EP1743002A2 - Oxydes metalliques a modification de surface, procedes de production desdits oxydes metalliques et leur utilisation dans des preparations cosmetiques - Google Patents

Oxydes metalliques a modification de surface, procedes de production desdits oxydes metalliques et leur utilisation dans des preparations cosmetiques

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Publication number
EP1743002A2
EP1743002A2 EP05716391A EP05716391A EP1743002A2 EP 1743002 A2 EP1743002 A2 EP 1743002A2 EP 05716391 A EP05716391 A EP 05716391A EP 05716391 A EP05716391 A EP 05716391A EP 1743002 A2 EP1743002 A2 EP 1743002A2
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EP
European Patent Office
Prior art keywords
acid
metal
modified
zinc
metal oxides
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05716391A
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German (de)
English (en)
Inventor
Valerie Andre
Jens Rieger
Heidrun Debus
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Priority claimed from DE200410016649 external-priority patent/DE102004016649A1/de
Priority claimed from DE200410020766 external-priority patent/DE102004020766A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP1743002A2 publication Critical patent/EP1743002A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • 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
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products 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
    • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12993—Surface feature [e.g., rough, mirror]

Definitions

  • the present invention relates to surface-modified nanoparticulate metal oxides, processes for their preparation and their use as UV filters in cosmetic preparations.
  • Metal oxides are used for a variety of purposes, e.g. as a white pigment, as a catalyst, as a component of antibacterial skin protection ointments and as an activator for rubber vulcanization.
  • Cosmetic sunscreens contain fine-particle zinc oxide or titanium dioxide as UV-absorbing pigments.
  • nanoparticles refers to particles with an average diameter of 5 to 10,000 nm, determined by means of electron microscopic methods.
  • Zinc oxide nanoparticles with particle sizes below approx. 30 nm are potentially suitable for use as UV absorbers in transparent organic-inorganic hybrid materials, plastics, paints and coatings. It can also be used to protect UV-sensitive organic pigments.
  • Particles, particle aggregates or agglomerates made of zinc oxide that are larger than approx. 30 nm lead to scattered light effects and thus to an undesirable decrease in transparency in the range of visible light. Therefore, the redispersibility, that is, the convertibility of the zinc oxide nanoparticles produced into a colloidally dispersed state, is an important prerequisite for the above-mentioned applications.
  • Zinc oxide nanoparticles with particle sizes below approx. 5 nm show a blue shift in the absorption edge due to the size quantization effect (L. Brus, J. Phys. Chem. (1986), 90, 2555-2560) and are therefore suitable for use as UV absorbers in UV A-area less suitable.
  • metal oxides for example zinc oxide
  • dry and wet processes The classic method of burning zinc, which is known as a dry process (e.g. Gmelin Volume 32, 8th Edition, Supplementary Volume, p. 772 ff.), Produces aggregated particles with a wide size distribution.
  • Gmelin Volume 32, 8th Edition, Supplementary Volume, p. 772 ff. a dry process
  • dispersions with average particle sizes in the lower nanometer range cannot be achieved from such powders due to the shear forces that are too low.
  • Particularly fine-particle zinc oxide is primarily produced by wet-chemical precipitation processes. Precipitation in aqueous solution usually gives and / or carbonate-containing materials that have to be thermally converted to zinc oxide.
  • the thermal aftertreatment has a negative effect on the fine particle size, since the particles are subjected to sintering processes that lead to the formation of micrometer-sized aggregates that can only be broken down incompletely onto the primary particles by grinding.
  • Nanoparticulate metal oxides can be obtained, for example, by the microemulsion process.
  • a solution of a metal alkoxide is added dropwise to a water-in-oil microemulsion.
  • the hydrolysis of the alkoxides to the nanoparticulate metal oxide then takes place in the inverse micelles of the microemulsion, the size of which is in the nanometer range.
  • the disadvantages of this process are in particular that the metal alkoxides are expensive starting materials, that additional emulsifiers have to be used and that the preparation of the emulsions with droplet sizes in the nanometer range is a complex process step.
  • the DE 199 07 704 describes a nanoparticulate zinc oxide produced by a precipitation reaction.
  • the nanoparticulate zinc oxide is produced from a zinc acetate solution via an alkaline precipitation.
  • the centrifuged zinc oxide can be redispersed to a sol by adding methylene chloride.
  • the zinc oxide dispersions produced in this way have the disadvantage that they do not have good long-term stability due to the lack of surface modification.
  • WO 00/50503 describes zinc oxide gels which contain nanoparticulate zinc oxide particles with a particle diameter of 15 15 nm and which are redispersible to sols.
  • the precipitates produced by basic hydrolysis of a zinc compound in alcohol or in an alcohol / water mixture are redispersed by adding dichloromethane or chloroform.
  • the disadvantage here is that no stable dispersions are obtained in water or in aqueous dispersants.
