CN1327952C - Titanium oxide sol, titanium oxide sol coat film and forming method - Google Patents
Titanium oxide sol, titanium oxide sol coat film and forming method Download PDFInfo
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- CN1327952C CN1327952C CNB2003101165709A CN200310116570A CN1327952C CN 1327952 C CN1327952 C CN 1327952C CN B2003101165709 A CNB2003101165709 A CN B2003101165709A CN 200310116570 A CN200310116570 A CN 200310116570A CN 1327952 C CN1327952 C CN 1327952C
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Abstract
Provided is a titanium oxide sol solution which is usable as a coating agent or its starting material having functions such as prevention of contamination, deodorization, clouding resistance, and antimicrobial activity. The titanium oxide sol contains negatively charged amorphous titanium oxide particles and titanium oxide particles responsive to a visible light of 50-99 pts.mass in total, >=1 kind(s) of anionic compound(s) selected from condensed phosphoric acid, condensed phosphates, and chelate compounds having carboxy groups of 1-50 pts.mass in total, and a solvent, and its pH is 5-10. In addition, a specific basic compound, an antioxidant, etc., can be contained. The titanium oxide coating film is formed by adhering the titanium oxide sol, volatilizing the solvent, heating at a temperature of >=200[deg.]C and then irradiating an electromagnetic wave with a wavelength of <650 nm.
Description
Technical field
The invention relates to colloid solution as the responding to visible light titanium dioxide of the photocatalyst applications of bringing into play function by radiation of visible light, mainly be can be used to prevent to stain, the smears of deodorization, various uses such as hydrophilic, antifog, antibiotic or as the titania sol solution of its prepared using.
Background technology
In the past, compare with organic system coating, the ceramic coating that performances such as heat-resistant antifriction are good has kinds such as alkali silicate system, phosphate-based, Ludox system, burning system.
It is the characteristic of coating that these coating have good inorganic of heat-resistant antifriction performance, but the metal oxide that had turned to ceramic diaphragm (epithelium) also to have new capability in recent years is the center.
In various potteries, titanium oxide also can be brought into play good photocatalysis effect, has given play to high oxidability after the ultraviolet ray irradiation.
Therefore, generally all know, after the titanium oxide that photocatalysis performance is good is formed at applied thing surfaces such as metal, glass, pottery, the purification of the decomposition that prevents the adhering to of dirt, odor pollutant, water quality, antirust, antibiotic, the breeding that prevents algae, difficult decomposition of decomposing discarded object etc. all there is very good effect.
Therefore, up to the present, the material surface forms various titanium oxide coating and the existing a lot of motions of manufacture method thereof that the titanium oxide diaphragm is a purpose.
Formation method for the titanium oxide diaphragm; the most generally adopt the alkoxide of titanium to add the sol-gel process that carries out coating after the water decomposition; technology is similarly reported; for example the spy opens that flat 4-83537 communique is described to add acid amides in the titanium alkoxide, and the method for ethylene glycol, spy open the method that adds alcamines in the described titanium alkoxide of flat 7-100378 communique.
In addition, the manufacture method of another titanium oxide sol allows titanium oxide microparticle form crystallization as opening the spy as described in the flat 6-293519 communique by hydrothermal treatment consists, and the acid solution as nitric acid etc. that adds pH then and be 3 below disperses by it, is coated with.
But methods such as the above sol-gel process, usefulness acidolysis glue, dispersion because of colloidal solution is acid, not only produce problems such as corrosion and material deterioration, the responsive to visible light type TiO that develops in recent years when being coated with on surfaces such as metal and paper
2Also there is the visible-light photocatalyst oxidation in series photocatalyst, to the reactive problem of deterioration easily of visible light.
Inventor of the present invention develops so far, disclosed relevant technologies example has No. 3080162, Japan's special permission and special permission openly communique 2001-81357 number.
Summary of the invention
The present invention solves the intrinsic problem of existing in the past responsive to visible light type photocatalyst oxidizes titanium colloidal sol, and the titanium oxide colloid colloidal sol that stable the visible light photocatalysis performance is arranged to form, can obtain water white diaphragm is purpose.
The visible light TiO that inventors of the present invention developed in recent years in research
2When light catalyzed coating and smears, necessary usefulness and TiO have in the past been drawn
2Photochemical catalyst colloidal sol of different nature is the conclusion of raw material.
