WO2005020940A1 - Kapsel deren kapselhülle bei topischer anwendung nicht mehr gesondert warhnembar ist - Google Patents
Kapsel deren kapselhülle bei topischer anwendung nicht mehr gesondert warhnembar ist Download PDFInfo
- Publication number
- WO2005020940A1 WO2005020940A1 PCT/EP2004/009563 EP2004009563W WO2005020940A1 WO 2005020940 A1 WO2005020940 A1 WO 2005020940A1 EP 2004009563 W EP2004009563 W EP 2004009563W WO 2005020940 A1 WO2005020940 A1 WO 2005020940A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- capsule
- filling
- cosmetic
- capsules
- shell
- 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.)
- Ceased
Links
- 0 *c1ccccc1C(c(c(O)c1)ccc1N(*)*)=O Chemical compound *c1ccccc1C(c(c(O)c1)ccc1N(*)*)=O 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/11—Encapsulated compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/31—Hydrocarbons
-
- 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
- A61K8/34—Alcohols
- A61K8/342—Alcohols having more than seven atoms in an unbroken chain
-
- 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
- A61K8/37—Esters of carboxylic acids
-
- 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
- A61K8/37—Esters of carboxylic acids
- A61K8/375—Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
-
- 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
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
-
- 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
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/925—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of animal origin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
Definitions
- the invention comprises cosmetic and dermatological preparations in the form of capsules comprising a capsule shell which is solid, semi-solid and / or dimensionally stable and essentially consists of waxes, emulsifiers, natural and / or synthetic polymers and / or mixtures thereof, and the process for their manufacture. Furthermore, the invention comprises a capsule with a filling consisting of one or more solid, semi-solid, pasty and / or liquid ingredients.
- the shell can additionally contain water and / or polyols.
- the property of the casing is characterized by the fact that • it melts when the preparation is rubbed and / or distributed onto the skin and / or the hair and / or becomes completely or partially liquid due to shear forces • and / or the filling and / or dissolves the skin sebum lipids or by mixing the inner phase and the wrapping material and so for the user no more than.
- the present component of the preparation is perceptible separately in addition to the filling.
- Pharmaceutical capsules are known from the prior art, for example soft or hard gelatin capsules, which consist of a shell made of gelatin and glycerol and occasionally dyes, and a liquid, pasty or particulate filling.
- the active ingredient is incorporated in the gelatin shell.
- nitroglycerin chewable capsules bits capsules
- biting capsules which also enable the active ingredient to be rapidly absorbed through the oral mucosa.
- single dosed drugs after piercing or slicing the tubular ointment capsules are applied by squeezing the contents (percutaneous application of nitroglycerin cardiac ointment).
- pralinees are known from the food sector, which contain liquid or pasty ingredients in a dimensionally stable chocolate shell.
- the shell melts in the mouth when sucking or biting or after swallowing.
- bath pearls In the cosmetics sector, so-called bath pearls are known, whose shell, e.g. made of gelatin, dissolves without residue in hot or warm bath water and releases their contents, for example surfactant preparations, emulsions, lipids, dyes and / or perfumes, into bath water. Since the shell is made of gelatin, the product must not contain water, otherwise the shell would soften during storage.
- a second group of cosmetic capsules includes all products for which the capsule shell is only a container for one-time dosing and application and the shell of which remains after use.
- the disadvantage of this is that the remaining shell is disruptive and must also be disposed of.
- the aim of such an encapsulation is, for example, to produce active ingredient-containing wax particles in the micrometer range (1 - 250 ⁇ m) which are to be incorporated into common pasty or liquid cosmetic preparations. It is not yet known to manufacture, store and use these microcapsules as an independent cosmetic preparation.
- DE 10210449 discloses wax-coated capsules which are loaded with an active ingredient. These capsules are produced using a so-called fluidized bed process, so that a maximum of 200 ⁇ m capsules can be produced.
- There are several approaches to encapsulating cosmetic active ingredients For example, liposomal encapsulation of drugs is known, which is said to lead to a delayed release of active ingredient.
- Nanoparticles are solid particles with particle sizes from 20 to 500 nm. Occasionally, larger particles with diameters up to 1000 nm are included in the nanoparticles. Such particles generally consist of polymers and have cavities or form a shell, so that guest molecules that are enclosed or adsorbed can remain in their interior. These guest molecules are then slowly released when the product containing the nanoparticles is used.
- Solid lipid nanoparticles which contain active substances distributed in a matrix of solid lipids, behave in a similar way. The size of the particles is comparable to that of the nanoparticles.
- EP 1064911 and EP 1064912 disclose active ingredient-containing microcapsules with a diameter of 0.1 to 5 mm, which are obtained by producing a matrix from gel formers, chitosan and active ingredient and dropping them into aqueous solutions of anionic polymers. A membrane is formed from chitosan and anionic polymer, which envelops the active ingredient solution. These microparticles are then in turn used as a component of common cosmetic preparations.
- General information on encapsulation techniques with chitosan can be found in Journal of Microencapsulation 14, pages 689-711 (1997).
- lipophilic active ingredients encapsulated in lipid particles are known per se to the person skilled in the art.
- EP 167825, DE 100 59 668, DE 199 45 203, EP 0934743, WO 94/20072, WO 00/10522 and WO 00/67728 describe lipid particles loaded with active substance.
- these writings could not solve the problem of providing capsule-like preparations with enclosed liquid, pasty or solid cosmetic ingredients which can be produced, stored and used topically as an independent cosmetic preparation.
- From DE 19852262, DE 9321186 and CH 692968 processes for the production of sweeteners, in particular chocolate articles, according to the so-called one-shot, frozen-cone or cold-stamp process are known. The methods described herein deal exclusively with the production of chocolate articles, chocolates.
- the object of the present invention is to provide a cosmetic preparation which is in the form of a solid, semi-solid or dimensionally stable capsule, so that it can be portioned individually and distributed as a whole on the skin.
- a cosmetic preparation which represents a new cosmetic product form and offers the user a new application experience and expands the range of applications of skin and / or hair care products.
- This bundle of tasks is solved by a cosmetic and / or dermatological preparation in capsule form according to the main requirements.
- Preferred embodiments of the preparation are disclosed in the subclaims.
- the invention also includes the method for applying the capsules to the skin and / or the hair, the method for their production and the combination with a blister pack and boxes for a cosmetic or dermatological product.
- a cosmetic and / or dermatological capsule for cosmetic and / or dermatological ingredients comprising a capsule shell which is solid, semi-solid and / or dimensionally stable and essentially consists of waxes, emulsifiers, natural and / or synthetic polymers and / or mixtures thereof.
- the capsule preferably comprises a filling consisting of one or more solid, semi-solid, pasty and / or liquid ingredients. It is further preferred that the capsule shell is solid, semi-solid and / or dimensionally stable shell up to a temperature of at least 35 ° C.
- the capsule shell optionally also contains water and / or polyols.
- the advantage and at the same time the property of the capsule according to the invention is that it • when rubbing and / or distributing the capsule on the skin and / or the hair melts and / or • it becomes completely or partially liquid due to shear forces and / or • the filling and / or the skin sebum lipids or by mixing the filling and Envelopes dissolves and so, especially for the user, is no longer perceptible, in particular as a component present separately from the filling.
- the capsule is advantageously completely absorbed when applied to the skin or hair without leaving any residue.
- the capsule shell of which remains after use according to the invention the capsule shell can remain completely on the skin, so that e.g. it is possible to incorporate active ingredients into the shell. This means that the capsule shell can make an active, nurturing contribution to the cosmetic and dermatological preparation and is not only used for packaging.
- capsules Many terms such as “spheres”, “capsules” or “capsule-like preparation” can in principle be used to describe the capsules according to the invention, but these terms may be assigned different meanings. In particular, the meaning of the term “capsule” is not specifically defined here
- the forms, manufacturing processes, ingredients and possible uses of the pharmaceutical preparations, which are also called “capsules”, are limited to, but include, etc.
- a capsule is, for example, an approximately round or ellipsoidal object which is clearly distinguishable from its surroundings and which can be touched with light pressure and, for example, by hand when it is removed from a packaging, its shape does not change, but other forms of the capsules or the preparations are also conceivable according to the invention, provided that the claimed features of the capsule, the capsule shell and the filling are observed.
- the capsule according to the invention comprises pre-portioned cosmetic products which consist of a solid or semi-solid shell and advantageously a filling.
- the term solid or semi-solid defines the state of the casing, corresponding to pharmaceutical technology.
- the rigid or semi-rigid shell can ideally also be called dimensionally stable.
- a capsule with a colloquially soft, wobbly or gelatinous shell is also according to the invention.
- the shell breaks, melts and / or dissolves when rubbed in and if necessary dissolves when distributed with the Ingredients of the filling on the skin or hair. This ensures that a preparation, for example as a cosmetic, can be applied to the skin or hair without disturbing residues.
- the capsules according to the invention have a size, i.e. average diameter, from 3, preferably 5, to 40 mm.
- the capsules can thus be handled and used individually.
- the capsule-like preparations according to the invention are stable in form of dragées, capsules, spheres or hollow spheres during storage and removal and only become liquid or dissolve when distributed. This is achieved by the special combination of the envelope or in combination with the capsule material.
- the capsule shell must be solid, semi-solid and / or dimensionally stable under storage conditions to which cosmetic products are usually exposed, that is to say that preferably the shape of the capsules according to the invention must not change during storage due to, for example, the influence of gravity or the temperature up to 35 Change ° C.
- the casings do not stick together during storage even if two capsules have been in contact for a long time. If this requirement is technologically impractical, the problem can be solved by individually repackaging each individual capsule, similar to an individual packaging (candy paper).
- the wrapping material must protect the filling from drying out during storage. This is especially true if the filling contains volatile substances such as water, short-chain alcohols (e.g. ethanol, isopropanol), perfumes and fragrances or low-boiling oils (e.g. cyclomethicone).
- volatile substances such as water, short-chain alcohols (e.g. ethanol, isopropanol), perfumes and fragrances or low-boiling oils (e.g. cyclomethicone).
- the wrapping material remains completely on the skin after use. According to the invention, it is of great importance that all raw materials from which the casing is constructed are very well tolerated by the skin. Ideally, they make a contribution to skin care, for example by strengthening the natural skin barrier and thus protecting the skin from drying out.
- the composition of the casing also has a significant influence on the skin feeling of the consumer when the preparations according to the invention are used: it is therefore advantageous to construct the casing from substances which, when used, give the skin a pleasant feeling, and the sensory properties of the casing and the filling are closely related vote.
- lipids which are liquid at room temperature or mixtures of lipids of different melting ranges which are liquid at room temperature by incorporating water droplets (production of a W / O emulsion) in such a way that the resulting W / O emulsion is solid enough even above room temperature to produce an envelope according to the invention.
- lipids, the melting point of which is close to the skin temperature of 32 ° C., that is to say between 30 ° C. and 40 ° C. can be used to produce such a casing according to the invention.
