CN101134598A - 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
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- CN101134598A CN101134598A CNA2006101608236A CN200610160823A CN101134598A CN 101134598 A CN101134598 A CN 101134598A CN A2006101608236 A CNA2006101608236 A CN A2006101608236A CN 200610160823 A CN200610160823 A CN 200610160823A CN 101134598 A CN101134598 A CN 101134598A
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- 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
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- 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 dioxide-organic complex colloidal sol, its preparation method, and a kind of composition 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 dioxide-organic complex colloidal sol of the filler in a kind of composition that is used to form medium, high and superelevation refractive index coating, described composition all need can be applicable to glasses, industrial safety glasses and the leisure eye-protection glasses of high-clarity, and described composition 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 composition 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 glass mirror is easily damaged by any external shock, 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 eye-protection glasses 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 composition 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 dioxide.
Usually, be coated with and use the wet coating of coating solution that titanium dioxide is applied to various coatings by the dry method that comprises evaporation.Be used for the form preparation of the coating solution of wet coating with TiO 2 sol, wherein, titanium dioxide is dispersed in the solvent.Yet as everyone knows, titanium dioxide 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 as SO
3Exist down with the high reactivity gas of chlorine, titanium dioxide 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 by the sol gel reaction preparation with stable dispersion has been proposed.According to described sol gel reaction, easily hydrolysis metal halide or alkoxide make TiO 2 sol.
Yet the mechanism of described sol gel reaction is so complicated, does not also explain fully so that prepare TiO 2 sol by sol gel reaction.The kind and the influence of other reaction conditionss of used alkoxide, solvent and tensio-active agent in having only the physical properties of the titanium dioxide by sol gel reaction preparation such as granularity, crystallinity and dispersion stabilization to be proved to be to be reacted.That is, the physical properties of TiO 2 sol is subjected to the very big influence of order of reaction conditions and adding additive.
Korean Patent Publication No. 2001-0028286 has described a kind of method that is scattered in the TiO 2 sol in the water for preparing under normal pressure.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 by sol gel reaction.This method has realized preparing titania nanoparticles with uniform and stable dispersion, but it must carry out under High Temperature High Pressure and show coagulation during the redispersion exsiccant titania nanoparticles in spreading solvent.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 anatase octahedrite photocatalyst titanium oxide sol according of excellent crystallinity and 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,, the sedimentation and the gelation of sol particle will be observed if solid content is higher than 10wt%.Except that desolvating, solid content can increase to 20wt% by 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 dioxide 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 dioxide 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, at first prepares amorphous titania under alkaline condition, then high-temperature calcination.Change the amorphous titania that makes into crystal titanium dioxide by high-temperature calcination, so that the titanium dioxide of gained is powder type, also greatly differs from each other with desirable monodisperse sol.
Simultaneously, Korean Patent Application No. 10-2005-0126113 has described method and a kind of coating composition that uses this colloidal sol of a kind of preparation monodispersed TiO 2 sol under 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 dioxide-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 dioxide-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 further object of the present invention provides a kind of titanium dioxide-organic complex that is used to form medium, height and superelevation refractive index coating that contains, since its excellence comprise physical propertiess such as transparency, hardness, wear resistance, gloss, tinctorial yield, homogeneity, it need can be effectively applied to those eyeglasses of high-clarity, as glasses, industrial safety glasses and leisure eye-protection glasses.
Above-mentioned purpose of the present invention can reach by following embodiment of the present invention.
In order to achieve the above object, the invention provides a kind of method for preparing titanium dioxide-organic complex colloidal sol, this method may further comprise the steps:
A) temperature that will contain the reaction soln of reaction solvent and titanium dioxide precursor is elevated to the sol gel reaction temperature;
B) carry out sol gel reaction after an acidic catalyst being added reaction soln, to generate TiO 2 sol;
C) by adding organic complex and making it and TiO 2 sol prepared in reaction titanium dioxide-organic complex colloidal sol;
D) contain the reaction soln of described titanium dioxide-organic complex colloidal sol by constant pressure and dry, vacuum-drying or lyophilize drying; And
E) redispersion exsiccant titanium dioxide-organic complex in spreading solvent.
