CN101687996B - Polyorganosiloxane, liquid crystal alignment film, and liquid crystal display element - Google Patents
Polyorganosiloxane, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
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- CN101687996B CN101687996B CN200880024085XA CN200880024085A CN101687996B CN 101687996 B CN101687996 B CN 101687996B CN 200880024085X A CN200880024085X A CN 200880024085XA CN 200880024085 A CN200880024085 A CN 200880024085A CN 101687996 B CN101687996 B CN 101687996B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- 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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- 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
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- 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
- G02F1/133742—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers for homeotropic alignment
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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
- G02F1/133765—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers without a surface treatment
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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
Disclosed is a polyorganosiloxane which has a repeating unit represented by the general formula (1) and has a weight average molecular weight of 1,000 to 100,000: (1) wherein Z represents a photosensitive group capable of causing a crosslinking reaction or an isomerization reaction when irradiated with light having a wavelength of 200 to 400 nm; and X represents a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkoxyl group having 1 to 20 carbon atoms, or may be crosslinked with X in other repeating unit through -O-. The polyorganosiloxane has excellent coatability and can be used for the liquid crystal alignment film formation which can impart a liquid crystal alignment capability through the irradiation with a polarized or non-polarized radioactive ray without the need of conducting any rubbing processing.
Description
Technical field
The present invention relates to new organopolysiloxane, liquid crystal orientation film and liquid crystal display device.More particularly, relate to do not carry out grinding process and by irradiation polarisation or non-polarisation ray can produce liquid crystal aligning can the formation of liquid crystal orientation film in operable organopolysiloxane, this liquid crystal orientation film and the liquid crystal display device with this liquid crystal orientation film.
Background technology
So far, known have the nematic liquid crystal that will have positive dielectric anisotropy form sandwich structure in the substrate with the transparency electrode with liquid crystal orientation film, and make as required the major axis of liquid crystal molecule reverse continuously 0～360 ° and the TN type (twisted-nematic) made and the liquid crystal display device (with reference to Japanese kokai publication sho 56-91277 communique and Japanese kokai publication hei 1-120528 communique) of the various liquid crystal cells such as STN (supertwist is to row) type, IP S (switching face in) type between substrate.
In this liquid crystal cell, be orientated with certain orientation for substrate surface in order to make mesomorphic phase, must liquid crystal orientation film be set at substrate surface.This liquid crystal orientation film forms by the method (polishing method) with formed organic membrane surface on the cloth rubbed substrate surfaces such as regenerated fiber usually.But, if the formation of liquid crystal orientation film is undertaken by grinding process, then exist owing to easily producing dust, static in the operation, thereby cause alignment layer surface to adhere to dust and become the problem of the reason that shows bad generation.Particularly have in the situation of substrate of TFT (thin film transistor) element in use, also exist the static that produces to cause the TFT element circuitry to be damaged and become the problem of the reason of decrease in yield.And from now on day by day in the liquid crystal display device of high-precision, along with the densification of pixel, substrate surface produces uneven unavoidably, thereby so that carries out equably grinding process and be a problem very much.
As other means that make the liquid crystal aligning in the liquid crystal cell, known by the ray to the irradiation polarisation such as the photosensitive film of being made by polyvinyl cinnamate, polyimide, azobenzene derivatives etc. that forms on the substrate surface or non-polarisation make its produce liquid crystal aligning can optical alignment method.If employing the method, then can not produce static and dust, can realize that uniform liquid crystal aligning is (with reference to Japanese kokai publication hei 6-287453 communique, Japanese kokai publication hei 10-251646 communique, Japanese kokai publication hei 11-2815 communique, Japanese kokai publication hei 11-152475 communique, TOHKEMY 2000-144136 communique, TOHKEMY 2000-319510 communique, TOHKEMY 2000-281724 communique, Japanese kokai publication hei 9-297313 communique, TOHKEMY 2003-307736 communique, TOHKEMY 2004-163646 communique and TOHKEMY 2002-250924 communique).
But, in the liquid crystal cell of TN type (twisted-nematic), STN (supertwist is to row) type etc., liquid crystal orientation film must have makes liquid crystal molecule with respect to the tilt angle characteristic of real estate with predetermined angle tilted alignment.In the situation that adopt optical alignment method to form liquid crystal orientation film, the tilt angle usually ray by making irradiation produces from the substrate normal run-off the straight to the incident direction of substrate.
In addition, as the operating mode of the liquid crystal display device beyond above-mentioned, known liquid crystal molecule vertical orientated vertical (homeotrophic) alignment mode on substrate with negative dielectric anisotropic that makes also.In this operating mode, when applying voltage between substrate liquid crystal molecule is tilted to the direction parallel with substrate, the direction of liquid crystal molecule in from the substrate normal direction to real estate tilted.As the means that reach this purpose, proposed such as the method that projection is set at substrate surface, make transparency electrode arrange band method, adopt the polishing alignment films to make the slightly method etc. of low dip (making its pre-tilt) of the direction of liquid crystal molecule in from the substrate normal direction to real estate.
Above-mentioned optical alignment method, known in the liquid crystal cell of vertical alignment mode the method as control liquid crystal molecules tilt direction also be of great use.That is to say, known to using the vertical alignment layer that is produced orientation control force and tilt angle by optical alignment method, can control equably the method for tilting (with reference to TOHKEMY 2003-307736 communique, TOHKEMY 2004-163646 communique, TOHKEMY 2004-83810 communique, Japanese kokai publication hei 9-211468 communique and TOHKEMY 2003-114437 communique) of the liquid crystal molecule when applying voltage.
Like this, the liquid crystal orientation film that adopts above-mentioned optical alignment method to make can be effectively applied to various liquid crystal display device.But although can obtain larger tilt angle, there is the very large problem of required radiation exposure in optical alignment film in the past.For example, have been reported, in containing the optical alignment film of azobenzene derivatives, in order to obtain enough large tilt angle, must irradiation 1J/cm
2The ray that above optical axis tilts from substrate normal is (with reference to TOHKEMY 2002-250924 communique, TOHKEMY 2004-83810 communique and J.ofthe SID 11/3,2003, p579).
