyl propionate, ethyl propionate, the propionic acid n-propyl, isopropyl propionate, n-butyl propionate, isobutyl propionate, isoamyl propionate, benzyl propionate, ethoxyethyl propionate, diethy-aceto oxalate, the oxalic acid di-n-butyl, methyl lactate, ethyl lactate, lactic acid n-propyl ester, isopropyl lactate, n-butyl lactate, the lactic acid n-pentyl ester, methyl formate, ethyl formate, the formic acid n-propyl, isopropyl formate, n-buty formate, iso-butyl formate, the formic acid n-pentyl ester, isoamyl formate, methyl butyrate, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, isobutyl isobutyrate (IBIB), diethyl malonate, dimethyl phthalate, diethyl phthalate, esters solvents such as ethyl pyruvate; N-NMF, N, dinethylformamide, N, amide solvents such as N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl propanamide, N-Methyl pyrrolidone; Dimethyl sulfide, ethyl sulfide, thiophene, thiophane, dimethyl sulfoxide (DMSO), sulfolane, 1, sulfur-bearing kind solvents such as 3-N-morpholinopropanesulfonic acid lactone etc.
These poor solvents use for example 50 weight portions or following, preferred 30 weight portions or following with respect to the organic solvent of the above-mentioned formula of 100 weight portions (3) expression.
Liquid crystal orientating agent of the present invention can also further add following beta-diketon:
1 kind or 2 kinds or above diacetone, 2,4-acetyl butyryl, 2,4-heptadione, 3,5-heptadione, 2,4-acetyl caproyl, 3,5-acetyl caproyl, 2,4-diketone in the ninth of the ten Heavenly Stems, 3,5-diketone in the ninth of the ten Heavenly Stems, 5-methyl-2,4-acetyl butyryl, 2,2,6,6-tetramethyl-3,5-heptadione, 1,1,1,5,5,5-hexafluoro-2,4-heptadione etc.
In the liquid crystal orientating agent of gained of the present invention, compositions such as the silica of all right further interpolation colloidal, the alumina of colloidal, organic polymer, surfactant.
So-called glue-like silica is meant the dispersion liquid that for example high-purity silicon dioxide is scattered in the above-mentioned hydrophilic organic solvent, and normally mean grain size is 5～30m μ, is preferably 10～20m μ, and the concentration of solid constituent is the dispersion liquid of 10～40 weight %.Such glue-like silica can be enumerated and for example produce methyl alcohol silicasol and the isopropyl alcohol silicasol that chemical industry (strain) is made daily; Catalyst changes into the OSCAL of industry (strain) manufacturing etc.
The colloidal alumina can be enumerated alumina sol 520, alumina sol 100, the alumina sol 200 that daily output chemical industry (strain) is made; Aluminium oxide vitreosol that Off ア イ Application ケ ミ ヵ Le (strain) makes, alumina sol 10, alumina sol 132 etc. are ground in the river.
Organic polymer can be enumerated the compound that for example has the polyalkylene oxide structure, the compound with sugar chain structure, ethernamine base polymer, (methyl) acrylate compounds, aromatic ethylene compound, dendrimer (デ Application De リ マ-), polyimide, polyamic acid, poly-propine, polyamide, polyquinoxaline, polyoxadiazole, fluoropolymer etc.
Surfactant can be enumerated for example non-ionic surfactant, anionic species surfactant, cationic surfactant, amphoteric surfactant etc., further can enumerate silicone surfactant, polyalkylene oxide class surfactant, fluorochemical surfactant etc.
In addition, from improving the adhering angle of substrate surface, liquid crystal orientating agent of the present invention can also comprise compound that contains functional silanes or the compound that contains epoxy radicals.This compound that contains functional silanes can be enumerated for example 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-carbethoxyl group-3-TSL 8330, N-carbethoxyl group-3-aminopropyltriethoxywerene werene, N-three ethoxy silylation propyl group diethylenetriamine, N-trimethoxy silylation propyl group diethylenetriamine, 10-trimethoxy silylation-1,4,7-three decane, 10-three ethoxy silylation-1,4,7-three decane, 9-trimethoxy silylation-3,6-diaza nonyl acetic acid esters, 9-three ethoxy silylation-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, N-two (hydroxyethyl)-3-TSL 8330, N-two (hydroxyethyl)-3-aminopropyltriethoxywerene werene etc.In addition, the compound that contains epoxy radicals preferably can be enumerated for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four diglycidyls-2, the 4-hexanediol, N, N, N ', benzene methanediamine between N '-four diglycidyl, 1,3-two (N, N-2-glycidyl amino methyl) cyclohexane, N, N, N ', N '-four diglycidyl-4,4 '-diaminodiphenyl-methane etc.
