CN100537430C - Ultra-fine particles of zinc oxide, method for preparing the same and cosmetic comprising the same - Google Patents
Ultra-fine particles of zinc oxide, method for preparing the same and cosmetic comprising the same Download PDFInfo
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- CN100537430C CN100537430C CNB2005101141900A CN200510114190A CN100537430C CN 100537430 C CN100537430 C CN 100537430C CN B2005101141900 A CNB2005101141900 A CN B2005101141900A CN 200510114190 A CN200510114190 A CN 200510114190A CN 100537430 C CN100537430 C CN 100537430C
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Abstract
Ultra-fine particles of zinc oxide which have a specific surface area of 10 to 200 m<2>/g as measured by one point BET method, have primary particles being substantially isotropic with respect to the form thereof, characterized in that it has a specific volume of 4 to 40 ml/g as measured by means of a tapping machine; a method for preparing the same; and a cosmetic comprising the same. The ultra-fine particles have a reduced degree of aggregation of primary particles and thus can be extremely easily dispersed into and suspended in an aqueous solvent with no pulverization steps or through a simple dry pulverization, can be suitably used, for example, as a powder for a cosmetic, and further have both of feeling of transparency and ultraviolet ray-shielding function.
Description
The application's application number that to be the applicant propose on February 4th, 2000 is dividing an application of 00805064.3 application.
The application numbers the 60/121st, No. 435 (February 23 1999 applying date) opinion application right according to U. S. application.
Technical field
The present invention relates to a kind of ultra-fine particles of zinc oxide and manufacture method thereof and the above-mentioned ultra-fine particles of zinc oxide of use cosmetic, the condensation degree of the primary particle of this ultra-fine particles of zinc oxide is low, pulverize condensation degree to be reduced to without pulverizing process or by slight dry type and can very easily disperse, be suspended to the degree in the water system solvent, be suitable as for example cosmetic powder, and have transparent feel and UV-preventing ability simultaneously.
Background technology
In the past, selling on the market has multiple Zinc oxide powder, as the pigment extender that is coupled to cosmetic etc. etc.As the known manufacturing methods of these Zinc oxide powders, liquid phase method and vapor phase process are arranged substantially, in liquid phase method, with liquid phase synthesis of oxalic acid zinc, zinc hydroxide, alkaline carbonic acid zinc etc., make its precipitation, after filtering separation is also cleaned, make its thermolysis, obtain zinc oxide, having obtained specific surface area is 50m
2The zinc oxide that/g is above, but owing to be essentially the batch treatment formula, so productivity is low, in addition, obtain under the state of solid-liquid mixed phase owing to generate micropartical, so, in order to obtain product, needing drying process, cost degradation is difficult to realize.In addition, because remaining impurity when synthetic, existence can not obtain the shortcoming of high purity product.On the other hand, in vapor phase process, have French method that makes the zinc fume oxidation and the American process of the zinc fume that produces being carried out oxidation in the smelting process of zinc ore.In this vapor phase process, can obtain specific surface area 30m
2The Zinc oxide powder that/g is above also proposes to have multiple modification method in recent years, for the product that obtains further to increase specific surface area and improved purity is attempted.
Yet the shape and the particle diameter of the primary particle of the Zinc oxide powder of being made by above-mentioned existing method are inhomogeneous, and are easy to condense and form huge offspring.With the occasion of such Zinc oxide powder, need fragmentation, pulverizing etc. to remove the operation of cohesion as cosmetic etc.In operations such as this fragmentation, pulverizing, unavoidably can cause impurity to be sneaked into by the wearing and tearing of the machine in the course of processing etc., purity is descended, and become granularity, the uneven powder of particle diameter inevitably.For this reason, when as cosmetic etc., sense of touch is relatively poor.In addition, owing to need a large amount of size reduction energies, so cost is also high.
