CN1324329A - Finely particulate titanium-containing substance, coating fluid containing the same, processes for producing these, and molded article having thin film comprising the substance - Google Patents
Finely particulate titanium-containing substance, coating fluid containing the same, processes for producing these, and molded article having thin film comprising the substance Download PDFInfo
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- CN1324329A CN1324329A CN 99812370 CN99812370A CN1324329A CN 1324329 A CN1324329 A CN 1324329A CN 99812370 CN99812370 CN 99812370 CN 99812370 A CN99812370 A CN 99812370A CN 1324329 A CN1324329 A CN 1324329A
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Abstract
A titanium-containing finely divided particulate material, characterized by exhibiting a light transmittance of at least 85% as measured at a wavelength of 450-700 nm for a thickness of 10 mm on an aqueous liquid containing the titanium-containing material in a concentration of 0.1 to 6.5 moles per liter as titanium even when the temperature of the liquid is elevated to the boiling point. The titanium-containing material usually has an average particle diameter of 0.8-50 nm, and gives a film having high photocatalytic activity and transparency. The titanium-containing finely divided particulate material is obtained by hydrolyzing titanium tetrachloride in an aqueous solution in the presence of a carboxylic acid.
Description
Technical field
The present invention relates to a kind of titaniferous fine particle material, contain the water-borne coatings liquid of titaniferous materials, a kind of method of making titaniferous materials, a kind ofly make the moulded products that this is coated with the method for feed liquid and has the titaniferous materials film.
Titaniferous fine particle material of the present invention is suitable for film forming on pottery or synthetic resins matrix with the feed liquid that is coated with that contains titaniferous materials.The film that forms like this shows the excellent transparency, high photocatalytic activity, to the good adhesion of matrix and the high ultraviolet ability of absorption.
Technical background
As everyone knows, titanyl compound is generated by the alkoxide of titanium or the hydrolysis of titanium tetrachloride aqueous solution, generates titanyl compound colloidal sol thus.
Known titanyl compound shows photocatalytic activity.The technology of multiple application photocatalytic activity has been proposed at present.For example, a kind of technology has been proposed, wherein with the surface of titanyl compound sol coating at light-emitting instrument, such as on the Glass tubing of fluorescent lamp or its cover go up to generate the titanyl compound film.According to this technology, the titanyl compound film plays photocatalysis makes organic substance as decomposing attached to the cigarette on pipe or the cover, thereby removes the pollutent on Glass tubing or the cover, and prevents that glass or cover from being polluted.
The titanyl compound film that forms on such as glass, plastics or other material requires film to have the high transparency and has high catalytic activity simultaneously again with under the situation of photocatalyst.
Summary of the invention
Main purpose of the present invention is to provide a kind of titaniferous fine particle material, and this material can form the film that has than high transparent, keeps high catalytic activity simultaneously again.
The inventor has made extensive studies to the method for preparing titanyl compound with titanium tetrachloride hydrolysis, and find, can obtain the water-borne coatings liquid that median size is the titaniferous fine particle of 0.8-50nm (a kind of colloidal sol) during hydrolysis in the aqueous solution of titanium tetrachloride in the presence of carboxylic acid is arranged, this is coated with feed liquid and is not made of so far, and the film that this colloidal sol forms shows the excellent transparency that had not obtained so far, and keeps high catalytic activity simultaneously.Based on these discoveries, the present invention is accomplished.
One aspect of the present invention provides a kind of median size very little titaniferous fine particle material, this material is characterised in that the thick waterborne liquid of 10mm is that the transparence of measuring under the 450-700nm is at least 85% at wavelength, the concentration of the titaniferous materials of this waterborne liquid be 0.1-6.5 mole titanium/liter, the temperature of liquid rises to boiling point.
The present invention provides a kind of titaniferous to be coated with feed liquid on the other hand, this is coated with the waterborne liquid that feed liquid is a kind of titaniferous fine particle material, its be concentration be 0.1-6.5 mole titanium/liter finely divided attitude, it is characterized in that, aqueous solution is that 10mm, wavelength are that the transparence of measuring under the 450-700nm is at least 85% at thickness, even is still when the temperature of liquid rises to boiling point so.