The ratio of reaction product in the liquid crystal orientating agent of the present invention (1) and solvent, consider to select from viscosity, volatility aspect, institute's silicon atoms in the reaction product (1) is converted into silicon dioxide, the ratio (solid component concentration) of reaction product in the liquid crystal orientating agent (1) is preferably 0.01～70 weight % for making concentration of silicon dioxide, more preferably 0.05～60 weight %, the ratio of 1～30 weight % more preferably.Liquid crystal orientating agent of the present invention, as described below, preferably by for example rolling method, spin-coating method, print processes etc. are coated on the substrate, then by it is carried out heat drying, formation is filmed as liquid crystal orientating membrane, when solid component concentration less than 0.01 weight %, then this film thickness of filming becomes too small, the situation of good liquid crystal orientating membrane can occur obtaining, when solid concentration surpassed 70 weight %, the film thickness of filming became excessive, the situation of good liquid crystal orientating membrane can appear being difficult to obtain, and the viscosity of liquid crystal orientating agent increases, and can make its coating performance variation.
The ratio of the solvent in the liquid crystal orientating agent of the present invention (II), shared ratio is preferably 1～100 weight % in total solvent, more preferably 30～100 weight %, more preferably 70～100 weight %.
Use liquid crystal orientating agent of the present invention, for example can make liquid crystal display cells by following method.
(1) by for example methods such as rolling method, spin-coating method, print process, ink-jet method, liquid crystal orientating agent of the present invention is coated on the real estate that is provided with the nesa coating that forms pattern, then,, coated face films by being added thermosetting.Environmental gas in coating and the heating process can carry out in inert gases such as nitrogen, helium, argon gas, can be further carries out in the atmosphere gas of sneaking into reducibility gas such as hydrogen as required.Here, substrate can use for example glass such as float glass, soda-lime glass; Plastics system transparency carriers such as polyethylene terephthalate, polybutyleneterephthalate, polyethersulfone, polymethylmethacrylate, polycarbonate.Substrate is simultaneously gone up set nesa coating can use tin oxide (SnO
2) the NESA film (U.S. PPG register of company trade mark), the indium oxide-tin oxide (In that make
2O
3-SnO
2) the ITO film made etc.The formation of these nesa coatings can be adopted photoetch method and use the method for mask in advance.When the coating of liquid crystal orientating agent,, can also on the surface of substrate, coating in advance contain the functional silanes compound, contain functionality titanium compound etc. for the cohesive of improving substrate surface and nesa coating and filming.Behind the coating of liquid crystalline directing agent, heating-up temperature is preferably 20～300 ℃, more preferably 120～300 ℃ for not causing the temperature of baseplate material distortion.As the thermal source of heat treated, can enumerate for example hot-air drying stove, infrared furnace, heating plate etc.The thickness of filming that forms is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) in addition, formed film coated surface is carried out surface finish, can control the liquid crystal aligning angle.In addition, by the step of electromagnetic radiation and particle beams impact surface, also can control the liquid crystal aligning angle.Here the used particle beams can be used ion beam, beam of neutral atoms, electron beam, molecular beam and elementary particle bundle etc.Irradiation energy, irradiating angle, irradiation time can be carried out suitable adjusting according to the kind of liquid crystal orientating membrane and the pre-tilt angle value that gives.When using ion beam, the ionic species of ion beam preferably uses the ion beam of inert gases such as nitrogen, helium, argon gas, neon.In addition, when ion beam irradiation or after the irradiation,, preferably provide electronics for neutralize ions.