- a thixotropic preparation with a high yield point can be produced which meets the requirements for the described casing. It is obvious to the person skilled in the art that the approaches mentioned, use of a W / O or O / W emulsion, use of lipids with advantageous melting points, use of thixotropic systems with a suitable yield point, can be combined with one another in any way in order to further increase the properties of the casing optimize.
- the capsule shell is thus characterized by the property that • it melts when the preparation is rubbed and / or distributed onto the skin and / or the hair and / or • becomes completely or partially liquid due to shear forces and / or • the filling and / or the skin sebum lipids or by mixing the filling and wrapping material and so especially for the user is no longer perceptible as a separate component of the preparation besides the filling.
- balls, hollow balls, dragees or capsules according to the invention can be stored together in a package made of paper, metal or plastic etc. or individually or in groups of one another by means of further thin packaging similar to candy paper or in a blister packaging.
- a particular advantage is the combination of the capsule-like preparations with a blister pack, which separates the individual coated tablets or capsules from one another during storage and thus prevents individual capsules from being joined together, for example by improper handling.
- This can also be achieved by wrapping the individual coated tablets or capsules with thin sheets of paper, metal or plastic.
- the capsules can also be packed in tubes, e.g. made of polystyrene, or sealed in foil.
- foils made of cellophane, aluminum and paper plastic foils can also be used.
- PE degree of polymerization of 3000-4000
- Further options are push-through packs in which, for example, an aluminum foil is sealed onto a plastic film, or shrink packs.
- the capsules can also be placed in folding boxes, boxes, cans, or plastic bags, for example.
- Individual hollow spheres, coated tablets or capsules can be removed by simply removing them by hand. However, it is also possible to facilitate the removal of the capsules according to the invention by means of a suitable dispenser system. For this, e.g. individual hollow spheres, dragees or capsules are released from the dispenser system by actuating a simple mechanism. Examples of this are the dispenser systems for candies and other confectionery sold by PEZ International AG under the "PEZ" brand.
- dispenser systems are also advantageous in which the emulsion capsules are embedded in a screw shape in recesses on a round disk and can be removed individually by means of a metering mechanism.
- Particularly advantageous are designs which, in terms of their outer shape, are pronounced of known cosmetic products, for example the well-known NIVEA can, since this reduces the risk of confusion with food.
- individual coated tablets are removed and rubbed onto the skin. The product becomes less viscous and easy to distribute by melting, shearing or dissolving the solid or semi-solid shell or filling components and dissolves on or in the skin or hair.
- the casing and / or filling can certainly contain solid constituents, the dissolving of which is neither possible nor desirable during application, namely solids as are already used in conventional cosmetics, without the consumer noticing that they are in solid form Form.
- solid constituents the dissolving of which is neither possible nor desirable during application, namely solids as are already used in conventional cosmetics, without the consumer noticing that they are in solid form Form.
- these are fillers, light protection and color pigments.
- the user removes one or more of the capsules and rubs them on the skin, as is otherwise usual with skin cream from a can or tube.
- skin cream from a can or tube.
- the advantage of the capsules according to the invention is the convenient, simple, single use in between. Similar to the make-up or greasing of the lips, creaming or skin care on the go is also possible. In addition, the consumer can also offer individual capsules to other consumers. Although this is also possible with conventional cosmetic products, the joint use of, for example, a cream from one and the same crucible is psychologically equivalent to a physical touch. Therefore there is an inhibition threshold here which is eliminated by the present invention.
- capsules according to the invention with different properties (e.g. perfume, color, skin feel, sun protection factor, active ingredients, and combinations of these properties) in one package, which is not possible with conventional skin care products.
- properties e.g. perfume, color, skin feel, sun protection factor, active ingredients, and combinations of these properties
- the use of the capsules according to the invention is more fun for some users, especially children, than the use of conventional cosmetic products. This can make it easier for parents to protect their children from harmful environmental influences such as UV radiation.
- a major problem is the protection of cosmetic products from fungi, yeasts and bacteria that are present in the product during use reach. This is done primarily by the consumer touching the product during removal.
- the capsules according to the invention offer a further advantage here, since the consumer only touches those capsules which he immediately uses. The remaining capsules are thus protected against microbial attack, which is why, compared to conventional cosmetic products, lower levels of preservatives can be used. Since preservatives are among the less compatible cosmetic raw materials, improved compatibility of the products can be achieved, which represents a further advantage of the present invention.
- the capsule-like preparations according to the invention can have any shape, but they are preferably spherical with a volume of 0.1 to 20 ml.
- the casing is made up of waxes, emulsifiers, polymers or mixtures thereof, optionally additionally containing water and / or polyols.
- the shell has sufficient impact stability to withstand mechanical stress during manufacture and storage and is thin enough to dissolve quickly when applied.
- the shell thickness is preferably 0.001 to 3 mm, in particular thicknesses in the range of 0.01-2 mm.
- the use of water in proportions of 50% or 60% is also possible without any problems.
- the shell is advantageously built up from waxes such as ceresin, ozokerite, ester waxes, glycerol waxes and / or fatty alcohols and solid emulsifiers and mixtures thereof.
- the waxes can be natural waxes, modified natural waxes, partially synthetic or fully synthetic, depending on their origin.
- polymers can be incorporated into the shell. Suitable polymers are cellulose ethers, polyvinylpyrrolidone, polyacrylates or polymethacrylates, and Eudragit.
- the wrapping material according to the invention is preferably composed of waxes from the group of Natural waxes, particularly preferably carnau wax, candelilla wax, shellack wax, berry wax (Rhus Verniciflura), hydrogenated vegetable oils, such as hydrogenated palm or rapeseed oil, beeswax, wool wax (Eucerit)
- Natural waxes particularly preferably carnau wax, candelilla wax, shellack wax, berry wax (Rhus Verniciflura), hydrogenated vegetable oils, such as hydrogenated palm or rapeseed oil, beeswax, wool wax (Eucerit)
- Higher saturated fatty alcohols particularly preferably those with 14-30 carbon atoms, very particularly preferably stearyl alcohol and / or behenyl alcohol and / or cetyl alcohol
- esters preferably C16-36 alkyl hydroxystearoyl stearate, stearyl stearate, cetearyl behenate, C20-40 alkyl stearate, particularly preferably cetyl palmitate, methyl palmitate, methyl stearate, myristyl myristate, myristyl lactate, cetyl lactate, stearyl lactate
- Polymer waxes preferably polyethylene, polypropylene, polyvinyl ether, polydecene, particularly preferably polyvinyl stearyl ether and hydrogenated polydecene,
- Copolymers particularly preferably those made from ethylene and vinyl acetate and from polyvinylpyrrolidone and hexadecene,
- hydrocarbons / paraffin waxes particularly preferred, Gera Microcristallina, paraffin wax, ceresin, ozokerite • silicone waxes
- Envelope compositions which contain raw materials and / or raw material combinations with as sharp as possible melting points or narrow melting ranges at approximately 30 ° C. are advantageous.
- These can be individual substances such as • esters of C12-C24 fatty acids with short-chain alcohols (C1-C6), • esters of short-chain organic acids (C2-C6) with medium- or long-chain fatty alcohols (C12-C24) • esters of pyrrolidone carboxylic acid with medium or long chain fatty alcohols (C12- C24)
- the acids or alcohols mentioned can comprise additional groups, such as, for example, alkyl or hydroxy groups (for example lactic acid).
- eutectic mixtures with an appropriate eutectic temperature can also be used, e.g. Mixtures of hydrogenated coconut fat with wax esters (C12-C24 fatty acid esterified with C12-C24 fatty alcohol).
- suitable eutectic mixtures by examining the melting behavior of mixtures is known to the person skilled in the art.
- Waxes which are particularly preferred according to the invention for the production of the casing according to the invention are cetyl palmitate, cetyl ricinoleate, bees wax, hydrogenated coconut glycerides, methyl palmitate, methyl stearate, methyl stearate, ethyl stearate, myristyl lactate, cetyl lactate, stearyl lactate, glyceryl wax, camauba wax, tripotalmate malt, melamine wax, triphmate wax, parama wax wax, tripamate wax, parama wax wax, tripama wax, tripama , hydrogenated rapeseed oil and C15-C40 alkyl stearyl stearate.
- lipids is sometimes used as a generic term for fats, oils, waxes and the like, as is well known to the person skilled in the art.
- oil phase and “lipid phase” are also used synonymously.
- Waxes in the sense of the present invention advantageously have a melting point of 20 to 90 ° C, preferably a melting point of 25 to 80 ° C and particularly preferably a melting point of 30 to 70 ° C.
- solid substances can also be contained in the shell, which are present in solid form at all times (production, storage, application) (for example inorganic ganic pigments, lipid thickeners based on aerosil, hectorite, bentonite or mineral in general) or have broad melting ranges above 30 ° C (natural fats and waxes such as shea or coconut butter, camauba or candelilla wax, hardened fats such as hydrogenated coconut fat, microcrystalline waxes , Ceresine etc.).
- inorganic ganic pigments, lipid thickeners based on aerosil, hectorite, bentonite or mineral in general or have broad melting ranges above 30 ° C (natural fats and waxes such as shea or coconut butter, camauba or candelilla wax, hardened fats such as hydrogenated coconut fat, microcrystalline waxes , Ceresine etc.).
- the filling can consist of a water-containing medium, for example an emulsion (o / w, w / o, w / o / w), a gel, a microemulsion or a hydrodispersion.
- the filling material can consist of all substances and preparations known in cosmetics, in particular O / W or W / O / W emulsions in the form of creams or aqueous gels are advantageous.
- the shell consists of a W / O emulsion and / or waxes and. Filling from O / W emulsions, water-containing compositions, hydrogels and / or hydrocolloids. This selection reduces the possible mixing of shell and filling components.
- the casing and filling can independently of one another contain the usual auxiliaries and additives which are of course known to the person skilled in the art.
- the additives can be present independently of one another in the casing and / or in the filling.
- dyes can thus only be introduced into the shell without changing the filling components and nevertheless achieving appealing aesthetic effects.
- the cosmetic preparations according to the invention can therefore contain both in the casing and in the filling cosmetic auxiliaries, as are usually used in cosmetics, for example preservatives, bactericides, deodorising substances, antiperspirants, insect repellents, vitamins, agents for preventing foaming, dyes, Pigments with a coloring effect, flavors, denaturants, perfumes, thickeners, softening substances, moisturizing and / or moisturizing substances, antioxidants, UV filter substances, sensor additives, film formers, surfactants, emulsifiers, fats, oils, waxes, active substances or other common components of a cosmetic Formulation such as alcohols, polyols, stabilizing polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.
- a cosmetic Formulation such as alcohols, polyols, stabilizing polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.
- O / W emulsifiers are O / W emulsifiers.