Summary of the invention
The purpose of this invention is to provide screening characteristics, electric property good, can not carry out grinding process and by irradiation polarisation or non-polarisation ray produce liquid crystal aligning can the formation of liquid crystal orientation film in operable organopolysiloxane, and manufacture method.
Another object of the present invention provides the liquid crystal orientation film of being made by above-mentioned organopolysiloxane.
Another purpose of the present invention provides liquid crystal display device.
Other purposes of the present invention and advantage can be learned by the following description.
According to the present invention, above object and advantages of the present invention, first, reached by a kind of organopolysiloxane, it is characterized in that having the repeating unit of following formula (1) expression, and weight-average molecular weight drops on 1000～100000 scope (hereinafter referred to as organopolysiloxane of the present invention)
Here, Z is for being the light generation crosslinking reaction of 200～400nm or the photosensitive group of isomerization reaction by wavelength, X be hydroxyl, carbonatoms be 1～20 alkyl, carbonatoms be 6～20 aryl, carbonatoms be 1～20 alkoxyl group or X that also can be in other repeating units of same formula (1) expression by-O-forms crosslinked.
According to the present invention, above object and advantages of the present invention, the second, preferably the repeating unit by wherein above-mentioned formula (1) expression is that the repeating unit of following formula (2) expression or the organopolysiloxane of the repeating unit that following formula (3) represents are reached,
Here, A
1, A
2Can be identical, also can be different, be 1～40 alkyl or 1 valency organic group of alicyclic group for containing the optional carbonatoms that can be replaced by fluorine atom, B
1, B
2Can be identical, also can be different, be fluorine atom or cyano group, p is 0～4 integer, S
1, S
2Can be identical, also can be different, for having the divalent organic group that carbonatoms is 1～20 alkylidene group, X
1, X
2Can be identical, also can be different, for hydroxyl, carbonatoms are that 1～20 alkyl, carbonatoms are that 6～20 aryl, carbonatoms are 1～20 alkoxyl group, perhaps also can with other repeating units of same formula (2) or (3) expression in X
1Or X
2Together by-O-forms crosslinked.
According to the present invention, above object and advantages of the present invention, the 3rd, the method for making organopolysiloxane of the present invention is provided, it will be selected from, and at least a in the group of the silane compound formation that following formula (4) and (5) represent separately is hydrolyzed, condensation.
Here, A
1, A
2, B
1, B
2, S
1, S
2With identical in the definition of p and above-mentioned formula (2), (3), R
1, R
2Can be identical, also can be different, for carbonatoms is that 1～20 alkyl or carbonatoms are 6～20 aryl, Y
1, Y
2Can be identical, also can be different, be 1～20 alkoxyl group or chlorine atom for carbonatoms, n is 2 or 3.
According to the present invention, above object and advantages of the present invention, the 4th, preferably the catalyzer by wherein hydrolysis, condensation is that the method that organic acid prepares organopolysiloxane is reached.
According to the present invention, above object and advantages of the present invention, the 5th, preferably by under the coexistence of the silane compound of following formula (7), be hydrolyzed, the preparation method of condensation reaches.
Si(R
3)
t(OR
4)
(4-t)(7)
Here, R
3For carbonatoms is 1～40, the optional alkyl that contains alicyclic group, perhaps 6～20 aryl, R
4Be 1～20 alkyl for carbonatoms, t is 0,1,2 or 3.
According to the present invention, above object and advantages of the present invention, the 6th, to be reached by a kind of liquid crystal orientation film, it makes by the ray that the film that is formed by above-mentioned organopolysiloxane is shone polarisation or non-polarisation.
According to the present invention, above object and advantages of the present invention, the 7th, reached by the liquid crystal display device with above-mentioned liquid crystal orientation film.
According to the present invention, above-mentioned liquid crystal display device preferably uses negative type liquid crystal.
Embodiment
Below, the present invention is described in detail.
Organopolysiloxane of the present invention has the repeating unit of above-mentioned formula (1) expression, and weight-average molecular weight is 1000～100000.
In the formula (1), Z is for being the light generation crosslinking reaction of 200～400nm or the photosensitive group of isomerization reaction by wavelength.X be hydroxyl, carbonatoms be 1～20 alkyl, carbonatoms be 1～20 aryl, carbonatoms be 1～20 alkoxyl group or X that also can be in other repeating units of same formula (1) expression by-O-forms crosslinked.
Preferred X is hydroxyl, methoxyl group, oxyethyl group or forms crosslinked group with the X of other repeating units by-O-.
As the repeating unit of above-mentioned formula (1) expression, preferably can enumerate the repeating unit of above-mentioned formula (2) expression or the repeating unit of above-mentioned formula (3) expression.
In above-mentioned formula (2) and above-mentioned formula (3), A
1, A
2Can be identical, also can be different, for carbonatoms be 1～40 contain the optional alkyl that can be replaced by fluorine atom or 1 valency organic group of alicyclic group.B
1, B
2Can be identical, also can be different, be fluorine atom or cyano group.P is 0～4 integer.S
1, S
2Can be identical, also can be different, for having the divalent organic group that carbonatoms is 1～20 alkylidene group.X
1, X
2Can be identical, also can be different, for hydroxyl, carbonatoms are that 1～20 alkyl, carbonatoms are that 1～20 aryl, carbonatoms are 1～20 alkoxyl group, perhaps also can with other repeating units of same formula (2) or (3) expression in X
1Or X
2Together by-O-forms crosslinked.
As the object lesson of the group that is positioned at Siliciumatom top in above-mentioned formula (2) and (3), the structure that the formula (6-1)～(6-14) for example can enumerated represents separately.
In these formulas, preferred m is 1～20 integer, and l is the following integer of 2m+1, and k is 1～10 integer, and q is 2～10 integer, and more preferably m is 3～18, l is 3～9, k is 2～6, q is 2～6.Particularly preferably m is 4～10, l is 3～7, k is 2～4, q is 2～4.
The preferable weight-average molecular weight of organopolysiloxane of the present invention is 1000～50000.