  • WO 93/21127 describes a process for producing surface-modified nanoparticulate ceramic powders.
  • a nanoparticulate ceramic powder is surface-modified by applying a low-molecular organic compound, for example propionic acid.
  • a low-molecular organic compound for example propionic acid.
  • This method cannot be used to modify the surface of zinc oxide because the modification reactions ions are carried out in aqueous solution and zinc oxide dissolves in aqueous organic acids. Therefore, this process cannot be used to produce zinc oxide dispersions; moreover, zinc oxide is not mentioned in this application as a possible starting material for nanoparticulate ceramic powders.
  • JP-A-04 164814 describes a process which leads to finely divided ZnO by precipitation in an aqueous medium at elevated temperature even without thermal aftertreatment.
  • the average particle size is given without specifying the degree of agglomeration, 20-50 nm. These particles are relatively large. Even with minimal agglomeration, this leads to scattering effects which are undesirable in transparent applications.
  • JP-A-07 232919 describes the production of 5 to 10,000 nm ZnO particles from zinc compounds by reaction with organic acids and other organic compounds such as alcohols at elevated temperature.
  • the hydrolysis takes place here in such a way that the by-products formed (esters of the acids used) can be distilled off.
  • the process allows the production of ZnO powders that can be redispersed by surface modification.
  • it is not possible to produce particles with an average diameter ⁇ 15 nm. Accordingly, in the examples listed in the application, the smallest average primary particle diameter is 15 nm.
  • Metal oxides which have been rendered hydrophobic with organosilicon compounds include described in DE 33 14 741 A1, DE 3642 794 A1 and EP 0 603 627 A1 and in WO 97/16156.
  • the object of the present invention was therefore to provide nanoparticulate metal oxides which allow the production of stable nanoparticulate dispersions in water or polar organic solvents and in cosmetic oils.
  • An irreversible aggregation of the particles should be avoided as far as possible so that a complex grinding process can be avoided.
  • nanoparticulate metal oxides the metal being selected from the group consisting of aluminum, cerium, Iron, titanium, zinc and zirconium, characterized in that the surface modification comprises a coating with polyaspartic acid.
  • polyaspartic acid encompasses both the free acid and the salts of polyaspartic acid, such as e.g. Sodium, potassium, lithium, magnesium, calcium, ammonium, alkylammonium, zinc and iron salts or mixtures thereof.
  • the surface coating used according to the invention for the nanoparticulate metal oxides preferably contains polyaspartic acid and / or its sodium salt.
  • a preferred embodiment of the surface-modified metal oxides according to the invention is characterized in that the surface coating contains polyaspartic acid with a molecular weight M w of 1000 to 100000, preferably 1000 to 20,000, particularly preferably 1000 to 7000, determined according to gel chromatography analysis.
  • a further advantageous embodiment of the metal oxides according to the invention is characterized in that the metal oxide particles have an average primary particle diameter of 5 to 10000 nm, preferably 10 to 200 nm, particularly preferably 10 to 50 nm, particle diameter determined by means of scanning and transmission electron microscopy.
  • preferred metal oxides are titanium dioxide and zinc oxide, particularly preferably zinc oxide.
  • the invention is based on the knowledge that a long-term stability of dispersions of the surface-modified metal oxides, in particular in cosmetic preparations, without undesirable pH changes in the storage of these preparations, can be achieved by surface modification of nanoparticulate metal oxides with polyaspartic acid and / or their salts.
  • Another object of the invention is a method for producing a surface-modified nanoparticulate metal oxide, the metal being selected from the group consisting of aluminum, cerium, iron, titanium, zinc and zirconium
  • a preferred embodiment of the process according to the invention is characterized in that the precipitation is carried out in the presence of polyaspartic acid with a molecular weight M w of 1000 to 100000, preferably 1000 to 20,000, particularly preferably 1000 to 7000, determined by gel chromatography analysis.
  • metal salts in process step a it can be metal halides, acetate, sulfates or nitrates.
  • Preferred metal salts are halides, for example zinc (II) chloride or titanium tetrachloride, and nitrates, for example zinc (II) nitrate.
  • the precipitation of the metal oxide in process step a. can be carried out at a temperature in the range from 20 ° C. to 100 ° C., preferably in the range from 25 ° C. to 40 ° C.
  • the precipitation can be carried out at a pH in the range from 3 to 13.
  • the pH during the precipitation is in the range from 7 to 11.
  • the concentration of the metal salts is generally in the range from 0.05 to 1 mol / l, preferably in the range from 0.1 to 0.5 mol / l, particularly preferably in the range from 0.2 to 0.4 mol / l ,
  • the precipitation time is generally 2 to 8 hours, preferably 3 to 7 hours, particularly preferably 4 to 6 hours.
