CN101134598B - Titania sol chelated organic complexes, its preparation method and composition comprising the same - Google Patents
Titania sol chelated organic complexes, its preparation method and composition comprising the same Download PDFInfo
- Publication number
- CN101134598B CN101134598B CN2006101608236A CN200610160823A CN101134598B CN 101134598 B CN101134598 B CN 101134598B CN 2006101608236 A CN2006101608236 A CN 2006101608236A CN 200610160823 A CN200610160823 A CN 200610160823A CN 101134598 B CN101134598 B CN 101134598B
- Authority
- CN
- China
- Prior art keywords
- organic complex
- titanium oxide
- sol
- colloidal sol
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The invention relates to a titanium dioxide-organic complex collosol, a preparing method thereof and a combination comprising the collosol is used for forming moderate, high and ultrahigh refractive index coating layers. The preparing method comprises following steps: through adding organic complex in titanium dioxide collosol generated by a collosol-gel reaction, preparing titanium dioxide-organic complex; drying the product; redispersing the product in a spreading solvent. The titanium dioxide-organic complex collosol has monodispersity, excellent compatibility with the organic solvent and storage stability. Specially, titanium dioxide nanometer particles are dispersed with high high concentration and redispersed in the organic solvent to keep transparent, so the titanium dioxide-organic complex collosol can be used for forming paint combination with moderate, high and ultrahigh refractive index coating layers.
Description
Technical field
The present invention relates to a kind of titanium oxide-organic complex colloidal sol, its preparation method, and a kind of compsn that comprises this colloidal sol that is used to form medium, high and superelevation refractive index coating.Or rather; The present invention relates to the titanium oxide-organic complex colloidal sol of the filler in a kind of compsn that is used to form medium, high and superelevation refractive index coating; Said compsn all need can be applicable to glasses, industrial safety glasses and the leisure visor of high-clarity, and said compsn colloidal sol has consistency, stability in storage and the monodispersity in the titania nanoparticles in good distribution under the high density excellent and organic solvent coating composition; A kind of method for preparing this colloidal sol, and a kind of compsn that comprises this colloidal sol that is used to form medium, high and superelevation refractive index coating.
Background technology
Because conventional glass mirror has excellent compressibility and wear resistance, can be used for high focal power eyeglass, therefore conventional glass mirror is used widely.Yet the easy quilt of glass mirror external shock arbitrarily damages, and is difficult to comprise some function that UV protects to glass mirror dyeing and generation.Therefore, glass mirror is replaced by the transparent plastics eyeglass.
The advantage of transparent, in light weight, anti-pulverizing that plastic material has and good dyeability, and also be easy to give its various functions.Therefore, glass lens is as optical glasses, industrial safety glasses, leisure visor etc.Yet because glass lens softish surface is abraded by external shock easily and breaks, the purposes of glass lens is limited.In order to overcome these shortcomings, with having the organic of excellent abrasive or silicon coating compsn coating plastic eyeglass.
Low-refraction eyeglass CR-39 (n=1.49) once was most popular eyeglass, but nearest medium refractive index eyeglass NK-55 (n=1.546) has become more popular owing to it is in light weight with the quality height.In addition, high refractive index eyeglass MR8 (n=1.593) and superelevation specific refractory power eyeglass MR7 (n=1.655) demand increase.Eyeglass with weight of high refractive index can be more frivolous.Because introduce aspherical lens, the distortion that is caused by aberration reduces, produces more comfortable vision.
The most general glass mirror becomes the medium refractive index eyeglass from the low-refraction eyeglass, and now high and superelevation specific refractory power eyeglass is just becoming general.Along with the increase of the specific refractory power of eyeglass, the coating specific refractory power must increase, and the amount that therefore joins the high refractive index titanium dioxide filler of coating solution must increase, and causes the increase in demand of high refractive index titanium oxide.
Usually, be coated with and use the wet coat of coating solution that titanium oxide is applied to various coatings through the dry method that comprises evaporation.Be used for the prepare of the coating solution of wet coat with TiO 2 sol, wherein, titanium oxide is dispersed in the solvent.Yet as as everyone knows, titanium oxide is chemically stable, mean that it is being insoluble in the vitriol oil of hydrofluoric acid, heating and the acid the fused alkali salt, alkali, water, organic solvent etc., so that it seldom forms colloidal sol.In addition, even like SO
3Exist down with the high reactivity gas of chlorine, titanium oxide does not also react at normal temperatures and pressures, so that is difficult to the hard coating solution of its preparation.
Therefore, a kind of method that can be used as the TiO 2 sol of coating solution through the sol gel reaction preparation with stable dispersion property has been proposed.According to said sol gel reaction, easily hydrolysis metal halide or alkoxide make TiO 2 sol.
Yet the mechanism of said sol gel reaction is so complicated, does not also explain fully so that prepare TiO 2 sol through sol gel reaction.The kind and the influence of other reaction conditionss of used alkoxide, solvent and tensio-active agent in having only physical properties such as granularity, crystallinity and the dispersion stabilization of the titanium oxide through sol gel reaction preparation to be proved to be to be reacted.
That is, the physical properties of TiO 2 sol receives reaction conditions and the very big influence of order that adds additive.
Korean Patent Publication No. 2001-0028286 has described a kind of method that is scattered in the TiO 2 sol in the water that under normal pressure, prepares.Product can be used as coating, can not be as the filler of high refractive hard coat but solid content is too low.Anhydrate to improve solid content if remove, will observe the particulate coagulation, show that granularity will increase.
Korean Patent Publication No. 2004-0100732 has described a kind of method that under high pressure prepares titania nanoparticles through sol gel reaction.This method has realized preparing titania nanoparticles with uniform and stable dispersion, but it must carry out under HTHP and in spreading solvent, show coagulation during the redispersion exsiccant titania nanoparticles.According to this method, can form stable sols, but the solid content in the colloidal sol is very low, cause output to reduce and the practical application difficulty.
A kind of method that has the excellent crystallinity and the anatase octahedrite photocatalyst titanium oxide sol according of dispersiveness based on Hydrothermal Preparation has been described for Korean Patent Publication No. 2002-0043133 number.According to this method, the gained TiO 2 sol has the high solids content that also is lower than 10wt% at most.According to specification sheets, if solid content is higher than 10wt%, with the sedimentation of observing sol particle and gelation.Except that desolvating, solid content can increase to 20wt% through underpressure distillation, if but like this, particle size will become big and coagulation.