Organopolysiloxane of the present invention can make by the condensation that for example silane compound of above-mentioned formula (4) or formula (5) is hydrolyzed.
In formula (4), (5), A
1, A
2, B
1, B
2, S
1, S
2With identical in the definition of p and above-mentioned formula (2), (3).As Y
1, Y
2, can enumerate such as alkoxyl groups such as chlorine atom and methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxies.Wherein be preferably chlorine atom, methoxyl group, oxyethyl group.As R
1, R
2Can enumerate aryl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, the just alkyl such as decyl, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base, and phenyl etc.Wherein, be preferably methyl, ethyl, phenyl.
In addition, the n in formula (4), (5) is preferably 3.
Formula (4) compound can make by for example currently known methods shown in the following synthetic route 1～3, but is not limited to these methods.Wherein, in the synthetic route 1～3, r is k-2.Formula (5) compound also can make by same method.
Synthetic route 1
Synthetic route 1: the precursor of formula (4) compound by will having alkene and triethoxyl silane heat, stir (hydrogen silylation), refining in the presence of the platinum catalyst of minute quantity, can make formula (4) compound.
Synthetic route 2
Synthetic route 2: precursor and the 3-glycidyl oxygen base propyl trimethoxy silicane of formula (4) compound by will having carboxylic acid heat, stir in the presence of such as basic catalysts such as triethylamines, can make formula (4) compound.
Synthetic route 3
Synthetic route 3: heat, stir in the presence of such as tin catalysts such as dibutyl tin two lauroleates by formula (4) compound and the tri-ethoxy silylpropyl isocyanic ester that will have hydroxyl, can make formula (4) compound.
The hydrolysis of organopolysiloxane, method of condensing
Organopolysiloxane of the present invention can be hydrolyzed by the silane compound that makes the expression of above-mentioned formula (4) or formula (5), condensation makes.Preferably make it carry out the cohydrolysis condensation under the silane compound coexistence of above-mentioned formula (7) expression this moment.
In the formula (7), R
3For carbonatoms is 1～40, chooses the alkyl that contains alicyclic group wantonly, perhaps carbonatoms is 6～20 aryl, R
4Be 1～20 alkyl for carbonatoms, t is 0,1,2 or 3.
As the silane compound of formula (7) expression, can enumerate for example tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, four sec-butoxy silane, four tert.-butoxy silane, methyltrimethoxy silane, Union carbide A-162, methyl three positive propoxy silane, methyl three isopropoxy silane, methyl three n-butoxy silane, methyl three sec-butoxy silane, methyl three tert.-butoxy silane, methyl triple phenoxyl silane, ethyl trimethoxy 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, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, the trimethylammonium methoxy silane, trimethylethoxysilane etc.Wherein preferred tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, trimethylammonium methoxy silane, trimethylethoxysilane.
With respect to the silane compound of 1 mole of formula (4) or formula (5), the silane compound of formula (7) can use 0～100 mole.1～100 mole of preferred use is more preferably used 2～20 moles.
Hydrolytic condensate can be reacted by making silane compound and water, makes that it is hydrolyzed, part condensation and obtaining.Silane compound is hydrolyzed in order to make, the part condensation, per 1 mole of siloxane key (formula (4)-Y
1, formula (5)-Y
2And the OR of formula (7)
4Total amount) preferably use 1.0～1.5 mole of water.If the amount of water is more than 1 mole, then the residual possibility of siloxane bond unreacted and former state is less, thus the danger that the homogeneity that can not occur filming descends, and the danger that the storage stability of liquid crystal aligning agent descends is also less, is preferred therefore.Water can intermittently or be added in the organic solvent of dissolving silane compound of the present invention continuously.Can use catalysts this moment.In the case, catalyzer can be joined in the organic solvent in advance, when adding water, also can be dissolved in or be scattered in the water.Temperature of reaction as this moment is preferably 0～100 ℃, more preferably 15～80 ℃.
As above-mentioned organic solvent, preferably can use alcoholic solvent, ketones solvent, amide solvent, esters solvent or non-protonic solvent.They can be used alone or in combination of two or more.
Here, as alcoholic solvent, can enumerate for example methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, the 2-methyl butanol, sec.-amyl alcohol, tertiary amyl alcohol, the 3-methoxybutanol, n-hexyl alcohol, the 2-methyl amyl alcohol, secondary hexyl alcohol, 2-ethyl butanol, secondary enanthol, the 3-enanthol, n-Octanol, 2-Ethylhexyl Alcohol, secondary octanol, nonanol-, 2, the 6-2,6-dimethyl-4-heptanol, nonylcarbinol, secondary hendecanol, Exxal 12, secondary tetradecanol, secondary heptadecanol, phenol, hexalin, methyl-cyclohexanol, 3,3,5-cyclonol, benzylalcohol, the unary alcohol solvents such as Pyranton;
Ethylene glycol, 1,2-PD, 1,3 butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexylene glycol, 2,4-heptanediol, 2-ethyl-1, the polyalcohols solvents such as 3-hexylene glycol, glycol ether, dipropylene glycol, triglycol, tripropylene glycol;
Ethylene glycol monomethyl 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-ethyl-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diglycol monotertiary propyl ether, the diglycol monotertiary butyl ether, the diglycol monotertiary hexyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, the propylene glycol single-butyl ether, dipropylene glycol monomethyl ether, DPE, the part ether solvent of the polyvalent alcohols such as dipropylene glycol list propyl ether etc.
These alcoholic solvents can one kind or two or morely be used in combination.
As ketones solvent, can enumerate for example acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, metacetone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, ethyl normal-butyl ketone, methyl n hexyl ketone, diisobutyl ketone, the trimethylammonium nonanone, pimelinketone, methyl-n-butyl ketone, methylcyclohexanone, 2, the 4-diacetylmethane, acetonyl-acetone, methyl phenyl ketone, fenchones etc. in addition, can also be enumerated methyl ethyl diketone, 2, the 4-hexanedione, 2, the 4-heptadione, 3,5-heptadione, 2,4-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-hexanedione, 2,2,6,6-tetramethyl--3, the 5-heptadione, 1,1,1,5,5,5-hexafluoro-2, the beta-diketon kind solvents such as 4-heptadione etc.
