CN101243149B - Method for producing coating liquid for film formation - Google Patents

Method for producing coating liquid for film formation Download PDF

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CN101243149B
CN101243149B CN2006800294371A CN200680029437A CN101243149B CN 101243149 B CN101243149 B CN 101243149B CN 2006800294371 A CN2006800294371 A CN 2006800294371A CN 200680029437 A CN200680029437 A CN 200680029437A CN 101243149 B CN101243149 B CN 101243149B
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tunicle
solvent
coating fluid
solution
obtains
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CN101243149A (en
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沼尻悟
元山贤一
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
    • H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating

Abstract

Disclosed is a method for producing a coating liquid which enables to form a coating film that is sufficiently cured under low-temperature curing conditions and enables to form an alignment film thereon which is suppressed in repelling or pinholes. Specifically disclosed is a method for producing a coating liquid for film formation characterized by comprising a step for obtaining a solution whichcontains a condensation product produced by subjecting a metal alkoxide (A) to a hydrolysis-condensation reaction in a solvent (B) [step 1], and a step for obtaining a solution by substituting the solution obtained in step 1 with a solvent (C) [step 2]. In this connection, the metal alkoxide (A) is at least one metal alkoxide selected from compounds represented by the following formula (1): Ti(OR<SUP>1</SUP>)<SUB>4</SUB> (1) (wherein R<SUP>1</SUP> represents an alkyl group having 1-5 carbon atoms); the solvent (B) is at least one organic solvent selected from the group consisting of alcohols having 1-10 carbon atoms, esters having 2-5 carbon atoms, tetrahydrofuran, and ethers having 2-5 carbon atoms; and the solvent (C) is at least one organic solvent selected from glycols having 2-10 carbon atoms.

Description

Tunicle forms the manufacture method with coating fluid
Technical field
The present invention relates to tunicle and form the manufacture method of using coating fluid.Specifically relate to the tunicle that forms the tunicle that contains titanium atom and form the manufacture method of using coating fluid.
Background technology
Be accompanied by the maximization of liquid crystal display device,, form the operation of oxide compound tunicle for the insulation of transparency electrode, the purpose of protection.The formation method of oxide compound tunicle, known have with vapour deposition method, sputtering method etc. be the vapor phase process of representative and use the oxide compound tunicle to form coating method with coating fluid.Wherein, the tunicle on productivity, the large substrate forms the viewpoint of easiness, adopts coating method more.As coating fluid, the known hydrolysate that tetraalkoxysilane arranged and with the mixture of other metal alkoxides, metallo-chelate.
When preparing coating fluid with metal alkoxides, except that the organosilane oxide compound, the hydrolysis rate of the general metal alkoxides that uses is slow.Therefore, in order to regulate the hydrolysis rate of metal alkoxides, attempt utilizing the effect of sequestrants such as methyl ethyl diketone.But the pyrolysis temperature of the compound behind the chelating improves usually, and sintering is be advisable more than 450 ℃ (for example with reference to patent documentation 1).
As additive method, having attempted at silica-titania is in the coating fluid, by add mineral acid in the hydrolysate of organosilane oxide compound and titan-alkoxide, makes transparent coating agent under the situation of not using stabilization means such as chelating.Even in this case, also need sintering (for example with reference to patent documentation 2) more than 300 ℃ at least.
In recent years, be accompanied by the lightening of liquid crystal display device, based on the resistance change of the ELD of using in the liquid crystal display device, the slimming of base plate glass, the problems such as thermotolerance of spectral filter, wish to reduce the formation temperature of insulating film (oxide compound tunicle).In addition, based on situations such as the manufacturing cost reduction of liquid crystal display device, energy-conservation orientations, particularly for more and more higher in the demand of solidified insulating film below 250 ℃ (oxide compound tunicle).
Meanwhile, become more meticulous about the height of liquid crystal display device, the depression of the liquid crystal orientation film that is caused by insulating film, pin hole etc. are big to the display characteristic influence of liquid crystal display device, therefore wish to improve insulating film.In addition, also wish to improve along with above-mentioned improvement makes the qualification rate of liquid crystal display device in manufacturing processed.
Patent documentation 1: the Japanese Patent spy opens clear 63-258959 communique
Patent documentation 2: the Japanese Patent spy opens clear 55-25487 communique
The announcement of invention
The object of the present invention is to provide the tunicle that can under 150～250 ℃ of such low-temperature curing conditions, form abundant solidified tunicle and can on this tunicle, form the alignment films that has suppressed depression and pin hole to form the manufacture method of using coating fluid.
The present inventor In view of the foregoing concentrates on studies, thereby has finished the present invention.
That is, technology contents of the present invention is as described below.
1. tunicle forms the manufacture method with coating fluid, it is characterized in that having following operation:
[operation 1] obtains containing the solution of the condenses that makes metal alkoxides (A) be hydrolyzed condensation reaction in solvent (B) and generate;
[operation 2], the solution after the solution that obtains obtaining in described [operation 1] is replaced with solvent (C).
Wherein, metal alkoxides (A) be the compound that is selected from formula (1) expression (in the formula, R 1The expression carbonatoms is 1～5 alkyl) at least a kind of metal alkoxides;
Ti(OR 1) 4 (1)
Solvent (B) is that to be selected from carbonatoms be that 1～10 alcohol, carbonatoms are that 2～5 ester, tetrahydrofuran (THF) and carbonatoms are at least a kind of organic solvent in 2～5 ethers; Solvent (C) is that to be selected from carbonatoms be at least a kind of organic solvent in 2～10 the glycol.
2. according to 1 described manufacture method, wherein, metal alkoxides (A) also contains at least a kind of organoalkoxysilane in the compound of the formula of being selected from (2) expression.
(R 2) nSi(OR 3) 4-n (2)
In the formula, R 2Expression alkyl, alkenyl or aryl, R 3The expression carbonatoms is 1～5 alkyl, and n represents 0～2 integer.
3. according to above-mentioned 2 described manufacture method, wherein, organoalkoxysilane is that the n that is selected from formula (2) is at least a kind of silicon compound in 0 the compound.
4. form manufacture method with coating fluid according to each described tunicle in above-mentioned 1～3, wherein, it is 0.05～4 mole organoalkoxysilane that metal alkoxides (A) contains with respect to 1 mole of alkoxy titanium.
5. according to each described manufacture method in above-mentioned 1～4, wherein, in [operation 1], use a kind or the multiple catalyzer that is selected from metallic salt.
6. according to each described manufacture method in above-mentioned 1～5, wherein, have [operation 3] that the solution that obtains to [operation 2] adds the solvent (D) that dissolves each other with this solution.
7. tunicle forms and to use coating fluid, obtains with each described manufacture method in above-mentioned 1～6.
8. tunicle obtains with coating fluid with above-mentioned 7 described tunicles formation.
9. insulating film obtains with coating fluid with above-mentioned 7 described tunicles formation.
10. the used for liquid crystal display element substrate has the tunicle that forms with coating fluid with above-mentioned 7 described tunicles formation.
11. liquid crystal display device has the tunicle that forms with coating fluid with above-mentioned 7 described tunicles formation.
Tunicle formation coating fluid with manufacture method of the present invention obtains can fully solidify under 150～250 ℃ of such low-temperature curing conditions, and can form the liquid crystal orientation film that has suppressed depression and pin hole on this tunicle.Therefore, useful in the manufacturing of the liquid crystal display device of display characteristic excellence.
The simple declaration of accompanying drawing
[Fig. 1] tunicle forms the weight decrement measurement result with the dried powder (comparative example) of the dried powder (embodiment) of coating fluid Z2 and coating fluid T1.