Therefore, the object of the present invention is to provide a kind of ultra-fine particles of zinc oxide and manufacture method thereof, the condensation degree of the primary particle of this ultra-fine particles of zinc oxide is low, without pulverizing process or by slight dry type pulverize can be when being applied to cosmetic etc. disperseing in stable conditionly, being suspended in the water system solvent with superfine ultramicron.
In addition, the object of the present invention is to provide a kind of cosmetic that has transparent feel and UV-preventing ability simultaneously.
Summary of the invention
The present invention relates to a kind of ultra-fine particles of zinc oxide, the specific surface area of being measured by the BET one point method of this ultra-fine particles of zinc oxide is 14～34m
2/ g, primary particle is shaped as isotropy in fact, it is characterized in that: the specific volume of being measured by tapping machine (tapping machine) is 4.65～7.1ml/g, the V/A value that obtains from specific volume V and specific surface area A is at 0.18ml/m
2More than, be 14～34m in specific surface area
2The scope of/g, the V/A value that obtains from specific volume V and specific surface area A is in 0.7～3 times scope of the Y value that is obtained by following (1) formula, Y=V/A=-0.152Ln (A)+0.745...... (1), wherein, Ln (A) is that (unit is m to specific surface area
2/ g) natural logarithm value.
The whiteness of above-mentioned ultra-fine particles of zinc oxide is big, thus UV-preventing ability height, and, have transparent feel at the light transmission height of visible region, can obtain very good characteristic in occasion as cosmetic.
In addition, the present invention relates to a kind of ultra-fine particles of zinc oxide, by poly-three Tegin ISOs (ト リ-イ ソ-ス テ ア リ Application acid Port リ ゲ リ セ リ De) the above-mentioned specific volume that suspends be the ultra-fine particles of zinc oxide of 4～40ml/g measure for the optical density (OD) of optical wavelength 370nm with for the ratio of the optical density (OD) of optical wavelength 530nm more than 4.
Above-mentioned ultra-fine particles of zinc oxide is good especially in the light transmission of visible region.
In addition, ultra-fine particles of zinc oxide manufacture method of the present invention makes the metallic zinc steam produce oxidizing reaction in the atmosphere that contains aerobic and water vapour, in this oxidizing reaction, from of the carrier gas of the 1st nozzle to reactor metal injection zinc fume and rare gas element, to reactor, spray the oxidizing gas that comprises oxygen and water vapour from the 2nd nozzle, make zinc produce oxidizing reaction.
In addition, ultra-fine particles of zinc oxide manufacture method of the present invention makes the metallic zinc steam produce oxidizing reaction in the atmosphere that contains aerobic and water vapour, in this oxidizing reaction, from of the carrier gas of the 1st nozzle to reactor metal injection zinc fume and rare gas element, to reactor, spray the oxidizing gas that comprises oxygen and water vapour from the 2nd nozzle, and, spray the oxidizing gas that comprises oxygen and water vapour that makes inflammable gas burning acquisitions such as propane, hydrogen by the superfluous combustion-supporting gas of oxygen or air from the 3rd nozzle to reactor, make zinc produce oxidizing reaction.
The condensation degree of the primary particle of the ultra-fine particles of zinc oxide of being made by aforesaid method is low, and shape, particle diameter are even.
In addition, be characterised in that, comprise the above-mentioned ultra-fine particles of zinc oxide of 1～40 weight %, have transparent feel and UV-preventing ability simultaneously according to cosmetic of the present invention.
Description of drawings
Fig. 1 is the synoptic diagram of an example of the reaction unit of enforcement manufacture method of the present invention.
Fig. 2 (a) and (b), (c) are the synoptic diagram that is used for the reaction unit of manufacture method of the present invention.
Fig. 3 is the figure that the specific volume/specific surface area of enforcement material of the present invention and comparative material (market sale product) is shown.
Fig. 4 is the curve that the light transmission rate of enforcement material of the present invention and comparative material (market sale product) is shown.