These ketones solvents can be used in combination more than a kind or 2 kinds.
As amide solvent; can enumerate for example methane amide, N-METHYLFORMAMIDE, N; dinethylformamide, N-ethyl-formamide, N; N-diethylformamide, ethanamide, N-methylacetamide, N; N-N,N-DIMETHYLACETAMIDE, N-ethyl acetamide, N, N-diethyl acetamide, N-methyl propanamide, N-Methyl pyrrolidone, N-formyl morpholine, N-formyl piperidine, N-carbonyl pyrrolidine, N-ethanoyl morpholine, N-ethanoyl piperidines, N-acetyl-pyrrolidine etc.
These amide solvents can be used in combination more than a kind or 2 kinds.
As esters solvent, can enumerate for example diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, ritalin, vinyl acetic monomer, gamma-butyrolactone, γ-valerolactone, n-propyl acetate, Iso Butyl Acetate, n-butyl acetate, isobutyl acetate, 2-butyl acetate, n-Amyl acetate, the secondary pentyl ester of acetic acid, acetic acid 3-methoxyl group butyl ester, acetic acid methyl pentyl ester, acetic acid 2-ethyl butyl ester, acetic acid 2-ethylhexyl, Benzyl Acetate, cyclohexyl acetate, methyl cyclohexanol acetate, acetic acid n-nonyl ester, methyl acetoacetate, methyl aceto acetate, the acetic acid ethylene glycol monomethyl 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, the acetic acid dipropylene glycol monomethyl ether, the acetic acid DPE, ethylene diacetate, methoxyl group triglycol acetic ester, ethyl propionate, n-butyl propionate, isoamyl propionate, oxalic acid diethyl ester, dibutyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, the lactic acid n-pentyl ester, diethyl malonate, dimethyl phthalate, diethyl phthalate etc.
These esters solvents can be used in combination more than a kind or 2 kinds.
As non-protonic solvent, can enumerate for example acetonitrile, dimethyl sulfoxide (DMSO), N, N, N ' N '-tetraethyl-sulphonamide, hexamethyl phosphoric triamide, N-methylmorpholine, N-methylpyrrole, N-N-ethyl pyrrole N-, N-methyl-Δ 3-pyrroline, N-methyl piperidine, N-ethylpiperidine, N, N-lupetazin, N-Methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, METHYLPYRROLIDONE, 1,3-dimethyl-2-imidazolinone, 1,3-dimethyl tetrahydro-2 (1H)-pyrimidone etc.In the middle of them, particularly preferably part ether solvent, the esters solvent of polyalcohols solvent, polyvalent alcohol.
In addition, in the hydrolysis of silane compound of the present invention, part condensation reaction, preferably use catalyzer.As this catalyzer, can enumerate following metal complex, organic acid, mineral acid, organic bases, mineral alkali.
As metal complex, can enumerate for example triethoxy list (methyl ethyl diketone) titanium, three positive propoxy list (methyl ethyl diketone) titaniums, three isopropoxy list (methyl ethyl diketone) titaniums, three n-butoxy list (methyl ethyl diketone) titaniums, three sec-butoxy list (methyl ethyl diketone) titaniums, three tert.-butoxy list (methyl ethyl diketone) 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 (methyl ethyl diketone) titanium, triethoxy list (methyl aceto acetate) titanium, three positive propoxy list (methyl aceto acetate) titaniums, three isopropoxy list (methyl aceto acetate) titaniums, three n-butoxy list (methyl aceto acetate) titaniums, three sec-butoxy list (methyl aceto acetate) titaniums, three tert.-butoxy list (methyl aceto acetate) titaniums, diethoxy two (methyl aceto acetate) titanium, two positive propoxy two (methyl aceto acetate) titaniums, diisopropoxy two (methyl aceto acetate) titanium, two n-butoxy two (methyl aceto acetate) titaniums, two sec-butoxy two (methyl aceto acetate) titaniums, two tert.-butoxy two (methyl aceto acetate) titaniums, monosubstituted ethoxy three (methyl aceto acetate) titanium, single positive propoxy three (methyl aceto acetate) titanium, single isopropoxy three (methyl aceto acetate) titanium, single n-butoxy three (methyl aceto acetate) titanium, single sec-butoxy three (methyl aceto acetate) titanium, single tert.-butoxy three (methyl aceto acetate) titanium, four (methyl aceto acetate) titanium, single (methyl ethyl diketone) three (methyl aceto acetate) titanium, two (methyl ethyl diketone) two (methyl aceto acetate) titaniums, the titanium coordination compoundes such as tri acetylacetonato list (methyl aceto acetate) titanium;
Triethoxy list (methyl ethyl diketone) zirconium, three positive propoxy list (methyl ethyl diketone) zirconiums, three isopropoxy list (methyl ethyl diketone) zirconiums, three n-butoxy list (methyl ethyl diketone) zirconiums, three sec-butoxy list (methyl ethyl diketone) zirconiums, three tert.-butoxy list (methyl ethyl diketone) zirconiums, diethoxy two (methyl ethyl diketone) zirconium, two positive propoxy two (methyl ethyl diketone) zirconiums, diisopropoxy two (methyl ethyl diketone) zirconium, two n-butoxy two (methyl ethyl diketone) zirconiums, two sec-butoxy two (methyl ethyl diketone) zirconiums, two tert.-butoxy two (methyl ethyl diketone) 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 (methyl ethyl diketone) zirconium, triethoxy list (methyl aceto acetate) zirconium, three positive propoxy list (methyl aceto acetate) zirconiums, three isopropoxy list (methyl aceto acetate) zirconiums, three n-butoxy list (methyl aceto acetate) zirconiums, three sec-butoxy list (methyl aceto acetate) zirconiums, three tert.-butoxy list (methyl aceto acetate) zirconiums, diethoxy two (methyl aceto acetate) zirconium, two positive propoxy two (methyl aceto acetate) zirconiums, diisopropoxy two (methyl aceto acetate) zirconium, two n-butoxy two (methyl aceto acetate) zirconiums, two sec-butoxy two (methyl aceto acetate) zirconiums, two tert.-butoxy two (methyl aceto acetate) zirconiums, monosubstituted ethoxy three (methyl aceto acetate) zirconium, single positive propoxy three (methyl aceto acetate) zirconium, single isopropoxy three (methyl aceto acetate) zirconium, single n-butoxy three (methyl aceto acetate) zirconium, single sec-butoxy three (methyl aceto acetate) zirconium, single tert.-butoxy three (methyl aceto acetate) zirconium, four (methyl aceto acetate) zirconium, single (methyl ethyl diketone) three (methyl aceto acetate) zirconium, two (methyl ethyl diketone) two (methyl aceto acetate) zirconiums, the zirconium coordination compoundes such as tri acetylacetonato list (methyl aceto acetate) zirconium;
The aluminium coordination compoundes such as aluminium tris(acetylacetonate), three (methyl aceto acetate) aluminium etc.