That is, the blue shift that causes for fear of quantum size effect is with the Detitanium-ore-type TiO in past
2Photochemical catalyst is compared, and these responsive to visible light type photocatalyst particles footpath is big, for visible light is shown activity, must obtain affirmation in the present invention by being difficult for the conclusion that oxidized sol solutions forms.
Inventors start with from the powder of visible-light photocatalyst, have carried out the distributed test in various solution repeatedly, found that, in the past in order to prepare TiO
2Dispersion colloidal sol and the normally used method that is scattered in the aqueous solution of nitric acid, because of its highly acid and oxidizing force, visible-light photocatalyst itself is rotten, makes the faint yellow outward appearance of itself become white, to the responsiveness forfeiture of visible light.
The inventor in order to obtain the aqueous dispersion colloidal sol of responsive to visible light type photochemical catalyst, has drawn good dispersiveness and oxidation-protective effect and near the conclusion of pH need neutrality of needs, and composition has been carried out various tests based on above viewpoint.
Inventors at first according to inorganic titanium salt such as titanium chloride, titanium sulfate and titanium alkoxide under acidity with the water reaction add the water decomposition method, modulated the amorphous titania colloidal solution that the crystallinity titanium particle is had good adhesive effect (particle is in conjunction with effect).
In addition, even having studied the titanium oxide colloid particle emphatically, inventors also make it to have the method for stable electric charge and dispersive property at neutral range.
Conclusion is; in the amorphous oxidation titanium of acidity colloidal solution, add condensed phosphoric acid; behind the chelating agents such as hydroxycarboxylic acid; add morpholine; organic base compositions such as alkanolamine; pH is reached more than 5; amorphous thus oxidation titanium colloidal particle is electronegative; obtain the colloidal sol of stable dispersion; and then the visible light type photocatalytic particle is disperseed wherein; responsive to visible light type photochemical catalyst is not rotten in the pH scope of faintly acid～alkalescence; and the photocatalysis that obtains stable dispersion disperses colloidal sol; this colloidal sol is coated on the object being treated; make it to possess good visible light photocatalysis performance; if the formation film is the diaphragm of water white transparency and homogeneous basically, thereby solved the problem that exists.
In addition, in the TiO 2 sol of making under the various conditions, contain the neutral colloidal sol of alkaline components such as electronegative titanium oxide colloid particle, the chelating agent of being with carboxyl, ammoniacal liquor, shown good stable and dispersiveness.
In addition, process shows the result of study of the manufacture method of the titanium oxide sol of this composition, contain and add alkaline components in the colloidal sol of chelating agent of titanium oxide colloid particle and band carboxyl and make it to become neutrality～alkalescence, and then this solution dialysed or after deionization such as ion exchange resin handles, can obtain impurity titanium oxide sol still less, thereby finish the present invention.
First invention of the present invention is characterised in that, contain electronegative amorphous oxidation titanium particle composition and become subtotaling 50～99 mass parts with Titanium particles that responding to visible light is arranged and particle, contain more than one anionic property compounds 1-50 mass parts in the chelate that is selected from condensed phosphoric acid, condensed phosphate and contains carboxyl, and pH is 5～10 scope.
In the titanium oxide sol of the present invention, preferably contain at least a organic basic composition that is selected from alkanolamine, tetra-allkylammonium, piperazine, piperidines and the choline, more preferably also contain the antioxidant composition.
The Titanium particles that contains in the titanium oxide sol of the present invention with responding to visible light, as enumerating:
(a) with the x-ray photoelectron optical spectroscopy half-peak breadth of the titanium between the binding energy 458eV～460eV of titanium oxide being carried out 4 times measures, the mean value as a result of the half-peak breadth that records for first and second times is as the A value, for the third time with the mean value as a result of the half-peak breadth that records for the 4th time as the B value, with A and the following formula of B value substitution:
X＝B/A (I)
The index X that is asked is below 0.97, simultaneously when measuring the UV, visible light diffuse reflection spectrum, as the C value, the integrated value of the spectral absorbance of wavelength 400nm～800nm is as D with the integrated value of the spectral absorbance of wavelength 220nm～800nm, C and the following formula of D substitution:
Y＝D/C (II)
Obtain index Y and be the titanium oxide (spy opens the 2001-72419 communique) more than 0.14;
(b) the g value of electron spin resonance spectroscopy has three with the superiors between 1.930～2.030, the titanium oxide (spy open 2001-190953 communique) of g value between 1.990～2.020 at maximum peak in these peaks;
(c) measure electron spin resonance spectroscopy behind the radiation of visible light and show that the spin concentration X that is asked is 1.50 * 10
16More than the spin/g, the ratio (X/Y) of the spin concentration Y that the electron spin resonance spectroscopy of measuring before spin concentration X that the electron spin resonance spectroscopy of measuring behind the radiation of visible light is tried to achieve and the radiation of visible light is tried to achieve is the titanium oxide (spy opens the 2001-316116 communique) greater than 1.00.