Korean patent No. 10-0489219 has described a kind of method for preparing crystal titanium dioxide, and wherein, titanium oxide is immersed in the porous silica colloidal sol, then baking at high temperature.This method needs high-temperature calcination with the preparation crystal titanium dioxide, and the titanium oxide of gained is powder type, greatly differs from each other with desirable monodisperse sol.
Japanese patent application publication No. 2004-91263 has described a kind of method for preparing crystal titanium dioxide, wherein, and at first preparation amorphous titania, high-temperature calcination then under alkaline condition.Change the amorphous titania that makes into crystal titanium dioxide through high-temperature calcination, so that the titanium oxide of gained is powder type, also greatly differs from each other with desirable monodisperse sol.
Simultaneously, korean 10-2005-0126113 has described a kind of method and a kind of coating composition that uses this colloidal sol that is prepared in monodispersed TiO 2 sol under the high density.According to this method, can prepare transparent medium and high refractive index coating composition.Yet product and organic solvent consistency are poor, so that are difficult to be applied to the coating composition of superelevation specific refractory power and highly transparent and guarantee stability in storage man-hour adding.
Summary of the invention
In order to address the above problem; An object of the present invention is to provide a kind of titanium oxide-organic complex colloidal sol with consistency, stability in storage and monodispersity excellent and organic solvent, show that wherein titania nanoparticles can disperse under high density and can be easily in organic solvent redispersion and do not damage transparency; And a kind of method for preparing this colloidal sol.
Another object of the present invention provides a kind of titanium oxide-organic complex colloidal sol that is used to form thin coating and preparation method thereof, wherein, does not need the multiple coating process to form high refractive index coating.
A purpose more of the present invention provides a kind of titanium oxide-organic complex that is used to form medium, height and superelevation refractive index coating that contains; Comprise physical propertiess such as transparency, hardness, wear resistance, gloss, tinctorial yield, homogeneity because it is excellent; It need can be effectively applied to those eyeglasses of high-clarity, like glasses, industrial safety glasses and leisure visor.
Above-mentioned purpose of the present invention can reach through following embodiment of the present invention.
In order to achieve the above object, the invention provides a kind of method for preparing titanium oxide-organic complex colloidal sol, this method may further comprise the steps:
The temperature that a) will contain the reaction soln of reaction solvent and titanium dioxide precursor is elevated to the sol gel reaction temperature;
B) after being added reaction soln, an acidic catalyst carries out sol gel reaction, to generate TiO 2 sol;
C) through adding organic complex and making it and TiO 2 sol prepared in reaction titanium oxide-organic complex colloidal sol;
D) contain the reaction soln of said titanium oxide-organic complex colloidal sol through constant pressure and dry, vacuum-drying or lyophilize drying; And
E) redispersion exsiccant titanium oxide-organic complex in spreading solvent.
The present invention provides a kind of method for preparing titanium oxide-organic complex colloidal sol in addition, and this method may further comprise the steps:
The temperature that a) will contain the reaction soln of reaction solvent and titanium dioxide precursor is elevated to the sol gel reaction temperature;
B) after being added reaction soln, an acidic catalyst carries out sol gel reaction, to generate TiO 2 sol;
D) through the dry said TiO 2 sol of constant pressure and dry, vacuum-drying or lyophilize;
E) the said exsiccant titanium oxide of redispersion in spreading solvent; And
C) through adding organic complex and making it and the TiO 2 sol prepared in reaction titanium oxide-organic complex colloidal sol of redispersion.
The present invention provides a kind of titanium oxide-organic complex colloidal sol in addition, and wherein, titanium oxide-organic complex particulate solid content is 5～50wt% of total titanium oxide-organic complex colloidal sol.
The present invention also provides a kind of compsn that is used to form medium, height and superelevation refractive index coating, and said composition contains said titanium oxide-organic complex colloidal sol with the concentration of 10～80wt% of said composition gross weight.
Hereinafter is described the present invention in detail.
Prepare TiO 2 sol through sol gel reaction and receive several factors influence, like the characteristic of pH, temperature of reaction and the time of reaction soln, concentration of reactants, catalyzer and concentration, H
2The kind of the mol ratio of O and metallic element (R), tensio-active agent, the kind of additive and drying conditions etc.In these variablees, the relative mol ratio (R) of the characteristic of pH, catalyzer and concentration, water and temperature of reaction are for crystal formation most important factor.The characteristic of particle surface is determined by additive.Therefore, for the characteristic of controlling TiO 2 sol, the network structure of titanium dioxide granule and the surface properties of titanium dioxide granule, it is important regulating these factors.
Consider above-mentioned factor, design preparation method of the present invention uniquely,, prepare titanium oxide-organic complex colloidal sol with through organic complex is added the TiO 2 sol through the preparation of the sol gel reaction under the high temperature; Or prepare titanium oxide-organic complex colloidal sol: prepare TiO 2 sol through sol gel reaction, the exsiccant titania powder of redispersion gained in spreading solvent, and the solution that organic complex is added redispersion through following steps.
According to the method for the invention, through regulating the titanium dioxide granule of crystalline surface property and growing and preparing nano-scale so that its have narrow size-grade distribution monodispersity and with the high-compatibility of the organic solvent that is used for coating composition.Therefore, though when titanium dioxide granule be water-dispersion or in organic spreading solvent redispersion, do not observe coagulation yet, show that it is still stable, therefore, it can disperse in spreading solvent under the high density up to 50wt% (solid content).
The first method for preparing titanium oxide of the present invention-organic complex colloidal sol may further comprise the steps:
The temperature that a) will contain the reaction soln of reaction solvent and titanium dioxide precursor is elevated to the sol gel reaction temperature;
B) after being added reaction soln, an acidic catalyst carries out sol gel reaction, to generate TiO 2 sol;
C) through adding organic complex and making it and TiO 2 sol prepared in reaction titanium oxide-organic complex colloidal sol;
D) contain the reaction soln of said titanium oxide-organic complex colloidal sol through constant pressure and dry, vacuum-drying or lyophilize drying; And
E) redispersion exsiccant titanium oxide-organic complex in spreading solvent.
First step for preparing titanium oxide-organic complex colloidal sol through this method is that titanium dioxide precursor is added reaction solvent, and its temperature is elevated to sol gel reaction temperature (step a).
Said titanium dioxide precursor is common acceptable organic titanic compound or inorganic titanium compound.Said organic titanic compound can be selected from the group that comprises like the titan-alkoxide of purity titanium tetraethoxide (TEOT), tetraisopropoxy titanium (TIPT) and four titanium butoxide (TBOT).
Said inorganic titanium compound can be selected from and comprise titanium chloride (TiCl
4), titanium sulfate (Ti (SO
4)
2) and titanyl sulfate (TiO (SO
4)) group.