Further aspect of the present invention has proposed a kind of method that is coated with feed liquid for preparing above-mentioned titaniferous fine particle material or above-mentioned titaniferous oxide compound, it is characterized in that titanium tetrachloride hydrolysis in the waterborne liquid that has carboxylic acid to exist.
Further aspect of the present invention provides a kind of moulded products, and these goods comprise by forming matrix and the film that forms in stromal surface; This film contains above-mentioned titaniferous fine particle material.
The accompanying drawing summary
Fig. 1 is the sectional view that the present invention prepares the hydrolysis reaction vessel that method adopted of titaniferous fine particle material.
Fig. 2 is that the waterborne liquid that contains the titaniferous fine particle material of embodiment 1 preparation is transparence figure under the 200-700nm at wavelength.
Fig. 3 contains the transparence figure of film under wavelength 200-700nm that the waterborne liquid of the titaniferous fine particle material of embodiment 1 preparation forms.
Implement optimal mode of the present invention
The trickle material of titaniferous that the inventor proposes can be by the hydrolysis preparation of titanium tetrachloride in the aqueous solution that has carboxylic acid to exist.Chemical constitution and CONSTRUCTED SPECIFICATION and unclear through the titaniferous fine particle material of hydrolysis preparation.But titaniferous materials is very trickle monodisperse particles shape, and obviously is different from the conventional titanium dioxide granule of hydrolysis titanium tetrachloride preparation in the aqueous solution in a usual manner.Kept high catalytic activity by containing the film that the finely divided titaniferous particulate matter of the present invention forms, its transparence is better than the film that conventional titanium dioxide forms.
The method that the present invention prepares titaniferous fine particle material comprises the hydrolyzing process of titanium tetrachloride in the aqueous solution that heats up, and it is characterized in that, hydrolysis is carried out having in the presence of the carboxylic acid.The hydrolysis of titanium tetrachloride also can be carried out in water-miscible organic solvent, but hydrolysis is not preferred scheme in this solvent.
If the concentration of titanium tetrachloride is too low in the used titanium tetrachloride aqueous solution of hydrolysis, the productivity of target titaniferous materials is not good.On the contrary, if excessive concentration, reaction is carried out very violent, is difficult to produce fine particle, gained particulate bad dispersibility.Therefore, preferred concentration range be 0.1-6.5 mole titanium/liter.
Carboxylic acid uses to be dissolved in aqueous medium, thereby preferably water miscible.If adopt the water-soluble carboxylic acid, can utilize the carboxylic acid of minimum to obtain maximum efficiency, can adopt water-fast carboxylic acid, but being it, condition may be dissolved in a kind of hydrophilic organic solvent as in low chain or medium-chain alcohol or the ketone, add in the entry then.Object lesson as preferred water-soluble carboxylic acid can be enumerated oxalic acid, citric acid, oxysuccinic acid, tartrate and succsinic acid, wherein special optimization citric acid and tartrate.Carboxylic acid usually separately uses, but can also at least two kinds of acid be used in combination.
The amount of used carboxylic acid should be in the 0.01-10 molar range, preferred 0.01-5 moles/mole titanium atom.Carboxylic acid should be in the 0.1-10 mol in the concentration of the solution that is used for hydrolysis.If the carboxylic acid concentration is low excessively, in hydrolytic process, can generate the muddy colloidal sol of inverse.On the contrary, if its amount is too high, carboxylate salt begins precipitation, and this is undesirable.
The carboxylic acid of predetermined amount should be added in the solvent before hydrolysis, and be dissolved in wherein fully, and then add titanium tetrachloride to this aqueous solution.
Titanium tetrachloride aqueous solution remained under the higher temperature make titanium tetrachloride hydrolysis.The hydrolysis temperature of titanium tetrachloride should be at 50 ℃ between the boiling point of titanium tetrachloride aqueous solution.If temperature is lower than 50 ℃, finish the time that hydrolysis need be grown.In order to be hydrolyzed, solution is heated in the above-mentioned temperature range, solution was reacted under this temperature 10 minutes-12 hours.If during the upper side of hydrolysis temperature in above-mentioned scope, the reaction times shortens.
