CN1938387B - Surface-modified metal oxides, methods for production and use thereof in cosmetic preparations - Google Patents

Surface-modified metal oxides, methods for production and use thereof in cosmetic preparations Download PDF

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CN1938387B
CN1938387B CN2005800108138A CN200580010813A CN1938387B CN 1938387 B CN1938387 B CN 1938387B CN 2005800108138 A CN2005800108138 A CN 2005800108138A CN 200580010813 A CN200580010813 A CN 200580010813A CN 1938387 B CN1938387 B CN 1938387B
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acid
metal oxide
surface modification
nano particle
carry out
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CN1938387A (en
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V·安德烈
J·里格尔
H·德布斯
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BASF SE
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BASF SE
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Priority claimed from PCT/EP2005/003217 external-priority patent/WO2005094156A2/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88—Polyamides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11—Encapsulated compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/145—After-treatment of oxides or hydroxides, e.g. pulverising, drying, decreasing the acidity
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/22—Compounds of iron
    • C09C1/24—Oxides of iron
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3676—Treatment with macro-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/413—Nanosized, i.e. having sizes below 100 nm
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention relates to surface-modified nanoparticulate metal oxides, methods for production and use thereof as UV filter in cosmetic preparations.

Description

The metal oxide of surface modification, its preparation method and the purposes in cosmetic formulations thereof
The present invention relates to a kind of nano particle metal oxide of surface modification, their preparation method and its purposes as UV lightscreening agent in the cosmetic formulations.
Metal oxide can be used for multiple use, for example as white pigment, as catalyzer, as the component of antibiotic skin care ointment with as the activator of the vulcanization of rubber.Found that zinc oxide in small, broken bits or titanium dioxide absorb pigment as the UV-in the cosmetics barrier agent.
Within the application's scope, term " nano particle " is used to represent that median size (method by electron microscopic is measured) is the particle of 5～10000nm.
Particle diameter is applicable to as the UV absorption agent in transparent organic and inorganic mixing material, plastics, paint and the coating potentially less than the Zinc oxide nanoparticle of about 30nm.Equally, also can be used to protect the pigment dyestuff of UV-sensitivity.
Particle diameter causes the scattered light effect greater than Zinc oxide particles, particle aggregate or the particle agglomeration cognition of about 30nm, and the transparency that causes thus not expecting in the visible region reduces.Therefore, redispersibility, just the Zinc oxide nanoparticle with preparation is converted into the ability of colloid dispersed, is the important prerequisite of above-mentioned application.
Particle diameter is less than the zinc oxide of about 5 nanometers, owing to size quantization effect demonstrate absorption limit blue shift (L.Brus, J.Phys.Chem. (1986), 90,2555-2560), and therefore not too be applicable to as the UV absorption agent in the UV-A district.
The preparation of metal oxide is known, for example prepares zinc oxide by dry method and wet method.The method of traditional combustion zinc (it is known as dry method) (as Gmelin Volume 32, the 8 editions, augment volume, the 772nd page and thereafter) generates the accumulative particle of wide distribution of sizes.Though can obtain the particle diameter of sub-micrometer range in principle by grinding technics, because the shearing force that can realize is too low, so can not obtain the dispersion of median size in lower nanometer range by this powder.Zinc oxide in small, broken bits especially mainly prepares with wet chemical method by depositing technology.Precipitation in the aqueous solution generates usually and contains oxyhydroxide and/or carbonato material, and this material must thermal transition be a zinc oxide.Hot aftertreatment has adverse influence to characteristic in small, broken bits, because carried out sintering processes to particle this moment, causes the formation of micro-meter scale aggregate, only it can be decomposed into primary particle by halves by grinding.
The nano particle metal oxide can for example obtain by the microemulsion method.In this method, metal alkoxide solution is dropwise added in the water-in-oil emulsion.The hydrolysis of alkoxide takes place in the reversed phase micelle of microemulsion (its size is in nanometer range) subsequently, forms the nano particle metal oxide.The shortcoming of this method is especially: metal alkoxide is expensive starting material, the method steps that must use the preparation of emulsifying agent and the emulsion of particle diameter in nanometer range to have complexity in addition.
DE19907704 has described a kind of nano particle zinc oxide by the precipitin reaction preparation.In the method, prepare nano particle zinc oxide from acetic acid zinc solution by alkali precipitation.Can disperse to obtain colloidal sol once more by adding the zinc oxide that methylene dichloride will be centrifugal comes out.The shortcoming that the zinc oxide dispersion that this mode prepares exists is that owing to do not carry out surface modification, they do not have good long term stability.
WO00/50503 has described the nano particle zinc oxide that comprises particle diameter≤15nm and can redispersion have obtained the zinc oxide gel of colloidal sol.In the method, by adding methylene dichloride or chloroform, the throw out that will generate by the alkaline hydrolysis of zn cpds in alcohol and/or alcohol/water mixture disperses once more.The shortcoming of this moment is at water or in aqueous dispersant, can not obtain stable dispersion.
At publication Chem.Mater.2000,12,2268-74 " Synthesis andCharacterization of Poly (vinylpyrrolidone)-Modified Zinc OxideNanoparticles ", the author is among Lin Guo and the Shihe Yang, the wurtzite Zinc oxide nanoparticle that used the Polyvinylpyrolidone (PVP) surface-coated.Shortcoming herein is, use Zinc oxide particles that Polyvinylpyrolidone (PVP) applies can not redispersion in water.
WO93/21127 describes a kind of method for preparing the nano particle ceramic powder of surface modification.In the method, come the surface-modified nano particles ceramic powder by applying low molecular weight organic compound (for example propionic acid).This method can not be used for the surface modification of zinc oxide because modified-reaction be in the aqueous solution, carry out and zinc oxide be dissolved in the water-based organic acid.Therefore, this method can not be used to prepare the zinc oxide dispersion; And in this was used, zinc oxide can not be classified the possible starting material of nano ceramic powder as.
JP-A-04164814 has described a kind of method that obtains ZnO in small, broken bits, and it obtains by the precipitation in the aqueous medium at elevated temperatures, does not even use hot aftertreatment.The median size of being stated is 20～50nm, but does not point out the degree of reuniting.These particles are relatively large.Be that agglomerated is minimal, it also can cause the scattering effect do not expected in the clear applications.
It is the preparation method of the ZnO of 5～10000 nanometers that JP-A-07232919 has described particle diameter, and it prepares with the reaction of organic acid and other organic compound (as alcohol) at elevated temperatures by zn cpds.Hydrolysis takes place this moment, makes and the by product that forms (ester of the acid of using) can be distilled.Because surface modification in advance, this method can be prepared redispersible ZnO powder.But,, can not prepare the particle of mean diameter＜15nm based on the disclosure of this application.Therefore, in the listed embodiment of this application, 15nm is described to minimum average primary particle diameter.
In DE3314741A1, DE3642794A1 and EP0603627A1 and WO97/16156, described especially by silicoorganic compound and come the hydrophobization metal oxide.
