CN1923163A - Sunscreen cream product - Google Patents
Sunscreen cream product Download PDFInfo
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- CN1923163A CN1923163A CN 200510097815 CN200510097815A CN1923163A CN 1923163 A CN1923163 A CN 1923163A CN 200510097815 CN200510097815 CN 200510097815 CN 200510097815 A CN200510097815 A CN 200510097815A CN 1923163 A CN1923163 A CN 1923163A
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- zinc oxide
- sunscreen cream
- cream product
- skin
- nano
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Abstract
The invention relates to a sun cream used to protect skin from ultraviolet radiation. Wherein, it comprises liquid carrier which is colorless and accepted by skin, and the nanometer oxide zinc particles with 15-200m<2/g BET surface and prepared from gas phase method; said particles are uniformly dispersed into said liquid carrier to form transparent sun cream. The invention can protect the skin from UV-A and UV-B radiations, while the particles are dispersed into said liquid carrier at said amount.
Description
Technical field
The present invention relates to a kind of improved sunscreen cream product that comprises nano-level zinc oxide powder with and preparation.
Background technology
The most widely used chemical sunscreen agents comprises for example para-aminobenzoic acid (PABA), PABA ester (glyceryl PABA, amyl group dimethyl PABA and octyldimethyl PABA), benzophenone (oxybenzone and sulisobenzone), cinnamate (octyl methoxycinnamate and cinoxate), salicylate (high cresotinic acid acid esters) and o-aminobenzoa.Up to now, had and surpassed go through " safety and effectively " reagent of preventing to tan severely as protection skin of 21 kinds of such chemicals.Yet, some problems have been proposed recently, be whether really to be inert and further about these chemical chemical compounds, whether the repeated use of these opacifiers can cause a considerable amount of absorptions of passing epidermis of these chemicals.Because chemical sunscreen agents is used with high relatively concentration usually, therefore may come in contact and contact sensitization and allergy, i.e. photo sensitive reaction with light.
On the other hand, physical sunscreen comprises the granule of relative physiologic inertia sunscreen cream,, is suspended in the ultraviolet absorber compounds in cream or the lotion usually that is.The material that often uses for this purpose comprises Kaolin, Talcum, titanium dioxide and zinc oxide.The two kinds of chemical compounds and the top inflammatory reaction of mentioning of back are not got in touch at all.Yet the physical sunscreen product is usually easily dirty and be air-locked.And they form observable, colored (for instance, white) layer again on the surface of skin, and this is unacceptable to many cosmetics aspects that need opacifier to protect.This has abandoned use to these products with regard to having caused many such people.The color of these constituents is owing to the particulate optical property that forms these materials.These performances at least partly depend on these particulate sizes, have the diameter in suitable " standard " scope of 1/10th microns usually.
In addition, present existing physical sunscreen is not easy to wash off from the health of user.On the contrary, they can melt usually along with the heat of the sun, can make the clothes dyeing or the decolouring of user so by way of parenthesis.And because they are as thick relatively filming (20-50 μ m) use, so the use of these products also may cause undesirable skin conditions.Thereby these physical sunscreen products are considered to be unacceptable aspect cosmetics.
The physical sunscreen frost goods of typical prior art can comprise " micronized " of titanium dioxide or the granule of " big surface area ".Use a shortcoming of titanium dioxide to be, it absorbs less ultraviolet radiation in long wave ultraviolet (UV-A) zone relative zinc oxide.And compare opaquer with those products made from zinc oxide based on the product of titanium dioxide.
Summary of the invention
The purpose of this invention is to provide a kind of sunscreen cream product of avoiding the prior art shortcoming.Particularly, it should show the high transparency in UV-A that provides and UV-B protection, and can not cause deleterious chemical reaction on the skin of user.
The injury that the present invention avoids ultraviolet radiation for protection skin provides a kind of part to use sunscreen cream product, and it comprises:
-colourless basically acceptable the liquid-carrier of skin and have 15～200m
2The Nano-class zinc oxide granule that passes through the vapor phase method preparation of/g BET surface area,
-described granule is evenly dispersed in the acceptable liquid-carrier of described colourless basically skin basically, forms the part sunscreen cream product of visually-clear basically, and
-the amount of damaging effect of avoiding UV-A and uv b radiation with the part of effective protection described visually-clear basically of coating on it with the skin of sunscreen cream product with described Dispersion of Particles in described liquid-carrier.
Within the scope of the invention, the Nano-class zinc oxide granule should be understood to be in the granule that has in the sunscreen cream product less than 100 nanometers in average diameter.
Within the scope of the invention, plasma method, atomizing pyrolysis or pyrolysismethod are considered to vapor phase method.
Preferably, Zinc oxide particles is by pyrolysismethod, for example flame oxidation or flame hydrolysis preparation.
Particularly preferably, Zinc oxide particles is by being characterised in that the method preparation of following aspect:
-comprise the starting mixt of the product of zinc fume, fuel gas and fuel gas and oxygen-containing gas oxidation
-react in flame in zoneofoxidation and oxygen-containing gas,
-in the cooling zone with the cooling of the reactant mixture of heat and with solid material and flow separation,
The amount of oxygen is greater than being used for fuel gas and the necessary amount of zinc fume complete oxidation in-the zoneofoxidation.
The mode that zinc fume is provided is unrestricted.For example, zinc powder or other zinc compounds that produces zinc when through heat-treated can be vaporized in vaporizer and be incorporated in the device that comprises starting mixt by means of inert gas flow.It can be the fuel gas of hydrogen, methane, ethane or propane or its mixture that starting mixt also comprises, and hydrogen is preferred.Be present in the product that also has water vapour and/or carbon dioxide, gas fuel burning in the starting mixt.Starting mixt preferably comprises water vapour.