Said reaction solvent can be selected from and comprise: water; C
1～C
5Lower alcohol is like methyl alcohol, ethanol, propyl alcohol, Virahol, butanols and isopropylcarbinol; Higher alcohols is like Z 150PH, pinakon; And composition thereof.Any solvent of more preferably selecting water (being used for hydrolysis) or being used to dissolve organic and inorganic titanium compound is as reaction solvent.The mixture of more preferably selecting water and one or more other solvents is as reaction solvent.
When mixing titanium dioxide precursor and water, strong exothermic reaction takes place, so must strong at low temperatures stirring carry out this mixing.
In reactor drum, mix said titanium dioxide precursor and reaction solvent equably, then the temperature of reactor drum is brought up to the sol gel reaction temperature, when said reaction solvent comprised water, it was 50～100 ℃.For total titanium dioxide precursor of 100 weight parts, the content of said reaction solvent is 100～1600 weight parts.
Dispersed in order to improve the TiO 2 sol particulate that forms through sol gel reaction, can add extra inorganic salt or tensio-active agent.
Said inorganic salt can be one or more that are selected from the group that comprises NaCl, KCl, NaBr and KBr.
Said tensio-active agent can be one or more negatively charged ion or the cats product that is selected from the group that comprises sodium lauryl sulphate (SDS), cetyl trimethylammonium bromide (CTAB) and palmityl trimethyl ammonium chloride (CTAC).
Consider particulate stability and redispersibility, for 100 parts by weight of titanium oxide, the amount of said inorganic salt and tensio-active agent can be regulated in the scope of 1～10 weight part.If the content of said tensio-active agent is lower than 1 weight part, it can not influence dispersion stabilization and redispersibility.On the contrary; If the content of tensio-active agent is higher than 10 weight parts; The additional process that said titanium dioxide granule distortion maybe need be removed unnecessary inorganic salt and tensio-active agent; If unnecessary inorganic salt and tensio-active agent can not be removed fully, make this process complicated, and make the poor performance of coating composition.
In step b), acid catalyst is added reaction soln, generate TiO 2 sol through sol gel reaction then.Particularly, said acid catalyst is joined the reaction soln that contains said titanium dioxide precursor and reaction solvent lentamente, carry out sol gel reaction then, or remove the reaction solvent in the reactor drum simultaneously in sol gel reaction.
In this step, the pH regulator to 0.1 of reaction soln～2.5, more preferably 0.2～2.0 are so that the functional group of said titanium dioxide precursor accepts hydrogen ion fast.As a result, the electron density around the titanium oxide atom reduces, and uprises with the affinity of electronics.This shows with the reaction of water and quickens, so hydrolysis rate also becomes faster, and because it is easy to attacked by nucleophile, causes cohesion fast, causes the polymerization of titanium dioxide granule.Therefore, said an acidic catalyst improves the speed of sol gel reaction, and plays the effect that is used for the polymeric peptizing agent simultaneously.
Except said an acidic catalyst, can add basic catalyst.Under the situation of using basic catalyst, the length of gelation is extended.Therefore, more preferably an acidic catalyst.In the presence of an acidic catalyst, in polymkeric substance, can form straight chain or free branched structure, show to prepare undersized titanium oxide.In the presence of basic catalyst, so seriously form piece, so that particle can not form gel, and therefore the size of the titanium oxide of preparation greater than the titanium oxide of formation in the presence of an acidic catalyst.
Acid catalyst of the present invention is preferably one or more acid that are selected from the group that comprises nitric acid, hydrochloric acid, sulfuric acid and acetate.
Through the crystallization of consideration titanium oxide and the boiling point of reaction solvent etc., confirm the temperature of reaction and the time of sol gel reaction.For example, if reaction solvent is moisture, temperature of reaction is confirmed as in 50～100 ℃ of scopes, and the reaction times is confirmed as in 0.5～4 hour scope.Especially, temperature of reaction is to influence important factor of titanium oxide crystalline.If temperature of reaction is lower than 50 ℃, can not induce the colloidal sol effect, show that crystal growth is slow and will observe amorphous titania.If temperature of reaction is higher than 100 ℃, and if reaction reagent contain water, all spreading solvents will evaporate under normal pressure, thus particle will condense, even show that redispersion is with bad and after the processing again that comprises restir, also will produce deposition.But if induced reaction under high pressure means that the boiling point of spreading solvent improves, any temperature that is lower than the boiling point of reaction solvent all is acceptable.
In step c), organic complex is added said TiO 2 sol, then through reaction, generate titanium oxide-organic complex colloidal sol.
Particularly, organic complex is added the TiO 2 sol through above-mentioned sol gel reaction preparation, have titanium oxide-organic complex colloidal sol raising and consistency organic solvent with formation.In this step, the coagulation of the titania nanoparticles that makes is suppressed.Titanium oxide-organic complex of the present invention is a kind of organic complex that contains part, for example, and titanium oxide-organic complex that the coordinate-covalent bond through inner complex and titanium oxide forms.This titanium oxide-organic complex comprises chemical bond, so through removing reaction solvent, after dry and atomizing step, complex compound wherein still can keep behind the redispersion in spreading solvent.
For 100 parts by weight of titanium oxide precursors, the content of said organic complex is 5～500 weight parts.If the content of organic complex is lower than 5 weight parts, the surface of titanium oxide will can not replaced by organic complex fully, cause reducing with the consistency of organic solvent.If content is higher than 500 weight parts,, cause particulate coagulation and because the production rate decline that the evaporation that postpones causes with being separated of spreading solvent taken place.
The temperature of reaction of said titanium oxide-organic complex by the boiling point of speed of response, reaction solvent and with the consistency decision of organic solvent.If spreading solvent is a water, preferably at least 50 ℃ of temperature of reaction, more preferably 60～100 ℃.If temperature of reaction is lower than 50 ℃, the treatment time that is used to form titanium oxide-organic complex will be longer, cause reaction efficiency to reduce and reduce with the consistency of organic solvent.If temperature of reaction is higher than 100 ℃, be higher than the boiling point of spreading solvent, all spreading solvents will evaporate.Calculate according to common chemical reaction, calculate speed of response (k) through Arrhenius equation: k=Ae-Ea/RT, and speed of response increases along with the increase of temperature of reaction.Therefore, preferably improve temperature of reaction to form titanium oxide-organic complex with the short treatment time.