- O / W emulsifiers can, for example, advantageously be selected from the group of the polyethoxylated or polypropoxylated or polyethoxylated and polypropoxylated products, for example: the fatty alcohol ethoxylates - the ethoxylated wool wax alcohols, the polyethylene glycol ethers of the general formula R-0 - (- CH 2 - CH 2 -0-) n -R ⁇ of the fatty acid ethoxylates of the general formula R-COO - (- CH 2 -CH 2 -0-) n -H, the etherified fatty acid ethoxylates of the general formula R-COO - (- CH 2 -CH 2 -0-) n -R ', the esterified fatty acid ethoxylates of the general formula R-COO - (- CH 2 -CH 2 -0-
- the polyethoxylated or polypropoxylated or polyethoxylated and polypropoxylated O / W emulsifiers selected are particularly advantageously selected from the group of substances with HLB values of 11-18, very particularly advantageously with HLB values of 14.5-15. 5, provided the O / W emulsifiers have saturated radicals R and R '. If the O / W emulsifiers have unsaturated radicals R and / or R ', or if isoalkyl derivatives are present, the preferred HLB value of such emulsifiers can also be lower or higher.
- fatty alcohol ethoxylates from the group of the ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols).
- Particularly preferred are: polyethylene glycol (13) stearyl ether (steareth-13), polyethylene glycol (14) stearyl ether (steareth-14), polyethylene glycol (15) stearyl ether (steareth-15), polyethylene glycol (16) stearyl ether (steareth-16) ), Polyethylene glycol (17) stearyl ether (Steareth-17), polyethylene glycol (18) stearyl ether (Steareth-18), polyethylene glycol (19) stearyl ether (Steareth-19), polyethylene glycol (20) stearyl ether (Steareth-20),
- Polyethylene glycol (12) lauryl ether (Laureth-12), polyethylene glycol (12) isolauryl ether (Isolaureth-12).
- fatty acid ethoxylates from the following group: polyethylene glycol (20) stearate, polyethylene glycol (21) stearate, polyethylene glycol (22) stearate, polyethylene glycol (23) stearate, polyethylene glycol (24) stearate, polyethylene glycol (25) stearate,
- the sodium laureth-11-carboxylate can advantageously be used as the ethoxylated alkyl ether carboxylic acid or its salt.
- Sodium laureth 1-4 sulfate can advantageously be used as alkyl ether sulfate.
- Polyethylene glycol (30) cholesteryl ether can advantageously be used as the ethoxylated cholesterol derivative.
- Polyethylene glycol (25) soyasterol has also proven itself.
- polyethylene glycol glycerol fatty acid esters from the group polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, polyethylene glycol (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate, polyethylene glycol (6) glyceryl capethylene / caprinate ) glyceryl oleate, polyethylene glycoi (20) glyceryl isostearate, polyethylene glycol (18) glyceryl oleate / cocoat to choose.
- sorbitan esters from the group consisting of polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate, polyethylene glycol (20) sorbitan monoisostearate, polyethylene! Englycol (20) sorbitan monopalmitate, polyethylene glycol (20) sorbitan monooleate.
- O / W emulsifiers are triceteareth-4-phosphate, polyglyceryl-3-methylglucose distearate, polyethylene glycol-40 stearate, glyceryl stearate citrate, ceteareth-20, ceteareth-2, cethyl-dimethicone copolyol; Wool wax alcohol, methyl glucose sesquearate, PEG-PPG block polymers (Pluronics F68 / 127), cetearyl glucoside, stearic acid.
- W / O emulsifiers that can be used are: fatty alcohols with 8 to 30 carbon atoms, monoglycerol esters of saturated and / or unsaturated, branched or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12 to 20 carbon atoms, diglycerol esters of saturated and / or unsaturated, branched or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12 to 20 carbon atoms, monoglycerol ethers of saturated and / or unsaturated, branched or unbranched alcohols with a chain length of 8 to 24, in particular 12 to 20 carbon atoms, diglycerol ethers saturated and / or unsaturated, branched or unbranched Alcohols with a chain length of 8 to 24, especially 12 to 20 carbon atoms, polypropylene glycol esters of saturated and / or unsaturated, branched or unbranched alkane carboxylic acids with a chain length
- Preferred W / O emulsifiers are branched or unbranched, saturated or unsaturated fatty acids with 12 to 26 carbon atoms, polyglyceryl-3 diisostearate, polyglyceryl-4 isostearate, polyglyceryl-2 dipolyhydroxystearate, cetyl PEG / PPG-10-1-dimethicone, PEG-30 dipolyhydroxystearate, PEG-40 Sorbitanperisostearat, Cetyldi- methiconecopolyol, PEG-7 Hydrogenated Castor Oil, PEG 45 / dodecyl, PEG 22 / Dodeceylglycolcopolymer, Pentaerythritylisostearat, Isostearyldiglycerylsuccinat, sorbitan isostearate, polyglyceryl-2 Sesquiisostearat, glyceryl isostearate, sorbitan stearate, glyceryl stearate, PEG
- W / O emulsifiers are polyethylene glycol 45 / dodecyl glycol copolymer, polyglyceryl 3-diisostearate, PEG-30 dipolyhydroxystearate, sorbitan isostate, sorbitan stearate, glyceryl isostearate, glyceryl stearate and sorbitan oleate.
- the oil phase of the formulations according to the invention is advantageously selected from the group of polar oils, for example from the group of lecithins and fatty acid triglycerides, in particular the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12 to 18 carbon atoms.
- the fatty acid triglycerides can for example be advantageously selected from the group of synthetic, semi-synthetic and natural oils, such as. B.
- cocoglyceride olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grape seed oil, safflower oil, evening primrose oil, macadamia nut oil and the like.
- further advantageous polar oil components can also be selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms and from the group of esters from aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms.
- ester oils can then advantageously be selected from the group octyl palmitate, octyl co-coat, octyl isostearate, octyl dodeceyl myristate, octyl dodecanol, cetearyl isononanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-stonolate, n-stonolate, n-stonyl-n-stonate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, stearyl heptanoate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate
- the oil phase can advantageously be selected from the group of dialkyl ethers and dialkyl carbonates.
- oil components from the group of isoeikosan, neopentyl glycol diheptanoate, propylene glycol dicaprylate / dicaprate, caprylic / capric / diglyceryl succinate, butylene glycol dicaprylate / dicaprate, C 12-13 alkyl lactate, di-C 12-13 aryl - rin, dipentaerythrityl hexacaprylate / hexacaprate, propylene glycol monoisostearate, tricapryline, dimethyl isosorbide. It is particularly advantageous if the oil phase of the formulations according to the invention has a content of C 12-15 -alkyl benzoate or consists entirely of this.
- Advantageous oil components are also e.g. B. butyl octyl salicylate (for example, available under the trade name Hallbrite BHB), hexadecyl benzoate and butyl octyl benzoate and mixtures thereof (Hallstar AB) and / or diethyl hexyl naphthalate (Hallbrite TQ or Corapan TQ from H&R).
- B. butyl octyl salicylate for example, available under the trade name Hallbrite BHB
- hexadecyl benzoate and butyl octyl benzoate and mixtures thereof Hallstar AB
- Hallbrite TQ or Corapan TQ from H&R diethyl hexyl naphthalate
- the oil phase can also advantageously also contain nonpolar oils, for example those which are selected from the group of branched and unbranched hydrocarbons and waxes, in particular mineral oil, petroleum jelly (petrolatum), paraffin oil, squalane and squalene, polyolefins, hydrogenated polyisobutenes and Isohexadecane.
- nonpolar oils for example those which are selected from the group of branched and unbranched hydrocarbons and waxes, in particular mineral oil, petroleum jelly (petrolatum), paraffin oil, squalane and squalene, polyolefins, hydrogenated polyisobutenes and Isohexadecane.
- polyolefins polydecenes are the preferred substances.
- the oil phase can also advantageously contain 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 in addition to the silicone oil or the silicone oils.
- Silicone oils are high-molecular synthetic polymeric compounds in which silicon atoms are linked in a chain and / or network-like manner via oxygen atoms and the remaining valences of silicon by hydrocarbon residues (mostly methyl, more rarely ethyl, propyl, phenyl groups) are saturated).
- the silicone oils are systematically referred to as polyorganosiloxanes.
- the methyl-substituted polyorganosiloxanes which are the most important compounds of this group in terms of quantity and are characterized by the following structural formula
- Dimethicone is available in different chain lengths or with different molecular weights.
- Particularly advantageous polyorganosiloxanes for the purposes of the present invention are, for example, dimethylpolysiloxanes [poly (dimethylsiloxane)], which are available, for example, under the trade names Abil 10 to 10,000 from Th. Goldschmidt.
- Phenylmethylpolysiloxanes INCI: phenyl dimethicone, phenyl trimethicone
- cyclic silicones octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane
- cyclomethicones are also advantageous, amino-modified silicones (INCI: amodimimethicones) and.
- polysiloxane-polyethylene copolymers ICI: stearyl dimethicone and cetyl dimethicone
- dialkoxydimethyl polysiloxanes stearoxy dimethicone and behenoxy stearyl dimethicone
- other silicone oils can also be used advantageously for the purposes of the present invention, for example cetyldimethicone, hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).
- oil phases described here advantageously can be present both in the casing and in the filling.
- antioxidants are advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-camosine, D-camosine, L- Camosin and its derivatives (e.g. anserine), carotenoids, carotenes (e.g.
- carotene ß-carotene, lycopene
- retinoids such as retinol, retinal and / or retinoic acid and the respective esters
- ⁇ -lipoic acid and their derivatives e.g. dihydroliponic acid
- aurothioglucose propylthiouracil and other thiols
- thioredoxin glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl) , Palmitoyl, oleyl, ⁇ -linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfo- oximine compounds (eg buthioninsulfoximines, homocysteine sulfoximine, buthioninsulfones, penta-, hexa-, heptathioninsulfoximine) in very low tolerable doses (eg pmol to
- citric acid citric acid, lactic acid, malefic acid
- humic acid bile acid, bile extracts, bilirubin, biliverdin, EDTA, IDS, EGTA and their derivatives
- unsaturated fatty acids and their derivatives e.g. ⁇ -linolenic acid, linoleic acid , Oleic acid
- folic acid and its derivatives -2-aminopropionic acid diacetic acid, flavonoids, polyphenols, catechins, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g.
- the amount of the antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05-20% by weight, in particular 0.1-10% by weight, based on the total weight of the preparation.
- vitamin E and / or its derivatives represent the antioxidant (s)
- UV filter substances can also be added to the preparation according to the invention. It is therefore preferred to use the preparations according to the invention as light protection formulations.
- ICI homomenthyl salicylate
- Preferred inorganic pigments are metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular oxides of titanium (Ti0 2 ), zinc (ZnO), iron (e.g. Fe 2 0 3 ), zirconium (Zr0 2 ), silicon ( Si0 2 ), manganese (e.g. MnO), aluminum (Al 2 0 3 ), cerium (e.g. Ce 2 0 3 ), mixed oxides of the corresponding metals as well as mixtures of such oxides and the sulfate of barium (BaS0 4 ).
- the pigments can also advantageously be used in the form of commercially available oily or aqueous predispersions. Dispersing aids and / or solubilizing agents can advantageously be added to these predispersions.
- the pigments can advantageously be surface-treated (“coated”), for example a hydrophilic, amphiphilic or hydrophobic character should be formed or retained. This surface treatment can consist in that the pigments are coated with a thin hydrophilic and / or or hydrophobic inorganic and / or organic layer.