The metal oxide that these apply with silicone compounds, for example zinc oxide or titanium dioxide, the shortcoming of its existence is that oil-in-water prepared therefrom or water-in-oil emulsion do not have required pH stability usually.
In addition, often observe each other incompatible of the various metal oxides that apply with silicone compounds, its aggregate that may cause not expecting forms and the throwing out of variable grain.
Therefore, the objective of the invention is, the nano particle metal oxide that can generate the stable nanoparticles dispersion in water or polar organic solvent and in cosmetics oil is provided.If possible, should avoid the irreversible gathering of particulate, make and to avoid complicated grinding technics.
Nano particle metal oxide by surface modification has been realized this purpose, and wherein metal is selected from aluminium, cerium, iron, titanium, zinc and zirconium, and wherein surface modification comprises that the use poly aspartic acid applies.
Within the scope of the present invention, term " poly aspartic acid " comprises the salt of free acid and poly aspartic acid simultaneously, for example sodium, potassium, lithium, magnesium, calcium, ammonium, alkylammonium, zinc and molysite or its mixture.
The top coat that is used for the nano particle metal oxide that uses according to the present invention preferably comprises poly aspartic acid and/or its sodium salt.
Preferred implementation according to surface modification of metals oxide compound of the present invention is that wherein top coat comprises molecular weight (being measured by the gel chromatography analysis) M wBe 1000～100000, be preferably 1000～20000, be preferably those of 1000～7000 poly aspartic acid especially.
Be that wherein the average primary particle diameter of metal oxide particle (it is measured by scanning and transmission electron microscopy) is 5～10000nm, is preferably 10～200nm, is preferably those of 10～50nm especially according to another useful embodiment of metal oxide of the present invention.
Within the scope of the present invention, described preferable alloy oxide compound is titanium dioxide and zinc oxide, is preferably zinc oxide especially.
The present invention is based on following discovery: carry out surface modification by using poly aspartic acid and/or its salt pair nano particle metal oxide, the dispersion that can realize the surface modification of metals oxide compound is the permanent stability in cosmetic formulations especially, do not have the pH that does not expect and change between the preservation period of these preparations.
The present invention further provides a kind of method for preparing the surface-modified nano particles metal oxide, wherein metal is selected from aluminium, cerium, iron, titanium, zinc and zirconium, and it passes through:
A. metal oxide is precipitated out from the aqueous solution of its a kind of metal-salt;
B. from aqueous reaction mixture, isolate sedimentary metal oxide; With
C. subsequent drying metal oxide,
Wherein, the precipitation of metal oxide is to carry out in the presence of poly aspartic acid among the method steps a..
Preferred implementation according to method of the present invention is that wherein precipitation is at molecular weight (being measured by the gel chromatography analysis) M wBe 1000～100000, be preferably 1000～20000, be preferably 1000～7000 poly aspartic acid especially and have those that carry out down.
Metal-salt among the method steps a. can be metal halide, acetate, vitriol or nitrate.Preferred herein metal-salt is a halogenide, for example zinc chloride (II) or titanium tetrachloride; And nitrate, for example zinc nitrate (II).
The precipitation of metal oxide can be 20 ℃～100 ℃ in temperature, be preferably under 25 ℃～40 ℃ and carry out among the method steps a..
Depend on employed metal-salt, precipitation can be to carry out for 3～13 times at pH.In the zinc oxide situation, the pH during the precipitation is 7～11.
Common 0.05～the 1mol/L of the concentration of metal-salt, be preferably 0.1～0.5mol/L, be preferably 0.2～0.4mol/L especially.
Sedimentation time is generally 2～8 hours, is preferably 3～7 hours, is preferably 4～6 hours especially.
The present invention provides a kind of method for preparing the nano particle zinc oxide of surface modification especially, and it passes through:
A. in the presence of alkali metal hydroxide or ammonium hydroxide, being 25～40 ℃ in temperature is 7～11 times with pH, is settled out zinc oxide from the aqueous solution of zinc chloride (II) or zinc nitrate (II);
B. from aqueous reaction mixture, isolate sedimentary zinc oxide; With
C. subsequent drying,
Wherein the precipitation of zinc oxide is at molecular weight M among the method steps a. wBe to carry out under the existence of 1000～7000 poly aspartic acid.
Among the method steps a. precipitation of zinc oxide can be for example with poly aspartic acid and alkali metal hydroxide or ammonium hydroxide, during especially zinc chloride (II) or zinc nitrate (II) are added in the mixture metering of NaOH to, perhaps carry out during adding poly aspartic acid solution in that zinc chloride (II) or zinc nitrate (II) aqueous solution and metal-salt oxyhydroxide or ammonium hydroxide aqueous solution are measured simultaneously.
Can be in known mode itself, for example by filtering or centrifugal sedimentary metal oxide being separated from aqueous reaction mixture.
Can the filter cake that be obtained under atmospheric pressure be dried to constant weight in known mode itself, be 40～100 ℃ for example in temperature, be preferably in 50～70 ℃ the loft drier dry.
The present invention further provides a kind of make-up composition, it comprises zinc oxide or zinc oxide dispersion according to surface-coated of the present invention.
The present invention further provides according to surface modification of metals oxide compound, the especially titanium dioxide of the inventive method preparation or the purposes of zinc oxide:
-be used for UV to protect
-as the anti-microbial activity composition.
According to preferred implementation of the present invention, the metal oxide of surface modification, especially titanium dioxide or zinc oxide, can redispersion in liquid medium and form stable dispersion.This point is useful especially, because do not need to disperse once more before further handling by prepare dispersion according to zinc oxide of the present invention, can directly handle.
According to preferred implementation of the present invention, the metal oxide of surface modification can redispersion in polar organic solvent and form stable dispersion.This point is useful especially, becomes possibility because it makes for example to be attached to equably in plastics or the film.
According to another preferred implementation of the present invention, the metal oxide of surface modification can redispersion in water and form stable dispersion.This point is useful especially, because it has opened up the possibility of for example using according to material of the present invention in cosmetic formulations (wherein with an organic solvent not being biggest advantage).Can conceivablely be the mixture of water and polar organic solvent equally.
According to preferred implementation of the present invention, the diameter of the metal oxide particle of surface modification is 10～200nm.This point is useful especially, because can guarantee good redispersibility in this distribution of sizes scope preparation.
According to special preferred implementation of the present invention, the metal oxide nanoparticles diameter is 10～50nm.This size range is useful especially, because after disperseing this Zinc oxide nanoparticle once more, the dispersion that is obtained is transparent, and can not influence color thus for example in adding cosmetic formulations to the time.And it has also brought the possibility that is used for transparent film.
When if metal oxide, especially titanium dioxide or zinc oxide are used as the UV absorption agent, the particle of diameter greater than 5nm used in suggestion, because absorption limit can be to shortwave scope skew (L.Brus under this limit, J.Phys., Chem. (1986), 90,2555-2560).
