CN102317848B - LIQUID-CRYSTAL ALIGNMENT MATERIAL FOR INK-JET COATING, LIQUID-CRYSTAL ALIGNMENT FILM, AND LIQUID-CRYSTAL DISPLAY ELEMENt - Google Patents
LIQUID-CRYSTAL ALIGNMENT MATERIAL FOR INK-JET COATING, LIQUID-CRYSTAL ALIGNMENT FILM, AND LIQUID-CRYSTAL DISPLAY ELEMENt Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
Abstract
The invention provides a silicon-based liquid-crystal alignment film and a liquid-crystal alignment material, the alignment material being suitable for application by ink-jet coating and the alignment film having excellent in-plane evenness and edge straightness. The liquid-crystal alignment material for ink-jet coating is characterized by comprising a polysiloxane (A) having a side chain comprising a C8-30 hydrocarbon group optionally substituted by a fluorine atom, a C2-7 glycol solvent (B), and the following solvent (C) and solvent (D): the solvent (C): a solvent represented by formula (A1) K1O(CH2)wOH (A1) (wherein K1 is a C1-4 alkyl and w is an integer of 1-3); the solvent (D): a solvent selected from a group consisting of: at least one compound selected from a group consisting of compounds of formulae (T1), (T2), and (T3); ketones having 3-6 carbon atoms; and alkyl alcohols having 5-12 carbon atoms. In the formulae (T1), (T2), and (T3), X1, X3, and X5 are a C1-4 alkyl; X2 and X6 are a hydrogen atom or a C1-4 alkyl; X4 is a C1-4 alkyl; P is a C1-3 alkyl; m, n, j, and k each independently is an integer of 1-3; and h is an integer of 2-3.
Description
Technical field
The present invention relates to mainly containing polysiloxane, particularly by alkoxy silane polycondensation polysiloxane, can form the aligning agent for liquid crystal of the film of homogeneous by ink-jet application, the liquid crystal orientation film being obtained by foregoing liquid crystal alignment agent and the liquid crystal display cells with this liquid crystal orientation film.
Background technology
Liquid crystal display cells is conventionally known has that 2 substrates that transparency electrode is provided with to liquid crystal orientation film configure relatively, the structure of filling liquid crystal material in gap betwixt.
Recently, as commercial use and the light source of liquid crystal projection apparatus (being called as the rear-projection TV of the 3rd slim TV machine) use for home theater, use the strong metal halid lamp of exposure intensity.Therefore, as the characteristic of liquid crystal orientation film, not only need high-fire resistance, also need high-light-fastness.
Conventionally liquid crystal aligning membrane material used has the liquid crystal aligning membrane material taking polyamic acid or polyimide as major component, and inorganic is that liquid crystal orientation film is also suggested.For example, form the liquid crystal aligning membrane material (for example, referring to patent documentation 1) of liquid crystal orientation film by evaporation.
In addition, be the alignment agent composition that has the reaction product that contains tetraalkoxysilane, trialkoxy silane, alcohol and oxalic acid that liquid crystal orientation film is suggested as the inorganic of application type, it was reported that title forms the liquid crystal orientation film (for example, referring to patent documentation 2) of vertical orientated property, thermotolerance and homogeneity excellence on the electrode base board of liquid crystal display cells.
In addition, the reaction product that has also proposed to contain tetraalkoxysilane, trialkoxy silane and water and the aligning agent for liquid crystal composition of alcohol ether series solvent, it was reported claim to form prevent from showing image retention characteristic after bad, long-time driving good, the ability that makes liquid crystal aligning can not reduce and voltage retention is affected by light and heat and the less liquid crystal orientation film (for example, referring to patent documentation 3) of degree that reduces.
Conventionally, as the one-tenth embrane method of liquid crystal orientation film, can exemplify spin-coating method, dip coating, hectographic printing method etc., in fact mostly use hectographic printing method.But, in hectographic printing, exist must according to be used to form liquid crystal orientation film substrate size exchange galley, for being stable into the problems such as the necessary false film forming of membrane process.
Therefore, ink-jet application method gets most of the attention as not using the Novel coating method of galley.Ink-jet application method is on substrate, to drip fine droplets, invasion by liquid and the method for film forming is not only used galley, and can freely set printed patterns, and therefore the manufacturing process of liquid crystal display cells can be simplified.And, do not need false film forming in addition and reduce the advantage of the waste of coating fluid.So, can expect the cost of liquid crystal display, the raising of production efficiency.
Under this situation, in the liquid crystal orientation film of the inorganic system of demand thermotolerance and excellent in light-resistance, also wish to introduce the method that forms liquid crystal orientation film by ink-jet application, expect that acquisition can be aligning agent for liquid crystal corresponding to the inorganic of these demands.
(patent documentation 1) Japanese Patent Laid-Open 2003-50397 communique
(patent documentation 2) Japanese patent laid-open 09-281502 communique
(patent documentation 3) Japanese Patent Laid-Open 2005-250244 communique
Summary of the invention
The silicon that the object of this invention is to provide a kind of available ink-jet application method film forming is aligning agent for liquid crystal and passes through the internal homogeneity of film that ink-jet application forms and the liquid crystal orientation film of the edge grazing excellence of film end.
That is to say, the present invention has following technology contents.
(1) ink-jet application aligning agent for liquid crystal, it is characterized in that, contain to have and replaced by fluorine atom or the polysiloxane (A) of the side chain that the alkyl of unsubstituted carbon number 8～30 forms, diol solvent (B), following solvents (C) and the solvent (D) of carbon number 2～7
Solvent (C): the solvent that formula (A1) represents,
K
1O(CH
2)
wOH (A1)
In formula, K
1for the alkyl of carbon number 1～4, the integer that w is 1～3,
Solvent (D): be selected from following solvent: be selected from the alkylol of formula (T1), formula (T2) and at least a kind of compound of formula (T3), the ketone that has 3～6 carbon atoms and carbon number 5～12,
In formula, X
1, X
3and X
5for the alkyl of carbon number 1～4, X
2and X
6for the alkyl of hydrogen atom or carbon number 1～4, X
4for the alkyl of carbon number 1～4, P is the alkyl of carbon number 1～3, and m, n, j, k are 1～3 integer independently of one another, the integer that h is 2～3.
(2) the ink-jet application aligning agent for liquid crystal as described in above-mentioned (1), wherein, solvent (D) is the solvent that is selected from the alkylol of compound, the ketone that has 3～6 carbon atoms and the carbon number 5～12 of formula (T1)～formula (T3) expression.
(3) the ink-jet application aligning agent for liquid crystal as described in above-mentioned (1) or (2), wherein, polysiloxane (A) is the polysiloxane being obtained by the alkoxy silane polycondensation of the alkoxy silane that contains formula (1) expression
R
1Si(OR
2)
3 (1)
R
1for being replaced by fluorine atom or the alkyl of unsubstituted carbon number 8～30, R
2for the alkyl of carbon number 1～5.
(4) the ink-jet application aligning agent for liquid crystal as described in above-mentioned (3), wherein, polysiloxane (A) is the polysiloxane being obtained by the alkoxy silane polycondensation of the alkoxy silane of the alkoxy silane that contains formula (1) expression and following formula (2) expression
(R
3)
nSi(OR
4)
4-n (2)
R
3for the alkyl of hydrogen atom, halogen atom, vinyl or carbon number 1～7; Now, any hydrogen atom of described alkyl can be by glycidoxy, sulfydryl, methacryloxy, acryloxy, isocyanate group, amino or Carbamido substituted, and can have heteroatoms; R
4for the alkyl of carbon number 1～5, the integer that n is 0～3.