Organic complex of the present invention can be the compound that contains methyl ethyl diketone functional group, cellosolve and composition thereof.The said compound that contains methyl ethyl diketone functional group is illustrated as methyl ethyl diketone, 1,3-diphenylpropane-1 (C
6H
5C (O) CH
2C (O) C
6H
5), tertiary butyl tertiary butyl ketone ((CH
3)
3CC (O) CC (CH
3)
3), 4-t-butyldimethylsilyloxy base-3-amylene-2-ketone, 4-(trimethylsiloxy)-3-amylene-2-ketone etc.The cellosolve here is illustrated as methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, ispropyl cellosolve etc.
In step d), drying contains the reaction soln of titanium oxide-organic complex colloidal sol.Particularly, the reaction soln that contains titanium oxide-organic complex colloidal sol through constant pressure and dry, vacuum-drying or lyophilize drying.If reaction solvent is a water, i) reaction solvent is in 25～150 ℃ of constant pressure and dries, and ii) reaction solvent is in 0～150 ℃ of vacuum-drying, or iii) reaction solvent in-180～0 ℃ of lyophilize.
The preferred temperature of constant pressure and dry is 25～150 ℃.If temperature is higher than 150 ℃, drying step finishes so apace, so that the crystallization of titanium oxide increases but observe the coagulation between the dry granules, has reduced the redispersibility in the spreading solvent.If temperature is lower than 25 ℃, drying step needs the longer time, and stays unreacted reactant, shows to make monodispersed transparent titanium dioxide-organic complex colloidal sol.
Against vacuum is dry, and 300～700mmHg, more preferably the pressure of 400～500mmHg is needed.Vacuum drying preferred temperature is 0～150 ℃, and more preferably 0～100 ℃.Can use conventional reliever during vacuum-drying, to remove reaction solvent.Can carry out drying process through lyophilize at-180～0 ℃.
In step e), redispersion exsiccant titanium oxide-organic complex in spreading solvent is to obtain titanium oxide-organic complex colloidal sol.Said spreading solvent can be selected from and comprise: water; C
1～C
6Lower alcohol is like methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol and Pyranton; Higher alcohols is like Z 150PH; Acetic ester is like methyl acetate, ETHYLE ACETATE, isopropyl acetate, n-butyl acetate, cellosolve acetate; Cellosolve is like methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, ispropyl cellosolve; N, dinethylformamide (DMF), N-crassitude diketone (NMP), THF (THF), propylene glycol monomethyl ether, pinakon, methyl ethyl diketone and composition thereof.
The second method for preparing titanium oxide of the present invention-organic complex colloidal sol may further comprise the steps:
The temperature that a) will contain the reaction soln of reaction solvent and titanium dioxide precursor is elevated to the sol gel reaction temperature;
B) after being added reaction soln, an acidic catalyst carries out sol gel reaction, to generate TiO 2 sol;
D) through the dry said TiO 2 sol of constant pressure and dry, vacuum-drying or lyophilize;
E) the said exsiccant titanium oxide of redispersion in spreading solvent; And
C) through adding organic complex and making it and the TiO 2 sol prepared in reaction titanium oxide-organic complex colloidal sol of redispersion.
Each step of can the mode identical carrying out above-mentioned preparation method with the corresponding steps of first method.
The titanium oxide of gained-organic complex colloidal sol is the solution that a kind of titanium oxide-organic complex is separated into colloidal sol.Titanium dioxide granule is preferably the crystal titanium dioxide particle, more preferably anatase octahedrite or rutile crystal particle.The primary particles of said titanium oxide-organic complex colloidal sol is mean diameter 1～20nm, more preferably 3～20nm, and it has the very narrow size-grade distribution of monodispersity.Be dispersed in titanium oxide-organic complex particulate solid content in the spreading solvent and be 5～50wt% of the gross weight of said titanium oxide-organic complex colloidal sol, preferred 8～50wt%, more preferably 15～50wt% and most preferably 30～45%.Above-mentioned content is compared higher with the solid content (it is 5wt%) of the TiO 2 sol for preparing through conventional sol gel reaction.
Titanium oxide-organic complex colloidal sol through method of the present invention preparation can be used as medium, height and the superelevation specific refractory power filler in the compsn that is used to form medium, height and superelevation refractive index coating.Said compsn is through the tetraethyl orthosilicate that mixes 1～20wt%, the 3-glycidyl oxygen base propyl trimethoxy silicane (glycidyloxypropyltrimethoxysilane) of 5～30wt%, titanium oxide-organic complex colloidal sol and the preparation of organic spreading solvent of 10～80wt%.According to the method for the invention; When titanium oxide-organic complex colloidal sol in organic spreading solvent during redispersion; The coagulation that its performance is less; So that particle can further be reduced to the secondary granule of mean diameter 10～200nm, shows that said particle has excellent transparency and therefore can be used as the filler in the compsn that is used to form medium, height and superelevation refractive index coating.
Said organic spreading solvent can be selected from and comprise: water; C
1～C
6Lower alcohol is like methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol and Pyranton; Higher alcohols is like Z 150PH; Acetic ester is like methyl acetate, ETHYLE ACETATE, isopropyl acetate, n-butyl acetate, cellosolve acetate; Cellosolve is like methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, ispropyl cellosolve; N, dinethylformamide (DMF), N-crassitude diketone (NMP), THF (THF), propylene glycol monomethyl ether, pinakon, methyl ethyl diketone and composition thereof.
The compsn that is used to form medium, height and superelevation refractive index coating need can be applicable to the glasses of high-clarity, industrial safety glasses, leisure visor etc.After being coated with the surface of said eyeglass and solidifying, it is 1.5～1.80 medium, height and superelevation refractive index coating that said compsn finally forms ranges of indices of refraction.
The method that is used to be coated with can be conventional wet coat, for example, and roller coating, spraying, dip-coating or spin coating.
Condition of cure is according to ratio of mixture or composition and difference, but under 60～150 ℃ of the softening temperature that is lower than substrate, carries out 20 minutes to several hours usually, to obtain having the coating of desirable hardness.
If necessary, coating is with the dye solution dyeing like dispersed dye of 0.1～1wt%.Coating is immersed in the dye solution 5～10 minutes with dyeing under 80～100 ℃.
Because method of the present invention is used TiO 2 sol, the coating for preparing through method of the present invention has lot of advantages, and wherein, the titanium oxide-organic complex composition granule with nano-scale of monodispersity disperses with high density in spreading solvent.Particularly, the titanium oxide of nano-scale is beneficial to the formation of highly transparent coating, and its monodispersity also is beneficial to and enhances the transparency.In addition, said titanium oxide has improved and consistency organic solvent, show its and any other with an organic solvent consistency raising of coating agent, so coating can have excellent transparency.The dispersion of titanium dioxide granule makes coating process simple and efficient (according to conventional methods, needing the multiple coating process to guarantee suitable specific refractory power) under high density.According to the method for the invention, the coating of gained has improved performances such as the hardness of comprising, wear resistance, transparency, gloss, tinctorial yield and homogeneity, and becomes thinner.