The present invention provides a kind of method for preparing titanium dioxide-organic complex colloidal sol in addition, and this method may further comprise the steps:
A) temperature that will contain the reaction soln of reaction solvent and titanium dioxide precursor is elevated to the sol gel reaction temperature;
B) carry out sol gel reaction after an acidic catalyst being added reaction soln, to generate TiO 2 sol;
D) by the dry described TiO 2 sol of constant pressure and dry, vacuum-drying or lyophilize;
E) the described exsiccant titanium dioxide of redispersion in spreading solvent; And
C) by adding organic complex and making it and the TiO 2 sol prepared in reaction titanium dioxide-organic complex colloidal sol of redispersion.
The present invention provides a kind of titanium dioxide-organic complex colloidal sol in addition, and wherein, titanium dioxide-organic complex particulate solid content is 5～50wt% of total titanium dioxide-organic complex colloidal sol.
The present invention also provides a kind of composition that is used to form medium, height and superelevation refractive index coating, and said composition contains described titanium dioxide-organic complex colloidal sol with the concentration of 10～80wt% of said composition gross weight.
Hereinafter, describe the present invention in detail.
Prepare TiO 2 sol by sol gel reaction and be subjected to several factors influence, as 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 dioxide-organic complex colloidal sol with by organic complex being added TiO 2 sol by the preparation of the sol gel reaction under the high temperature; Or prepare titanium dioxide-organic complex colloidal sol: prepare TiO 2 sol by sol gel reaction, the exsiccant titania powder of redispersion gained in spreading solvent, and the solution that organic complex is added redispersion by following steps.
The method according to this invention, by 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 dioxide of the present invention-organic complex colloidal sol may further comprise the steps:
A) temperature that will contain the reaction soln of reaction solvent and titanium dioxide precursor is elevated to the sol gel reaction temperature;
B) carry out sol gel reaction after an acidic catalyst being added reaction soln, to generate TiO 2 sol;
C) by adding organic complex and making it and TiO 2 sol prepared in reaction titanium dioxide-organic complex colloidal sol;
D) contain the reaction soln of described titanium dioxide-organic complex colloidal sol by constant pressure and dry, vacuum-drying or lyophilize drying; And
E) redispersion exsiccant titanium dioxide-organic complex in spreading solvent.
First step for preparing titanium dioxide-organic complex colloidal sol by this method is that titanium dioxide precursor is added reaction solvent, and its temperature is elevated to sol gel reaction temperature (step a).
Described titanium dioxide precursor is common acceptable organic titanic compound or inorganic titanium compound.Described organic titanic compound can be selected from the group that comprises as the titan-alkoxide of purity titanium tetraethoxide (TEOT), tetraisopropoxy titanium (TIPT) and four titanium butoxide (TBOT).
Described 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.
Described reaction solvent can be selected from and comprise: water; C
1～C
5Lower alcohol is as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols and isopropylcarbinol; Higher alcohols is as polyvinyl alcohol, hexylene glycol; 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.
Mix described titanium dioxide precursor and reaction solvent equably in reactor, then the temperature of reactor is brought up to the sol gel reaction temperature, when described reaction solvent comprised water, it was 50～100 ℃.For total titanium dioxide precursor of 100 weight parts, the content of described reaction solvent is 100～1600 weight parts.
In order to improve the TiO 2 sol particulate dispersiveness that forms by sol gel reaction, can add extra inorganic salt or tensio-active agent.
Described inorganic salt can be one or more that are selected from the group that comprises NaCl, KCl, NaBr and KBr.
Described 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 described inorganic salt and tensio-active agent can be regulated in the scope of 1～10 weight part.If the content of described 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 described titanium dioxide granule distortion maybe needs to remove unnecessary inorganic salt and tensio-active agent, if unnecessary inorganic salt and tensio-active agent can not be removed fully, make this process complexity, and make the poor performance of coating composition.
In step b), acid catalyst is added reaction soln, generate TiO 2 sol by sol gel reaction then.Particularly, described acid catalyst is joined the reaction soln that contains described titanium dioxide precursor and reaction solvent lentamente, carry out sol gel reaction then, or remove reaction solvent in the reactor 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 described titanium dioxide precursor accepts hydrogen ion fast.As a result, the electron density around the titanium dioxide 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 be attacked by nucleophile, causes cohesion fast, causes the polymerization of titanium dioxide granule.Therefore, described an acidic catalyst improves the speed of sol gel reaction, and plays the effect that is used for the polymeric peptizing agent simultaneously.