  • the present invention relates in particular to a process for the production of surface-modified nanoparticulate zinc oxide by
  • the precipitation of the zinc oxide in process step a. can be done, for example, by metering in a mixture of polyaspartic acid and an alkali metal hydroxide or ammonium hydroxide, in particular NaOH, to the aqueous solution of zinc (II) chloride or Zn (II) nitrate or by simultaneously metering in each case an aqueous solution of zinc (II) chloride orZn ( ll) nitrate and an aqueous solution of an alkali metal hydroxide or ammonium hydroxide to an aqueous polyaspartic acid solution.
  • an alkali metal hydroxide or ammonium hydroxide in particular NaOH
  • the precipitated metal oxide can be separated from the aqueous reaction mixture in a manner known per se, for example by filtration or centrifugation.
  • the filter cake obtained can be dried in a manner known per se, for example in a drying cabinet at temperatures between 40 and 100 ° C., preferably between 50 and 70 ° C. under normal pressure to constant weight.
  • Another object of the present invention is a cosmetic agent which contains a zinc oxide or a zinc oxide dispersion surface-coated according to the invention.
  • the present invention furthermore relates to the use of surface-modified metal oxide, in particular titanium dioxide or zinc oxide, which are produced by the process according to the invention: for UV protection as an antimicrobial active substance
  • the surface-modified metal oxide in particular titanium dioxide or zinc oxide
  • the surface-modified metal oxide is redispersible in a liquid medium and forms stable dispersions. This is particularly advantageous because the dispersions produced from the zinc oxide according to the invention do not have to be redispersed before further processing, but rather can be processed directly.
  • the surface-modified metal oxide is redispersible in polar organic solvents and forms stable dispersions. This is particularly advantageous since it enables uniform incorporation into plastics or foils, for example.
  • the surface-modified metal oxide is redispersible in water and forms stable dispersions there. This is particularly advantageous, since it opens up the possibility of using the material according to the invention, for example, in cosmetic formulations, the elimination of organic solvents being a great advantage. Mixtures of water and polar organic solvents are also conceivable.
  • the surface-modified metal oxide particles have a diameter of 10 to 200 nm. This is particularly advantageous since good redispersibility is ensured within this size distribution.
  • the metal oxide nanoparticles have a diameter of 10 to 50 nm. This size range is particularly advantageous since, after redispersion of such zinc oxide nanoparticles, the resulting dispersions are transparent and therefore do not influence the color, for example when added to cosmetic formulations. In addition, this also offers the possibility of use in transparent films.
  • metal oxides especially titanium dioxide or zinc oxide are to be used as UV absorbers, it is advisable to use particles with a diameter of more than 5 nm, since below this limit the absorption edge is shifted into the short-wave range (L. Brus , J. Phys., Chem. (1986) 90, 2555-2560).
  • the present invention furthermore relates to a cosmetic agent which contains a metal oxide, in particular titanium dioxide and / or zinc oxide, which has been surface-modified according to the invention.
  • a cosmetic agent which contains a metal oxide, in particular titanium dioxide and / or zinc oxide, which has been surface-modified according to the invention.
  • Another advantage is that when applied to e.g. the skin does not rub due to the small particle size, but a gentle application is possible, which causes a pleasant feeling on the skin.
  • the cosmetic agent is used for the care or protection of the skin, in particular for sun protection or for care when exposed to sunlight, and is in the form of an emulsion, a dispersion, a suspension, an aqueous surfactant preparation, a milk, a lotion, a cream, a balm, an ointment, a gel, a granulate, a powder, a stick preparation such as a lipstick, a foam, an aerosol or a spray.
  • Suitable emulsions are oil-in-water emulsions and water-in-oil emulsions or microemulsions.
  • the use in sunscreen means that the UV-absorbing and skin-calming effects of zinc oxide, for example, can be used simultaneously.
  • the metal oxides modified according to the invention are very suitable for use in sunscreens, since the particles can be produced in a size which makes them appear transparent to the human eye. This means that there is no white veil on the skin during use.
  • Topical preparations are to be understood here as those preparations which are suitable for applying the active substances to the skin in a finely divided form and preferably in a form which can be absorbed by the skin. For this, e.g.
  • aqueous and aqueous-alcoholic solutions sprays, foams, foam aerosols, ointments, aqueous gels, emulsions of the O / W or W / O type, microemulsions or cosmetic stick preparations.
  • the agent contains a carrier.
  • the preferred carrier is water, a gas, a water-based liquid, an oil, a gel, an emulsion or microemulsion, a dispersion or a mixture thereof.
  • the carriers mentioned show good skin tolerance.
  • Aqueous gels, emulsions or microemulsions are particularly advantageous for topical preparations.
  • Nonionic surfactants, zwitterionic surfactants, ampholytic surfactants or anionic emulsifiers can be used as emulsifiers.
  • the emulsifiers can be contained in the composition according to the invention in amounts of 0.1 to 10, preferably 1 to 5,% by weight, based on the composition.
