WO2005104213A2 - COSMETIC FORMULATIONS COMPRISING ZnO NANOPARTICLES - Google Patents
COSMETIC FORMULATIONS COMPRISING ZnO NANOPARTICLES Download PDFInfo
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- WO2005104213A2 WO2005104213A2 PCT/US2005/007779 US2005007779W WO2005104213A2 WO 2005104213 A2 WO2005104213 A2 WO 2005104213A2 US 2005007779 W US2005007779 W US 2005007779W WO 2005104213 A2 WO2005104213 A2 WO 2005104213A2
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- zinc oxide
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K51/00—Preparations containing radioactive substances for use in therapy or testing in vivo
- A61K51/12—Preparations containing radioactive substances for use in therapy or testing in vivo characterised by a special physical form, e.g. emulsion, microcapsules, liposomes, characterized by a special physical form, e.g. emulsions, dispersions, microcapsules
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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
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/11—Encapsulated compositions
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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
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
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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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
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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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
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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
- A61K8/91—Graft copolymers
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- 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
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- 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
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- 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
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- 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
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- 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
- C09C1/3684—Treatment with organo-silicon compounds
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- 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
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- 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
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/61—Surface treated
- A61K2800/62—Coated
- A61K2800/622—Coated by organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
Definitions
- Particulate surfaces, and in particular nanoparticle surfaces may be surface treated by star-graft copolymers to form uniform coatings according to the methods disclosed in US Patents 5,993,967 and 6,033,781, which are incorporated herein by reference.
- the present invention relates in particular to problems encountered when particulate zinc oxide, and in particular nanoparticulate zinc oxide, is formulated with charged organic moieties, such as acrylate-based polymers, ⁇ - and ⁇ -hydroxy acids, etc.
- Contemporary skin care formulations are dispersions.
- the charged organic moieties will reside in the aqueous phase ofthe dispersion and the inorganic ingredients, zinc oxide and titania, reside in the oil phase ofthe dispersion.
- a cosmetically acceptable base such as triethanol amine or sodium hydroxide, extend to thicken the formulation by increasing the viscosity ofthe aqueous phase.
- Other charged organic moieties such as ⁇ - and ⁇ -hydroxy acids, may have other functions such as enhancing epithelial cell regeneration.
- zinc ions from the particulate zinc oxide migrate from the oil phase to the aqueous phase and adversely interact with the charged organic moieties to either cause collapse ofthe acrylate-based polymers or the formation of organic salts with concomitant dissolution ofthe particulate inorganic.
- surface treatments for all inorganic, semi-metallic, and/or metallic oxide particles for all applications except (a) the product(s) per se, defined as surface treated ZnO and/or TiO 2 (titania), and (b) the use ofthe product(s) ?er se in personal care formulations.
- Personal care formulations are defined as cosmetic or dermatological preparations for skin care, hair care, foot care, sun care, oral care, baby care, toiletries, color cosmetics, personal cleaning, and topical human sunscreens.
- the present invention relates to the formation of surface treated zinc oxide and titania particles, and in particular zinc oxide and titania nanoparticles, with a siloxane star-graft copolymer coating, comprising a looped and/or linear polymeric structure on a star-graft copolymer coating, on a particle surface to control the interfacial surface interactions between the particle and the oil phase ofthe cosmetic skin formulation.
- a siloxane star-graft copolymer coating comprising a looped and/or linear polymeric structure on a star-graft copolymer coating, on a particle surface to control the interfacial surface interactions between the particle and the oil phase ofthe cosmetic skin formulation.
- the siloxane star-graft copolymer that may or may not contain topological loops, is formed in the "particle surface proximity" by a heterogeneous polymerization reaction.
- the resulting surface treatment will passivate the zinc oxide surface to prevent ion leakage and render the surface treated zinc oxide compatible with charged organic moieties, such as acrylate-based polymers and ⁇ - and ⁇ -hydroxy acids, etc.
- the surface treatment on zinc oxide and titania can be tailored to render the surface treated particle thermodynamically compatible with different oil phase components of a cosmetic skin formulation.
- Reactions that enable covalent bonding to particle surfaces generally involve reactions with a surface-bound hydroxyl group.
- These coatings are thin surface treatments which afford a degree of formulation and product compatibility and for the best available technology no particulate aggregation, but can not prevent ion migration from reactive particles or affect ultimate control of interfacial material properties.