Except described 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 dioxide.In the presence of basic catalyst, so seriously form piece, so that particle can not form gel, and therefore the size of the titanium dioxide of preparation greater than the titanium dioxide 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.
By the crystallization of consideration titanium dioxide and the boiling point of reaction solvent etc., determine the temperature of reaction and the time of sol gel reaction.For example, if reaction solvent is moisture, temperature of reaction is defined as in 50～100 ℃ of scopes, and the reaction times is defined as in 0.5～4 hour scope.Especially, temperature of reaction is to influence important factor of titanium dioxide 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 also will produce precipitation after the processing again that comprises restir.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 described TiO 2 sol, then by reaction, generate titanium dioxide-organic complex colloidal sol.
Particularly, organic complex is added the TiO 2 sol for preparing by above-mentioned sol gel reaction, have titanium dioxide-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 dioxide-organic complex of the present invention is a kind of organic complex that contains part, for example, and titanium dioxide-organic complex that the coordinate-covalent bond by inner complex and titanium dioxide forms.This titanium dioxide-organic complex comprises chemical bond, so by 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 described organic complex is 5～500 weight parts.If the content of organic complex is lower than 5 weight parts, the surface of titanium dioxide will can not replaced by organic complex fully, cause reducing with the consistency of organic solvent.If content is higher than 500 weight parts, being separated of spreading solvent will be taken place, cause particulate coagulation and because the production rate decline that the evaporation that postpones causes.
The temperature of reaction of described titanium dioxide-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 dioxide-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, pass through Arrhenius equation: k=Ae-Ea/RT calculates speed of response (k), and speed of response increases along with the increase of temperature of reaction.Therefore, preferably improve temperature of reaction to form titanium dioxide-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 described 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 dioxide-organic complex colloidal sol.Particularly, the reaction soln that contains titanium dioxide-organic complex colloidal sol by 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 dioxide increases but observe 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.
The against vacuum drying, 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 by lyophilize at-180～0 ℃.
In step e), redispersion exsiccant titanium dioxide-organic complex in spreading solvent is to obtain titanium dioxide-organic complex colloidal sol.Described spreading solvent can be selected from and comprise: water; C
1～C
6Lower alcohol is as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol and Pyranton; Higher alcohols is as polyvinyl alcohol; Acetic ester is as methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, cellosolve acetate; Cellosolve is as methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, ispropyl cellosolve; N, dinethylformamide (DMF), N-crassitude diketone (NMP), tetrahydrofuran (THF) (THF), propylene glycol monomethyl ether, hexylene glycol, methyl ethyl diketone and composition thereof.
The second method for preparing titanium dioxide of the present invention-organic complex colloidal sol may further comprise the steps:
A) temperature that will contain the reaction soln of reaction solvent and titanium dioxide precursor is elevated to the sol gel reaction temperature;
B) carry out sol gel reaction after an acidic catalyst being added reaction soln, to generate TiO 2 sol;
D) by the dry described TiO 2 sol of constant pressure and dry, vacuum-drying or lyophilize;
E) the described exsiccant titanium dioxide of redispersion in spreading solvent; And
C) by adding organic complex and making it and the TiO 2 sol prepared in reaction titanium dioxide-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 dioxide of gained-organic complex colloidal sol is the solution that a kind of titanium dioxide-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 described titanium dioxide-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 dioxide-organic complex particulate solid content in the spreading solvent and be 5～50wt% of the gross weight of described titanium dioxide-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 by conventional sol gel reaction.
Titanium dioxide-organic complex colloidal sol by method of the present invention preparation can be used as medium, height and the superelevation specific refractory power filler in the composition that is used to form medium, height and superelevation refractive index coating.Described composition is by the tetraethyl orthosilicate that mixes 1～20wt%, the 3-glycidyl oxygen base propyl trimethoxy silicane (glycidyloxypropyltrimethoxysilane) of 5～30wt%, titanium dioxide-organic complex colloidal sol and the preparation of organic spreading solvent of 10～80wt%.The method according to this invention, when titanium dioxide-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 described particle has excellent transparency and therefore can be used as filler in the composition that is used to form medium, height and superelevation refractive index coating.
Described organic spreading solvent can be selected from and comprise: water; C
1～C
6Lower alcohol is as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol and Pyranton; Higher alcohols is as polyvinyl alcohol; Acetic ester is as methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, cellosolve acetate; Cellosolve is as methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, ispropyl cellosolve; N, dinethylformamide (DMF), N-crassitude diketone (NMP), tetrahydrofuran (THF) (THF), propylene glycol monomethyl ether, hexylene glycol, methyl ethyl diketone and composition thereof.
The composition 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 eye-protection glasses etc.After being coated with the surface of described eyeglass and solidifying, it is 1.5～1.80 medium, height and superelevation refractive index coating that described composition finally forms ranges of indices of refraction.
The method that is used to be coated with can be conventional wet coating, 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 carries out under 60～150 ℃ of the softening temperature that is lower than substrate 20 minutes to several hours usually, to obtain having the coating of desirable hardness.
If necessary, coating dyes with the dye solution as 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 by method of the present invention has lot of advantages, and wherein, the titanium dioxide-organic complex composition granule with nano-scale of monodispersity disperses with high density in spreading solvent.Particularly, the titanium dioxide 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, described titanium dioxide 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.The method according to this 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 dioxide-organic complex colloidal sol of preparation among the embodiment 1.
Fig. 2 is between the titanium dioxide-organic complex colloidal sol of preparation among organic solvent and the embodiment 1, and the photo of the compatibility test result between the TiO 2 sol of preparation in organic solvent and the comparing embodiment 1.
Fig. 3 is for showing the diagram of the size-grade distribution of the titanium dioxide-organic complex colloidal sol of preparation among the embodiment 1.
Fig. 4 is for showing the diagram of the size-grade distribution of the titanium dioxide-organic complex colloidal sol of preparation among the embodiment 1 that is dispersed in the organic solvent.
Fig. 5 is for showing the diagram of the size-grade distribution of the TiO 2 sol of preparation in the comparing embodiment 1 that is dispersed in the organic solvent.
Embodiment
Practicality of the present invention and preferred embodiment as shown in following examples, describe at present.
Yet, it will be understood by those skilled in the art that and consider the disclosure, can in essence of the present invention and scope, modify and improve.
[embodiment 1]
In reactor, add 1500g distilled water, in distilled water, slowly add 40g Virahol and the 240g four different third titanium oxide (TTIP; DuPont).
The temperature of reactor 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 dioxide-organic complex powder.
With described titanium dioxide-organic complex powder cool to room temperature, add 200g water as spreading solvent, with the titanium dioxide-organic complex colloidal sol that obtains redispersion.
[embodiment 2]
Except the temperature with reactor is elevated to 90 ℃, prepare titanium dioxide-organic complex colloidal sol in embodiment 1 described identical mode.
[embodiment 3]
Except the temperature with reactor is elevated to 99 ℃, prepare titanium dioxide-organic complex colloidal sol in 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 is brought up to 25 ℃, to prepare titanium dioxide-organic complex colloidal sol with embodiment 1 described identical mode.
[embodiment 4]
Add the organic complex of 40g by the TiO 2 sol of preparation in comparing embodiment 1, stir this mixture preparation in 1 hour titanium dioxide-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 results are shown in (granularity of discrete particles and dispersed expression are by the size of the secondary granule of the cohesion formation of primary particles) in the table 1.
[table 1]
| Solid content | Fineness of dispersion (dispersiveness) | Initial particle size (TEM) | Crystallization | |
| Embodiment 1 | 32 | 10±2nm | 3～5nm | Anatase octahedrite |
| Embodiment 2 | 32 | 10±2nm | 3～5nm | Anatase octahedrite |
| 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 dioxide-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 the 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 dioxide-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 dioxide comes into line, forms amorphous titania.
[EXPERIMENTAL EXAMPLE 2] transmission electron micrograph
Granularity by the TiO 2 sol of preparation among the transmission electron microscope measurement embodiment 1 the results are shown among Fig. 1.Preparation has the crystal titanium dioxide-organic complex of the granularity of 3～5nm.