  • a surfactant from at least one of the following groups can be used as the nonionic surfactant: Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group;
  • polyglycerol esters such as e.g. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate. Mixtures of compounds from several of these classes of substances are also suitable;
  • Partial esters based on linear, branched, unsaturated or saturated C 6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerin, polyglycerol ⁇ pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, Butyl glucoside, lauryl glucoside) and polyglucosides (eg cellulose);
  • Zwitterionic surfactants can also be used as emulsifiers.
  • Zwitterionic surfactants are surface-active compounds that carry at least one quaternary ammonium group and at least one carboxylate or sulfonate group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylamino-propyl-N, N dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl- 3-carboxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the coconut acylaminoethyl hydroxyethyl carboxymethyl glycinate.
  • the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred.
  • Suitable emulsifiers are ampholytic surfactants.
  • Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C 8 , i8-alkyl or acyl group, contain at least one free amino group and at least one -COOH or -S0 3 H group in the molecule and are capable of forming internal salts.
  • ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylamino-butyric acids, N alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamido-propylglycines, N-alkyltaurines, N alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group.
  • ampholytic surfactants are the N-coconut alkyl aminopropionate, coconut acylaminoethyl aminopropionate and the C 12 / ⁇ a acyl sarcosine.
  • ampholytic emulsifiers quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.
  • alkyl ether sulfates, monoglyceride sulfates, fatty acid sulfates, sulfosuccinates and / or ether carboxylic acids can be used as anionic emulsifiers.
  • Suitable oil components are Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C 6 -C 22 fatty acids with linear C 6 -C 22 -Fettaikohoien, esters of branched C 6 -C 13 - Carboxylic acids with linear C 6 -C 22 fatty alcohols, esters of linear Ce-C ⁇ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C 6 -C ⁇ 0 fatty acids, liquid mono- / di-, Trigly- ceridmischept based on C 6 -C ⁇ 8 fatty acids, esters of C 6 -C 22 fatty alcohols and / or Guerbet alcohols with
  • Silicone compounds can also be used as oil bodies, for example dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, alkyl and / or glycoside-modified silicone compounds which can be both liquid and resinous at room temperature.
  • the oil bodies can be present in the agents according to the invention in amounts of 1 to 90, preferably 5 to 80, and in particular 10 to 50% by weight, based on the composition.
  • the composition according to the invention contains further UV light protection filters in the form of soluble compounds or other pigments.
  • the zinc oxide particles according to the invention may be used to create a sunscreen which achieves good UV absorption properties without further UV filter substances, it may be desirable in individual cases to add further UV to the cosmetic agent or the sunscreen. Add filter substances. This can e.g. be necessary if a special focus is to be placed on filter performance.
  • One or more further UV light protection filters can be added to the composition according to the invention.
  • UV light protection filters are to be understood as organic substances which are able to absorb ultraviolet rays and which absorb the energy in the form of longer-wave radiation, e.g. Warmth to give up again.
  • the organic substances can be oil-soluble or water-soluble.
  • oil-soluble UV-B filters e.g. the following substances are used:
  • 4-aminobenzoic acid derivatives preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate;
  • Esters of cinnamic acid preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4 methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isamyl ester, 4 methoxycinnamic acid isopentyl ester, 2-cyano-3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene);
  • esters of salicylic acid preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester;
  • benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
  • Esters of benzalmalonic acid preferably di-2-ethylhexyl 4-methoxybenzmalonate
  • Triazine derivatives such as 2,4,6-trianilino- (p-carbo-2 '-ethyl-r-hexyloxy) -1,3,5-triazine (octyl tyltriazone) and Dioctyl Butamido Triazone (Uvasorb HEB ®).
  • Propane-1,3-diones e.g. 1 - (4-tert-Butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione.
  • Sulfonic acid derivatives of benzophenones preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;
  • Sulfonic acid derivatives of 3-benzylidene camphor e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.
  • esters of cinnamic acid preferably 2-ethylhexyl 4-methoxycinnamate, isopentyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3-phenylcinnamate (octocrylene).
  • UV-A filters are:
  • benzoylmethane such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl-4'-methoxydibenzoylmethane or 1-phenyl-3 - (4'-Isopropylphenyl) propane-1,3-dione;
  • Amino hydroxy substituted derivatives of benzophenones such as e.g. N, N-diethylamino-hydroxybenzoyl-n-hexylbenzoate.
  • UV-A and UV-B filters can of course also be used in mixtures.
  • insoluble pigments e.g. finely dispersed metal oxides or salts such as titanium dioxide, iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (talc), barium sulfate and zinc stearate can be used.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm.
  • secondary light stabilizers of the antioxidant type can also be used, which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin.
  • Typical examples are superoxide dismutase, tocopherols (vitamin E) and ascorbic acid (vitamin C).