As organic acid, can enumerate for example acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, oxalic acid, toxilic acid, Methylpropanedioic acid, hexanodioic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2 ethyl hexanoic acid, oleic acid, stearic acid, linolic acid, linolenic acid (acid of リ ノ レ イ Application), Whitfield's ointment, M-nitro benzoic acid, para-aminobenzoic acid, tosic acid, Phenylsulfonic acid, Monochloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), trifluoroacetic acid, formic acid, propanedioic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartrate etc.
As mineral acid, can enumerate such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid etc.
As organic bases, can enumerate such as pyridine, pyrroles, piperazine, tetramethyleneimine, piperidines, picoline, Trimethylamine 99, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine, trolamine, diazabicyclooctane (ジ ア ザ PVC シ Network ロ オ Network ラ Application), diazabicyclononane, diazabicylo undecylene, tetramethyl ammonium hydroxide etc.
As mineral alkali, can enumerate such as ammonia, sodium hydroxide, potassium hydroxide, hydrated barta, calcium hydroxide etc.
In these catalyzer, preferable alloy coordination compound, organic acid, mineral acid more preferably can be enumerated titanium coordination compound, organic acid.They can use more than a kind or 2 kinds together.
The usage quantity of above-mentioned catalyzer, combination (being converted into the complete hydrolysis condenses) with respect to 100 weight part compounds (4), compound (5) and compound (7), be preferably 0.001～10 weight part, more preferably the scope of 0.001～1 weight part.
Liquid crystal aligning agent of the present invention preferably is dissolved in the said hydrolyzed condenses or be scattered in the organic solvent and consists of.
As organic solvent, the organic solvent that can use following formula (8), (9) and (10) to represent separately.
In the formula (8), R
3Be hydrogen, methyl, ethyl or ethanoyl, R
4Be 1～4 alkyl for carbonatoms, s is 1～3 integer.In the formula (9), R
5Be hydrogen, methyl, ethyl or ethanoyl, R
6Be 1～4 alkyl for carbonatoms, n is 1～3 integer.In addition, in the formula (10), R
7It is 2～5 alkyl for carbonatoms.
As the object lesson of the organic solvent of formula (8) expression, can enumerate 1-oxyethyl group-2-propyl alcohol, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ether, dipropylene glycol propyl ether, dipropylene glycol dme etc.Wherein preferably can enumerate dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether.
As the object lesson of the organic solvent of formula (9) expression, can enumerate ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether (ethylene glycol butyl ether), glycol monomethyl amyl ether, ethylene glycol ether, glycol ether, methylcellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetic ester, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl group Trivalin SF, diethylene glycol monobutyl ether etc.Wherein preferably can enumerate ethylene glycol ether, ethylene glycol monobutyl ether (ethylene glycol butyl ether), glycol monomethyl amyl ether.
As the object lesson of the organic solvent of above-mentioned formula (10) expression, can enumerate n-propyl acetate, Iso Butyl Acetate, n-butyl acetate, isobutyl acetate, 2-butyl acetate, n-Amyl acetate, the secondary pentyl ester of acetic acid, acetic acid 3-methoxyl group butyl ester, acetic acid methyl pentyl ester, acetic acid 2-ethyl butyl ester, acetic acid 2-ethylhexyl, Benzyl Acetate, the just own ester of acetic acid, cyclohexyl acetate, octyl acetate, amyl acetate-n, isoamyl acetate etc.Wherein preferably can enumerate n-propyl acetate, Iso Butyl Acetate, n-butyl acetate, isobutyl acetate, 2-butyl acetate, n-Amyl acetate, the secondary pentyl ester of acetic acid.
In the liquid crystal aligning agent that makes among the present invention, can also add the compositions such as tensio-active agent.As tensio-active agent, can enumerate such as nonionogenic tenside, anion surfactant, cats product, amphoterics etc.And, can also enumerate silicone tensio-active agent, polyalkylene oxide tensio-active agent, fluorochemical surfactant etc.
In addition, in the liquid crystal aligning agent of the present invention, from improving the fusible angle to substrate surface, can also contain the compound of functional silanes or contain the compound of epoxy group(ing).As this compound that contains functional silanes, can enumerate for example 3-TSL 8330, APTES, 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-ethoxycarbonyl-3-TSL 8330, N-ethoxycarbonyl-APTES, N-tri-ethoxy silylpropyl diethylenetriamine, N-Trimethoxy silane base propyl group diethylenetriamine, 10-Trimethoxy silane base-1,4,7-three azepine decane, 10-triethoxysilicane alkyl-1,4,7-three azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, N-two (oxyethylene group)-3-TSL 8330, N-two (oxyethylene group)-APTES, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl triethoxysilane etc.In addition, as the compound that contains epoxy group(ing), preferably can enumerate 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 diglycidylether, 1,3,5,6-four glycidyl group-2, the 4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3-two (N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.