[Fig. 2] tunicle forms the differential thermal measurement result with the dried powder (comparative example) of the dried powder (embodiment) of coating fluid Z2 and coating fluid T1.
The best mode that carries out an invention
The present invention is that the maximum that tunicle forms with the manufacture method of coating fluid is characterised in that, has that promptly to be selected from carbonatoms from solvent (B) be that 1～10 alcohol, carbonatoms are that 2～5 ester, tetrahydrofuran (THF) and carbonatoms are that at least a kind of organic solvent 2～5 the ether is the solvent exchange operation of diol replaces to solvent (C).Use coating fluid with the tunicle formation that manufacture method of the present invention obtains, can be provided at abundant solidified tunicle under 150～250 ℃ of such low temperature.And, when this tunicle is used as the electrode protective membrane (insulating film) of liquid crystal display device, have the effect of following excellence: can on this tunicle, print liquid crystal orientation film, and then can form the alignment films that has suppressed depression and pin hole.
In the past, used the hydrolysis-condensation reaction of titan-alkoxide, in pure equal solvent, in the presence of stablizers such as methyl ethyl diketone or glycol, carried out for the hydrolysis rate of regulating titan-alkoxide.This makes the titan-alkoxide condensation reaction that is hydrolyzed under stable status, generate condenses.Relative therewith, the present invention is hydrolyzed condensation reaction and after generating condenses, carries out solvent exchange with glycol at the metal alkoxides that contains titan-alkoxide.
Be that stablizer coordinate titan-alkoxides such as glycol or the metal alkoxides that contains titan-alkoxide are hydrolyzed condensation reaction and generate condenses in the past.The latter (the present invention) is hydrolyzed condensation reaction and carries out the glycol coordination after generating condenses at titan-alkoxide or the metal alkoxides that contains titan-alkoxide.
The unusual effect that consideration obtains by the present invention is inferred the condenses that generates in the reaction of in the past carrying out and is very different states as the co-ordination state between the glycol of stablizer and condenses and the co-ordination state between the glycol by the present invention's generation.
The particularly titanium atom of condensation body and the co-ordination state between the glycol, glycol is in the state of easier disengaging in the present invention.
And this co-ordination state continues to keep in coating fluid and therefrom filming, and therefore infers that it is achieved effect of the present invention.
In other words,, can think that the disengaging of glycol is relatively easy among the latter (the present invention) for the former, thereby the easily curing of filming at low temperatures.
In addition, when using as the electrode protective membrane (insulating film) of liquid crystal display device filming, the coordinate glycol is few on the titanium atom in filming, and this depression and pin hole with the inhibition liquid crystal orientation film is relevant.That is,, when using as the electrode protective membrane (insulating film) of liquid crystal display device, has good this very excellent effect of the printing that makes liquid crystal orientation film with filming for the present invention.
Below, specify the present invention.
About [operation 1]:
In this operation 1, with metal alkoxides (A) condensation reaction that in solvent (B), is hydrolyzed.
As the metal alkoxides (A) that uses in this operation 1, adopt at least a kind of titan-alkoxide in the compound that is selected from formula (1) expression.
Ti(OR 1) 4 (1)
In the formula, R 1The expression carbonatoms is 1～5, is preferably 2～4 alkyl.
As the object lesson of four titan-alkoxides of formula (1) expression, can enumerate tetramethoxy titanium, purity titanium tetraethoxide, tetraisopropoxy titanium, four positive propoxy titaniums, four titanium n-butoxide, four isobutoxy titaniums, four tert.-butoxy titaniums, four pentyloxy titaniums etc.Be preferably purity titanium tetraethoxide, tetraisopropoxy titanium or four titanium n-butoxide.
(A) composition that uses in the operation 1, if with at least a kind in the titan-alkoxide of formula (1) expression as must composition, be not subjected to particular restriction.Therefore, for example can be also with the metal alkoxides (hereinafter referred to as other metal alkoxides) beyond the titan-alkoxide of formula (1) expression.As these other metal alkoxides, can enumerate the metal alkoxides of Si, Al, Sn, In, Bi, Zn, Pb, Ti, Ta, Mn, Zr etc.These other metal alkoxides can suitably selectively use from the compound with 1 above alkoxyl group as required, also can multiple and usefulness.
Wherein, organosilane oxide compound (hereinafter referred to as organoalkoxysilane) enriches owing to kind and is easy to buy from market, thereby easy to use.In the time of particularly will being used for liquid crystal display device with coating fluid by the tunicle that manufacture method of the present invention obtains, the specific refractory power of the tunicle that is obtained with coating fluid by tunicle is easy to regulate, thereby preferred.
The organoalkoxysilane that use this moment can be a monomer, also can use the condensation body of methyl silicate and tetraethyl silicate, can use a kind of therefrom selecting or multiple.
Object lesson as the condensation body of methyl silicate and tetraethyl silicate, can enumerate ethyl silicate 40 (trade(brand)name, the chemical industrial company's system of rubbing) more, tetraethyl silicate 48 (trade(brand)names, Japan's Crockett (COLCOAT) corporate system), MKC silicon ester (MKC Silicate, trade(brand)name, Mitsubishi Chemical Ind's system), east beautiful DOW CORNING (TORAYDOW CORNING) corporate system silicone resin, GE Toshiba organosilicon (GETOSHIBA SILICONES) corporate system silicone resin, chemical industrial company of SHIN-ETSU HANTOTAI is shaped on the machine silicone resin, the polydimethylsiloxane of DOW CORNING Asia (DOW CORNINGASIA) corporate system hydroxyl, Japan You Lika (UNICA) corporate system organosilicon oligopolymer etc.
In the present invention, especially preferably use the organoalkoxysilane of formula (2) expression, can use a kind of therefrom selecting or multiple.
(R 2) nSi(OR 3) 4-n (2)
In the formula, R 2Expression alkyl, alkenyl, aryl, R 3The expression carbonatoms is 1～5 alkyl, and n represents 0～2 integer.
Below, enumerate the object lesson of the organoalkoxysilane of above-mentioned formula (2) expression, but be not limited thereto.
Can enumerate tetraalkoxysilanes such as tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes; Methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, butyl trimethoxy silane, the butyl triethoxyl silane, amyltrimethoxysilane, amyl triethoxysilane, the heptyl Trimethoxy silane, the heptyl triethoxyl silane, the octyl group Trimethoxy silane, octyltri-ethoxysilane, the dodecyl Trimethoxy silane, the dodecyl triethoxyl silane, the hexadecyl Trimethoxy silane, the hexadecyl triethoxyl silane, the octadecyl Trimethoxy silane, octadecyltriethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, γ-urea groups propyl trimethoxy silicane, γ-urea groups propyl-triethoxysilicane, the trifluoro propyl Trimethoxy silane, the trifluoro propyl triethoxyl silane, ten trifluoro octyl group Trimethoxy silanes, ten trifluoro octyltri-ethoxysilane, 17 fluorine decyl Trimethoxy silanes, trialkoxy silanes such as 17 fluorine decyl triethoxyl silanes; Dialkoxy silicane such as dimethyldimethoxysil,ne, dimethyldiethoxysilane.
In the above-mentioned organoalkoxysilane, n is 0 the easiest acquisition of tetraalkoxysilane, and low price, thereby easy to use.
As (A) composition, when the organoalkoxysilane of use formula (2) expression, with respect to 1 mole of titan-alkoxide, organoalkoxysilane is preferably 0.05～4 mole, is preferably 0.25～4 mole especially, this is easy to obtain following effect: can fully solidify under 150～250 ℃ low temperature, form good the filming of printing of liquid crystal aligning material.
This effect depend in the operation 1 in the condensation body that generates titanium atom and as the co-ordination state between the glycol of (C) composition.Therefore, when organoalkoxysilane during more than 4 moles, the amount of the glycol under above-mentioned coordination and the bonding state reduces relatively, is difficult to obtain effect of the present invention.