Use ion beam, make method that shadow surface has a liquid crystal aligning performance open in the flat 11-271773 communique etc. open the spy.But, in this communique, the carbon covalent bond materials such as (DLC) that uses the hydrogenation diamond-like is as the material that forms liquid crystal alignment layer, form liquid crystal alignment layer by non-aqueous gaseous environment adhesion method such as chemical gaseous phase adhesion, rather than with as painting process such as the rolling method of available liquid crystal oriented layer formation method widespread use, spin-coating method, print process, ink-jet methods as object.Because liquid crystal orientating agent of the present invention provides with the solution shape, has the advantage that directly to utilize the used device of existing liquid crystal orientating membrane coating such as spin-coating method, print process.
As object lesson, be included in the liquid crystal orientating agent spy who uses polyamic acid or soluble polyimide and open that flat 8-313912 communique, spy are opened flat 8-313913 communique, the spy opens flat 8-313916 communique and the spy opens flat 11-237638 communique the effective liquid crystal orientating agent of ion beam.For behind the harsh and unforgiving environments that stands light and heat as mentioned above or long-time back liquid crystal aligning and the image retention characteristic of driving,, can realize existing polyamic acid or the superperformance that soluble polyimide did not have in the present invention by using silicon class material.
Use electron beam, make method that shadow surface has a liquid crystal aligning performance open in the flat 06-130389 communique etc. open the spy.But, owing in this communique, also be to use existing polyamic acid or soluble polyimide as the material that forms liquid crystal alignment layer, thereby be difficult to form as disclosed in the present invention for the few liquid crystal alignment layer of light and heat voltage residual rate decline.
Use molecular beam, beam of neutral atoms, elementary particle bundle and electromagnetic radiation, the method that makes the shadow surface orientation is opened in the flat 10-96928 communique etc. open the spy.But, owing in this communique, also be to use existing polyimide as the material that forms liquid crystal alignment layer, thereby be difficult to form as disclosed in the present invention for the few liquid crystal alignment layer of light and heat voltage residual rate decline.
In the use of liquid crystal orientating agent of the present invention, make 1.0～50 mole %s of compound (2) in overall be R wherein
2For the compound of photonasty groups such as chalcone base or cinnamoyl,, can control the liquid crystal aligning angle by electromagnetic radiation such as irradiation ultraviolet radiations.
In addition, the liquid crystal orientating membrane that forms by liquid crystal orientating agent of the present invention, by for example opening flat 6-222366 communique or the special method of opening disclosed part irradiation ultraviolet radiation in the flat 6-281937 communique as the spy, perhaps open disclosed method of the liquid crystal orientating membrane surface being carried out suddenly irradiation ion beam in regioselectivity ground through multistep in the flat 10-96928 communique as the spy, perhaps as special open in the flat 11-242225 communique disclosedly, can improve the field-of-view characteristics of liquid crystal display cells by the structure of control orientation method is set.
(3) substrate of 2 aforesaid formation liquid crystal orientating membranes of manufacturing, the surrounding edge position of a substrate is with the sealant of suitable pattern application Thermocurable therein.Make the vertical or antiparallel of liquid crystal aligning direction in the liquid crystal orientating membrane separately, make two substrates staggered relatively by gap (space between cells), make two baseplate-laminatings after, heating makes sealant cures.Inject filling liquid crystal in the space between cells that substrate surface and sealant are partitioned into, the sealing filling orifice forms liquid crystal cell line.
Can use liquid crystal to splash into mode from the operation that two baseplate-laminatings to liquid crystal is injected, i.e. ODF (One Drop Fill) mode.The monolithic substrate that has been coated with liquid crystal orientating membrane and given above-mentioned liquid crystal aligning performance with the ultra-violet solidified sealant of suitable pattern application, after necessary position splashes into liquid crystal, is made itself and another piece baseplate-laminating, utilize ultraviolet ray to make sealant cures.UV-irradiation is not limited to overall exposing, can adopt suitable modes such as mask exposure, scan exposure.
Then,, promptly constitute the polaroid of fitting on the another side of each substrate of liquid crystal cell line, make its polarization direction consistent or vertical, make liquid crystal display cells with the liquid crystal aligning direction of the liquid crystal orientating membrane that forms this substrate another side at the outside surface of liquid crystal cell line.