  • the total proportion of light stabilizers in the sunscreen according to the invention is usually 1 to 20, preferably 5 to 15% by weight.
  • the composition according to the invention as such can contain 1 to 95, preferably 5 to 80, and in particular 10 to 60% by weight of water.
  • the cosmetic composition according to the invention further contains nourishing substances, further cosmetic active ingredients and / or auxiliaries and additives.
  • Skin moisturizers, antimicrobial substances and / or deodorant or antiperspirant substances are used in particular as further cosmetic active substances. This has the advantage that further desired effects can be achieved which contribute to the care or treatment of the skin or, for example, increase the well-being of the user of the cosmetic composition when using this composition.
  • the cosmetic composition in addition to the carrier, the surface-modified zinc oxide, water and physiologically suitable solvents, can also contain, among other things, care ingredients, such as oils, waxes, fats, lipid-replenishing substances, thickeners, emulsifiers and fragrances.
  • a high proportion of nourishing substances is particularly advantageous for topical prophylactic or cosmetic treatment of the skin.
  • the composition also contains further care components.
  • the group of nourishing active ingredients that can be used includes, for example: fatty alcohols with 8-22 carbon atoms, especially fatty alcohols from natural fatty acids; animal and vegetable protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein, silk protein, oat protein, pea protein, almond protein and wheat protein hydrolysates; Vitamins and vitamin precursors, especially those of vitamin groups A and B; Mono-, di- and oligosaccharides; Plant extracts; Honey extracts; ceramides; phospholipids; Petroleum jelly, paraffin and silicone oils; Fatty acid and fatty alcohol esters, especially the monoesters of fatty acids with alcohols with 3 to 24 carbon atoms.
  • the vitamins, provitamins or vitamin precursors to be used preferably in the composition according to the invention include:
  • Vitamins, provitamins and vitamin precursors from groups A, C, E and F in particular 3,4-didehydroretinol, ß-carotene (provitamin of vitamin A), ascorbic acid (vitamin C), as well as the palmitic acid esters, glucosides or phosphates of ascorbic acid , Tocopherols, especially ⁇ -tocopherol and its esters, for example the acetate, nicotinate, phosphate, and succinate; also vitamin F, which is understood to mean essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid;
  • Vitamin A and its derivatives and provitamins advantageously show a special skin-smoothing effect.
  • the vitamins, provitamins or vitamin precursors of the vitamin B group or their derivatives and the derivatives of 2-furanone which are preferably to be used in the composition according to the invention include:
  • Vitamin common name thiamine, chemical name 3 - [(4'-amino-2'-methyl-5'-pyrimidinyl) methyl] -5- (2-hydroxyethyl) -4-methylthiazolium chloride.
  • Thiamine hydrochloride is preferably used in amounts of 0.05 to 1% by weight, based on the total agent.
  • Vitamin B 2 common name riboflavin, chemical name 7,8-dimethyl-10- (1-D-ribityl) -benzo [g] pteridine-2,4 (3H, 10H) -dione.
  • riboflavin comes e.g. B. in whey before, other riboflavin derivatives can be isolated from bacteria and yeast.
  • a stereoisomer of riboflavin which is also suitable according to the invention is lyxoflavin which can be isolated from fishmeal or liver and which carries a D-arabityl radical instead of D-ribityl.
  • Riboflavin or its derivatives are preferably used in amounts of 0.05 to 1% by weight, based on the total agent.
  • Vitamin B 3 The compounds nicotinic acid and nicotinamide (niacinamide) are often listed under this name. According to the invention, preference is given to nicotinamide, which is preferably present in the agents according to the invention in amounts of 0.05 to 1% by weight, based on the total agent.
  • Vitamin B 5 pantothenic acid and panthenol.
  • Panthenol is preferably used.
  • Derivatives of panthenol which can be used according to the invention are in particular the esters and ethers of panthenol and cationically derivatized panthenols.
  • derivatives of 2-furanone can also be used in addition to pantothenic acid or panthenol.
  • Particularly preferred derivatives are the dihydro-3 hydroxy-4,4-dimethyl-2 (3H) -furanone substances which are also commercially available.
  • pantolactone (Merck), 4 hydroxymethyl- ⁇ -butyrolactone (Merck), 3,3-dimethyl-2-hydroxy- ⁇ -butyrolactone (Aldrich) and 2,5-dihydro-5-methoxy-2-furanone (Merck) , with all stereoisomers expressly included.
  • the compounds of the vitamin B 5 type mentioned and the 2-furanone derivatives are preferably present in the agents according to the invention in a total amount of 0.05 to 10% by weight, based on the agent as a whole. Total amounts of 0.1 to 5% by weight are particularly preferred.
  • Vitamin B 6 which does not mean a uniform substance, but rather the derivatives of 5 hydroxymethyl-2-methylpyridin-3-ol known under the trivial names pyridoxine, pyridoxamine and pyridoxal. Vitamin B 6 is contained in the agents according to the invention preferably in amounts of 0.0001 to 1.0% by weight, in particular in amounts of 0.001 to 0.01% by weight.