Reaction product organopolysiloxane in the liquid crystal aligning agent of the present invention and the ratio of solvent, consider viscosity, volatility etc. and select, and the ratio of the organopolysiloxane in the liquid crystal aligning agent of the present invention (solids content concn) is converted into SiO with Siliciumatom contained in the organopolysiloxane
2SiO
2Densitometer is preferably 0.01～70 % by weight, more preferably 0.05～60 % by weight, more preferably 1～30 % by weight.Liquid crystal aligning agent of the present invention, as described below, be coated on substrate surface by preferred employing rolling method, spin-coating method, print process etc., then it is carried out heat drying, formation is filmed as liquid crystal orientation film, when solids content concn less than 0.01 % by weight, it is too small and can not obtain the situation of good liquid crystal orientation film that this thickness of filming then can appear, when solids content concn surpasses 70 % by weight, it is blocked up and be difficult to obtain good liquid crystal orientation film that coating thickness then can appear, and the viscosity of liquid crystal aligning agent increases, and causes the situation of coating property variation.
Liquid crystal orientation film
As the method that forms liquid crystal orientation film with liquid crystal aligning agent of the present invention, can enumerate for example following method.At first, adopt nesa coating one side that liquid crystal aligning agent of the present invention is coated on the substrate that is provided with nesa coating such as rolling method, spin-coating method, print process, ink jet method etc., heating and forming is filmed under 40～300 ℃ temperature for example again.This moment, crosslinking reaction occured in organopolysiloxane each other.Crosslinked in order fully to occur, preferably under 150～250 ℃, carry out 10 minutes～3 hours processing.Heating can be carried out in air, also can carry out in nitrogen.The thickness of filming as solids component, is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
As aforesaid substrate, can example such as the glass such as float glass, soda-lime glass; The plastics transparency carriers such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate.
As above-mentioned nesa coating, can example such as SnO
2NESA film, the In of system
2O
3-SnO
2The ITO film of system etc.The formation of the pattern of these nesa coatings can be adopted photolithography, use the method etc. of mask in advance.
When the coating of liquid crystal aligning agent, for the binding property of further improving substrate or nesa coating and filming, can also on substrate and nesa coating, apply in advance functional silanes compound, titanic acid ester etc.
Then, by ray or the non-polarisation ray to above-mentioned film irradiation linear polarization or part polarisation, and according to circumstances further under 150～250 ℃ temperature, carry out heat treated, make it produce the liquid crystal aligning energy.As ray, can use ultraviolet ray and visible rays with 200～400nm wavelength.When used ray was linear polarization or part polarisation, irradiation can be carried out from the direction perpendicular to real estate, also can carry out from oblique direction in order to produce pre-tilt angle, and, they combinations can also be carried out.When the non-polarisation ray of irradiation, direction of illumination must be tilted direction.
As above-mentioned light source, can example such as low pressure mercury lamp, high voltage mercury lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer laser etc.In addition, the ultraviolet ray of above-mentioned preferred wavelength range can be by obtaining means of spectral filter, diffraction grating etc. and above-mentioned light source coupling etc.
In addition, so-called among the present invention " tilt angle " refers to the angle that liquid crystal molecule tilts from the direction parallel with real estate.
Liquid crystal display device
The liquid crystal display device that adopts liquid crystal aligning agent of the present invention to form can followingly be made.Preparation has formed the substrate of above-mentioned liquid crystal orientation film, makes the polarization direction of the polarisation ray of irradiating liquid crystal alignment films become predetermined angle, with two these substrates relatively to, with sealing agent the peripheral position between substrate is sealed, filling liquid crystal seals filling orifice again, consists of liquid crystal cell.Then, need to be heated to the temperature that used liquid crystal is isotropic phase to liquid crystal cell after, be cooled to room temperature, the flow orientation when injecting to eliminate.
Then, the angle that the polarization direction that makes polaroid becomes to be scheduled to the easy axis of orientation of the liquid crystal orientation film of substrate separately, the polaroid of fitting on its two sides is made liquid crystal display device.When liquid crystal orientation film is horizontal alignment, form the polarization direction angulation of linear polarization ray of the irradiation in two substrates of liquid crystal orientation film and the angle of each substrate and polaroid by adjustment, can obtain arbitrarily to have the liquid crystal display device of TN type or STN type liquid crystal cell.On the other hand, when liquid crystal orientation film is vertical orientated property, the direction of the easy axis of orientation by making two substrates that formed liquid crystal orientation film is parallel to consist of liquid crystal cell, and make polaroid become miter angle and fit thereon with easy axis of orientation with its polarization direction, can make the liquid crystal display device with vertical alignment-type liquid crystal box.
As above-mentioned sealing agent, can example as containing Resins, epoxy as the alumina balls of solidifying agent and separator etc.
As above-mentioned liquid crystal, can example such as nematic liquid crystal, dish shape type liquid crystal etc.In addition, when being the vertical alignment-type liquid crystal box, preferably make its liquid crystal with negative dielectric anisotropic that forms nematic liquid crystal, can example such as diaminobenzene class liquid crystal, pyridazine class liquid crystal, schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal etc.
As the employed polaroid in the liquid crystal cell outside, can enumerate polyvinyl alcohol extended that the light polarizing film that is referred to as " H film " that orientation absorbs iodine simultaneously is clipped in the cellulose acetate protective membrane and polaroid, the perhaps polaroid made of H film self etc.
Embodiment
Below, by embodiment the present invention is carried out more specific description, but the present invention is not limited to these embodiment.
Synthesis example 1
In the 300ml three-necked flask that agitator, nitrogen ingress pipe and thermometer are housed, add compound, 8.29g salt of wormwood, 1.00g potassiumiodide, 4.46g 4-butyl-1-butylene and the 120ml 1-Methyl-2-Pyrrolidone of the following formula of 11.8g (6-5-1-1) expression, under nitrogen, under 90 ℃, stirred 3 hours.After reaction finishes, add toluene and water and extract, use dried over mgso, and after concentrated, carry out recrystallization with methyl alcohol, obtain the compound of the following formula of 9g (6-5-1-2) expression.
Synthesis example 2
In the 100ml three-necked flask that return line and nitrogen ingress pipe are housed, the compound, 5.88g triethoxyl silane and the hexahydrated aqueous isopropanol of 40 μ l0.2M Platinic chlorides that add the following formula of 8.0g (6-5-1-2) expression, after carrying out exhaust, it was refluxed 10 hours.Then, by short silicagel column, after then concentrating, make it fully dry reaction solution, obtain white thick liquid.Again this thick liquid is made with extra care with silicagel column, obtained the compound of the following formula of 3.5g (6-5-1) expression.