Liquid crystal can be enumerated nematic crystal and dish shape type liquid crystal, wherein preferred nematic crystal can use for example schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, phenylcyclohexane class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl thiacyclohexane class liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.In addition, also can add cholesteryl liquid crystal such as for example cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal and the chirality agent (カ イ ラ Le drug) of selling with trade name " C-15 ", " CB-15 " (メ Le Network corporate system) and using.And, can also use oxygen base benzylidene in the last of the ten Heavenly stems-p-amino-2-methyl butyl cinnamic acid ester (strong dielectricity liquid crystal such as シ Application Na メ-ト).
The polaroid that the liquid crystal cell line outside surface is fitted can be enumerated polyvinyl alcohol (PVA) is extended that the directed polarizing coating that is referred to as the H film that absorbs the iodine gained simultaneously is clipped in the acetate fiber diaphragm and the polaroid of polaroid of making or H film formation itself.
Embodiment
By the following examples the present invention is carried out more specific description, but the present invention only otherwise exceed its main points, and be confined to these embodiment never in any form.Wherein, in the following embodiments, part all is meant weight portion.
Synthesis example 1
After 106.3g methyl triethoxysilane, 6.82g octadecyltriethoxy silane and 12.67g tetramethoxy-silicane be dissolved in the 261.1g ethylene glycol monobutyl ether, stir with stirring machine, make solution temperature be stabilized in 60 ℃ with the laboratory.The ion exchange water that then 46.8g is dissolved with the 1.06g maleic acid joined in the solution through 1 hour.Then, reacted 4 hours down, obtain 435g with SiO at 60 ℃
2Concentration conversion reaction product (1) is the solution of 10 weight %.After this solution is cooled to room temperature, 50 ℃ down evaporation remove methyl alcohol, alcohol mixed solutions in the solution, add the 65.3g ethylene glycol monobutyl ether then, be the membrane filtration of 0.2 μ m with the aperture, obtain liquid crystal orientating agent (A).
Synthesis example 2
With 106.3g methyl triethoxysilane, 6.64g 1-TMS-3,3-two fluoro-4, after 4-dimethyl norbornane and 12.67g tetramethoxy-silicane are dissolved in the 260.8g ethylene glycol monobutyl ether, stir with stirring machine, make solution temperature be stabilized in 60 ℃ with the laboratory.The ion exchange water that then 47.3g is dissolved with the 1.07g maleic acid joined in the solution through 1 hour.Then, reacted 4 hours down at 60 ℃, obtaining 430g is the solution of 10 weight % with SiO2 concentration conversion reaction product (1).After this solution is cooled to room temperature, 50 ℃ down evaporation remove methyl alcohol, alcohol mixed solutions in the solution, add the 65.2g ethylene glycol monobutyl ether then, be the membrane filtration of 0.2 μ m with the aperture, obtain liquid crystal orientating agent (B).
Synthesis example 3
After 106.3g methyl triethoxysilane, 5.79g 3-trimethyl silicane alcoxyl base cholestane and 12.67g tetramethoxy-silicane be dissolved in the 262.2g ethylene glycol monobutyl ether, stir with stirring machine, make solution temperature be stabilized in 60 ℃ with the laboratory.The ion exchange water that then 46.5g is dissolved with the 1.06g maleic acid joined in the solution through 1 hour.Then, reacted 4 hours down at 60 ℃, obtaining 420g is the solution of 10 weight % with SiO2 concentration conversion reaction product (1).After this solution is cooled to room temperature, 50 ℃ down evaporation remove methyl alcohol, alcohol mixed solutions in the solution, add the 65.5g ethylene glycol monobutyl ether then, be the membrane filtration of 0.2 μ m with the aperture, obtain liquid crystal orientating agent (C).
Synthesis example 4
After 92.98g methyl triethoxysilane, 6.64g 4 '-trimethyl silicane alcoxyl base chalcone, 6.82g octadecyltriethoxy silane and 12.67g tetramethoxy-silicane be dissolved in the 259.6g ethylene glycol monobutyl ether, stir with stirring machine with the laboratory, make solution temperature be stabilized in 60 ℃.The ion exchange water that then 49.4g is dissolved with the 1.12g maleic acid joined in the solution through 1 hour.Then, reacted 4 hours down at 60 ℃, obtaining 430g is the solution of 10 weight % with SiO2 concentration conversion reaction product (1).After this solution is cooled to room temperature, 50 ℃ down evaporation remove methyl alcohol, alcohol mixed solutions in the solution, add the 65.0g ethylene glycol monobutyl ether then, be the membrane filtration of 0.2 μ m with the aperture, obtain liquid crystal orientating agent (D).