To titanium tetrachloride hydrolysis at elevated temperatures, can adopt the program that in the reaction vessel titanium tetrachloride aqueous solution is heated to preset temperature that is included in, promptly in container, heat water to preset temperature, in preheating water, add titanium tetrachloride, then the aqueous solution is heated to preset temperature.
Should prevent the hydrogenchloride effusion reactive system that hydrolysis produces, though it is a certain amount of to overflow, as long as this amount is controlled.Method for control hydrogenchloride escaped quantity does not have concrete restriction, and a kind of possible method is sealing.But the easiest and effective means is to be hydrolyzed in the conversion unit of an equipment reflux exchanger.A preferred example of this equipment is shown in Fig. 1.Among Fig. 1, reaction vessel 1 device that is added with titanium tetrachloride aqueous solution 2 is deposited reflux exchanger 3, agitator 4, thermometer 5 and is made the heating unit 6 of container heating.Titanium tetrachloride hydrolysis produces the steam of being made up of water and hydrogenchloride, but the condensation and return container 1 in reflux exchanger 3 of most steam.Therefore, hydrogenchloride is also considerably less if any with the effusion in the capacity 1.
The water-sol that hydrolysis produces can be dry, to obtain the titaniferous fine particle material of dry powder.But because powder is the form of ultrafine particle, it is aggegation very easily, thereby powder is difficult to reclaim with powdery.Be difficult to like this reach the excellent effect that the present invention tries hard to reach, thereby this drying process is unpractical.
If the water-sol that hydrolysis produces is used like this, then as required, the water-sol can carry out dechlorination after hydrolysis handles.Handle through dechlorination, obtain having the high photocatalytic activity and the film of high transparent easilier.The ion-exchange and the electrolysis of resin can be carried out, utilize to dechlorination according to a conventional method as electrodialysis.When carrying out dechlorination, the pH of the water-sol can be used as the index of dechlorination program.Chlorine ion concentration is under the situation of 50-10000ppm, and the pH value drops in the scope of 0.5-5; Chlorine ion concentration is at preferred 100-4, and in the 000ppm scope, the pH value drops in the scope of 1-4.
The water-sol that has titaniferous fine particle material of the present invention to be scattered in wherein may combine with a kind of organic solvent, thereby can obtain the dispersion of titaniferous materials in water and organic solvent mixed solvent.
If wherein contain the water-sol system film of titaniferous fine particle material, then preferred the employing through hydrolysis, again through the undried water-sol of dechlorination itself.Should not be dried powdered, powder is distributed in the water to make the water-sol that film forming is used again.This is because the fine particle of hydrolysis substance has high surfactivity, and surfactivity is with the reducing and uprise of granularity, and this just is difficult to fine particle is disperseed in water; In other words, the fine dispersion particle is through cohesion, and the film that is formed by flocculated particle then can represent the bad transparency and low photocatalytic activity.
If desired, can add stablizer to prevent the cohesion of the water liquid or the water-sol with the waterborne liquid of hydrolysis preparation or in by the water-sol of waterborne liquid preparation.Used stablizer comprises that for example, various tensio-active agents are as common used nonionic surface active agent.The amount of stablizer should be in 0.1%-1% (weight) by the weight of the waterborne liquid or the water-sol.
Manufacture method of the present invention should comprise following operation: the effusion of the hydrogenchloride that produces in the control titanium tetrachloride aqueous solution hydrolytic process; Add stablizer to this liquid and prevent particle aggregation; Gained liquid is carried out dechlorination to be handled and moist this liquid.Zhi Bei colloidal sol forms the film with highlight catalytic active and high-clarity easily like this.
The chemical constitution and the structure of the titaniferous fine particle material that particle diameter of the present invention is very little are not understood fully as yet fully, but, be clear that titaniferous fine particle material of the present invention is different from according to the sol particle of ordinary method by the titanyl compound of titanium tetrachloride hydrolysis preparation according to analytical results and characteristic.
By the trickle material of titaniferous of method preparation of the present invention, average particle diameter d
50At 0.0008-0.050 μ m (0.8-50nm), preferred 0.0008-0.015 μ m (0.8-15nm). term " median size d used herein
50" mean 50% particle diameter corresponding to integration particle diameter distribution curve.