Embodiment
Zinc oxide powder for prior art, as described above, the primary particle cohesion forms huge offspring, so, in fragmentation, pulverizing process, make it separately, but unavoidably cause purity to descend, become the uneven powder of granularity and particle diameter, so when as cosmetic etc., sense of touch is relatively poor.The inventor finds that the specific volume of these Zinc oxide powders can only obtain the smaller value below 3.5ml/g after through more detailed research.Therefore, conscientiously having studied not carry out operations such as granularity, the inhomogeneous such fragmentation of particle diameter, pulverizing basically is the value of the specific volume that does not promptly form the such ultramicron zinc of huge offspring of prerequisite, found that, the specific volume that is obtained by the aftermentioned manufacture method is low at the condensation degree of the ultra-fine particles of zinc oxide of the scope of 4～40ml/g, fully or basically do not need pulverizing process, can directly be used as the cosmetic raw material, make the present invention thus.
Find also that in addition the whiteness of such ultra-fine particles of zinc oxide is big, thus UV-preventing ability height, and, have transparent feel at the light transmission height of visible region, obtain very good characteristic in occasion as cosmetic.
The following describes the measuring method of specific volume.
Under 105 ℃, sample is carried out drying up to becoming constant in advance, make it pass through standard sieve 177 μ m.Correctly it is weighed up 3.0g, be encased in lightly in the band 20ml scale test tube.This test tube is encased in metal tube, the cover loam cake, from the place of height 45mm with 2 seconds 1 time speed fall 400 times, then, read volume (ml), the V that will be obtained by formula V=volume (ml)/3 (g) is as the specific volume of this sample.
The following describes the UV-preventing ability.
With poly-three Tegin ISO 20g and dry up to the powder sample 200mg that becomes constant, as blending agent under 105 ℃ of degree
ZrO
2Ball 200g,
ZrO
210 in ball is encased in the container, is processed 30 minutes by desk-top ball milling under the condition of 100rpm.By the UV, visible light spectrophotometer it is measured the optical density (OD) (suitable with the denary logarithm of the inverse of transmittance) of each wavelength.The container that uses is the 0.1mm quartz container, measures under the wavelength of 200～800nm.Certainly, gather three Tegin ISOs (コ ス モ-Le 43) and also carry out blank (プ ラ Application Network) correction.Wherein, be that the ratio of optical density (OD) of 370nm and 530nm is as the index of UV-preventing ability and transparent feel (light transmission of visible region) with wavelength.
Existing Zinc oxide powder is no more than 1～3 for the optical density (OD) of optical wavelength 370nm and ratio for the optical density (OD) of optical wavelength 530nm, but ultra-fine particles of zinc oxide of the present invention measure for the optical density (OD) of optical wavelength 370nm with for the ratio of the optical density (OD) of optical wavelength 530nm more than 4, particularly compared with prior art, the light transmission in the visible region is especially good.
In addition, the present invention proposes the manufacture method of ultra-fine particles of zinc oxide with above-mentioned unexistent characteristic of past, this manufacture method is characterised in that: make the metallic zinc steam produce oxidizing reaction in the atmosphere that contains aerobic and water vapour, in this oxidizing reaction, from of the carrier gas of the 1st nozzle to reactor metal injection zinc fume and rare gas element, to reactor, spray the oxidizing gas that comprises oxygen and water vapour from the 2nd nozzle, make zinc produce oxidizing reaction.
In addition, the present invention proposes the manufacture method of ultra-fine particles of zinc oxide with above-mentioned unexistent characteristic of past, this manufacture method is characterised in that: make the metallic zinc steam produce oxidizing reaction in the atmosphere that contains aerobic and water vapour, in this oxidizing reaction, from of the carrier gas of the 1st nozzle to reactor metal injection zinc fume and rare gas element, to reactor, spray the oxidizing gas that comprises oxygen and water vapour from the 2nd nozzle, and, make propane from the 3rd nozzle ejection by superfluous combustion-supporting gases such as oxygen and air, the oxidizing gas that the burning of inflammable gass such as hydrogen obtains makes zinc produce oxidizing reaction.