Synthetic route 4
Synthesis example 3,4
Adopt the method identical with the synthetic route 4 of the compound of preparation above-mentioned (6-5-1) expression, make the compound of following formula (6-2-1) expression and the compound that following formula (6-13-1) represents.
[weight-average molecular weight]
By GPC, calculate with polystyrene conversion.
[tilt angle]
According to T.J.Scheffer etc., J.Appl.Phys., the 19th volume, the methods of record are measured by the crystallization rotational method of using He-Ne laser in 2013 (1980).
[liquid crystal aligning]
To liquid crystal display device, open, have or not abnormal area when cutting off (apply, remove) voltage by polarized light microscope observing, be not evaluated as " well " when having abnormal area.
[voltage retention]
In 167 milliseconds time span, liquid crystal display device is applied the 5V voltage of 60 microsecond application times, then measure from voltage and remove voltage retention after 167 milliseconds.Determinator adopts the (VHR-1 of strain) East Yang テ Network ニ カ system.When voltage retention is 90% when above, be evaluated as " well ", the average evaluation beyond it is " bad ".
[printing evaluation]
Prepare in advance the glass substrate that has formed the 127mm (D) of ITO film * 127mm (W) * 1.1mm (H) whole an of side, be after the millipore filter of 0.2 μ m filters with the liquid crystal aligning agent that makes in above-described embodiment with the aperture, adopting liquid crystal orientation film to be coated with application printing press (Japan's description printing (strain) is made, オ Application グ ス ト ロ one マ one S-40L ") is coated on the transparent electrical pole-face of this glass substrate.Dry in the hot-plate seal type pre-dryers that is set as 80 ℃, 200 ℃ of lower roastings 60 minutes, namely form liquid crystal orientation film at the glass substrate with the ITO film again.The speckle of visual assessment gained alignment films does not have brindled being evaluated as " well ", finds be evaluated as " bad " of speckle.
Embodiment 1
In the 200ml three-necked flask that prolong is housed, add compound 3.1g (5mmol), the tetraethoxysilane 12.7g of above-mentioned formula (6-5-1) expression (referred to as TEOS, 60mmol), 1-oxyethyl group-2-propyl alcohol 37.4g, under 60 ℃, carry out heated and stirred.Be the 0.165g maleic anhydride of modulating in the flask of 20ml, the maleic anhydride aqueous solution of 6.95g water to the capacity that wherein is added in, under 60 ℃, reheat and stirred 4 hours.Distill desolventizing from the gained polymeric solution, making weight is 30.2g, obtains stock polymer solution.Add N-BUTYL ACETATE, being made into solids content concn is the alignment agent coating liquid S-1 of 4 % by weight again.
Measuring weight-average molecular weight by GPC is 2200.
Embodiment 2～4
Adopt method similarly to Example 1, by the condensation that is hydrolyzed that forms shown in the table 1, synthesized the alignment agent coating liquid.
Table 1
| Silane compound | TEOS | Molecular weight | The alignment agent coating liquid | |
| Embodiment 1 | (6-5-1)5mmol | 60mmol | 2200 | S-1 |
| Embodiment 2 | (6-2-1)5mmol | 60mmol | 2100 | S-2 |
| Embodiment 3 | (6-13-1)5mmol | 60mmol | 1900 | S-3 |
| Embodiment 4 | (6-5-1)5mmol | 45mmol | 2100 | S-4 |
Embodiment 5
Adopt spin-coating method to be coated on the transparent electrical pole-face with the glass substrate of ITO transparency electrode processed above-mentioned alignment agent coating liquid S-1, making thickness is 0.1 μ m, makes its dry 1 hour, the formation film in 200 ℃ in by the baking oven of nitrogen ventilation.
Then, by with Hg-Xe lamp and Glan-Taylor prism this film surface being shone 0.1J/cm with the direction of 40 degree that tilt from substrate normal
2The polarisation ultraviolet ray that contains the 313nm bright line.Then, to having carried out a pair of substrate that uviolizing is processed, on the face that has formed liquid crystal orientation film, after having added the epoxy resin binder of alumina balls that diameter is 5.5 μ m by silk screen printing coating, make the mutual antiparallel of the projecting direction of ultraviolet optical axis on real estate and with substrates while stacking and pressing, under 150 ℃, made tackiness agent carry out thermofixation through 1 hour again.Then, from liquid crystal injecting port to fill between a pair of substrate negative type liquid crystal (メ Le Network society produces, MLC-6608) after, with epoxy base class adhesive closure liquid crystal injecting port.And the flow orientation when eliminating Liquid crystal pour after heating under 150 ℃, slowly cools to room temperature with it.Then, outside substrate, survey the two sides polaroid of fitting, make its polarization direction mutually vertical, and become the angles of 45 degree with the projecting direction of ultraviolet optical axis on real estate of liquid crystal orientation film, so make liquid crystal display device, all demonstrate good vertical orientated property.If apply the voltage of 5V, respond executing alive ON-OFF, the light and shade of observing liquid crystal display device changes.When above-mentioned box was estimated, tilt angle was 89.3 °, and liquid crystal aligning and voltage retention are " well ".In addition, when the printing of above-mentioned alignment agent coating liquid S-1 is estimated, be " well ".
Embodiment 6～8
Adopt method similarly to Example 5, S-2～S-4 estimates to the alignment agent coating liquid.The results are shown in table 2.
Table 2
| The alignment agent coating liquid | Tilt angle (°) | Liquid crystal aligning | Voltage retention | Printing | |
| Embodiment 5 | S-1 | 89.3 | Well | Well | Well |
| Embodiment 6 | S-2 | 89.2 | Well | Well | Well |
| Embodiment 7 | S-3 | 89.5 | Well | Well | Well |
| Embodiment 8 | S-4 | 89.3 | Well | Well | Well |
Hence one can see that, and organopolysiloxane screening characteristics of the present invention, susceptibility, liquid crystal aligning, electric property are good, can be very beneficial for being applied to liquid crystal display device.