Description of drawings
Understand the application of preferred implementation of the present invention best with reference to accompanying drawing, wherein,
Fig. 1 is the transmission electron micrograph of the titanium oxide-organic complex colloidal sol of preparation among the embodiment 1.
Fig. 2 is between the titanium oxide-organic complex colloidal sol of preparation among organic solvent and the embodiment 1, and the compatibility test result's between the TiO 2 sol of preparation in organic solvent and the comparing embodiment 1 photo.
Fig. 3 is for showing the diagram of the size-grade distribution of the titanium oxide-organic complex colloidal sol of preparation among the embodiment 1.
Fig. 4 is for showing the diagram that is dispersed in the size-grade distribution of the titanium oxide-organic complex colloidal sol of preparation among the embodiment 1 in the organic solvent.
Fig. 5 is for showing the diagram that is dispersed in the size-grade distribution of the TiO 2 sol of preparation in the comparing embodiment 1 in the organic solvent.
Embodiment
Practicality of the present invention with preferred embodiment shown in following examples, describe at present.
Yet, it will be understood by those skilled in the art that and consider that this openly, can modify and improve in essence of the present invention and scope.
[embodiment 1]
In reactor drum, add 1500g zero(ppm) water, in zero(ppm) water, slowly add 40g Virahol and the 240g four different third titanium oxide (TTIP; DuPont).
The temperature of reactor drum is elevated to 80 ℃, adds 42g nitric acid (65wt%) then, carries out sol gel reaction 2 hours at 80 ℃ then.Add the 40g methyl ethyl diketone, a kind of organic complex is then 80 ℃ of reactions 5 hours.
80 ℃ of following dry reagent contained within 14 hours, to obtain titanium oxide-organic complex powder.
With said titanium oxide-organic complex powder cool to room temperature, add 200g water as spreading solvent, with the titanium oxide-organic complex colloidal sol that obtains redispersion.
[embodiment 2]
Except the temperature with reactor drum is elevated to 90 ℃, prepare titanium oxide-organic complex colloidal sol with embodiment 1 described identical mode.
[embodiment 3]
Except the temperature with reactor drum is elevated to 99 ℃, prepare titanium oxide-organic complex colloidal sol with embodiment 1 described identical mode.
[comparing embodiment 1]
Add the step of methyl ethyl diketone as organic complex, except removing to prepare TiO 2 sol with embodiment 1 described identical mode.
[comparing embodiment 2]
Except the temperature of reactor drum is brought up to 25 ℃, to prepare titanium oxide-organic complex colloidal sol with embodiment 1 described identical mode.
[embodiment 4]
Add the organic complex of 40g through the TiO 2 sol of preparation in comparing embodiment 1, stir this mixture preparation in 1 hour titanium oxide-organic complex colloidal sol down at 80 ℃ then.
[EXPERIMENTAL EXAMPLE 1]
Study solid content, dispersiveness and the granularity of each TiO 2 sol for preparing in the foregoing description and the comparing embodiment, the result is shown in Table 1 (granularity of discrete particles and the size of dispersed expression through the secondary granule of the cohesion formation of primary particles).
[table 1]
| ? | Solid content | Fineness of dispersion (dispersiveness) | Initial particle size (TEM) | Crystallization |
| Embodiment 1 | 32 | 10± |
3～5nm | Anatase octahedrite |
| Embodiment 2 | 32 | 10± |
3～5nm | |
| Embodiment | ||||
| 3 | 32 | 11±2nm | 4～6nm | Anatase octahedrite |
| Comparing embodiment 1 | 32 | 10±2nm | 4～6nm | Anatase octahedrite |
| Comparing embodiment 2 | 32 | 10nm～5nm | 4～50nm | Amorphous+anatase octahedrite |
| Embodiment 4 | 32 | 10±2nm | 4～6nm | Anatase octahedrite |
As shown in table 1, the titanium oxide-organic complex colloidal sol size of preparation is 3～6nm among the embodiment 1～4, and it is at nano level, and the anatase titania-organic complex of its nanometer size is scattered in the spreading solvent particle stabilizedly.The solid content of TiO 2 sol is up to 32%.An index of redispersion degree, the granularity of discrete particles turns out to be nanometer size, has narrow size-grade distribution.
The size of the TiO 2 sol of preparation is 4～6nm in the comparing embodiment 1, shows that the anatase titania particle of nanometer size is dispersed in the spreading solvent with high density.Titanium oxide-organic complex the colloidal sol of preparation and the colloidal sol of comparing embodiment 1 have equal redispersibility among the embodiment 1～3 of adding organic complex.
In comparing embodiment 2, at room temperature carry out sol gel reaction, so induce the colloidal sol effect lentamente.This makes monodisperse particles be difficult to preparation, and because the atom that does not have enough energy to be used for titanium oxide comes into line, forms amorphous titania.
[EXPERIMENTAL EXAMPLE 2] transmission electron micrograph
Through the granularity of the TiO 2 sol of preparation among the transmission electron microscope measurement embodiment 1, the result is shown among Fig. 1.Preparation has the crystal titanium dioxide-organic complex of the granularity of 3～5nm.
[EXPERIMENTAL EXAMPLE 3] estimated the consistency with organic spreading solvent
Fig. 2 is between the titanium oxide-organic complex colloidal sol of preparation among organic solvent and the embodiment 1, and the compatibility test result's between the TiO 2 sol of preparation in organic solvent and the comparing embodiment 1 photo.In organic spreading solvent behind the redispersion; The titanium oxide-organic complex colloidal sol of preparation performance transparency among the embodiment 1, thus the background letter can clearly read, yet; When the TiO 2 sol of preparation in the comparing embodiment 1 in organic spreading solvent during redispersion; Even the particle of nanometer size singly disperses well, since the particulate coagulation, the transparency that its performance reduces.
[EXPERIMENTAL EXAMPLE 4] sreen analysis
The granularity of the TiO 2 sol of preparation in the titanium oxide-organic complex of preparation and the comparing embodiment 1 among the employing particle-size analyzer research embodiment 1.As a result, as shown in Figure 3, particle wherein is monodispersed.