In addition, by using the organoalkoxysilane of above-mentioned amount, the specific refractory power that easily will solidify tunicle is regulated arbitrarily in 1.50～2.1 scope.
The solvent (B) that uses in the operation 1 is that to be selected from carbonatoms be 1～10, be preferably 1～8, be preferably 1～4 alcohol, carbonatoms especially is that 2～5 ester, tetrahydrofuran (THF) and carbonatoms are at least a kind of organic solvent in 2～5 the ether.Therefore, multiple can and the using in the solvent (B).
And this solvent (B) is not subjected to particular restriction so long as the solvent of dissolving (A) composition gets final product.Its object lesson is as follows.
For example, can enumerate methyl alcohol, ethanol, 1-propyl alcohol (n-propyl alcohol), 2-propyl alcohol (Virahol), 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, hexanol, octanol, diacetone alcohol, 1-methoxyl group-2-ethanol, 1-oxyethyl group-2-ethanol, 1-methoxyl group-alcohol such as 2-propyl alcohol; Esters such as ethyl acetate, ethyl lactate, butylacetate; Tetrahydrofuran (THF), ether, 1,4-two
Figure 2006800294371_0
Ethers such as alkane etc.
In these solvents (B), preferably select to be difficult to solvent described later (C) azeotropic and normal pressure under vapour pressure be higher than the solvent of solvent (C).By selecting such solvent (B), can carry out efficiently from the displacement of solvent (B) to solvent (C).
In addition, consider, be easy to use methyl alcohol, ethanol, propyl alcohol, butanols etc. from economic aspect.
In the operation 1,,, preferably use catalyzer in order to promote the condensation of (A) composition with the condensation reaction that in solvent (B), is hydrolyzed of (A) composition.The usage quantity of catalyzer with respect to 1 mole of the atoms metal in the metal alkoxides, is preferably 0.005～0.5 mole.
As catalyzer, use acid, alkali, metal inorganic hydrochlorate, organometallic compound etc.Usually, preferably use acid or metal inorganic hydrochlorate.The object lesson of this catalyzer is as follows, but is not limited thereto.
In the acid,, can enumerate hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid etc. as mineral acid.As organic acid, can enumerate monocarboxylic acid classes such as formic acid, acetate, propionic acid; Polycarboxylic acid classes such as oxalic acid, citric acid, oxysuccinic acid, succsinic acid.As alkali, can enumerate mineral alkalis such as ammonia, caustic soda, potassium hydroxide; Monoethanolamine; Diethanolamine; Trolamine; Pyridine etc.
As the metal inorganic hydrochlorate that catalyzer uses, be inorganic acid salt, their subsalt or their hydrate of the hydrochloric acid, nitric acid, sulfuric acid etc. of the metal of IIIa, IVa, Va family or transition metal.
As the metal of IIIa, IVa, Va family, can enumerate Al, In, Sn, Sb, Pb, Bi etc.As transition metal, can enumerate Ti, Mn, Fe, Ni, Zn, Y, Zr, Mo, Cu, W, Ce etc.
As the object lesson of such metal inorganic hydrochlorate, can enumerate aluminum chloride, aluminum nitrate, Tai-Ace S 150, aluminium chlorohydroxide, indium chloride, indium nitrate, tin chloride, antimony chloride, lead chloride, lead nitrate, lead sulfate, bismuth chloride, Bismuth trinitrate, iron(ic) chloride, iron nitrate, ferric sulfate, nickelous chloride, nickelous nitrate, zinc chloride, zinc nitrate, zinc sulfate, Yttrium trichloride, Yttrium trinitrate, zirconium chloride, zirconium nitrate, zirconium sulfate, basic zirconium chloride, zirconyl hydroxynitrate, molybdenum chloride, cupric chloride, cupric nitrate, copper sulfate, tungsten chloride, nitric acid tungsten, Cerium II Chloride, cerous nitrate etc. or their hydrate etc.
In addition, as the object lesson of organometallic compound, can enumerate aluminum acetate, zinc acetate, dibutyl tin laurate, the toxilic acid dibutyl tin, dibutyltin diacetate, stannous octoate, naphthenic acid tin, two (acetopyruvic acid) dibutyl tin, aluminium isopropoxide, diisopropoxy ethyl acetoacetic acid aluminium, diisopropoxy acetopyruvic acid aluminium, isopropoxy two (ethyl acetoacetic acid) aluminium, isopropoxy two (acetopyruvic acid) aluminium, three (ethyl acetoacetic acid) aluminium, three (acetopyruvic acid) aluminium, single acetyl pyruvic acid two (ethyl acetoacetic acid) aluminium, four n-butoxy zirconiums, three n-butoxy ethyl acetoacetic acid zirconiums, two n-butoxy two (ethyl acetoacetic acid) zirconiums, n-butoxy three (ethyl acetoacetic acid) zirconium, four (n-propyl etheric acid) zirconium, four (ethyl acetoacetic acid) zirconium, the partial hydrolysate of four (ethyl acetoacetic acid) zirconium etc. or their compound.
Above-mentioned metal inorganic hydrochlorate and organometallic compound can suitably selectively use as required as long as dissolving in solvent (B) is not subjected to particular restriction.At this moment, can use a kind or multiple and usefulness.
When being used for field of electronic materials, preferable alloy nitrate, its subsalt or its hydrate or organometallic compound.The more preferably nitrate of Al, In, Zn, Zr, Ce, Sn, its subsalt or its hydrate or organometallic compound.
In addition, in operation 1, only otherwise damage effect of the present invention, can be with above-mentioned metal inorganic salt, organometallic compound and other catalyzer and usefulness.
Hydrolysis-condensation reaction in the operation 1 can be in partial hydrolysis and/or the complete hydrolysis any.During complete hydrolysis, in theory, the water that adds 0.5 times of mole of the total alkoxyl group in (A) composition gets final product, and adding is more than the water of 0.5 times excess quantity usually.During partial hydrolysis, the water that adds 0.2～0.5 times of mole gets final product.
Among the present invention, the amount of the water that uses in the above-mentioned reaction can suitably be selected as required, generally is 0.2～2.5 times of mole of the total alkoxyl group in (A) composition.When metal-salt was moisture salt, its moisture was also counted the amount of the water that uses in the said hydrolyzed.
Operation 1 is with the condensation reaction that is hydrolyzed in solvent (B) of (A) composition, and (A) interpolation of composition and solvent (B) order is not subjected to particular restriction.Usually, adopt the method for adding compositions such as water, catalyzer in the solution that obtains mixing titan-alkoxide in (A) composition and solvent (B) in advance.With other metal alkoxides and time spent, can mix with solvent (B) simultaneously with titan-alkoxide, also can add afterwards.At this moment, other metal alkoxides can be used solvent (B) dilution in advance.
In addition, in order to suppress the hydrolysis of titan-alkoxide, carry out hydrolysis-condensation reaction after can cooling off in advance.In addition, also can in hydrolysis-condensation reaction, cool off, can also be at the hydrolysis-condensation reaction postcooling.
Water and catalyzer can mix the back to be added, and also can add respectively.Usually, the solution made after solvent (B) dilution of water and catalyzer adds.
And, in order to promote the hydrolysis-condensation reaction of (A) composition, also can the mixing solutions of (A) composition and solvent (B) be heated.Heating temperature and heat-up time, can suitably select as required.For example, can enumerate 50 ℃ of following heated and stirred 24 hours, or under refluxing method such as heated and stirred 8 hours.
In addition, can also in the heat-processed of the mixing solutions of (A) composition and solvent (B), add water and catalyzer.