  • Vitamin B 7 also known as vitamin H or "skin vitamin”.
  • Biotin is (3aS, 4S, 6aR) -2-oxohexahydrothienol [3,4-d] imidazole-4-valeric acid.
  • Biotin is contained in the agents according to the invention preferably in amounts of 0.0001 to 1.0% by weight, in particular in amounts of 0.001 to 0.01% by weight.
  • Panthenol, pantolactone, nicotinamide and biotin are very particularly preferred according to the invention.
  • Auxiliaries and additives are substances that are suitable for improving the aesthetic, application technology and / or cosmetic properties, such as 6.
  • auxiliaries and additives can be used:
  • Antioxidants advantageously improve the stability of the compositions according to the invention.
  • Antioxidants include amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazole and imidazole derivatives (e.g. urocanic acid), peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. Anserine), carotenoids, carotenes (eg.
  • octyl and dodecyl gallate flavonoids
  • catechins bilirubin
  • biliverdin and their derivatives unsaturated fatty acids and their derivatives (e.g. ⁇ -linolenic acid, linoleic acid, arachidonic acid, oleic acid), folic acid re and their derivatives, hydroquinone and its derivatives (e.g. arbutin), ubiquinone and ubiquinol as well as their derivatives, vitamin C and its derivatives (e.g.
  • vitamin A palmitate the coniferyl benzoate of benzoin, rutin, rutinic acid and its derivatives, disodium rutinyl disulfate, cinnamic acid and their derivatives (e.g. Ferulic acid, ethyl ferulate, caffeic acid), kojic acid, chitosan glycolate and - salicylate, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and their derivative ate, mannose and their derivatives, zinc and zinc derivatives (e.g. B. ZnO, ZnS04), selenium and selenium derivatives (e.g. selenium methionine), stilbene and stilbene derivatives (e.g. stilbene oxide, trans-stilbene oxide).
  • benzoin e.g. Ferulic acid, ethyl ferulate
  • suitable derivatives salts, esters, sugars, nucleotides, nucleosides, peptides and lipids
  • mixtures of these active substances or plant extracts e.g. tea tree oil, rosemary extract and rosemary acid
  • Preferred lipophilic, oil-soluble antioxidants from this group are tocopherol and its derivatives, gallic acid esters, flavonoids and carotenoids, and butylated hydroxytoluene / anisole.
  • water-soluble antioxidants are amino acids, e.g. B. tyrosine and cysteine and their derivatives and tannins, especially those of plant origin are preferred.
  • the total amount of the antioxidants in the cosmetic compositions according to the invention is 0.001-20% by weight, preferably 0.05-10% by weight, in particular 0.1-5% by weight and very particularly preferably 0.1-2% by weight. -%.
  • Triterpenes in particular triterpenic acids such as ursolic acid, rosmaric acid, betulinic acid, boswellic acid and bryonolic acid,
  • Monomeric catechins especially catechin and epicatechin, leukoanthocyanidins, catechin polymers (catechin tannins) and gallotannins,
  • Thickeners e.g. B. gelatin, vegetable gums such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum or locust bean gum, natural and synthetic clays and layered silicates, e.g. B. bentonite, hectorite, montmorillonite or Laponite ® , fully synthetic hydrocolloids such as polyvinyl alcohol, and also Ca, Mg or Zn soaps of fatty acids, Vegetable lycosides,
  • Structurants such as maleic acid and lactic acid
  • Solvents, swelling and penetration substances such as ethanol, isopropanol, ethylene glycol, propylene glycol, propylene glycol monoethyl ether, glycerin and diethylene glycol, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates
  • Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
  • Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate,
  • Blowing agents such as propane-butane mixtures, N 2 O, dimethyl ether, CO 2 and air.
  • the cosmetic composition according to the invention can contain minor amounts of further surfactants that are compatible with the other ingredients.
  • anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkylethersulfonates, glycerolethersulfonates, methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxymixed ether sulfates, sulfosate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfates, fatty acid sulfate sulfates, fatty acid
  • anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • nonionic surfactants are fatty alcohol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides or glucoronic acid derivatives, fatty acid-N-t-alkylacyl amides (especially vegetable hydrolysates), in particular hydrofluoric acid products (N-alkylactyls) Wheat base), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • cationic surfactants are quaternary ammonium compounds and ester quats, in particular quaternized fatty acid trialkanolamine ester salts.
  • amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
  • the cosmetic composition according to the invention is used as a sunscreen.
  • the use of the zinc oxide dispersions according to the invention is also particularly possible in hair cosmetics such as shampoos, conditioners, conditioners, hair lotions, hair gel, hair spray etc.
  • hair cosmetics such as shampoos, conditioners, conditioners, hair lotions, hair gel, hair spray etc.
  • leave-on products which remain on the hair or scalp after application are particularly suitable.
  • the zinc oxide applied to the scalp and hair in this way can thus also act as a UV protective agent there or develop its skin-soothing effect on the scalp.
  • the cosmetic agent is applied topically to the surface of the body to be treated or protected.
  • This form of application is particularly advantageous since it is easy to handle, so that incorrect dosing is largely excluded. Furthermore, an additional skin care effect can be achieved. If only individual parts of the body are exposed to solar radiation, the sunscreen can also only be applied specifically to these parts of the body.
  • Another object of the present invention is the use of the metal oxides surface-modified according to the invention for UV protection. This is particularly advantageous because, due to the fine particle size, for example of the surface-modified zinc oxide and the good distribution, a particularly high UV absorption is achieved.
  • Another object of the present invention is the use of the metal oxides surface-modified according to the invention, in particular zinc oxide as an antimicrobial active ingredient.
  • the use of these particles is particularly advantageous for this purpose, since due to the fine particle size and the resulting large surface area, the antimicrobial effect is greatly improved and, on the other hand, the zinc oxide is present in finely divided form due to the good dispersing properties of the material.
  • the zinc oxide can be used in various dosage forms such as creams, skin milk, lotions or tonics without any problems.
  • Another object of the present invention is a pharmaceutical agent which contains a surface-modified metal oxide according to the invention.
  • This pharmaceutical agent is characterized in that the pharmaceutical effectiveness is greatly increased due to the fine particle size of the particles.
  • the pharmaceutical according to the invention has the advantage that, due to the good long-term stability already described above, the zinc oxide dispersions, for example, do not require the addition of stabilizers which prevent segregation. This additionally increases the tolerance of the pharmaceutical agent.
  • 500 ml of a 0.4 M zinc nitrate solution were heated to 40 ° C.
  • 500 ml of a 0.8 M NaOH solution likewise heated to 40 ° C. and additionally containing 40 g / l polyaspartic acid, were metered in at 5 l / h with stirring.
  • the precipitate was stirred at 40 ° C for 4 hours.
  • the ZnO modified with polyaspartic acid was then filtered and dried at room temperature.
  • phase A and C were heated separately to approx. 85 ° C.
  • Phase C and the metal oxide were then stirred into phase A with homogenization.
  • the emulsion was cooled to room temperature with stirring and filled. All quantities are based on the total weight of the preparations.
  • Emulsion A comprising 3 wt .-% Uvinul ® T150 and 4 wt .-% of zinc oxide prepared according to Example 5
  • Example 8 Emulsion B containing 3 wt .-% Uvinul ® T150, 2 wt .-% Uvinul ® A Plus and 4 wt .-% of zinc oxide prepared according to Example 5
  • Emulsion A comprising 3 wt .-% Uvinul ® T150 and 4 wt .-% of zinc oxide prepared according to Example 2
  • Emulsion B containing 3% by weight of Uvinul ® T150, 2% by weight of Uvinul ® A Plus and 4% by weight of zinc oxide, prepared according to Example 2

Abstract

Oxydes métalliques nanoparticulaires à modification de surface, procédés de production desdits oxydes métalliques et leur utilisation en tant que filtres anti-UV dans des préparations cosmétiques.
EP05716391A 2004-03-31 2005-03-26 Oxydes metalliques a modification de surface, procedes de production desdits oxydes metalliques et leur utilisation dans des preparations cosmetiques Withdrawn EP1743002A2 (fr)

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DE200410016649 DE102004016649A1 (de) 2004-03-31 2004-03-31 Oberflächenmodifizierte Metalloxide, Verfahren zur Herstellung und deren Verwendung in kosmetischen Zubereitungen
DE200410020766 DE102004020766A1 (de) 2004-04-27 2004-04-27 Oberflächenmodifizierte Metalloxide, Verfahren zur Herstellung und deren Verwendung in kosmetischen Zubereitungen
PCT/EP2005/003217 WO2005094156A2 (fr) 2004-03-31 2005-03-26 Oxydes metalliques a modification de surface, procedes de production desdits oxydes metalliques et leur utilisation dans des preparations cosmetiques

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Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7309482B2 (en) * 2003-09-08 2007-12-18 E.I. Du Pont De Nemours And Company Long lasting waterproof sunscreen comprising metal oxide and peptide conditioner
FR2889529B1 (fr) * 2005-08-05 2008-07-25 Centre Nat Rech Scient Materiau mixte mineral/organique
DE102005046263A1 (de) * 2005-09-27 2007-03-29 Basf Ag Verfahren zur Herstellung oberflächenmodifizierter nanopartikulärer Metalloxide, Metallhydroxide, und/oder Metalloxidhydroxide
KR101370664B1 (ko) 2005-10-14 2014-03-04 비브 나노, 인코포레이티드 복합 나노입자, 나노입자 및 이의 제조방법
WO2007083174A1 (fr) * 2006-01-20 2007-07-26 Carlo Ghisalberti Pigments curatifs et maquillage comprenant ceux-ci
JP4999412B2 (ja) * 2006-09-20 2012-08-15 ポーラ化成工業株式会社 微粒子粉体及びその製造方法
US20100003203A1 (en) * 2006-10-11 2010-01-07 Basf Se Method of producing surface-modified nanoparticulate metal oxides, metal hydroxides and/or metal oxyhydroxides
CA2681153A1 (fr) * 2007-03-23 2008-10-02 Basf Se Procede de fabrication d'oxydes metalliques, hydroxydes metalliques et/ou oxydes-hydroxydes metalliques nanoparticulaires, modifies en surface
EP2146930A2 (fr) 2007-05-14 2010-01-27 INVISTA Technologies S.à.r.l. Réacteur et procédé à haut rendement
US20090092561A1 (en) * 2007-10-09 2009-04-09 Lupia Joseph A Body-care and household products and compositions comprising specific sulfur-containing compounds
KR100943043B1 (ko) 2008-02-05 2010-02-24 전북대학교산학협력단 산화철 나노입자가 봉입된 수용성 키토산-소수성 리놀레산복합체 자기-조립 나노입자, 이의 제조방법 및 이를포함하는 간질환 진단용 조영제
CN102099297B (zh) * 2008-07-18 2015-02-25 巴斯夫欧洲公司 改性氧化锌颗粒
JP2012503642A (ja) 2008-09-25 2012-02-09 バイブ ナノ， インコーポレイテッド ポリマーナノ粒子を製造する方法および活性成分の処方
WO2011058155A2 (fr) 2009-11-16 2011-05-19 Basf Se Nanocomposites d'oxyde métallique pour une protection contre les rayons uv
JP5649051B2 (ja) * 2010-03-31 2015-01-07 株式会社コーセー 微粒子金属酸化物分散組成物
AU2012311247B2 (en) 2011-08-23 2016-10-13 Vive Crop Protection Inc. Pyrethroid formulations
EP2793574A4 (fr) 2011-12-22 2015-09-02 Vive Crop Prot Inc Formulations de strobilurine
KR101642038B1 (ko) * 2016-01-21 2016-07-22 주식회사 브니엘월드 항균용기의 제조방법
KR101960678B1 (ko) 2016-11-10 2019-03-21 이주연 건물의 건축 방법
KR102167111B1 (ko) * 2017-07-28 2020-10-20 경희대학교 산학협력단 황칠나무 추출물을 포함하는 산화아연 나노복합체 제조용 조성물 및 이의 용도
US11517013B2 (en) 2017-08-25 2022-12-06 Vive Crop Protection Inc. Multi-component, soil-applied, pesticidal compositions
CN116437890A (zh) 2020-09-15 2023-07-14 三井化学株式会社 粉体化妆品及化妆品组合物
KR102551776B1 (ko) 2022-12-23 2023-07-05 주식회사 키움이엔지 각관들을 바탕으로 내진설계가 가능한 구조물 및 그 구조물의 시공 방법

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57145007A (en) * 1981-03-04 1982-09-07 Shiseido Co Ltd Preparation of modified inorganic powder
US4640943A (en) * 1983-09-22 1987-02-03 Ajinomoto Co., Inc. Surface modifier for inorganic substances
US5827508A (en) * 1996-09-27 1998-10-27 The Procter & Gamble Company Stable photoprotective compositions
US5756595A (en) * 1997-03-03 1998-05-26 Donlar Corporation Production of polysuccinimide in cyclic carbonate solvent
DE19822603A1 (de) * 1998-05-20 1999-11-25 Goldschmidt Ag Th Pigmentpasten enthaltend hydrophob modifizierte Polyasparaginsäurederivate
FR2789602B1 (fr) * 1999-02-17 2001-05-11 Rhodia Chimie Sa Sol organique et compose solide a base d'oxyde de titane et d'un compose amphiphile et procedes de preparation
US6174988B1 (en) * 1999-04-07 2001-01-16 National Starch & Chemical Company Use of polyamino acid salts in water-borne adhesive applications
DE10027948A1 (de) * 2000-06-08 2001-12-20 Henkel Kgaa Verfahren zur Herstellung von Nanopartikel-Suspensionen
DE10063090A1 (de) * 2000-12-18 2002-06-20 Henkel Kgaa Nanoskaliges ZnO in Hygiene-Produkten
AU2003244461A1 (en) * 2002-02-04 2003-09-02 The Circle For The Promotion Of Science And Engineering Organic substance having ferrite bonded thereto and process for producing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005094156A2 *

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AU2005227690A1 (en) 2005-10-13
WO2005094156A3 (fr) 2005-12-01
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US20070218019A1 (en) 2007-09-20
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