For the TiO 2 sol and the consistency of organic solvent of preparation in titanium oxide-organic complex of studying among the embodiment 1 preparation and the comparing embodiment 1, each compound of equivalent is dispersed in the organic solvent, passes through use particle size analyzer granularity then.The result is shown in table 4 and the table 5.Said titanium oxide-organic complex colloidal sol and TiO 2 sol are formed by monodisperse particles, but the consistency of their performances and organic solvent different levels.Said titanium oxide-organic complex shows the climax at 20nm, and said TiO 2 sol shows the climax at 400nm.The above results shows that the titanium oxide-organic complex of preparation among the embodiment 1 has improved and consistency organic solvent.
[embodiment 5]
Preparation contains the TiO 2 sol for preparing among the embodiment 1, the compsn that is used to form the medium refractive index coating.
Particularly, remain in the jacketed reactor of room temperature, add tetraethyl orthosilicate, the 3-glycidyl oxygen base propyl trimethoxy silicane of 250g and the methyl alcohol of 100g of 50g to temperature.TiO 2 sol (the solid content: 32wt%), stirred then 3 hours that adds 130g to this mixture.Add the methyl ethyl diketone of 145g and the methyl alcohol of 200g to this reaction mixture, with the preparation coating solution.
[embodiment 6]
Except the TiO 2 sol that adds 260g replaces preparing the compsn that is used to form high refractive index coating with the identical mode described in the embodiment 5 the 130g TiO 2 sol of preparation among the embodiment 1.
[embodiment 7]
Except the TiO 2 sol that adds 390g replaces preparing the compsn that is used to form the superelevation refractive index coating with the identical mode described in the embodiment 5 the 130g TiO 2 sol of preparation among the embodiment 1.
[comparing embodiment 3]
TiO 2 sol (the solid content: 32 weight parts), prepare the compsn that is used to form the medium refractive index coating of preparation in using comparing embodiment 1 with the identical mode described in the embodiment 5.
[comparing embodiment 4]
TiO 2 sol (the solid content: 32 weight parts), prepare the compsn that is used to form the medium refractive index coating of preparation in using comparing embodiment 1 with the identical mode described in the embodiment 6.
[comparing embodiment 5]
TiO 2 sol (the solid content: 32 weight parts), prepare the compsn that is used to form the medium refractive index coating of preparation in using comparing embodiment 1 with the identical mode described in the embodiment 7.
[EXPERIMENTAL EXAMPLE 5]
Be carried on the substrate through the coating solution of wet coat, then in 60 ℃ of dryings and in 120 ℃ of curing, with the preparation coating preparation in embodiment 5～7 and the comparing embodiment 3～5.Study the physical properties of these coatings, the result is shown in Table 2.
A: specific refractory power
With coating composition coating silicon chip and curing.Use prism coupler each area measure specific refractory power 5 times, obtain MV then.
B: coat-thickness (μ m)
With coating composition coating silicon chip and curing.Use the prism coupler refractive Index Measurement, and the measuring reservoir spacing.Each area measure 5 times is also obtained MV.
C: wear resistance
Use is bundled in the #0000 steel wool friction eyeglass 30 times on the 1kg hammer, with the research wear resistance.
◎: scratch number: 0
Zero: the scratch number: up to 5 scratches up to 1cm length.
△: scratch number: more than 5 up to the scratch of 1cm length or 1～3 the long scratch of 1cm at least.
X: scratch number: more than 3 long scratches of 1cm length at least.
D: heatproof water-based
To be coated with eyeglass and be immersed in 100 ℃ of boiling water 10 minutes, estimate then.
◎: fracture number: 0
Zero: fracture number: up to 5 cracks up to 5mm length
△: fracture number: more than 5 crack or 1～3 long cracks more than 5mm up to 5mm length.
X: fracture number: more than 3 long cracks more than 5mm
E: homogeneity
Through the surface of visual inspection coating eyeglass, and surface elevation place, indenture district and the thickness of research coating.
F: clinging power
Measure clinging power through ASTM D3359.Particularly, on coating, draw 1mm * 1mm line, process 100 subregions.Carry out spalling test 10 times through use 24mm zona pellucida (Nichiban ltd, Japan), and record still adheres to the sectional quantity of not peeling off.
G: mist degree
Through using haze meter to measure the substrate mist degree, to estimate the transparency of coating.The wet coat substrate is measured the mist degree of coating, and observes the variation of mist degree (Hz).
[table 2]
As shown in table 2, the coating of the coating solution preparation through embodiment 5～7 has 1.55～1.65 specific refractory power, means that it shows medium, height and superelevation specific refractory power respectively.In addition, those layers show excellent abrasive, heatproof water-based, homogeneity, clinging power and transparency.
The coating solution of embodiment 5 has 1.55 specific refractory power (medium refractive index), so it can be used as the coating composition that is used to form the medium refractive index coating.The coating solution of embodiment 6 has 1.60 specific refractory power, means that it can be used as the coating composition that is used to form high refractive index coating.The coating solution of embodiment 7 has 1.65 specific refractory power, so it can be used as the coating composition that is used to form the superelevation refractive index coating.
The coating of the coating solution preparation through comparing embodiment 4～6 has 1.55～1.65 specific refractory power, means that it has medium, height and superelevation specific refractory power and excellent abrasive, heatproof water-based, homogeneity and clinging power.Yet it has reduction and consistency organic solvent, shows that it need not act on the coating composition of high-clarity eyeglass.
Industrial applicability
Explain like preceding text; Titanium oxide of the present invention-organic complex colloidal sol not only has excellent and consistency, high solids content and stability in storage organic solvent; It also can not need the multiple painting process to form thin coating, so it is applicable to high refractive index coating.
In addition; Titanium oxide of the present invention-organic complex colloidal sol can form has the excellent coating that comprises transparency, wear resistance, gloss, tinctorial yield and inhomogeneity physical properties, so it can be used in the compsn that is used for glasses, industrial safety glasses, leisure visor etc. that is used to form highly transparent effectively.
One skilled in the art will understand that disclosed notion can be easily as other embodiments that change or be designed for the identical purpose of embodiment of the present invention with embodiment in the above-mentioned specification sheets.Those skilled in the art should be understood that also the equal embodiment of this type does not depart from essence of the present invention and the scope of illustrating in the appended claims.