(d) carry out determination and analysis 8 times with the x-ray photoelectron optical spectroscopy, electronic state for titanium, try to achieve first and second times analysis result accumulation spectrogram and the 7th, the 8th time the accumulation spectrogram of analysis result, find out in the accumulation spectrogram separately binding energy at the peak of 458eV～460eV, the half-peak breadth at the peak in the accumulation spectrogram of analyzing for first and second times is A
1, the half-peak breadth at the peak in the 7th and the 8th time the accumulation spectrogram is B
1The time, according to following formula (III):
X
1＝B
1/A
1 (III)
Calculate X
1Index below 0.9 and UV, visible light diffuse reflection spectrum medium wavelength be that the absorbance integrated value of 250nm～550nm is made as C
1, the absorbance integrated value of wavelength 400nm～550nm is made as D
1, following formula (IV)
Y
1＝D
1/C
1 (IV)
The Y that calculates
1Value is the titanium oxide (spy opens the 2001-322816 communique) more than 0.075
(e) carry out determination and analysis 8 times with the x-ray photoelectron optical spectroscopy, electronic state for titanium, try to achieve the accumulation spectrogram and the 7th of first and second times analysis, the accumulation spectrogram of the 8th time analysis, the position binding energy that has a peak in first and second times the accumulation spectrogram at least is between 459eV～460eV, the position binding energy that has a peak in the 7th and the 8th time the accumulation spectrogram at least is between 458eV～459eV, and it is the titanium oxide (spy opens the 2001-29749 communique) of 0.005～3.0mol% that the content of transition metal converts with respect to the titanium in the titanium oxide with element;
(f) the thermobalance quality analysis simultaneously the ratio m/e of the charge number e of the mass number m in the determination method mass spectrogram of trying to achieve and ion be that the disengaging peak of 28 composition is the titanium oxide more than 600 ℃, perhaps in the thermobalance quality analysis mass spectrogram that simultaneously determination method records, mass-to-charge ratio m/e be 28 composition the disengaging peak more than 600 ℃, below 950 ℃, m/e is that the disengaging peak of 14 composition is at the titanium oxide more than 600 ℃, below 950 ℃.(spy opens the 2002-97019 communique);
Titanium oxide, the material (WO 01/10552 brochure) of nitrogen atom doping between crystalline titanium dioxide grain circle of doping nitrogen-atoms between the titanium oxide after (g) a part of oxygen position of crystalline titanium dioxide is replaced by nitrogen-atoms, the lattice of crystalline titanium dioxide;
(h) the titanium oxide after stable with oxygen defect, wherein, in a vacuum, in the electron spin resonance spectroscopy that 77K, dark condition are measured down, observe the g value and be 2.003～2.004 signal, with in a vacuum, under the 77K, penetrate the signal of measuring down in the illumination of 420nm～600nm scope at least and compare, the titanium oxide that this signal strength signal intensity is big (speciallyying permit No. 3252136 communique) or
(i) halogenation platinum compounds (PtCl is contained on the surface
2, PtCl
4, PtCl
42H
2O, H
2[Pt (OH)
2Cl
4] nH
2O, PtBr
2, PtBr
4, PtI
2, PtI
4, PtF
4, chloroplatinic acid, chloroplatinate, platinibromide, iodine platinate etc.) spindle shape titanium oxide (spy opens the 2002-239395 communique) etc.
In addition, Titanium particles with responding to visible light can be enumerated and open 2001-278625 communique, spy by the spy and open 2001-278626 communique, spy and open 2001-278627 communique, spy and open 2001-302241 communique, spy and open 2001-335321 communique, spy and open 2001-354422 communique, spy and open 2002-29750 communique, spy and open 2002-47012 communique, spy and open 2002-60221 communique, spy and open 2002-193618 communique, spy and open titanium oxide that the method put down in writing in the 2002-249319 communique makes etc.