With the mixture of zinc fume, fuel gas and water vapour or water vapour/carbon dioxide, and other noble gas nitrogen for example, transfer to zoneofoxidation, the oxygen-containing gas of it and zoneofoxidation reacts in flame there.The amount of oxygen is greater than being used for fuel gas and the necessary amount of zinc fume complete oxidation in the zoneofoxidation.In zoneofoxidation, according to the fuel gas of equation 1 for example hydrogen oxidation reaction and according to parallel generation of oxidation reaction of the zinc fume of equation 2.
Equation 1:
Equation 2:
Although the oxidation meeting of fuel gas forms water in zoneofoxidation, have been found that the existence in starting mixt of water and/or carbon dioxide is indispensable to the formation of Zinc oxide particles of the present invention.Water is preferred.Water and/or carbon dioxide can produce by for example using the dioxygen oxidation fuel gas.The mol ratio of water and zinc fume can be preferably 15: 1～35: 1, is preferably 20: 1～30: 1 especially.If in the starting mixt mol ratio of fuel gas and zinc fume be 5: 1～25: 1 also be favourable.10: 1～20: 1 ratio is particularly advantageous.When starting mixt entered zoneofoxidation, 3: 1～20: 1 mol ratio of oxygen and fuel gas may be favourable.6: 1～15: 1 ratio may be particularly advantageous.When starting mixt entered zoneofoxidation, 5: 1～30: 1 mol ratio of oxygen and zinc fume may be more favourable.10: 1～20: 1 ratio may be particularly advantageous.The temperature of starting mixt can be 920 ℃～1250 ℃.In the preferred embodiment of this method, zinc fume can the reduction vaporizing zone by zinc powder by means of the inert gas flow in the pipe at the center of being placed in by being arranged in the flame vaporization around the center configuration pipe and obtaining, its flame is produced by the reaction of fuel gas and oxygen-containing gas, and fuel gas is with superfluous and exist with respect to the oxygen content of oxygen-containing gas on the stoichiometry.
In the particularly preferred embodiment of this method, the pipe of adjusting the center that is placed in makes it avoid contacting with flame.The reduction vaporizing zone is understood that the wherein dominant zone of atmosphere of oxygen shortage within the scope of the invention.Prevented that like this zinc powder is oxidized before vaporization.Mol ratio at the oxygen content of reduction vaporizing zone fuel gas and oxygen-containing gas can be preferably 1.5: 1～3.5: 1, is preferably 2: 1～2.5: 1 especially.
Another method feature that is used to prepare Zinc oxide particles is
-zinc powder is vaporized and is oxidized to zinc oxide in reactor, wherein
-at the reduction vaporizing zone, zinc powder is metered into by means of inert gas flow in the pipe of input reactor vaporizing zone at the center of being placed in,
-by means of the externally-arranged flame vaporization that produces by fuel gas and oxygen-containing gas reaction,
Provide in-fuel gas and oxygen-containing gas the pipe by arranged concentric around central canal, and
-be placed in the center pipe range in the pipe of arranged concentric around it, and
-fuel gas is with superfluous and exist with respect to the oxygen content of oxygen-containing gas on the stoichiometry,
-then excessive oxygen is incorporated into the gas stream from the reduction vaporizing zone with the form of oxygen-containing gas, so that will be from the excessive fuel gas of vaporizing zone and zinc fume at the zoneofoxidation complete oxidation,
-then at the reactant mixture of the cooling zone heat of cooling, and solid material separated from gas stream.
This method can be preferably is that 1.5: 1～3.5: 1 mode is implemented with the mol ratio at the oxygen content of reduction vaporizing zone fuel gas and oxygen-containing gas.This ratio can be preferably 2: 1～2.5: 1 especially.Mol ratio for oxygen that enters zoneofoxidation and fuel gas is preferably 3: 1～20: 1 also may be preferred, be preferably 6: 1～15: 1 especially.For the mol ratio of oxygen that enters zoneofoxidation and zinc fume be 5: 1～30: 1 also can be favourable.10: 1～20: 1 ratio can be particularly advantageous.In order to reach the high-purity of oxide powder and zinc, using highly purified zinc powder is favourable as parent material.High-purity is understood that to mean at least 99% purity, is at least 99.9% purity under the situation of special requirement.Be used in particular at oxide powder and zinc under the situation of cosmetics or pharmaceutical applications, the content of plumbous (being no more than 20ppm), arsenic (being no more than 3ppm), cadmium (being no more than 15ppm), ferrum (being no more than 200ppm), antimony (being no more than 1ppm) and hydrargyrum (being no more than 1ppm) will be noted.
Entering zoneofoxidation in the method wants the temperature of oxidized mixture to be preferably 920 ℃～1250 ℃.The limited reactions mixture also may be favourable in the holdup time of 5 milliseconds～200 milliseconds of zoneofoxidations, and 10 milliseconds～30 milliseconds scope is particularly advantageous.Before quench gas added at once, the temperature in the cooling zone can be preferably 600 ℃～850 ℃, and the cooldown rate in the cooling zone can for 1000 open/second～50,000 open/second.
The Nano-class zinc oxide granule can be the form of aggregation.Aggregation is by the granulometric composition (DIN53206) of identical or approximately uniform primary particle.Often can find accumulative granule when using pyrolysismethod.In course of reaction along with the formation primary particle of the sintered surface formation aggregation that connects together.