The present invention further provides a kind of make-up composition, it comprises metal oxide, especially titanium dioxide and/or zinc oxide according to surface modification of the present invention.This point is useful especially, because based on the fine dispersion of metal oxide particle, especially Zinc oxide particles, these make-up compositions can more effectively improve their Lavender Extract effect.
Another advantage is, when for example being used for skin, because small particle size can not produce friction effect, but can flexibly use, and it has brought the comfort on the skin.
Another embodiment according to this make-up composition; it is used for nursing or protection skin; in particular for sun-proof or be used to be exposed to the nursing of DT, and be emulsion, dispersion, suspensoid, aqueous tenside preparation, emulsion, lotion, frost, fragrant liquid, ointment, gel, particle, powder, paste formulation (for example as lipstick), foam, aerosol or Sprayable.Such prescription is highly suitable for topical formulations.Suitable emulsion is O/w emulsion and water-in-oil emulsion or microemulsion.This point is useful especially, because by use them in opalizer, can utilize for example UV-absorption of zinc oxide and the effect of Lavender Extract simultaneously.And foundation surface modification of metals oxide compound of the present invention is applicable to extraordinarily and is used for opalizer, is shown as transparent particle because can prepare size concerning human eye.Therefore, on skin, can not produce white mist between the usage period.
Another advantage is, a kind of in particular UV wide band of zinc oxide lightscreening agent, and its UV absorptive character can provide the opalizer that no longer needs other chemical UV lightscreening agent material.Therefore, can avoid by the degradation production of chemical lightscreening agent or the skin irritation or the anaphylactoid danger of these materials self generation, it has improved the general consistency of the opalizer of preparation in this way significantly.Usually, make-up composition is used for the topical application on the skin.Herein, the implication that topical formulations is understood is, is applicable to the fine dispersion form and preferably can activeconstituents being administered to those preparations on the skin by the form of skin absorption.For this purpose, suitable for example is water-based and water-alcohol solution, spraying, foam, foamed aerosol, ointment, hydrogel, O/W or w/o type emulsion, microemulsion or makeup viscosity preparation.
According to the preferred implementation of make-up composition of the present invention, said composition comprises carrier.Preferred carrier is water, gas, water fluid, oil, gel, emulsion or microemulsion, dispersion or its mixture.Described carrier has the advantages of good skin consistency.Hydrogel, emulsion or microemulsion are useful especially for topical formulations.
Operable emulsifying agent is nonionicization (nonionogenic) tensio-active agent, zwitterionics, amphoterics or anionic emulsifier.According in the composition of the present invention, the amount of emulsifying agent (based on said composition) can be for 0.1～10 weight %, be preferably 1～5 weight %.
Employed nonionic tensio-active agent for example can be selected from following tensio-active agent at least a:
2～30mol oxyethane and/or 0～5mol propylene oxide add to straight-chain fatty alcohol with 8～22 carbon atoms, add to the lipid acid with 12～22 carbon atoms and add to adduct on the alkylphenol that has 8～15 carbon atoms in alkyl;
Add to the C of the adduct on the glycerine by 1～30mol oxyethane 12/18-fatty acid monoester and dibasic acid esters; Monoglyceride and dibasic acid esters and sorbitan monoester and dibasic acid esters and its oxirane additive product with saturated and unsaturated fatty acids of 6～22 carbon atoms;
Have the alkyl monoglycosides of 8～22 carbon atoms and the analogue of oligoglycosides and its ethoxylation in the alkyl;
Add to adduct on Viscotrol C and/or the hydrogenated castor oil by 15～60mol oxyethane; Polyvalent alcohol, and polyglycerol esters especially, for example poly-glycerine polyricinoleate, poly-glycerine many-12-hydroxy stearic acid ester or poly-glycerine dimerization thing (polyglycerol dimerate).Same suitable is the mixture of two or more compounds in this class material;
2～15mol oxyethane adds to the adduct on Viscotrol C and/or the hydrogenated castor oil; Based on straight chain, branching, unsaturated or saturated C 6/22-lipid acid, ricinolic acid, with the 12-oxystearic acid, with the partial ester of glycerine, poly-glycerine, tetramethylolmethane, Dipentaerythritol, sugar alcohol (as Sorbitol Powder), alkyl glycoside (as methylglycoside, butyl glycoside, Plantacare APG 1200G) and polysaccharide glycosides (as Mierocrystalline cellulose);
Single, double and trialkyl phosphates and single, double and/or three-PEG-alkyl phosphate and salt thereof; Wool wax alcohol;
Polysiloxane-poly-alkyl-copolyether and corresponding derivative;
According to the mixed ester of tetramethylolmethane, lipid acid, citric acid and the Fatty Alcohol(C12-C14 and C12-C18) of German Patent 1165574, and/or has the mixed ester of lipid acid, methyl glucoside and polyvalent alcohol, preferably glycerine or the poly-glycerine of 6～22 carbon atoms; With
Polyalkylene glycol;
Trimethyl-glycine.
In addition, zwitterionics also can be used as emulsifying agent.Term " zwitterionics " is used for being illustrated in those surface active cpds that molecule has at least one quaternary ammonium group and at least one carboxylate salt or sulfonate groups.The zwitterionics of particularly suitable is so-called betaines, as glycine N-alkyl-N, and N-Dimethyl Ammonium, for example glycine cocounut oil alkyl dimethyl ammonium; Glycine N-acyl amino propyl group-N, N-Dimethyl Ammonium, for example glycine cocoyl aminopropyl Dimethyl Ammonium; With the 2-alkyl that in alkyl or acyl group, has 8～18 carbon atoms in every kind of situation-3-carboxymethyl-3-hydroxyethyl imidazole quinoline; With cocoyl amino-ethyl hydroxyethyl-carboxymethyl glycinate.Particularly preferably be known fatty acid amide derivant, name is called the cocamidopropyl betaine of CTFA.
Same suitable emulsifying agent is an amphoterics.The implication that amphoterics is understood is, in the molecule except C 8,18-alkyl or-also contain outside the acyl group at least one free amino group and at least one-COOH or-SO 3The H group and those surface active cpds that can form inner salt.Suitable examples of amphoteric surfactants is N-alkyl glycine, N-alkyl propionic acid, N-alkylamino butyric acid, N-alkyl imino dipropionic acid, N-hydroxyethyl-N-alkylamidoalkyl propyl group glycine, N-alkyl taurine, N-alkyl sarkosine, 2-alkyl aminopropionic acid and p dialkylaminobenzoic acid (having about 8～18 carbon atoms in every kind of situation in alkyl).
Particularly preferred amphoterics is N-coco alkyl amino propionic acid ester, cocoyl aminoethylamino propionic ester and C 12/18-acyl group sarkosine.Except amphoterics, quaternized emulsifying agent (quaternary emulsifier) also is suitable, those emulsifying agents of preferably quaternized ester (esterquat) type, preferable methyl-quaternised difatty acid triethanolamine ester salts.In addition, also operable anionic emulsifier is sulfated alkyl ether, direactive glyceride vitriol, lipid acid vitriol, sulfosuccinate and/or ether carboxylic acid.