(5) the ink-jet application aligning agent for liquid crystal as described in above-mentioned (3) or (4), wherein, polysiloxane (A) is the polysiloxane being obtained by the alkoxy silane polycondensation of the alkoxy silane of the alkoxy silane that contains formula (1) expression and following formula (3) expression
Si(OR
4)
4 (3)
R
4for the alkyl of carbon number 1～5.
(6) the ink-jet application aligning agent for liquid crystal as described in any one in above-mentioned (1)～(5), wherein, diol solvent (B) is selected from ethylene glycol, diethylene glycol, dipropylene glycol, 2-methyl-2, 4-pentanediol, 1, 2-propylene glycol, 1, ammediol, 1, 2-butylene glycol, 1, 3-butylene glycol, 2, 3-butylene glycol, 1, 4-butylene glycol, 1, 2-pentanediol, 1, 3-pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, 2, 3-pentanediol, 2, 4-pentanediol, 1, 2-hexanediol, 1, 3-hexanediol, 1, 4-hexanediol, 1, 5-hexanediol, 1, 6-hexanediol, 2, 3-hexanediol, 2, 4-hexanediol, 2, 5-hexanediol, 3, 4-hexanediol, 1, 2-heptandiol, 2, 3-heptandiol, 3, 4-heptandiol, 1, 3-heptandiol, 2, 4-heptandiol, 3, 5-heptandiol, 1, 4-heptandiol, 2, 5-heptandiol, 1, 5-heptandiol, 2, 6-heptandiol, 1, 6-heptandiol and 1, 1 kind of above solvent of 7-heptandiol.
(7) the ink-jet application aligning agent for liquid crystal as described in any one in above-mentioned (1)～(6), wherein, the X in described formula (T1)
2for hydrogen atom.
(8) the ink-jet application aligning agent for liquid crystal as described in any one in above-mentioned (1)～(7), wherein, is scaled SiO with respect to the silicon atom that polysiloxane (A) is had
2total amount 100 mass parts of value, diol solvent (B) is 20～18000 mass parts, solvent (C) is 2～17500 mass parts, solvent (D) is 2～17500 mass parts.
(9) the ink-jet application aligning agent for liquid crystal as described in any one in above-mentioned (1)～(8), wherein, is scaled SiO with respect to the silicon atom that polysiloxane (A) is had
2total amount 100 mass parts of value, diol solvent (B) is 120～17000 mass parts, solvent (C) is 2～16800 mass parts, solvent (D) is 2～16800 mass parts.
(10) the ink-jet application aligning agent for liquid crystal as described in any one in above-mentioned (1)～(9), wherein, the viscosity of described alignment agent is 1.8～18mPas.
(11) the ink-jet application aligning agent for liquid crystal as described in any one in above-mentioned (1)～(10), wherein, the surface tension of described alignment agent is 20～40mN/m.
(12) liquid crystal orientation film, burns till after the ink-jet application described in any one in above-mentioned (1)～(11) is coated on substrate with aligning agent for liquid crystal ink discharge device and obtains.
(13) the formation method of liquid crystal orientation film, burns till after the ink-jet application described in any one in above-mentioned (1)～(11) is coated on substrate with aligning agent for liquid crystal ink discharge device and obtains liquid crystal orientation film.
(14) liquid crystal display cells, has above-mentioned (12) described liquid crystal orientation film.
Aligning agent for liquid crystal of the present invention, by ink-jet application method, can form the liquid crystal orientation film of the internal homogeneity of film and the edge grazing excellence of film end.
Embodiment
Below, the present invention is described in detail.
< polysiloxane A>
The present invention's polysiloxane (A) used is to have to be replaced by fluorine atom or the polysiloxane of unsubstituted carbon number 8～30, side chain (below also referred to as " specific organic group ") that preferably 8～22 alkyl forms.
Above-mentioned specific organic group is to have the organic group that makes the effect that liquid crystal is orientated toward the direction, as long as the organic group of having that effect, is not particularly limited.As its example, can exemplified by alkyl groups, fluoro-alkyl, alkenyl, phenethyl, fluorophenyl alkyl, styryl alkyl, naphthyl etc.
Wherein, alkyl easily obtains thereby preferably.
In the present invention, in polysiloxane (A) used, can there is multiple specific organic group.
In the present invention polysiloxane (A) used taking improve with the adaptation of substrate and with the affinity of liquid crystal molecule etc. as object, do not damage under the prerequisite of effect of the present invention, can there is the side chain different with specific organic group (below also referred to as " the second organic group).Above-mentioned the second organic group is carbon number 1～7, preferred 1～6, more preferably 1～5 organic group.The second organic group can have aliphatic hydrocarbon; Aliphatics ring, aromatic ring, the such ring structure of heterocycle; Unsaturated link; The heteroatomss such as oxygen atom, nitrogen-atoms or sulphur atom; Apparatus derivatorius.The second organic group can be the alkyl of vinyl or carbon number 1～7, and any hydrogen atom of this alkyl can, by glycidoxy, sulfydryl, methacryloxy, acryloxy, isocyanate group, amino or Carbamido substituted, also can have heteroatoms.The present invention's polysiloxane (A) used can have a kind of the second organic group, also can have multiple the second organic group.
There is no particular limitation to obtain the method for above-mentioned polysiloxane (A), conventionally obtained by alkoxy silane polycondensation.
Specifically, can obtain polysiloxane (A) as the alkoxy silane polycondensation of neccessary composition by the alkoxy silane representing taking following formula (1).
R
1Si(OR
2)
3 (1)
In formula (1), R
1represent specific organic group, the record of its example and above-mentioned specific organic group is identical.Wherein, R
1for the alkoxy silane of alkyl easily obtains with less expensive commercially available product thereby preferably.R
2for carbon number 1～5, preferred 1～4 alkyl.
Exemplify the object lesson of the alkoxy silane of above-mentioned formula (1) expression below, but be not limited to this.
For example, can exemplify octyl group trimethoxy silane, octyltri-ethoxysilane, decyl trimethoxy silane, decyl triethoxysilane, dodecyltrimethoxysilane, dodecyl triethoxysilane, cetyl trimethoxy silane, cetyl triethoxysilane, heptadecyl trimethoxy silane, heptadecyl triethoxysilane, octadecyl trimethoxy silane, octadecyltriethoxy silane, nonadecyl trimethoxy silane, nonadecyl triethoxysilane, undecyl triethoxysilane, undecyl trimethoxy silane, 21-docosyl triethoxysilane, ten trifluoro octyl group trimethoxy silanes, ten trifluoro octyltri-ethoxysilane, 17 fluorine decyl trimethoxy silanes, 17 fluorine decyl triethoxysilanes, iso-octyl triethoxysilane, phenethyl triethoxysilane, seven fluorophenyl propyl trimethoxy silicanes, between-ethenylphenyl ethyl trimethoxy silane, right-ethenylphenyl ethyl trimethoxy silane, (1-naphthyl) triethoxysilane, (1-naphthyl) trimethoxy silane, allyloxy undecyl triethoxysilane, benzoyloxy propyl trimethoxy silicane, 3-(4-methoxyphenoxy) propyl trimethoxy silicane, 1-[(2-triethoxysilicane alkyl) ethyl] cyclohexane-3,4-epoxide, 2-(diphenylphosphino) ethyl triethoxysilane, diethoxymethyl octadecylsilane, dimethoxy-methyl octadecylsilane, diethoxy dodecyl methyl silane, dimethoxy dodecyl methyl silane, diethoxy decyl methyl-monosilane, dimethoxy decyl methyl-monosilane, diethoxy octyl group methyl-monosilane, dimethoxy octyl group methyl-monosilane, ethoxy dimethyl stearyl silane, methoxyl dimethyl stearyl silane etc.
Wherein, preferably octyl group trimethoxy silane, octyltri-ethoxysilane, decyl trimethoxy silane, decyl triethoxysilane, dodecyltrimethoxysilane, dodecyl triethoxysilane, cetyl trimethoxy silane, cetyl triethoxysilane, heptadecyl trimethoxy silane, heptadecyl triethoxysilane, octadecyl trimethoxy silane, octadecyltriethoxy silane, nonadecyl trimethoxy silane, nonadecyl triethoxysilane, undecyl triethoxysilane, or undecyl trimethoxy silane, diethoxymethyl octadecylsilane, diethoxy dodecyl methyl silane.
In the present invention, the alkoxy silane can and representing by multiple formula (1).
For obtaining in whole alkoxy silanes that polysiloxane (A) uses, the usage rate of alkoxy silane that formula (1) represents can not obtain good liquid crystal aligning during less than 0.1 % by mole sometimes, therefore preferably more than 0.1 % by mole, more preferably more than 0.5 % by mole.In addition, the liquid crystal orientation film sometimes forming while exceeding 30 % by mole can not be fully curing, therefore preferably below 30 % by mole, more preferably, below 22 % by mole, is more preferably at below 15 % by mole.
In addition, in the present invention by contain formula (1) represent alkoxy silane and following formula (2) represent alkoxy silane alkoxy silane polycondensation and polysiloxane be preferred.
(R
3)
nSi(OR
4)
4-n (2)
R
3for the alkyl of hydrogen atom, halogen atom, vinyl or carbon number 1～7, be preferably the alkyl of hydrogen atom or carbon number 1～7.Any hydrogen atom of aforementioned alkyl can, by glycidoxy, sulfydryl, methacryloxy, acryloxy, isocyanate group, amino or Carbamido substituted, also can have heteroatoms; R
4for carbon number 1～5, preferred 1～4, more preferably 1～3 alkyl, n is 0～3, preferably 0～2 integer.
In addition the R of formula (2),
3during for vinyl or alkyl, R
3represent above-mentioned the second organic group.Therefore, under this occasion, R
3example identical with the record of above-mentioned the second organic group.
The alkoxy silane representing as formula (2), can exemplified by methyl trimethoxy silane, methyl triethoxysilane, methyl tripropoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, butyl trimethoxy silane, butyl triethoxysilane, amyltrimethoxysilane, amyl triethoxysilane, hexyl trimethoxy silane, hexyl triethoxysilane, 3-TSL 8330, APTES, N-2 (amino-ethyl) APTES, N-2 (amino-ethyl) 3-TSL 8330, 3-(2-aminoethylamino propyl group) trimethoxy silane, 3-(2-aminoethylamino propyl group) triethoxysilane, 2-aminoethylamino methyltrimethoxy silane, 2-(2-amino-ethyl thio-ethyl) triethoxysilane, 3-sulfydryl propyl-triethoxysilicane, mercapto methyl trimethoxy silane, 3-urea groups propyl-triethoxysilicane, vinyltriethoxysilane, vinyltrimethoxy silane, allyltriethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxysilane, 3-acryloxy propyl trimethoxy silicane, 3-acryloxy propyl-triethoxysilicane, 3-isocyanates propyl-triethoxysilicane, trifluoro propyl trimethoxy silane, chloropropyl triethoxysilane, bromopropyl triethoxysilane, 3-sulfydryl propyl trimethoxy silicane etc.
In the alkoxy silane of formula (2), as R
3the object lesson of the alkoxy silane during for hydrogen atom, can exemplify trimethoxy silane, triethoxysilane, tripropoxy silane, three butoxy silanes etc.
In the alkoxy silane of formula (2), the tetraalkoxysilane of the alkoxy silane expression (3) that n is 0.
Si(OR
4)
4 (3)
In formula (3), R
4for carbon number 1～5, preferred 1～4, more preferably 1～3 alkyl.Therefore the alkoxy silane condensation that tetraalkoxysilane is easy and formula (1) represents that formula (3) represents is preferred obtaining on polysiloxane (A).As the object lesson of the tetraalkoxysilane of formula (3), can exemplify tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes etc.
While using the alkoxy silane of above-mentioned formula (2) or (3) expression, one or more can suitably be used as required.
In the time of the alkoxy silane also representing by formula (2) or formula (3), for obtaining in whole alkoxy silanes that polysiloxane (A) uses, the total use amount of the alkoxy silane that formula (2) or formula (3) represent is preferably 70～99.7 % by mole, more preferably 78～99.7 % by mole.More preferably, the alkoxy silane that formula (2) or formula (3) represent is 85～99.7 % by mole.
In the present invention, polysiloxane (A) used is by containing alkoxy silane that above-mentioned formula (1) represents as the condensation and obtaining in organic solvent of the alkoxy silane of neccessary composition.The alkoxy silane of the alkoxy silane that now, contains formula (1), formula (2) and formula (3) expression is preferred.Conventionally, polysiloxane (A) can be used as by this alkoxy silane polycondensation, is dissolved in the solution in organic solvent equably and obtains.
In the present invention, there is no particular limitation for the method for condensation polysiloxane (A) used, for example, can exemplify the method for alkoxy silane hydrolytic condensation in alcohol or diol solvent.Now, hydrolysis-condensation reaction can be any in partial hydrolysis and complete hydrolysis.Under the occasion of complete hydrolysis, can add in theory the water of 0.5 times mole of whole alkoxys in alkoxy silane, conventionally add than the water of the excess quantity more than 0.5 times mole.
In the present invention, in above-mentioned reaction, the amount of water used can suitably be selected as required, conventionally taking 0.5～2.5 times mole of the whole alkoxys in alkoxy silane as preferably.
In addition, conventionally, be facilitation of hydrolysis condensation reaction, can use the acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, fumaric acid, the alkali such as ammonia, methylamine, ethamine, monoethanolamine, triethanolamine, and the catalyzer such as the slaine of hydrochloric acid, sulfuric acid, nitric acid etc.Moreover, conventionally heating for dissolving the further facilitation of hydrolysis condensation reaction of solution of alkoxy silane.Now, heating-up temperature and heat time can suitably be selected as required, for example, can exemplify and at 50 DEG C, add thermal agitation 24 hours, or add the methods such as thermal agitation 1 hour under refluxing.
In addition, as other method, for example, can exemplify the method for the potpourri heating aftercondensated of alkoxy silane, solvent and oxalic acid.Specifically, be in advance oxalic acid is added to the alcoholic solution that forms oxalic acid in alcohol after, under the state of this solution of heating, sneak into the method for alkoxy silane.Now, 1 mole of the whole alkoxy that have with respect to alkoxy silane, the amount of oxalic acid used is preferably 0.2～2 mole.Heating in the method can be carried out at 50～180 DEG C of liquid temperatures, preferably with do not cause liquid evaporation, wave loose etc. mode, for example under the backflow in the container that possesses recirculatory pipe, carry out dozens of minutes～tenss' hour heating.
While obtaining polysiloxane (A), using under the occasion of multiple alkoxy silane, alkoxy silane can mixed as the potpourri being pre-mixed, also multiple alkoxy silane can mixed successively.
, as long as the solvent of dissolvane TMOS, there is no particular limitation for solvent (below also referred to as " polymer solvent ") used when alkoxy silane polycondensation.In addition, though can be also also can be when the polycondensation reaction of alkoxy silane be carried out under the undissolved occasion of alkoxy silane the solvent of dissolvane TMOS.Conventionally, generate alcohol by the polycondensation reaction of alkoxy silane, therefore can use alcohols, glycols, alcohol ethers or the organic solvent good with alcohols intermiscibility.
As the object lesson of this polymer solvent, can exemplify methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 2-methyl-2, 4-pentanediol, ethyl carbitol, butyl carbitol, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol bisthioglycolate propyl ether, butyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol butyl oxide, METHYLPYRROLIDONE, N, dinethylformamide, N, N-dimethyl acetamide, gamma-butyrolacton, dimethyl sulfoxide, tetramethylurea (TMU), 6-methyl phosphonic triamide, metacresol etc.
In the present invention, above-mentioned polymer solvent can use after multiple mixing.
The silicon atom that has carried out the whole alkoxy silanes that add as raw material in the solution of gained after this method is scaled SiO
2concentration (below also referred to as " SiO
2conversion concentration ") conventionally below 20 quality %, preferably below 15 quality %.By select concentration arbitrarily in this concentration range, can suppress the generation of gel, obtain the solution of homogeneous.
The solution > of < polysiloxane (A)
In the present invention, the solution that said method can be obtained is directly as the solution of polysiloxane (A), the solution that also can as required said method be obtained through concentrated, solubilizer dilution or after being replaced into other solvent as the solution of polysiloxane (A).
Now, solvent (below also referred to as " interpolation solvent ") used can be with polycondensation in solvent phase used with solvent, can be also other solvent.As long as this solvent can dissolve polysiloxane (A) equably, there is no particular limitation, arbitrarily choice for use one or more.
As the object lesson of this interpolation solvent, can exemplify the alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, diacetone alcohol; The ketones such as acetone, MEK, methyl isobutyl ketone; Ethylene glycol, diethylene glycol, propylene glycol, 2-methyl-2, the glycolss such as 4-pentanediol; The glycol ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol bisthioglycolate propyl ether, butyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; The ester classes such as methyl acetate, ethyl acetate, ethyl lactate; METHYLPYRROLIDONE, DMF, DMA, gamma-butyrolacton, dimethyl sulfoxide, tetramethylurea (TMU), 6-methyl phosphonic triamide, metacresol etc.
In the present invention, the solution of the polysiloxane (A) obtaining as mentioned above can use a kind, also can use multiple.
< diol solvent (B) >
Diol solvent (B) used in the present invention is carbon number 2～7, preferably 2～5 diol solvent, as its object lesson, can exemplify ethylene glycol, diethylene glycol, dipropylene glycol, 2-methyl-2, 4-pentanediol, 1, 2-propylene glycol, 1, ammediol, 1, 2-butylene glycol, 1, 3-butylene glycol, 2, 3-butylene glycol, 1, 4-butylene glycol, 1, 2-pentanediol, 1, 3-pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, 2, 3-pentanediol, 2, 4-pentanediol, 1, 2-hexanediol, 1, 3-hexanediol, 1, 4-hexanediol, 1, 5-hexanediol, 1, 6-hexanediol, 2, 3-hexanediol, 2, 4-hexanediol, 2, 5-hexanediol, 3, 4-hexanediol, 1, 2-heptandiol, 2, 3-heptandiol, 3, 4-heptandiol, 1, 3-heptandiol, 2, 4-heptandiol, 3, 5-heptandiol, 1, 4-heptandiol, 2, 5-heptandiol, 1, 5-heptandiol, 2, 6-heptandiol, 1, 6-heptandiol, 1, 7-heptandiol etc.Diol solvent (B) can multiple and use.Wherein, ethylene glycol, diethylene glycol, dipropylene glycol, 2-methyl-2, 4-pentanediol, 1, 2-propylene glycol, 1, ammediol, 1, 2-butylene glycol, 1, 3-butylene glycol, 2, 3-butylene glycol, 1, 4-butylene glycol, 1, 2-pentanediol, 1, 3-pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, 2, 3-pentanediol, 2, 4-pentanediol, 1, 2-hexanediol, 1, 3-hexanediol, 1, 4-hexanediol, 1, 5-hexanediol, 1, 6-hexanediol, 2, 3-hexanediol, 2, 4-hexanediol, 2, 5-hexanediol, 3, 4-hexanediol or their mixed solvent are preferred.
Polymer solvent when this diol solvent (B) can be used as polysiloxane (A) polycondensation or add solvent all or part of use, also can after add in the polysiloxane synthetic with other solvent (A).
In aligning agent for liquid crystal, be scaled SiO with respect to the silicon atom that polysiloxane (A) is had
2total amount 100 mass parts of value, in the present invention, the content of diol solvent (B) used is 20～18000 mass parts, is preferably 120～17000 mass parts, 150～16000 mass parts more preferably.Can not obtain good coating than 20 mass parts when few.
When diol solvent (B) used has coating especially in the present invention, suppress the effect of liquid diffusion, particularly can obtain the film of edge grazing excellence.
< solvent (C) >
In the present invention, solvent (C) used is the a kind of above solvent that is selected from the solvent of formula (A1) expression.
K
1O(CH
2)
wOH (A1)
In formula, K
1for the alkyl of carbon number 1～4, the integer that w is 1～3.
As the object lesson of solvent (C), can exemplify 2-methyl cellosolve, cellosolvo, 2-propoxyl group ethanol, butoxy ethanol etc.
The polymer solvent when solvent (C) using in the present invention can be used as polysiloxane (A) polycondensation or add solvent all or part of use, also can after add in the polysiloxane synthetic with other solvent (A).
Be scaled SiO with respect to the silicon atom that polysiloxane (A) is had
2total amount 100 mass parts of value, the content of solvent (C) is 2～175000 mass parts, be preferably 2～16800 mass parts, 2～16000 mass parts more preferably.Can not obtain good coating than 2 mass parts when few.
Described solvent (C) has the effect of the liquid diffusion while making to be coated with, particularly can obtain the film of homogeneity excellence in film.
< solvent (D) >
In the present invention, solvent (D) used is the a kind of above solvent that is selected from following solvent: the alkylol that is selected from formula (T1), formula (T2) and at least a kind of compound of formula (T3), the ketone that has 3～6 carbon atoms and carbon number 5～12
In formula, X
1, X
3and X
5for the alkyl of carbon number 1～4, X
2and X
6for the alkyl of hydrogen atom or carbon number 1～4, X
4for the alkyl of carbon number 1～4, P is the alkyl of carbon number 1～3, and m, n, j, k are 1～3 integer independently of one another, the integer that h is 2～3.
In the present invention, solvent (D) used is preferably selected from a kind of above solvent of compound, the ketone of carbon number 3～6 and the alkylol of carbon number 5～12 of formula (T1)～formula (T3).
In the present invention, solvent (D) used can be for example the separate solvent of compound, above-mentioned formula (T3) that above-mentioned formula (T1) the represents compound, the ketone of carbon number 3～6 or the alkylol of carbon number 5～12 that represent, also can be the compound of formula (T1) expression and the mixed solvent of the compound that formula (T2) represents, can also be the mixed solvent of the compound of formula (T1) expression and the alkylol of carbon number 5～12.
In addition above-mentioned formula (T1) and X (T3),
2and X
6be preferably hydrogen atom.
The object lesson of the compound representing as formula (T1), preferably 1-methoxy-2-propanol (propylene glycol monomethyl ether), 1-ethoxy-2-propyl alcohol (dihydroxypropane single-ether), 1-propoxyl group-2-propyl alcohol (propylene glycol monopropyl ether), 1-butoxy-2-propyl alcohol (propylene glycol monobutyl ether), 1,2-dimethoxy propane (Propylene Glycol Dimethyl Ether), 1,2-di ethyl propyl ether (propylene glycol diethyl ether), 1,2-dipropoxy propane (propylene glycol dipropyl ether), 1,2-dibutoxy propane (propylene glycol butyl oxide).Wherein, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-propoxyl group-2-propyl alcohol or 1-butoxy-2-propyl alcohol are preferred.
The object lesson of the compound representing as formula (T2), can exemplify glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol bisthioglycolate propyl ether, butyl cellosolve etc.Wherein, glycol dimethyl ether or butyl cellosolve are preferred.
The object lesson of the compound representing as formula (T3), can exemplify diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether etc.Wherein, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether or dibutyl ethylene glycol ether are preferred.
As the object lesson of the ketone of the carbon number 3～6 of solvent (D), can exemplify MEK, methyl isopropyl Ketone etc.
As the object lesson of the alkyl alcohols of the carbon number 5～12 of solvent (D), can exemplify hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, hendecanol, dodecanol etc.Wherein, hexanol, enanthol, octanol, nonyl alcohol or decyl alcohol are preferred.
The polymer solvent when solvent (D) using in the present invention can be used as polysiloxane (A) polycondensation or add solvent all or part of use, also can after add in the polysiloxane synthetic with other solvent (A).
Be scaled SiO with respect to the silicon atom that polysiloxane (A) is had
2total amount 100 mass parts of value, the content of solvent (D) is 2～175000 mass parts, be preferably 2～16800 mass parts, 2～16000 mass parts more preferably.Can not obtain good coating than 2 mass parts when few.
This solvent (D) has the effect of the liquid diffusion while making to be coated with, particularly can obtain the film of internal homogeneity excellence.
Other solvent of < >
In the present invention, do not damaging under the prerequisite of effect of the present invention, can and use diol solvent (B), solvent (C) and solvent (D) solvent in addition.As the object lesson of other solvent, can exemplify the alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, diacetone alcohol; The ester classes such as acetone, methyl acetate, ethyl acetate, ethyl lactate; METHYLPYRROLIDONE, DMF, DMA, gamma-butyrolacton, dimethyl sulfoxide, tetramethylurea (TMU), 6-methyl phosphonic triamide, metacresol etc.
Other composition of < >
In the present invention, do not damaging under the prerequisite of effect of the present invention, can comprise other composition except polysiloxane (A), diol solvent (B), solvent (C) and solvent (D), the compositions such as such as inorganic particles, metal oxygen alkane (メ タ ロ キ サ Application) oligomer, metal oxygen alkane polymkeric substance, levelling agent and surfactant.
As inorganic particles, the preferably particulate such as silicon dioxide microparticle, alumina particulate, titanium dioxide fine particles and magnesium fluoride particulate, the colloidal solution of these inorganic particles is particularly preferably.This colloidal solution can be inorganic particles powder is scattered in to dispersion medium and colloidal solution, can be also commercially available colloidal solution.
In the present invention, by containing inorganic particles, can give surface configuration and other function of formed curing tunicle.As inorganic particles, its mean grain size is preferably 0.001～0.2 μ m, is more preferably 0.001～0.1 μ m.When the mean grain size of inorganic particles exceedes 0.2 μ m, use the transparency of the curing tunicle of the coating fluid formation of modulating to decline sometimes.
As the dispersion medium of inorganic particles, can exemplify water and organic solvent.As colloidal solution, form the angle by the stability of coating fluid from tunicle, pH or pKa preferably adjust to 1～10, more preferably adjust to 2～7.
As the organic solvent of the dispersion medium for colloidal solution, can exemplify methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, propylene glycol, butylene glycol, pentanediol, 2-methyl-2, the alcohols such as 4-pentanediol, diethylene glycol, dipropylene glycol, ethylene glycol ether; The ketone such as MEK, methyl isobutyl ketone; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; The amide-types such as dimethyl formamide, dimethyl acetamide, 1-METHYLPYRROLIDONE; The ester classes such as ethyl acetate, butyl acetate, gamma-butyrolacton; Tetrahydrofuran, Isosorbide-5-Nitrae-bis-
the ethers such as alkane.Wherein, alcohols and ketone are preferred.These organic solvents can be separately or two or more mixing be used as dispersion medium and use.
As metal oxygen alkane oligomer or metal oxygen alkane polymkeric substance, can use oxide alone precursor or the precursor of compound oxide of silicon, titanium, zirconium, aluminium, tantalum, antimony, bismuth, tin, indium, zinc etc.As metal oxygen alkane oligomer or metal oxygen alkane polymkeric substance, can be commercially available product, can be also the goods that obtained by monomers such as metal alkoxide, nitrate, hydrochloride, carboxylates by common methods such as hydrolysis.
In the present invention, by containing metal oxygen alkane oligomer or metal oxygen alkane polymkeric substance, can make the refractive index of solidifying tunicle improve, or give photonasty.While using metal oxygen alkane oligomer or metal oxygen alkane polymkeric substance, can in the time of synthetic polysiloxane (A), use simultaneously, also can after synthetic, be added in polysiloxane (A).
As the object lesson of commercially available metal oxygen alkane oligomer or metal oxygen alkane polymkeric substance, can exemplify siloxane oligomer or the siloxane polymers such as Colcoat Co., Ltd. (コ Le コ mono-ト society) methyl silicate 51 processed, methyl silicate 53A, ethyl silicate 40, silester 48, EMS-485, SS-101, the (Off East of Kanto Kagaku K. K. chemistry society) titanoxane (the チ タ ノ キ サ Application) oligomer such as the titanium n-butoxide tetramer processed.They can be separately or two or more mix and use.
In addition, levelling agent and surfactant etc. can use known reagent, and particularly commercially available product is because easily obtaining preferably.
In addition, the method for mixing other above-mentioned composition in polysiloxane (A) can be to mix with solution and the diol solvent (B) of polysiloxane (A) simultaneously, also can after they mix, mix, and is not particularly limited.
The modulation > of < aligning agent for liquid crystal
The modulator approach of aligning agent for liquid crystal of the present invention is not particularly limited.As long as polysiloxane (A) and diol solvent (B), solvent (C) and solvent (D) and other composition are the state that homogeneous mixes.
Conventionally, polysiloxane (A) polycondensation in solvent, so obtain with the state of solution.Therefore, easy method is the polymeric solution that directly uses above-mentioned polysiloxane (A).Be diol solvent (B) or solvent (C) or solvent (D) at the polymer solvent of polysiloxane (A), can add afterwards diol solvent (B) or solvent (C) or solvent (D).In addition, do not contain diol solvent (B) or solvent (C) or solvent (D) at the solution of polysiloxane (A), can in the time of modulation aligning agent for liquid crystal, add diol solvent (B) or solvent (C) or solvent (D) to use.
When modulation aligning agent for liquid crystal, the SiO in aligning agent for liquid crystal
2conversion concentration is preferably 0.5～15 quality %, more preferably 1～6 quality %.If at such SiO
2in conversion concentration range, easily just obtain required thickness by being once coated with, easily obtain the storage life of enough solution.
In addition, now for SiO
2the solvent of the adjustment of conversion concentration can use at least a kind of solvent of the polymer solvent, interpolation solvent and the diol solvent (B) that are selected from polysiloxane (A).
Aligning agent for liquid crystal of the present invention, by ink-jet application, can form the liquid crystal orientation film of the internal homogeneity of film and the edge grazing excellence of film end.
< liquid crystal orientation film and forming method thereof >
As the coating process of aligning agent for liquid crystal that is used to form liquid crystal orientation film, can exemplify spin-coating method, print process, ink-jet application method, spraying process, rolling method etc., but can expect that the ink-jet application method that productivity is higher gets most of the attention.
Ink-jet application method is by the fine droplets of dripping on substrate, invasion by liquid and the method for film forming.
Aligning agent for liquid crystal of the present invention has good coating, using under the occasion of ink-jet application method, can stably be coated with, and can obtain liquid crystal orientation film by this rubbing method.In addition, after coating, burn till and can obtain cured film.
For using more equably ink-jet application method film forming, must be from the nozzle of the ink-jet liquid that stably spues.One of the key factor of liquid that stably spues is relevant with the viscosity of liquid.The preferred liquid viscosity of aligning agent for liquid crystal is according to the difference of ink-jet coating apparatus used and difference, for example, for E type viscosity meter ((of Toki Sangyo Co., Ltd. Shu Machine industry society) TV-20 processed) for be preferably about the scope of 1.8～18mPas (measure temperature 25 DEG C), more preferably 3～15mPas.
In addition, one of key factor spreading as the drop that makes to drip, the surface tension of liquid also has a significant impact.The surface tension of liquid of aligning agent for liquid crystal is according to the difference of material therefor kind and difference, for example, for sessile drop method (the (Association of the interface science of coordinating Co., Ltd. and interface science society) AUTO DISPENCER AD-3 processed, measure 25 DEG C of temperature) be preferably about the scope of 20～40mN/m.
Aligning agent for liquid crystal preferred viscosities of the present invention is 1.8～18mPas (measuring 25 DEG C of temperature), and surface tension is 20～40mN/m (measuring 25 DEG C of temperature).
Drying process after coating of liquid crystalline alignment agent is optional, but in coating afterwards to during this period of time each piece substrate is not burnt till after fixing or coating immediately before burning till, preferably include drying process.During this is dry, solvent is evaporated to the degree that film shape is not out of shape because of the carrying of substrate etc., is not particularly limited for this drying means.For example, can exemplify in 40～150 DEG C of temperature, preferably dry 0.5～30 minute, the preferred method of 1～5 minute on the heating plate of 60～100 DEG C.
The film forming by above-mentioned method coating of liquid crystalline alignment agent can burn till makes cured film.Now, firing temperature can be the arbitrary temp of 100～350 DEG C, preferably 140 DEG C～300 DEG C, be more preferably 150 DEG C～230 DEG C, and being more preferably is 160 DEG C～220 DEG C.
Polysiloxane (A) in liquid crystal orientation film carries out polycondensation in firing process.But, in the present invention, do not damaging under the prerequisite of effect of the present invention, do not need to make its complete polycondensation.But, preferably in than the manufacturing process of liquid crystal structure cell, at the high more than 10 DEG C temperature of heat treatment temperature of required sealant cures etc., burn till.
The thickness of this cured film can be selected as required.The thickness of cured film is in the time that 5nm is above, and the reliability of liquid crystal display cells easily obtains, so be preferred.Be more preferably more than 10nm.In addition, below 300nm time, the power consumption of liquid crystal display cells can be not excessive, so be preferred.Be more preferably below 150nm.
Such cured film can directly be used as liquid crystal orientation film, but also can carry out friction treatment or irradiate the light etc. of polarized light or specific wavelength this cured film, or carries out the processing etc. of ion beam etc., thereby makes liquid crystal orientation film.
The liquid crystal orientation film of the present invention being formed by said method demonstrates high hydrophobicity, therefore can obtain good liquid crystal vertical-tropism.
< liquid crystal display cells >
Liquid crystal display cells of the present invention can form after liquid crystal orientation film in the method by above-mentioned on substrate, makes liquid crystal structure cell obtain with known method.
If exemplify the example that liquid crystal structure cell is made, usual method is that the 1 pair of substrate that has formed liquid crystal orientation film is clipped to sept, fixes with sealant, after injection liquid crystal, seals.At this moment, the sept of use is of a size of 1～30 μ m, preferably 2～10 μ m.The method of injection liquid crystal is not particularly limited, and can exemplify the vacuum method, the dripping method that the laggard row of dropping liquid crystal seals etc. that inject liquid crystal by rear decompression in the liquid crystal structure cell of making.
As the substrate for liquid crystal display cells, as long as the high substrate of the transparency, be not particularly limited, normally on substrate, be formed with the substrate of the transparency electrode for driving liquid crystal.As concrete example, can exemplify the substrate that is formed with transparency electrode on plastic plates such as glass plate or polycarbonate, poly-(methyl) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfones, polyethers, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (methyl) vinyl cyanide, tri acetyl cellulose, diacetyl cellulose, cellulose acetate-butyrate etc.
In addition,, in the such high function element of TFT type liquid crystal display cells, can use and between the electrode for liquid crystal drive and substrate, be formed with the substrate such as transistorized element.
Under the occasion of the liquid crystal cell of transmission-type, conventionally use substrate as above, but for reflection type liquid crystal display element, also can only use the opaque substrates such as silicon wafer at a side group plate.Now, the electrode forming on substrate also can use the catoptrical material such as aluminium.
Embodiment
Carry out more specific description by embodiments of the invention below, be limited by this but be not interpreted as.
In the present embodiment, the abbreviation of compound used is as follows.
TEOS: tetraethoxysilane
C18: octadecyltriethoxy silane
UPS:3-urea groups propyl-triethoxysilicane
HG:2-methyl-2,4-pentanediol
BCS:2-butyl cellosolve
PB:1-butoxy-2-propyl alcohol
1,3-BDO:1,3-butylene glycol
NMP:N-N-methyl-2-2-pyrrolidone N-
DEDE: diethylene glycol diethyl ether
EDM: glycol dimethyl ether
MIBK: methyl isobutyl ketone
C8OH:1-octanol
< synthesis example 1>
In 1 liter of (L) four-hole reaction flask that thermometer, recirculatory pipe are housed, drop into the TEOS of BCS, 39.6g and the C18 of 4.2g the stirring of HG, the 7.5g of 22.6g, make the solution of alkoxy silane monomer.In this solution, under room temperature with within 30 minutes, dripping that the water of BCS, 10.8g of HG, 3.8g of 11.3g and the oxalic acid as catalyzer of 0.2g are pre-mixed and oxalic acid solution, drip after finishing and under room temperature, stir 30 minutes.Then, under refluxing, let cool after heating 1 hour, obtaining SiO2 conversion solid component concentration is the polysiloxane solution (K1) of 12 quality %.
< synthesis example 2>
In the 1L four-hole reaction flask that thermometer, recirculatory pipe are housed, drop into the TEOS of HG, 39.6g and the C18 of 4.2g of 30.2g and stir, making the solution of alkoxy silane monomer.In this solution, under room temperature with within 30 minutes, dripping that the water of HG, 10.8g of 15.1g and the oxalic acid as catalyzer of 0.2g are pre-mixed and oxalic acid solution, drip after finishing and under room temperature, stir 30 minutes.Then, under refluxing, let cool after heating 1 hour, obtain SiO
2conversion solid component concentration is the polysiloxane solution (K2) of 12 quality %.
< synthesis example 3>
In the 1L four-hole reaction flask that thermometer, recirculatory pipe are housed, drop into the TEOS of BCS, 39.6g and the C18 of 4.2g of 30.2g and stir, making the solution of alkoxy silane monomer.In this solution, under room temperature with within 30 minutes, dripping that the water of BCS, 10.8g of 15.1g and the oxalic acid as catalyzer of 0.2g are pre-mixed and oxalic acid solution, drip after finishing and under room temperature, stir 30 minutes.Then, under refluxing, let cool after heating 1 hour, obtain SiO
2conversion solid component concentration is the polysiloxane solution (K3) of 12 quality %.
< synthesis example 4>
In the 1L four-hole reaction flask that thermometer, recirculatory pipe are housed, drop into the TEOS of BCS, 40.4g and the C18 of 0.8g the stirring of HG, the 7.7g of 23.0g, make the solution of alkoxy silane monomer.In this solution, under room temperature with within 30 minutes, dripping that the water of BCS, 10.8g of HG, 3.8g of 11.5g and the oxalic acid as catalyzer of 0.2g are pre-mixed and oxalic acid solution, drip after finishing and under room temperature, stir 30 minutes.Then, under refluxing, drop into the mixed solution of the BCS of HG, the 0.16g of UPS 92 quality % methanol solutions, the 0.48g of 1.15g after heating 1 hour, then let cool after refluxing lower overheated 30 minutes, obtain SiO
2conversion solid component concentration is the polysiloxane solution (K4) of 12 quality %.
Table 1
< embodiment 1～7, comparative example 3 and 4>
The polysiloxane solution obtaining in 50g synthesis example 1 (K1) and each solvent, to reach the solvent composition shown in table 1, are obtained to SiO
2conversion solid component concentration is the aligning agent for liquid crystal (KL1～7, KM3～4) of 3 quality %.
< embodiment 8>
The polysiloxane solution obtaining in 50g synthesis example 4 (K4) and each solvent, to reach the solvent composition shown in table 2, are obtained to SiO
2conversion solid component concentration is the aligning agent for liquid crystal (KL8) of 3 quality %.
< comparative example 1>
The polysiloxane solution obtaining in 50g synthesis example 2 (K2) is mixed and stirred with the HG of 150g, obtain SiO
2conversion solid component concentration is the aligning agent for liquid crystal (KM1) of 3 quality %.
< comparative example 2>
The polysiloxane solution obtaining in 50g synthesis example 3 (K3) is mixed and stirred with the BCS of 150g, obtain SiO
2conversion solid component concentration is the aligning agent for liquid crystal (KM2) of 3 quality %.
Table 2
Solution viscosity and the surface tension of the aligning agent for liquid crystal obtaining in embodiment 1～8 and comparative example 1～4 are shown in table 3.In addition, solution viscosity and surface tension are measured with following methods.
[solution viscosity]
Use E type viscosity meter ((Shu Machine industry society of Toki Sangyo Co., Ltd.) TV-20 processed), mensuration at 25 DEG C of temperature.
[surface tension]
Use the consonance (Association of interface science Co., Ltd. and interface science society) AUTO DISPENCER AD-3 mensuration processed.
Table 3
[ink-jet application]
For ink-jet application, following apparatus, condition are carried out.
Device name: device technique Co., Ltd. of Hitachi (the プ ラ of Hitachi Application ト テ Network ノ ロ ジ mono-society) system, fine pattern apparatus for coating HIS-200-1H.
Coated substrates: 100 × 100mm ito substrate
Spreading area: 30 × 40mm
Coating condition: resolution 25 μ m, step velocity 50mm/ second, frequency 1000Hz, pulsewidth 9.6 microseconds, drop amount 42pl, spacing width 70.5 μ m, gap length 125 μ m, apply voltage: 14～19V (adjust to thickness and reach 100nm), nozzle gap 0.5mm, 30 seconds leveling time, 60 DEG C of baking temperatures, 2 minutes drying times (heating plate).
[coating]
By film visual and microscopic examination gained, confirm coating.
Can film forming: can zero defect ground film forming person be zero, not able one be ×.
Internal homogeneity: in the face of film all one be zero, produce orange peel or wire inequality person be ×.
Edge grazing: the very good person of grazing is zero, the poor person of grazing for ×.
Table 4
As seen from Table 4, comparative example 1 and comparative example 4 can not film forming, and embodiment 1～8 is compared with comparative example 2,3, and internal homogeneity and edge grazing are good, and coating improves.
[making of liquid crystal structure cell]
Prepare 2 glass substrates of having the transparency electrode that has formed liquid crystal orientation film, scatter after the sept of 6 μ m at the liquid crystal aligning face of a substrate, after the outer edge of substrate is coated with epoxy by silk screen print method and is bonding agent, bonding and the crimping in the relative mode of liquid crystal orientation film, then solidifies and makes empty structure cell.Inject after the MLC-6608 processed (trade name) of Merck & Co., Inc. (メ ルク society) by vacuum impregnation to this empty structure cell, by UV cured resin sealing filling orifice, make liquid crystal structure cell (cell).Now, use is to form film, on the heating plate of 80 DEG C of temperature, after dry 5 minutes, burn till 60 minutes with the heated air circulation type cleaning oven of 200 DEG C of temperature and the liquid crystal orientation film of the thickness 80nm that obtains by method of recording in above-mentioned in embodiment [ink-jet application].And in comparative example, use be the liquid crystal orientation film except replace the thickness 100nm that the method identical with embodiment obtains ink-jet application with spin-coating method.
[liquid crystal aligning]
The liquid crystal structure cell of making by above-mentioned [making of liquid crystal structure cell] method with polarized light microscope observing, the state of orientation of confirmation liquid crystal.The situation that liquid crystal structure cell entirety is flawless homogeneous state of orientation is zero, the part of liquid crystal structure cell find situation and the not vertical orientated situation of orientation defect be ×.The results are shown in table 5.
[contact angle]
Drip 3 μ L pure water to liquid crystal orientation film, use consonance the (Association of interface science Co., Ltd. and interface science (strain) society) the automatic contact angle meter CA-Z type of system, measure contact angle.The results are shown in table 5.
What use is to form film, on the heating plate of 80 DEG C of temperature, after dry 5 minutes, burn till 60 minutes with the heated air circulation type cleaning oven of 200 DEG C of temperature and the liquid crystal orientation film of the thickness 80nm that obtains by method of recording in above-mentioned in embodiment [ink-jet application].And in reference example, use be the liquid crystal orientation film except replace the thickness 100nm that the method identical with embodiment obtains ink-jet application with spin-coating method.
Table 5
| Alignment agent | Coating process | Liquid crystal aligning | The contact angle of water/° | |
| Measure example | KL1 | Ink-jet application method | ○ | 89 |
| Reference example | KL1 | Spin-coating method | ○ | 87 |
As known from Table 5, even the liquid crystal orientation film being obtained by ink-jet application method also demonstrates and the equal vertical orientated property of film that obtained by other method.
In industry, utilize possibility
The edge grazing excellence of the internal homogeneity of the film of the liquid crystal orientation film being obtained with aligning agent for liquid crystal by ink-jet application of the present invention and film end, is therefore used the liquid crystal display cells of this liquid crystal orientation film can be suitable as the liquid crystal display device use that reliability is high.
In addition, the full content of instructions, claims and summary of quoting No. 2008-329123, the Japanese patent application of filing an application on Dec 25th, 2008 and the Japanese patent application of filing an application on January 7th, 2009 No. 2009-001359 is here as the announcement of instructions of the present invention.
Claims (14)
1. ink-jet application aligning agent for liquid crystal, is characterized in that, contain to have to be replaced by fluorine atom or polysiloxane A, diol solvent B, following solvents C and the solvent D of carbon number 2～7 of the side chain that the alkyl of unsubstituted carbon number 8～30 forms,
Solvent C: the solvent that formula (A1) represents,
K
1O（CH
2）
wOH （A1）
In formula, K
1for the alkyl of carbon number 1～4, the integer that w is 1～3,
Solvent D: be selected from following solvent: be selected from the alkylol of formula (T1), formula (T2) and at least a kind of compound of formula (T3), the ketone that has 3～6 carbon atoms and carbon number 5～12,
In formula, X
1, X
3and X
5for the alkyl of carbon number 1～4, X
2and X
6for the alkyl of oxygen atom or carbon number 1～4, X
4for the alkyl of carbon number 1～4, P is the alkyl of carbon number 1～3, and m, n, j, k are 1～3 integer independently of one another, the integer that h is 2～3.
2. ink-jet application aligning agent for liquid crystal as claimed in claim 1, is characterized in that, solvent D is the solvent of the alkylol of the compound that is selected from formula (T1)～formula (T3), the ketone that has 3～6 carbon atoms and carbon number 5～12.
3. ink-jet application aligning agent for liquid crystal as claimed in claim 1, is characterized in that, polysiloxane A is the polysiloxane being obtained by the alkoxy silane polycondensation of the alkoxy silane that contains formula (1) expression,
R
1Si（OR
2）
3 （1）
R
1for being replaced by fluorine atom or the alkyl of unsubstituted carbon number 8～30, R
2for the alkyl of carbon number 1～5.
4. ink-jet application aligning agent for liquid crystal as claimed in claim 3, is characterized in that, polysiloxane A is the polysiloxane being obtained by the alkoxy silane polycondensation of the alkoxy silane of the alkoxy silane that contains formula (1) expression and following formula (2) expression,
(R
3)
nSi(OR
4)
4－n （2）
R
3for the alkyl of hydrogen atom, halogen atom, vinyl or carbon number 1～7; Now, any hydrogen atom of described alkyl can be by glycidoxy, sulfydryl, methacryloxy, acryloxy, isocyanate group, amino or Carbamido substituted, and can have heteroatoms; R
4for the alkyl of carbon number 1～5, the integer that n is 0～3.
5. the ink-jet application aligning agent for liquid crystal as described in claim 3 or 4, is characterized in that, polysiloxane A is the polysiloxane being obtained by the alkoxy silane polycondensation of the alkoxy silane of the alkoxy silane that contains formula (1) expression and following formula (3) expression,
Si(OR
4)
4 （3）
R
4for the alkyl of carbon number 1～5.
6. ink-jet application aligning agent for liquid crystal as claimed in claim 1, it is characterized in that, diol solvent B is selected from ethylene glycol, diethylene glycol, dipropylene glycol, 2-methyl-2, 4-pentanediol, 1, 2-propylene glycol, 1, ammediol, 1, 2-butylene glycol, 1, 3-butylene glycol, 2, 3-butylene glycol, 1, 4-butylene glycol, 1, 2-pentanediol, 1, 3-pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, 2, 3-pentanediol, 2, 4-pentanediol, 1, 2-hexanediol, 1, 3-hexanediol, 1, 4-hexanediol, 1, 5-hexanediol, 1, 6-hexanediol, 2, 3-hexanediol, 2, 4-hexanediol, 2, 5-hexanediol, 3, 4-hexanediol, 1, 2-heptandiol, 2, 3-heptandiol, 3, 4-heptandiol, 1, 3-heptandiol, 2, 4-heptandiol, 3, 5-heptandiol, 1, 4-heptandiol, 2, 5-heptandiol, 1, 5-heptandiol, 2, 6-heptandiol, 1, 6-heptandiol and 1, 1 kind of above solvent of 7-heptandiol.
7. ink-jet application aligning agent for liquid crystal as claimed in claim 1, is characterized in that, the X in described formula (T1)
2for hydrogen atom.
8. ink-jet application aligning agent for liquid crystal as claimed in claim 1, is characterized in that, is scaled SiO with respect to the silicon atom that polysiloxane A is had
2total amount 100 mass parts of value, diol solvent B is 20～18000 mass parts, solvent C is 2～17500 mass parts, solvent D is 2～17500 mass parts.
9. ink-jet application aligning agent for liquid crystal as claimed in claim 1, is characterized in that, is scaled SiO with respect to the silicon atom that polysiloxane A is had
2total amount 100 mass parts of value, diol solvent B is 120～17000 mass parts, solvent C is 2～16800 mass parts, solvent D is 2～16800 mass parts.
10. ink-jet application aligning agent for liquid crystal as claimed in claim 1, is characterized in that, the viscosity of described alignment agent is 1.8～18mPas.
11. ink-jet application aligning agent for liquid crystal as claimed in claim 1, is characterized in that, the surface tension of described alignment agent is 20～40mN/m.
12. liquid crystal orientation films, burn till and obtain after the ink-jet application described in any one in claim 1～11 is coated on substrate with aligning agent for liquid crystal ink discharge device.
The formation method of 13. liquid crystal orientation films, burns till and obtains liquid crystal orientation film after the ink-jet application described in any one in claim 1～11 is coated on substrate with aligning agent for liquid crystal ink discharge device.
14. liquid crystal display cells, have the liquid crystal orientation film described in claim 12.
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| JP2008-329123 | 2008-12-25 | ||
| JP2008329123 | 2008-12-25 | ||
| JP2009-001359 | 2009-01-07 | ||
| JP2009001359 | 2009-01-07 | ||
| PCT/JP2009/071670 WO2010074261A1 (en) | 2008-12-25 | 2009-12-25 | Liquid-crystal alignment material for ink-jet coating, liquid-crystal alignment film, and liquid-crystal display element |
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| CN102317848A CN102317848A (en) | 2012-01-11 |
| CN102317848B true CN102317848B (en) | 2014-06-11 |
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| CN (1) | CN102317848B (en) |
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| KR101883521B1 (en) * | 2011-05-27 | 2018-07-30 | 닛산 가가쿠 고교 가부시키 가이샤 | Silicon-based liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| JP5830978B2 (en) * | 2011-07-04 | 2015-12-09 | 東レ株式会社 | Siloxane resin composition and method for producing the same, cured film obtained by curing the same, optical article having the same, and solid-state imaging device |
| KR102082525B1 (en) * | 2011-11-17 | 2020-02-27 | 닛산 가가쿠 가부시키가이샤 | Silicon-based liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| JP6146135B2 (en) * | 2012-08-30 | 2017-06-14 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, method for producing liquid crystal aligning film, and liquid crystal display element |
| WO2014054748A1 (en) * | 2012-10-03 | 2014-04-10 | 日産化学工業株式会社 | Application liquid capable of fine application, for forming inorganic oxide coating film, and method for manufacturing fine inorganic oxide coating film |
| KR102113892B1 (en) * | 2012-10-05 | 2020-05-21 | 닛산 가가쿠 가부시키가이샤 | Manufacturing method for substrate having liquid crystal alignment film for in-plane switching-type liquid crystal display element |
| JP6409494B2 (en) * | 2014-10-21 | 2018-10-24 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| JP6672815B2 (en) * | 2015-04-14 | 2020-03-25 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element |
| KR102159503B1 (en) * | 2017-09-29 | 2020-09-25 | 주식회사 엘지화학 | Preparation Method for Optical Device |
| JP6904216B2 (en) * | 2017-10-30 | 2021-07-14 | Jnc株式会社 | A liquid crystal alignment agent for forming a liquid crystal alignment film, a liquid crystal alignment film, and a liquid crystal display element using the same. |
| JP2022027233A (en) * | 2020-07-31 | 2022-02-10 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal element |
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