Compare synthesis example 1
With 218.1g (1.0 moles) pyromellitic acid dicarboxylic anhydride and 198.27g (1 mole) 4, after 4 '-diaminodiphenylmethane is dissolved in 1600g N-N-methyl-2-2-pyrrolidone N-, this solution was reacted 6 hours down at 20 ℃.Then the gained reaction solution is poured in a large amount of excessive acetone, made the reaction product precipitation, to obtain the 400.3g polyamic acid polymer by reaction product is carried out the separating, washing drying.This polymkeric substance is dissolved in the gamma-butyrolacton, is the membrane filtration of 0.2 μ m with the aperture, obtains solid component concentration and be 4% liquid crystal orientating agent (E).
The directionality of liquid crystal
Liquid crystal display cells voltage is opened when cutting off,, when having abnormal area, be not evaluated as " well " with having or not abnormal area in the microscopic examination liquid crystal cell line.After liquid crystal display cells is made, carry out following rayed, thermal treatment immediately, detect then.
The liquid crystal display cells image retention is eliminated the time
Under 70 ℃ environment temperature to liquid crystal display cells apply stack 3.0V direct current, 6.0V exchange (peak value-peak value) and 30 hertz, 3.0V square wave 20 hours, after driving liquid crystal display cells, cut off voltage, visual mensuration is eliminated the required time until image retention.
The voltage residual rate of liquid crystal display cells
Apply the voltage of 5V in 167 milliseconds time span to liquid crystal display cells, the voltage application time is 60 microseconds, measures from voltage and removes voltage residual rate after 167 milliseconds.(VHR-1 of strain) East Yang テ Network ニ カ system carries out under 60 ℃ in the determinator employing.After liquid crystal display cells is made, carry out following rayed, thermal treatment immediately, measure then.
Rayed
After liquid crystal display cells is made, be light source, whole element is carried out rayed with the metal halide lamp.Use light filter to select the wave band of illumination wavelength, with 2J/cm as 300-450nm
2Energy shine.
Thermal treatment
After placing 100 ℃ baking oven to place for 3 weeks the liquid crystal display cells of manufacturing, take out and slowly cool to room temperature.
Embodiment 1
Adopt spin coater liquid crystal orientating agent (A) to be coated on the transparency electrode face of the glass substrate that has ITO film transparency electrode, heat drying is 30 minutes in 300 ℃ hot blast, and forming dry average film thickness is filming of 700 dusts.
Make two substrates that as above form liquid crystal orientating membrane, to the peripheral position of each substrate, contain the alumina balls epoxyn by the silk screen print method coating, make coated surface staggered relatively by the gap two substrates, make between the peripheral position and dock pressing, bonding agent is solidified.In the space between cells that substrate surface and peripheral position bonding agent are divided into, inject and fill the negativity nematic crystal, then, filling orifice is sealed with epoxy adhesive, make vertical orientation type liquid crystal display cells.
To the as above liquid crystal display cells that has just made of gained, carry out liquid crystal aligning observation and voltage residual rate and measure.Prepare 3 liquid crystal display cells of as above making with liquid crystal orientating agent (A), one is carried out illumination, carrying out liquid crystal aligning observation and voltage residual rate then measures, another part is heat-treated, carry out liquid crystal aligning observation and voltage residual rate then and measure, remaining one measures image retention according to described method and eliminates the time.The result is as shown in table 1.
Embodiment 2～3
With the liquid crystal orientating agent of gained in the synthesis example 2～3, liquid crystal display cells is made in operation similarly to Example 1.With the liquid crystal display cells of each gained, shown in embodiment 1, liquid crystal aligning, voltage residual rate, image retention elimination time are estimated.The result is as shown in table 1.
Embodiment 4
Adopt spin coater liquid crystal orientating agent (A) to be coated on the transparency electrode face of the glass substrate that has ITO film transparency electrode, heat drying is 30 minutes in 300 ℃ hot blast, and forming dry average film thickness is filming of 700 dusts.
Accelerating potential by 200V from the direction that becomes 40 degree angles with substrate to this film shine 10 second ar-ion beam.