[EXPERIMENTAL EXAMPLE 3] estimates the consistency with organic spreading solvent
Fig. 2 is between the titanium dioxide-organic complex colloidal sol of preparation among organic solvent and the embodiment 1, and the photo of the compatibility test result between the TiO 2 sol of preparation in organic solvent and the comparing embodiment 1.In organic spreading solvent behind the redispersion, the titanium dioxide of preparation among the embodiment 1-organic complex colloidal sol performance transparency, so the background letter can clearly be 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 dioxide-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 the titanium dioxide-organic complex of studying among the embodiment 1 preparation and the comparing embodiment 1, each compound of equivalent is dispersed in the organic solvent, then by use particle size analyzer granularity.The results are shown in table 4 and the table 5.Described titanium dioxide-organic complex colloidal sol and TiO 2 sol are formed by monodisperse particles, but the consistency of their performances and organic solvent different levels.Described titanium dioxide-organic complex shows the climax at 20nm, and described TiO 2 sol shows the climax at 400nm.The above results shows that the titanium dioxide-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 composition 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 composition that is used to form high refractive index coating in 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 composition that is used to form the superelevation refractive index coating in 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 composition that is used to form the medium refractive index coating of preparation in using comparing embodiment 1 in the identical mode described in the embodiment 5.
[comparing embodiment 4]
TiO 2 sol (the solid content: 32 weight parts), prepare the composition that is used to form the medium refractive index coating of preparation in using comparing embodiment 1 in the identical mode described in the embodiment 6.
[comparing embodiment 5]
TiO 2 sol (the solid content: 32 weight parts), prepare the composition that is used to form the medium refractive index coating of preparation in using comparing embodiment 1 in the identical mode described in the embodiment 7.
[EXPERIMENTAL EXAMPLE 5]
Be carried on the substrate by the coating solution of wet coating, 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 results are shown in the 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 mean value then.
B: coat-thickness (μ m)
With coating composition coating silicon chip and curing.Use prism coupler to measure specific refractory power, and the measuring reservoir spacing.Each area measure 5 times is also obtained mean value.
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
By 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 by ASTMD3359.Particularly, on coating, draw 1mm * 1mm line, make 100 subregions.Carry out spalling test 10 times by use 24mm zona pellucida (Nichiban company limited, Japan), and record still adheres to the sectional quantity of not peeling off.
G: mist degree
By using haze meter to measure the substrate mist degree, to estimate the transparency of coating.The wet coating substrate is measured the mist degree of coating, and observes the variation of mist degree (Hz).
[table 2]
| Physical properties | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparing embodiment 4 | Comparing embodiment 5 | Comparing embodiment 6 |
| Specific refractory power (prism coupler) | 1.55 | 1.60 | 1.65 | 1.55 | 1.60 | 1.65 |
| Coat-thickness (μ m) | 2.5 | 2.8 | 3.0 | 2.5 | 2.8 | 3.0 |
| Wear resistance (steel wool #0000,1kg) | ◎ | ◎ | ◎ | ◎ | ◎ | ○ |
| The heatproof water-based | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Homogeneity (homogenizing) | ○ | ○ | ○ | ○ | ○ | ○ |
| Clinging power | 100/100 | 100/100 | 100/100 | 100/100 | 100/100 | 100/100 |
| Hz(％) | 0.1 | 0.2 | 0.3 | 0.5 | 1 | 1.3 |
| ◎: fine zero: good △: good X: poor | ||||||
As shown in table 2, the coating of the coating solution preparation by 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 by 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
As explained above, titanium dioxide 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 dioxide 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 composition that is used for glasses, industrial safety glasses, leisure eye-protection glasses 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 enforcement identical purpose 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 class does not depart from essence of the present invention and the scope of illustrating in the appended claims.
Claims (20)
1. method for preparing titanium dioxide-organic complex colloidal sol, this method may further comprise the steps:
A) temperature that will contain the reaction soln of reaction solvent and titanium dioxide precursor is elevated to the sol gel reaction temperature;
B) carry out sol gel reaction after acid catalyst being added reaction soln, to generate TiO 2 sol;
C), and prepare titanium dioxide-organic complex colloidal sol by adding organic complex and make it and the TiO 2 sol reaction;
D) contain the reaction soln of described titanium dioxide-organic complex colloidal sol by constant pressure and dry, vacuum-drying or lyophilize drying; And
E) redispersion exsiccant titanium dioxide-organic complex in spreading solvent.
2. method for preparing titanium dioxide-organic complex colloidal sol, this method may further comprise the steps:
A) temperature that will contain the reaction soln of reaction solvent and titanium dioxide precursor is elevated to the sol gel reaction temperature;
B) carry out sol gel reaction after acid catalyst being added reaction soln, to generate TiO 2 sol;
D) by the dry described TiO 2 sol of constant pressure and dry, vacuum-drying or lyophilize;
E) the described exsiccant titanium dioxide of redispersion in spreading solvent; And
C) by adding organic complex and making it and the TiO 2 sol prepared in reaction titanium dioxide-organic complex colloidal sol of redispersion.
3. according to claim 1 or the described method for preparing titanium dioxide-organic complex colloidal sol of claim 2, wherein, described reaction solvent is a water, and the temperature of the sol gel reaction of step a) and step b) is 50～100 ℃.
4. according to claim 1 or the described method for preparing titanium dioxide-organic complex colloidal sol of claim 2, wherein, be removed during the sol gel reaction of described reaction solvent in step b).
5. according to claim 1 or the described method for preparing titanium dioxide-organic complex colloidal sol of claim 2, wherein, under 50 ℃ or higher temperature, carry out by adding step that organic complex prepares titanium dioxide-organic complex colloidal sol.
6. according to claim 1 or the described method for preparing titanium dioxide-organic complex colloidal sol of claim 2, wherein, described organic complex is selected from and comprises methyl ethyl diketone, 1, the group of 3-diphenylpropane-1, 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 and composition thereof.
7. according to claim 1 or the described method for preparing titanium dioxide-organic complex colloidal sol of claim 2, wherein, for 100 parts by weight of titanium oxide precursors, the content of described organic complex is 5～500 weight parts.
8. according to claim 1 or the described method for preparing titanium dioxide-organic complex colloidal sol of claim 2, wherein, described reaction solvent is selected from the group that comprises water, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, polyvinyl alcohol, hexylene glycol and composition thereof.
9. according to claim 1 or the described method for preparing titanium dioxide-organic complex colloidal sol of claim 2, wherein, described spreading solvent is selected from and comprises water, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, Pyranton, polyvinyl alcohol, methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, cellosolve acetate, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, ispropyl cellosolve, N, dinethylformamide, N-crassitude diketone, tetrahydrofuran (THF), propylene glycol monomethyl ether, hexylene glycol, the group of methyl ethyl diketone and composition thereof.
10. according to claim 1 or the described method for preparing titanium dioxide-organic complex colloidal sol of claim 2, wherein, described titanium dioxide precursor is selected from and comprises 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 group.
11. according to claim 1 or the described method for preparing titanium dioxide-organic complex colloidal sol of claim 2, wherein, described acid catalyst be selected from comprise nitric acid, sulfuric acid, hydrochloric acid, acetate, and composition thereof group.
12. according to claim 1 or the described method for preparing titanium dioxide-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.
13. according to claim 1 or the described method for preparing titanium dioxide-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 ℃ by constant pressure and dry, ii) at 0～100 ℃ by vacuum-drying or iii) undertaken by lyophilize at-180～0 ℃.
14. titanium dioxide-organic complex colloidal sol, wherein, titanium dioxide in the spreading solvent-organic complex particulate solid content is 5～50wt% of titanium dioxide-organic complex colloidal sol gross weight.
15. titanium dioxide according to claim 14-organic complex colloidal sol, wherein, described titanium dioxide-organic complex colloidal sol comprises that the dispersive mean diameter is the primary particles of 1～20nm.
16. titanium dioxide according to claim 14-organic complex colloidal sol, wherein, described titanium dioxide-organic complex colloidal sol comprises the secondary granule that the dispersive mean diameter is 10～200nm.
17. titanium dioxide according to claim 14-organic complex colloidal sol, wherein, described titanium dioxide-organic complex composition granule is anatase octahedrite or rutile crystal particle.
18. titanium dioxide according to claim 14-organic complex colloidal sol, wherein, described titanium dioxide-organic complex colloidal sol is the method preparation by the method for claim 1 or claim 2.
19. being the amounts with 10～80wt% of the gross weight of described composition, a composition that is used to form medium, height and superelevation refractive index coating, said composition comprise titanium dioxide-organic complex colloidal sol by the method preparation of claim 1 or claim 2.
20. the composition that is used to form medium, height and superelevation refractive index coating according to claim 19, said composition is with the coating that acts on glasses, industrial safety glasses or leisure eye-protection glasses.
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| KR1020060084252 | 2006-09-01 | ||
| 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 |
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2006
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Also Published As
| Publication number | Publication date |
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| CN101134598B (en) | 2012-07-18 |
| KR20080020848A (en) | 2008-03-06 |
| KR100950853B1 (en) | 2010-03-31 |
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