- Particulate surfaces, and in particular nanoparticulate surfaces may be surface treated by siloxane star-graft copolymers to form uniform coatings according to the methods disclosed in US Patents 5,993,967 and 6,033,781 which are incorporated herein by reference. These uniform particulate surface treatments enable compatibility without particulate aggregation but they are subject to the limitations enumerated above.
- These star-graft copolymers may be formulated to have pendant groups that are reactive.
- difunctional monomers are graft copolymerized to form looped and/or linear chains.
- the star-graft copolymers may be applied to zinc oxide and/or titania particles, and in particular nanoparticles.
- the star-graft copolymer coatings are formed by reacting specific monomers to form a siloxane-based polymer.
- the surface treatment encapsulates the nanoparticulate zinc oxide and/or titania.
- a plurality of nanoparticle zinc oxide and/or titania is surface treated with the star-graft copolymer and the surface treatment encapsulates at least a portion ofthe particles discretely, preferably all ofthe particles discretely.
- the star-graft copolymer disclosed in US 5,993,967 and 6,033,781, comprises: Si (w, x, y, z) where w, x, y, and z are the mole percent tefrafunctional, trifunctional, difunctional, and monofunctional monomeric units, respectively and wherein w, x, y, and z ranges of about 45- 75, 5-25, 5-45, and 5-10, respectively.
- a star-graft copolymer capable of coating and encapsulating nanoparticles, required a relatively large percentage of tetrafunctional monomers to yield a high degree of branching.
- difunctional monomers directed coating conformation
- difunctional monomers were the linear polymer segments, and monofunctional monomers controlled the overall size
- difunctional monomers are polymerized to this star-graft polymer to form looped and/or linear polymer chains that extend from the particle surface into the solvating fluid or matrix structure, one skilled in the art would expect that a decrease the monofunctional monomer to enable the star-graft polymer surface treatment to retain functionality, and increase the difunctional monomers to form additional linear polymer segments would be yield the desired surface treatment.
- the present invention relates to a surface treated particle comprising a plurality of zinc oxide and/or titania particles and a star-graft copolymer with looped and/or linear polymeric structure on a star-graft copolymer encapsulating at least a portion of said particles, said surface treatment comprising:
- x is selected from the group of trifunctional monomers that have cosmetically acceptable non-reactive ligands comprising of methyltrimethoxysilane, n- propyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, n- octyltrimethoxysilane, n-octadecyltrimethoxysilane, phenyltrimethoxysilane, and the triethoxy-containing counterparts of these monomers; and y is selected from the group of difunctional monomers that have cosmetically acceptable non-reactive ligands comprising of dicyclohexyldimethoxysilane, diethyldiethoxysilane, dimethyldichlorosilane, dimethyldiethoxysilane, di
- x is selected from the group of n-octyltrimethoxysilane, n-octyltriethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane; and y is selected from the group of diphenyldiethoxysilane and diphenyldimethoxysilane.
- the values of x and y in the above silicon-based polymers have ranged from 1-50 and 50-99, respectively.
- the values of x and y in the above silicon-based polymers have ranged from 1-40 and 60-99, respectively.
- Most preferably the values of x and y in the above silicon-based polymers have ranged from 10-30 and 70-90, respectively.
- the surface treatment is applied to zinc oxide and/or titania particles, and in particular nanoparticles.
- the nanoparticle mean particle size range is from about 1 nm to about 900 nm.
- the preferred nanoparticle mean particle size range is from about 2 nm to about 500 nm.
- the most preferred nanoparticle mean particle size range is from about 5 nm to about 100 nm.
- the preferred method of preparing the surface treated zinc oxide and/or titania comprises mixing the particulate comprising substantially spherical nanocrystalline particles with surface treatment precursors.
- the siloxane star-graft copolymer that contains loops and/or linear polymer chains, is formed in the "particle surface proximity" by a heterogeneous polymerization reaction.
- the mixture is carried out at a temperature, in an environment, and for a time that is effective for the star-graft copolymer to coat the nanocrystalline particle and the difunctional precursors to polymerize to form the looped and/or linear chain surface treatment morphology. Volatile by-products may be driven off as the surface treated powder is heated.
- the nanoparticles and the coating precursor are added in quantities effective to enable chemically passive surface treatments that prevent ion leakage and render the surface treated zinc oxide compatible with charged organic moieties, such as acrylate-based polymers, ⁇ - and ⁇ -hydroxy acids.
- the amount of coating precursor used is directly related to the particle surface area or the particle size.
- the surface treatment contains predominantly phenyl chemistry.