Second invention is, comprising first invention amorphous oxidation titanium particle that obtains and the titanium oxide with Titanium particles of responding to visible light films, the 3rd invention is the formation method that titanium oxide is filmed, it is characterized in that, the titanium oxide sol of first invention is attached to substrate surface, implement at least one processing in following after the solvent evaporates, that is, A) processings, B are burnt till in heating under the temperature more than 200 ℃) the electromagnetic wave irradiation processing of discontented 650nm wavelength.
The specific embodiment of invention
In the titanium oxide sol of the present invention, must contain amorphous oxidation titanium particle and have the Titanium particles of responding to visible light to add up to 50～99 mass parts, and be necessary to make Titanium particles electronegative in neutral sol solution.The interior Titanium particles positively charged of pH value scope beyond acid, the dispersion instability of Titanium particles and gelation are so be not preferred.Charged positive and negative being easy to of particle known by the zeta potential measurement device.
Titanium oxide with responding to visible light, the titanium oxide that excites with visible light (as the light of wavelength 400nm～600nm) is that the photochemical catalyst titanium oxide of main component is for well, preferably as carrying out illumination by visible light sources such as fluorescent lamp, Halogen lamp LED, incandescent lamp, light emitting diodes penetrate and can decompose down such as carboxylic acids such as aldehyde such as acetaldehyde, acetic acid, also have photochemical catalyst titanium oxide such as the ketone of acetone etc., particularly, the titanium oxide of preferably aforementioned (a)～(f).These titanium oxide can be used alone, and also can be used in combination.
The not special regulation of the particle diameter of amorphous oxidation titanium particle, preferred 1nm～500nm, more preferably 3～120nm.
Amorphous oxidation titanium particle makes by following method,, inorganic titanium compounds such as titanium chloride, titanium oxychloride, titanium sulfate, titanyl sulfate is dissolved in water that is, adds catalyst such as hydrochloric acid, nitric acid as required, and adding water decomposition under the normal temperature can make.Also can add water decomposition with organic titanic compounds such as titanium alkoxide, titanium acetylacetones makes.This Titanium particles that makes in acid solution is the colloidal particle size below the common 0.1 μ m, obtains because of positively charged is mutually exclusive disperseing.But because of the forfeiture gelation of positive charge,, be necessary to add specific anionic property dispersant under the pH of faintly acid～alkalescence, add alkaline components then and regulate the pH value, make particle electronegative in order to improve pH.
Therefore, in the titanium oxide sol of the present invention, more than one anionic property compounds that must contain in the chelating agent that is selected from condensed phosphoric acid, condensed phosphate and contains carboxyl add up to 1～50 mass parts.These compounds are adsorbed in the Titanium particles surface in sol solution, perhaps because of having free Ti
4+Ion carries out the effect of chelating, thereby makes Titanium particles have stable negative electrical charge, has the effect of the good dispersion colloidal sol of in the pH of faintly acid～alkalescence scope formation.
In anionic property compound used in the present invention, as the different mixture of ingredients of condensed phosphoric acid, pyrophosphoric acid, tripolyphosphate and polyphosphoric acid city dealer's condensation level etc. is preferred, also preferred these salts such as alkanolamine corrective that add sodium pyrophosphate, polyphosphoric acid.At least should contain a carboxyl in the molecular structure of carboxylic chelating agent, to Ti
4+The material that chelating effect is strong is preferred.If also contain hydroxyl more preferably, as the kind of chelating agent, they are hydroxycarboxylic acid or polybasic carboxylic acid etc., oxalic acid, malonic acid, gluconic acid, glycolic, lactic acid, tartaric acid, citric acid, malic acid, succinic acid etc. in the molecular structure.
In the neutral titanium oxide sol, for the formation of the neutralization of acid ion remaining in the carboxyl of chelating agent and the colloidal sol and stable electric double layer, it is preferred containing alkaline organic compound, more preferably contains 1～20 weight portion.
As alkaline organic compound, can use inorganic bases such as ammonium hydroxide (ammoniacal liquor), NaOH, potassium hydroxide, lithium hydroxide, but more preferably be selected from the alkaline organic compound in piperazine class, piperidines and the choline of tetra-allkylammonium salt, morpholine etc. of alkanol amines such as triethanolamine, monoethanolamine and derivative thereof, tetramethyl-ammonium class.The reason of preferred these alkaline organic compounds is, by with the effect of anionic property dispersant, the surface of titanium oxide forms electric double layer, has the effect that prevents aggegation and gelation between particle.