Then, the periphery separately that two blocks of liquid crystal through Ion Beam Treatment is held substrate with liquid crystal orientating membrane, having added diameter by the silk screen print method coating is the epoxyn of the alumina balls of 5.5 μ m, it is staggered relatively to make two blocks of liquid crystal hold two liquid crystal aligning faces of substrate then, and make it vertical with the ion beam irradiation direction and carry out overlapping pressing, make bonding agent solidify.
Then between two substrates, fill nematic crystal (メ Le Network corporate system by liquid crystal injecting port, MLC-6221), then with acrylic compounds Photocurable adhesive sealing liquid crystal injecting port, the polaroid of on two lateral surfaces of substrate, fitting, make the polaroid polarization direction consistent, make liquid crystal display cells with the ion beam irradiation direction of the liquid crystal orientating membrane of substrate separately.
With each liquid crystal display cells that so makes, shown in embodiment 1, liquid crystal aligning, voltage residual rate, image retention elimination time are estimated.The result is as shown in table 1.
Embodiment 5～6
Adopt the liquid crystal orientating agent of synthesis example 2～3 gained, liquid crystal display cells is made in operation similarly to Example 4.With the liquid crystal display cells of each gained, shown in embodiment 1, liquid crystal aligning, voltage residual rate, image retention elimination time are estimated.The result is as shown in table 1.
Embodiment 7
Adopt spin coater liquid crystal orientating agent (D) to be coated on the transparency electrode face of the glass substrate that has ITO film transparency electrode, heat drying is 30 minutes in 300 ℃ hot blast, and forming dry average film thickness is filming of 700 dusts.
Adopt the Hg-Xe lamp, the short-wavelength light by the polaroid SPF-50C-32 (シ グ マ ray machine system) of hard (パ イ レ Star Network ス) (registered trademark) glass cuts off 320nm shines 1.0J/cm from the real estate normal direction to this film coated surface
2Rectilinearly polarized light based on 365nm.
Make two as above substrates of the formation liquid crystal orientating membrane of treatment with irradiation, at each piece substrate periphery position, contain the alumina balls epoxyn by the silk screen print method coating, then two substrates are overlapped by the gap, its ultraviolet plane of polarization direction with irradiation is parallel to each other, with the butt joint pressing of peripheral position, bonding agent is solidified.In the space between cells that substrate surface and peripheral position bonding agent are divided into, (メ Le Network corporate system MLC-6221), then, is sealed filling orifice with epoxy adhesive, makes liquid crystal display cells to fill nematic crystal.
With each liquid crystal display cells that so makes, shown in embodiment 1, liquid crystal aligning, voltage residual rate, image retention elimination time are estimated.The result is as shown in table 1.
Comparing embodiment 1
Adopt spin coater will compare that gained liquid crystal orientating agent (E) is coated on the transparency electrode face of the glass substrate that has ITO film transparency electrode in the synthesis example 1, heat drying is 20 minutes in 200 ℃ hot blast, and forming dry average film thickness is filming of 600 dusts.
The sander of roller with cloth of the regenerated fiber system of being tied with is filmed to this and is carried out grinding process, and the rotational speed of roller is 400rpm, and (ス テ-ジ) translational speed is 30mm/ second to section, and it is 0.4mm that fine hair is pressed into length.
With each liquid crystal display cells that so makes, shown in embodiment 1, liquid crystal aligning, voltage residual rate, image retention elimination time are estimated.The result is as shown in table 1.
Table 1
Claims (7)
1. liquid crystal orientating agent is characterized in that comprising:
(I) silicon compound of following formula (1) expression, the silicon compound of following formula (2) expression and the reaction product of water, and
(II) solvent of following formula (3) expression,
Si(OR
1)
4..................(1)
R wherein
1Be any monovalent organic radical group that from methyl, ethyl, propyl group and butyl, selects,
RSi(OR
2)
3..................(2)
Wherein R is an any monovalent organic radical group, and R
2Be any monovalent organic radical group that from methyl, ethyl, propyl group and butyl, selects,
Wherein, R
3Be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl or the tert-butyl group, m is 1, and n is 2 or 3,
And the silicon compound of above-mentioned formula (2) expression is the potpourri of following silicon compound (A) and silicon compound (B):
(A) silicon compound of alkyl, vinyl or the phenyl of C1～4 that R replaces for the optional substituting group that can be selected from amino, glycidoxy and trifluoromethyl in the above-mentioned formula (2),
(B) R is the silicon compound of following group in the above-mentioned formula (2):
(a) carbon number is 16 or above straight chained alkyl;
(b) has norbornane ring and be selected from any monovalent organic radical group of following formula (4)～(16);
(c) has steroid backbone and be selected from any monovalent organic radical group of following formula (17)～(26);
(d) having aromatic rings and carbon number is 8 or the above any monovalent organic radical group that is selected from following formula (27)～(30);
Perhaps
(e) has the photonasty group of cinnamoyl or chalcone base.