- the various surface coatings can also contain water for the purposes of the present invention.
- Inorganic surface coatings in the sense of the present invention can consist of aluminum oxide (Al 2 0 3 ), aluminum hydroxide Al (OH) 3 , or aluminum oxide hydrate (also: alumina, CAS no .: 1333-84-2), sodium hexametaphosphate (NaP0 3 ) 6 , sodium metaphosphate (NaP0 3 ) n , silicon dioxide (Si0 2 ) (also: silica, CAS No .: 7631-86- 9), or iron oxide (Fe 2 0 3 ).
- Al 2 0 3 aluminum oxide
- Al (OH) 3 aluminum hydroxide Al
- aluminum oxide hydrate also: alumina, CAS no .: 1333-84-2
- sodium hexametaphosphate (NaP0 3 ) 6 sodium metaphosphate (NaP0 3 ) n
- silicon dioxide (Si0 2 ) also: silica, CAS No .: 7631-86- 9
- iron oxide Fe 2
- Organic surface coatings in the sense of the present invention can consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane (also: dimethicone), methylpolysiloxane (methicone), simethicone (a mixture of dimethylpolysiloxane with an average chain length of 200 to 350 dimethylsiloxane Units and silica gel) or alginic acid.
- dimethylpolysiloxane also: dimethicone
- methicone methylpolysiloxane
- simethicone a mixture of dimethylpolysiloxane with an average chain length of 200 to 350 dimethylsiloxane Units and silica gel
- alginic acid can consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane (also: dimethicone), methylpolysiloxan
- Zinc oxide particles and predispersions of zinc oxide particles suitable according to the invention are available under the following trade names from the listed companies:
- Suitable titanium dioxide particles and predispersions of titanium dioxide particles are available under the following trade names from the companies listed:
- UV-A filter substances for the purposes of the present invention are dibenzoyimethane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which is available from Givaudan under the Parsol brand ® 1789 and is sold by Merck under the trade name Eusolex® 9020.
- dibenzoyimethane derivatives in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which is available from Givaudan under the Parsol brand ® 1789 and is sold by Merck under the trade name Eusolex® 9020.
- UV-A filter substances are hydroxybenzophenones. These are characterized by the following structural formula:
- R 1 and R 2 are independently hydrogen, C r C 20 alkyl, C 3 -C 10 cycloalkyl or C 3 -C 10 cycloalkenyl, wherein the substituents R 1 and R 2 together with the nitrogen atom to which they are bound, can form a 5- or 6-ring and R 3 is a CC 20 alkyl radical.
- a particularly advantageous hydroxybenzophenone in the sense of the present invention is 2- (4'-diethylamino-2'-hydoxybe ⁇ zoyl) benzoic acid hexyl ester (also: aminobenzophenone), which is characterized by the following structure:
- the total amount of one or more hydroxybenzophenones in the finished cosmetic or dermatological preparations is advantageously chosen from the range from 0.01% by weight to 20% by weight, preferably from 0.1 to 10% by weight, based in each case on the Total weight of the preparations.
- Advantageous further UV filter substances in the sense of the present invention are sulfonated, water-soluble UV filters, such as. B .:
- 1,4-di (2-oxo-10-sulfo-3-bomylidene-methyl) -benzene also: 3,3 '- (1,4-phenylenedimethylene)) -bis- (7,7-dimethyl-2- oxo-bicyclo- [2.2.1] hept-1-ylmethane sulfonic acid) and its salts (especially the corresponding 10-sulfato compounds, especially the corresponding sodium, potassium or triethanolammonium salt), which is also called benzene-1, 4-di (2-oxo-3-bomylidenemethyl-10-sulfonic acid) Benzene-1,4-di (2-oxo-3-bomylidenemethyl-10-sulfonic acid) has the INCI name Terephtalidene Dicampher Sulfonic Acid (CAS.
- UV filter substances in the sense of the present invention are also so-called broadband filters, ie filter substances that absorb both UV-A and UV-B radiation.
- Advantageous broadband filters or UV-B filter substances are, for example, triazine derivatives, such as. B.
- An advantageous broadband filter in the sense of the present invention is also the 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyl) phenol), which is sold under the trade name Tinosorb® M.
- Another advantageous broadband filter for the purposes of the present invention is 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1, 3,3,3-tetramethyl- 1 - [(trimethylsilyl) oxy] disiloxanylpropylj-phenol (CAS No .: 155633-54-8) with the INCI name Drometrizole " Trisiloxane, which is available under the trade name Mexoryl® XL.
- the other UV filter substances can be oil-soluble or water-soluble.
- Advantageous oil-soluble UV-B and / or broadband filter substances in the sense of the present invention are e.g.
- ⁇ 3-benzylidene camphor derivatives preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor
- ⁇ 4-aminobenzoic acid derivatives preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester
- ⁇ Derivatives of benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone ⁇ and UV filters bound to polymers.
- Advantageous water-soluble filter substances are e.g. B.: Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bomylidene methyl) benzoisulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene methyl) sulfonic acid and salts thereof.
- a further light protection filter substance according to the invention to be used advantageously is ethylhexyl-2-cyano-3,3-diphenylacrylate, obtainable (octocrylene) under the name Uvinul ® N 539th
- Particularly advantageous preparations within the meaning of the present invention which are distinguished by a high or very high UV-A and / or UV-B protection, preferably contain further UV-A and in addition to the filter substance (s) according to the invention / or broadband filter, in particular dibenzoylmethane derivatives [for example the 4- (tert-butyl) -4'-methoxydibenzoylmethane], phenylene-1, 4-bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and / or their salts, the 1,4-di (2-oxo-10-sulfo-3-bomylidenemethyl) benzene and / or its salts and / or the 2,4-bis - ⁇ [4- (2-ethyl- hexyloxy) -2-hydroxy] phenyl ⁇ -6- (4-methoxyphenyl) -1, 3,5-triazine, in each case individually or in any
- the preparations according to the invention advantageously contain the substances which absorb UV radiation in the UV-A and / or UV-B range in a total amount of, for. B. 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 20 wt .-%, in particular 1, 0 to 15.0 wt .-%, each based on the total weight of the preparations to cosmetic
- 0.1 wt .-% to 30 wt .-% preferably 0.5 to 20 wt .-%, in particular 1, 0 to 15.0 wt .-%, each based on the total weight of the preparations to cosmetic
- Preparations according to the invention particularly advantageously contain one or more hydrocolloids.
- These hydrocolloids can advantageously be selected from the group consisting of gums, polysaccharides, cellulose derivatives, layered silicates, polyacrylates and / or other polymers.
- Gums include plant or tree sap that harden in the air and form resins or extracts from aquatic plants. Gum arabic, locust bean gum, tragacanth, karaya, guar gum, pectin, gellan gum, carrageenan, agar, algine, chondrus, xanthan gum can advantageously be selected from this group for the purposes of the present invention.
- derivatized gums such as e.g. Hydroxy-propyl guar (Jaguar® HP 8).
- polysaccharides and derivatives are e.g. Hyaluronic acid, chitin and chitosan, chondroitin sulfates, starch and starch derivatives.
- cellulose derivatives are e.g. Methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyiceilulose.
- Layered silicates contain naturally occurring and synthetic clays such as Montmorillonite, bentonite, hectorite, laponite, magnesium aluminum silicates such as Veegum®. These can be used as such or in a modified form such as e.g. Stearylalkonium hektorite.
- silica gels can also advantageously be used.
- Taurates are also advantageous, e.g. Ammonium acryloyldimethyl taurate / VP copolymer.
- the polyacrylates include e.g. Carbopol types from Goodrich (Carbopol 980, 981, 1382, 5984, 2984, ETD 2001, ETD 2020, ETD 2050, Ultrez-10 or Pemulen TR1 & TR2).
- Carbopol types from Goodrich (Carbopol 980, 981, 1382, 5984, 2984, ETD 2001, ETD 2020, ETD 2050, Ultrez-10 or Pemulen TR1 & TR2).
- polymers e.g. Polyacrylamides (Seppigel 305), polyvinyl alcohols, PVP, PVP / VA copolymers, polyglycols.
- the water phase of the preparations according to the present invention can advantageously contain customary cosmetic auxiliaries, such as, in particular, alcohols such a low C number, preferably ethanol and / or isopropanol, diols or polyols of low C number and their ethers, preferably propylene glycol, glycerol, butylene glycol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or - monobutyl ether, diethylene glycol monomethyl or monoethyl ether, ethyl hexyloglycerol, methyl propanediol and analog products, polymers, foam stabilizers, electrolytes such as sodium chloride or magnesium sulfate and in particular one or more thickeners, which one or more can advantageously be selected from the group consisting of silicon dioxide, aluminosilicates, polysaccharides and polysaccharides their derivatives, for example
- the preparations according to the present invention can furthermore advantageously also contain self-tanning substances, such as, for example, dihydroxyacetone and / or melanin derivatives in concentrations of 1% by weight to 10% by weight, based on the total weight of the preparation.
- self-tanning substances such as, for example, dihydroxyacetone and / or melanin derivatives in concentrations of 1% by weight to 10% by weight, based on the total weight of the preparation.
- the preparations according to the present invention can also advantageously contain repellents for protection against mosquitoes, ticks and spiders and the like.
- repellents for protection against mosquitoes, ticks and spiders and the like.
- B N, N-diethyl-3-methylbenzamide (trade name: Metadolphene, "DEET"), dimethyl phthalate (trade name: Palatino! M, DMP) and in particular ethyl 3- (Nn-butyl-N-acetylamino) propionate (Available under the trade name Insekt Repellent® 3535.)
- the repellents can be used both individually and in combination.
- Moisturizers and / or skin-moisturizing substances are substances or mixtures of substances that give cosmetic or dermatological preparations the property of reducing and / or reducing the release of moisture from the horny layer (also called transepidermal water loss (TEWL)) after application or distribution on the skin surface to positively influence the hydration of the horny layer.
- TEWL transepidermal water loss
- moisturizers for the purposes of the present invention are, for example, glycerol, lactic acid and / or lactates, in particular sodium lactate, butylene glycol, propylene glycol, panthenol, fucogel, glycine soy, ethylhexyloxyglycerol, pyrrolidone carboxylic acid and their Derivatives and urea.
- polymeric moisturizers from the group of water-soluble and / or water-swellable and / or water-gelable polysaccharides.
- hyaluronic acid chitosan and / or a fucose-rich polysaccharide
- Fucogel®1000 is available under the name Fucogel®1000.
- Moisturizers can also advantageously be used as anti-wrinkle agents for the prophylaxis and treatment of cosmetic or dermatological skin changes, such as those described for example in US Pat. B. occur in skin aging, are used.
- the cosmetic or dermatological preparations according to the invention can furthermore advantageously, although not necessarily, contain fillers which, for. B. further improve the sensory and cosmetic properties of the formulations and, for example, cause or intensify a velvety or silky feeling on the skin.