Suitable oil body is for based on having 6～18, the Guerbet alcohol of the Fatty Alcohol(C12-C14 and C12-C18) of preferred 8～10 carbon atoms, straight chain C 6-C 22-lipid acid and straight chain C 6-C 22The ester of-lipid acid, branching C 6-C 13-carboxylic acid and straight chain C 6-C 22The ester of-Fatty Alcohol(C12-C14 and C12-C18), straight chain C 6-C 22The ester of-lipid acid and branching alcohol, especially 2-Ethylhexyl Alcohol, the ester of straight chain and/or branching lipid acid and polyhydroxy-alcohol (for example as propylene glycol, dimer diol or trimerization triol) and/or Guerbet alcohol is based on C 6-C 10The Witepsol W-S 55 of-lipid acid is based on C 6-C 18The liquid list of-lipid acid-/pair-, Witepsol W-S 55, C 6-C 22-Fatty Alcohol(C12-C14 and C12-C18) and/or Guerbet alcohol and aromatic carboxylic acid, especially benzoic ester, C 2-C 12-dicarboxylic acid with have the straight chain or the branching alcohol of 1～22 carbon atom or have the ester of the polyvalent alcohol of 2～10 carbon atoms and 2～6 hydroxyls, vegetables oil, the primary alconol of branching, the hexanaphthene of replacement, straight chain C 6-C 22-Fatty Alcohol(C12-C14 and C12-C18) carbonic ether, Guerbet carbonic ether, phenylformic acid and straight chain and/or branching C 6-C 22-alcohol is (as Finsolv
Figure 058108138_0
TN) ester, dialkyl ether, the open-loop products of epoxidized fatty acid ester and polyvalent alcohol, silicone oil, and/or aliphatics or alicyclic hydro carbons.Also operable other oil body is a silicone compounds, for example dimethyl polysiloxane, methyl phenyl silicone, cyclosiloxane, and amino-, lipid acid-, alcohol-, polyethers-, epoxy-, fluoro-, alkyl-and/or the silicone compounds of glucosides modification, it at room temperature can be liquid form or resin form.In foundation composition of the present invention, the amount of oil body (based on said composition) is 1～90 weight %, preferred 5～80 weight % and is 10～50 weight % especially.
According to particularly preferred embodiment, comprise other UV shading (photoprotective) lightscreening agent or other pigment of soluble compound form according to composition of the present invention.
Though as top as described in, by means of foundation Zinc oxide particles of the present invention, a kind of barrier compositions can be provided, said composition also can realize good UV absorptive character when not having other lightscreening agent material, but what can expect in various situations is that other UV lightscreening agent material is added in make-up composition or the barrier compositions.For example, if this point may be necessary during lay special stress on optical filtering performance.One or more other UV shading lightscreening agents can be added to according in the composition of the present invention.
In the soluble compound situation, the implication that UV shading lightscreening agent is understood is, can absorb ultraviolet ray and with the more form of long wavelength radiation such as the organic substance that heat discharges the energy that is absorbed once more.This organic substance can be oil-soluble or water miscible.
Operable oil soluble UV-B lightscreening agent for example is following material:
3-benzylidene camphor and its derivative are as 3-(4-methyl benzylidene) camphor;
The 4-aminobenzoic acid derivative, preferred 4-(dimethylamino) phenylformic acid 2-ethylhexyl, 4-(dimethylamino) phenylformic acid 2-monooctyl ester and 4-(dimethylamino) amyl benzoate;
The ester of styracin, preferred 4-methoxy cinnamic acid 2-ethylhexyl, 4-methoxy cinnamic acid propyl ester, 4-methoxy cinnamic acid isopentyl ester, 4-methoxy cinnamic acid isopentyl ester, 2-cyano group-3-phenyl-cinnamic acid 2-ethylhexyl (otocrylene);
Salicylic ester, preferred Whitfield's ointment 2-ethylhexyl, Whitfield's ointment 4-isopropyl benzyl ester, the equal menthyl ester of Whitfield's ointment;
The derivative of benzophenone, preferred 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-methoxyl group-4 '-methyldiphenyl ketone, 2,2 '-dihydroxyl-4-methoxy benzophenone;
The ester of phenmethyl propanedioic acid, preferred 4-methoxyl group benzylidene malonic acid 2-ethylhexyl; Pyrrolotriazine derivatives, as 2,4,6-triphen amido (p-carbon-2 '-ethyl-1 '-hexyloxy)-1,3,5-triazines (UVINUL T-150) and dioctyl butyl amide base triazone (Uvasorb
Figure 058108138_1
HEB);
Propane-1,3-two ketones, 1-(4-tert-butyl-phenyl)-3-(4 '-p-methoxy-phenyl) propane-1 for example, 3-diketone.
Suitable water-soluble substances is:
2-Phenylbenzimidazole-5-sulfonic acid and its basic metal, alkaline-earth metal, ammonium, alkylammonium, silane alcohol base ammonium and its glucose ammonium salt;
The sulfonic acid of benzophenone, preferred 2-hydroxyl-4-methoxy benzophenone-5-sulfonic acid and its salt;
The sulfonic acid of 3-benzylidene camphor, for example 4-(the bornenyl methyl of 2-oxygen-3-) Phenylsulfonic acid and 2-methyl-5-(2-oxygen-3-is bornenyl) sulfonic acid and salt thereof.
The particularly preferred ester that is to use styracin, preferred 4-methoxy cinnamic acid 2-ethylhexyl, 4-methoxy cinnamic acid isopentyl ester, 2-cyano group-3-phenyl-cinnamic acid 2-ethylhexyl (otocrylene).
In addition, preferably use the derivative of benzophenone, especially 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-methoxyl group-4 '-methyldiphenyl ketone, 2,2 '-dihydroxyl-4-methoxy benzophenone; The preferred propane-1 that uses, 3-two ketones, 1-(4-tert-butyl-phenyl)-3-(4 '-p-methoxy-phenyl) propane-1 for example, 3-diketone.
Suitable typical UV-A lightscreening agent is:
The derivative of benzoyl methane, 1-(4 '-tert-butyl-phenyl)-3-(4 '-p-methoxy-phenyl) propane-1 for example, 3-diketone, the 4-tertiary butyl-4 '-methoxy dibenzoyl methylmethane or 1-phenyl-3-(4 '-isopropyl phenyl) propane-1,3-diketone;
The hydroxy amino substitutive derivative of benzophenone, N for example, N-diethylamino hydroxy benzoyl-positive hexyl phenenyl manthanoate.
Certainly UV-A and UV-B lightscreening agent also use in mixture.
But operable other shading lightscreening agent also can be other insoluble pigment, as finely-dispersed metallic oxide compound and salt, and for example titanium dioxide, ferric oxide, aluminum oxide, cerium oxide, zirconium white, silicate (talcum), barium sulfate and Zinic stearas.Particle should have the mean diameter less than 100nm, is preferably 5～50nm, and is 15～30nm especially.
Except above-mentioned two groups of main shading materials, also can use the less important opalizer of anti-oxidant type, the photochemical reaction chain that it has caused when having interrupted in the UV radiation penetrates to the skin.Its typical example is superoxide dismutase, tocopherol (vitamin-E) and xitix (vitamins C).
In foundation barrier compositions of the present invention, the total content of opalizer is generally 1～20 weight %, is preferably 5～15 weight %.Can contain 1～95 weight %, be preferably 5～80 weight % and be the water of 10～60 weight % especially according to composition of the present invention.
According to particularly preferred embodiment, also comprise care substance, other cosmetic active ingredient and/or auxiliary agent and additive according to make-up composition of the present invention.
Employed other cosmetic active ingredient is skin moisturizer, antimicrobial substance and/or deodorizing or hidroschesis material especially.Its advantage that has is, can obtain other desired effects, and it helps the nursing or the processing of skin, perhaps for example is increased in the good order and condition of this make-up composition user when using said composition.
For example, on zinc oxide, water and the physiology of carrier, surface modification, the suitable solvent, also can comprise the nursing composition especially among this make-up composition, for example oil, wax, fat, increase fat material, thickening material, emulsifying agent and spices again.The care substance of vast scale is useful especially for the local preventative or cosmetic processing of skin.
Useful especially is if that except animal and plant fat and oil (it has nursing efficacy similarly in many situations), said composition also comprises other nursing component.Operable nursing activeconstituents for example is: have the Fatty Alcohol(C12-C14 and C12-C18) of 8～22 carbon atoms, especially the Fatty Alcohol(C12-C14 and C12-C18) of natural acid; Animal and plant protein hydrolyzate, especially elastin, collagen, Keratin sulfate, milk protein, soy-protein, avenin matter, pea protein, almond protein matter and aleuronat hydrolysate; Those of VITAMIN and previtamin, especially vitamin A and B series; Single-, two-and oligosaccharides; Plant milk extract; Mel extract; Ceramide; Phosphatide; Vaseline, paraffin and silicone oil; Lipid acid and aliphatic alcohol ester, especially lipid acid and monoesters with alcohol of 3～24 carbon atoms.According to preferred VITAMIN, pro-vitamin or the previtamin that uses in the composition of the present invention comprising:
VITAMIN, pro-vitamin and the previtamin of A, C, E and F series, especially 3,4-two vitamin A-2s (didehydroretinol), β-Hu Luobusu (pro-vitamin of vitamin A), palm (palmitic) ester, glucosides or the phosphoric acid ester of xitix (vitamins C) and xitix, tocopherols, especially alpha-tocopherol and its ester are as acetic ester, nicotine acid esters, phosphoric acid ester and succinate; And vitamin F, the implication of its understanding is lipid acid, especially linolic acid, linolenic acid and the arachidonic acid that refines;
The former skin smooth effect that has uniqueness valuably of vitamin A and its derivative and microorganism.
According to preferred VITAMIN, pro-vitamin or the microorganism precursor of vitamins B series or the derivative of its derivative and 2-furanone (2-furanone) of using in the composition of the present invention, wherein particularly including:
Vitamins B 1, be commonly called as thiamines, chemical name is chlorination 3-[(4 '-amino-2 '-methyl-5 '-pyrimidyl) methyl]-5-(2-hydroxyethyl)-4-methylthiazol quinoline.The consumption of preferably salt allithiamine (based on the composition gross weight) is 0.05～1 weight %.
Vitamins B 2, being commonly called as riboflavin, chemical name is 7,8-dimethyl-10-(1-D-ribosyl)-benzo [g] pteridine-2,4 (3H, 10H)-diketone (7,8-dimethyl-10-(1-D-ribityl)-benzo[g] pteridine-2,4 (3H, 10H)-dione).Pteridine is with free form, for example occur with the whey form, and can separate other pteridine derivatives from bacterium and yeast.The lyxoflavin of pteridine steric isomer (it is fit to equally according to the present invention) for can from fish meal or liver, separating and have the D-arabinose base that replaces the D-ribosyl.The consumption of riboflavin or derivatives thereof (based on the composition gross weight) is preferably 0.05～1 weight %.
Vitamins B 3, this title is through being usually used in compound nicotinic acid and niacinamide (nicotine).According to the present invention, be preferably 0.05～1 weight % at amount (based on the composition gross weight) according to niacinamide in the composition of the present invention.
Vitamins B 5(pantothenic acid and panthenol).The preferred panthenol that uses.The panthenol derivative that can use according to the present invention is ester and the ether and the positively charged ion deutero-panthenol of panthenol especially.In another preferred implementation of the present invention, except pantothenic acid or panthenol, also can use the derivative of 2-furanone.Particularly preferred derivative is commercially available material, be commonly called as the dihydro-3-hydroxyl-4 of pantolactone (pantolactone), 4-dimethyl-2 (3H)-furanone (Merck), 4-methylol-gamma-butyrolactone (Merck), 3,3-dimethyl-2-hydroxyl-gamma-butyrolactone (Aldrich) and 2,5-dihydro-5-methoxyl group-2-furanone (Merck) (comprising all steric isomers clearly).
These compounds have been given valuably according to make-up composition of the present invention and having been preserved moisture and the performance of Lavender Extract.
Preferably according in the composition of the present invention, vitamins B 5The described compound of type and the total amount of 2-furanone derivatives (based on the composition gross weight) are preferably 0.05～10 weight %.Total amount is preferably 0.1～5 weight % especially.
Vitamins B 6, its implication of understanding not is the material of homogeneous, but the derivative that the 5-methylol-2-picoline-3-is pure, its known being commonly called as is pyridoxol, Pyridoxylamine and pyridoxal.Vitamins B 6Be preferably 0.0001～1.0 weight %, especially 0.001～0.01 weight % according to the amount in the composition of the present invention.
Vitamins B 7(vitamin H) is also referred to as vitamin H or " skin VITAMIN ".Vitamin H is (3aS, 4S, 6aR) 2-oxygen six hydrogen thiophene alcohol [3,4-d] imidazoles-4-valeric acids.Vitamin H is being preferably 0.0001～1.0 weight %, especially 0.001～0.01 weight % according to the amount in the composition of the present invention.
According to the present invention, very particularly preferably be panthenol, pantolactone, niacinamide and vitamin H.
The implication that auxiliary agent and additive are understood is to be applicable to the material that improves sensation, performance and/or cosmetic properties, for example assistant for emulsifying agent, organic solvent, super fatting agent, stablizer, oxidation inhibitor, wax or fat, consistency modifiers, thickening material, suntan, VITAMIN, cationic polymers, biogenic activeconstituents, sanitas, the water solubles, solubilizing agent, dyestuff and spices.
For example, can use following auxiliary agent and additive:
Wallantoin,
Aloe vera (Aloe Vera),
Bisabolol,
Ceramide and false manifestation of vitality are through acid amides.
Oxidation inhibitor has improved the stability according to composition of the present invention valuably.Oxidation inhibitor for example is that amino acid is (as glycine; Histidine; tyrosine; tryptophane) and its derivative; imidazoles and imdazole derivatives (as urocanic acid); peptide; D for example; the L-carnosine; the D-carnosine; L-carnosine and its derivative (as anserine); carotenoid; carotene is (as alpha-carotene; β-Hu Luobusu; Lyeopene) and its derivative; Thioctic Acid and its derivative (as Thioctic acid, dihydro-); Aurothioglucose; propylthiouracil and other thio-compounds are (as thioglycerin; the sulfo-sorbyl alcohol; thioglycolic acid; the sulfo-reductone; gsh; halfcystine; Gelucystine; cystamine and its glycosyl; the N-ethanoyl; methyl; ethyl; propyl group; amyl group; butyl; lauryl; palmitoyl; oleyl; γ-flax base; cholesteryl and glyceryl ester); with its salt; Tyox B; distearylthiodi-propionate; thio-2 acid and its derivative (ester; ether; peptide; lipid; Nucleotide; nucleosides and salt); very low tolerance dose is (as sulfo group oxime compound (butyl thionine (buthionine) the sulfo group oxime of pmol/kg～pmol/kg); homocysteine sulfo group oxime; butyl thionine sulfone; five-; six-; seven thionine sulfo group oximes); and metal chelator is (as alpha-hydroxy fatty acid; EDTA; EGTA; phytinic acid; lactoferrin); alpha hydroxy acid is (as citric acid; lactic acid; oxysuccinic acid); humic acid; bile acide; bile extract; gallic acid ester is (as Propylgallate; monooctyl ester and dodecyl ester); flavonoid; catechin; bilirubin; uteroverdine and its derivative; unsaturated fatty acids and its derivative are (as gamma-linolenic acid; linolic acid; arachidonic acid; oleic acid); folic acid and its derivative; quinhydrones and its derivative (as arbutin); ubiquinone and panthenol; with its derivative; vitamins C and its derivative are (as anti-bad blood base cetylate; stearate; dipalmitate; acetic ester; Mg resists bad blood base phosphoric acid ester; sodium ascorbate and magnesium; anti-bad serium inorganic phosphorus acid esters of disodium and sulfuric ester; the anti-bad blood base of potassium is given birth to basic phosphoric acid ester; the chitosan acid ascorbyl ester); saccharosonic acid and its derivative; tocopherol and its derivative are (as the fertility yl acetate; linoleate; oleic acid ester and succinate; tocophereth-5; tocophereth-10; tocophereth-12; tocophereth-18; tocophereth-50; tocophersolan); vitamin A and derivative (as Vitamin A Palmitate 1.7 M.I.U/Gram); styrax resinoid; violaguercitrin; the coniferyl benzoic ether of rutinic acid and its derivative; disodium violaguercitrin base di-sulfate; styracin and its derivative are (as forulic acid; Ferulic acid ethylester; coffic acid); kojic acid; chitosan glycolate and salicylate; butylhydroxy toluene; the butylhydroxy phenylcarbinol; nordihydroguaiaretic acid (nordihyroguaiacic acid); go to first dihydroguaiaretic acid; THBP 2,4,5 trihydroxybutyrophenone; uric acid and its derivative; seminose and its derivative; zinc and zinc derivative (as ZnO, ZnSO 4), selenium and selenium derivative (as Sethotope), stilbene and stilbene derivatives (as oxidation stilbene and trans-oxidation stilbene).
According to the present invention, can use the suitable derivative (as salt, ester, sugar, Nucleotide, nucleosides, peptide and lipid) and the mixture (it comprises these oxidation inhibitor) of these described activeconstituentss or plant milk extract (as tea tree oil, rosemary extract and rosmarinic acid).As lipotropy, the oil soluble oxidation inhibitor in this group, preferably tocopherol and its derivative, gallic acid, flavonoid and carotenoid, and butylhydroxy toluene/phenylcarbinol.As water-soluble oxidation inhibitor, preferred amino acid (as tyrosine and halfcystine) and its derivative, and tannin, especially plant-derived those.According in the make-up composition of the present invention, the total amount of oxidation inhibitor is 0.001～20 weight %, be preferably 0.05～10 weight %, especially 0.1～5 weight % and very particularly preferably be 0.1～2 weight %.
Triterpene, especially triterpene system acid, for example ursolic acid, rosmarinic acid, betulinic acid, masticinic acid and byronolic acid.
The plain class of the monomer bitter edible plant, especially catechin and l-Epicatechol, white cell cyanidin(e) (leukoanthocyanidin), catechin polymkeric substance (catechin tannin) and Nutgalls tannin, thickening material, as gelatin, vegetable jelly such as agar, guar gum, alginate, xanthan gum, Sudan Gum-arabic, kuteera gum or angle beans, natural and synthesis of clay and sheet silicate are as wilkinite, hectorite, polynite or Laponite , complete synthetic hydrocolloid, the Ca of for example polyvinyl alcohol, and lipid acid, Mg or Zn soap,
The plant glucosides,
Structurizing reagent, as toxilic acid and lactic acid,
Isosorbide dimethyl ether,
α, β and γ-Huan Hujing, in particular for stablizing rosinol,
Solvent, swelling and permeate substance, as ethanol, Virahol, ethylene glycol, propylene glycol, propylene glycol list ethyl ether, glycerine and Diethylene Glycol, carbonate, supercarbonate, guanidine, urea and primary, stretch phosphoric acid ester with uncle,
Perfume oil, the pigment and the dyestuff of the said composition that is used to dye,
Be used to regulate the material of pH, as α-and beta-hydroxycarboxylic acids,
Coordination agent, as EDTA, NTA, β-Beta Alanine oxalic acid and phosphoric acid,
Opalizer, as latex, vinylbenzene/PVP and vinylbenzene/acrylamide copolymer,
Pearling agent (pearlizing agent), as glycol monomethyl-and two stearates and two stearates of PEG-3,
Propelling agent, as propane/butane mix, N 2O, dme, CO 2And air.
Wallantoin, bisabolol and/or aloe vera are added to according in the make-up composition of the present invention with form of extract, also can improve this prescription the Lavender Extract, preserve moisture and the skin care performance, and be particularly preferred therefore.
As other composition,, can comprise a small amount of other tensio-active agent compatible with other composition according to make-up composition of the present invention.
The representative instance of anion surfactant is a soap, alkylbenzene sulfonate, alkane sulfonate; alkene sulfonate; alkylether sulfonate, glycerol ether sulfonate, Alpha-Methyl sulfonated ester; sulfo-fatty acid; alkyl-sulphate, fatty alcohol ether sulphate, glycerol ether sulfate; hydroxyl mixed ether vitriol; fatty acid amide (ether) vitriol, single-and double alkyl sulfo amber acid salt, single-and two alkyl sulphosuccinamate; the sulfo group tri-glyceride; the acid amides soap, ether carboxylic acid and its salt, lipid acid isethionate; the lipid acid sarcosinate; fatty acid amino esilate, N-acylamino acid, for example acyl-lactate; acyl group tartaric acid salt; acyl glutamate and acyl group asparagus fern amino acid salt; alkyl oligoglycosides vitriol, the protein fatty acid condensation product plant prod of wheat (especially based on) and alkyl (ether) phosphoric acid salt.
When if anion surfactant comprises the polyglycol ether chain, they can have common homologue distribution, distribute but preferably have narrow homologue.
The representative instance of nonionogenic tenside is the poly alkyl alcohol glycol ethers, the fatty acid polyglycol diol ester, the fatty acid amide polyglycol ether, the aliphatic amide polyglycol ether, the alkoxylate Witepsol W-S 55, mixed ether and mixed aldehyde, if be suitable for the basic oligoglycosides of alkane (alkene) and glyconic acid (glucoronic acid) derivative of partial oxidation, lipid acid N-alkyl glucose amide, the protein hydrolyzate plant prod of wheat (especially based on), polyhydric alcohol fatty acid ester, sugar ester, sorbitan ester, polysorbate and amine oxide.When if ionic surfactant pack contains the polyglycol ether chain, they can have common homologue distribution, distribute but preferably have narrow homologue.
The representative instance of cats product is quaternary ammonium compound and quaternized ester (esterquats), especially quaternary fatty acid three alkanolamine ester salt.
The representative instance of both sexes and zwitterionics is an alkyl betaine, alkylamidoalkyl trimethyl-glycine, alanine ester, amino glycinate, imidazolinium betaine and sultaine.
According to another particularly preferred embodiment, be used as barrier compositions according to make-up composition of the present invention.The advantage that it had is described in detail.
Can be used for cosmetic hair equally especially according to zinc oxide dispersion of the present invention, as shampoo, conditioning agent, purificant, hair tonic, hair gel, hair hair spray etc.Especially, the product of staying the hair life that is retained on hair or the scalp subsequent applications is a particularly suitable.In this way zinc oxide is administered on scalp and the hair, also can be used as the UV opalizer thus and/or promote the effect of its Lavender Extract on scalp.
Preferred implementation according to make-up composition of the present invention is administered to this make-up composition on the body surface pending or to be protected partly.This administration form is useful especially, because its easy processing means and got rid of wrong dosage widely.In addition, also realized extra skin care effect.Be exposed under the solar radiation iff a few part bodies, this barrier compositions also can only be administered on these parts of body in the target mode.
The present invention further provides the purposes that is used for the UV protection according to surface modification of metals oxide compound of the present invention.This point is useful especially, because owing to for example characteristic in small, broken bits and the good dispersion of surface modification zinc oxide, realized extra high UV absorptivity.
The present invention further provides according to surface modification of metals oxide compound, especially zinc oxide of the present invention purposes as the anti-microbial activity composition.This purposes of these particulate is useful especially for this purpose, because because this particulate characteristic in small, broken bits and thus obtained large specific surface have significantly improved antibiotic effect; And on the other hand, because the good distribution performance of this material, zinc oxide exists with form in small, broken bits.Can use zinc oxide with various application forms (for example frost, emulsion, washing lotion or tonic) like this, and not have any problem.
The present invention further provides a kind of pharmaceutical composition that comprises according to surface modification of metals oxide compound of the present invention.The noticeable fact of this pharmaceutical composition is, because this particulate characteristic in small, broken bits has significantly improved pharmaceutical efficacy.
In addition, the advantage that has according to pharmaceutical composition of the present invention is, because the good long of zinc oxide dispersion (top describe) for example, can add and restrain isolating stablizer and make up a prescription.Increased the consistency of this pharmaceutical composition thus extraly.
With reference to the following example, set forth the present invention in more detail.
The preparation of surface modification zinc oxide
Embodiment 1:
To comprise the aqueous solution of the poly aspartic acid of the NaOH of 8g/L and 10g/L, with zinc nitrate (II) aqueous solution of 15g/L, metering feeding is 0.15mm to volume continuously 3Mixing section in, and flow velocity is 100mL/min in every kind of situation.After reacting about 4 seconds, reaction mixture is pumped in the beaker continuously, and uses the further homogenizing of Ultra Turrax.Use after the magnetic agitation ageing 2.5 hours, form cream, filter out the zinc oxide of poly aspartic acid surface modification thus, and in 50 ℃ of loft drier dry 9 hours subsequently.
Embodiment 2:
0.2M zinc nitrate (II) solution of 1000mL is heated to 40 ℃, and under agitation in 4 hours with its metering feeding in the 0.2M NaOH solution of 1000mL (its equally also be heated to 40 ℃ and contain 20g poly aspartic acid (sodium salt) in addition).Sedimentary zinc oxide by the poly aspartic acid surface modification is filtered out, and in 50 ℃ of loft drier, carry out drying.
Embodiment 3:
0.2M zinc chloride (II) solution of 1000mL is heated to 40 ℃, and under agitation in 4 hours with its metering feeding in the 0.2M NaOH solution of 1000mL (its equally also be heated to 40 ℃ and contain 20g poly aspartic acid (sodium salt) in addition).Sedimentary zinc oxide by the poly aspartic acid surface modification is filtered out, and in 50 ℃ of loft drier, carry out drying.
Embodiment 4:
The 0.4M zinc nitrate solution of 500mL is heated to 40 ℃.By peristaltic pump, will be heated to 40 ℃ and contain the 0.8M NaOH solution of the 500mL of 40g/L poly aspartic acid in addition equally, under agitation with the speed metering feeding of 5L/h.Stirred throw out 4 hours down at 40 ℃.To filter out by the ZnO of poly aspartic acid surface modification subsequently, and at room temperature carry out drying.
Embodiment 5:
40 ℃ the 0.5M zinc nitrate solution of 200mL and the 1MNaOH solution of 200mL will all be heated to, by the speed of peristaltic pump with about 1.68L/h in every kind of situation, under agitation metering feeding is to being heated in 40 ℃ the 600mL poly aspartic acid solution (33.34g/L).Stirred throw out 2 hours down at 40 ℃.The ZnO of poly aspartic acid surface modification is passed through in centrifugation subsequently, and at room temperature carries out drying.
Embodiment 6:
The 0.4M NaOH solution (it contains the poly aspartic acid of 20g/L in addition) of 250mL is heated to 40 ℃, and in about 5 seconds and under stirring, it is oscillated in the 250mL 0.2M acetic acid zinc solution that is heated to 40 ℃ equally.Stirred throw out 2 hours down at 40 ℃.To filter by the ZnO of poly aspartic acid surface modification subsequently, and at room temperature carry out drying.
Cosmetic formulations embodiment
Preparation is according to the general operation of the preparation as emulsion of the present invention
Each of phase A and C is heated to about 85 ℃ mutually respectively.By homogenizing phase C and metal oxide are stirred to mutually among the A subsequently.After the homogenizing of simple back, stir down with emulsion cool to room temperature and bottling.All quantitative datas are all with reference to the gross weight of said preparation.
Embodiment 7:
Latex A comprises 3 weight %Uvinul
Figure 058108138_3
The zinc oxide of preparation among T150 and 4 weight % such as the embodiment 5.
Phase ％ INCI
?A 8.00 Polycizer W 260
8.00 Phenylformic acid C 12～C 15Alkyl ester
12.00 Cocounut oil glyceryl ester (Cocoglyceride)
1.00 Sodium?Cetearyl?Sulfate
4.00 The lauryl glucoside, Polyglyceryl-2
2.00 Cetearyl?Alcohol
3.00 Ethylhexyl triazone (Uvinul
Figure 058108138_4
T150)
1.00 The acetate tocoretinate
B 4.0 Zinc oxide
C 3.00 Glycerine
0.20 Wallantoin
0.30 Xanthan gum
0.02 Trolamine
To 100 Aqua?dem.
Embodiment 8:
Emulsion B comprises 3 weight %Uvinul T150,2 weight %Uvinul
Figure 058108138_6
The zinc oxide of preparation among A Plus and 4 weight % such as the embodiment 5.
Phase ％ INCI
?A 8.00 Polycizer W 260
8.00 Phenylformic acid C 12～C 15Alkyl ester
Phase ％ INCI
12.00 Cocounut oil glyceryl ester
1.00 Sodium?Cetearyl?Sulfate
4.00 The lauryl glucoside, Polyglyceryl-2
2.00 Cetearyl?Alcohol
3.00 Ethylhexyl triazone (Uvinul T150)
1.00 The acetate tocoretinate
2.00 Diethylamino hydroxy benzoyl hexyl benzene manthanoate (Uvinul A?Plus)
B 4.0 Zinc oxide
C 3.00 Glycerine
0.20 Wallantoin
0.30 Xanthan gum
1.50 Neusilin
To 100 Aqua?dem.
Embodiment 9:
Latex A comprises 3 weight %Uvinul The zinc oxide of preparation among T150 and 4 weight % such as the embodiment 2.
Phase ％ INCI
A 8.00 Polycizer W 260
8.00 Phenylformic acid C 12～C 15Alkyl ester
Phase ％ INCI
12.00 Cocounut oil glyceryl ester
1.00 Sodium?Cetearyl?Sulfate
4.00 The lauryl glucoside, Polyglyceryl-2
2.00 Cetearyl?Alcohol
3.00 Ethylhexyl triazone (Uvinul T150)
1.00 The acetate tocoretinate
B 4.0 Zinc oxide
C 3.00 Glycerine
0.20 Wallantoin
0.30 Xanthan gum
0.02 Trolamine
To 100 Aqua?dem.
Embodiment 10:
Emulsion B comprises 3 weight %Uvinul
Figure 058108138_11
T150,2 weight %Uvinul
Figure 058108138_12
The zinc oxide of preparation among A Plus and 4 weight % such as the embodiment 2.
Phase ％ INCI
A 8.00 Polycizer W 260
8.00 Phenylformic acid C 12～C 15Alkyl ester
12.00 Cocounut oil glyceryl ester
1.00 Sodium?Cetearyl?Sulfate
Phase ％ INCI
4.00 The lauryl glucoside, Polyglyceryl-2
2.00 Cetearyl?Alcohol
3.00 Ethylhexyl triazone (Uvinul T150)
1.00 The acetate tocoretinate
2.00 Diethylamino hydroxy benzoyl hexyl benzene manthanoate (Uvinul
Figure 058108138_14
A?Plus)
B 4.0 Zinc oxide
C 3.00 Glycerine
0.20 Wallantoin
0.30 Xanthan gum
1.50 Neusilin
To 100 Aqua?dem.

Claims (16)

1. the nano particle metal oxide of a surface modification, wherein metal is selected from aluminium, cerium, iron, titanium, zinc and zirconium, wherein:
A) surface modification comprises use molecular weight M wBe that 1000～100000 poly aspartic acid applies; With
B) average primary particle diameter of nano particle metal oxide is 10～200nm.
2. according to the nano particle metal oxide of claim 1, it is the zinc oxide of surface modification.
3. method for preparing the nano particle metal oxide of surface modification, wherein metal is selected from aluminium, cerium, iron, titanium, zinc and zirconium, is undertaken by following steps:
A. metal oxide is precipitated out from the aqueous solution of its a kind of metal-salt;
B. from aqueous reaction mixture, isolate sedimentary metal oxide; With
C. subsequent drying metal oxide,
Wherein, carry out under the existence that is deposited in poly aspartic acid of metal oxide among the method steps a., and the average primary particle diameter of nano particle metal oxide is 10～200nm.
4. according to the method for claim 3, wherein metal-salt is metal halide, acetate, vitriol or nitrate.
5. according to the method for claim 3, wherein be deposited in molecular weight M wBe to carry out under the existence of 1000～100000 poly aspartic acid.
6. according to the method for claim 4, wherein be deposited in molecular weight M wBe to carry out under the existence of 1000～100000 poly aspartic acid.
7. according to the method for claim 3, wherein being deposited in temperature is to carry out under 20 ℃～100 ℃.
8. according to the method for claim 4, wherein being deposited in temperature is to carry out under 20 ℃～100 ℃.
9. according to the method for claim 5, wherein being deposited in temperature is to carry out under 20 ℃～100 ℃.
10. according to the method for claim 6, wherein being deposited in temperature is to carry out under 20 ℃～100 ℃.
11., wherein be deposited in pH and be 3～12 times and carry out according to each method in the claim 3～10.
12., be used to prepare the nano particle zinc oxide of surface modification according to each method in the claim 3～10.
13., be used to prepare the nano particle zinc oxide of surface modification according to the method for claim 11.
14. the purposes according to the nano particle metal oxide of each defined surface modification in the claim 1～2 is used to prepare cosmetic formulations.
15., be used to prepare the cosmetics barrier preparation according to the purposes of claim 14.
16. a cosmetic formulations comprises the nano particle metal oxide according to claim 1 or 2 defined surface modifications.
CN2005800108138A 2004-03-31 2005-03-26 Surface-modified metal oxides, methods for production and use thereof in cosmetic preparations Expired - Fee Related CN1938387B (en)

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DE200410016649 DE102004016649A1 (en) 2004-03-31 2004-03-31 Surface-modified metal oxides useful in cosmetics comprise nanoparticulate aluminum, cerium, iron, titanium, zinc or zirconium oxides coated with polyaspartic acid
DE102004016649.8 2004-03-31
DE200410020766 DE102004020766A1 (en) 2004-04-27 2004-04-27 Surface-modified metal oxides useful in cosmetics comprise nanoparticulate aluminum, cerium, iron, titanium, zinc or zirconium oxides coated with polyaspartic acid
DE102004020766.6 2004-04-27
PCT/EP2005/003217 WO2005094156A2 (en) 2004-03-31 2005-03-26 Polyasparaginic acid surface-modified metal oxides methods for production and use thereof in cosmetic preparations

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