Manufacture method to the ultra-fine particles of zinc oxide of vapor phase process carries out finding after the conscientious research, spray the unstripped gas that the carrier gas of the metallic zinc steam gasified in advance as described above and rare gas element constitutes from the 1st nozzle to reactor, to reactor, spray the oxidizing gas that comprises oxygen and water vapour from the 2nd nozzle, and/or make propane by superfluous combustion-supporting gases such as oxygen and air from the 2nd and 3 nozzle ejection, the oxidizing gas that the burning of inflammable gass such as hydrogen obtains, make zinc produce oxidizing reaction, thereby can make the low and shape of condensation degree of primary particle, the uniform ultra-fine particles of zinc oxide of particle diameter.
The oxidizing gas that comprises oxygen and water vapour also can be made inflammable gas burnings such as propane, hydrogen obtain by the superfluous combustion-supporting gas of oxygen or air, and the nozzle of the nozzle of jet paraffin oxidation gas and injection unstripped gas also can be a plurality of.
From the temperature of the carrier gas of the metallic zinc steam of the 1st nozzle ejection and rare gas element is 900～1800 ℃, then better when being 1000～1500 ℃.
From the temperature of the oxidizing gas that comprises oxygen and water vapour of the 2nd nozzle or the 3rd nozzle ejection is 900～1200 ℃, then better when being 1000～1200 ℃.
In addition, from the oxygen concn of the air-flow of the oxidizing gas that comprises oxygen and water vapour of the 2nd nozzle or the 3rd nozzle ejection scope, then better when 50 volume %～100 volume % at 5 volume %～100 volume %.The oxygen concn of this air-flow and the total of water vapor concentration are not less than 5 volume % but less than 100 volume %.
From the jet velocity of the carrier gas of the 1st nozzle ejection metallic zinc steam and rare gas element is 10～200m/ second, is that 15～100m/ is then better during second.
In addition, the speed from the oxidizing gas that comprises oxygen and water vapour of the 2nd nozzle or the 3rd nozzle ejection is preferably 2～250m/ second.
After the oxidizing reaction of zinc, preferably control to the uncondensable temperature of water, the uncondensable temperature of water is more than 100 ℃, is preferably 100～150 ℃.
Investigation can find that by the V/A value that the specific volume V and the specific surface area A of the ultra-fine particles of zinc oxide by this manufacture method manufacturing obtains though it is littler than 0.15 to have this value of Zinc oxide powder now, this V/A value of the present invention is at 0.18ml/m
2More than, become very big.
Be in 0.7～3 times scope of the Y value that obtains by following (1) formula by the V/A value of the ultra-fine particles of zinc oxide of this manufacture method manufacturing, have very outstanding characteristic and be inclined to.
Y＝V/A＝-0.152Ln(A)+0.745......(1)
Wherein, (unit is m to Ln (A) for specific surface area
2/ g) natural logarithm value.
Manufacture method of the present invention is described below with reference to the accompanying drawings.
Fig. 1 is the synoptic diagram that an example of the manufacturing installation that is suitable for ultra-fine particles of zinc oxide of the present invention is shown.As shown in Figure 1, the raw material zinc that supplies to hopper 4 is transported to zinc vaporizer 2 by carrier gas, and the zinc fume that produces at zinc vaporizer 2 is directed into reactor 1 by rare gas element by the 1st nozzle 7.
On the other hand, the oxidizing gas that comprises oxygen and water vapour is directed into gas heater 9, be directed into reactor 1 by the 2nd nozzle 10, and/or will be in burner 3 inflammable gass burnings such as propane, hydrogen be obtained by the 3rd nozzle 8 by the superfluous combustion-supporting property gas of oxygen or air oxidizing gas be directed into reactor 1, make zinc oxidation (reference example such as Fig. 2 (a)～Fig. 2 (c)).
The operation that this reaction is stopped is a refrigerating work procedure, in this refrigerating work procedure, to the zinc oxide shower cooling air that is transported to water cooler 5, reaction is stopped.
Length, the residence time of the reacting environment by changing this moment, the granularity of may command zinc oxide, particle shape, and particle diameter.Afterwards, zinc oxide is captured by capture means (device) such as deep bed filter or cyclonic separators, obtains product.
The ultra-fine particles of zinc oxide powder of above-mentioned capture is as required by silica-coated, but tunicle formation method is not restricted especially, for example can use WO98/47, the method that No. 476 communiques are put down in writing.
Say in principle, the ultra-fine particles of zinc oxide powder is distributed to the formation of silicon-dioxide tunicle uses constituent, remain in specified temperature, thereby optionally be deposited to the surface of above-mentioned ultra-fine particles of zinc oxide powder, can form silicon dioxide film.Also can modulate tunicle in advance and form with dropping into Zinc oxide powder behind the constituent, form silicon dioxide film, or in advance Zinc oxide powder is suspended to interpolation other material composition in back in the solvent, the formation tunicle forms uses constituent, thereby forms silicon dioxide film.That is, drop into tunicle formation and do not do special restriction with the raw material of constituent, the order of ultra-fine particles of zinc oxide powder, which side formerly all can form tunicle.
Ultra-fine particles of zinc oxide powder of the present invention and silicon-dioxide tunicle ultra-fine particles of zinc oxide powder also can be widely used in pigment, UV-preventing material, have controlled active photocatalyst etc. except that can be applicable to cosmetic.
Cosmetic of the present invention can use and comprise above-mentioned ultra-fine particles of zinc oxide powder and/or silica-coated ultra-fine particles of zinc oxide powder and can be coupled to common raw material in the cosmetic, is made by common manufacture method.
Cosmetic of the present invention contains the ultra-fine particles of zinc oxide powder of 1～40 quality % or the silica-coated ultra-fine particles of zinc oxide powder of 1～40 quality %.Consider ultraviolet screening effect, the amount of ultra-fine particles of zinc oxide powder and/or silica-coated ultra-fine particles of zinc oxide powder is preferably 3～25 quality %, and is then better when being 5～20 quality %.
The amount of ultra-fine particles of zinc oxide powder and/or silica-coated ultra-fine particles of zinc oxide powder than 1 quality % after a little while, ultraviolet screening effect is insufficient, when surpassing 40 quality %, is difficult to preparationization, and is undesirable.
Cosmetic of the present invention does not then limit especially as including powder, and comprises powder is distributed to occasion in solvent or the solution.For example, that the cosmetic with powder has is Powdered, the cosmetic of briquetting shape, bar-shaped, aqueous shape, specifically can list white powder, foundation cream, face powder, kermes, eyelid black pigment used by women in ancient times to paint their eyebrows, lipstick, eye liner pencil, mascara, eyebrow pencil etc.In addition, as the cosmetic that powder is distributed in solvent or the solution, have and to list vanishing cream, essence, washing lotion, astringent, emulsion, mousse etc.Be particularly suitable for solid shape powder cosmetic.
With embodiment and comparative example the present invention is described below, but the invention is not restricted to these embodiment.
(evaluation of physical property method)
Rerum natura is measured and is estimated by following method.
X-ray diffraction uses the 2000/PC type device of the Li Kake of Co., Ltd. (リ ガ Network) system.
Specific surface area is used Mo Luosuobu (モ ノ ソ-Block) the type device of Quantachrome system, measures under the condition of BET one point method.
Specific volume is held the science machine by the Tibetan and is made the method mensuration of the tapping machine of manufacturing according to the cosmetic material benchmark.
In addition, for carrying out the initial stage, the transparent feel to zinc oxide (sample) estimates, by going into desk-top ball milling V-1M type that the river makes manufacturing suspension sample 200mg in poly-three Tegin ISOs (day these mole 43 (コ ス モ Le 43) of card that clear system oil is made) 20g, the visible spectrophotometer UV-160 of ultraviolet ray that is made by Shimadzu Seisakusho Ltd. method in accordance with regulations measures the transmittance of optical wavelength 280～700nm.