Claims (15)
1. method for preparing titanium oxide-organic complex colloidal sol, this method may further comprise the steps:
The temperature that a) will contain the reaction soln of reaction solvent and titanium dioxide precursor is elevated to the sol gel reaction temperature;
B) after being added reaction soln, acid catalyst carries out sol gel reaction, to generate TiO 2 sol;
C), and prepare titanium oxide-organic complex colloidal sol through adding organic complex and make it and the TiO 2 sol reaction;
D) contain the reaction soln of said titanium oxide-organic complex colloidal sol through constant pressure and dry, vacuum-drying or lyophilize drying; And
E) redispersion exsiccant titanium oxide-organic complex in spreading solvent,
Wherein, said titanium dioxide precursor is selected from by purity titanium tetraethoxide, tetraisopropoxy titanium, four titanium butoxide, titanium chloride (TiCl
4), titanium sulfate (Ti (SO
4)
2) and titanyl sulfate (TiO (SO
4)) and composition thereof in the group formed; Said organic complex is a methyl ethyl diketone, 1; 3-phenylbenzene-1; 3-propanedione, tertiary butyl tertiary butyl ketone, 4-t-butyldimethylsilyloxy base-3-amylene-2-ketone, 4-(trimethylsiloxy)-3-amylene-2-ketone, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, ispropyl cellosolve or its mixture
Wherein, the temperature of the sol gel reaction of step a) and step b) is 50～100 ℃, and
Wherein, for 100 parts by weight of titanium oxide precursors, the content of said organic complex is 5～500 weight parts.
2. method for preparing titanium oxide-organic complex colloidal sol, this method may further comprise the steps:
The temperature that a) will contain the reaction soln of reaction solvent and titanium dioxide precursor is elevated to the sol gel reaction temperature;
B) after being added reaction soln, acid catalyst carries out sol gel reaction, to generate TiO 2 sol;
D) through the dry said TiO 2 sol of constant pressure and dry, vacuum-drying or lyophilize;
E) the said exsiccant titanium oxide of redispersion in spreading solvent; And
C) through adding organic complex and make it and the TiO 2 sol prepared in reaction titanium oxide-organic complex colloidal sol of redispersion,
Wherein, said titanium dioxide precursor is selected from by purity titanium tetraethoxide, tetraisopropoxy titanium, four titanium butoxide, titanium chloride (TiCl
4), titanium sulfate (Ti (SO
4)
2) and titanyl sulfate (TiO (SO
4)) and composition thereof in the group formed; Said organic complex is a methyl ethyl diketone, 1; 3-phenylbenzene-1; 3-propanedione, tertiary butyl tertiary butyl ketone, 4-t-butyldimethylsilyloxy base-3-amylene-2-ketone, 4-(trimethylsiloxy)-3-amylene-2-ketone, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, ispropyl cellosolve or its mixture
Wherein, the temperature of the sol gel reaction of step a) and step b) is 50～100 ℃, and
Wherein, for 100 parts by weight of titanium oxide precursors, the content of said organic complex is 5～500 weight parts.
3. according to claim 1 or the described method for preparing titanium oxide-organic complex colloidal sol of claim 2, wherein, said reaction solvent is a water.
4. according to claim 1 or the described method for preparing titanium oxide-organic complex colloidal sol of claim 2, wherein, be removed during the sol gel reaction of said reaction solvent in step b).
5. according to claim 1 or the described method for preparing titanium oxide-organic complex colloidal sol of claim 2, wherein, under 50 ℃ or higher temperature, carry out through adding step that organic complex prepares titanium oxide-organic complex colloidal sol.
6. according to claim 1 or the described method for preparing titanium oxide-organic complex colloidal sol of claim 2; Wherein, said reaction solvent selects in the group of free water, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, Z 150PH, pinakon and composition thereof composition.
7. according to claim 1 or the described method for preparing titanium oxide-organic complex colloidal sol of claim 2; Wherein, Said spreading solvent selects free water, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, Pyranton, Z 150PH, methyl acetate, ETHYLE ACETATE, isopropyl acetate, n-butyl acetate, cellosolve acetate, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, ispropyl cellosolve, N, in the group that dinethylformamide, N-crassitude diketone, THF, propylene glycol monomethyl ether, pinakon, methyl ethyl diketone and composition thereof are formed.
8. according to claim 1 or the described method for preparing titanium oxide-organic complex colloidal sol of claim 2, wherein, said acid catalyst be selected from by nitric acid, sulfuric acid, hydrochloric acid, acetate, and composition thereof in the group formed.
9. according to claim 1 or the described method for preparing titanium oxide-organic complex colloidal sol of claim 2; Wherein, acid catalyst is added to carry out sol gel reaction behind the reaction soln be to carry out under the pH in 0.1～2.5 scope with the step b) that generates TiO 2 sol.
10. according to claim 1 or the described method for preparing titanium oxide-organic complex colloidal sol of claim 2; Wherein, The reaction solvent of step a) is a water, and the drying process of step d) is i) 25～150 ℃ through constant pressure and dry, ii) at 0～100 ℃ through vacuum-drying or iii) carry out through lyophilize at-180～0 ℃.
11. titanium oxide-organic complex colloidal sol; Wherein, Titanium oxide in the spreading solvent-organic complex particulate solid content is 5～50wt% of titanium oxide-organic complex colloidal sol gross weight, and wherein said organic complex is a methyl ethyl diketone, 1,3-phenylbenzene-1; 3-propanedione, tertiary butyl tertiary butyl ketone, 4-t-butyldimethylsilyloxy base-3-amylene-2-ketone, 4-(trimethylsiloxy)-3-amylene-2-ketone, cellosolve or its mixture
Wherein, said titanium oxide-organic complex colloidal sol comprises that the dispersive mean diameter is that primary particles or the dispersive mean diameter of 1～20nm is the secondary granule of 10～200nm.
12. titanium oxide according to claim 11-organic complex colloidal sol, wherein, said titanium oxide-organic complex composition granule is anatase octahedrite or rutile crystal particle.
13. titanium oxide according to claim 11-organic complex colloidal sol, wherein, said titanium oxide-organic complex colloidal sol is the method preparation through the method for claim 1 or claim 2.
14. being the amounts with 10～80wt% of the gross weight of said compsn, a compsn that is used to form medium, height and superelevation refractive index coating, said composition comprise titanium oxide-organic complex colloidal sol through the method preparation of claim 1 or claim 2,
Wherein said medium, height and superelevation ranges of indices of refraction are 1.5～1.80.