- the surface treatment on zinc oxide and titania can be tailored to render the surface treated particle thermodynamically compatible with different oil phase components of a cosmetic skin formulation, by judicious selection of non- phenyl containing precursors.
- the surface treatment is applied to zinc oxide and/or titania particles, and in particular nanoparticles.
- the nanoparticle mean particle size range is from about 1 nm to about 900 n .
- the preferred nanoparticle mean particle size range is from about 2 nm to about 500 nm.
- the most preferred nanoparticle mean particle size range is from about 5 nm to about 100 nm.
- the values of x and y in the above silicon-based polymers have ranged from 1-50 and 50-99, respectively.
- the values of x and y in the above silicon-based polymers have ranged from 1-40 and 60-99, respectively.
- Most preferably the values of x and y in the above silicon-based polymers have ranged from 10-30 and 70-90, respectively.
- Various combinations are employed to control the branching ofthe siloxane backbone, the degree of looped and/or linear chains, and its chemical nature, that is, the degree of thermodynamic compatibility with specific oil phase components of a cosmetic skin formulation.
- the invention also relates to a method of protecting human skin or human hair from ultraviolet radiation comprising treating said skin or hair with an effective protecting concentration of a surface treated particle comprising a plurality of zinc oxide and/or titania particles and a star-graft copolymer with looped and/or linear polymeric structure on a star- graft copolymer encapsulating at least a portion of said particles, said surface treatment comprising: Si (x 5 y) where x and y are mole percent trifunctional and difunctional monomeric units, respectively and wherein x and y are about 1-50 and 50 - 99, respectively, wherein: x is selected from the group of trifunctional monomers that have cosmetically acceptable non-reactive ligands comprising of methyltrimethoxysilane, n- propyltrimethoxysilane, iso
- the surface treatment comprising: Si (x, y) wherein x and y are about 10-30 and 70-90, respectively, wherein: x is selected from the group of n-octyltrimethoxysilane, n-octyltriethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane, and y is selected from the group of n-octyltrimethoxysilane, n-octyltriethoxysilane.
- the said effective protecting concentration ranges between 0.1 %> and 25%) by weight, preferably between 0.1% and 10%>, particularly preferably between 1% and 7%, based on the total weight ofthe personal care formulation.
- the said personal care formulation comprises surface treated zinc oxide and/or titanium dioxide particles alone or together with compounds which absorb in the UV region and are known for cosmetic and pharmaceutical preparations.
- the present invention also relates to sunscreen-containing personal care formulations for protecting human skin or human hair from ultraviolet radiation, which comprises, in a cosmetically and pharmaceutically suitable carrier, an effective protecting concentration of a surface treated particle comprising a plurality of zinc oxide and/or titania particles and a star-graft copolymer with looped and/or linear polymeric structure on a star- graft copolymer encapsulating at least a portion of said particles, said coating polymer comprising:
- x is selected from the group of trifunctional monomers that have cosmetically acceptable non-reactive ligands comprising of methyltrimethoxysilane, n- propyltrimefhoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, n- octyltrimethoxysilane, n-octadecyltrimethoxysilane, phenyltrimethoxysilane, and the triethoxy-containing counterparts of these monomers;
- y is selected from the group of difunctional monomers that have cosmetically acceptable non-reactive ligands comprising of dicyclohexyldimethoxysilane, diethyldiethoxysilane, dimethyldichlorosilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, diphenyldimethoxysilane, di-n- hexyldichlorosilane, n-hexylmethyldichlorosilane, methyldodecyldiethoxysilane, n- octylmethyldimethoxysilane, and the diethoxy-containing counterparts of these monomers.
- x and y are about 10-30 and 70-90, respectively, wherein: x is selected from the group of n-octyltrimethoxysilane, n-octyltriethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane, and y is selected from the group of n-octyltrimethoxysilane, n-octyltriethoxysilane.
- the cosmetic and dermatological preparations according to the invention can comprise cosmetic active ingredients, auxiliaries and/or additives, for example, coemulsifiers, fats and waxes, stabilizers, thickeners, biogenic active ingredients, film formers, fragrances, dyes, pearlizing agents, preservatives, pigments, electrolytes (e.g. magnesium sulfate) and pH regulators.
- Suitable coemulsifiers are, preferably, known W/O and also O/W emulsifiers, such as, for example, polyglycerol esters, sorbitan esters or partially esterified glycerides.
- Typical examples of fats are glycerides; waxes which may be mentioned are inter alia beeswax, paraffin wax or microcrystalline waxes, optionally in combination with hydrophilic waxes.