- Advantageous fillers for the purposes of the present invention are starch and starch derivatives (such as, for example, tapioca starch, distarch phosphate, aluminum or sodium starch octenyl succinate and the like), pigments which have neither mainly UV filter nor coloring effect have (such as boron nitride etc.) and / or Aerosile ® (CAS No. 7631-86-9).
- the capsule according to the invention can also be used as a cleaning capsule.
- the filling then contains surfactants or washing-active substances that are released on the skin when rubbed.
- the incorporation as a filling component takes place without any complications.
- the combination of the washing-active substances in the filling with the wax in the shell is particularly advantageous when the capsule is provided with surfactants. So you have one when dissolving the capsules while rubbing in or under warm water Formulation that foams and is also able to remove waterproof residues such as make-up due to the wax content.
- the face and skin When traveling, the face and skin can thus be cleaned in a targeted manner and in between without having to take along the complex cleaning agent.
- Surfactants are amphiphilic substances that can dissolve organic, non-polar substances in water. Due to their specific molecular structure with at least one hydrophilic and one hydrophobic part of the molecule, they ensure a reduction in the surface tension of the water, wetting of the skin, facilitating dirt removal and removal, easy rinsing and - if desired - foam regulation.
- hydrophilic parts of a surfactant molecule are mostly polar functional groups, for example -COO " , -OS0 3 2" , -S0 3 " , while the hydrophobic parts generally represent non-polar hydrocarbon residues.
- surfactants are generally of type and charge of the hydrophilic part of the molecule. There are four groups:
- Anionic surfactants generally have carboxylate, sulfate or sulfonate groups as functional groups. In an aqueous solution they form negatively charged organic ions in an acidic or neutral environment. Cationic surfactants are characterized almost exclusively by the presence of a quaternary ammonium group. In aqueous solution they form positively charged organic ions in an acidic or neutral environment. Amphoteric surfactants contain both anionic and cationic groups and accordingly behave like anionic or cationic surfactants in aqueous solution depending on the pH. They have a positive charge in a strongly acidic environment and a negative charge in an alkaline environment. In the neutral pH range, however, they are zwitterionic, as the following example will illustrate:
- Non-ionic surfactants do not form ions in an aqueous medium.
- Anionic surfactants to be used advantageously are acylamino acids (and their salts), such as 1. acylglutamates, for example sodium acylglutamate, di-TEA-palmitoylaspartate and sodium caprylic / capric glutamate,
- acyl peptides for example palmitoyl-hydrolyzed milk protein, sodium cocoyl-hydrolyzed soy protein and sodium / potassium-cocoyl-hydrolyzed collagen,
- sarcosinates for example myristoyl sarcosin, TEA-lauroyl sarcosinate, sodium lauroyl sarcosinate and sodium cocoyl sarcosinate,
- taurates for example sodium lauroyl taurate and sodium methyl cocoyl taurate
- alaninate carboxylic acids and derivatives such as 1.
- carboxylic acids for example lauric acid, aluminum stearate, magnesium alkanoate and zinc undecylenate,
- ester carboxylic acids for example calcium stearoyl lactylate, laureth-6 citrate and sodium PEG-4 lauramide carboxylate,
- ether carboxylic acids for example sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate,
- Phosphoric acid esters and salts such as DEA-oleth-10-phosphate and dilureth-4-phosphate
- alkyl sulfonates for example sodium coconut monoglyceride sulfate, sodium C 12-14 olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate
- Sulfosuccinates for example dioctyl sodium sulfosuccinate, disodium laurethsuifosuccinate, disodium lauryl sulfosuccinate, disodium undecylenamido MEA sulfosuccinate and PEG-5 lauryl citrate sulfosuccinate.
- sulfuric acid esters such as
- alkyl ether sulfate for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulfate, sodium myreth sulfate and sodium C 12-13 pareth sulfate,
- Alkyl sulfates for example sodium, ammonium and TEA lauryl sulfate.
- Quaternary surfactants contain at least one N atom which is covalently linked to 4 alkyl and / or aryl groups. Regardless of the pH value, this leads to a positive charge.
- Advantageous quaternary surfactants are alkyl betaine, alkyl amidopropyl betaine and alkyl amidopropyl hydroxysulfain.
- Cationic surfactants can also preferred according to the present invention are selected from the group of quaternary ammonium compounds, especially benzyltrialkylammonium chlorides or bromides, for example benzyldimethylstearylammonium chloride, also ze Aikyltrialkylammoniumsal-, for example cetyltrimethylammonium chloride or bromide, methylhydroxyethylammoniumchloride alkyl di- or bromides, dialkyldimethylammonium chlorides or bromides, alkylamidethyltrimethylammonium ether sulfates, alkylpyridinium salts, for example lauryl or cetylpyrimidinium chloride, imidazoline derivatives and compounds with a cationic character such as amine oxides, for example alkyldimethylamine oxides or alkylaminoethyldimethylamine oxides. Cetyltrimethylammonium salts are particularly advantageous.
- Amphoteric Surfactants are amphoteric surfactants that can be used advantageously 1. acyl / dialkyl ethylenediamine, for example sodium acyl amphoacetate, disodium acyl amphodipropionate, disodium alkyl amphodiacetate, sodium acylamphohydroxypropyl sulfonate, disodium acylamphodiacetate and sodium acyl amphopropionate,
- N-alkylamino acids for example aminopropylalkylglutamide, alkylaminopropionic acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate.
- Nonionic surfactants to be used advantageously are 1. alcohols, 2. alkanolamides, such as Cocamide MEA / DEA / MIPA,
- amine oxides such as cocoamidopropylamine oxide
- esters which are formed by esterification of carboxylic acids with ethylene oxide, glycerol, sorbitan or other alcohols,
- ethers for example ethoxylated / propoxylated alcohols, ethoxylated / propoxylated esters, ethoxylated / propoxylated glycerol esters, ethoxylated / propoxylated cholesterol esters, ethoxylated / propoxylated triglyceride esters, ethoxylated propoxylated es lanolin, ethoxylated / propoxylated polysiloxanes and propoxylated POE ethers Alkyl polyglycosides such as lauryl glucoside, decyl glycoside and cocoglycoside.
- sucrose esters, ethers 7 polyglycerol esters, diglycerol esters, monoglycerol esters 8. methyl glucose esters, esters of hydroxy acids
- the capsule-like preparations are applied to the skin and / or the hair in the manner customary for cosmetics, and are rubbed or distributed.
- the advantage essential to the invention is the first-time provision of individual, manageable cosmetic preparations in capsule form, which offer the consumer simplified removal, improved hygiene when sharing the product with others and a new form of application.
- the cosmetic and / or dermatological preparations according to the invention can be composed like conventional cosmetic and / or dermatological preparations and can be used for cosmetic and / or dermatological light protection, for changing or influencing certain skin conditions, furthermore for the treatment, care and cleaning of the skin and / or Hair and as a make-up product in decorative cosmetics.
- cosmetic and / or topical dermatological compositions in the sense of the present.
- Invention can be used, for example, as a skin care product, skin protection product, cleaning product, sunscreen product, hair treatment, body cleaning product, for day or night care, the care of certain skin areas such as hands, face, feet, etc.
- a single capsule containing ubiquinone, ubiquinol, retinol and derivatives, dehydroepiandrosterone (DHEA), isoflavonoids (in particular genistein, daidzein), creatine, phytoestrogens, estrogens, oestradiol and derivatives, niacinamide, polyphenols or other (AGR) can advantageously be used , apply and distribute anti-wrinkle substance to the facial skin.
- Suitable active ingredients for this purpose are: natural oils (sunflower, evening primrose, jojoba, macadamia, castor oil), ceramides, especially ceramides I, III and VI, cholesterol, phytosterols, fatty acids with a chain length of C16-26, carnitine and its derivatives, urea, polyols such as glycerin, butylene glycol, propylene glycol and dipropylene glycol, pseudoceramides; Electrolytes such as sodium chloride and taurine, fatty alcohols and waxes.
- Preferred active ingredients for this purpose are: Milk thistle substances, in particular silymarin, witch hazel extract, chamomile extract, licorice plant ingredients (glycerrhizic acid, licochalcone A & B), allantoin, acetylsalicylic acid, diclofenac, pentacyclic triterpenes (sericoside, ursolic acid) and panthenol.
- capsular cosmetic preparations according to the invention for the prophylaxis and treatment of the symptoms of the mispigmented skin is advantageous.
- active ingredients for this purpose are: tyrosinase inhibitors, hydroquinone derivatives, dioic acid, lipoic acid and its derivatives and kojic acid.
- compositions according to the invention as the basis for pharmaceutical formulations.
- the use of the capsular cosmetic preparations according to the invention for the prophylaxis and treatment of the symptoms of diseased skin is preferred, relevant but not exclusive diseased skin conditions are psoriasis, acne, neurodermatitis and other atopic diseases such as atopic dermatitis, skin cancer, herpes, mycoses, ichthyosis, pityriasis, seborrhea , Pellagra, contact eczema and allergies.
- Suitable active substances for such uses are antibiotics such as fusidic acid, erythromycin, sulfadiazine, clindamycin, tetracyclines, tyrothricin aminoglycosides, bacitracin, chloramphenicol, virustatics (e.g. aciciovir, idoxuridine, penciciovir), anti-mycotics, amphinocotrimotics, e.g. ninolinazolotics (e.g.
- nystinolotol eg nolinocinol
- Ketoconazole.naftifin, terbinafine allethrin
- cytostatics 5-fluorouracil
- antiphlogistics hydrocortisone, bethamasone; prednisolone, triamcinolone acetonide, dexamethasone, diclofenac, bufexamac
- immunosuppressants interferonporinanol
- antipsoronorinol cyclosporonorinol
- acne agents retinoic acid, isotretinoin, benzoyl peroxide, adapalene
- One possible application which is particularly advantageous according to the invention is to offer capsules with different uses in one pack, for example those for day and night care, those with different colors, fragrances, different sun protection factors or different active ingredients. With such a use, it is particularly advantageous to use the capsules of different Make the user distinguishable by different shapes and / or colors.
- the use of the cosmetic and / or dermatological preparations according to the invention for the prophylaxis, treatment and cleaning of oily skin and for the prophylaxis and treatment of impure skin and cellulite is according to the invention.
- the casing and the filling are first produced separately from one another.
- the coating of the filling with the covering material can be carried out in various ways, regardless of the composition of the filling material or the covering.
- the filling material can be frozen and then immersed in melted covering material, as a result of which a solid, closed covering forms on the filling material.
- hollow spheres can also be cast from molten enveloping material, which may be filled with filling material through a hole in the spherical wall. The hole is then closed by a plug made of casing material. It is also possible first to cast half hollow spheres, to fill them if necessary, to cover them and finally to fuse them together by thermal treatment. In addition, two such hemispheres can be produced, one or both of which have a hole for later filling, then welded to form a hollow sphere and finally filled through the filling hole. be closed as described above.
- a particularly preferred method according to the invention for producing the capsules or their shell is based on the principle of the frozen-cone or cold-stamp method as described, for example, in DE 19852262 or DE 9321186. According to the invention, these processes from food technology have been adapted to the production of cosmetic preparations.
