CN102317848A - 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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- 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
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- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
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Abstract
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). 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). 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 to contain polysiloxane, particularly by the alkoxy silane polycondensation polysiloxane, can form the aligning agent for liquid crystal of the film of homogeneous through ink-jet application, the liquid crystal orientation film that obtains by the foregoing liquid crystal alignment agent and liquid crystal display cells with this liquid crystal orientation film.
Background technology
Liquid crystal display cells is usually known to have that 2 substrates that transparency electrode is provided with liquid crystal orientation film dispose relatively, the structure of filling liquid crystal material in the clearance therebetween.
Recently, as commercial use and home theater light source, use the strong metal halid lamp of exposure intensity with liquid crystal projection apparatus (the rear-projection TV that is called as the 3rd slim TV machine) usefulness.Therefore,, not only need high-fire resistance, also need high-light-fastness as the characteristic of liquid crystal orientation film.
It is the liquid crystal aligning membrane material of major component that common used liquid crystal aligning membrane material has with polyamic acid or polyimide, and inorganic is that liquid crystal orientation film also is suggested.For example, form the liquid crystal aligning membrane material (for example referring to patent documentation 1) of liquid crystal orientation film through vapor deposition.
In addition; As the inorganic of application type is the alignment agent composition that the reaction product that contains tetraalkoxysilane, trialkoxy silane, pure and mild oxalic acid is arranged that liquid crystal orientation film is suggested, and it was reported and claims on the electrode base board of liquid crystal display cells, to form the excellent liquid crystal orientation film (for example referring to patent documentation 2) of vertical orientated property, thermotolerance and homogeneity.
In addition; Also proposed to contain the reaction product of tetraalkoxysilane, trialkoxy silane and water and the aligning agent for liquid crystal composition of alcohol ether series solvent, it was reported to claim to form to prevent to show bad, the long-time less liquid crystal orientation film (for example referring to patent documentation 3) of degree that image retention characteristic ability good, that make liquid crystal aligning in back can not reduce and voltage retention is influenced by light and heat and reduce that drives.
Usually, as the one-tenth embrane method of liquid crystal orientation film, the spin-coating method of can giving an example, dip coating, hectographic printing method etc. are used the hectographic printing method in fact mostly.But in hectographic printing, existing must be according to the size exchange galley of the substrate that is used to form liquid crystal orientation film, for stablizing problem such as the necessary false film forming of film formation process.
Therefore, the ink-jet application method gets most of the attention as not using the novel coating process of galley.The ink-jet application method is on substrate, to drip fine droplets, the infiltration diffusion through liquid and the method for film forming is not only used galley, and can freely set printed patterns, so the manufacturing process of liquid crystal display cells can obtain simplifying.And, do not need false film forming in addition and reduce the advantage of the waste of coating fluid.So, can expect that the cost of liquid crystal display reduces, the raising of production efficiency.
Under this situation, in the liquid crystal orientation film of the excellent inorganic system of demand thermotolerance and photostability, also hope to introduce the method that forms liquid crystal orientation film through ink-jet application, it can be aligning agent for liquid crystal corresponding to the inorganic of these demands that expectation obtains.
(patent documentation 1) Japanese Patent Laid is opened the 2003-50397 communique
(patent documentation 2) japanese patent laid-open 09-281502 communique
(patent documentation 3) Japanese Patent Laid is opened the 2005-250244 communique
Summary of the invention
The silicon that the purpose of this invention is to provide a kind of available ink-jet application method film forming is the excellent liquid crystal orientation film of edge grazing of aligning agent for liquid crystal and internal homogeneity that passes through the film that ink-jet application forms and film end.
That is to say that the present invention has following technology contents.
(1) ink-jet application is used aligning agent for liquid crystal, it is characterized in that, contains the polysiloxane (A) with the side chain that is constituted by the alkyl of fluorine atom replacement or unsubstituted carbon number 8～30, diol solvent (B), following solvents (C) and the solvent (D) of carbon number 2～7,
Solvent (C): the solvent of formula (A1) expression,
K
1O(CH
2)
wOH (A1)
In the formula, K
1Be the alkyl of carbon number 1～4, w is 1～3 integer,
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 3～6 carbon atoms are arranged and carbon number 5～12,
In the formula, X
1, X
3And X
5Be the alkyl of carbon number 1～4, X
2And X
6Be the alkyl of hydrogen atom or carbon number 1～4, X
4Be 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, and h is 2～3 integer.
(2) use aligning agent for liquid crystal like above-mentioned (1) described ink-jet application, wherein, solvent (D) is the solvent of alkylol that is selected from compound, the ketone that 3～6 carbon atoms are arranged and the carbon number 5～12 of the expression of formula (T1)～formula (T3).
(3) use aligning agent for liquid crystal like above-mentioned (1) or (2) described ink-jet application, wherein, polysiloxane (A) is the polysiloxane that is got by the alkoxy silane polycondensation of the alkoxy silane that contains formula (1) expression,
R
1Si(OR
2)
3 (1)
R
1For replaced or the alkyl of unsubstituted carbon number 8～30 R by fluorine atom
2Alkyl for carbon number 1～5.
(4) use aligning agent for liquid crystal like above-mentioned (3) described ink-jet application, wherein, polysiloxane (A) is the polysiloxane that is got by the alkoxy silane polycondensation of the alkoxy silane of alkoxy silane that contains formula (1) expression and following formula (2) expression,
(R
3)
nSi(OR
4)
4-n (2)
R
3Alkyl for hydrogen atom, halogen atom, vinyl or carbon number 1～7; At this moment, any hydrogen atom of said alkyl can be replaced by glycidoxy, sulfydryl, methacryloxy, acryloxy, NCO, amino or urea groups, and can have heteroatoms; R
4Be the alkyl of carbon number 1～5, n is 0～3 integer.
(5) use aligning agent for liquid crystal like above-mentioned (3) or (4) described ink-jet application, wherein, polysiloxane (A) is the polysiloxane that is got by the alkoxy silane polycondensation of the alkoxy silane of alkoxy silane that contains formula (1) expression and following formula (3) expression,
Si(OR
4)
4 (3)
R
4Alkyl for carbon number 1～5.
(6) use aligning agent for liquid crystal like each described ink-jet application in above-mentioned (1)～(5), wherein, diol solvent (B) is to be selected from monoethylene glycol, diethylene glycol, DPG, 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, the solvent more than a kind of 7-heptandiol.
(7) use aligning agent for liquid crystal like each described ink-jet application in above-mentioned (1)～(6), wherein, the X in the said formula (T1)
2Be hydrogen atom.
(8) use aligning agent for liquid crystal like each described ink-jet application in above-mentioned (1)～(7), wherein, be scaled SiO with respect to the silicon atom that polysiloxane (A) is had
2The total of value measure 100 mass parts, diol solvent (B) is 20～18000 mass parts, solvent (C) is 2～17500 mass parts, solvent (D) is 2～17500 mass parts.
(9) use aligning agent for liquid crystal like each described ink-jet application in above-mentioned (1)～(8), wherein, be scaled SiO with respect to the silicon atom that polysiloxane (A) is had
2The total of value measure 100 mass parts, diol solvent (B) is 120～17000 mass parts, solvent (C) is 2～16800 mass parts, solvent (D) is 2～16800 mass parts.
(10) use aligning agent for liquid crystal like each described ink-jet application in above-mentioned (1)～(9), wherein, the viscosity of said alignment agent is 1.8～18mPas.
(11) use aligning agent for liquid crystal like each described ink-jet application in above-mentioned (1)～(10), wherein, the surface tension of said alignment agent is 20～40mN/m.
(12) liquid crystal orientation film burns till after coating on the substrate with aligning agent for liquid crystal with ink discharge device each described ink-jet application in above-mentioned (1)～(11) and gets.
(13) the formation method of liquid crystal orientation film is burnt till after coating on the substrate with aligning agent for liquid crystal with ink discharge device each described ink-jet application in above-mentioned (1)～(11) and is obtained 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 can form the internal homogeneity of film and the excellent liquid crystal orientation film of edge grazing of film end through the ink-jet application method.
Embodiment
Below, the present invention is detailed.
< polysiloxane A >
The used polysiloxane (A) of the present invention is the polysiloxane that has by fluorine atom replaces or unsubstituted carbon number 8～30, preferred 8～22 alkyl constitute side chain (below be also referred to as " specific organic group ").
Above-mentioned specific organic group is to have the organic group that makes the effect that liquid crystal is orientated toward the direction, so long as the organic group of having that effect does not then have special the qualification.As its example, but exemplified by alkyl groups, fluoro-alkyl, alkenyl, phenethyl, fluorophenyl alkyl, styryl alkyl, naphthyl etc.
Wherein, alkyl obtains thereby preferably easily.
Can have multiple specific organic group in the used polysiloxane (A) among the present invention.
Used polysiloxane (A) is being purpose, is not damaging under the prerequisite of effect of the present invention to improve with the adaptation of substrate with the affinity of liquid crystal molecule etc. among the present invention, can have the side chain different with specific organic group (below be also referred to as " second organic group).Above-mentioned second organic group is carbon number 1～7, preferred 1～6, more preferably 1～5 organic group.Second organic group can have aliphatic hydrocarbon; Aliphatics ring, aromatic ring, the such ring structure of heterocycle; Unsaturated link; Heteroatomss such as oxygen atom, nitrogen-atoms or sulphur atom; Apparatus derivatorius.Second organic group can be the alkyl of vinyl or carbon number 1～7, and any hydrogen atom of this alkyl can be replaced by glycidoxy, sulfydryl, methacryloxy, acryloxy, NCO, amino or urea groups, also can have heteroatoms.The used polysiloxane (A) of the present invention can have a kind of second organic group, also can have multiple second organic group.
The method that obtains above-mentioned polysiloxane (A) does not have special qualification, is got by the alkoxy silane polycondensation usually.
Specifically, can be that the alkoxy silane polycondensation of neccessary composition obtains polysiloxane (A) by alkoxy silane with following formula (1) expression.
R
1Si(OR
2)
3 (1)
In the 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 obtains with less expensive commercially available article thereby preferably easily.R
2Be carbon number 1～5, preferred 1～4 alkyl.
The object lesson of the alkoxy silane of the above-mentioned formula of giving an example below (1) expression, but be not limited thereto.
For example; The octyl group of can giving an example trimethoxy silane, octyltri-ethoxysilane, decyl trimethoxy silane, decyl triethoxysilane, dodecyl trimethoxy silane, 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 ,-ethenylphenyl ethyl trimethoxy silane, right-the ethenylphenyl ethyl trimethoxy silane, (1-naphthyl) triethoxysilane, (1-naphthyl) trimethoxy silane, allyloxy undecyl triethoxysilane, benzoyloxy propyl trimethoxy silicane, 3-(4-methoxyl phenoxy group) 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, preferred octyl group trimethoxy silane, octyltri-ethoxysilane, decyl trimethoxy silane, decyl triethoxysilane, dodecyl trimethoxy silane, 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.
Among the present invention, the alkoxy silane that can also represent with multiple formula (1).
For obtaining in whole alkoxy silanes that polysiloxane (A) uses; The usage rate of the alkoxy silane of formula (1) expression can not obtain good liquid crystal aligning property during less than 0.1 mole of % sometimes; Therefore preferably at 0.1 mole more than the %, more preferably at 0.5 mole more than the %.In addition, the liquid crystal orientation film that forms sometimes when surpassing 30 moles of % can not fully solidify, and therefore preferably at 30 moles below the %, more preferably at 22 moles below the %, is more preferably at 15 moles below the %.
In addition, among the present invention by the alkoxy silane polycondensation of the alkoxy silane of alkoxy silane that contains formula (1) expression and following formula (2) expression polysiloxane be preferred.
(R
3)
nSi(OR
4)
4-n (2)
R
3Be 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 be replaced by glycidoxy, sulfydryl, methacryloxy, acryloxy, NCO, amino or urea groups, also can have heteroatoms; R
4Be carbon number 1～5, preferred 1～4, more preferably 1～3 alkyl, n is 0～3, preferred 0～2 integer.
In addition, the R of formula (2)
3During for vinyl or alkyl, R
3Represent above-mentioned second organic group.Therefore, under this occasion, R
3Example identical with the record of above-mentioned second organic group.
As the alkoxy silane of formula (2) expression, but exemplified by methyl trimethoxy silane, MTES, 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 8330,3-aminopropyltriethoxywerene werene, N-2 (amino-ethyl) 3-aminopropyltriethoxywerene werene, N-2 (amino-ethyl) 3-TSL 8330,3-(2-aminoethylamino propyl group) trimethoxy silane, 3-(2-aminoethylamino propyl group) triethoxysilane, 2-aminoethylamino MTMS, 2-(2-amino-ethyl thio-ethyl) triethoxysilane, 3-sulfydryl propyl-triethoxysilicane, mercapto methyl trimethoxy silane, 3-urea groups propyl-triethoxysilicane, VTES, 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, the trimethoxy silane of can giving an example, triethoxysilane, tripropoxy silane, three butoxy silanes etc.
In the alkoxy silane of formula (2), n is the tetraalkoxysilane of 0 alkoxy silane expression (3).
Si(OR
4)
4 (3)
In the formula (3), R
4Be carbon number 1～5, preferred 1～4, more preferably 1～3 alkyl.Therefore the alkoxy silane condensation that tetraalkoxysilane is easy and formula (1) is represented of formula (3) expression is preferred obtaining on the polysiloxane (A).As the object lesson of the tetraalkoxysilane of formula (3), the tetramethoxy-silicane of can giving an example, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes etc.
When using the alkoxy silane of above-mentioned formula (2) or (3) expression, one or more can suitably be used as required.
And during the alkoxy silane represented with formula (2) or formula (3); For obtaining in whole alkoxy silanes that polysiloxane (A) uses; The total use amount of the alkoxy silane of formula (2) or formula (3) expression is preferably 70～99.7 moles of %, more preferably 78～99.7 moles of %.More preferably, the alkoxy silane of formula (2) or formula (3) expression is 85～99.7 moles of %.
Among the present invention used polysiloxane (A) by the alkoxy silane that contains above-mentioned formula (1) expression as the condensation and getting in organic solvent of the alkoxy silane of neccessary composition.At this moment, the alkoxy silane that contains the alkoxy silane of formula (1), formula (2) and formula (3) expression is preferred.Usually, polysiloxane (A) can be used as by this alkoxy silane polycondensation, is dissolved in the solution in the organic solvent equably and obtains.
The method of used condensation polysiloxane (A) does not have special qualification among the present invention, for example, can give an example the method for alkoxy silane hydrolytic condensation in alcohol or diol solvent.At this moment, hydrolysis-condensation reaction can be any in partial hydrolysis and the complete hydrolysis.Under the occasion of complete hydrolysis, can add the water of 0.5 times of mole of whole alkoxys in the alkoxy silane in theory, add the water of the excess quantity of Duoing usually than 0.5 times of mole.
Among the present invention, the amount of used water can suitably be selected as required in the above-mentioned reaction, and 0.5～2.5 times of mole with the whole alkoxys in the alkoxy silane serves as preferred usually.
In addition; Usually, for promoting hydrolysis-condensation reaction, can use acid such as hydrochloric acid, sulfuric acid, nitric acid, acetate, formic acid, oxalic acid, maleic acid, fumaric acid; The catalyzer such as slaine of alkali such as ammonia, methylamine, ethamine, monoethanolamine, triethanolamine and hydrochloric acid, sulfuric acid, nitric acid etc.Moreover, usually heating for dissolving the solution of alkoxy silane can further promote hydrolysis-condensation reaction.At this moment, heating-up temperature and heat time heating time can suitably be selected as required, for example, can give an example 50 ℃ of following heated and stirred 24 hours, or under refluxing method such as heated and stirred 1 hour.
In addition, as other method, for example, can give an example the method for the mixture heated aftercondensated of alkoxy silane, solvent and oxalic acid.Specifically, be in advance oxalic acid to be added in the alcohol after the alcoholic solution that forms oxalic acid, under the state of this solution of heating, sneaks into the method for alkoxy silane.At this moment, with respect to 1 mole of whole alkoxy that alkoxy silane had, the amount of used oxalic acid is preferably 0.2～2 mole.Heating in this method can be carried out under 50～180 ℃ of liquid temperature, preferably not cause evaporation of liquid, to wave diffusing etc. mode, for example carries out dozens of minutes～tenss' hour heating under the backflow in possessing the container of recirculatory pipe.
When obtaining polysiloxane (A), under the occasion of using multiple alkoxy silane, can alkoxy silane be mixed as the potpourri that is pre-mixed, also can multiple alkoxy silane be mixed successively.
Used solvent during the alkoxy silane polycondensation (below be also referred to as " polymer solvent ") so long as the solvent of dissolvane TMOS gets final product, does not have special qualification.In addition, though also can be 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.Usually, therefore the polycondensation reaction generation alcohol by alkoxy silane can use alcohols, glycols, pure ethers or the organic solvent good with the alcohols intermiscibility.
Object lesson as this polymer solvent; Can give an example methyl alcohol, ethanol, propyl alcohol, butanols, monoethylene glycol, diethylene glycol, propylene glycol, DPG, 2-methyl-2; 4-pentanediol, ethyl carbitol, BC, 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, N-N-methyl-2-2-pyrrolidone N-, N; Dinethylformamide, DMAC N,N, gamma-butyrolacton, dimethyl sulfoxide, tetramethylurea (TMU), 6-methyl phosphonic triamide, metacresol etc.
Among the present invention, above-mentioned polymer solvent can use multiple mixing back.
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 be also referred to as " SiO
2Conversion concentration ") usually below 20 quality %, preferably below 15 quality %.Through in this concentration range, selecting concentration arbitrarily, can suppress the generation of gel, obtain the solution of homogeneous.
< solution of polysiloxane (A) >
Among the present invention, the solution that can said method be obtained is directly as the solution of polysiloxane (A), the solution that also can be as required said method be obtained through concentrate, the solubilizer dilution or be replaced into other solvent after as the solution of polysiloxane (A).
At this moment, used solvent (below be also referred to as " interpolation solvent ") can be with polycondensation in the used identical solvent of solvent, also can be other solvent.As long as this solvent can dissolve polysiloxane (A) equably, there is not special qualification, can select to use one or more arbitrarily.
As the object lesson of this interpolation solvent, the alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, diacetone alcohol of can giving an example; Ketones such as acetone, MEK, methyl isobutyl ketone; Monoethylene glycol, diethylene glycol, propylene glycol, 2-methyl-2, glycolss such as 4-pentanediol; 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; Ester classes such as methyl acetate, ethyl acetate, ethyl lactate; N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide, DMAC N,N, gamma-butyrolacton, dimethyl sulfoxide, tetramethylurea (TMU), 6-methyl phosphonic triamide, metacresol etc.
Among the present invention, the solution of the polysiloxane that obtains as stated (A) can use a kind, also can use multiple.
< diol solvent (B) >
Used diol solvent (B) is carbon number 2～7, preferred 2～5 diol solvent among the present invention, as its object lesson, and the monoethylene glycol of can giving an example, diethylene glycol, DPG, 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 usefulness.Wherein, monoethylene glycol, diethylene glycol, DPG, 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 (A) that synthesizes with other solvent.
In aligning agent for liquid crystal, be scaled SiO with respect to the silicon atom that polysiloxane (A) is had
2The total of value measure 100 mass parts, the content of used diol solvent (B) is 20～18000 mass parts, is preferably 120～17000 mass parts, 150～16000 mass parts more preferably among the present invention.Can not obtain good coating than 20 mass parts after a little while.
The effect that suppresses the liquid diffusion when used diol solvent (B) has coating especially among the present invention particularly can obtain the excellent film of edge grazing.
< solvent (C) >
Used solvent (C) is the solvent more than a kind that is selected from the solvent of formula (A1) expression among the present invention.
K
1O(CH
2)
wOH (A1)
In the formula, K
1Be the alkyl of carbon number 1～4, w is 1～3 integer.
As the object lesson of solvent (C), the 2-methyl cellosolve of can giving an example, cellosolvo, 2-propoxyl group ethanol, butoxy ethanol etc.
Polymer solvent when the solvent that uses among the present invention (C) can be used as polysiloxane (A) polycondensation or add solvent all or part of use, also can after add in the polysiloxane (A) that synthesizes with other solvent.
Silicon atom with respect to polysiloxane (A) is had is scaled SiO
2The total of value measure 100 mass parts, 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 after a little while.
Said solvent (C) has the effect of the liquid diffusion when making coating, particularly can obtain the excellent film of homogeneity in the film.
< solvent (D) >
Solvent (D) used among the present invention is the solvent more than a kind that is 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 3～6 carbon atoms are arranged and carbon number 5～12,
In the formula, X
1, X
3And X
5Be the alkyl of carbon number 1～4, X
2And X
6Be the alkyl of hydrogen atom or carbon number 1～4, X
4Be 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, and h is 2～3 integer.
Used solvent (D) preferably is selected from the solvent more than a kind of the alkylol of formula (the T1)～compound of formula (T3), the ketone of carbon number 3～6 and carbon number 5～12 among the present invention.
Used solvent (D) for example can be the independent solvent of alkylol of ketone or carbon number 5～12 of compound, the carbon number 3～6 of compound, above-mentioned formula (T3) expression of above-mentioned formula (T1) expression among the present invention; Also can be the compound of formula (T1) expression and the mixed solvent of the compound of formula (T2) expression, can also be the mixed solvent of the alkylol of the compound represented of formula (T1) and carbon number 5～12.
In addition, above-mentioned formula (T1) and X (T3)
2And X
6Be preferably hydrogen atom.
Object lesson as the compound of formula (T1) expression; Preferred 1-methoxyl-2-propyl alcohol (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-methoxyl-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, 1-propoxyl group-2-propyl alcohol or 1-butoxy-2-propyl alcohol are preferred.
As the object lesson of the compound of formula (T2) expression, the glycol dimethyl ether of can giving an example, ethylene glycol diethyl ether, ethylene glycol bisthioglycolate propyl ether, butyl cellosolve etc.Wherein, glycol dimethyl ether or butyl cellosolve are preferred.
As the object lesson of the compound of formula (T3) expression, the diethylene glycol monomethyl ether of can giving an example, 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 give an example MEK, methyl isopropyl Ketone etc.
As the object lesson of the alkyl alcohols of the carbon number 5～12 of solvent (D), can give an example hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, hendecanol, dodecanol etc.Wherein, hexanol, enanthol, octanol, nonyl alcohol or decyl alcohol are preferred.
Polymer solvent when the solvent that uses among the present invention (D) can be used as polysiloxane (A) polycondensation or add solvent all or part of use, also can after add in the polysiloxane (A) that synthesizes with other solvent.
Silicon atom with respect to polysiloxane (A) is had is scaled SiO
2The total of value measure 100 mass parts, 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 after a little while.
This solvent (D) has the effect of the liquid diffusion when making coating, particularly can obtain the excellent film of internal homogeneity.
< other solvent >
Among the present invention, under the prerequisite of not damaging effect of the present invention, can be also with diol solvent (B), solvent (C) and solvent (D) solvent in addition.As the object lesson of other solvent, the alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, diacetone alcohol of can giving an example; Ester classes such as acetone, methyl acetate, ethyl acetate, ethyl lactate; N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide, DMAC N,N, gamma-butyrolacton, dimethyl sulfoxide, tetramethylurea (TMU), 6-methyl phosphonic triamide, metacresol etc.
< other composition >
Among the present invention; Under the prerequisite of not damaging effect of the present invention; Can comprise except that polysiloxane (A), diol solvent (B), solvent (C) and other composition the solvent (D), for example compositions 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, particulates such as silicon dioxide microparticle, alumina particulate, titanium dioxide fine particles and magnesium fluoride particulate preferably, the colloidal solution of these inorganic particles is preferred especially.This colloidal solution can be with the inorganic particles powder be scattered in dispersion medium and colloidal solution, also can be commercially available colloidal solution.
Among the present invention,, can give the surface configuration and other function of formed curing tunicle through containing inorganic particles.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 surpasses 0.2 μ m, use the transparency of the curing tunicle of the coating fluid formation of being modulated to descend sometimes.
As the dispersion medium of inorganic particles, can give an example water and organic solvent.As colloidal solution, form angle from tunicle with the stability of coating fluid, pH or pKa preferably adjust to 1～10, more preferably adjust to 2～7.
As the organic solvent of the dispersion medium that is used for colloidal solution, the methyl alcohol of can giving an example, ethanol, propyl alcohol, butanols, monoethylene glycol, propylene glycol, butylene glycol, pentanediol, 2-methyl-2, alcohols such as 4-pentanediol, diethylene glycol, DPG, ethylene glycol ether; Ketone such as MEK, methyl isobutyl ketone; Toluene, xylene etc. are aromatic hydrocarbon based; Amide-types such as dimethyl formamide, dimethyl acetamide, N-Methyl pyrrolidone; Ester classes such as ethyl acetate, butyl acetate, gamma-butyrolacton; Tetrahydrofuran, 1, ethers such as 4-two
alkane.Wherein, alcohols and ketone are preferred.These organic solvents can be separately or are mixed more than 2 kinds and be used as dispersion medium and use.
As metal oxygen alkane oligomer or metal oxygen alkane polymkeric substance, can use the 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 article, also can be the goods that obtain by monomers such as metal alkoxide, nitrate, hydrochloride, carboxylates through common methods such as hydrolysis.
Among the present invention,, the refractive index of solidifying tunicle is improved, perhaps give photonasty through containing metal oxygen alkane oligomer or metal oxygen alkane polymkeric substance.When using metal oxygen alkane oligomer or metal oxygen alkane polymkeric substance, can when synthetic polysiloxane (A), use simultaneously, also can after synthetic, be added in the polysiloxane (A).
Examples of commercially available metal oxide or a metal oxide oligomer, specific examples of hydrocarbon polymers may, for example to children Quality Corporation (co-co-a coat Hikaru company) Built methyl silicate 51, Methyl Silicate 53A, ethyl silicate ester 40, ethyl silicate 48, EMS-485, SS-101 and other silicone oligomer or silicone polymer, Kanto Chemical Co., Inc. (manufactured by Kanto Chemical Co., Inc.) made of titanium n-butoxy titanium tetramer siloxane (チ Tatari Bruno キ thermal nn) oligomers.They can separately or mix more than 2 kinds and use.
In addition, levelling agent and surfactant etc. can use known reagent, and particularly commercially available article are preferred because of obtaining easily.
In addition, the method for in polysiloxane (A), mixing other above-mentioned composition can be to mix simultaneously with the solution and the diol solvent (B) of polysiloxane (A), also can after they mix, mix, not special the qualification.
< modulation of aligning agent for liquid crystal >
The modulator approach of aligning agent for liquid crystal of the present invention is not special to be limited.As long as polysiloxane (A) and diol solvent (B), solvent (C) and solvent (D) and other composition are the state that homogeneous mixes.
Usually, polysiloxane (A) polycondensation in solvent is so obtain with the state of solution.Therefore, easy method is directly to use the polymeric solution of above-mentioned polysiloxane (A).Polymer solvent at polysiloxane (A) is under the situation of diol solvent (B) or solvent (C) or solvent (D), can add diol solvent (B) or solvent (C) or solvent (D) afterwards.In addition, do not contain under the situation of diol solvent (B) or solvent (C) or solvent (D), can when the modulation aligning agent for liquid crystal, add diol solvent (B) or solvent (C) or solvent (D) and use at the solution of polysiloxane (A).
During the modulation aligning agent for liquid crystal, the SiO in the aligning agent for liquid crystal
2Conversion concentration is preferably 0.5～15 quality %, more preferably 1～6 quality %.If at such SiO
2In the conversion concentration range, then just obtain required thickness through once being coated with easily, obtain the storage life of enough solution easily.
In addition, be used for SiO this moment
2The solvent of the adjustment of conversion concentration can use the polymer solvent that is selected from polysiloxane (A), at least a kind of solvent that adds solvent and diol solvent (B).
Aligning agent for liquid crystal of the present invention can form the internal homogeneity of film and the excellent liquid crystal orientation film of edge grazing of film end through ink-jet application.
< liquid crystal orientation film and forming method thereof >
As the coating process of the aligning agent for liquid crystal that is used to form liquid crystal orientation film, the spin-coating method of can giving an example, print process, ink-jet application method, spraying process, rolling method etc., but can expect that the higher ink-jet application method of productivity gets most of the attention.
The ink-jet application method is with the fine droplets of on substrate, dripping, infiltration diffusion and the method for film forming through liquid.
Aligning agent for liquid crystal of the present invention has good coating, under the occasion of using the 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 to obtain cured film.
For using ink-jet application method film forming more equably, liquid must stably spue from the nozzle of ink-jet.One of the key factor of liquid of stably spuing is relevant with the viscosity of liquid.The preferred liquid viscosity of aligning agent for liquid crystal is according to the difference of used ink-jet coating apparatus and difference; The scope that for E type viscosimeter (the for example system TV-20 of Toki Sangyo Co., Ltd. (bundle machine industry society)), preferably is about 1.8～18mPas (measuring 25 ℃ of temperature), more preferably 3～15mPas.
In addition, as one of key factor that makes the drop diffusion of dripping, the surface tension of liquid also has very big influence.The surface tension of liquid of aligning agent for liquid crystal is according to the difference of material therefor kind and difference, sessile drop method (the system AUTO DISPENCER AD-3 of the interface science of for example coordinating Co., Ltd. (consonance interface science society), measure 25 ℃ of temperature) preferably is about the scope of 20～40mN/m.
Aligning agent for liquid crystal preferred viscosities of the present invention is 1.8～18mPas (measuring 25 ℃ of temperature), and surface tension is 20～40mN/m (measuring 25 ℃ of temperature).
Drying process behind the coating of liquid crystalline alignment agent is optional, but after coating, under the situation of during this period of time each piece substrate not being burnt till after the fixing or coating immediately before burn till, preferably includes drying process.In this drying, solvent evaporation to the shape of filming does not limit for this drying means is special not because of the degree that the carrying of substrate etc. is out of shape gets final product.For example, can give an example on 40～150 ℃ of temperature, preferred 60～100 ℃ heating plate dry 0.5～30 minute, preferred 1～5 minute method.
Film to burn till and process cured film through what above-mentioned method coating of liquid crystalline alignment agent formed.At this moment, firing temperature can be 100～350 ℃ a arbitrary temp, preferably 140 ℃～300 ℃, be more preferably 150 ℃～230 ℃, and being more preferably is 160 ℃～220 ℃.
Polysiloxane in the liquid crystal orientation film (A) carries out polycondensation in firing process.But, among the present invention, under the prerequisite of not damaging effect of the present invention, need not make its complete polycondensation.But, preferably in manufacturing process, burn till under the high temperature more than 10 ℃ of heat treatment temperature of required sealant cures etc. than liquid crystal structure cell.
The thickness of this cured film can be selected as required.The thickness of cured film is when 5nm is above, and the reliability of liquid crystal display cells obtains easily, so be preferred.Be more preferably more than 10nm.In addition, when 300nm was following, the consumes electric power 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 the light etc. of friction treatment or irradiation polarized light or specific wavelength to this cured film, or carries out the processing etc. of ion beam etc., thereby processes liquid crystal orientation film.
The liquid crystal orientation film of the present invention that is formed by said method demonstrates high hydrophobicity, therefore can obtain good liquid crystal vertical-tropism property.
< liquid crystal display cells >
Liquid crystal display cells of the present invention can through above-mentioned method after forming liquid crystal orientation film on the substrate, process the liquid crystal structure cell with known method and obtain.
The example that the liquid crystal structure cell is made if will give an example, usual method is that the 1 pair of substrate that has formed liquid crystal orientation film is clipped sept, fixes with sealant, seals behind the injection liquid crystal.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 special to be limited, and can give an example the vacuum method that injects liquid crystal after the decompression in the liquid crystal structure cell of processing, drip the dripping method of the laggard row sealing of liquid crystal etc.
As the substrate that is used for liquid crystal display cells, so long as the high substrate of the transparency get final product, not special qualification normally is formed with the substrate of the transparency electrode that is used to drive liquid crystal on substrate.As concrete example, can give an example at glass plate or polycarbonate, gather the substrate that is formed with transparency electrode on plastic plates such as (methyl) acrylic ester, 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 the substrate that between electrode that is used for liquid crystal drive and substrate, is formed with such as transistorized element.
Under the occasion of the liquid crystal cell of transmission-type, use aforesaid substrate usually, but, also can only use opaque substrates such as silicon wafer at a side group plate for reflection type liquid crystal display element.At this moment, the electrode that on substrate, forms also can use catoptrical material such as aluminium.
Embodiment
Below explain more specifically through embodiments of the invention, but be not interpreted as receive this limit.
The abbreviation of used compound is following in the present embodiment.
TEOS: tetraethoxysilane
C18: octadecyltriethoxy silane
UPS:3-urea groups propyl-triethoxysilicane
HG:2-methyl-2, the 4-pentanediol
The BCS:2-butyl cellosolve
PB:1-butoxy-2-propyl alcohol
1,3-BDO:1,3-butylene glycol
The NMP:N-N-methyl-2-2-pyrrolidone N-
DEDE: diethylene glycol diethyl ether
EDM: glycol dimethyl ether
MIBK: methyl isobutyl ketone
The C8OH:1-octanol
< synthetic example 1 >
In 1 liter of (L) four-hole reaction flask of thermometer, recirculatory pipe is housed, drop into the HG of 22.6g, the BCS of 7.5g, the TEOS of 39.6g and C18 and the stirring of 4.2g, process the solution of alkoxy silane monomer.In this solution, under room temperature, be pre-mixed with the oxalic acid of the water of the BCS of the HG that dripped 11.3g in 30 minutes, 3.8g, 10.8g and 0.2g as catalyzer and oxalic acid solution, drip and finish the back and under room temperature, stirred 30 minutes.Then, put after heating 1 hour down coldly refluxing, obtaining SiO2 conversion solid component concentration is the polysiloxane solution (K1) of 12 quality %.
< synthetic example 2 >
In the 1L four-hole reaction flask of thermometer, recirculatory pipe is housed, drop into the HG of 30.2g, the TEOS of 39.6g and C18 and the stirring of 4.2g, process the solution of alkoxy silane monomer.In this solution, under room temperature, be pre-mixed with the oxalic acid of the water of the HG that dripped 15.1g in 30 minutes, 10.8g and 0.2g as catalyzer and oxalic acid solution, drip and finish the back and under room temperature, stirred 30 minutes.Then, put after heating 1 hour down coldly refluxing, obtain SiO
2The conversion solid component concentration is the polysiloxane solution (K2) of 12 quality %.
< synthetic example 3 >
In the 1L four-hole reaction flask of thermometer, recirculatory pipe is housed, drop into the BCS of 30.2g, the TEOS of 39.6g and C18 and the stirring of 4.2g, process the solution of alkoxy silane monomer.In this solution, under room temperature, be pre-mixed with the oxalic acid of the water of the BCS that dripped 15.1g in 30 minutes, 10.8g and 0.2g as catalyzer and oxalic acid solution, drip and finish the back and under room temperature, stirred 30 minutes.Then, put after heating 1 hour down coldly refluxing, obtain SiO
2The conversion solid component concentration is the polysiloxane solution (K3) of 12 quality %.
< synthetic example 4 >
In the 1L four-hole reaction flask of thermometer, recirculatory pipe is housed, drop into the HG of 23.0g, the BCS of 7.7g, the TEOS of 40.4g and C18 and the stirring of 0.8g, process the solution of alkoxy silane monomer.In this solution, under room temperature, be pre-mixed with the oxalic acid of the water of the BCS of the HG that dripped 11.5g in 30 minutes, 3.8g, 10.8g and 0.2g as catalyzer and oxalic acid solution, drip and finish the back and under room temperature, stirred 30 minutes.Then, drop into the mixed solution of BCS of HG, the 0.16g of UPS 92 quality % methanol solutions, the 0.48g of 1.15g after 1 hour in the heating down that refluxes, under refluxing, put coldly again after overheated 30 minutes, obtain SiO
2The conversion solid component concentration is the polysiloxane solution (K4) of 12 quality %.
Table 1
< embodiment 1～7, comparative example 3 and 4 >
The polysiloxane solution (K1) that obtains in the synthetic example 1 of 50g and each solvent to reach the solvent composition shown in the table 1, are obtained SiO
2The conversion solid component concentration is the aligning agent for liquid crystal (KL1～7, KM3～4) of 3 quality %.
< embodiment 8 >
The polysiloxane solution (K4) that obtains in the synthetic example 4 of 50g and each solvent to reach the solvent composition shown in the table 2, are obtained SiO
2The conversion solid component concentration is the aligning agent for liquid crystal (KL8) of 3 quality %.
< comparative example 1 >
The polysiloxane solution (K2) that obtains in the synthetic example 2 of 50g is mixed with the HG of 150g and stirs, obtain SiO
2The conversion solid component concentration is the aligning agent for liquid crystal (KM1) of 3 quality %.
< comparative example 2 >
The polysiloxane solution (K3) that obtains in the synthetic example 3 of 50g is mixed with the BCS of 150g and stirs, obtain SiO
2The conversion solid component concentration is the aligning agent for liquid crystal (KM2) of 3 quality %.
Table 2
The solution viscosity and the surface tension of the aligning agent for liquid crystal that obtains in embodiment 1～8 and the comparative example 1～4 are shown in table 3.In addition, solution viscosity and surface tension are measured in order to following method.
[solution viscosity]
Use E type viscosimeter (the system TV-20 of Toki Sangyo Co., Ltd. (bundle machine industry society)), measure down for 25 ℃ in temperature.
[surface tension]
Use the system AUTO DISPENCER AD-3 of consonance interface science Co., Ltd. (consonance interface science society) to measure.
Table 3
[ink-jet application]
Ink-jet application is carried out with following apparatus, condition.
Device name: device technique Co., Ltd. of Hitachi (the プ ラ of Hitachi Application ト テ Network ノ ロ ジ one 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 ℃ of baking temperatures, 2 minutes drying times (heating plate).
[coating]
Through film visual and the microscopic examination gained, confirm coating.
Can film forming: can zero defect ground film forming person be zero, not the able one be *.
Internal homogeneity: in the face of film the homogeneous person be zero, produce orange peel or wire inequality person be *.
The edge grazing: the very good person of grazing is zero, grazing difference person for *.
Table 4
Visible from table 4, comparative example 1 and comparative example 4 can not film forming, and embodiment 1～8 compares with comparative example 2,3, and internal homogeneity and edge grazing are good, the coating raising.
[making of liquid crystal structure cell]
Prepare 2 glass substrates with the transparency electrode that has formed liquid crystal orientation film; After the liquid crystal aligning face of a substrate scatters the sept of 6 μ m; After the outer edge of substrate is bonding agent through silk screen print method coating epoxy; With the bonding and crimping of the relative mode of liquid crystal orientation film, solidify then and process empty structure cell.After this empty structure cell injects the system MLC-6608 of Merck & Co., Inc. (メ Le Network society) (trade name) through vacuum impregnation,, process liquid crystal structure cell (cell) through UV cured resin sealing filling orifice.At this moment, use is the liquid crystal orientation film that method with record in above-mentioned among the embodiment [ink-jet application] forms the thickness 80nm that films, after on the heating plate of 80 ℃ of temperature dry 5 minutes, burnt till 60 minutes with the heated air circulation type cleaning oven of 200 ℃ of temperature and get.And in the comparative example, use be except replace the liquid crystal orientation film of the thickness 100nm that the method identical with embodiment obtains the ink-jet application with spin-coating method.
[liquid crystal aligning property]
With the liquid crystal structure cell that polarized light microscope observing is processed through above-mentioned [making of liquid crystal structure cell] method, confirm the state of orientation of liquid crystal.The situation that liquid crystal structure cell integral body is flawless homogeneous state of orientation is zero, the part of liquid crystal structure cell find the situation and the not vertical orientated situation of orientation defective be *.Its result is shown in table 5.
[contact angle]
Drip 3 μ L pure water to liquid crystal orientation film, use the automatic contact angle meter CA-Z type of consonance interface science Co., Ltd. (consonance interface science (strain) society) system, measure contact angle.Its result is shown in table 5.
What use is the liquid crystal orientation film that method with record in above-mentioned among the embodiment [ink-jet application] forms the thickness 80nm that films, after on the heating plate of 80 ℃ of temperature dry 5 minutes, burnt till 60 minutes with the heated air circulation type cleaning oven of 200 ℃ of temperature and get.And in the reference example, use be except replace the liquid crystal orientation film of the thickness 100nm that the method identical with embodiment obtains the ink-jet application with spin-coating method.
Table 5
| Alignment agent | Coating process | Liquid crystal aligning property | The contact angle of water/° | |
| Measure example | KL1 | The ink-jet application method | ○ | 89 |
| Reference example | KL1 | Spin-coating method | ○ | 87 |
Can know from table 5, even the liquid crystal orientation film that is obtained by the ink-jet application method also demonstrates and the equal vertical orientated property of film that obtained by other method.
Utilize possibility on the industry
The internal homogeneity of the film of the liquid crystal orientation film that is obtained with aligning agent for liquid crystal by ink-jet application of the present invention and the edge grazing of film end are excellent, therefore use the liquid crystal display cells of this liquid crystal orientation film can be suitable as the high liquid crystal display device of reliability and use.
In addition, quote of the announcement of the full content of Japanese patent application 2008-329123 number of filing an application on Dec 25th, 2008 and Japanese patent application 2009-001359 number instructions, claims and the summary of filing an application on January 7th, 2009 here as instructions of the present invention.
Claims (14)
1. ink-jet application is used aligning agent for liquid crystal, it is characterized in that, contains the polysiloxane (A) with the side chain that is constituted by the alkyl of fluorine atom replacement or unsubstituted carbon number 8～30, diol solvent (B), following solvents (C) and the solvent (D) of carbon number 2～7,
Solvent (C): the solvent of formula (A1) expression,
K
1O(CH
2)
wOH (A1)
In the formula, K
1Be the alkyl of carbon number 1～4, w is 1～3 integer,
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 3～6 carbon atoms are arranged and carbon number 5～12,
In the formula, X
1, X
3And X
5Be the alkyl of carbon number 1～4, X
2And X
6Be the alkyl of hydrogen atom or carbon number 1～4, X
4Be 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, and h is 2～3 integer.
2. ink-jet application as claimed in claim 1 is used aligning agent for liquid crystal, it is characterized in that, solvent (D) is the solvent that is selected from the alkylol of formula (the T1)～compound of formula (T3), the ketone that 3～6 carbon atoms are arranged and carbon number 5～12.
3. according to claim 1 or claim 2 ink-jet application is used aligning agent for liquid crystal, it is characterized in that, polysiloxane (A) be by the alkoxy silane polycondensation of the alkoxy silane that contains formula (1) expression polysiloxane,
R
1Si(OR
2)
3 (1)
R
1For replaced or the alkyl of unsubstituted carbon number 8～30 R by fluorine atom
2Alkyl for carbon number 1～5.
4. ink-jet application as claimed in claim 3 is used aligning agent for liquid crystal, it is characterized in that, polysiloxane (A) is the polysiloxane that is got by the alkoxy silane polycondensation of the alkoxy silane of alkoxy silane that contains formula (1) expression and following formula (2) expression,
(R
3)
nSi(OR
4)
4-n (2)
R
3Alkyl for hydrogen atom, halogen atom, vinyl or carbon number 1～7; At this moment, any hydrogen atom of said alkyl can be replaced by glycidoxy, sulfydryl, methacryloxy, acryloxy, NCO, amino or urea groups, and can have heteroatoms; R
4Be the alkyl of carbon number 1～5, n is 0～3 integer.
5. use aligning agent for liquid crystal like claim 3 or 4 described ink-jet application, it is characterized in that, polysiloxane (A) is the polysiloxane that is got by the alkoxy silane polycondensation of the alkoxy silane of alkoxy silane that contains formula (1) expression and following formula (3) expression,
Si(OR
4)
4 (3)
R
4Alkyl for carbon number 1～5.
6. use aligning agent for liquid crystal like each described ink-jet application in the claim 1～5, it is characterized in that, diol solvent (B) is to be selected from monoethylene glycol, diethylene glycol, DPG, 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, the solvent more than a kind of 7-heptandiol.
7. use aligning agent for liquid crystal like each described ink-jet application in the claim 1～6, it is characterized in that, the X in the said formula (T1)
2Be hydrogen atom.
8. use aligning agent for liquid crystal like each described ink-jet application in the claim 1～7, it is characterized in that, be scaled SiO with respect to the silicon atom that polysiloxane (A) is had
2The total of value measure 100 mass parts, diol solvent (B) is 20～18000 mass parts, solvent (C) is 2～17500 mass parts, solvent (D) is 2～17500 mass parts.
9. use aligning agent for liquid crystal like each described ink-jet application in the claim 1～8, it is characterized in that, be scaled SiO with respect to the silicon atom that polysiloxane (A) is had
2The total of value measure 100 mass parts, diol solvent (B) is 120～17000 mass parts, solvent (C) is 2～16800 mass parts, solvent (D) is 2～16800 mass parts.
10. use aligning agent for liquid crystal like each described ink-jet application in the claim 1～9, it is characterized in that, the viscosity of said alignment agent is 1.8～18mPas.
11. use aligning agent for liquid crystal, it is characterized in that the surface tension of said alignment agent is 20～40mN/m like each described ink-jet application in the claim 1～10.
12. liquid crystal orientation film burns till after coating on the substrate with aligning agent for liquid crystal with ink discharge device each described ink-jet application in the claim 1～11 and gets.
13. the formation method of liquid crystal orientation film is burnt till after coating on the substrate with aligning agent for liquid crystal with ink discharge device each described ink-jet application in the claim 1～11 and is obtained liquid crystal orientation film.
14. liquid crystal display cells has the described liquid crystal orientation film of claim 12.
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| JP2008-329123 | 2008-12-25 | ||
| JP2008329123 | 2008-12-25 | ||
| JP2009001359 | 2009-01-07 | ||
| JP2009-001359 | 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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| CN102317848B CN102317848B (en) | 2014-06-11 |
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| CN103666486A (en) * | 2012-08-30 | 2014-03-26 | Jsr株式会社 | Liquid crystal orientation agent, liquid crystal orientation film, manufacturing method of liquid crystal orientation film, and liquid crystal display element |
| CN104822783A (en) * | 2012-10-03 | 2015-08-05 | 日产化学工业株式会社 | Application liquid capable of fine application, for forming inorganic oxide coating film, and method for manufacturing fine inorganic oxide coating film |
| CN104903785A (en) * | 2012-10-05 | 2015-09-09 | 日产化学工业株式会社 | Manufacturing method for substrate having liquid crystal alignment film for in-plane switching-type liquid crystal display element |
| CN106047373A (en) * | 2015-04-14 | 2016-10-26 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, and liqud crystal element |
| CN109722259A (en) * | 2017-10-30 | 2019-05-07 | 捷恩智株式会社 | The preparation method of aligning agent for liquid crystal, the forming method of liquid crystal orientation film and display element |
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| TWI553040B (en) * | 2011-05-27 | 2016-10-11 | Nissan Chemical Ind Ltd | Silicon liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display components |
| 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 |
| CN104054019B (en) * | 2011-11-17 | 2016-11-09 | 日产化学工业株式会社 | Silicon system aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells |
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Also Published As
| Publication number | Publication date |
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| TWI457370B (en) | 2014-10-21 |
| TW201038628A (en) | 2010-11-01 |
| WO2010074261A1 (en) | 2010-07-01 |
| KR101708949B1 (en) | 2017-02-21 |
| KR20110104535A (en) | 2011-09-22 |
| CN102317848B (en) | 2014-06-11 |
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