The invention effect
If use organopolysiloxane of the present invention, compare during with the optical alignment method that adopts in the past, can obtain liquid crystal orientation film with radiation exposure still less.Therefore, when this liquid crystal orientation film is applied to liquid crystal display device, can make more at an easy rate liquid crystal display device with comparing in the past.Therefore, these liquid crystal display device can be effectively applied to various devices, such as being applicable to the devices such as desk calculator, wrist-watch, table clock, counting display screen, word processor, Personal Computer or liquid crystal TV set.
Claims (7)
1. the preparation method of an organopolysiloxane, this organopolysiloxane has the repeating unit of following formula (1) expression, and weight-average molecular weight drops in 1000～100000 the scope,
Here, Z is for being the light generation crosslinking reaction of 200～400nm or the photosensitive group of isomerization reaction by wavelength, following formula (6-3)～(6-10), any one of the structure that (6-12)～(6-14) represents separately, X is hydroxyl, carbonatoms is 1～20 alkyl, carbonatoms is 6～20 aryl, carbonatoms is 1～20 alkoxyl group, X that perhaps also can be in other repeating units of same formula (1) expression by-O-forms crosslinked
Here, among formula (6-3)～(6-10), (6-12)～(6-14), m is 1～20 integer, and 1 is the following integer of 2m+1, and k is 1～10 integer, and q is 2～10 integer;
It is characterized in that being selected from that at least a in the group that the silane compound of following formula (1 ') expression consists of is hydrolyzed, condensation,
Here, identical in the definition of Z and the above-mentioned formula (1), R
1For carbonatoms is that 1～20 alkyl or carbonatoms are 6～20 aryl, Y
1Be 1～20 alkoxyl group or chlorine atom for carbonatoms, n is 2 or 3.
2. preparation method claimed in claim 1, wherein said method is the manufacture method of the organopolysiloxane of liquid crystal aligning agent purposes.
3. preparation method claimed in claim 1, wherein the catalyzer of hydrolysis, condensation is organic acid.
4. claim 1 or 3 described preparation methods, it carries out said hydrolyzed, condensation under the coexistence of the silane compound of following formula (7) expression,
Si(R
3)
t(OR
4)
(4-t) (7)
Here, R
3Be 1～40 the optional alkyl that contains alicyclic group for carbonatoms, perhaps carbonatoms is 6～20 aryl, R
4Be 1～20 alkyl for carbonatoms, t is 0,1,2 or 3.
5. a liquid crystal orientation film makes by the ray that the film that is formed by the defined organopolysiloxane of claim 1 is shone polarisation or non-polarisation.
6. liquid crystal display device, it has liquid crystal orientation film claimed in claim 5.
7. liquid crystal display device claimed in claim 6, it adopts negative type liquid crystal.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP200650/2007 | 2007-08-01 | ||
| JP2007200650A JP5071644B2 (en) | 2007-08-01 | 2007-08-01 | Polyorganosiloxane, liquid crystal alignment film, and liquid crystal display element |
| PCT/JP2008/063930 WO2009017240A1 (en) | 2007-08-01 | 2008-07-29 | Polyorganosiloxane, liquid crystal alignment film, and liquid crystal display element |
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| JP5164254B2 (en) * | 2007-10-15 | 2013-03-21 | 日東電工株式会社 | γ-Oryzanol derivative, liquid crystal compound, liquid crystal compound polymer, method for producing optical element, optical element, polarizing plate, and image display device |
| JP5423021B2 (en) * | 2008-02-27 | 2014-02-19 | Ｊｎｃ株式会社 | Polymerizable liquid crystal compound, composition and polymer |
| JP5370646B2 (en) * | 2009-02-12 | 2013-12-18 | Ｊｓｒ株式会社 | Method for producing radiation-sensitive polyorganosiloxane |
| 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 |
| JP5668906B2 (en) * | 2009-02-19 | 2015-02-12 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| 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 |
| JP5412939B2 (en) * | 2009-04-28 | 2014-02-12 | Ｊｎｃ株式会社 | Polymerizable cholesteric liquid crystal composition and use thereof |
| WO2011126019A1 (en) | 2010-04-08 | 2011-10-13 | 日産化学工業株式会社 | Composition forming heat-cured film having photo-alignment properties |
| JP5668577B2 (en) * | 2010-05-06 | 2015-02-12 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, and polyorganosiloxane compound |
| JP5552894B2 (en) * | 2010-05-14 | 2014-07-16 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| JP5640471B2 (en) * | 2010-06-02 | 2014-12-17 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, method for forming liquid crystal alignment film, and liquid crystal display element |
| JP5790358B2 (en) * | 2010-10-27 | 2015-10-07 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| CN102643387B (en) | 2011-11-29 | 2014-09-10 | 北京京东方光电科技有限公司 | Liquid crystal display panel and preparation method thereof |
| JP6048117B2 (en) | 2012-03-22 | 2016-12-21 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and method for manufacturing liquid crystal display element |
| CN104020609A (en) * | 2014-05-16 | 2014-09-03 | 京东方科技集团股份有限公司 | Liquid crystal coating method and display panel manufacturing method |
| KR20170117033A (en) * | 2015-02-12 | 2017-10-20 | 닛산 가가쿠 고교 가부시키 가이샤 | Liquid crystal orientation agent |
| EP3374416A1 (en) * | 2015-11-11 | 2018-09-19 | ROLIC Technologies AG | Photoalignment materials |
| CN108350363A (en) * | 2015-11-11 | 2018-07-31 | 罗利克技术有限公司 | Can photo-alignment material composition |
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| Publication number | Publication date |
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| CN101687996A (en) | 2010-03-31 |
| TW200922975A (en) | 2009-06-01 |
| JP2009036966A (en) | 2009-02-19 |
| KR20100037125A (en) | 2010-04-08 |
| KR101214750B1 (en) | 2012-12-21 |
| TWI453236B (en) | 2014-09-21 |
| WO2009017240A1 (en) | 2009-02-05 |
| JP5071644B2 (en) | 2012-11-14 |
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