In preferred embodiments, described Nano-class zinc oxide granule has the equivalent circle diameter (ECD) less than 100nm.In particularly preferred embodiments, described Nano-class zinc oxide granule has less than 10 000nm
2Averaging projection's aggregate surface long-pending and less than the average perimeter of 600nm.These values can obtain by the graphical analysis to about 1000～2000 aggregations from transmission electron microscope (TEM) image.In particularly preferred embodiments, described Nano-class zinc oxide granule has 2000～8000nm
2Long-pending, the equivalent circle diameter (ECD) of 25～80nm of averaging projection's aggregate surface and the average perimeter of 200～550nm.
Aggregation can show circle, ellipse, line style and branched form.Fig. 1 a-c is the representative configuration of ellipse, line style and the branch aggregation of oxide powder and zinc of the present invention.0-10% is that line style, 20-30% be that the aggregation of ramiform distributes are preferred for circular, 30-50% for oval, 30-50%.30～40% is oval and line style, 20～25% is that ramiform and 2～6% aggregations distributions for circle are particularly preferred.
In preferred embodiments, according to invention local with the described Nano-class zinc oxide granule in the sunscreen cream product can comprise lead less than 20ppm, less than the arsenic of 3ppm, less than the cadmium of 15ppm and less than the hydrargyrum of 1ppm.In particularly preferred embodiments, locally also comprise less than the ferrum of 200ppm with less than the antimony of 1ppm with the described Nano-class zinc oxide granule in the sunscreen cream product.
The present invention is local also can be by surface modification with the Nano-class zinc oxide granule in the sunscreen cream product.
Following chemical compound can be used as surface modifier:
A) (RO)
3Si (C
nH
2n+1) and (RO)
3Si (C
nH
2n-1) organosilan of type
The R=alkyl, as methyl-, ethyl-, n-pro-pyl-, isopropyl-, butyl-; N=1-20
B) R '
x(RO)
ySi (C
nH
2n+1) and R '
x(RO)
ySi (C
nH
2n-1) organosilan of type
The R=alkyl, as methyl-, ethyl-, n-pro-pyl-, isopropyl-, butyl-; R '=alkyl, as methyl-, ethyl-, n-pro-pyl-, isopropyl-, butyl-, cycloalkyl; N=1-20; X+y=3; X=1,2; Y=1,2
C) X
3Si (C
nH
2n+1) and X
3Si (C
nH
2n-1) halo-organosilan of type
X＝Cl、Br；n＝1-20
D) X
2(R ') Si (C
nH
2n+1) and X
2(R ') Si (C
nH
2n-1) halo-organosilan of type
X=Cl, Br; R '=alkyl, as methyl-, ethyl-, n-pro-pyl-, isopropyl-, butyl-, cycloalkyl; N=1-20
E) X (R ')
2Si (C
nH
2n+1) and X (R ')
2Si (C
nH
2n-1) type halo-organosilan
X=Cl, Br; R '=alkyl, as methyl-, ethyl-, n-pro-pyl-, isopropyl-, butyl-, cycloalkyl; N=1-20
F) (RO)
3Si (CH
2)
mThe organosilan of-R ' type
The R=alkyl, as methyl-, ethyl-, propyl group-; M=0,1-20; R '=methyl-, aryl (for example-C
6H
5, the phenyl group that replaces) ,-NH
2,-CH=CH
2,-NH-CH
2-CH
2-NH
2,-N-(CH
2-CH
2-NH
2)
2,-OOC (CH
3) C=CH
2,-OCH
2-CH (O) CH
2,-NH-CO-N-CO-(CH
2)
5,-NH-COO-CH
3,-NH-COO-CH
2-CH
3,-NH-(CH
2)
3Si (OR)
3,-S
x-(CH
2)
3Si (OR)
3,-NR ' R " R (R '=alkyl, aryl; R "=H, alkyl, aryl; R =H, alkyl, aryl, phenyl), C
2H
4NR " " R " (wherein R " "=H, alkyl, R " =H, alkyl)
G) (R ")
x(RO)
ySi (CH
2)
mThe organosilan of-R ' type
R "=alkyl, x+y=2; R "=cycloalkyl, x=1,2; Y=1,2; M=0,1～20
R '=methyl-, aryl (for example-C
6H
5, the phenyl group that replaces) ,-NH
2,-CH=CH
2,-NH-CH
2-CH
2-NH
2,-N-(CH
2-CH
2-NH
2)
2,-OOC (CH
3) C=CH
2,-OCH
2-CH (O) CH
2,-NH-CO-N-CO-(CH
2)
5,-NH-COO-CH
3,-NH-COO-CH
2-CH
3,-NH-(CH
2)
3Si (OR)
3,-S
x-(CH
2)
3Si (OR)
3,-SH ,-NR ' R " R (R '=alkyl, aryl; R "=H, alkyl, aryl; R =H, alkyl, aryl, phenyl), C
2H
4NR " " R " (wherein R " "=H, alkyl, R " =H, alkyl)
H) X
3Si (CH
2)
m-R ' type halo-organosilan
X=Cl, Br; M=0,1-20; R '=methyl-, aryl (for example-C
6H
5, the phenyl group that replaces) ,-NH
2,-CH=CH
2,-NH-CH
2-CH
2-NH
2,-N-(CH
2-CH
2-NH
2)
2,-OOC (CH
3) C=CH
2,-OCH
2-CH (O) CH
2,-NH-CO-N-CO-(CH
2)
5,-NH-COO-CH
3,-NH-COO-CH
2-CH
3,-NH (CH
2)
3Si (OR)
3
I) (R) X
2Si (CH
2)
mHalo-the organosilan of-R ' type
X=Cl, Br; The R=alkyl, as methyl-, ethyl-, propyl group-; M=0,1-20; R '=methyl-, aryl (for instance-C
6H
5, the phenyl group that replaces) ,-NH