- the frozen cone process is illustrated in the attached Figure 1.
- a defined amount of coating material 3 is filled into a mold 1 through a nozzle 2.
- a cooled molded body 4 "frozen cone” or “cold stamp"
- the introduced encapsulation is shaped and at the same time cooled in such a way that it does not or only does not change its shape until the filler 6 is filled in through a further nozzle 5 changed insignificantly.
- further covering compound 3a is applied through the nozzle 2a.
- the nozzles 2 and 2a and the masses 3 and 3a can, but do not have to be identical. It is advantageous to choose masses 3 and 3a identically.
- the finished emulsion capsule 7 is removed from the mold.
- two still unsealed half-capsules can be brought to cover one another and their casings can be fused together.
- the shell thicknesses can be variably adjusted in the range from 0.001 to 3 mm with high reproducibility.
- extremely thin-walled capsule preparations can be produced for the first time.
- the filling to be added subsequently does not need to be heated.
- the filling contains temperature-sensitive substances that e.g. oxidatively (vitamins A, B, C and E or their derivatives such as acetates, phosphates or palmitates, provitamin B5) or hydrolytically (acetylcarnitine, parabens).
- temperature-sensitive substances e.g. oxidatively (vitamins A, B, C and E or their derivatives such as acetates, phosphates or palmitates, provitamin B5) or hydrolytically (acetylcarnitine, parabens).
- oxidatively vitamins A, B, C and E or their derivatives such as acetates, phosphates or palmitates, provitamin B5
- hydrolytically acetylcarnitine, parabens
- a shape 1 is formed from an upper and a lower half-shape (1a and b) (see Figure 2), the upper half-shape 1a having an opening 5.
- a double nozzle 2 in which an inner channel 2a is arranged concentrically in an outer channel 2b, is moved into the mold 1.
- some casing mass 3 is conveyed into the mold through the outer channel, so that a closed bottom is formed from the casing mass.
- the filling 4 is also conveyed through the inner channel 2a.
- the nozzle 2 moves upwards out of the mold 1.
- the conveying of the filling is again briefly suspended so that a closed lid 6 can also be created.
- the finished emulsion capsule 7 can be removed from the mold by subsequently separating the two half molds 1a and b from one another.
- the upper half mold 1 a can also be dispensed with, so that the opening 5 is formed directly by the opening or its open side of the lower half mold 1 b.
- the masses 3 and 4 are filled directly through the double nozzle 2, similar to the process according to Figure 1. So capsules cannot be produced in spherical form, but only bodies with a flat base (e.g. as known from the food sector) Chocolate praline, toffee fairy or Mozart balls). But these forms are also in accordance with the invention.
- the least possible smoothness of the filling compound is necessary.
- Speed means the property of not tearing off immediately when a part of a liquid or semi-solid preparation is removed, but rather pulling threads between the removed and the untouched part of the preparation.
- melted cheese is extremely quick, while pure water is not quick, so it doesn't pull any strings.
- the filling compound now pulls threads, it will not tear off cleanly when its conveyance stops. Due to the resulting threads, a completely closed cover made of covering material cannot form, as a result of which the mechanical (shape stability, hardness, elasticity) and other properties (water loss, leakage of the filling compound) are adversely affected in terms of their mechanical properties.
- Cosmetic raw materials such as, for example, polyols (especially glycerol, propylene glycol, butylene glycol, polyethylene glycol, pentanediols, hexanediols, octanediols) or hydrocolloids (especially polysaccharides such as starches and starch derivatives, mannans, glucans, xanthan gum, guar gum, gum arabic, and polymers or Copolymers of acrylic acid or its esters)
- polyols especially glycerol, propylene glycol, butylene glycol, polyethylene glycol, pentanediols, hexanediols, octanediols
- hydrocolloids especially polysaccharides such as starches and starch derivatives, mannans, glucans, xanthan gum, guar gum, gum arabic, and polymers or Copolymers of acrylic acid or its
- W / O emulsifiers are branched or unbranched, saturated or unsaturated fatty acids with 12 to 26 carbon atoms, polyglyceryl-3 diisostearate, polyglyceryl-4 isostearate, polyglyceryl-2 dipolyhydroxystearate, cetyl PEG / PPG-10-1-dimethicone, PEG-30 Dipolyhydroxystearate, PEG-40 sorbitan perisostearate, cetyldimethiconecopolyol, PEG-7 hydrogenated Castor Oil, PEG 45 / dodecylglycol copolymer, PEG 22 / dodeceylglycol copolymer, pentaerythrityl isostearate, isostearyl diglyceryl succinate, sorbitan isostearate, polyglyceryl
- waxes with contents of surface-active substances can also be used, especially those with contents of free fatty acids and / or fatty acid mono- or diglycerides (eg beeswaxes). They thus make it much easier to fill fillings that contain glycerin, hydrocolloids and / or the substances described above.
- the thread that otherwise forms is cut through the sheath by the addition of the surface-active substances. The addition thus ensures problem-free closing of the case.
- the problem of filling is solved according to the invention by shell components.
- the frozen-cone or cold-stamp process is characterized by its excellent accuracy and reproducibility in the thickness and uniformity of the casing. It is particularly suitable for casting very thin shells ( ⁇ 1 mm).
- the advantage of the one-shot process is its exceptional flexibility: by setting a few machine parameters, capsules with different thicknesses can be produced with identical nozzles, machines and shapes. The same machine can be used to change the shape of the capsule (e.g. oval instead of round), only the half-shapes need to be replaced.
- the molds into which casting is carried out in both processes can be produced from different materials, particularly preferably thermoplastic plastics such as polyolefins, vinyl polymers, polyamides, polyesters, polyacetals and polycarbonates. They are advantageously produced as disposable forms (blisters) that can be used to package the finished capsule.
- thermoplastic plastics such as polyolefins, vinyl polymers, polyamides, polyesters, polyacetals and polycarbonates. They are advantageously produced as disposable forms (blisters) that can be used to package the finished capsule.
- Both of the methods according to the invention explained above enable industrial, machine-compatible production of the capsule-shaped cosmetic preparations, so that the production costs are reduced and thus inexpensive capsule-shaped cosmetics can also be offered.
- the preparation according to the invention also has improved sensory properties which are not to be expected with wax-containing preparations from the prior art. Improved spreadability, retraction, consistency, smoothing of the skin and reduced stickiness were found. With regard to suitable methods for determining these parameters, reference can be made to the knowledge of the person skilled in the art.
- the capsule according to the invention can be used without a filling, as a hollow sphere, and also as an independent cosmetic.
- the substances containing for the cosmetic or dermatological purpose are then all in the capsule shell.
- the size information such as the diameter of the capsules, is to be understood as the diameter in the direction of the longitudinal expansion of the capsule particles.
- the casing or filling can contain, independently of one another, auxiliaries such as UV filters, active ingredients, sensor additives, thickeners, gel formers, dyes, colorants, effect or UV pigments, preservatives, antioxidants, complexing agents, flavors, denaturants or perfumes.
- auxiliaries such as UV filters, active ingredients, sensor additives, thickeners, gel formers, dyes, colorants, effect or UV pigments, preservatives, antioxidants, complexing agents, flavors, denaturants or perfumes.
- the various fillings can be surrounded by one of the shells listed as examples.
- the selection of the fillings and casings shown as examples depends on the respective application.
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Emergency Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dermatology (AREA)
- Zoology (AREA)
- Cosmetics (AREA)
- Medicinal Preparation (AREA)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/569,382 US8741321B2 (en) | 2003-08-27 | 2004-08-27 | Capsule whose envelope is separately imperceptible during the topical use thereof |
| EP04764537A EP1660023B1 (de) | 2003-08-27 | 2004-08-27 | Kapsel deren kapselhülle bei topischer anwendung nicht mehr gesondert wahrnehmbar ist |
| DE502004008832T DE502004008832D1 (de) | 2003-08-27 | 2004-08-27 | Kapsel deren kapselhülle bei topischer anwendung nicht mehr gesondert wahrnehmbar ist |
| JP2006524332A JP2007503418A (ja) | 2003-08-27 | 2004-08-27 | 局所使用中に個別には感知不能になる外皮を有するカプセル |
| US14/255,298 US20140227330A1 (en) | 2003-08-27 | 2014-04-17 | Capsule whose envelope is separately imperceptible during the topical use thereof |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10339747 | 2003-08-27 | ||
| DE10339747.7 | 2003-08-27 | ||