About the solution that obtains after above-mentioned operation 1, preferably below 20 quality %, good especially be below the 15 quality % to the concentration (metal oxide solid composition conversion concentration) that the total atoms metal in this solution is converted into oxide compound.By in this concentration range, selecting concentration arbitrarily, can suppress the generation of gel, obtain the solution of even matter.As mentioned above, through operation 1, can obtain containing the solution (hereinafter referred to as solution before the displacement) of the condenses that makes (A) composition in solvent (B), be hydrolyzed condensation and generate.
About [operation 2]:
Operation 2 is the operations that are replaced as the solvent exchange of solvent (C) based on the solvent (B) of solution before the displacement that will obtain in the above-mentioned operation 1.
Here, solvent (C) is that to be selected from carbonatoms be 2～10, be preferably at least a kind of organic solvent in 2～6 the glycol, also can and with the multiple solvent that is selected from solvent (C).Enumerate the object lesson of solvent (C) below, but be not limited thereto.
Can enumerate ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,3-butyleneglycol, 2,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 2-methyl-2,4-pentanediol (hexylene glycol), 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol, 2-ethyl-1,3-hexylene glycol etc.
Wherein, hexylene glycol is good to the wettability of substrate, thereby preferred.
In the operation 2, with solvent (C) method of replacement, be not subjected to particular determination about solution before will replacing.
As short-cut method, can enumerate the solution that from solution before displacement, has mixed solvent (C) and heat up in a steamer method based on the solvent of solvent (B).Can also enumerate that limit solution before replace heats up in a steamer based on the method for the solvent limit interpolation solvent (C) of solvent (B) etc.
Condition during about solvent exchange in order to improve the displacement efficiency of solvent, is under reduced pressure carried out usually, also can carry out under normal pressure.That is, can be preferably under 0.1mmHg (13.3Pa)～760mmHg (101.3kPa), condition, carry out solvent exchange particularly preferably in 5mmHg (666.6Pa)～200mmHg (26.7kPa).At this moment, in order further to improve the displacement efficiency of solvent, also can heat.Consider cost, Heating temperature is preferably the temperature below 100 ℃, gets final product so long as be lower than the temperature of the boiling point of solvent (C).
In the present invention, the organic solvent before will not replacing in the solution is all used solvent (C) displacement, is replaced as solvent (C) more than the 80 quality % of the total organic solvent before the preferred displacement in the solution, is preferably especially more than the 85 quality %.Like this, form for tunicle described later and use coating fluid, be easy to obtain good coating, and the coating formation during flexible printing becomes easy.And, though it is indeterminate, but when the solvent exchange of operation 2, water is removed a part with the organic solvent azeotropic of the preceding solution of displacement, amount of moisture in the solution that obtains after operation 2 (hereinafter referred to as substitutional solution) reduces, and the storage stability that substitutional solution and the tunicle that uses this substitutional solution to obtain form with coating fluid significantly improves.
In the operation 2, by regulating the amount of solvent (C), the metal oxide solid composition conversion concentration that also can regulate substitutional solution.At this moment, metal oxide solid composition conversion concentration is preferably below the 20 quality %, is preferably especially below the 15 quality %.In addition, can select required concentration as required.
As mentioned above, by carrying out above-mentioned operation 1 and operation 2, can obtain making (A) composition in solvent (B), be hydrolyzed condensation and the solution (solution before the displacement) of the condenses that generates is replaced with solvent (C) and the solution that obtains, i.e. substitutional solution with containing.
About [operation 3]:
Operation 3 is that the preparation tunicle forms the operation with coating fluid, but will the above-mentioned substitutional solution that obtains when directly coating fluid is used in formation as tunicle, also can omit this operation.
Usually, form oxide solid composition conversion concentration in order to regulate tunicle, improve coating and further add solvent (D), preparation tunicle formation coating fluid with coating fluid.
In addition, only otherwise damage effect of the present invention, can also add other compositions such as inorganic particles, tensio-active agent, levelling agent as required.
In the present invention, the metal oxide conversion concentration that tunicle forms with coating fluid is preferably 0.5～20 quality %, is preferably 1～15 quality % especially.When using inorganic particles, preferably making the atoms metal in the substitutional solution and the concentration of total amount after oxide compound converts of the atoms metal in the inorganic particles is 0.5～20 quality %.
About adding the method for above-mentioned solvent (D) and other compositions,, be not subjected to particular determination as long as can obtain the solution of even matter.
As solvent (D), use the solvent that dissolves each other with substitutional solution, be not subjected to particular restriction in addition, also can multiple and usefulness.
As its object lesson, can enumerate methyl alcohol, ethanol, 1-propyl alcohol (n-propyl alcohol), 2-propyl alcohol (Virahol), 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 1, alcohols such as 1-dimethyl ethanol, hexanol, octanol, diacetone alcohol; Ester classes such as ethyl acetate, ethyl lactate, butylacetate, gamma-butyrolactone; Tetrahydrofuran (THF), ether, 1,4-two
Figure 2006800294371_1
Ethers such as alkane; Ketones such as acetone, 2-butanone, 3-methyl-2-butanone, 4-methyl-2 pentanone; Ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,3-butyleneglycol, 2,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 2-methyl-2,4-pentanediol (hexylene glycol), 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol, 2-ethyl-1, glycolss such as 3-hexylene glycol; Ketones such as acetone, 2-butanone, 3-methyl-2-butanone, 4-methyl-2 pentanone; 1-methoxyl group-2-ethanol, 1-oxyethyl group-2-ethanol, 1-propoxy--2-ethanol, 1-butoxy-2-ethanol, 1-methoxyl group-2-propyl alcohol, 1-oxyethyl group-2-propyl alcohol, 1-butoxy-2-propyl alcohol, diethylene glycol monomethyl ether, TC, the Diethylene Glycol single-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the Diethylene Glycol dibutyl ether, DPGME, dihydroxypropane single-ethyl ether, the dipropylene glycol single-butyl ether, the dipropylene glycol dimethyl ether, the dipropylene glycol Anaesthetie Ether, the dipropylene glycol dibutyl ether, ethyl carbitol, diethylene glycol monobutyl ether, glycol ethers such as diethylene glycol diethyl ether; N-Methyl pyrrolidone; Amides such as dimethyl formamide, N,N-DIMETHYLACETAMIDE etc.
As inorganic particles, metal oxide microparticles such as preferred silicon dioxide microparticle, aluminum oxide, titanium dioxide, zeolite; Antimony-tin oxide), ITO (indium tin oxide: indium-tinoxide), IZO (indium-zinc oxide: composite oxide particle such as indium-zinc oxide) ATO (titanium tetrachloride:.Preferred especially colloidal solution.This colloidal solution can be the colloidal solution that inorganic particles is disperseed formation in dispersion medium, also can be commercially available colloidal solution.
Among the present invention,, can give surface shape and other functions of the curing tunicle of formation by containing inorganic particles.As inorganic particles, its median size is preferably 0.001～0.2 μ m, more preferably 0.001～0.1 μ m.When the median size of inorganic particles surpasses 0.2 μ m, reduce sometimes with the transparency of the curing tunicle of the coating fluid formation of preparation.
About the dispersion medium of inorganic particles, form with the good storage stability of coating fluid in order to keep tunicle, be preferably organic solvent.As colloidal solution, form viewpoint from tunicle with the stability of coating fluid, pH or pKa preferably are adjusted to 2～10, and particularly 3～7.
As the organic solvent that the dispersion medium of colloidal solution uses, can enumerate alcohols such as methyl alcohol, ethanol, Virahol (2-propyl alcohol), 1-butanols; Glycolss such as ethylene glycol, propylene glycol, hexylene glycol, glycol monomethyl propyl ether; Ketones such as acetone, methyl ethyl ketone (2-butanone), methyl iso-butyl ketone (MIBK) (3-methyl-2-butanone), 4-methyl-2 pentanone; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; Amidess such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone; Ester classes such as ethyl acetate, butylacetate, gamma-butyrolactone; Tetrahydrofuran (THF), 1,4-two
Figure 2006800294371_2
Ethers such as alkane, and the solvent of crossing in above-mentioned illustration respectively as solvent (B), solvent (C), solvent (D).Wherein, preferred alcohols or glycols.These organic solvents can separately or mix the back more than 2 kinds uses as dispersion medium.
In addition, levelling agent and tensio-active agent etc. can use known material, and preferred especially commercially available product is because of it is easy to obtain.
As mentioned above, the tunicle formation that obtains by the present invention prepares with the manufacture method that comprises [operation 1] and [operation 2] with coating fluid, also can prepare with the method that comprises [operation 3] as required.
[formation of tunicle]
Use coating fluid by the tunicle formation that manufacture method of the present invention obtains, by being coated with on base material, thermofixation can obtain required curing tunicle.Coating process can adopt known or known method.For example, can adopt dip coating, the coating method that flows, spray method, rod to be coated with method, intaglio plate coating method, rolling method, scraper coating method, airblade coating method, flexible printing method, ink jet method etc.Wherein, the flexible printing method can form good filming.
At this moment, the base materials employed plastics of enumerating; Glass; Fluorine-dopedtin oxide), the glass of band transparency electrodes such as ITO, IZO ATO, FTO (mix the stannic oxide of fluorine:; Base materials such as pottery.As plastics, can enumerate polycarbonate, poly-(methyl) acrylate, polyethersulfone, polyarylate, urethane, polysulfones, polyethers, polyetherketone, polyolefine, polyethylene terephthalate, polyacrylonitrile, tri acetyl cellulose, diacetyl cellulose, butylacetate Mierocrystalline cellulose etc.Its shape can be enumerated tabular or film like etc.
Tunicle form with coating fluid before coating usually with filtrations such as strainers.
What form on base material films, after drying under the temperature of room temperature～120 ℃, and preferably thermofixation under 150～250 ℃ of temperature.At this moment, dry required time is more than 30 seconds below 10 minutes.
The thermofixation required time can suitably be selected by membrane property according to required curing, gets final product more than 10 minutes.When selecting to hang down solidification value, by prolonging the curing tunicle that is easy to obtain to have abundant hardness set time.
In addition, tunicle of the present invention forms uses coating fluid, even surpassing the curing tunicle that also can obtain having abundant hardness under the solidification value of 250 ℃ of temperature.
In addition, before thermofixation, also effective with irradiation energy lines (ultraviolet ray etc.) such as mercury lamp, metal halide lamp, xenon lamp, Excimer lamps.By irradiation energy line on dried coating, can further reduce solidification value, improve the hardness of tunicle, improve specific refractory power.The irradiation dose of energy line can suitably be selected as required, but usually with hundreds of～thousands of mJ/cm 2Be advisable.
Use coating fluid by the tunicle formation that the present invention obtains, the formation ability of the filming excellence in the flexible printing field can form fully solidified tunicle at low temperatures.
And, because the printing of the liquid crystal aligning material on this tunicle is good, thereby can form the liquid crystal orientation film that has suppressed depression and pin hole.
Therefore, the tunicle that obtains by the present invention forms use coating fluid, owing to can form tunicle with above-mentioned characteristic, thereby very useful to the display characteristic of raising liquid crystal display device.
[embodiment]
Below, enumerate embodiment and comparative example, specify the present invention, but the invention is not restricted to following embodiment.
Shown in being described as follows of shortenings in the present embodiment.
TEOS: tetraethoxysilane
MTES: Union carbide A-162
TET: purity titanium tetraethoxide
TIPT: tetraisopropoxy titanium
HG: hexylene glycol (another name: 2-methyl-2,4-pentanediol)
THF: tetrahydrofuran (THF)
PG: propylene glycol (another name: 1, the 2-propylene glycol)
EG: ethylene glycol
PGME: propylene glycol monomethyl ether (another name: 1-methoxyl group-2-propyl alcohol)
BCS: ethylene glycol butyl ether (another name: 1-butoxy-2-ethanol)
PB: propylene glycol single-butyl ether (another name: 1-butoxy-2-propyl alcohol)
AN: aluminum nitrate nonahydrate
CN: cerous nitrate hexahydrate
IN: indium nitrate trihydrate
Measuring method among the following embodiment is as follows.
[measuring method of residual solvent (B)]
With the Diethylene Glycol dibutyl ether as diluting solvent, with diethylene glycol diethyl ether as internal standard substance matter, the mass ratio that preparation diluting solvent/internal standard substance matter/tunicle forms with coating fluid is the sample of 97.5/0.5/2.0, by having used the marker method of gas-chromatography (hereinafter referred to as GC), measure tunicle and form the amount of using solvent (B) residual in the coating fluid.The condition determination of GC is as follows.
The GC condition determination:
Device: Shimadzu GC-14B.
Pillar: capillary column, CBP1-W25-100 (25mm * 0.53mm Φ * 1 μ m).
Column temperature: column temperature is controlled with heating schedule.Starting temperature keeps down after 4 minutes for 40 ℃, and with 15 ℃ of/minute intensifications, final temperature kept 3 minutes down for 300 ℃.
Sample size: 1 μ L.
Sample introduction temperature: 270 ℃.
Detector temperature: 320 ℃.
Carrier gas: nitrogen (flow 30mL/min).
Detection method: FID method.
[preparation example 1]
In the 300mL flask, pack into pure water 2.70g, as the ethanol 62.53g of solvent (B) and as the AN 2.96g of catalyzer, stir and obtain uniform solution.In this solution, add TEOS 24.98g, stirred 30 minutes under the room temperature as other metal alkoxides.Then, add TET 6.84g, stirred 30 minutes under the room temperature.With this solution as the displacement before solution (P1).
[preparation example 2～11]
Press the composition shown in the table 1, use with the same method preparation displacement of preparation example 1 before solution (P2～P11).
But, in preparation example 4, do not use other metal alkoxides.
In addition, the nitric acid in the table 1 is represented 60 quality % aqueous nitric acid.
[table 1]
Solution before the displacement Titan-alkoxide (g) Other metal alkoxides (g) (g) Catalyzer (g) Solvent (B) (g) Pure water (g)
Preparation example 1 P1 TET 6.84 TEOS 24.98 AN 2.96 Ethanol 62.53 2.70
Preparation example 2 P2 TET 15.70 TEOS 14.33 AN 2.72 Ethanol 64.77 2.48
Preparation example 3 P3 TET 23.22 TEOS 5.30 AN 2.51 Ethanol 66.68 2.29
Preparation example 4 P4 TET 27.63 AN 2.39 Ethanol 67.80 2.18
Preparation example 5 P5 TET 14.51 TEOS 13.25 CN 2.91 Ethanol 67.05 2.29
Preparation example 6 P6 TET 14.76 TEOS 13.48 IN 2.33 Ethanol 67.02 2.33
Preparation example 7 P7 TET 15.70 TEOS 7.17 MTES 6.13 AN 2.72 Ethanol 65.80 2.48
Preparation example 8 P8 TET 16.53 TEOS 15.08 Nitric acid 1.05 Ethanol 65.15 2.19
Preparation example 9 P9 TET 16.53 TEOS 15.08 Nitric acid 1.05 THF 65.15 2.19
Preparation example 10 P10 TET 16.53 TEOS 15.08 Nitric acid 1.05 Butanols 65.15 2.19
Preparation example 11 P11 TIPT 19.55 TEOS 14.33 AN 2.72 Ethanol 60.92 2.48
[embodiment 1]
In the 300mL flask, mix with solution (P1) 24.00g before the displacement that obtains in the preparation example 1 with as the HG 25.87g of solvent (C).Then, (Tokyo physics and chemistry apparatus corporate system NE-1) is heated up in a steamer and is desolvated on 60 ℃ of bottoms 20mmHg (2.67kPa) limit of slowly reducing pressure, and obtains 28.91g substitutional solution (Q1) to utilize novel evacuated rotatory evaporator.Then, mix the PGME 11.09g as solvent (D) in substitutional solution (Q1) 28.91g, the preparation tunicle forms with coating fluid (Z1).To this coating fluid (Z1), measure the residual quantity of solvent (B) with GC, the result is 5.7 quality %.