2. the described liquid crystal orientating agent of claim 1, in the compound of wherein above-mentioned formula (2) expression, R is that the compound of photonasty group (e) accounts for 1～50 mole of % in the formula (2).
3. the formation method of a liquid crystal orientating membrane is characterized in that comprising claim 1 or 2 described liquid crystal orientating agents is coated the operation of substrate and the operation of the substrate cured coating film that heating is coated with.
4. a formation method of controlling the liquid crystal orientating membrane of liquid crystal aligning angle is characterized in that grinding process is carried out on the film surface of the described liquid crystal orientating membrane of claim 3.
5. formation method of controlling the liquid crystal orientating membrane of liquid crystal aligning angle, it is characterized in that be selected from X ray and ultraviolet electromagnetic radiation, be selected from ion beam, the particle beams of beam of neutral atoms, electron beam, molecular beam and elementary particle bundle or electromagnetic radiation and the particle beams shine the film surface of the described liquid crystal orientating membrane of claim 3 together.
6. by any liquid crystal orientating membrane that described method is made of claim 3～5.
7. a liquid crystal display cells is characterized in that having the described liquid crystal orientating membrane of claim 6.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004062344A JP4513950B2 (en) | 2004-03-05 | 2004-03-05 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| JP062344/2004 | 2004-03-05 | ||
| JP062344/04 | 2004-03-05 |
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| CN1664657A CN1664657A (en) | 2005-09-07 |
| CN100501532C true CN100501532C (en) | 2009-06-17 |
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| JP (1) | JP4513950B2 (en) |
| KR (1) | KR101067163B1 (en) |
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| US20080315201A1 (en) * | 2005-09-16 | 2008-12-25 | Tadahiro Ohmi | Apparatus for Producing Electronic Device Such as Display Device, Method of Producing Electronic Device Such as Display Device, and Electronic Device Such as Display Device |
| KR101364921B1 (en) * | 2006-03-07 | 2014-02-19 | 닛산 가가쿠 고교 가부시키 가이샤 | Silicon-containing liquid crystal aligning agent, liquid crystal alignment film and their production methods |
| JP4844721B2 (en) * | 2006-03-22 | 2011-12-28 | Ｊｓｒ株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| KR101319206B1 (en) * | 2006-03-22 | 2013-10-16 | 제이에스알 가부시끼가이샤 | Liquid crystal aligning agent and liquid crystal display device |
| JP4685713B2 (en) * | 2006-06-09 | 2011-05-18 | セイコーエプソン株式会社 | Method for manufacturing substrate for liquid crystal device |
| TWI427121B (en) * | 2006-09-01 | 2014-02-21 | Jnc Corp | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| CN101523280B (en) * | 2006-10-06 | 2012-09-19 | 日产化学工业株式会社 | Silicon-containing liquid crystal aligning agent and liquid crystal alignment film |
| JP5088561B2 (en) * | 2007-02-23 | 2012-12-05 | Ｊｓｒ株式会社 | Liquid crystal alignment agent |
| WO2008108493A1 (en) * | 2007-03-08 | 2008-09-12 | Jsr Corporation | Liquid crystal aligning agent and in-plane switching mode liquid crystal display |
| US8310636B2 (en) | 2007-03-26 | 2012-11-13 | Sharp Kabushiki Kaisha | Liquid crystal display device and polymer for aligning film material |
| JP5067570B2 (en) * | 2007-08-01 | 2012-11-07 | Ｊｓｒ株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| KR100969330B1 (en) * | 2007-12-07 | 2010-07-09 | 제일모직주식회사 | Alignment agent of liquid crystal, alignment film of liquid crystal including the same, and liquid crystal display including the same |
| KR101049550B1 (en) * | 2008-09-29 | 2011-07-14 | 제일모직주식회사 | Liquid crystal aligning agent, Liquid crystal aligning film containing this, Liquid crystal display containing this |
| CN102317848B (en) * | 2008-12-25 | 2014-06-11 | 日产化学工业株式会社 | LIQUID-CRYSTAL ALIGNMENT MATERIAL FOR INK-JET COATING, LIQUID-CRYSTAL ALIGNMENT FILM, AND LIQUID-CRYSTAL DISPLAY ELEMENt |
| WO2010074264A1 (en) * | 2008-12-26 | 2010-07-01 | 日産化学工業株式会社 | Liquid crystal aligning agent for inkjet coating, liquid crystal alignment film, and liquid crystal display element |
| JP5626510B2 (en) * | 2009-02-18 | 2014-11-19 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film forming method, and liquid crystal display element manufacturing method |
| JP5311054B2 (en) * | 2009-02-19 | 2013-10-09 | Ｊｓｒ株式会社 | Liquid crystal aligning agent, liquid crystal display element and manufacturing method thereof |
| KR101647537B1 (en) | 2009-05-01 | 2016-08-10 | 닛산 가가쿠 고교 가부시키 가이샤 | Silicon liquid crystal orientation agent, liquid crystal oriented film, and liquid crystal display element |
| KR101708962B1 (en) * | 2009-12-02 | 2017-02-21 | 닛산 가가쿠 고교 가부시키 가이샤 | Liquid crystal aligning agent and liquid crystal display element using same |
| WO2012017883A1 (en) | 2010-08-03 | 2012-02-09 | シャープ株式会社 | Liquid crystal display device and liquid crystal display device manufacturing method |
| US9195097B2 (en) | 2010-08-03 | 2015-11-24 | Sharp Kabushiki Kaisha | Liquid crystal display device and process for producing liquid-crystal display device |
| CN103097948B (en) * | 2010-08-30 | 2015-05-13 | 夏普株式会社 | Liquid crystal display panel, liquid crystal display device, and polymer for alignment layer material |
| CN103080824B (en) | 2010-09-07 | 2016-03-09 | 夏普株式会社 | Liquid crystal layer forms the manufacture method with composition, liquid crystal indicator and liquid crystal indicator |
| WO2012077668A1 (en) | 2010-12-06 | 2012-06-14 | シャープ株式会社 | Liquid crystal display device and method for producing liquid crystal display device |
| WO2012086715A1 (en) | 2010-12-22 | 2012-06-28 | シャープ株式会社 | Liquid crystal orienting agent, lcd device, and method for producing lcd device |
| JP5999084B2 (en) | 2011-02-24 | 2016-09-28 | 日産化学工業株式会社 | Silicon-based liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| TWI553040B (en) | 2011-05-27 | 2016-10-11 | Nissan Chemical Ind Ltd | Silicon liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display components |
| JP2013117681A (en) * | 2011-12-05 | 2013-06-13 | Jsr Corp | Liquid crystal aligning agent |
| CN104737069B (en) * | 2012-08-30 | 2018-08-10 | 日产化学工业株式会社 | Aligning agent for liquid crystal and the liquid crystal display element for using the aligning agent for liquid crystal |
| JP6458949B2 (en) * | 2013-04-16 | 2019-01-30 | 日産化学株式会社 | Cured film forming composition, alignment material and retardation material |
| WO2014196540A1 (en) | 2013-06-06 | 2014-12-11 | 日産化学工業株式会社 | Alkoxysilane compound, liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| JP6470204B2 (en) * | 2016-02-25 | 2019-02-13 | 富士フイルム株式会社 | Manufacturing method of liquid crystal display panel |
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| JP3757514B2 (en) * | 1996-02-16 | 2006-03-22 | 日産化学工業株式会社 | Method for forming liquid crystal vertical alignment film |
| JP2003073471A (en) * | 2001-08-31 | 2003-03-12 | Jsr Corp | Vertically aligning-type liquid crystal aligner and liquid crystal display element using the same |
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| KR20060043402A (en) | 2006-05-15 |
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