| DE10340106 | 2003-08-30 | ||
| DE10340106.7 | 2003-08-30 | ||
| DE10357639A DE10357639A1 (de) | 2003-08-27 | 2003-12-10 | Kosmetische und/oder dermatologische Kapsel |
| DE10357639.8 | 2003-12-10 |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/569,382 A-371-Of-International US8741321B2 (en) | 2003-08-27 | 2004-08-27 | Capsule whose envelope is separately imperceptible during the topical use thereof |
| US14/255,298 Continuation US20140227330A1 (en) | 2003-08-27 | 2014-04-17 | Capsule whose envelope is separately imperceptible during the topical use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2005020940A1 true WO2005020940A1 (de) | 2005-03-10 |
Family
ID=34279297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2004/009563 Ceased WO2005020940A1 (de) | 2003-08-27 | 2004-08-27 | Kapsel deren kapselhülle bei topischer anwendung nicht mehr gesondert warhnembar ist |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US8741321B2 (https=) |
| EP (1) | EP1660023B1 (https=) |
| JP (1) | JP2007503418A (https=) |
| WO (1) | WO2005020940A1 (https=) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006298834A (ja) * | 2005-04-21 | 2006-11-02 | Shiseido Co Ltd | 水中油型乳化皮膚化粧料 |
| WO2008034565A1 (de) | 2006-09-22 | 2008-03-27 | Beiersdorf Ag | Peelingkapseln |
| DE202007002295U1 (de) | 2007-02-13 | 2008-06-26 | Lorenz, Anneliese F. | Seifen mit optischen oder elastischen Eigenschaften |
| JP2008535502A (ja) * | 2005-04-13 | 2008-09-04 | ビューラー アーゲー | 充填された食品を製造する方法 |
| JP2008543946A (ja) * | 2005-06-27 | 2008-12-04 | イーエルシー マネージメント エルエルシー | カプセル化された化粧用組成物 |
| WO2010097174A1 (de) * | 2009-02-24 | 2010-09-02 | Beiersdorf Ag | Stabilisierte peelingkapsel |
| US8741320B2 (en) | 2003-08-27 | 2014-06-03 | Beiersdorf Ag | Spherical cosmetic preparations for topical application |
| EP3178465A1 (en) | 2010-12-06 | 2017-06-14 | Follica, Inc. | Methods for treating baldness and promoting hair growth |
| EP2922598B1 (de) * | 2012-11-20 | 2019-01-09 | Beiersdorf AG | Sensorisch attraktive hydrodispersion mit wachsen |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10357640A1 (de) * | 2003-08-27 | 2005-03-24 | Beiersdorf Ag | Kosmetische kugelförmige Zubereitungen zur topischen Anwendung |
| US8221778B2 (en) | 2005-01-12 | 2012-07-17 | The Trustees Of The University Of Pennsylvania | Drug-containing implants and methods of use thereof |
| ES2809302T3 (es) | 2004-01-22 | 2021-03-03 | Univ Miami | Formulaciones de coenzima Q10 para tratar tumores sólidos mediante administración intravenosa |
| CA2680825C (en) | 2007-03-22 | 2013-10-29 | Cytotech Labs, Llc | Topical formulations having enhanced bioavailability |
| EP2218446A4 (en) * | 2007-11-07 | 2014-07-30 | Kaneka Corp | METHOD OF PRODUCING MICROCAPSULES USING SOLID FAT |
| AU2009233785B2 (en) | 2008-04-11 | 2015-08-20 | Berg Llc | Methods and use of inducing apoptosis in cancer cells |
| AU2010247800A1 (en) | 2009-05-11 | 2011-12-15 | Berg Llc | Methods for the diagnosis of metabolic disorders using epimetabolic shifters, multidimensional intracellular molecules, or environmental influencers |
| DE102010001905A1 (de) * | 2010-02-12 | 2011-08-18 | ROVI Cosmetics International GmbH, 36381 | UV-Schutzmittel für die Haut oder die Haare mit einer in einem vesikulären Trägersystem verkapselten UV-Filtersubstanz |
| CN105168135A (zh) | 2010-03-12 | 2015-12-23 | 博格有限责任公司 | 辅酶Q10(CoQ10)的静脉内制剂及其使用方法 |
| CA2832324C (en) | 2011-04-04 | 2022-03-15 | Berg Llc | Methods of treating central nervous system tumors |
| US10973763B2 (en) | 2011-06-17 | 2021-04-13 | Berg Llc | Inhalable pharmaceutical compositions |
| KR101133098B1 (ko) * | 2011-07-14 | 2012-04-04 | 주식회사 에버코스 | 고형 화장료 제형 |
| US9549891B2 (en) | 2012-03-19 | 2017-01-24 | The Procter & Gamble Company | Superabsorbent polymers and sunscreen actives for use in skin care compositions |
| US9145221B2 (en) * | 2012-03-20 | 2015-09-29 | La Prairie, Inc. | Convertible two compartment container |
| KR101191268B1 (ko) * | 2012-05-11 | 2012-10-16 | (주)바이오제닉스 | 하이드로겔을 형성할 수 있는 고분자를 이용한 자외선차단제용 나노무기입자를 함유하는 캡슐 조성물 및 이의 제조방법 |
| SG10201903112WA (en) | 2013-04-08 | 2019-05-30 | Berg Llc | Treatment of cancer using coenzyme q10 combination therapies |
| KR102370843B1 (ko) | 2013-09-04 | 2022-03-04 | 버그 엘엘씨 | 코엔자임 q10의 연속주입에 의한 암치료 방법 |
| US9731151B2 (en) | 2014-04-08 | 2017-08-15 | Honeywell International Inc. | Sprayable sunscreen compositions and methods |
| JP6604637B2 (ja) | 2015-06-29 | 2019-11-13 | ザ プロクター アンド ギャンブル カンパニー | スキンケア組成物において使用するための超吸収性ポリマー及びデンプン粉末 |
| WO2017087576A1 (en) | 2015-11-16 | 2017-05-26 | Berg Llc | Methods of treatment of temozolomide-resistant glioma using coenzyme q10 |
| KR101993976B1 (ko) * | 2017-06-30 | 2019-10-01 | 주식회사 태성산업 | 구슬 크림 화장품 보관용 용기 |
| US20190070078A1 (en) * | 2017-09-05 | 2019-03-07 | Robb Akridge | Truffle configured cosmetic article |
| JP7292656B2 (ja) * | 2018-12-04 | 2023-06-19 | エルジー ハウスホールド アンド ヘルスケア リミテッド | 高含量及び徐放型レチノイドカプセル及びこれを含むしわ改善用の組成物 |
| US11497692B2 (en) | 2019-10-15 | 2022-11-15 | Rea Innovations, Inc. | Systems and methods for blending solid-shell cosmetic ingredient capsules and blendable cosmetic ingredient capsules |
| US11660578B2 (en) | 2019-10-15 | 2023-05-30 | Rea Innovations, Inc. | Systems and methods for blending solid-shell cosmetic ingredient capsules and blendable cosmetic ingredient capsules |
| ES2849750B2 (es) * | 2020-02-19 | 2022-07-29 | Fingerclik S L | Capsula galenica rompible |
| FR3115200B1 (fr) * | 2020-10-21 | 2023-11-03 | Oreal | Composition cosmetique contenant des capsules de type cœur/enveloppe |
| KR102566783B1 (ko) * | 2021-04-29 | 2023-08-11 | 이화진 | 연고캡슐이 내재된 밴드 |
| KR102680093B1 (ko) * | 2021-07-21 | 2024-06-28 | 동국대학교 산학협력단 | 화장품 제조 장치 |
| FR3133126B1 (fr) * | 2022-03-07 | 2024-01-19 | Sederma Sa | Procédé d’encapsulation d’un composé hydrophobe, suspension de particules lipidiques structurées selon ce procédé et utilisations de ladite suspension |
| CN115813878B (zh) * | 2022-12-09 | 2024-06-28 | 浙江省食品药品检验研究院 | 一种隔水涂层溶液及制备隔水胶囊的应用 |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0234078A1 (en) * | 1985-01-29 | 1987-09-02 | Ohkawara Kakohki Co., Ltd. | Mono-core type microcapsules and process for producing them |
| DE4223004A1 (de) * | 1992-07-13 | 1994-01-20 | Liedtke Pharmed Gmbh | Einzeldosierte halbfeste topische Arzneiform zur Transdermaltherapie |
| WO2001003538A1 (fr) * | 1999-07-09 | 2001-01-18 | Bourjois | Article pour l'application d'une composition topique et son procede de preparation |
| WO2001038174A1 (fr) * | 1999-11-23 | 2001-05-31 | Delviel | Procede d'encapsulation d'une composition topique |
| EP1129771A1 (de) * | 2000-03-04 | 2001-09-05 | Primacare S.A. | Mikrokapseln |
| US20020022038A1 (en) * | 2000-05-05 | 2002-02-21 | Bruno Biatry | Microcapsules with an aqueous core containing at least one water-soluble cosmetic or dermatological active principle and cosmetic or dermatological compositions containing them |
| EP1201219A1 (fr) * | 2000-10-27 | 2002-05-02 | L'oreal | Utilisation de microcapsules thermostabilisatrices pour améliorer l'activité ou la pénétration de principes actifs cosmétiques ou pharmaceutiques |
| JP2003073230A (ja) * | 2001-08-29 | 2003-03-12 | Shiseido Co Ltd | カプセル含有組成物、および、これを用いた外用組成物 |
| DE10209111A1 (de) * | 2002-03-01 | 2003-09-18 | Beiersdorf Ag | Tücher mit Produktreservoir |
Family Cites Families (46)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5973510A (ja) | 1982-10-19 | 1984-04-25 | Pola Chem Ind Inc | 化粧料 |
| JPH0694416B2 (ja) * | 1984-04-20 | 1994-11-24 | ポーラ化成工業株式会社 | メークアップ化粧料 |
| DE3421468A1 (de) | 1984-06-08 | 1985-12-19 | Dr. Rentschler Arzneimittel Gmbh & Co, 7958 Laupheim | Lipidnanopellets als traegersystem fuer arzneimittel zur peroralen anwendung |
| CN1003578B (zh) | 1984-10-25 | 1989-03-15 | 沃纳·兰伯特公司 | 改进的胶囊形状 |
| JPH01268622A (ja) * | 1988-04-18 | 1989-10-26 | Shiseido Co Ltd | 外用剤 |
| JPH02282311A (ja) * | 1989-04-24 | 1990-11-19 | Noevir Co Ltd | カプセル状化粧料を充填収容した化粧品 |
| JP2798224B2 (ja) * | 1991-06-26 | 1998-09-17 | 三粧化研株式会社 | 化粧用品 |
| DE4127665A1 (de) | 1991-08-22 | 1993-02-25 | Beiersdorf Ag | Galenische matrix |
| JP3176984B2 (ja) * | 1992-04-28 | 2001-06-18 | 御木本製薬株式会社 | 化粧料 |
| US5270054A (en) | 1992-09-03 | 1993-12-14 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Cosmetic capsules |
| DK172603B1 (da) | 1992-09-23 | 1999-02-22 | Aasted Mikroverk Aps | Fremgangsmåde og anlæg til fremstilling af chokoladeartikler |
| US6048520A (en) * | 1992-09-24 | 2000-04-11 | Helene Curtis, Inc. | Clear leave-on hair treatment composition and method |
| US5885486A (en) | 1993-03-05 | 1999-03-23 | Pharmaciaand Upjohn Ab | Solid lipid particles, particles of bioactive agents and methods for the manufacture and use thereof |
| CA2091152C (en) | 1993-03-05 | 2005-05-03 | Kirsten Westesen | Solid lipid particles, particles of bioactive agents and methods for the manfuacture and use thereof |
| US5785976A (en) | 1993-03-05 | 1998-07-28 | Pharmacia & Upjohn Ab | Solid lipid particles, particles of bioactive agents and methods for the manufacture and use thereof |
| FR2714597B1 (fr) * | 1993-12-30 | 1996-02-09 | Oreal | Composition hydratante pour le traitement simultané des couches superficielles et profondes de la peau, son utilisation. |
| EP0808152A1 (en) | 1995-02-07 | 1997-11-26 | Unichema Chemie B.V. | Cosmetic cleansing compositions comprising esters of alkylglycosides |
| GB9606371D0 (en) | 1996-03-26 | 1996-06-05 | Brown Malcolm D | An encapsulation process |
| JP3573440B2 (ja) | 1996-12-20 | 2004-10-06 | 株式会社ノエビア | 固形状乳化組成物及びその製造方法 |
| US6197281B1 (en) * | 1997-06-04 | 2001-03-06 | Ernest G. Stewart | Wet appliable, instant protection sunscreen and makeup and method of use |
| CH692968A5 (de) | 1997-06-11 | 2003-01-15 | Awema Ag | Ventilanordnung. |
| FR2774587B1 (fr) | 1998-02-09 | 2000-03-10 | Oreal | Utilisation d'une microdispersion de cire dans une composition cosmetique ou dermatologique |
| US6045813A (en) * | 1998-03-30 | 2000-04-04 | Bath & Body Works, Inc. | Lotions and gels with active ingredients in beads |
| DE19837191A1 (de) | 1998-08-17 | 2000-02-24 | Henkel Kgaa | Kosmetische und dermatologische Hautbehandlungsmittel |
| DE19846772A1 (de) | 1998-10-10 | 2000-04-13 | Beiersdorf Ag | Kosmetische und dermatoligische Hydrodispersionen mit einem Gehalt an Triglyceridwachsen |
| DE19852262C2 (de) | 1998-11-13 | 2001-08-16 | Bindler Maschf Gebr Gmbh Co Kg | Stempeleinrichtung zum Prägen von offenen Hohlformen |
| JP3622832B2 (ja) * | 1999-04-21 | 2005-02-23 | 株式会社ノエビア | カプセル含有ゲル状化粧料 |
| MXPA01011343A (es) | 1999-05-07 | 2002-06-04 | Pharmasol Gmbh | Particulas de lipidos a base de mezclas de lipidos liquidos y solidos asi como procedimiento para su produccion. |
| DE19945203A1 (de) | 1999-05-07 | 2000-12-21 | Dds Drug Delivery Service Ges | Fest-flüssig (halbfeste) Lipidpartikel (Nano-Compartiment-Carrier-NCC) und Verfahren zur Herstellung hochkonzentrierter Lipidpartikel |
| ATE258777T1 (de) | 1999-07-02 | 2004-02-15 | Cognis Iberia Sl | Mikrokapseln - ii |
| EP1064912B1 (de) | 1999-07-02 | 2004-01-28 | Cognis Iberia, S.L. | Mikrokapseln - I |
| GB9916033D0 (en) | 1999-07-09 | 1999-09-08 | Bioprogress Tech Int Inc | A multiple delivery capsule |
| JP4637991B2 (ja) * | 1999-07-27 | 2011-02-23 | 株式会社資生堂 | マイクロカプセル及びその製造方法 |
| AU2001254824A1 (en) | 2000-05-12 | 2001-11-20 | Unilever Plc | Unit dose cleaning product |
| JP4159231B2 (ja) | 2000-06-06 | 2008-10-01 | 花王株式会社 | 油中水型固形メイクアップ化粧料 |
| DE10044062B4 (de) | 2000-08-31 | 2004-10-07 | Coty B.V. | Hochviskoses kosmetisches Produkt |
| JP3674684B2 (ja) * | 2000-09-08 | 2005-07-20 | 株式会社日本天然物研究所 | カプセル入りジェル化粧品 |
| DE10048125A1 (de) | 2000-09-28 | 2002-04-18 | Beiersdorf Ag | Zubereitungen von Emulsionstyp W/O mit erhöhtem Wassergehalt, mit mittelpolaren und/oder unpolaren Lipiden und einem oder mehreren grenzflächenaktiven Polyethern vom Typ A-O-B-O-A |
| DE10059668A1 (de) | 2000-12-01 | 2002-06-20 | Henkel Kgaa | Verwendung von nanopartikulären Wachsen in der Hautkosmetik |
| WO2003028690A1 (de) | 2001-09-29 | 2003-04-10 | Beiersdorf Ag | Kosmetische und dermatologische stifte |
| DE10149143A1 (de) | 2001-10-05 | 2003-04-30 | Henkel Kgaa | Wasserlöslicher Behälter mit umlaufendem Rand |
| DE10210449B4 (de) | 2002-03-09 | 2005-01-13 | Beiersdorf Ag | Beschichtete kosmetische und/oder dermatologische Wirkstoffpartikel, diese enthaltende Zubereitungen sowie ihre Verwendung in Kosmetika und Dermatika |
| FR2854323B1 (fr) | 2003-04-30 | 2005-07-08 | Oreal | Compositions cosmetiques de type emulsion solide eau-dans-huile. |
| US8246970B2 (en) | 2003-04-30 | 2012-08-21 | L'oreal | Water-in-oil solid emulsion-type cosmetic compositions |
| WO2005020949A1 (de) | 2003-08-27 | 2005-03-10 | Beiersdorf Ag | Kosmetische kugelförmige zubereitungen zur topischen anwendung |
| DE202008001135U1 (de) | 2008-01-23 | 2008-08-21 | Stein, Eva | Badekugel |
-
2004
- 2004-08-27 WO PCT/EP2004/009563 patent/WO2005020940A1/de not_active Ceased
- 2004-08-27 JP JP2006524332A patent/JP2007503418A/ja active Pending
- 2004-08-27 US US10/569,382 patent/US8741321B2/en not_active Expired - Fee Related
- 2004-08-27 EP EP04764537A patent/EP1660023B1/de not_active Expired - Lifetime
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0234078A1 (en) * | 1985-01-29 | 1987-09-02 | Ohkawara Kakohki Co., Ltd. | Mono-core type microcapsules and process for producing them |
| DE4223004A1 (de) * | 1992-07-13 | 1994-01-20 | Liedtke Pharmed Gmbh | Einzeldosierte halbfeste topische Arzneiform zur Transdermaltherapie |
| WO2001003538A1 (fr) * | 1999-07-09 | 2001-01-18 | Bourjois | Article pour l'application d'une composition topique et son procede de preparation |
| WO2001038174A1 (fr) * | 1999-11-23 | 2001-05-31 | Delviel | Procede d'encapsulation d'une composition topique |
| EP1129771A1 (de) * | 2000-03-04 | 2001-09-05 | Primacare S.A. | Mikrokapseln |
| US20020022038A1 (en) * | 2000-05-05 | 2002-02-21 | Bruno Biatry | Microcapsules with an aqueous core containing at least one water-soluble cosmetic or dermatological active principle and cosmetic or dermatological compositions containing them |
| EP1201219A1 (fr) * | 2000-10-27 | 2002-05-02 | L'oreal | Utilisation de microcapsules thermostabilisatrices pour améliorer l'activité ou la pénétration de principes actifs cosmétiques ou pharmaceutiques |
| JP2003073230A (ja) * | 2001-08-29 | 2003-03-12 | Shiseido Co Ltd | カプセル含有組成物、および、これを用いた外用組成物 |
| DE10209111A1 (de) * | 2002-03-01 | 2003-09-18 | Beiersdorf Ag | Tücher mit Produktreservoir |
Non-Patent Citations (1)
| Title |
|---|
| DATABASE WPI Section Ch Week 200355, Derwent World Patents Index; Class A14, AN 2003-580900, XP002313041 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8741320B2 (en) | 2003-08-27 | 2014-06-03 | Beiersdorf Ag | Spherical cosmetic preparations for topical application |
| JP2008535502A (ja) * | 2005-04-13 | 2008-09-04 | ビューラー アーゲー | 充填された食品を製造する方法 |
| JP2006298834A (ja) * | 2005-04-21 | 2006-11-02 | Shiseido Co Ltd | 水中油型乳化皮膚化粧料 |
| JP2008543946A (ja) * | 2005-06-27 | 2008-12-04 | イーエルシー マネージメント エルエルシー | カプセル化された化粧用組成物 |
| EP1904024A4 (en) * | 2005-06-27 | 2012-12-26 | Elc Man Llc | CAPSULATED COSMETIC COMPOSITIONS |
| US8691249B2 (en) | 2006-09-22 | 2014-04-08 | Beiersdorf Ag | Peeling capsules |
| WO2008034565A1 (de) | 2006-09-22 | 2008-03-27 | Beiersdorf Ag | Peelingkapseln |
| DE102006044942A1 (de) * | 2006-09-22 | 2008-04-03 | Beiersdorf Ag | Peelingkapseln |
| US20110097396A1 (en) * | 2006-09-22 | 2011-04-28 | Svea Wischhoefer | Peeling capsule with integrated care effect |
| EP2066287B1 (de) * | 2006-09-22 | 2012-04-18 | Beiersdorf AG | Peelingkapsel mit integrierter pflegewirkung |
| DE202007002295U1 (de) | 2007-02-13 | 2008-06-26 | Lorenz, Anneliese F. | Seifen mit optischen oder elastischen Eigenschaften |
| WO2010097174A1 (de) * | 2009-02-24 | 2010-09-02 | Beiersdorf Ag | Stabilisierte peelingkapsel |
| EP3178465A1 (en) | 2010-12-06 | 2017-06-14 | Follica, Inc. | Methods for treating baldness and promoting hair growth |
| EP2922598B1 (de) * | 2012-11-20 | 2019-01-09 | Beiersdorf AG | Sensorisch attraktive hydrodispersion mit wachsen |
Also Published As
| Publication number | Publication date |
|---|---|
| US8741321B2 (en) | 2014-06-03 |
| EP1660023B1 (de) | 2009-01-07 |
| EP1660023A1 (de) | 2006-05-31 |
| US20080089913A1 (en) | 2008-04-17 |
| JP2007503418A (ja) | 2007-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1660023B1 (de) | Kapsel deren kapselhülle bei topischer anwendung nicht mehr gesondert wahrnehmbar ist | |
| US20140227330A1 (en) | Capsule whose envelope is separately imperceptible during the topical use thereof | |
| EP1660033B1 (de) | Kosmetische kugelförmige zubereitungen zur topischen anwendung | |
| EP3038591A1 (de) | Emulgatorfreie, hautkonditionierende und wirkstoffhaltige kosmetische oder dermatologische zubereitung | |
| EP3406243B1 (de) | Wirkstoffkombinationen aus licochalcon a oder einem extrakt aus radix glycyrrhizae inflatae, enthaltend licochalcon a, phenoxyethanol und gewünschtenfalls glycerin | |
| AU2013323808A1 (en) | Foaming skincare formulations | |
| US20200171083A1 (en) | Compositions of silver and cannabinoids | |
| EP2603194B1 (de) | Stabilisierte w/o-emulsionen | |
| EP1477152B1 (de) | Trägersystem für kosmetische oder pharmazeutische Wirkstoffe | |
| DE102005007293A1 (de) | Kapselförmige Reinigungszubereitungen | |
| JP6783512B2 (ja) | 皮膚外用剤 | |
| DE102004010246A1 (de) | Kosmetische Zubereitung enthaltend C24-Fettsäuren | |
| KR20210124197A (ko) | 입자 크기 분포를 갖는 사이클로덱스트린을 포함하는 화장 조성물 | |
| JP6845608B2 (ja) | 皮膚外用剤 | |
| JP6783511B2 (ja) | 皮膚外用剤 | |
| JP7546341B2 (ja) | コレステロール及び/又はフィトステロールを含有する外用組成物 | |
| JP6918543B2 (ja) | 皮膚外用剤または化粧料用組成物 | |
| DE202005002183U1 (de) | Hautverwöhnende Cremelotion | |
| ES2354883T3 (es) | Preparados cosméticos en forma de bola para la aplicación tópica. | |
| DE202010011395U1 (de) | Stabilisierte W/O-Emulsionen | |
| DE10356723A1 (de) | Desodorierende und/oder antitranspirierend wirkende kosmetische Zubereitungen mit einem Gehalt an Licochalcon A oder eines Licocalchon A enthaltenden Extraktes aus Radix Gly-cyrrhizae inflatae | |
| DE10209110A1 (de) | Hautschutzstift | |
| JP2022000422A (ja) | 水中油型乳化化粧料 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| WWE | Wipo information: entry into national phase |
Ref document number: 2004764537 Country of ref document: EP |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2006524332 Country of ref document: JP |
|
| WWP | Wipo information: published in national office |
Ref document number: 2004764537 Country of ref document: EP |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 10569382 Country of ref document: US |
|
| WWP | Wipo information: published in national office |
Ref document number: 10569382 Country of ref document: US |