In addition, the tunicle that obtains is formed with coating fluid (Z1), estimate pencil hardness, specific refractory power, printing and liquid crystal orientation film printing with method described later.The result is as shown in table 3.
[embodiment 2～15]
Press the composition shown in the table 2, (P2～P11) replace by method similarly to Example 1 with solvent (C) obtains substitutional solution (Q2～Q15) to solution before will replacing.And, press the composition shown in the table 2, (add solvent (D) among the Q2～Q15), the preparation tunicle forms with coating fluid (Z2～Z15) at substitutional solution.Measure this coating fluid (amount of the residual solvent (B) among the Z2～Z15) with GC.
In addition, the tunicle that obtains is formed with coating fluid (Z2～Z15), estimate pencil hardness, specific refractory power, printing and liquid crystal orientation film printing with method described later.The result is as shown in table 3.
[table 2]
Tunicle forms uses coating fluid Solution (g) before the displacement Solvent (C) is (g) (g) Substitutional solution (g) Solvent (D) (g) Residual solvent (B) (quality %)
Embodiment 1 Z1 P1 24.00 HG 25.75 Q1 28.96 PGME 11.04 5.7
Embodiment 2 Z2 P2 24.00 HG 25.18 Q2 29.21 PGME 10.79 6.5
Embodiment 3 Z3 P3 24.00 HG 25.84 Q3 28.93 PGME 11.07 5.5
Embodiment 4 Z4 P4 24.00 HG 26.30 Q4 28.73 PGME 11.27 4.3
Embodiment 5 Z5 P5 24.00 HG 25.31 Q5 29.16 PGME 10.85 8.5
Embodiment 6 Z6 P6 24.00 HG 24.79 Q6 29.38 PGME 10.62 5.8
Embodiment 7 Z7 P7 24.00 HG 25.84 Q7 28.93 PGME 11.07 5.1
Embodiment 8 Z8 P8 24.00 HG 26.01 Q8 28.85 PGME 11.15 6.4
Embodiment 9 Z9 P9 24.00 HG 24.47 Q9 29.51 PGME 10.49 9.6
Embodiment 10 Z10 P10 24.00 HG 25.62 Q10 29.02 PGME 10.98 5.7
Embodiment 11 Z11 P11 24.00 HG 25.80 Q11 28.94 PGME 11.06 5.5
Embodiment 12 Z12 P2 24.00 PG 26.02 Q12 28.85 PGME 11.15 5.6
Embodiment 13 Z13 P2 24.00 HG 22.27 EG 3.71 Q13 28.86 PGME 11.14 5.0
Embodiment 14 Z14 P2 24.00 HG 25.94 Q14 28.89 BCS 11.12 5.1
Embodiment 15 Z15 P2 24.00 HG 25.89 Q15 28.91 PB 11.09 5.2
[embodiment 16]
TEOS 20.8g is being mixed in the solution that obtains in the ethanol, will in ethanol 23.2g, dissolving, mixing water 5.4g and the solution that obtains as 28 quality % ammonia soln 0.6g of basic catalyst, at room temperature mixing while stirring.After 30 minutes, solution begins to be the colloid look, turns out to be granular resultant.Then, at room temperature continue to stir 24 hours, what obtain SiO2 conversion concentration and be 6 quality % is scattered in alcoholic acid dioxide/silica gel liquid solution.With the particle diameter of the colloidal particle of gained solution with DLS-7000 (Da mound electronics corporation system) measure, the result: the median size that dynamic light scattering method obtains is 20nm.
Then, in the 300mL flask, dioxide/silica gel liquid solution 40.0g and the HG 22.8 that obtains mixed.Then, (Tokyo physics and chemistry apparatus corporate system NE-1) is heated up in a steamer and is desolvated on 60 ℃ of bottoms 20mmHg (2.67kPa) limit of slowly reducing pressure, and obtains the dioxide/silica gel liquid solution that 25.3g is scattered in HG to utilize novel evacuated rotatory evaporator.Afterwards, in the dioxide/silica gel liquid solution that is scattered in HG that obtains, add PGME14.7g, preparation particle dispersing solution K.
Tunicle shown in the table 2 is formed with coating fluid (Z2) 10.00g and particle dispersing solution K 10.00g mixing, and the preparation tunicle forms with coating fluid (Z16).
In addition, the tunicle that obtains is formed with coating fluid (Z16), estimate pencil hardness, specific refractory power, printing and liquid crystal orientation film printing with method described later.The result is as shown in table 3.
[comparative example 1]
In the 300mL flask, will in pure water 1.49g, dissolve solution and PGME23.66g and HG 26.94g mixing that AN 1.63g obtains.Add TEOS 8.60g therein, stirred 30 minutes under the room temperature.Then, add and mix the solution that TET 9.42g and HG 28.26g obtain in advance, stir under the room temperature and obtained coating fluid (T1) in 30 minutes.
In addition, to the coating fluid (T1) that obtains, estimate pencil hardness, specific refractory power, printing and liquid crystal orientation film printing with method described later.The result is as shown in table 3.
[comparative example 2]
In the 300mL flask, will in pure water 1.31g, dissolve solution and PGME24.20g and HG 6.74g mixing that AN 1.43g obtains.Add therein and mix the solution that TET 16.58g and HG 49.74g obtain in advance, stir under the room temperature and obtained coating fluid (T2) in 30 minutes.
In addition, to the coating fluid (T2) that obtains, estimate pencil hardness, specific refractory power, printing and liquid crystal orientation film printing with method described later.The result is as shown in table 3.
[comparative example 3]
In the 300mL flask, will in pure water 1.49g, dissolve solution and PGME23.66g and EG 7.89g and HG 19.07g mixing that AN1.63g obtains.Add TEOS 8.60g therein, stirred 30 minutes under the room temperature.Then, add and mix the solution that TET 9.42g and HG 28.25g obtain in advance, stir under the room temperature and obtained coating fluid (T3) in 30 minutes.
In addition, to the coating fluid (T3) that obtains, estimate pencil hardness, specific refractory power, printing and liquid crystal orientation film printing with method described later.The result is as shown in table 3.
[pencil hardness]
The tunicle of embodiment is formed with chromatodisk (Cangfu textile company system, the aperture 0.45 μ m) filtration of the coating fluid of coating fluid and comparative example.Then, be added drop-wise on the glass substrate (thickness of ITO is 0.7mm) of band ITO, (Mi Kasa (MIKASA) corporate system 1H-DX2), was rotated 20 seconds with rotating speed 4000rpm after 5 seconds with the pre-rotation of rotating speed 300rpm, and formation is filmed with the rotary coating machine.Then, after on the hot plate of 80 ℃ of temperature dry 3 minutes, on hot plate,, obtain solidifying tunicle with 180 ℃ of heating of solidification value 15 minutes.Measure the pencil hardness of the curing tunicle of gained according to test method(s) (JIS K5400).
In embodiment 3, embodiment 14 and comparative example 3, solidification value is 200 ℃, and in embodiment 4 and comparative example 2, solidification value is 250 ℃.
[specific refractory power]
Solidify tunicle except substrate is replaced the glass substrate of band ITO, use to estimate identical method formation with organosilicon substrate (100) with above-mentioned [pencil hardness].Measure the specific refractory power at wavelength 633nm place with ellipsometer (ditch buttocks optics industry corporate system, DVA-36L type).
[printing]
The tunicle of embodiment is formed with chromatodisk (Cangfu textile company system, the aperture 0.45 μ m) filtration of the coating fluid of coating fluid and comparative example.Then, use DR type printing press (Japan description printing firm system, anilox roll (360#), relief printing plate (site 400L30%70 ℃)), go up formation at the glass substrate (thickness of ITO is 0.7mm) of band ITO and film.This is filmed after on the hot plate of 80 ℃ of temperature dry 3 minutes, on hot plate,, obtain solidifying tunicle with 180 ℃ of heating of solidification value 15 minutes.The curing tunicle that visual inspection obtains is designated as zero when not having the good order and condition of pin hole inequality on solidifying tunicle, the situation that has produced the pin hole inequality is designated as △, produce depression and not on substrate abundant film forming state be designated as *.
In embodiment 3, embodiment 14 and comparative example 3, solidification value is 200 ℃, and in embodiment 4 and comparative example 2, solidification value is 250 ℃.
[liquid crystal orientation film printing]
On the curing tunicle of using the method identical to form with above-mentioned [printing], with DR type printing press (Japan description printing firm system, anilox roll (360#), relief printing plate (site 400L30%70 ℃)), coating of liquid crystalline oriented material (daily output chemical industrial company system, SUNEVER (registered trademark) SE-5291032B (trade(brand)name)).Then, on the hot plate of 80 ℃ of temperature, dry 3 minutes formation liquid crystal orientation films.The formed liquid crystal orientation film of visual inspection when being designated as zero when not having depression, pin hole and uneven good order and condition on the liquid crystal orientation film, has produced pin hole or uneven situation is designated as △, produce depression and not on substrate abundant film forming state be designated as *.
[table 3]
Tunicle forms uses coating fluid Pencil hardness Specific refractory power Printing The liquid crystal orientation film printing
Embodiment
1 Z1 5H 1.50 ○ ○
Embodiment 2 Z2 5H 1.56 ○ ○
Embodiment 3 Z3 5H 1.74 ○ ○
Embodiment 4 Z4 6H 1.88 ○ ○
Embodiment 5 Z5 5H 1.59 ○ ○
Embodiment 6 Z6 5H 1.56 ○ ○
Embodiment 7 Z7 5H 1.54 ○ ○
Embodiment 8 Z8 5H 1.57 ○ ○
Embodiment 9 Z9 5H 1.57 ○ ○
Embodiment 10 Z10 5H 1.57 ○ ○
Embodiment 11 Z11 5H 1.56 ○ ○
Embodiment 12 Z12 5H 1.50 ○ ○
Embodiment 13 Z13 5H 1.50 ○ ○
Embodiment 14 Z14 5H 1.74 ○ ○
Embodiment 15 Z15 5H 1.56 ○ ○
Embodiment 16 Z16 5H 1.47 ○ ○
Comparative example 1 T1 H 1.54 △ ×
Comparative example 2 T2 4H 1.87 △ ×
Comparative example 3 T3 4H 1.60 ○ ×
[embodiment 17]
The tunicle that obtains among the embodiment 1 is formed with coating fluid (Z1),, estimate pencil hardness (the UV irradiation is arranged), specific refractory power (the UV irradiation is arranged) and liquid crystal orientation film printing (the UV irradiation is arranged) by following method.The result is as shown in table 4.
[embodiment 18]
The tunicle that obtains among the embodiment 2 is formed with coating fluid (Z2),, estimate pencil hardness (the UV irradiation is arranged), specific refractory power (the UV irradiation is arranged) and liquid crystal orientation film printing (the UV irradiation is arranged) by following method.The result is as shown in table 4.
[pencil hardness (the UV irradiation is arranged)]
Tunicle is formed with coating fluid chromatodisk (Cangfu textile company system, aperture 0.45 μ m) after the filtration, be added drop-wise on the glass substrate of band ITO, with rotary coating machine (Mi Kasa (MIKASA) corporate system, 1H-DX2),, rotated 20 seconds with rotating speed 4000rpm after 5 seconds with the pre-rotation of rotating speed 300rpm, formation is filmed.Then, on the hot plate of 80 ℃ of temperature dry 3 minutes.Afterwards, use UV irradiation equipment (this (EYEGRAPHICS) corporate system of Ai Gula Fick, UB 011-3A shape), high voltage mercury lamp (input power supply 1000W) with 50mW/cm 22 minutes (accumulation 6000mJ/cm of (wavelength 350nm conversion) irradiation 2), on hot plate,, obtain solidifying tunicle with 150 ℃ of heating of solidification value 15 minutes.Measure the pencil hardness of the curing tunicle of gained according to test method(s) (JISK5400).
[specific refractory power (the UV irradiation is arranged)]
Except substrate is replaced with organosilicon substrate (100) the glass substrate of band ITO, use the method identical to form and solidify tunicle with above-mentioned [pencil hardness (the UV irradiation is arranged)] evaluation.Measure the specific refractory power at wavelength 633nm place with ellipsometer (ditch buttocks optics industry corporate system, DVA-36L type).
[liquid crystal orientation film printing]
On the curing tunicle of using the method identical to form with above-mentioned [pencil hardness (the UV irradiation is arranged)] evaluation, with DR type printing press (Japan description printing firm system, anilox roll (360#), relief printing plate (site 400L30%70 ℃)), coating of liquid crystalline oriented material (daily output chemical industrial company system, SUNEVER (registered trademark) SE-5291032B (trade(brand)name)).Afterwards, on the hot plate of 80 ℃ of temperature, dry 3 minutes formation liquid crystal orientation films.The formed liquid crystal orientation film of visual inspection when being designated as zero when not having depression, pin hole and uneven good order and condition on the liquid crystal orientation film, has produced pin hole or uneven situation is designated as △, produce depression and not on substrate abundant film forming state be designated as *.
[table 4]
Tunicle forms uses coating fluid Pencil hardness Specific refractory power The liquid crystal orientation film printing
Embodiment 17 Z1 6H 1.53 ○
Embodiment 18 Z2 8H 1.66 ○
[reference example 1]
The tunicle that obtains among the embodiment 1 is formed with coating fluid (Z1), except solidification value is become 300 ℃ by 150 ℃, with method similarly to Example 17, estimate pencil hardness (the UV irradiation is arranged), specific refractory power (the UV irradiation is arranged) and liquid crystal orientation film printing (the UV irradiation is arranged).The result is as shown in table 5.
[reference example 2]
The tunicle that obtains among the embodiment 2 is formed with coating fluid (Z2), except solidification value is become 300 ℃ by 150 ℃, with method similarly to Example 18, estimate pencil hardness (the UV irradiation is arranged), specific refractory power (the UV irradiation is arranged) and liquid crystal orientation film printing (the UV irradiation is arranged).The result is as shown in table 5.
[table 5]
Tunicle forms uses coating fluid Pencil hardness Specific refractory power The liquid crystal orientation film printing
Reference example 1 Z1 9H 1.76 ○
Reference example 2 Z2 9H 2.07 ○
[embodiment 19]
The tunicle of weighing 1g embodiment 2 forms with coating fluid (Z2) in weighing bottle, with baking oven 120 ℃ of temperature down after dry 1 hour, 180 ℃ of following sintering of temperature 2 hours.Measure the quality of the residual branch of sintering, calculate residual organic composition amount with following formula.At this moment, tunicle is formed the value of calculating as oxide compound with the whole atoms metals that contain in the coating fluid and become component as metal oxide solid.The result is as shown in table 6.
(i) residual organic composition amount (quality %)={ (quality of the residual branch of sintering-metal oxide solid composition)/(quality of the residual branch of sintering) } * 100
(ii) solid component concentration (quality %)={ (quality of the residual branch of sintering)/(tunicle forms the quality with coating fluid) } * 100
(iii) metal oxide conversion concentration (quality %)={ (metal oxide solid becomes component)/(tunicle with the quality that forms coating fluid) }
[comparative example 4]
To the coating fluid (T1) of comparative example 1, except the tunicle formation with embodiment 19 substitutes with coating fluid (T1) with coating fluid (Z2), similarly to Example 19, calculate residual organic composition amount.The result is as shown in table 6.
[table 6]
Tunicle forms uses coating fluid Solid component concentration (quality %) Metal oxide conversion concentration (quality %) Residual organic composition amount (quality %)
Embodiment 19 Z2 10.1 6.0 40.6
Comparative example 4 T1 10.9 6.0 45.0
[embodiment 20]
Tunicle to embodiment 2 forms with coating fluid (Z2), and Z2 is added drop-wise on the glass substrate, and (Mi Kasa (MIKASA) corporate system 1H-DX2), after 5 seconds, was rotated 20 seconds film forming with the pre-rotation of rotating speed 300rpm with rotating speed 4000rpm with the rotary coating machine.Then, the glass substrate after the film forming is following dry 3 minutes in 80 ℃ of temperature on hot plate.Cut and get this and film, obtain the dried powder of Z2.The powder that obtains with thermogravimetric amount differential thermal analysis determinator (mark's scientific company (Mac Science) system, MODEL WS 002), is warming up to 500 ℃ from room temperature with the speed of 5 ℃ of per minutes, measures the TG (weight decrement) and the DTA (differential thermal) of powder.Measurement result as depicted in figs. 1 and 2.
Near the weight that is accompanied by heat absorption this result has confirmed 140 ℃ reduces, and near the weight that is accompanied by heat release 200 ℃ after the heat absorption reduces.
[comparative example 5]
Except the tunicle among the embodiment 20 is formed substitute with the coating fluid (T1) of comparative example 1 with coating fluid (Z2), similarly to Example 20, measure the weight decrement and the differential thermal of the dried powder of T1.Measurement result as depicted in figs. 1 and 2.
Near the weight that is accompanied by heat absorption this result has confirmed 160 ℃ reduces, near the weight that is accompanied by heat absorption 230 ℃ reduce and 270 ℃ near be accompanied by heat release weight reduce.
[summary]
By result's (with reference to table 3) of embodiment 1～embodiment 16 as can be known: the tunicle that obtains by the present invention forms uses coating fluid; under cryogenic solidification value; when usually its tunicle being used as the electrode protective membrane (insulating film) of liquid crystal display device, demonstrating sufficient hardness is the above pencil hardness of 5H.
And, also confirm on this tunicle, to form the liquid crystal orientation film that has suppressed depression and pin hole.
In addition, before the thermofixation, by irradiation ultraviolet radiation on filming at exsiccant, can further reduce solidification value, 150 ℃ of hardness and specific refractory poweres that can improve tunicle down, in addition, the liquid crystal orientation film that forms on this tunicle demonstrates the film-forming properties of the excellence of not having depression and pin hole.
In addition, formed and in 1.5～2.1 scope, to have regulated the tunicle of specific refractory power arbitrarily.
In addition, (Q1～Q16) and tunicle form with coating fluid and (even Z1～Z16) does not find the generation of precipitate after preserving 1 month under 25 ℃, humidity 50%RH, proves very excellence of storage stability yet the substitutional solution of embodiment 1～embodiment 16.
The result of embodiment 19 and comparative example 4 (with reference to table 6) confirms that by the tunicle formation coating fluid that the present invention obtains, it is few to solidify organic composition (carbon component) residual in the tunicle that obtains at low temperatures.Can infer that thus decomposition takes place to break away from organic composition under cryogenic condition of cure (being mainly glycol).
Result (Fig. 1 and Fig. 2) by the thermogravimetric amount differential thermal analysis of embodiment 20 and comparative example 5 can infer, uses the tunicle that obtains by the present invention to form the state that the residual organic composition of filming that forms with coating fluid is in easier disengaging decomposition.Think this state and the curing that promotes to film, easier at low temperatures curing is relevant.
The possibility of utilizing on the industry
Use coating fluid by the tunicle formation that the present invention obtains, the formation ability of the filming excellence in the flexible printing field can form the tunicle that can fully solidify at low temperatures. In addition, on this tunicle, can form the liquid crystal orientation film that has suppressed depression and pin hole.
Therefore, useful in various electronic components, display unit, particularly liquid crystal indicator.
Quote of the announcement of the full content of Japanese patent application 2005-239057 number specification sheets, claims, accompanying drawing and the summary of filing an application on August 19th, 2005 at this as specification sheets of the present invention.

Claims (9)

1. tunicle forms the manufacture method with coating fluid, it is characterized in that having following operation:
Obtain containing the operation 1 of the solution of the condenses that makes metal alkoxides (A) in solvent (B), be hydrolyzed condensation reaction and generate,
The operation 2 of the solution after the solution that obtains obtaining in the described operation 1 is replaced with solvent (C);
Wherein, metal alkoxides (A) is at least a kind of metal alkoxides that is selected from the compound of formula (1) expression,
Ti(OR 1) 4 (1)
In the formula, R 1The expression carbonatoms is 1～5 alkyl;
Solvent (B) is that to be selected from carbonatoms be that 1～10 alcohol, carbonatoms are that 2～5 ester, tetrahydrofuran (THF) and carbonatoms are at least a kind of organic solvent in 2～5 ethers;
Solvent (C) is that to be selected from carbonatoms be at least a kind of organic solvent in 2～10 the glycol.
2. tunicle as claimed in claim 1 forms the manufacture method with coating fluid, it is characterized in that, metal alkoxides (A) is also and with at least a kind of organoalkoxysilane in the compound that is selected from formula (2) expression,
(R 2) nSi(OR 3) 4-n (2)
In the formula, R 2Expression alkyl, alkenyl or aryl, R 3The alkyl of expression carbonatoms 1～5, n represents 0～2 integer.
3. tunicle as claimed in claim 2 forms the manufacture method with coating fluid, it is characterized in that, organoalkoxysilane is that the n that is selected from formula (2) is at least a kind of silicon compound in 0 the compound.
4. tunicle as claimed in claim 1 forms the manufacture method with coating fluid, it is characterized in that metal alkoxides (A) and to use with respect to 1 mole of alkoxy titanium be 0.05～4 mole organoalkoxysilane.
5. tunicle as claimed in claim 2 forms the manufacture method with coating fluid, it is characterized in that metal alkoxides (A) and to use with respect to 1 mole of alkoxy titanium be 0.05～4 mole organoalkoxysilane.
6. tunicle as claimed in claim 1 forms the manufacture method with coating fluid, it is characterized in that, uses a kind or the multiple catalyzer that is selected from metallic salt in operation 1.
7. form the manufacture method of using coating fluid as claim 2 or 5 described tunicles, it is characterized in that, use a kind or the multiple catalyzer that is selected from metallic salt in operation 1.
8. tunicle as claimed in claim 1 forms the manufacture method with coating fluid, it is characterized in that, has the operation 3 of adding the solvent (D) that dissolves each other with this solution in the solution that operation 2 obtains.
9. form the manufacture method of using coating fluid as claim 2 or 5 described tunicles, it is characterized in that having the operation 3 of in the solution that operation 2 obtains, adding the solvent (D) that dissolves each other with this solution.
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