(embodiment 1)
Utilize above-mentioned reaction unit shown in Figure 1 to carry out the manufacturing of ultra-fine particles of zinc oxide (aftermentioned embodiment 2～4 too).
The container that will have the big heat transfer area of the metallic zinc steam output that can obtain 9kg/hr is heated to 1150 ℃, will be as the nitrogen 4Nm of carrier gas
3/ hr is blown into wherein, is directed into reaction tubes from nozzle 7 under the state of insulation.On the other hand, with air flow quantity 20Nm
3/ hr, water 700cc/hr are heated to 1100 ℃, are directed into reaction tubes from nozzle 10, with the above-mentioned raw materials gas reaction.When the white powder that obtains like this by X-ray diffraction analysis, be found to be Zincite, confirm as zinc oxide.Detailed creating conditions is as shown in table 1.
The rerum natura of the ultra-fine particles of zinc oxide of Huo Deing (implementing material 1) is as shown in table 2 like this.
(embodiment 2)
The container that will have the big heat transfer area of the metallic zinc steam output that can obtain 4kg/hr is heated to 1100 ℃.Will be as the nitrogen 1Nm of carrier gas
3/ hr is blown into wherein, is directed into reaction tubes from nozzle 7 under the state of insulation.On the other hand, with oxygen flow 40Nm
3/ hr, 6 liters/hr of water are heated to 1100 ℃, are directed into reaction tubes from nozzle 10, with the above-mentioned raw materials gas reaction.When the white powder that obtains like this by X-ray diffraction analysis, be found to be Zincite, confirm as zinc oxide.Detailed creating conditions is as shown in table 1.
The rerum natura of the ultra-fine particles of zinc oxide of Huo Deing (implementing material 2) is as shown in table 2 like this.
(embodiment 3)
The container that will have the big heat transfer area of the metallic zinc steam output that can obtain 10kg/hr is heated to 1100 ℃.Will be as the nitrogen 2Nm of carrier gas
3/ hr is blown into wherein, is directed into reaction tubes from nozzle 7 under the state of insulation.On the other hand, with oxygen flow 120Nm
3/ hr, 15 liters/hr of water are heated to 1150 ℃, are directed into reaction tubes from nozzle 10, with the above-mentioned raw materials gas reaction.When the white powder that obtains like this by X-ray diffraction analysis, be found to be Zincite, confirm as zinc oxide.Detailed creating conditions is as shown in table 1.
The rerum natura of the ultra-fine particles of zinc oxide of Huo Deing (implementing material 3) is as shown in table 2 like this.
(embodiment 4)
The container that will have the big heat transfer area of the metallic zinc steam output that can obtain 6kg/hr is heated to 1150 ℃.Will be as the nitrogen 2Nm of carrier gas
3/ hr is blown into wherein, is directed into reaction tubes from nozzle 7 under the state of insulation.On the other hand, with oxygen flow 20Nm
3/ hr, water 400cc/hr are heated to 1150 ℃, are directed into reaction tubes from nozzle 10, with the above-mentioned raw materials gas reaction.When the white powder that obtains like this by X-ray diffraction analysis, be found to be Zincite, confirm as zinc oxide.Detailed creating conditions is as shown in table 1.
The rerum natura of the ultra-fine particles of zinc oxide of Huo Deing (implementing material 4) is as shown in table 2 like this.
Table 1
| Create conditions | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| The unstripped gas temperature [℃] Zn steam output [kg/hr] carrier gas feed rate [Nm 3/ hr] Zn concentration [vol%] oxidizing gas flow Air[Nm in the unstripped gas 3/ hr] oxidizing gas flow O 2[Nm 3/ hr] steam vapour amount H 2O[g/hr] oxidizing gas total flux [Nm 3/ hr] the oxidizing gas temperature [℃] O in the oxidizing gas 2Concentration and H 2The nozzle that the nozzle of the total of O concentration [%] unstripped gas blows out flow velocity [m/s] oxidizing gas blow out flow velocity [m/s] oxygen excess rate [%] capture temperature [℃] | 1150 9 4 44 20 0 700 21 1100 24 33 23 273 120 | 1100 4 1 58 0 40 6000 47 1100 100 11 53 5839 130 | 1150 10 2 63 0 120 15000 139 1150 100 100 160 7007 130 | 1150 6 2 51 0 20 400 20 1150 100 19 24 1946 130 |
The definition of the oxygen excess rate in the table:
(comparative material A～D)
4 kinds of the Zinc oxide powders of selling on the selection market, promptly, the Z-COTE product (comparative material C) that the FINEX-50 product (comparative material B) that the ZnO-350 product (comparative material A) that Sumitomo Osaka Cement Co., Ltd. makes, KCC make, Sun Smart make, the USP-1 product (comparative material D) that reaches Zinc of America manufacturing are illustrated in its rerum natura in the table 2.
(evaluation of physical property)
As shown in Table 2, the ultra-fine particles of zinc oxide of enforcement material 1～4 of the present invention is that specific volume is big, the less powder of bulk specific weight.Can also learn that in addition the value of the specific volume V/ specific surface area A of the ultra-fine particles of zinc oxide of enforcement material 1～4 of the present invention is all at 0.18ml/m
2More than, be that comparative material A～D compares with the Zinc oxide powder of selling on the market, very big (with reference to Fig. 3).The surface-area that compares is drawn this V/A value, after the analyte sexual orientation, obtained surprising discovery, promptly, occasion at enforcement material 1～4 of the present invention, the curve values of V/A=-0.152Ln (A)+0.745 (wherein, Ln (A) is the natural logarithm value of specific surface area) is present in from the scope of (V/A)+200% to-30%.This tendency is compared very special with the characteristic movement (curve) of comparative material.
In addition, find during the ultraviolet-visible absorption spectroscopy of mensuration dispersed system that for implementing material 1～4, A～D compares with comparative material, observes the very outstanding transparency (with reference to Fig. 4).Particularly implement material 1～4, for the optical density (OD) (OD370) of optical wavelength 370nm with for the ratio of the optical density (OD) (OD530) of optical wavelength 530nm more than 4, very outstanding.For the L value of being measured by the Hunter color difference meter, it is also very outstanding to implement material 1～4.
The following describes the embodiment of prescription of the foundation cream of the lining of silicon-dioxide of ultra-fine particles of zinc oxide powder and above-mentioned silica-coated zinc powder body.
(embodiment 5)
In the 5L reactor, mix deionized water 991ml, ethanol (pure chemistry is made) 1083ml, reach 25 weight % ammoniacal liquor 6.7ml (containing the chemical industry manufacturing greatly), make the oxide powder and zinc (MZ0350 that Sumitomo Osaka Cement Co., Ltd. makes, primary particle diameter 37nm) 67g is distributed to wherein, modulation suspension.Then, mix tetraethoxy-silicane (that is scolded La Yitesike (Na カ ラ イ テ ス Network) and makes) 135ml and ethanol 60ml, modulation solution.
By agitator above-mentioned suspension is stirred on one side, with certain speed 8.5 hour in add above-mentioned solution on one side, afterwards, slaking 12 hours.The film forming slaking is carried out under 35 ℃ of pH10.5, temperature.Afterwards, by centrifuging separate solid composition,, obtain silicon-dioxide tunicle ultra-fine particles of zinc oxide powder 50 ℃ of following heating under vacuum 12 hours.
(embodiment 6)
Make the foundation cream of following prescription according to the method for prior art.As silica-coated ultra-fine particles of zinc oxide powder, use the silica-coated ultra-fine particles of zinc oxide powder that in embodiment 5, obtains.