The water-sol of titaniferous fine particle material of the present invention or to be coated with feed liquid opposite with conventional titanyl compound colloidal sol, it is not white-muddiness at ambient temperature, even still keeps the water white transparency state in the situation that is heated to boiling point.The water-sol or be coated with the quartzy cell of square box formula that feed liquid places 10mm * 10mm * 45mm (height), promptly the transmittance of the thick 10mm of light path under the 450-700nm wavelength is at least 85%, and preferably at least 95%.
The concentration of titaniferous fine particle material is counted the 0.1-6.5 mol with titanium in the water-sol, and preferential 0.1-4 mol in colloidal sol weight, then is in 1-30% (weight) scope.If the concentration of titaniferous materials is low excessively, the time of the film forming range request excessively of coating colloidal sol shape is long, thereby film forming expense uprises.On the contrary, if the excessive concentration of titaniferous materials, particle contains cohesion, thereby makes the water-sol become unstable.Secondly, titaniferous materials concentration is difficult to preparation above the colloidal sol of 6.5 mol (in titanium).
In order to improve the easy plasticity of film, can be to according to the water-sol of the titaniferous fine particle material of method preparation of the present invention or be coated with and add water-soluble polymers in the feed liquid.Can enumerate polyvinyl acid, methylcellulose gum, ethyl cellulose and Nitrocellulose as the water-sol that adds titaniferous fine particle material to or the object lesson that is coated with the water-soluble polymers in the feed liquid.This polymkeric substance should be dissolved in the water-sol fully.Consider that from the photocatalytic activity of film the amount of polymers in the water-sol should not be greater than 10% (weight).Polymkeric substance should be added in the water-sol after dechlorination is handled, but also can add before dechlorination is handled.
Narrated the batch methods of hydrolytic process above, but also can adopt continuation method, wherein single reaction vessel can be used as flow reactor effectively, titanium tetrachloride adds by the charging opening of container continuously simultaneously, reaction soln flows out by being positioned at the discharge port of charging opening opposite position continuously, and then solution is handled through dechlorination.
The water-sol of the particulate matter that titaniferous is trickle or be coated with on the surface that feed liquid can be coated in matrix such as various materials and pressing forms film on the surface of each basic unit.The type of matrix is not had concrete restriction, and matrix comprises, for example pottery, metal, plastics, timber and paper.When employing for example comprises aluminum oxide or zirconic support of the catalyst as matrix, when applying the water-sol with film forming thereon, the film coating that then forms on carrier is as the film carried catalyst.When making film forming matrix such as the Glass tubing of lighting apparatuss such as fluorescent lamp or plastic lousing, then the film of Sheng Chenging can effectively prevent impurity adhering on Glass tubing or cover surface, because film shows higher photocatalytic activity, and can decompose the lip-deep organic substance of film, such as dim.When the water-sol had been used on the glass surface of buildings or wall matrix film forming, then film also can prevent adhering to of dirt.
As the water-sol of titaniferous fine particle material of the present invention or be coated with feed liquid and be coated on the matrix with film forming method, here can adopt, for example matrix is soaked into colloidal sol method, with colloidal sol be sprayed to method on the matrix, with brush with the method for sol coating on the matrix.The thickness of the water-sol of coating is preferably 0.01-0.2mm in the liquid state measurement.After coating, contained solvent is removed the film that obtains expecting with dry in the colloidal sol.The film useful as catalysts of Xing Chenging or other purposes like this.
When matrix is a kind of heat-resisting matrix, such as metal, pottery or glass, but the film roasting that on matrix, forms.The result of roasting makes film more tightly attached on the matrix, and the hardness of film increases.Maturing temperature should at least 200 ℃.The highest maturing temperature is not had concrete restriction, and this temperature should be by the concrete heat-resisting degree decision of matrix.Maturing temperature should be about 800 ℃ because even under the too high situation of maturing temperature, the hardness of film and to can be again increasing adhering to not of matrix with the increase of maturing temperature.