In the colloidal sol, contain the chlorion that is derived from the titanium material that uses, sulfate ion, alcohol etc. as other composition, remove the impurity of chlorion, sulfate ion etc. so preferably use scattering and permeating film and ion exchange resin etc., the occasion that contains alcohol, post processing such as preferably distill as required, make with extra care.
In addition, as the occasion that the smears uses, can add Ludox and silane derivative etc. as adhesive etc.
Among the present invention,, colloid is fully disperseed, can not form stable sols, so be not preferred if the weight ratio of chelating agent is crossed with respect to amorphous oxidation titanium colloidal particle and have the total weight of the Titanium particles of responding to visible light.If the weight ratio of chelating agent surpasses scope of the present invention then makes the hardness step-down of filming, and is not preferred equally.
Among the present invention, to the storage stability of the keeping of visible light photocatalysis performance, colloidal sol, variable color prevent, be used for the metal coating time corrosion prevent etc. that the aspect considers, preferably add the antioxidant of less than 10 mass parts again.As long as the kind of antioxidant can prevent the oxidation that caused by dissolved oxygen from not having special qualification, can use phosphite, hypophosphites, phosphatic hydroxylamine, hydrazine etc. most preferably, also can use sulphite, nitrite etc.
Be necessary that making the pH of colloidal sol is 5～10, discontented 5 o'clock of pH, low not preferred because of dispersiveness, be higher than at 10 o'clock, may make the performance step-down of photochemical catalyst, easily corrosion material and not preferred with responding to visible light.
Titanium oxide sol among the present invention, more preferably carrying out deionization handles refining, the diffusion dialysis of the preferred pellicle of method that deionization is handled, the electrodialysis of amberplex or with the processing that contacts of ion exchange resin, by these processing, remove foreign ions such as alkali ion in the titanium oxide sol, acidic anionic, improve the purity of titanium oxide, thereby can make more high performance colloidal sol.The pH of the titanium oxide sol after deionization is handled is 5～9, more preferably 6～8.5.
Of the present invention second titanium oxide is filmed and is, methods such as use coating are attached to titanium oxide sol of the present invention on the surface of processed base material, make the volatilization of water equal solvent then, what heat drying or electromagnetic wave irradiation made it to solidify after handling films, by organic decomposition reaction, dehydration amorphous oxidation titanium is solidified, intensity that this is filmed and chemically stable sexual satisfaction as the needs of filming with abundant practicality.
Object being treated is coated with the occasion of neutral titanium oxide sol, and most preferably the adhesion amount with titanium dioxide is 50～1000mg/m
2Be coated with.The not only available heat drying of drying also can be in drying at room temperature, preferably at the temperature heat drying more than 200 ℃, also preferably with the electromagnetic wave irradiation of not enough 650nm more than 1 minute.
Embodiment
The present invention describes with the following examples.But it is described that the present invention is not limited to following embodiment.
It below is the experiment material therefor.
(amorphous oxidation titanium particle)
The colloidal sol of the amorphous oxidation titanium particle that uses among comparative example and the embodiment makes in order to the below method.That is, to the east of solution behind nation's titanium (strain) system titanium chloride aqueous solution (Ti:15～16%) dilute with water as raw material, it is at room temperature carried out the deionization processing with Asahi Glass (strain) system anion-exchange membrane after, obtain amorphous oxidation titanium (ortho-titanic acid) colloidal sol.The colloidal sol pH that generates is about 2, and solid component concentration is with TiO
2Be calculated as 5 quality %.With the sub-micro analyzer detect amorphous oxidation titanium to get the average mark shot directly be about 0.02 μ m.
(Titanium particles) with responding to visible light
Titanyl sulfate (trade name " TM " crystallization, outward appearance: white solid, テ イ カ system) 3324g is dissolved in the 2216g ion exchange water, the preparation aqueous solution of titanyle sulfate.Under ice-cooled, in above aqueous solution of titanyle sulfate, add the aquae hydrogenii dioxidi 1530g of 31 weight %, obtain mauve mixed solution.Add the 4700g ion exchange water in the reaction vessel that possesses electrode and pH controller, this pH controller has with the pH electrode and links to each other, by 25 weight % ammoniacal liquor (reagent superfine and light pure pharmaceutical worker already make) are provided pH is adjusted into certain mechanism.The pH of pH controller is set at 4.The feed speed of ammoniacal liquor is set at the 50ml/ branch.In this reaction vessel, when the pH of liquid in container was lower than setting value, the supply of ammoniacal liquor began, and supplies with ammoniacal liquor continuously with aforementioned speed and reaches setting value up to pH.
Speed with 145rpm in the reaction vessel stirs content, adds the mixed solution that obtains above with the speed that 50ml/ divides, and makes itself and the ammoniacal liquor reaction that supplies to by the pH controller in the reaction vessel.Reaction temperature is 25 ℃～50 ℃ scope.The gained reaction product kept 1 hour while stirring, then supplied with the ammoniacal liquor (reagent superfine and light pure pharmaceutical worker already make) of 25 weight %, obtained slurry like material.The amount of the ammoniacal liquor of supplying with in the reaction vessel adds up to 3794g, is the twice that titanyl sulfate is become addition that titanium hydroxide is answered.
Filter above-mentioned slurry like material, the ion-exchange water washing of gained solid content obtains the precursor of titanium oxide.The precursor of this titanium oxide continues to carry out burning till in 2 hours in 340 ℃ air through burning till in 320 ℃ air 2 hours then.Be cooled to room temperature then, obtain the powder of titanium oxide.The anatase rate of this titanium dioxide powder is 74%, crystal grain (crystallization) particle diameter 11.5nm, BET specific area 152m
2/ g.Anatase rate here and size of microcrystal are measured in order to following method.
The size of crystal grain:
Use X-ray diffraction device (motor system of science, trade name RAD-IIA), (X-ray tube: Cu, tube voltage: 40kV impose a condition, tube current: 35mA, divergent slit: 1 degree, scatter slit: 1 spends, is subjected to optical slits: 0.30mm, it is wide to take a sample: 0.020 degree, and sweep speed: 2.00 degree/minute, measure cumulative frequency: 1 time.) measure.Try to achieve the half-peak breadth β (radian) and peak position 2 θ (radian) at peak of the strongest interference line (facial index 101) of titanium oxide, the Scherrer formula is as follows:
E
1(nm)＝K·λ/(βcosθ) (V)
[in the formula, K is a constant 0.94, λ (nm) for the wavelength of measuring X ray (CuK α line: 0.154056nm)], calculate thus the big or small E of crystal grain
1
The anatase rate:
Use X-ray diffraction device (motor system of science, trade name RAD-IIA), use condition identical when asking grain size to measure, try to achieve the peak area of the strongest interference line (facial index 101) of titanium oxide, calculate the anatase rate.Standard adopt anatase-type titanium oxide (with the pure medicine of light, reagent one-level, trade name: titanium dioxide (Detitanium-ore-type), and to set its anatase rate be 1 (100%).
(anionic property compound)
The anionic property compound that uses among comparative example 2 and the embodiment 1～6 is polyphosphoric acid (Japanese chemical industry system), glycolic, gluconic acid and lactic acid.Use nitric acid in the comparative example 1.The reagent primes that medicine beyond the polyphosphoric acid all is and the pure medicine of light (strain) is made.
(alkaline organic compound)
From triethanolamine, morpholine (tetrahydrochysene-1,4- piperazine), tetramethyl ammonium hydroxide, select.What use as alkaline organic compound in the comparative example 1 and 2 is inorganic compound NaOH, has used organic compound in other example.Embodiment 1 and the alkaline organic compound of implementing in 4 are triethanolamine, use morpholine among the embodiment 2 and 5, have used tetramethyl ammonium hydroxide among the embodiment 3 and 6.Medicine is reagent one-level or suitable product.
(antioxidant)
Use hypophosphorous acid or phosphatic hydroxylamine as antioxidant.Using the amount of hypophosphorous acid among the embodiment 3 and 5 is 1 mass parts, and the amount of phosphatic hydroxylamine is 1 mass parts among the embodiment 4 and 6.
The composition of having represented the titanium oxide sol that uses among comparative example and the embodiment in the table 1.With charged positive and negative measure of zeta potential measurement device to the Titanium particles in the colloidal sol of preparation.In addition, use the scraper spreader with 10mL/m at substrate surfaces such as aluminium, acidic paper, galvanized steel plain sheet and corrosion resistant plates
2Speed coating, 80 ℃ of following dryings after, measure appearance of film quality and photocatalytic activity (aliphatic acid decomposition rate: the mg/m of unit
2My god)
For base material, used aluminium alloy among comparative example 1, embodiment 1 and the embodiment 5, other uses corrosion resistant plate.
The preparation method of the titanium oxide sol that uses among the embodiment is: add the anionic property compound in the acid amorphous oxidation titanium colloidal sol, add alkaline organic compound then, obtain the pH value and be 8～9 sol solutions, material after it is disperseed with the dispersion machine homogeneous is removed chlorion with the pellicle dialysis treatment, add Titanium particles again, its homogeneous is disperseed with grinder with responding to visible light.
The dry curing condition of filming, comparative example 1,2 and embodiment 1～2 are drying at room temperature in the dark 5 hours, and embodiment 3 and 4 is drying at room temperature 10 minutes, and wavelength is that the above illumination with Halogen lamp LED of 450nm was penetrated 10 hours then.Embodiment 5 and 6 is a heat drying 20 minutes in 250 ℃ of baking ovens.
Following experimental method and evaluation criterion are used in the evaluation of film performance.
(appearance of film)
Whether get rusty and the whether visual judgement of variable color.
(adherence)
The adherence of filming is that benchmark is judged the adherence of filming with the adhesion test of filming of JIS-K5400 basal disc order adhesive tape method.(only metal being estimated)
(diaphragm hardness)
Draw with pencil with the JIS-K5400 pencil test and to film, judge the hardness of filming with the hardness of pencil.(only metal being estimated)
(visible light photocatalysis active)
Test film is coated with, for dried test film, stearic acid after coating is diluted with ethanol, Y45 optical filter (promptly the light of discontented 450nm wavelength is cut out) is installed on the Halogen lamp LED of 150W, luminous ray 48 hours irradiation is calculated decomposition of fatty acids speed according to the weight difference behind per 24 hours pre-irradiations.
Listed as table 1, in the comparative example 1～2, used titanium oxide sol in the past and its manufacture method, can not reach satisfied effect to the material of perishable deterioration.Among the embodiment 1～6 relevant with the present invention, based on the manufacture method of neutral titanium oxide sol and neutral titanium oxide sol, above problem does not take place on the performance.
[table 1]
The composition of titanium oxide solution and film performance
| No. | Generate composition, the proterties of titania solution | Film performance | ||||||||
| TiO 2(mass parts) | Electric charge | Anionic property compound (mass parts) | Alkali compounds | pH | Dispersity | The coating outward appearance | Adherence | Hardness of film | The visible light catalytic performance | |
| Comparative example 1 | 60 | - | -(-) | 17 | 7.8 | Aggegation | *: albefaction | × | 2B | 60 |
| Comparative example 2 | 80 | + | Nitric acid (12) | 0.1 | 1.8 | Disperse | *: albefaction | △ | B | ＜10 |
| Embodiment 1 | 80 | - | Polyphosphoric acid (20) | 5 | 5.5 | Disperse | ○ | ○ | H | 100 |
| Embodiment 2 | 60 | - | Glycolic (60) | 15 | 8.5 | Disperse | ○ | ○ | H | 105 |
| Embodiment 3 | 90 | - | Polyphosphoric acid (2) | 8 | 7.6 | Disperse | ○ | ○ | 2H | 130 |
| Embodiment 4 | 52 | - | Gluconic acid (25) | 4 | 7.2 | Disperse | ○ | ○ | 2H | 120 |
| Embodiment 5 | 80 | - | Polyphosphoric acid (8) | 12 | 8.2 | Disperse | ○ | ○ | 3H | 135 |
| Embodiment 6 | 70 | - | Lactic acid (10) | 8 | 9.5 | Disperse | ○ | ○ | 3H | 120 |
The effect of invention
As described above, use titanium oxide sol of the present invention and titanium oxide-coating film, the visible light performance that the visible light type photochemical catalyst can be played stably and and can obtain good film performance. For using smears corrosion-prone metal material and easy deteriorated organic material of difficulty, can use the present invention to make the smears, can be stablized, the titanium oxide sol of good dispersion or film. Titanium oxide is used for all can being used various purposes such as dirt decomposition, ultraviolet absorption, sterilization, gas decomposition, purification of water qualitys, and is applicable to widely material, thereby have very large use value.
Claims (5)
1. titanium oxide sol, it is characterized in that, contain electronegative amorphous oxidation titanium particle that adds up to 50～99 mass parts and Titanium particles with responding to visible light, contain more than one that add up to the 1-50 mass parts and be selected from the material of condensed phosphoric acid, condensed phosphate and anionic property compound, wherein said anionic property compound is selected from the chelate compound with carboxyl, and contain solvent, and the pH value is in the scope of 5-10.
2. the titanium oxide sol of record in the claim 1 is characterized in that, also contains at least a alkaline organic compound that is selected from alkanolamine, tetra-allkylammonium, piperazine, piperidines and the choline.
3. the titanium oxide sol of claim 1 or claim 2 record wherein also contains antioxidant.
4. titanium oxide is filmed, and it is characterized in that, contains to use amorphous oxidation titanium particle that the titanium oxide sol of claim 1-3 in each form and the Titanium particles with responding to visible light.
5. the titanium oxide formation method of filming, it is characterized in that, the titanium oxide sol of arbitrary record in the claim 1～3 is attached to substrate surface, after making solvent evaporates, carry out at least one processing in the following processing, that is, A) burn till processing, B in the heating of the temperature more than 200 ℃) the electromagnetic treatment with irradiation of the not enough 650nm of wavelength.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002331599A JP2004161573A (en) | 2002-11-15 | 2002-11-15 | Titanium oxide sol, titanium oxide coating film, and its forming method |
| JP331599/02 | 2002-11-15 | ||
| JP331599/2002 | 2002-11-15 |
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| CN1500549A CN1500549A (en) | 2004-06-02 |
| CN1327952C true CN1327952C (en) | 2007-07-25 |
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| CNB2003101165709A Expired - Fee Related CN1327952C (en) | 2002-11-15 | 2003-11-14 | Titanium oxide sol, titanium oxide sol coat film and forming method |
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| JP (1) | JP2004161573A (en) |
| CN (1) | CN1327952C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4542322B2 (en) * | 2003-09-10 | 2010-09-15 | 株式会社Ｙｏｏコーポレーション | Amorphous coating and anti-fogging amorphous coating |
| US9011890B2 (en) * | 2005-12-12 | 2015-04-21 | Qinhuangdao Yipeng Special Glass Co., Ltd. | Antibacterial sol-gel coating solution |
| US7820724B2 (en) * | 2008-02-14 | 2010-10-26 | Millennium Inorganic Chemicals, Inc. | Colloidal titanium dioxide sols |
| CN102031722B (en) * | 2010-10-25 | 2012-05-09 | 华南理工大学 | Zeolite-loaded and vanadium ion-doped titanium dioxide antibacterial paper and preparation method thereof |
| KR102374217B1 (en) * | 2014-09-30 | 2022-03-14 | 스미토모 오사카 세멘토 가부시키가이샤 | Method for producing titanium oxide particles, titanium oxide particles, dispersion solution of titanium oxide particles, titanium oxide paste, titanium oxide film, and dye-sensitized solar cell |
| TWI779203B (en) * | 2018-12-10 | 2022-10-01 | 愛爾蘭商卡斯特斯科技公司 | P-doped surface coatings and process of preparation thereof |
| CN114570297A (en) * | 2021-12-31 | 2022-06-03 | 杭州大岸科技有限公司 | Preparation method and application of titanium oxide modified sol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06293519A (en) * | 1992-07-28 | 1994-10-21 | Ishihara Sangyo Kaisha Ltd | Production of titanium oxide particles and film |
| JP2001081357A (en) * | 1999-09-17 | 2001-03-27 | Nippon Parkerizing Co Ltd | Titanium oxide coating liquid and formation of titanium oxide coating film |
| CN1309621A (en) * | 1998-05-14 | 2001-08-22 | 昭和电工株式会社 | Titanium oxide sol, thin film, and process for producing these |
-
2002
- 2002-11-15 JP JP2002331599A patent/JP2004161573A/en active Pending
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2003
- 2003-11-14 CN CNB2003101165709A patent/CN1327952C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06293519A (en) * | 1992-07-28 | 1994-10-21 | Ishihara Sangyo Kaisha Ltd | Production of titanium oxide particles and film |
| CN1309621A (en) * | 1998-05-14 | 2001-08-22 | 昭和电工株式会社 | Titanium oxide sol, thin film, and process for producing these |
| JP2001081357A (en) * | 1999-09-17 | 2001-03-27 | Nippon Parkerizing Co Ltd | Titanium oxide coating liquid and formation of titanium oxide coating film |
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| Publication number | Publication date |
|---|---|
| CN1500549A (en) | 2004-06-02 |
| JP2004161573A (en) | 2004-06-10 |
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