The prescription of foundation cream is
Ultrafine particulate titanium oxide 10.0 quality %
Silica-coated ultra-fine particles of zinc oxide powder 15.0 quality %
Mica 20.0 quality %
Talcum 10.0 quality %
Zinc white 5.0 quality %
Ferric oxide (red) is an amount of
Ferric oxide (Huang) is an amount of
Glycerine 10.0 quality %
Distilled water 30.0 quality %
Spices is an amount of
The possibility of utilizing on the industry
As described above, the condensation degree of the primary particle of ultra-fine particles of zinc oxide of the present invention is low, pulverizes without pulverizing process or by slight dry type and can very easily disperse, be suspended in the water system solvent, is suitable as such as cosmetic etc. And can have transparent feel and UV-preventing ability this moment.
The manufacture method of ultra-fine particles of zinc oxide of the present invention does not use special equipment and medicament namely to make serially the ultra-fine particles of zinc oxide with above-mentioned action effect, and practical value is high.
In addition, cosmetic transparent feel of the present invention is high, and the UV-preventing ability is good, so practical value is high.
Claims (1)
1, a kind of ultra-fine particles of zinc oxide, the specific surface area of being measured by the BET one point method is 14～34m
2/ g, primary particle is shaped as isotropy in fact, it is characterized in that: the specific volume of being measured by tapping machine is 4.65～7.1ml/g,
The V/A value that obtains from specific volume V and specific surface area A is at 0.18ml/m
2More than,
In specific surface area is 14～34m
2The scope of/g, the V/A value that obtains from specific volume V and specific surface area A is in 0.7～3 times scope by the Y value of following (1) formula acquisition,
Y＝V/A＝-0.152Ln(A)+0.745......(1)
Wherein, (unit is m to Ln (A) for specific surface area
2/ g) natural logarithm value.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2933999 | 1999-02-05 | ||
| JP29339/1999 | 1999-02-05 | ||
| US60/121,435 | 1999-02-23 |
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|---|---|---|---|
| CNB008050643A Division CN1238255C (en) | 1999-02-05 | 2000-02-04 | Ultra-fine particles of zinc oxide, method for preparing the same and cosmetic comprising the same |
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| CN1772626A CN1772626A (en) | 2006-05-17 |
| CN100537430C true CN100537430C (en) | 2009-09-09 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107207275A (en) * | 2015-01-30 | 2017-09-26 | 住友大阪水泥股份有限公司 | Zinc oxide powder, dispersion liquid, coating and cosmetic preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5560871A (en) * | 1992-11-09 | 1996-10-01 | Mitsui Mining & Smelting Co., Ltd. | Method for preparing electrically-conductive zinc oxide |
| JP4164814B2 (en) * | 2004-02-23 | 2008-10-15 | 豊田合成株式会社 | Manufacturing method of long molded products |
| JP4280814B2 (en) * | 2002-01-17 | 2009-06-17 | 国立がんセンター総長 | Liver cancer diagnostic marker, liver cancer detection method, liver cancer diagnosis method, liver cancer analysis quantitative kit, liver cancer cell screening kit, liver cancer analysis method |
-
2000
- 2000-02-04 CN CNB2005101141900A patent/CN100537430C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5560871A (en) * | 1992-11-09 | 1996-10-01 | Mitsui Mining & Smelting Co., Ltd. | Method for preparing electrically-conductive zinc oxide |
| JP4280814B2 (en) * | 2002-01-17 | 2009-06-17 | 国立がんセンター総長 | Liver cancer diagnostic marker, liver cancer detection method, liver cancer diagnosis method, liver cancer analysis quantitative kit, liver cancer cell screening kit, liver cancer analysis method |
| JP4164814B2 (en) * | 2004-02-23 | 2008-10-15 | 豊田合成株式会社 | Manufacturing method of long molded products |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107207275A (en) * | 2015-01-30 | 2017-09-26 | 住友大阪水泥股份有限公司 | Zinc oxide powder, dispersion liquid, coating and cosmetic preparation |
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| CN1772626A (en) | 2006-05-17 |
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