Calcination atmosphere is not had concrete restriction, and roasting can be carried out in air.In addition, roasting time is not had concrete restriction, for example roasting can be finished at 1-60 minute.If the applied thickness of the water-sol reaches as mentioned above, then the thickness of baked film is about 0.02-1.0 μ m.
The present invention will set forth more specifically with following operation embodiment, but does not mean that restriction originally
Scope of invention.
Embodiment 1
Distilled water (300g) is put into the reaction vessel that reflux exchanger is housed that is shown in Fig. 1, and (38.4g) is soluble in water with citric acid, simultaneously stirring velocity is maintained at about 200rpm.Then add titanium tetrachloride aqueous solution (63.4g) (Ti content: 16.3% (weight), proportion: 1.59, purity 99.9%) to the aqueous solution.After interpolation was finished, obtained aqueous solution was heated to about 100 ℃, kept 60 minutes under this temperature, thereby finished hydrolysis reaction.The residual nitrogen that the cooling afterreaction produces is removed by electrodialysis, reaches 600ppm until the concentration of chlorine.Then the pH value of reaction soln being transferred to 2, adding the water-soluble polymers polyvinyl alcohol to solution again, as film coalescence aid, is that the titaniferous of 1.0% (weight) is coated with feed liquid to obtain polymer content.
The coating liquid that obtains is like this composed with measuring printing opacity under the wavelength of spectrophotometer (Ubest300 of Nippon Spectrum) at 200-700nm in being of a size of the quartzy cell of 10mm * 10mm * 45mm.The results are shown in Fig. 2.As ise apparent from FIG. 2, the absorbancy of liquid is low in the scope between the 380nm-700nm of visible light, and liquid is transparent substantially.The liquid transmittance is 95% under the wavelength of 450-700nm.
In the UV scope, promptly light wavelength is no more than the feature UV absorption that 380nm can find titanyl compound.Secondly, measure the size-grade distribution discovery of liquid with measuring particles distribution instrument (DLS-7000, Otsuka Denshi provides), the median size d50 of this titaniferous materials is 2.56nm.
Contain this titaniferous materials to be coated with feed liquid very stable, the fine particle that is produced even make one week of back or the longer time is not precipitated at liquid.Particle takes out from liquid under 60 ℃ with vacuum drier, carries out electron diffraction with the light-transmission type electron microscope then.But qualification result does not show that particle is by specific compound is formed.Dry granules is defined as amorphous with X-ray diffraction.When particle once 400 ℃ of following roastings, the peak of discovery is indicated as the rutile-type titanyl compound.
In addition, the above-mentioned feed liquid that is coated with is evenly coated in the surface of glass matrix with spinner, with drying machine 100 ℃ dry down, on glass surface, form transparent film.Measured the printing opacity spectrum of glass matrix in the 200-700nm wavelength region of filming.The results are shown in Fig. 3.Find out obviously that from Fig. 3 the transmittance of visible-range inner membrance is at least 97%, promptly film almost is transparent.Secondly, the absorption peak of finding in the UV optical range is similar to the feature UV absorption of titanium oxide.
The look die-away test of the photocatalytic activity of transparent film is undertaken by following program: the chilli oil China ink that will contain organic pigment is evenly coated on the surface of film; The UV photoirradiation of film usefulness UV lamp (black light) 1 hour; Absorption after 550nm (being the centre wavelength of ruddiness) down measures decay, again with decay before specific absorption.The results are shown in table 1.Red as can be seen from Table 1 decay and proof show photocatalytic activity when absorbing UV light time film.
Embodiment 2
Repeat the program of embodiment 1, just the quantitative change of the citric acid that adds is 153.6g, is coated with feed liquid (being a kind of water-sol of titaniferous materials) with the preparation titaniferous.The printing opacity spectrum of the water-sol that obtains like this measured find that the specific absorption of liquid is low in visible-range, liquid is almost transparent.The feature UV of absorption peak and titanyl compound absorbs close in the UV scope.In addition, the measurement of size-grade distribution shows that the median size d50 of titaniferous materials is 4.14nm.
Secondly, above-mentioned colloidal sol evenly is coated onto the surface of glass matrix with spinner, and descends drying at 100 ℃ in moisture eliminator, to form transparent film on the surface.Then film roasting 30 minutes in the air atmosphere under 400 ℃ in electric furnace makes film attached on the glass matrix.The printing opacity spectrum of the glass matrix of band film measured show that be at least 95% at visible-range iuuminting degree, film is almost transparent.In addition, the feature UV of the approximate titanyl compound of the absorption peak of measuring in the UV scope absorbs.
The photocatalytic activity of titaniferous materials adopts embodiment 1 identical evaluating with chilli oil China ink die-away test.It the results are shown in table 1.Can obviously find out red decay from table 1, prove that film shows photocatalytic activity.
Embodiment 3
Repeat the program of embodiment 1, just replace citric acid, with preparation titaniferous liquid (a kind of titaniferous water-sol) with tartrate (60g).The absorbancy of gained colloidal sol is identical with embodiment's 1.The median size d of titaniferous material
50Be 3.5nm.
Secondly, above-mentioned colloidal sol is coated onto on the glass matrix, with film forming on glass matrix.Film at air drying, makes film attached on the matrix under 200 ℃.The printing opacity spectrum of the glass matrix of band film is identical with embodiment's 1.The chilli oil China ink die-away test evaluation identical with embodiment 1 of the photocatalytic activity of titaniferous material the results are shown in table 1.
Embodiment 4
The vitreosol of embodiment 1 preparation is coated to through on the steel plate of precoating, and plate is 400 ℃ of following sintering 15 minutes, so that form the titanyl compound transparent film then.The pencil hardness of the film of Xing Chenging is 5H like this, and the value that the crosscut test of film provides is 90/100.
Embodiment 5
Prepare three kinds of titaniferous materials colloidal sols by following condition: the concentration of titanium tetrachloride is 0.25 mole of Ti/ liter in the titanium tetrachloride aqueous solution, and the mol ratio of institute's adding citric acid is 0.01,1.0 or 10 (citric acid concentration/titanium transforms the mol ratios of concentration).It is identical that other condition and operation and embodiment 1 are adopted.For mol ratio 0.01,1.0 and 10, the median size of titanyl compound is respectively 1.10nm, 4.4nm and 12.5nm.Comparative Examples 1
Repeat the program of the preparation water-based titaniferous liquid of embodiment 1, just adding citric acid not.The transparency of solution has kept about 5 minutes behind the interpolation titanium tetrachloride.But along with the temperature of solution rises to 60 ℃ or higher, solution gradually becomes the white casse body, and solution becomes white under about 90 ℃ or higher temperature.The measurement of size-grade distribution shows, titaniferous particulate median size d in the liquid that makes like this
50Be 65nm.The chilli oil China ink die-away test evaluation identical of the photocatalytic activity of titaniferous materials with embodiment 1.But film becomes the white casse body, and measurement can not be carried out.Comparative Examples 2
Particle diameter is that the Detitanium-ore-type titanyl compound particle of 7nm is scattered in the water with ultra-sonic dispersion equipment, is the titaniferous oxide compound liquid of water-based of 2% (weight) with preparation concentration.Add hydrochloric acid to liquid and make deflocculation agent, the pH value of solution is transferred to 1, thereby obtains a kind of water-sol of titaniferous oxide compound.Particle size distribution measurement shows that the median size of titaniferous oxide particle is 35nm in the colloidal sol.But colloidal sol is the white casse body.The chilli oil China ink die-away test evaluation identical with embodiment 1 of the photocatalytic activity of titaniferous oxide material the results are shown in table 1.
Table 1
Chilli oil China ink die-away test
(variation of transmittance under the 550nm)
Transmittance (%)
Behind the pre-irradiation irradiation
Embodiment 1 15 85
Embodiment 2 21 86
Embodiment 3 12 84
Comparative Examples 1 is because white casse body energy measurement not
But Comparative Examples 2 15 80 industry practicality
Can prepare a kind of titaniferous fine particle material according to the present invention by titanium tetrachloride hydrolysis in the aqueous solution that has carboxylic acid to exist, the granularity of this material is 2-5nm (this granularity can not obtain with ordinary method), and prepares and a kind ofly contain the colloidal sol of titaniferous fine particle material or be coated with feed liquid.This titaniferous fine particle material shows the excellent transparency, keeps high photocatalytic activity simultaneously, and such material was not made in the past.That is to say that the waterborne liquid of titaniferous fine particle material is at least 85% to the light permeable rate that 10mm light path thickness is measured under the 450-700nm wavelength, even also be like this when waterborne liquid is heated under the situation of boiling point.
Transparent at the visible-range inner height according to the resulting water-sol of preparation method of the present invention, the film that is formed by this water-sol shows the excellent emerging catalytic activity and the high transparency.These characteristics are based on such fact, and promptly fine particle is so little, cause them can not scattering or absorb visible light, and particle almost completely exists with the form of primary particle, do not condense in dispersion system.
Titaniferous materials of the present invention and its are coated with feed liquid or colloidal sol shows high photocatalysis and high ultraviolet absorption, thereby can be used as the photocatalyst material and the UV protective material of high-clarity.
Titaniferous fine particle material of the present invention and colloidal sol thereof or be coated with feed liquid and can be used on coated substrate surface as pottery, metal, plastics, timber and the various materials such as paper and pressing are so that the film that formation has above-mentioned characteristic.When for example comprising aluminum oxide or zirconic support of the catalyst as matrix, apply water-sol film forming thereon, the film coating that forms at carrier is as the catalyzer with film carrier tape.Under the situation that the Glass tubing or the plastic housing of lighting apparatus such as fluorescent lamp is used as into membrane matrix, the film of making is transparent and have catalytic activity, and can prevent effectively that impurity is at Glass tubing or shell is lip-deep adheres to.Not shading of film and surface go out higher photocatalytic activity, and can decompose the organic substance such as dim that is present in the surface.If the water-sol is film forming on glass surface that is used for building structure or wall material, then this film can prevent that equally dirt from adhering to.Therefore, the sheet glass of Highrise buildings and wall material need not clean, thereby reduce the maintenance cost of buildings.
Claims (17)
1. titaniferous fine particle material with tiny median size, it is characterized in that, under the 450-700nm wavelength, be the waterborne liquid of the titaniferous materials of 10mm to light path thickness, in its concentration is that 0.1-6.5 mole Ti/ liter, its temperature are increased under the condition of boiling point, and the transparence of measuring is at least 85%.
2. the titaniferous fine particle material of claim 1, the median size of this material is in the 0.8-50nm scope.
3. claim 1 or 2 titaniferous fine particle material, this material is present in the aqueous phase liquid with a kind of dispersive form, and the concentration of titaniferous materials is 0.1-6.5 mole Ti/ liter in the aqueous phase liquid.
4. one kind is used for preparing each the method for titaniferous fine particle material of claim 1-3, it is characterized in that titanium tetrachloride is hydrolyzed in the aqueous phase liquid that has carboxylic acid to exist.
5. the method that is used to prepare titaniferous fine particle material of claim 4, wherein the amount of carboxylic acid is at 0.01-10 moles/mole titanium atom and 0.01-10 mol water-based liquid.
6. claim 4 or 5 the method that is used to prepare titaniferous fine particle material, wherein titanium tetrachloride aqueous solution is at least 50 ℃, but is not higher than hydrolysis under the temperature of aqueous solution boiling point.
7. each the method that is used to prepare titaniferous fine particle material among the claim 4-6 is wherein controlled the hydrogenchloride that is produced by hydrolysis when hydrolysis is carried out, causes it not overflow from reaction system.
8. each the method that is used to prepare titaniferous fine particle material among the claim 4-7, after wherein hydrolysis was finished, the gained waterborne liquid was handled through dechlorination.
9. titaniferous feed liquid that is coated with, this is coated with feed liquid is a kind of titaniferous fine particle material that is finely divided form that contains, its titanium concentration is the waterborne liquid of 0.1-6.5 mol, it is characterized in that this waterborne liquid is 10mm, rises to the transparence that the condition of boiling temperature measures at fluid temperature and be not less than 85% light path thickness under the 450-700nm wavelength.
10. the titaniferous of claim 9 is coated with feed liquid, and wherein the median size of titaniferous fine particle material is in the 0.8-50nm scope.
11. the titaniferous of claim 9 or 10 is coated with feed liquid, wherein waterborne liquid also contains the water-soluble high polymers that is no more than 10% (weight).
12. one kind is used for preparing the method that each titaniferous of claim 9-11 is coated with feed liquid, it is characterized in that titanium tetrachloride is hydrolyzed in the waterborne liquid that has carboxylic acid to exist.
13. claim 12 be used to prepare the method that titaniferous is coated with feed liquid, wherein the amount of carboxylic acid is in the scope of 0.01-10 moles/mole titanium atom and 0.01-10 mol water-based liquid.
14. claim 12 or 13 be used to prepare the method that titaniferous is coated with feed liquid, wherein titanium tetrachloride aqueous solution is at least 50 ℃, but is not higher than hydrolysis under the temperature of aqueous solution boiling point.
15. among the claim 12-14 each be used to prepare the method that titaniferous is coated with feed liquid, wherein the hydrogenchloride that is produced by hydrolysis is controlled in hydrolysis simultaneously, causes it not overflow from reaction system.
16. among the claim 12-15 each be used to prepare the method that titaniferous is coated with feed liquid, wherein after hydrolysis was finished, the gained waterborne liquid was handled through dechlorination.
17. the moulded products of a film that comprises forming matrix and on stromal surface, form; This film contains right and requires among the 1-3 each titaniferous fine particle material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP233011/1998 | 1998-08-19 | ||
| JP10233011A JPH11171544A (en) | 1997-08-20 | 1998-08-19 | Titanium-containing material and its production |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100558230A Division CN1310840C (en) | 1998-08-19 | 1999-05-24 | Titanium-containing finely divided particulate material, aqueous sol composition and coating liquid containing same, process for producing same, and shaped article having film thereof |
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| CN1324329A true CN1324329A (en) | 2001-11-28 |
| CN1168663C CN1168663C (en) | 2004-09-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100558230A Expired - Fee Related CN1310840C (en) | 1998-08-19 | 1999-05-24 | Titanium-containing finely divided particulate material, aqueous sol composition and coating liquid containing same, process for producing same, and shaped article having film thereof |
| CNB998123706A Expired - Fee Related CN1168663C (en) | 1998-08-19 | 1999-05-24 | Finely particulate titanium-containing substance, coating fluid containing the same, processes for producing these, and molded article having thin film comprising the substance |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100558230A Expired - Fee Related CN1310840C (en) | 1998-08-19 | 1999-05-24 | Titanium-containing finely divided particulate material, aqueous sol composition and coating liquid containing same, process for producing same, and shaped article having film thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1310840C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457256C (en) * | 2002-06-25 | 2009-02-04 | 住友化学工业株式会社 | Titanium dioxide dispersion composition and storing method and storing container thereof |
| TWI730626B (en) * | 2019-02-19 | 2021-06-11 | 日商昭和電工股份有限公司 | Manufacturing method of titanium oxide |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7017565B2 (en) | 2016-10-17 | 2022-02-08 | ウニヴェアズィテート バーゼル | Lossless cryogrid preparation by controlled sample evaporation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3861946A (en) * | 1972-07-21 | 1975-01-21 | Mearl Corp | Titanium dioxide nacreous pigments and process for the preparation thereof |
| JPS61283629A (en) * | 1985-06-10 | 1986-12-13 | Nippon Shokubai Kagaku Kogyo Co Ltd | Plastic composite material |
-
1999
- 1999-05-24 CN CNB2004100558230A patent/CN1310840C/en not_active Expired - Fee Related
- 1999-05-24 CN CNB998123706A patent/CN1168663C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457256C (en) * | 2002-06-25 | 2009-02-04 | 住友化学工业株式会社 | Titanium dioxide dispersion composition and storing method and storing container thereof |
| TWI730626B (en) * | 2019-02-19 | 2021-06-11 | 日商昭和電工股份有限公司 | Manufacturing method of titanium oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1605566A (en) | 2005-04-13 |
| CN1168663C (en) | 2004-09-29 |
| CN1310840C (en) | 2007-04-18 |
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