- Stabilizers which may be used are metal salts of fatty acids, such as, for example, magnesium, aluminum and/or zinc stearate.
- suitable thickeners are crosslinked polyacrylic acids and derivatives thereof, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethylcellulose and hydroxyethylcellulose, and also fatty alcohols, monoglycerides and fatty acids, polycrylates, polyvinyl alcohol and polyvinylpyrrolidone.
- biogenic active ingredients means, for example, plant extracts, protein hydrolyzates and vitamin complexes.
- Customary film formers are, for example, hydrocolloids, such as chitosan, microcrystalline chitosan or quaternary chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers ofthe acrylic acid series, quaternary cellulose derivatives and similar compounds.
- suitable preservatives are formaldehyde solution, p-hydroxybenzoate or sorbic acid.
- suitable pearlizing agents are glycol distearic esters, such as ethylene glycol distearate, but also fatty acids and fatty acid monoglycol esters.
- Dyes which may be used are the substances suitable and approved for cosmetic purposes, as listed, for example, in the publication "Kosmetician mistakestoff" [Cosmetic Colorants] from the Farbstoffkommission der Deutschen Anlagenstician [Dyes Commission ofthe German Research Council], published by Verlag Chemie, Weinheim, 1984. These dyes are usually used in a concentration of from 0.001 to 0.1% by weight, based on the total mixture. It is likewise advantageous to add customary antioxidants to the preparations for the purposes ofthe present invention. According to the invention, all antioxidants which are customary or suitable for cosmetic and dermatological applications may be used as favorable antioxidants.
- the antioxidants are advantageously chosen from the group consisting of amino acids (e.g.
- glycine glycine, histidine, tyrosine, tryptophan
- imidazoles e.g. urocanic acid
- peptides such as D,L-carnosine, D-carnosine, L-
- carnosine and derivatives thereof e.g. anserine
- carotenoids e.g. carotenoids
- carotenes e.g. ⁇ -carotene, ⁇ -
- retinoids such as, for example, retinol, retinal
- retinoic acid and the respective esters, ⁇ -lipoic acid and derivatives thereof e.g.
- thiols e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl,
- dilauryl thiodipropionate distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), and sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, heptathionine sulfoximine) in very low tolerated doses
- sulfoximine compounds e.g. buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, heptathionine sulfoximine
- ⁇ -hydroxy acids e.g. citric acid, lactic acid, maleic acid
- humic acid bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives
- unsaturated fatty acids and derivatives thereof e.g. ⁇ -linolenic acid, linoleic acid,
- oleic acid folic acid and derivatives thereof, 2-aminopropionic acid diacetic acid, flavonoids, polyphenols, catechins, ubiquinone and ubiquinol and derivatives thereof, vitamin
- C and derivatives e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), and coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, ferulic acid and derivatives thereof, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacic acid, nordihyrdoguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, zinc and derivatives thereof, (e.g. ZnO, ZnSO.sub.4), selenium and derivatives thereof (e.g.
- antioxidants one or more compounds
- the amount of antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05 to 20% by weight, in particular 0.1 to 10%) by weight, based on the total weight ofthe preparation. If vitamin E and/or derivatives thereof are the antioxidant or antioxidants, it is advantageous to choose their respective concentrations from the range 0.001 to 10% by weight, based on the total weight ofthe formulation.
- vitamin A and/or derivatives thereof or carotenoids are the antioxidant or antioxidants, it is advantageous to choose the respective concentration thereof from the range 0.001 to 10% by weight, based on the total weight ofthe formulation.
- the solvents used may be: water or aqueous solutions; oils, such as triglycerides of capric acid or of caprylic acid, but preferably castor oil; fats, waxes and other natural and synthetic fatty substances, preferably esters of fatty acids with alcohols of low carbon number, e.g.
- the oil phase ofthe emulsions, oleogels or hydrodispersions or lipodispersions for the purposes ofthe present invention is advantageously chosen from the group of esters of saturated and/or unsaturated, branched and/or unbranched alkanecarboxylic acids with a chain length of from 3 to 30 carbon atoms and saturated and/or unsaturated, branched and/or unbranched alcohols with a chain length of from 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acids and saturated and/or unsaturated, branched and/or unbranched alcohols with a chain length of from 3 to 30 carbon atoms.
- ester oils can then advantageously be chosen from the group consisting of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, diisopropyl adipate, n-hexyl laurate, n-decyl oleate, glyceryl stearate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2- octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate, and synthetic, semisynthetic and natural mixtures of said esters, e
- the oil phase can advantageously be chosen from the group of branched and unbranched hydrocarbons and hydrocarbon waxes, silicone oils, dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and fatty acid triglycerides, namely the triglycerol esters of saturated and/or unsaturated, branched and/or unbranched alkanecarboxylic acids with a chain length of from 8 to 24, in particular 12-18, carbon atoms.
- the fatty acid triglycerides can, for example, be chosen advantageously from the group of synthetic, semisynthetic and natural oils, e.g.
- the oil phase is advantageously chosen from the group consisting of 2-ethylhexyl isostearate, isohexadecane, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2- ethylhexyl cocoate, C 12 -C ⁇ 5 -alkyl benzoate, caprylic/capric acid triglyceride, dicaprylyl ether.
- Oil components are also, for example, butyloctyl salicylate (for example that available under the trade name Hallbrite BHB from CP Hall), hexadecyl benzoate and butyloctyl benzoate and mixtures thereof (Hallstar AB) and/or diethylhexyl naphthalate (Hallbrite TQ).
- the oil phase can also advantageously have a content of cyclic or linear silicone oils, or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components apart from the silicone oil or the silicone oils.
- cyclomethicone octamethylcyclotetrasiloxane is used as silicone oil to be used according to the invention.
- silicone oils can also be used advantageously for the purposes ofthe present invention, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly(methylphenylsiloxane) .
- Mixtures of cyclomethicone and isotridecyl isononanoate, and of cyclomethicone and 2-ethylhexyl isostearate are also particularly advantageous.
- Solid sticks comprise, for example, natural or synthetic waxes, fatty alcohols or fatty acid esters. Preference is given to using lip care sticks, and stick formulations for deodorizing the body.
- Customary basic substances which are suitable for use as cosmetic sticks for the purposes ofthe present invention are liquid oils (e.g.
- Suitable propellants for cosmetic and/or dermatological preparations for the purposes ofthe present invention which can be sprayed from aerosol containers are the customary known readily volatile, liquefied propellants, for example hydrocarbons (propane, butane, isobutane), which can be used on their own or in a mixture with one another. Compressed air can also be used advantageously.
- Cosmetic preparations for the purposes ofthe present invention may also be in the form of gels which, besides an effective content of active ingredient according to the invention and solvents customarily used therefore, preferably water, also comprise organic thickeners, e.g.
- the thickener is present in the gel, for example, in an amount between 0.1 and 30% by weight, preferably between 0.5 and 15% by weight.
- the cosmetic and pharmaceutical preparations comprising light protection agents are generally based on a carrier which comprises at least one oil phase. Preparations based solely on aqueous components are, however, also possible.
- suitable preparations are oils, oil-in- water and water-in-oil emulsions, creams and pastes, lip-protection stick compositions or grease-free gels.
- Gels used according to the invention usually comprise alcohols of low carbon number, e.g. ethanol, isopropanol, 1,2-propanediol, glycerol and water or an abovementioned oil in the presence of a thickener, which in the case of oily-alcoholic gels is preferably silicon dioxide or an aluminum silicate, and in the case of aqueous-alcoholic or alcoholic gels is preferably a polyacrylate.
- the total proportion of auxiliaries and additives can be 1 to 80%) by weight, preferably 6 to 40% by weight, and the nonaqueous proportion ("active substance") can be 20 to 80%> by weight, preferably 30 to 70% by weight, based on the compositions.
- the compositions can be prepared in a manner known per se, i.e. for example by hot, cold, hot-hot/cold or PIT emulsification. This is a purely mechanical process, and no chemical reaction takes place.
- sunscreen preparations can accordingly be in liquid, paste or solid form, for example as water-in-oil creams, oil-in-water creams and lotions, aerosol foam creams, gels, oils, marking pencils, powders, sprays or alcohol-aqueous lotions.
- the surface treated particles can be added either to the oil or to the aqueous phase ofthe cosmetic preparation.
- further substances known per se which absorb in the UV region provided they are stable in the overall system ofthe combination of UV filters to be used according to the invention.
- the majority of light protection agents in the cosmetic and pharmaceutical preparations used to protect the human epidermis consists of compounds which absorb UV light in the UV-B region, i.e. in the range from 280 to 320 nm and UN-A region, i.e. in the range from 320 to 400 nm.
- the proportion ofthe UN-A absorbers to be used according to the invention is 10 to 90% by weight, preferably 20 to 50%) by weight, based on the total amount of UN-B and UN-A absorbing substances.
- Suitable UN filter substances which are used in combination with the formulations to be used according to the invention are any UN-A and UN-B filter substances. Examples which may be mentioned are:
- the cosmetic and dermatological preparations according to the invention can additionally advantageously comprise inorganic pigments based on metal oxides and/or other metal compounds which are insoluble or sparingly soluble in water, selected from the group consisting ofthe oxides of iron (e.g. Fe 2 O 3 ), zirconium (ZrO 2 ), silicon (SiO 2 ), manganese (e.g. MnO), aluminum (Al 2 O 3 ), cerium (e.g. Ce 2 O 3 ), mixed oxides ofthe corresponding metals, and mixtures of such oxides.
- iron e.g. Fe 2 O 3
- ZrO 2 zirconium
- silicon SiO 2
- manganese e.g. MnO
- Al 2 O 3 aluminum
- Ce 2 O 3 cerium
- mixed oxides ofthe corresponding metals and mixtures of such oxides.
- the inorganic pigments it is particularly advantageous, although not obligatory, for the inorganic pigments to be in coated form, i.e. to have been surface-treated.
- This surface treatment may involve for example providing the pigments with a thin hydrophobic layer by a method known per se, as described in DE-A-33 14 742.
- the light protection agent formulations according to the invention can be incorporated into shampoos, lotions, gels, hairsprays, aerosol foam creams or emulsions in concentrations of from 0.1 to 10% by weight, preferably 1 to 7% by weight.
- the respective formulations can inter alia be used for washing, coloring and for styling hair.
- the formulations to be used according to the invention are usually notable for a particularly high absorbance in the UN-A radiation region with a sharp band structure. Moreover, they are readily soluble in cosmetic oils and can easily be incorporated into cosmetic formulations.
- the emulsions prepared with the formulations are particularly notable for their high stability, the formulations I themselves are notable for their high photostability, and the preparations prepared therewith are notable for their pleasant feel on the skin.
- the UV filter action ofthe formulations according to the invention can also be utilized for stabilizing active ingredients and auxiliaries in cosmetic and pharmaceutical formulations.
- the preparations according to the invention are notable for particularly high absorbance in the UV-A radiation region with a sharp band structure and high light protection factors.
- Example 1 General Batch Process for Surface Treating Zinc Oxide and/or Titania Particles
- the method comprises introducing zinc oxide and/or titania particles comprising a plurality of nanoparticles into a surface treatment vessel that is capable of mixing and heating its contents under a controlled environment.
- suitable surface treatment vessels comprise a Buchi Rotovap (small scale available from Brinkmann Instruments), V-blender (commercial scale available from Patterson-Kelley), ribbon-blender (commercial scale available from Jaygo), rotary oven (commercial scale available from Thermal Processing Solutions), and a fluidized bed (commercial scale available from Littleford Day).
- the particles are introduced into the surface treatment vessel using methods known to those skilled in the art.
- Oxygen is removed from the vessel, typically by vacuum followed by inert gas flush, and the plurality of nanoparticles is mixed by methods such as, but not limited to, rotating the vessel or by rotating elements within the vessel.
- the particles are substantially spherical nanocrystalline nanoparticles and readily flow using standard unit operation methodologies.
- Particle mixing is carried out at a temperature, in an environment, and for a time that is effective at exposing particulate surface area to the environment ofthe surface treatment vessel enabling conditioning ofthe particle surface. Mixing may occur continuously, or at programmed intervals, and at a range of mixing rates. Mixing may occur at room temperature or at temperatures above or below room temperature depending on the chemistry ofthe surface treated particles.
- Particle surface conditioning comprises, but is not limited to, removing material sorbed to the particle surface, adding dopants to the particle surface, or a combination of conditioning steps. Particle surface conditioning may be accomplished by, but is not limited to, the following unit operations: vacuum treatment, plasma treatment, washing or flushing or fluidizing with a gas, fluid washing, reactive gas or fluid treatment, etc. In all instances reactive by-products and residues are removed prior to the application of surface treatment precursors.
- the particles are mixed with surface treatment precursors and heated in an environment, to a pre-determined temperature, and for a time effective for the star-graft copolymer to coat the nanocrystalline zinc oxide and/or titania particle and the difunctional precursors to polymerize to form the looped and/or linear chains on the star-graft copolymer.
- surface treatment particulate mixing enables continuous surface exposure and promotes application of a uniform surface treatment to the plurality of particles.
- the nanoparticles and the coating precursor are added in relative quantities effective to enable a personal care application.
- the amount of coating precursor used is directly related to the particle surface area or the particle size.
- Surface treatment sequences may include, but are not limited by, the followings process sequences: particle conditioning followed by surface treatment as in b) and c) above, multiple particle conditioning steps followed by surface treatment, particle conditioning followed by multiple surface treatment steps, sequential particle conditioning - surface treatment - particle conditioning - surface treatment steps, and others imagined by those skilled in the art.
- the particles may comprise a single composition or multiple compositions.
- Methods of introducing the surface treatment precursors may include, but are not limited by, fluid spray or vapor flow, employing any metered technique known to those skilled in the art.
- the surface treatment precursors may be introduced as a precursor mixture, as a precursor mixture followed by a single precursor, or by sequential single precursor additions.
- the surface treated particles are dried, if wet, cooled to room temperature, if reaction occurs at elevated temperature, and removed from the surface treatment vessel.
- Example 2 Batch Process for Surface Treating Zinc Oxide The following process description is for preparing surface treated zinc oxide particles.
- the surface treated zinc oxide is an active physical sunscreen ingredient for cosmetic formulations.
- the product is prepared by the batch process detailed in Example 1. a) 8-kg of zinc oxide nanoparticles, with a surface area of 14-m /g, is weighed into a plastic bag and manually charged into a clean, 2-ft 3 V-blender. Oxygen is removed by evacuating the V-blender to full vacuum level followed by vacuum relief of the V- blender with nitrogen. The evacuation and relieve cycle is repeated twice.
- the N-blender With the N-blender filled with inert gas, the N-blender is rotated at 5 RPM, and the N- blender is constantly flushed with nitrogen to condition the particles by removing sorbed materials.
- Diphenyldimethoxysilane (168 g) and octyltriethoxysilane (42 g) monomers are homogeneously mixed using a paddle mixer to form approximately a Si(0, 20, 80, and 0) surface treatment precursor mixture (210 g total weight).
- the surface treatment precursor mixture is introduced into the N-blender through a nozzle by inert pressure displacement and sprayed on the particles as the particles are mixing at room temperature.
- the temperature continues to ramp to 105 to 115°C.
- Particle mixing and vapor-phase transport enable surface treatment precursors to wet the particles and react to coat the nanocrystalline zinc oxide.
- the temperature is maintained at 105 to 115°C for 1-hour, e)
- the surface treated zinc oxide is dried by pulling a vacuum, while purging the vessel with inert gas, N 2 , on the surface treatment vessel. Vacuum removes un-reacted surface treatment precursors and reaction by-products.
- the temperature ofthe vessel is cooled to room temperature.
- the surface treated zinc oxide is removed from the vessel at room temperature.
- the surface treatment on the zinc oxide product when added to cosmetic formulation, prevents ion leakage and renders the surface treated zinc oxide compatible with charged organic moieties, such as acrylate-based polymers, ⁇ - and ⁇ -hydroxy acids.
- No other known commercial product or known surface treatment on zinc oxide particles enables the observed chemically passive behavior.
- the above batch process may be scaled to surface treat larger amounts of particles or rendered continuous, as will be recognized by persons skilled in the art, by employing continuous mixing and heating equipment and appropriate process modifications.
- Example 3 Specific Surface Treatment Examples 1) Physical sunscreen ingredients - Si(20, 80) / octyltriethoxysilane, diphenyldimethoxysilane; 4.3 wt% surface treatment precursor mixture applied to ZnO (23 m 2 /g). 2) Physical sunscreen ingredients - Si(20, 80) / octyltriethoxysilane, diphenyldimethoxysilane; approximately 9.4 wt%> surface treatment precursor mixture applied to TiO 2 (50 m 2 /g).
- Example 4 Cosmetic Formulations Surface treated zinc oxide nanoparticles, produced by methods disclosed above, were incorporated into the oil in water formulations given in Tables 1-20 using the procedure following each respective table. Table 1 - Formulation 1
- Formulation 4 Heat Phase A ingredients to 80°C 2. Add Phase B with Phase A and mix to form Mixture 1 using a homogenizer at 15000 rpm for 3 minutes 3. Mix Phase C ingredients and heat them to 80°C 4. Mix Mixture 1 and Phase C to form Mixture 2 using a homogenizer at 11000 rpm for 3 minutes Add Phase D ingredients to Mixture 2 to form Mixture 3 using a homogenizer at 11000 rpm 30sec-lmin 6. Cool Mixture 3 to room temperature under gentle planetary mixing 7. Stir Mixture 1 at 11000 rpm using a homogenizer for 30sec-lmin Table 5 - Formulation 5
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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CA002562047A CA2562047A1 (en) | 2004-04-06 | 2005-03-09 | Cosmetic formulations comprising zno nanoparticles |
EP05732993A EP1734915A2 (en) | 2004-04-06 | 2005-03-09 | COSMETIC FORMULATIONS COMPRISING ZnO NANOPARTICLES |
AU2005236840A AU2005236840B9 (en) | 2004-04-06 | 2005-03-09 | Cosmetic formulations comprising ZnO nanoparticles |
BRPI0509712-6A BRPI0509712A (en) | 2004-04-06 | 2005-03-09 | method of protecting human skin or human hair from ultraviolet radiation, personal care formulation containing sunscreen to protect human skin or human hair from ultraviolet radiation, and particulate surface treated |
JP2007507318A JP2007532541A (en) | 2004-04-06 | 2005-03-09 | Cosmetic preparations containing ZnO nanoparticles |
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US55985704P | 2004-04-06 | 2004-04-06 | |
US60/559,857 | 2004-04-06 | ||
US59213304P | 2004-07-30 | 2004-07-30 | |
US60/592,133 | 2004-07-30 |
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WO2005104213A2 true WO2005104213A2 (en) | 2005-11-03 |
WO2005104213A3 WO2005104213A3 (en) | 2006-09-21 |
WO2005104213B1 WO2005104213B1 (en) | 2006-11-09 |
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PCT/US2005/007779 WO2005104213A2 (en) | 2004-04-06 | 2005-03-09 | COSMETIC FORMULATIONS COMPRISING ZnO NANOPARTICLES |
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US (1) | US7182938B2 (en) |
EP (1) | EP1734915A2 (en) |
KR (1) | KR20070001262A (en) |
AU (1) | AU2005236840B9 (en) |
BR (1) | BRPI0509712A (en) |
WO (1) | WO2005104213A2 (en) |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5993967A (en) * | 1997-03-28 | 1999-11-30 | Nanophase Technologies Corporation | Siloxane star-graft polymers, ceramic powders coated therewith and method of preparing coated ceramic powders |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU715859B2 (en) * | 1996-04-04 | 2000-02-10 | Nanophase Technologies Corporation | Siloxane star-graft polymers, ceramic powders coated therewith and method of preparing coated ceramic powders |
US7303819B2 (en) * | 2004-04-06 | 2007-12-04 | Nanophase Technologies Corporation | Surface treatment of nanoparticles to control interfacial properties and method of manufacture |
-
2005
- 2005-03-09 AU AU2005236840A patent/AU2005236840B9/en not_active Ceased
- 2005-03-09 BR BRPI0509712-6A patent/BRPI0509712A/en not_active IP Right Cessation
- 2005-03-09 WO PCT/US2005/007779 patent/WO2005104213A2/en active Application Filing
- 2005-03-09 EP EP05732993A patent/EP1734915A2/en not_active Withdrawn
- 2005-03-09 US US11/074,760 patent/US7182938B2/en active Active
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Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5993967A (en) * | 1997-03-28 | 1999-11-30 | Nanophase Technologies Corporation | Siloxane star-graft polymers, ceramic powders coated therewith and method of preparing coated ceramic powders |
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US8785004B2 (en) | 2009-01-30 | 2014-07-22 | Hewlett-Packard Development Company, L.P. | UV light-emissive fluorene-based copolymers |
TWI465511B (en) * | 2009-01-30 | 2014-12-21 | Hewlett Packard Development Co | Block copolymers and block copolymer nanoparticle compositions |
WO2012084603A3 (en) * | 2010-12-22 | 2012-09-27 | Beiersdorf Ag | Cosmetic or dermatological uv protection preparations comprising a combination of polyacylate and polyacrylamide thickener |
EP3148440A4 (en) * | 2014-06-02 | 2018-01-03 | Turner Innovations, LLC | Radiation shielding and processes for producing and using the same |
Also Published As
Publication number | Publication date |
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AU2005236840B2 (en) | 2009-09-10 |
AU2005236840B9 (en) | 2009-12-10 |
WO2005104213B1 (en) | 2006-11-09 |
US7182938B2 (en) | 2007-02-27 |
EP1734915A2 (en) | 2006-12-27 |
AU2005236840A1 (en) | 2005-11-03 |
KR20070001262A (en) | 2007-01-03 |
BRPI0509712A (en) | 2007-09-18 |
US20050255057A1 (en) | 2005-11-17 |
WO2005104213A3 (en) | 2006-09-21 |
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