2,-CH=CH
2,-NH-CH
2-CH
2-NH
2,-N-(CH
2-CH
2-NH
2)
2,-OOC (CH
3) C=CH
2,-OCH
2-CH (O) CH
2,-NH-CO-N-CO-(CH
2)
5,-NH-COO-CH
3,-NH-COO-CH
2-CH
3,-NH (CH
2)
3Si (OR)
3, wherein R can be methyl-, ethyl-, propyl group-, butyl-;
J) (R)
2XSi (CH
2)
mHalo-the organosilan of-R ' type
X=Cl, Br; The R=alkyl; M=0,1-20; R '=methyl-, aryl (for instance-C
6H
5, the substituted-phenyl group) ,-NH
2,-CH=CH
2,-NH-CH
2-CH
2-NH
2,-N-(CH
2-CH
2-NH
2)
2,-OOC (CH
3) C=CH
2,-OCH
2-CH (O) CH
2,-NH-CO-N-CO-(CH
2)
5,-NH-COO-CH
3,-NH-COO-CH
2-CH
3,-NH-(CH
2)
3Si (OR)
3
K) R ' R
2Si-NH-SiR
2The silazane of R ' type
R=alkyl, vinyl, aryl; R '=alkyl, vinyl, aryl
1) cyclopolysiloxane of D3, D4, D5 type, wherein D3, D4 and D5 are understood that-O-Si (CH
2)
2-type have 3,4 or 5 unitary cyclopolysiloxanes.For instance, octamethylcy-clotetrasiloxane=D4
The polysiloxanes of type or silicone oil
m＝0，1，2，3，...∞；n＝0，1，2，3，...∞；u＝0，1，2，3，...∞
Y＝CH
3、H、C
nH
2n+1；n＝1-20
Y＝Si(CH
3)
3、Si(CH
3)
2H、Si(CH
3)
2OH、Si(CH
3)
2(OCH
3)、Si(CH
3)
2(C
nH
2n+1)；n＝1-20
The R=alkyl is as C
nH
2n+1, n=1～20 wherein; Aryl is as the phenyl group of phenyl and replacement; (CH
2)
n-NH
2H
R '=alkyl is as C
nH
2n+1, n=1～20 wherein; Aryl is as the phenyl group of phenyl and replacement; (CH
2)
n-NH
2H
"=alkyl is as C for R
nH
2n+1, n=1～20 wherein; Aryl is as the phenyl group of phenyl and replacement; (CH
2)
n-NH
2H
R =alkyl is as C
nH
2n+1, n=1～20 wherein; Aryl is as the phenyl group of phenyl and replacement; (CH
2)
n-NH
2H
In a preferred embodiment of the invention, the Zinc oxide particles of surface modification has 18 ± 5m
2The BET surface area of/g and the C content of about 0.1～5.0wt.%.These Zinc oxide particles can further have 0.1～0.2% drying loss and 0.8～1.4% burning decrement.
Zinc oxide particles (choose wantonly water spray after) at room temperature can atomize with surface modifier, then with mixture heat treatment 1～6 hour and prepare the zinc oxide of surface modification under 50～400 ℃ temperature.
Perhaps, can be by handle Zinc oxide particles (choosing wantonly after the water spray) with the surface modifier of steam form, thermally treated mixture 0.5～6 hour and the Zinc oxide particles of preparation surface modification under 50～800 ℃ temperature then.
Heat treatment can carry out under inert gas shielding, for example nitrogen.
Surface modification can be carried out in heatable blender that has sprayer unit and exsiccator continuously or in batches.For example Shi Yi equipment can be that the plough formula is shared blender or flat board, fluid bed or thermopnore exsiccator.
Part in preferred embodiment is used in the sunscreen cream product, and Zinc oxide particles carries out surface modification with octyl group-trimethoxy silane, octyl group-trimethoxy silane and/or polydimethylsiloxane.
Suitable be used for forming local carrier and comprise SD alcohol, lanoline, tristerin, cocoa butter, sorbitan sesquioleate, propylene glycol, mineral oil, isopropyl myristate, vaseline and acrylate copolymer with sunscreen cream product.Also can use two or more the mixture in these materials.These materials are considered to " suiting " aspect Dermatology in this area, that is, they can not cause or cause side effect to the skin of user.
The amount of carrier only need enough provide particulate homodisperse, makes when they are applied to skin to guarantee the abundant covering of ultraviolet absorption material to skin.By total emulsion weight granular materials preferably comprise be no more than about 20% and by its weight preferably between about 1-10%.To the unique real restriction in this concentration range lower end is must comprise the granule of Sq so that goods absorb the ultraviolet of desired amount.
In some cases, by the weight of total composition less than about 1% concentration even may be useful.
Because just in time being lower than, the size of Zinc oxide particles is the necessary size of the most effective light scattering, so be dispersed in these the particulate films in the suitable liquid vehicle, thereby can see through enough big percentile visible light and look visually-clear, residue is then opaque fully to ultraviolet radiation.
Another embodiment of the invention comprises sunlight lotion, and it comprises some commercially available, though dispensable, be preferably part by the formed diameter range of the plastics of visually-clear spheric plastic grain between about 0.01-100 μ m.This plastics are well-known in the art, and it can comprise, for example, and as the acrylic resin of polymethyl methacrylate (" PMMA "); Styrene polymer; The copolymer of styrene and acrylic resin; Styrene-acrylonitrile (" SAN "); Merlon; Methylpentene; Acrylonitrile, butadiene and cinnamic terpolymer (" ABS ") and allyl diglycol carbonates (" ADC ").Yet the present invention is not limited to the use of these plastics, and is as described below, as long as the plastics of any visually-clear have, or can have after the modification, thereby desirable optical property makes its visually-clear except that can ultraviolet radiation-absorbing, all is suitable for the present invention.
In order to control the UV absorbing properties of these plastics, one or more ultra-violet absorption additives also are called " ultra-violet stabilizer ", can merge to be used to make spheroidal particle in the plastics in their forming process.Though ultra-violet stabilizer is joined in the plastic substrate known already in the art, for example in the forming process of the ultra-violet absorption plastics of sheet, also not known but this ultra-violet stabilizer merges to the application that is used for opacifier in the little baton round of the type of describing here.This ultraviolet additive be in the art well-known (referring to, for instance, modern plastics encyclopedia 1976-1977, people's such as 222-227 page or leaf and 708-709 page or leaf and Kadokura United States Patent (USP) the 4th, 882, No. 143, the 7th row, 61-65 is capable), it comprises the materials such as acrylonitrile, metal complex and inorganic pigment of for example salicyclic acid derivatives, benzoic acid, cinnamic acid and benzophenone, benzotriazole, aromatic ester, replacement.
Yet the present invention is not limited to the use of these concrete materials, because any intended purposes that meets, that is, the ultraviolet additive of ultraviolet radiation-absorbing can use with the goods that embodiment of the present invention are described.
These additive materials are incorporated into are used for comprising in the described plastic sphere making the spheroid of these visually-clear can ultraviolet radiation-absorbing.Thereby, with these spheroid transparent, ultra-violet absorption in by emulsion weight scope between about 1-20%, concentration between more preferably about by weight 1-10% is dispersed on the basis of the liquid-carrier in the described emulsion of embodiment of the present invention of the quite pure Zinc oxide particles of for example use, resulting goods can local be used for the skin of user, so it has kept visual transparent when absorbing the irradiated ultraviolet radiation of quite most of user institute.
In addition; in inventing further embodiment; above-describedly be used to be included in local granule sunscreen cream material with the opacifier goods of the present invention and for example can be incorporated into various cosmetic products, lip pomade, eye shadow, foundation cream, emollient cream, kermes and other people protect in the product and protect the bottom skin of user to avoid the ability of ultraviolet radiation damaging action to improve these goods.These materials can mix with the matrix of cosmetics as relying on Henschel blender, ribbon mixer, double-cylinder type blender or similar blender by known mixed method.
The amount of the granular materials in this cosmetics goods that are present in invention comprise by weight be no more than about 20%, by weight preferably between about 1-10%.Most preferably, by total product weight, the granule sunscreen cream comprises and is less than 1%.
Above-described cosmetics goods also can comprise various interpolation materials.These additives are well-known in the art and its adding is in order to realize the purpose of their internal actions.Preferred additives comprises material for example thickening agent, softening agent, superfatting agent, waterproofing agent, lubricant, wetting agent and surfactant, and antiseptic, anti-foam agent, perfume and composition thereof, and perhaps any other is generally used for the compatible composition in the cosmetics.
The present invention further provides a kind of method that is used to prepare sunscreen cream product that may further comprise the steps:
-select the colourless basically acceptable liquid-carrier of skin and by the 15～200m that has of vapor phase method preparation
2The Zinc oxide particles of/g BET surface area,
-equably described Zinc oxide particles is dispersed in basically in the acceptable liquid-carrier of colourless basically skin forming the part sunscreen cream product of visually-clear basically,
-described granule is dispersed in the described carrier with the amount of effective protection skin.
Embodiment
Below general introduction according in the combination of ZnO (w.c.=coating=Trimethoxyoctylsilane)-ethyl hexyl oxy anisyl triazine two with the two bezene acrylic acids (Octocrylene) of OC=cyanogen, OMC=ethylhexyl Methoxycinnamate, PISA=Phenylbenzimidazolesulfonic acid or BEMT=show the goods of the invention of cooperative effect.
For the reason of statistics, suppose that if mention synergism SPF should surpass or equal the total SPF Senior Two measurement unit than single goods so.SPF (SPF (sun protection factor)) measures and uses Optometrics SPF 290-S device to carry out in test tube.
Embodiment 1-3 (table 1)
The standardized products that is used for Water-In-Oil (W/O) emulsion in these embodiments.Nano-class zinc oxide (having cover layer) is introduced the oil phase of system.The other content of zinc oxide is deducted from oil phase (ethylhexyl stearate and mineral oil).
1 contains the standardized products W/O emulsion of ZnO (w.c.)
2 contain the standardized products W/O emulsion of OC
3 contain the standardized products W/O emulsion of ZnO (w.c.) and OC
Embodiment 4-7 (table 2)
The standardized products that is used for oil-in-water (O/W) emulsion in these embodiments.Nano-class zinc oxide (having cover layer) is introduced the oil phase of system.The other content of zinc oxide is deducted from water (Aqua).Use isostearic acid as surface modifier and pH stabilizing agent in the experiment.
4 contain the standardized products O/W emulsion of ZnO (w.c.)
5 contain the standardized products O/W emulsion of OC
6 contain the standardized products O/W emulsion of ZnO (w.c.) and OC
7 contain the standardized products O/W emulsion of ZnO (w.c.), OC and isostearic acid
Embodiment 8-10 (table 3)
The standardized products that is used for Water-In-Oil (W/O) emulsion in these embodiments.Nano-class zinc oxide (having cover layer) is introduced the oil phase of system.The other content of zinc oxide is deducted from oil phase (ethylhexyl stearate and mineral oil).
8 contain the standardized products W/O emulsion of ZnO (w.c.)
9 contain the standardized products W/O emulsion of OMC
10 contain the standardized products W/O emulsion of ZnO (w.c.) and OMC
Embodiment 11-14 (table 4)
The standardized products that is used for oil-in-water (O/W) emulsion in these embodiments.Nano-class zinc oxide (having cover layer) is introduced the oil phase of system.The other content of zinc oxide is deducted from water (Aqua).Use isostearic acid as surface modifier and pH stabilizing agent in the experiment.
11 contain the standardized products O/W emulsion of ZnO (w.c.)
12 contain the standardized products O/W emulsion of OMC
13 contain the standardized products O/W emulsion of ZnO (w.c.) and OMC
14 contain the standardized products O/W emulsion of ZnO (w.c.), OMC and isostearic acid
Embodiment 15-17 (table 5)
The standardized products that is used for Water-In-Oil (W/O) emulsion in these embodiments.Nano-class zinc oxide (having cover layer) is introduced the oil phase of system.The other content of zinc oxide is deducted from oil phase (ethylhexyl stearate and mineral oil).
15 contain the standardized products W/O emulsion of ZnO (w.c.)
16 contain the standardized products W/O emulsion of PISA
17 contain the standardized products W/O emulsion of ZnO (w.c.) and PISA
Embodiment 18-20 (table 6)
The standardized products that is used for oil-in-water (O/W) emulsion in these embodiments.Nano-class zinc oxide (having cover layer) is introduced the oil phase of system.The other content of zinc oxide is deducted from water (Aqua).Use isostearic acid as surface modifier and pH stabilizing agent in the experiment.
18 contain the standardized products O/W emulsion of ZnO (w.c.)
19 contain the standardized products O/W emulsion of PISA
20 contain the standardized products O/W emulsion of ZnO (w.c.) and PISA
Embodiment 21-23 (table 7)
The standardized products that is used for Water-In-Oil (W/O) emulsion in these embodiments.Nano-class zinc oxide (having cover layer) is introduced the oil phase of system.The other content of zinc oxide is from oil phase (C
12-15Alkyl benzoate) deduction in.
21 contain the standardized products W/O emulsion of ZnO (w.c.)
22 contain the standardized products W/O emulsion of BEMT
23 contain the standardized products W/O emulsion of ZnO (w.c.) and BEMT
Embodiment 24-27 (table 8)
The standardized products that is used for oil-in-water (O/W) emulsion in these embodiments.Nano-class zinc oxide (having cover layer) is introduced the oil phase of system.The other content of zinc oxide is deducted from water (Aqua).Use isostearic acid as surface modifier and pH stabilizing agent in the experiment.
24 contain the standardized products O/W emulsion of ZnO (w.c.)
25 contain the standardized products O/W emulsion of BEMT
26 contain the standardized products O/W emulsion of ZnO (w.c.) and BEMT
27 contain the standardized products O/W emulsion of ZnO (w.c.), BEMT and isostearic acid
Table 1: the W/O goods (wt.%) among the embodiment 1-3
| Phase | INCI (international specialty name cosmetic material) | 1 | 2 | 3 |
| A | Cetyl Polyethylene Glycol (PEG)/polypropylene glycol (PPG)-10/1 dimethicone | 2.5 | 2.5 | 2.5 |
| The ethylhexyl stearate | 12.5 | 12.5 | 10.0 | |
| Mineral oil | 12.5 | 12.5 | 10.0 | |
| Isostearic acid | 1.0 | 1.0 | 1.0 | |
| Castor oil hydrogenated | 0.5 | 0.5 | 0.5 | |
| Microwax | 1.0 | 1.0 | 1.0 | |
| The two bezene acrylic acids (Octocrylene) of cyanogen | 5.0 | 5.0 | ||
| Zinc oxide (w.c.) | 5.0 | 5.0 | ||
| B | Sodium chloride | 0.5 | 0.5 | 0.5 |
| Water | 64.45 | 64.45 | 64.45 | |
| 2-bromo-2-nitropropane-1, the 3-glycol | 0.05 | 0.05 | 0.05 | |
| SPF | 2 | 3 | 6 |
Table 2: the O/W goods (wt.%) among the embodiment 4-7
| Phase | INCI | 4 | 5 | 6 | 7 |
| A | Ceteareth-15, glyceryl stearate | 2.5 | 2.5 | 2.5 | 2.5 |
| Glyceryl stearate | 1.0 | 1.0 | 1.0 | 1.0 | |
| Octadecanol | 2.0 | 2.0 | 2.0 | 2.0 | |
| C 12-15Alkyl benzoate | 14.5 | 9.5 | 9.5 | 8.5 | |
| The two bezene acrylic acids (Octocrylene) of cyanogen | 5.0 | 5.0 | 5.0 | ||
| Zinc oxide (w.c.) | 10.0 | 10.0 | 10.0 | ||
| Isostearic acid | 1.0 | ||||
| B | Glycerol | 3.0 | 3.0 | 3.0 | 3.0 |
| Water | 66.5 | 76.5 | 66.5 | 66.5 | |
| Chloroacetamide | 0.1 | 0.1 | 0.1 | 0.1 | |
| C | Xanthan gum | 0.4 | 0.4 | 0.4 | 0.4 |
| SPF | 2 | 3 | 8 | 9 |
Table 3: the W/O goods (wt.%) among the embodiment 8-10
| Phase | INCI | 8 | 9 | 10 |
| A | Cetyl Polyethylene Glycol (PEG)/polypropylene glycol (PPG)-10/1 dimethicone | 2.5 | 2.5 | 2.5 |
| The ethylhexyl stearate | 12.5 | 12.5 | 10.0 | |
| Mineral oil | 12.5 | 12.5 | 10.0 | |
| Isostearic acid | 1.0 | 1.0 | 1.0 | |
| Castor oil hydrogenated | 0.5 | 0.5 | 0.5 | |
| Microwax | 1.0 | 1.0 | 1.0 | |
| The ethylhexyl Methoxycinnamate | 5.0 | 5.0 | ||
| Zinc oxide (w.c.) | 5.0 | 5.0 | ||
| B | Sodium chloride | 0.5 | 0.5 | 0.5 |
| Water | 64.45 | 64.45 | 64.45 | |
| 2-bromo-2-nitropropane-1, the 3-glycol | 0.05 | 0.05 | 0.05 | |
| SPF | 2 | 7 | 13 |
Table 4: the O/W goods (wt.%) among the embodiment 11-14
| Phase | INCI | 11 | 12 | 13 | 14 |
| A | Ceteareth-15, glyceryl stearate | 2.5 | 2.5 | 2.5 | 2.5 |
| Glyceryl stearate | 1.0 | 1.0 | 1.0 | 1.0 | |
| Octadecanol | 2.0 | 2.0 | 2.0 | 2.0 | |
| C 12-15Alkyl benzoate | 14.5 | 9.5 | 9.5 | 8.5 | |
| The ethylhexyl Methoxycinnamate | 5.0 | 5.0 | 5.0 | ||
| Zinc oxide (w.c.) | 10.0 | 10.0 | 10.0 | ||
| Isostearic acid | 1.0 | ||||
| B | Glycerol | 3.0 | 3.0 | 3.0 | 3.0 |
| Water | 66.5 | 76.5 | 66.5 | 66.5 | |
| Chloroacetamide | 0.1 | 0.1 | 0.1 | 0.1 | |
| C | Xanthan gum | 0.4 | 0.4 | 0.4 | 0.4 |
| SPF | 2 | 6 | 11 | 16 |
Table 5: the W/O goods (wt.%) among the embodiment 15-17
| Phase | INCI | 15 | 16 | 17 |
| A | Cetyl Polyethylene Glycol (PEG)/polypropylene glycol (PPG)-10/1 dimethicone | 2.5 | 2.5 | 2.5 |
| The ethylhexyl stearate | 12.5 | 15.0 | 12.5 | |
| Mineral oil | 12.5 | 15.0 | 12.5 | |
| Isostearic acid | 1.0 | 1.0 | 1.0 | |
| Castor oil hydrogenated | 0.5 | 0.5 | 0.5 | |
| Microwax | 1.0 | 1.0 | 1.0 | |
| Zinc oxide (w.c.) | 5.0 | 5.0 | ||
| B | Sodium chloride | 0.5 | 0.5 | 0.5 |
| Water | 64.45 | 49.45 | 49.45 | |
| 2-bromo-2-nitropropane-1, the 3-glycol | 0.05 | 0.05 | 0.05 | |
| Phenylbenzimidazolesulfonic acid (20% aqueous solution) | 15.0 | 15.0 | ||
| SPF | 2 | 5 | 9 |
Table 6: the O/W goods (wt.%) among the embodiment 18-21
| Phase | INCI | 18 | 19 | 20 | 21 |
| A | Ceteareth-15, glyceryl stearate | 2.5 | 2.5 | 2.5 | 2.5 |
| Glyceryl stearate | 1.0 | 1.0 | 1.0 | 1.0 | |
| Octadecanol | 2.0 | 2.0 | 2.0 | 2.0 | |
| C 12-15Alkyl benzoate | 14.5 | 14.5 | 14.5 | 13.5 | |
| Zinc oxide (w.c.) | 10.0 | 10.0 | 10.0 | ||
| Isostearic acid | 1.0 | ||||
| B | Glycerol | 3.0 | 3.0 | 3.0 | 3.0 |
| Water | 66.5 | 61.5 | 51.5 | 51.5 | |
| Chloroacetamide | 0.1 | 0.1 | 0.1 | 0.1 | |
| Phenylbenzimidazolesulfonic acid (20% aqueous solution) | 15.0 | 15.0 | 15.0 | ||
| C | Xanthan gum | 0.4 | 0.4 | 0.4 | 0.4 |
| SPF | 2 | 5 | 11 | 15 |
Table 7: the W/O goods (wt.%) among the embodiment 22-24
| Phase | INCI | 22 | 23 | 24 |
| A | Cetyl Polyethylene Glycol (PEG)/polypropylene glycol (PPG)-10/1 dimethicone | 2.5 | 2.5 | 2.5 |
| C 12-15Alkyl benzoate | 27.00 | 25.00 | 22.00 | |
| Isostearic acid | 1.0 | 1.0 | 1.0 | |
| Castor oil hydrogenated | 0.5 | 0.5 | 0.5 | |
| Microwax | 1.0 | 1.0 | 1.0 | |
| Two-ethyl hexyl oxy anisyl triazine | 3.0 | 3.0 | ||
| Zinc oxide (w.c.) | 5.0 | 5.0 | ||
| B | Sodium chloride | 0.5 | 0.5 | 0.5 |
| Water | 64.45 | 64.45 | 64.45 | |
| 2-bromo-2-nitropropane-1, the 3-glycol | 0.05 | 0.05 | 0.05 | |
| SPF | 2 | 8 | 13 |
Table 8: the O/W goods (wt.%) among the embodiment 25-28
| Phase | INCI | 25 | 26 | 27 | 28 |
| A | Ceteareth-15, glyceryl stearate | 2.5 | 2.5 | 2.5 | 2.5 |
| Glyceryl stearate | 1.0 | 1.0 | 1.0 | 1.0 | |
| Octadecanol | 2.0 | 2.0 | 2.0 | 2.0 | |
| C 12-15Alkyl benzoate | 14.5 | 12.5 | 12.5 | 11.5 | |
| Two-ethyl hexyl oxy anisyl triazine | 2.0 | 2.0 | 2.0 | ||
| Zinc oxide (w.c.) | 10.0 | 10.0 | 10.0 | ||
| Isostearic acid | 1.0 | ||||
| B | Glycerol | 3.0 | 3.0 | 3.0 | 3.0 |
| Water | 66.5 | 76.5 | 66.5 | 66.5 | |
| Chloroacetamide | 0.1 | 0.1 | 0.1 | 0.1 | |
| C | Xanthan gum | 0.4 | 0.4 | 0.4 | 0.4 |
| SPF | 2 | 3 | 6 | 8 |
Claims (14)
1, a kind ofly be used to protect skin to avoid the part sunscreen cream product of ultraviolet radiation, described goods comprise:
-colourless basically, acceptable liquid-carrier of skin and the 15～200m that has by the vapor phase method preparation
2The Nano-class zinc oxide granule of/g BET surface area,
-described granule is evenly dispersed in the acceptable liquid-carrier of described colourless basically skin basically, with the part that forms a kind of visually-clear basically with sunscreen cream product and
-the amount of damaging effect of avoiding UV-A and uv b radiation with the part of effective protection described visually-clear basically of coating on it with the skin of sunscreen cream product with described Dispersion of Particles in described liquid-carrier.
2, the part sunscreen cream product of claim 1, wherein said Nano-class zinc oxide granule prepares by pyrolysismethod.
3, claim 1 or 2 part sunscreen cream product, wherein said Nano-class zinc oxide granule is a state of aggregation.
4, the part sunscreen cream product of claim 3, wherein said Nano-class zinc oxide agglomeration of particles body has the equivalent circle diameter (ECD) less than 100nm.
5, claim 3 or 4 part sunscreen cream product, wherein said Nano-class zinc oxide agglomeration of particles body has less than 10 000nm
2Averaging projection's aggregate surface long-pending and less than the average perimeter of 600nm.
6, the part sunscreen cream product of one of claim 3～5, the 0-10% of wherein said Nano-class zinc oxide aggregation is branch shape for oval, 30-50% for linear, 20-30% for circular, 30-50%.
7, the hydrargyrum that the part sunscreen cream product of one of claim 1～6, wherein said Nano-class zinc oxide granule comprise the lead that is lower than 20ppm, the arsenic that is lower than 3ppm, are lower than the cadmium of 15ppm and are lower than 1ppm.
8, the part sunscreen cream product of one of claim 1～7, the Zinc oxide particles of wherein said pyrolysismethod preparation comprises ferrum that is lower than 200ppm and the antimony that is lower than 1ppm.
9, the part sunscreen cream product of one of claim 1～8, the Zinc oxide particles of wherein said pyrolysismethod preparation is through surface modification.
10, the part sunscreen cream product of claim 9, the BET surface area of wherein said Zinc oxide particles is 18 ± 5m
2/ g and C content are 0.5～1.0wt.%.
11, claim 9 or 10 part sunscreen cream product, wherein said Zinc oxide particles utilizes octyl group-trimethoxy silane, octyl group-trimethoxy silane and/or polydimethylsiloxane to carry out surface modification.
12, the part sunscreen cream product of one of claim 1～11, the Zinc oxide particles of wherein said pyrolysismethod preparation accounts for the about below 20% of described product weight.
13, the part sunscreen cream product of one of claim 1～12, wherein said aspect Dermatology the appropriate liquid carrier be selected from SD alcohol, lanoline, tristerin, cocoa butter, sorbitan sesquioleate, propylene glycol, mineral oil, isopropyl myristate, vaseline and acrylate copolymer.
14, a kind of method that is used to prepare the sunscreen cream product of one of claim 1～13, it may further comprise the steps:
-select the colourless basically acceptable liquid-carrier of skin and have 15～200m
2The Zinc oxide particles by the vapor phase method preparation of/gBET surface area,
-equably described Zinc oxide particles is dispersed in basically in the acceptable liquid-carrier of described colourless basically skin, forming the part sunscreen cream product of visually-clear basically,
-described granule is dispersed in the described carrier with the amount of effective protection skin.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510097815 CN1923163A (en) | 2005-08-30 | 2005-08-30 | Sunscreen cream product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510097815 CN1923163A (en) | 2005-08-30 | 2005-08-30 | Sunscreen cream product |
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| Publication Number | Publication Date |
|---|---|
| CN1923163A true CN1923163A (en) | 2007-03-07 |
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| CN 200510097815 Pending CN1923163A (en) | 2005-08-30 | 2005-08-30 | Sunscreen cream product |
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| CN (1) | CN1923163A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102860926A (en) * | 2012-10-23 | 2013-01-09 | 重庆大学 | Intelligent ultraviolet-proof additive used for cosmetics |
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2005
- 2005-08-30 CN CN 200510097815 patent/CN1923163A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102860926A (en) * | 2012-10-23 | 2013-01-09 | 重庆大学 | Intelligent ultraviolet-proof additive used for cosmetics |
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