15. the compsn that is used to form medium, height and superelevation refractive index coating according to claim 14, said composition is with the coating that acts on glasses.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2006-0084252 | 2006-09-01 | ||
| KR1020060084252A KR100950853B1 (en) | 2006-09-01 | 2006-09-01 | Titania sol chelated with an organic complex, a method thereof, and a composition including said titania sol for forming medium, high, super-high refractive index coating layer |
| KR1020060084252 | 2006-09-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101134598A CN101134598A (en) | 2008-03-05 |
| CN101134598B true CN101134598B (en) | 2012-07-18 |
Family
ID=39158959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006101608236A Active CN101134598B (en) | 2006-09-01 | 2006-11-30 | Titania sol chelated organic complexes, its preparation method and composition comprising the same |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100950853B1 (en) |
| CN (1) | CN101134598B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101133969B1 (en) * | 2009-02-13 | 2012-04-09 | (주)엘지하우시스 | Wallpaper with Deodorizing function and Method of Maunfacturing of the Wallpaper |
| KR101158806B1 (en) * | 2009-09-25 | 2012-06-26 | 김영인 | Zinc oxide dispersion sol composition for uv-protection and method of preparing zinc oxide dispersion sol using thereof |
| CN102061115A (en) * | 2010-12-13 | 2011-05-18 | 中国航天科工集团八五一一研究所 | Coating liquid suitable for preparing boiling-resistance high-obstruction film and preparation method of coating liquid |
| CN103619470A (en) * | 2011-06-21 | 2014-03-05 | 优美科股份公司及两合公司 | Method for the deposition of metals on support oxides |
| CN107915254B (en) * | 2016-10-08 | 2020-05-26 | 瞿海锋 | Preparation method of nano titanium dioxide powder |
| CN111699165A (en) * | 2018-02-14 | 2020-09-22 | 日本碍子株式会社 | Titanium dioxide porous body and method for producing same |
| CN112310288B (en) * | 2019-07-25 | 2022-01-18 | Tcl科技集团股份有限公司 | Modified metal oxide, preparation method thereof and quantum dot light-emitting diode |
| CN113493476B (en) * | 2021-09-07 | 2021-11-30 | 苏州源展材料科技有限公司 | Preparation method of ALD precursor titanium complex |
| CN117658207A (en) * | 2023-11-09 | 2024-03-08 | 广州市浩立生物科技有限公司 | Preparation method and application of nano titanium dioxide powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454474A (en) * | 2002-04-30 | 2003-11-12 | 香港中文大学 | Method of preparing mesoporous titanium dioxide film with high disinfecting photoactivity |
| CN1593747A (en) * | 2004-06-25 | 2005-03-16 | 清华大学 | Preparation method of highly active titanium dioxide membrane photocatalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100297809B1 (en) | 1998-12-17 | 2001-10-29 | 김충섭 | Room temperature production method of crystalline titania particles using sol-gel method |
| KR20030021304A (en) * | 2001-09-05 | 2003-03-15 | (주)이앤비코리아 | Manufacturing method on transparent anatase type TiO2 sol |
| KR100727579B1 (en) | 2005-12-20 | 2007-06-14 | 주식회사 엘지화학 | Titania sol, preparing method thereof and composition for coating comprising thereof |
-
2006
- 2006-09-01 KR KR1020060084252A patent/KR100950853B1/en not_active IP Right Cessation
- 2006-11-30 CN CN2006101608236A patent/CN101134598B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454474A (en) * | 2002-04-30 | 2003-11-12 | 香港中文大学 | Method of preparing mesoporous titanium dioxide film with high disinfecting photoactivity |
| CN1593747A (en) * | 2004-06-25 | 2005-03-16 | 清华大学 | Preparation method of highly active titanium dioxide membrane photocatalyst |
Non-Patent Citations (3)
| Title |
|---|
| JP特开2000-219515A 2000.08.08 |
| 陈娜等.酸催化剂对溶胶-凝胶法制备TiO2粉末的影响.功能材料与器件学报11 2.2005,11(2),163-167. |
| 陈娜等.酸催化剂对溶胶-凝胶法制备TiO2粉末的影响.功能材料与器件学报11 2.2005,11(2),163-167. * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100950853B1 (en) | 2010-03-31 |
| KR20080020848A (en) | 2008-03-06 |
| CN101134598A (en) | 2008-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101134598B (en) | Titania sol chelated organic complexes, its preparation method and composition comprising the same | |
| JP5085559B2 (en) | Titanium dioxide sol, method for producing the same, and coating composition containing the same | |
| JP2009519890A5 (en) | ||
| CN102471060B (en) | Liquid dispersion of core/shell complex oxide particles, method for producing liquid dispersion, and coating composition containing particles | |
| TWI428282B (en) | Metal oxide complex sol, coating composition and optical member | |
| JP5591530B2 (en) | Method for producing silica-based fine particle dispersed sol, silica-based fine particle dispersed sol, coating composition containing the dispersed sol, curable coating film, and substrate with curable coating film | |
| KR100541750B1 (en) | Non-acidic, non-basic colloid solution containing dispersed titanium dioxide, method for preparing the same, and coating material comprising the colloid solution | |
| JP4841880B2 (en) | Inorganic oxide particles | |
| JP5717252B2 (en) | High refractive index powder, production method and use thereof | |
| CN101815676B (en) | Modified metal-oxide composite sol, coating composition, and optical member | |
| CN101238071B (en) | Zirconium oxide-tin oxide composite sol, coating composition and optical member | |
| WO2006129411A1 (en) | DISPERSION CONTAINING HOLLOW SiO2, COATING COMPOSITION, AND SUBSTRATE WITH ANTIREFLECTION COATING FILM | |
| KR20100016493A (en) | Sol of surface-coated titanium oxide, process for producing the same, and coating composition containing the same | |
| JP2008037700A (en) | Aggregate of silica-based compound oxide particle and method for manufacturing the same | |
| TW201641429A (en) | Method for producing dispersion of particles of titanium oxide in organic solvent | |
| JP6959290B2 (en) | Monoclinic zirconia nanoparticles and their manufacturing methods | |
| JPWO2008007708A1 (en) | Method for producing modified zirconium oxide-stannic oxide composite sol | |
| JP5004492B2 (en) | Silica-based composite oxide fine particles and method for producing the same | |
| KR101959045B1 (en) | Process for preparing high refractive organic-inorganic hybrid sol | |
| JP5084418B2 (en) | Bulk composition redispersible in organic solvent, process for producing the same, and organic solvent-dispersed sol in which the bulk composition is redispersed | |
| JP2000143984A (en) | Fluorinated polyimide resin composition and its production | |
| JP2820251B2 (en) | Titanium oxide sol | |
| JPH03279210A (en) | Organotitania-silica sol and production thereof | |
| JP2019167276A (en) | Manufacturing method of silica composite particle | |
| JP2014125593A (en) | Aluminum pigment composition and method of producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |