WO2001093822A2 - Dispersions aqueuses de filtres protegeant contre les ultraviolets a base de nanoparticules - Google Patents

Dispersions aqueuses de filtres protegeant contre les ultraviolets a base de nanoparticules Download PDF

Info

Publication number
WO2001093822A2
WO2001093822A2 PCT/EP2001/006076 EP0106076W WO0193822A2 WO 2001093822 A2 WO2001093822 A2 WO 2001093822A2 EP 0106076 W EP0106076 W EP 0106076W WO 0193822 A2 WO0193822 A2 WO 0193822A2
Authority
WO
WIPO (PCT)
Prior art keywords
light protection
protection filter
soluble
suspension according
water
Prior art date
Application number
PCT/EP2001/006076
Other languages
German (de)
English (en)
Other versions
WO2001093822A3 (fr
Inventor
Hans Dolhaine
Michael Neuss
Marcel Roth
Christine Schröder
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to AU2001276349A priority Critical patent/AU2001276349A1/en
Publication of WO2001093822A2 publication Critical patent/WO2001093822A2/fr
Publication of WO2001093822A3 publication Critical patent/WO2001093822A3/fr

Links

Classifications

    • 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
    • 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
    • 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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • 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
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • 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
    • 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
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • 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
    • 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
    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/652—The particulate/core comprising organic material

Definitions

  • the invention relates to aqueous suspensions of solid particles of light protection filters, the particles having an average diameter in the range from 10 to 500 nm and containing at least one light protection filter and preferably at least one surface modification agent.
  • Sun protection filters are substances that are able to absorb ultraviolet rays and to release the absorbed energy in the form of longer-wave radiation, eg heat.
  • a large number of substances of this type are known from the prior art and are used in particular in sunscreens, but also in other cosmetic products for hair and body care, in order to counteract the harmful effects of sunlight, such as erythema, hyperkeratosis, skin aging and in the worst case Counteract skin cancer.
  • a corresponding overview of suitable UV light protection filters has been published by P.Finkel in S ⁇ FW-Journal 122, 543 (1996); for the use of nanoparticulate inorganic light protection pigments, see C.Müller-Goymann et al.
  • sunscreens which have sufficient adhesive strength on the body surface and in particular good water resistance
  • light-protection filters which are sparingly soluble in water, which makes the formulation of these preparations considerably more difficult. This applies particularly to sunscreens based on O / W emulsions or other aqueous bases.
  • EP-B1 0 666 075 describes cosmetic or dermatological preparations for UV protection of the skin or hair which contain an aqueous dispersion of solid particles of a homopolymer filter with an average diameter between 10 and 400 nm.
  • a homopolymer filter In the homopolymer filter, UV-absorbing functional groups are chemically bound to a polymer structure.
  • Special polymer-bound light protection filters are therefore required to formulate such preparations, and the well-known conventional raw materials available on the market cannot be used.
  • organic solvents such as 1,2-dichloroethane is required to prepare the dispersions, which is toxicologically unsafe and undesirable for cosmetic purposes.
  • the invention relates to an aqueous suspension of solid particles of light protection filters, the particles having an average diameter in the range from 10 to 500 nm and contain at least one light protection filter and preferably at least one surface modification agent.
  • Sunscreen filters which can be used in the sense of the invention are to be understood as meaning oil-soluble or water-soluble substances which are solid at room temperature and which are able to absorb ultraviolet rays and absorb the energy absorbed in the form of longer-wave radiation, e.g. To give off heat again.
  • the light protection filters that can be used according to the invention are preferably meltable without decomposition and are present as monomers, i. H. they are not polymers. Depending on the absorption spectrum of the light protection filter, a distinction is made between UV-A, UV-B and broadband filters.
  • the UV-B filters can be oil-soluble or water-soluble. As oil-soluble substances such. B. To name:
  • 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives e.g. 3- (4-methylbenzylidene) camphor as described in EP-B1 0693471;
  • 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 isoamyl ester 2-cyano-3,3-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;
  • Esters of benzalmalonic acid preferably di-2-ethylhexyl 4-methoxybenzmalonate
  • Triazine derivatives such as, for example, 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine, octyl triazone, as described in EP-A1 0818450 , and Dioctyl Butamido Triazone (Uvasorb® HEB) ;
  • Propane-1,3-diones e.g. 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione;
  • Suitable water-soluble substances are:
  • Sulfonic acid derivatives of 3-benzylidene camphor e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and their salts.
  • benzoyl methane such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) prppan-1, 3-dione, 4-, are particularly suitable as typical UV-A light protection filters.
  • tert-Butyl-4'-methoxydibenzoyl-methane (Parsol 1789), or 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione.
  • UV-A, UV-B and broadband filters can of course also be used in mixtures.
  • the light protection filters in the form of the nanoparticulate suspension are oil-soluble.
  • Light protection filters are particularly preferably selected from the group formed by 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, 4-aminobenzoic acid derivatives, cinnamic acid esters, salicylic acid esters, benzalmalonic acid esters, benzophenone derivatives, benzoylmethane derivatives, triazine derivatives, propane-1,3 -diones, ketotricyclo (5.2.1.0) decane derivatives and mixtures thereof.
  • the light protection filter particles are coated with one or more surface modification agents.
  • Surface modification agents are understood to mean substances which physically adhere to the surface of the nanoparticles, but preferably do not react chemically with them.
  • the individual molecules of the surface modification agents adsorbed on the surface are essentially free of intermolecular bonds with one another.
  • Surface modifiers are to be understood in particular as dispersants. Dispersants are also known to the person skilled in the art, for example, under the terms emulsifiers, protective colloids, wetting agents and detergents.
  • Suitable surface modifiers are emulsifiers of the nonionic surfactant type from at least one of the following groups:
  • alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs
  • polyol and in particular polyglycerol esters such as polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate.
  • polyglycerol esters such as polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate.
  • Mixtures of compounds from several of these classes of substances are suitable;
  • partial esters based on linear, branched, unsaturated or saturated C 6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerin, polyglycerin, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, Lauryl glucoside) and polyglucosides (eg cellulose);
  • the adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or with castor oil are known, commercially available products. These are mixtures of homologs, the middle of which Degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out.
  • C 8 / i 8 alkyl mono- and oligoglycosides their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms.
  • glycoside residue both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to preferably about 8 are suitable.
  • the degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.
  • anionic emulsifiers are soaps, alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, alkyl ether sulfates such as, for example, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxymate ether sulfates, hydroxymate ether sulfates, hydroxymate sulfate ethersulfates, fatty acid sulfate amide sulfates, hydroxymate ether sulfate, fatty acid sulfate amate sulfate, hydroxymate ether sulfate, fatty acid ether sulfate, fatty acid ether sul
  • Zwitterionic surfactants can also be used as emulsifiers.
  • Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one 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 the cocoalkyldimethylammonium glycinate, N-acylamino-propyl-N, N-dimethylammonium glycinate, for example the cocoacylamino propyldimethylammonium glycinate, and 2 -Alkyl-3-carboxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
  • betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyldimethylammonium glycinate, N-acylamino-propyl-N, N-dimethylammonium
  • Suitable emulsifiers are ampholytic surfactants.
  • Ampholytic surfactants are surface-active compounds which, in addition to a Cs-alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO 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-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 C atoms in the alkyl group.
  • ampholytic surfactants are the N-coconut alkyl aminopropionate, the coconut acylaminoethyl aminopropionate and the C 2 / i 8 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.
  • Protective colloids suitable as surface modifiers are e.g. natural water-soluble polymers such as B. gelatin, casein, gum arabic, lysalbic acid, starch, albumin, alginic acid and their alkali and alkaline earth metal salts, water-soluble derivatives of water-insoluble polymeric natural substances such.
  • B. cellulose ethers such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose or modified carboxymethyl cellulose, hydroxyethyl starch or hydroxypropyl guar
  • synthetic water-soluble polymers such as.
  • surface modification agents which are selected from the group formed by the nonionic surfactants and mixtures thereof, addition products from 2 to 60 mol of ethylene oxide and castor oil and / or hardened castor oil, alkylmono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and polyalkylene glycols are to be understood.
  • the amount of surface modification agent with respect to the light protection filter corresponds at least to the amount that is required to provide a stable dispersion Obtain light protection filter nanoparticles. This minimum amount can be determined by simple routine tests.
  • light protection filters and surface modification agents are used in a weight ratio of 1:10 to 10: 1 and preferably 1: 2 to 2: 1.
  • the average diameter of the light protection filter particles in the suspensions is in the range from 20 to 150 nm.
  • the size specifications are to be understood as the diameter in the direction of the greatest longitudinal expansion of the particles.
  • particles are always obtained with a size that follows a distribution curve.
  • the method of dynamic light scattering known to the person skilled in the art can be used for the experimental determination of the particle size.
  • the suspensions contain, in addition to at least one oil-soluble, at least one water-soluble light protection filter, the water-soluble light protection filter preferably being selected from the group formed by 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium -, Alkylammonium, alkanolammonium and glucammonium salts, sulfonic acid derivatives of benzophenones, sulfonic acid derivatives of 3-benzylidene camphor and their mixtures.
  • the water-soluble light protection filter preferably being selected from the group formed by 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium -, Alkylammonium, alkanolammonium and glucammonium salts, sulfonic acid derivatives of benzophenones, sulfonic acid derivatives of 3-benzylidene camphor and their mixtures.
  • such light protection filter suspensions are particularly stable and, above all, particularly effective with regard to their UV-absorbing properties if at least some and particularly preferably the majority of the water-soluble light protection filters are part of the solid nanoparticulate particles are present. It is assumed that here molecules of the water-soluble light protection filter accumulate on the surface of the core from the oil-soluble light protection filters and, in the event that a surface modifier is additionally present in the suspension, the surface of the particles formed from the oil-soluble light protection filters partly by molecules of the surface modification agent and is partially surrounded by molecules of the water-soluble light protection filter. The high UV-absorbing effectiveness of such suspensions is attributed to a synergistic effect between the oil-soluble and the water-soluble light protection filters.
  • the majority of the water-soluble light protection filter is present in the suspension as a component of the solid nanoparticulate light protection filter particles.
  • the suspension contains benzophenone-3 as an oil-soluble light protection filter and 2-phenylbenzimidazole-sulfonic acid or one of its salts as a water-soluble light protection filter.
  • the proportion of oil-soluble light protection filters is preferably 70 to 100% by weight, based on the total amount of light protection filters contained in the solid nanoparticles.
  • the suspensions according to the invention contain 30 to 100% by weight and preferably 40 to 60% by weight of oil-soluble light protection filters, based on the total amount of the light protection filters contained in the suspensions.
  • suspensions according to the invention and / or the nanoparticulate light protection filter particles contained in the suspensions according to the invention can be produced by different processes.
  • the light protection filter is first in a suitable organic solvent, such as. B. an alkane, edible oil, alcohol, ether, ester, ketone or acetal dissolved.
  • a suitable organic solvent such as. B. an alkane, edible oil, alcohol, ether, ester, ketone or acetal dissolved.
  • This solution is then added to a non-solvent for the light protection filter, preferably water, a lower alcohol or mixtures of several non-solvents, if appropriate in the presence of a surface modifier dissolved therein, in such a way that the organic solvent and non-solvent are mixed together
  • a non-solvent for the light protection filter preferably water, a lower alcohol or mixtures of several non-solvents, if appropriate in the presence of a surface modifier dissolved therein, in such a way that the organic solvent and non-solvent are mixed together
  • This mixing is preferably carried out in a manner in which the organic solvent evaporates and is largely separated from the system.
  • the solvent can also
  • an O / W emulsion or O / W microemulsion can also be used, in which the oil component takes the place of the solution.
  • the surface modification agents already explained at the beginning can be used as surface-active compounds.
  • GAS process Gas Anti Solvent Recrystallization
  • the GAS process uses a highly compressed gas or supercritical fluid (eg carbon dioxide) as a non-solvent for the crystallization of solutes.
  • the condense The gaseous phase is introduced into the solution of the light protection filter in a suitable organic solvent, as described above, and absorbed there.
  • the volume of liquid increases, the solubility of the light protection filter decreases and it is separated in the form of fine particles.
  • the solvent is then removed before or after the addition of one or more non-solvents for the light protection filter, preferably water.
  • the PCA process (Precipitation with a Compressed Fluid Anti-Solvent) is also suitable.
  • a suitable organic solvent as described above, is injected into a supercritical fluid, such as carbon dioxide. This creates finely divided droplets in which diffusion processes take place, which lead to the precipitation of very fine particles.
  • the solvent is then removed before or after the addition of one or more non-solvents for the light protection filter, preferably water.
  • the light protection filter is melted by injecting gas (e.g. carbon dioxide or propane). Pressure and temperature reach near or supercritical values. The gas phase dissolves in the solid and causes a lowering of the melting temperature, the viscosity and the surface tension. When expanding through a nozzle, cooling effects lead to the formation of fine particles, which are then dispersed in one or more non-solvents for the light protection filter, preferably water.
  • gas e.g. carbon dioxide or propane
  • the light protection filter is placed in a pressure vessel, the reactor is closed and the supercritical solvent (CO 2 , ethylene, propane, ammonia, methanol, N 2 O, N 2 O 2 , SF 6 , Difluoromethane, trifluoromethane, water, toluene, etc., but preferably CO 2 ) pressed in while increasing the temperature until the desired supercritical Conditions are reached.
  • the supercritical solvent CO 2 , ethylene, propane, ammonia, methanol, N 2 O, N 2 O 2 , SF 6 , Difluoromethane, trifluoromethane, water, toluene, etc., but preferably CO 2
  • a surface modification agent can also be submitted together with the light protection filter.
  • the solution is expanded through a nozzle, with the formation of nanoparticles.
  • the expansion can take place in air, another gas or else into a liquid, for example water, which liquid in turn can contain a surface modifier in order to prevent undesirable caking of the particles.
  • the light protection filter is comminuted by grinding, for example in a vibrating mill, bead mill or stirred ball mill, using grinding media with an average diameter below 200 ⁇ m. Possibly. the grinding is carried out in the presence of a surface modifier.
  • the grinding process can be carried out dry or in one or more non-solvents for the light protection filter, preferably water.
  • the grinding process can also be carried out with cooling.
  • the light protection filter is placed in a liquid in which it is not soluble (non-solvent).
  • Water or mixtures of water and non-aqueous polar solvents such as, for example, ethanol, glycerol, ethylene glycol, propylene glycol or N-methylpyrrolidone, are suitable as non-solvents.
  • the mixture is then heated above the melting point of the light protection filter to form a two-phase system.
  • the liquid phase of the molten light protection filter is emulsified in such a way that very fine droplets of the desired size are formed.
  • the light protection filter and the non-solvent can be introduced together with the surface modification agent, melted and dispersed, or the melt of the light protection filter and surface modification agent can be mixed with the non-solvent.
  • the melt of the light protection filter can be mixed with a solution of the surface modification agent in the non-solvent and dispersed. After the emulsion has formed, it is cooled below the melting point of the light protection filter, a nanoparticulate suspension being formed.
  • the type and amount of the surface modification agents and the intensity and duration of the mechanical energy to be introduced for the emulsification are to be selected so that the particles of the dispersion obtain the desired size.
  • the respective parameters can be determined by simple routine tests.
  • the light protection filter is melted together with the surface modification agent.
  • the non-solvent is heated to a temperature above, preferably 5 to 10 ° C. above, the melting point of the light protection filter, preferably in the presence of a water-soluble light protection filter.
  • the melt of light protection filter and surface modification agent is then combined with the non-solvent and dispersed by introducing mechanical energy and then cooled below the melting point of the dispersed light protection filter.
  • the suspensions of nanoparticulate light protection filter particles according to the invention are preferably produced by the melt-emulsifying method.
  • the light protection filter together with the surface modification agent used, should be able to produce nanoparticles which are stably dispersible in water according to at least one of the production processes described above, wherein the average particle diameter of the nanoparticles is in the range from 10 to 500 nm.
  • the usable combinations of light protection filters and surface modification agents can be selected by simple routine tests.
  • the suspensions are preferably produced in such a way that the total amount of the light protection filters is 1 to 50 and particularly preferably 5 to 20% by weight, based on the total weight of the suspension.
  • the suspensions according to the invention are preferably used for the cosmetic treatment of the body, which is preferably a treatment of the skin and / or the hair, particularly preferably the skin, for protection against UV radiation.
  • the suspensions according to the invention are used to produce a preparation for the topical treatment of the skin and / or the hair.
  • Another object of the invention is thus a preparation for topical application to the body, comprising a suspension according to the invention as described above.
  • the cosmetic preparations according to the invention are preferably compositions for protecting human skin or hair against UV rays, preferably compositions for sun protection or make-up.
  • the cosmetic preparation is preferably an aqueous or aqueous-alcoholic solution, an emulsion, a dispersion, a lotion, a milk, a gel, a cream, a wax / fat mass, a stick preparation, a spray or a foam aerosol.
  • Cosmetic preparations are furthermore to be understood as means for cleaning and / or caring for the body, in the sense of the invention in particular the skin or the hair, wherein, in addition to the preparation forms described above, hair shampoos, hair lotions, hair styling agents, hair setting agents, foam baths and shower baths are also suitable , In hair treatment products, the light-protecting effect is directed towards the hair and / or the scalp.
  • the cosmetic preparations additionally comprise a physiologically compatible carrier.
  • the physiologically acceptable carrier comprises one or more adjuvants, such as are commonly used in such preparations, such as. B. thickeners, moisturizing and / or moisturizing substances, surfactants, emulsifiers, plasticizers, anti-foaming agents, fats, oils, waxes, silicones, sequestering agents, anionic, cationic, nonionic or amphoteric polymers, alkalizing or acidifying agents, alcohols, polyols , Softeners, adsorbents, electrolytes, blowing agents, organic solvents, preservatives, bactericides, antioxidants, fragrances, flavors, sweeteners, dyes, pigments and light stabilizers.
  • Light stabilizers are understood to mean substances which absorb or reflect UV radiation.
  • the former are also known under the name of light protection factors, light protection filters or UV filters and generally provide organic or liquid organic or liquid at room temperature Substances, while the latter include in particular the light protection pigments.
  • the cosmetic preparations according to the invention contain the suspension according to the invention of the solid particles of the light protection filter in such an amount that the total concentration of the light protection filters in the preparation is between 0.5 and 20% by weight, preferably between 5 and 15% by weight, based on the Total weight of the preparation.
  • the suspensions according to the invention can be produced economically and, on the other hand, show both good incorporability and stability in preparations and high UV-absorbing activity.
  • the nanoparticles contained in the dispersions according to the invention have a very large surface area, based on the amount of light protection filter used, so that UV absorption is particularly effective.
  • the nanoparticles When used in the form of the preparations according to the invention, the nanoparticles are deposited on the skin or hair due to their small particle size in such a way that they cover the surface in a very thin layer which on the one hand can efficiently absorb UV radiation and on the other hand through mechanical impacts are not easily removable. Since the nanoparticulate particles also agglomerate when the carrier evaporates or is drawn in, a film that adheres very well to the skin and is particularly waterproof is created.
  • the suspensions according to the invention can be used, for example, in purely aqueous preparations and also in emulsions. With the latter there is the possibility of an oil-soluble light protection filter in the oil phase, and a suspension of an oil-soluble light protection filter, optionally in combination with a water-soluble light protection filter, in the water phase to achieve a particularly high UV protection. It is understood that a plurality of different light protection filters can always be used in each case.
  • Neo Heliopan BB (Benzophenone-3) were mixed with 5.0 g Eumulgin HRE 455 (hardened castor oil with 40 mol ethylene oxide in propylene glycol / water) and 5.0 g Eumulgin RO 40 (castor oil with 35 to 40 mol ethylene oxide) melted at approx. 80 ° C. This melt was slowly dropped into 85.0 g of water at 65 ° C, stirred for about 5 minutes, and then cooled with a water bath at 20 ° C. A stable opaque suspension was obtained. In the light scattering, the suspended particles showed a maximum with a particle size of 80 nm with volumetric weighting.
  • Example 2 Preparation of a nanoparticulate suspension of benzophenone-3 and 2-phenylbenzimidazole sulfonic acid
  • Neo Heliopan BB (Benzophenone-3) were melted with 10.0 g Eumulgin RO 40 at approx. 70 ° C.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • General Engineering & Computer Science (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Biophysics (AREA)
  • Biotechnology (AREA)
  • Emergency Medicine (AREA)
  • Medical Informatics (AREA)
  • Medicinal Chemistry (AREA)
  • Molecular Biology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)

Abstract

L'invention concerne des dispersions aqueuses de particules solides de filtres protégeant contre les ultraviolets, les particules ayant un diamètre moyen compris entre 10 et 500 nm et contenant au moins un filtre protégeant contre les ultraviolets et, de préférence, au moins un agent de modification de surface. Les suspensions conviennent à la production de préparations cosmétiques, notamment de produits solaires, ayant un effet protecteur élevé contre les ultraviolets, une formulation très stable et une protection contre les ultraviolets très résistante à l'eau.
PCT/EP2001/006076 2000-06-08 2001-05-29 Dispersions aqueuses de filtres protegeant contre les ultraviolets a base de nanoparticules WO2001093822A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001276349A AU2001276349A1 (en) 2000-06-08 2001-05-29 Aqueous dispersions of nano-particulate uv-filters

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10027950.3 2000-06-08
DE2000127950 DE10027950B4 (de) 2000-06-08 2000-06-08 Wäßrige Suspension nanopartikulärer Lichtschutzfilter, Verfahren zu ihrer Herstellung sowie deren Verwendung und Zubereitungen

Publications (2)

Publication Number Publication Date
WO2001093822A2 true WO2001093822A2 (fr) 2001-12-13
WO2001093822A3 WO2001093822A3 (fr) 2002-06-06

Family

ID=7644844

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/006076 WO2001093822A2 (fr) 2000-06-08 2001-05-29 Dispersions aqueuses de filtres protegeant contre les ultraviolets a base de nanoparticules

Country Status (3)

Country Link
AU (1) AU2001276349A1 (fr)
DE (1) DE10027950B4 (fr)
WO (1) WO2001093822A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002080839A2 (fr) * 2001-04-06 2002-10-17 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Nouveaux agents photoprotecteurs et de soins pour la peau contenant des composants photoprotecteurs stabilises et reduisant les produits nocifs
US7754801B2 (en) 2005-12-30 2010-07-13 Columbia Insurance Company Translucent coating compositions providing improved UV degradation resistance
WO2017112992A1 (fr) * 2015-12-29 2017-07-06 Natura Cosméticos S.A. Composition de butylméthoxydibenzoylméthane, de diéthylaminohydroxybenzoylhexylbenzoate, d'éthylhexylsalycilate, d'homosalate et d'octrocrylène nanoencapsulée dans une nanostructure à film mince polymère

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2827510B1 (fr) * 2001-07-18 2005-07-01 Oreal Filtres uv organiques insolubles de type aryl vinylene cetone et leur utilisation en cosmetique
DE10261806A1 (de) * 2002-12-19 2004-07-01 Universität Potsdam Polymer-modifizierte Nanopartikel
BRPI0808405A2 (pt) * 2007-03-07 2014-07-15 Basf Se Usos de animais e amidas, composição comsmética, e, uso da composição cosmética
WO2012105060A1 (fr) * 2011-02-04 2012-08-09 L'oreal Pigment composite et son procédé de préparation
WO2014010101A1 (fr) 2012-07-13 2014-01-16 L'oreal Pigment composite et son procédé de préparation
JP6096898B2 (ja) 2012-07-13 2017-03-15 ロレアル 化粧料組成物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2303548A (en) * 1995-07-22 1997-02-26 Ciba Geigy Ag Solutions of UV absorbing 1,3,5 triazines
US5733531A (en) * 1991-02-05 1998-03-31 Sunsmart, Inc. Composite UV sunblock compositions
US5997888A (en) * 1996-12-13 1999-12-07 Vesifact Ag Cosmetic preparations
WO1999066896A1 (fr) * 1998-06-22 1999-12-29 Ciba Specialty Chemicals Holding Inc. Formulations de protection contre le soleil

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19856728B4 (de) * 1998-12-09 2004-04-22 Henkel Kgaa Verfahren zur Herstellung von Nanopartikeldispersionen
DE10016155A1 (de) * 1999-07-13 2001-01-18 Pharmasol Gmbh Mittel mit UV-Strahlung absorbierender und/oder reflektierender Wirkung zum Schutz vor gesundheitsschädlicher UV-Strahlung und Stärkung der natürlichen Hautbarriere

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5733531A (en) * 1991-02-05 1998-03-31 Sunsmart, Inc. Composite UV sunblock compositions
GB2303548A (en) * 1995-07-22 1997-02-26 Ciba Geigy Ag Solutions of UV absorbing 1,3,5 triazines
US5997888A (en) * 1996-12-13 1999-12-07 Vesifact Ag Cosmetic preparations
WO1999066896A1 (fr) * 1998-06-22 1999-12-29 Ciba Specialty Chemicals Holding Inc. Formulations de protection contre le soleil

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
G. MARTI-MESTRES ET AL.: "Effect of the addition of Oxybenzone or Octyl-methoxycinnamate on particle size of submicron emulsions" DRUG DEVELOPMENT AND INDUSTRIAL PHARMACY, Bd. 26, Nr. 3, 2000, Seiten 349-356, XP001058911 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002080839A2 (fr) * 2001-04-06 2002-10-17 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Nouveaux agents photoprotecteurs et de soins pour la peau contenant des composants photoprotecteurs stabilises et reduisant les produits nocifs
WO2002080839A3 (fr) * 2001-04-06 2003-09-04 Max Planck Gesellschaft Nouveaux agents photoprotecteurs et de soins pour la peau contenant des composants photoprotecteurs stabilises et reduisant les produits nocifs
AU2002256609B2 (en) * 2001-04-06 2006-08-31 Max-Planck-Gesellschaft Zur Forderung Der Wissenschaften E.V. Novel stabilising light-protection and skincare agents containing stabilised light-protection components and reduction of damaging light products
US7754801B2 (en) 2005-12-30 2010-07-13 Columbia Insurance Company Translucent coating compositions providing improved UV degradation resistance
WO2017112992A1 (fr) * 2015-12-29 2017-07-06 Natura Cosméticos S.A. Composition de butylméthoxydibenzoylméthane, de diéthylaminohydroxybenzoylhexylbenzoate, d'éthylhexylsalycilate, d'homosalate et d'octrocrylène nanoencapsulée dans une nanostructure à film mince polymère

Also Published As

Publication number Publication date
AU2001276349A1 (en) 2001-12-17
DE10027950B4 (de) 2007-05-03
WO2001093822A3 (fr) 2002-06-06
DE10027950A1 (de) 2001-12-20

Similar Documents

Publication Publication Date Title
DE69500034T2 (de) Lagerstabile, fluide und/oder fluidisierbare kosmetische Sonnenschutzmittel
DE69833739T2 (de) Kosmetisches Präparat
EP1743000B1 (fr) Oxydes metalliques a surface modifiee, procede pour les produire et leur utilisation dans des preparations cosmetiques
DE69500026T2 (de) Anti-UV kosmetische Mittel und Verwendungen
DE19933464A1 (de) Emulgatorfreie, disperse topische Zubereitungen
WO2001019945A1 (fr) Composition tensioactive contenant des tensioactifs gemini et des co-amphiphiles, sa production et son utilisation
DE3629241A1 (de) Uv-strahlung-filtrierende polyaminoamide, verfahren zu deren herstellung und verwendung derselben als haut- und haarschutz
EP0957886B1 (fr) Agents de protection contre le soleil, sous forme de micro-emulsions du type huile dans l'eau
DE102005025972A1 (de) Oberflächenmodifizierte Metalloxide, Verfahren zur Herstellung und deren Verwendung in kosmetischen Zubereitungen
WO2008122481A1 (fr) Agent de protection contre le rayonnement uv à base de systèmes mixtes minéraux-organiques
DE10327728A1 (de) Nanopartikuläres redispergierbares Zinkoxidpulver III
DE10027950B4 (de) Wäßrige Suspension nanopartikulärer Lichtschutzfilter, Verfahren zu ihrer Herstellung sowie deren Verwendung und Zubereitungen
DE19716070C2 (de) Sonnenschutzmittel
EP0813861B1 (fr) Compositions antisolaires sous forme de microémulsions huile-dans-eau
EP1567121B1 (fr) Poudre d'oxyde de zinc nanoparticulaire redispersible
EP2206489A1 (fr) Concentrés d'émulsions pouvant s'écouler
DE19632044A1 (de) Sonnenschutzmittel
EP1677742A1 (fr) Preparations pulverulentes contenant du diethylamino-hydroxybenzoyl-hexyl-benzoate
EP1337231B1 (fr) Utilisation de cires nanoparticulaires en cosmetique capillaire
DE19632043A1 (de) Sonnenschutzmittel
DE10055558A1 (de) Kosmetische Zusammensetzung zur Behandlung, zur Pflege oder zum Schutz der Haut
DE19952410B4 (de) Lichtschutzzubereitungen umfassend feste Lipidnanopartikel
DE20213787U1 (de) Hautpflegemittel
DE19645320B4 (de) Schaumförmige Lichtschutzzubereitungen mit einem Gehalt an wasserlöslichen Lichtschutzfiltersubstanzen und grenzflächenaktiven Substanzen und deren Verwendung
DE102007015757A1 (de) Kosmetische Zubereitung mit hydrophob modifizierten Polysacchariden und einem ionischen Wirkstoff

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AU BG BR BY CA CN CZ DZ HU ID IL IN JP KR MX NO NZ PL RO RU SG SI SK UA US UZ VN YU ZA

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
AK Designated states

Kind code of ref document: A3

Designated state(s): AU BG BR BY CA CN CZ DZ HU ID IL IN JP KR MX NO NZ PL RO RU SG SI SK UA US UZ VN YU ZA

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP