EP2155148A2 - Surfactant-free foam formulations - Google Patents

Surfactant-free foam formulations

Info

Publication number
EP2155148A2
EP2155148A2 EP08759493A EP08759493A EP2155148A2 EP 2155148 A2 EP2155148 A2 EP 2155148A2 EP 08759493 A EP08759493 A EP 08759493A EP 08759493 A EP08759493 A EP 08759493A EP 2155148 A2 EP2155148 A2 EP 2155148A2
Authority
EP
European Patent Office
Prior art keywords
foam formulation
emulsion
formulation according
pickering emulsion
foam
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
Application number
EP08759493A
Other languages
German (de)
French (fr)
Inventor
Rolf Daniels
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Neubourg Skin Care GmbH and Co KG
Original Assignee
Neubourg Skin Care GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Neubourg Skin Care GmbH and Co KG filed Critical Neubourg Skin Care GmbH and Co KG
Priority to EP08759493A priority Critical patent/EP2155148A2/en
Publication of EP2155148A2 publication Critical patent/EP2155148A2/en
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K51/00—Preparations containing radioactive substances for use in therapy or testing in vivo
    • A61K51/12—Preparations containing radioactive substances for use in therapy or testing in vivo characterised by a special physical form, e.g. emulsion, microcapsules, liposomes, characterized by a special physical form, e.g. emulsions, dispersions, microcapsules
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A61K47/14—Esters of carboxylic acids, e.g. fatty acid monoglycerides, medium-chain triglycerides, parabens or PEG fatty acid esters
    • 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
    • A61K8/04—Dispersions; Emulsions
    • A61K8/046—Aerosols; Foams
    • 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
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • 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
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/062—Oil-in-water emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/731—Cellulose; Quaternized cellulose derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/10—Dispersions; Emulsions
    • A61K9/12—Aerosols; Foams
    • A61K9/124—Aerosols; Foams characterised by the propellant
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A61P17/02—Drugs for dermatological disorders for treating wounds, ulcers, burns, scars, keloids, or the like
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A61P17/16—Emollients or protectives, e.g. against radiation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/30—Characterized by the absence of a particular group of ingredients
    • A61K2800/33—Free of surfactant

Definitions

  • the present invention relates to cosmetic and dermatological
  • the invention relates to the use of Pickering emulsions for the production of foams.
  • Emulsion is generally understood to mean heterogeneous systems which consist of two liquids which are immiscible or only slightly miscible with one another, which are usually referred to as phases.
  • one of the two liquids is dispersed in the form of very fine droplets in the other liquid.
  • the two liquids are water and oil and oil droplets are finely dispersed in water, then it is an oil-in-water emulsion (O / W emulsion, for example, milk).
  • O / W emulsion for example, milk
  • the basic character of an O / W emulsion is characterized by the water.
  • a water-in-oil emulsion (W / O emulsion, e.g., butter) is the reverse principle, with the basic character here being determined by the oil.
  • Emulsifiers In order to achieve the permanent dispersion of one liquid in another, emulsions in the conventional sense require the addition of a surface-active substance (emulsifier).
  • Emulsifiers have an amphiphilic molecular structure consisting of a polar (hydrophilic) and a nonpolar (lipophilic) moiety, which are spatially separated.
  • emulsifier enclosed droplets of the second phase water droplets in W / O or lipid vesicles in O / W emulsions
  • Emulsifiers reduce the interfacial tension between the phases by being located at the interface between the two liquids. They form interface surfaces at the oil / water phase interface, which counteracts irreversible coalescence of the droplets.
  • Emulsifier mixtures are often used to stabilize emulsions.
  • emulsifier or "conventional emulsifier” is known in the art. Conventional emulsifiers and their use are described, for example, in the publications: Vietnamesekosmetik, 4th edition,ticianliche Verlagsgesellschaft mbH Stuttgart, pages 151 to 159, and Fiedler Lexikon der Hilfsstoffe, 5th edition Editio Cantor Verlag Aulendorf, pages 97 to 121 described.
  • emulsifiers can be broken down into ionic (anionic, cationic and amphoteric) and nonionic according to their hydrophilic moiety:
  • an anionic emulsifier is the soap, usually referred to as the water-soluble sodium or potassium salts of the saturated and unsaturated higher fatty acids.
  • hydrophilic part of the molecule of nonionic emulsifiers often consists of glycerol, polyglycerol, sorbitans, carbohydrates or
  • Emulsions represent an important product type in the field of cosmetic and / or dermatological preparations, which is used in the most diverse fields of application.
  • a variety of products - such as lotions and creams - are available for the care of the skin, in particular for the refatting of dry skin.
  • the aim of skin care is to compensate for the loss of fat and water caused by daily washing of the skin.
  • skin care products should protect against environmental influences - especially from sun and wind - and delay the aging of the skin.
  • Cosmetic emulsions are also used as deodorants. Such formulations serve to eliminate body odor that results when the odorless fresh sweat is decomposed by microorganisms.
  • emulsions in the form of cleaning emulsions use. They are mostly used for facial cleansing and in particular for removing decorative cosmetics.
  • Cleaning emulsions have - in contrast to other cleaning preparations such as soap - the advantage of being particularly tolerated by the skin, as they may contain nourishing oils and / or non-polar active substances such as vitamin E in their lipophilic phase.
  • emulsifier-free emulsions are emulsifier-free emulsions. These are free of emulsifiers in the strict sense, i. of low molecular weight amphiphilic substances (molecular weight ⁇ 5000) which can form micelles and / or other liquid crystalline aggregates in higher concentrations.
  • emulsifier is to be understood here as customary in the art: IUPAC defines the properties of an emulsifier as follows: Emulsifiers are surface-active substances which preferentially adhere to the interface between the oil and water phases and thus reduce the interfacial tension In addition, these substances are able to improve the stability of emulsions by reducing the rate of aggregation and / or coalescence.
  • emulsifiers for the stabilization of pharmaceutical and cosmetic emulsions predominantly so-called genuine emulsifiers, ie conventional emulsifiers in the sense of the present description, are used, which according to their structure and their physicochemical behavior belong to the substance class of the surfactants. They are characterized by an amphiphilic structure and the ability to micellar association.
  • emulsifier-free has also been established in the field of medicine, according to a definition of the concept adopted by the Society for Dermopharmacy in an interdisciplinary consensus between pharmacists, dermatologists and other experts (http://www.dermotopics.de/de/ausgabe_ 1 _03_e / emulgatorok_ 1 _2003_d.
  • emulsifier-free if it is stabilized with surface-active macromolecules (molecular weight above 5000) instead of emulsifiers in the narrower sense (conventional emulsifiers).
  • a special form of the emulsifier-free emulsion is the Pickering emulsion.
  • Pickering / solids-stabilized emulsions are stabilized by finely divided solid particles and make it possible to dispense with conventional emulsifiers as far as possible.
  • the solid substance In Pickering emulsions, the solid substance accumulates at the phase interface oil / water in the form of a layer, which prevents the disperse phases from flowing together. Of particular importance in this case are the wetting properties of the solid particles, which should be wetted by both hydrophilic and lipophilic phases.
  • a particular application of cosmetic and / or dermatological emulsions is the application as foams.
  • Foam formulations have the
  • Foams are complicated physical structures that require special tuning of the foam-forming components.
  • Foams are generally obtained by spraying an emulsion formulation or an aqueous surfactant (stabilizer) solution.
  • the propellant-added emulsion is discharged from a pressurized container (such systems are also referred to in the literature and patent literature as aerosol foams).
  • the pressurized mixture of emulsion and propellant gas expands and forms the foam bubbles.
  • foams can also be produced using other systems, such as pump sprays.
  • Coordinated foam formulations have a stable two- or more-phase polydisperse structure on application which forms a network structure on the skin comparable to a membrane.
  • Such network structures have the advantage that they form a protective function, for example before contact with water, but allow unimpeded gas exchange with the environment. In such foams, there is virtually no obstruction of Perspiratio insensibiles and no corresponding heat accumulation. Thus, the positive properties of a protective and care function are associated with an unchanged skin respiration.
  • Foam formulations known heretofore include conventional surfactants / emulsifiers which provide for the stabilization of the emulsion and for the subsequent foam stability.
  • WO 2004/017930 describes further Pickering emulsions, which are distinguished, in particular, by a low viscosity and are thus suitable for dermatological wipes. Such low viscosity Pickering emulsions can even be sprayed under mist formation.
  • foam formulations associated with those of the Pickering emulsions can be prepared without conventional emulsifiers or with very low levels of conventional emulsifiers, which combine the positive properties of the foam, namely the physical structure and pleasant applicability, with good skin tolerance. This combination of properties makes such foam formulation particularly useful for cosmetic and dermatological formulations for sensitive skin types. It Compatibility and ease of use are advantageously combined.
  • Foam products leads.
  • foams are obtained, for example, by incorporating propellant gases in O / W emulsion systems. If the propellant gas dissolved in the dispersed oil phase evaporates during foaming, a foam forms (gas in liquid dispersion). Upon evaporation or expansion of the propellant gas dissolved in the disperse oil phase, dilatation of the dispersed oil phase occurs. It is now surprising that the solids network at the phase interface of this strain load withstands and it does not break the preparation during foaming.
  • the invention thus relates to foam formulations comprising a
  • Pickering emulsion of the oil-in-water type comprising an oil phase and a water phase, and optionally propellant gas.
  • the invention relates to foam formulations containing not more than 0.5% by weight of conventional emulsifiers, preferably not more than 0.3% by weight, more preferably not more than 0.1% by weight, and more preferably free from conventional emulsifiers.
  • the levies are each related to the total weight of the emulsion without propellant gas.
  • the invention relates to the use of Pickering emulsions, in particular Pickering emulsions, which are substantially free or free of conventional emulsifiers, for the production of foam formulations. Furthermore, the invention relates to the use of foam formulations based on Pickering emulsions as a carrier for active ingredients, as skin care agents, as skin cleansers or as sunscreen. The foam formulation can therefore be used as a cosmetic, medical device or pharmaceutical.
  • the invention includes a process for the preparation of foam formulations based on Pickering emulsions.
  • the method comprises the steps:
  • foam formulations are formulations, in particular emulsions, which are prepared to produce foam.
  • the formulations may either be filled with propellant gas into a pressure vessel or be bottled without propellant in a container other than a pressure vessel, which makes it possible, when dispensing the
  • substantially emulsifier-free emulsions are those emulsions which are not more than 0.5% by weight, preferably not more than 0.3% by weight, more preferably not more than 0.1% by weight of conventional emulsifiers contain.
  • emulsifier-free emulsions are those which contain no conventional emulsifiers.
  • a Pickering emulsion is a solids-stabilized emulsion.
  • it is a solids-stabilized emulsion of the oil-in-water type (O / W emulsion).
  • a solids-stabilized emulsion according to the invention comprises not more than 0.5% by weight, preferably not more than 0.3% by weight, more preferably not more than 0.1% by weight of conventional emulsifiers.
  • conventional emulsifiers according to the present invention are anionic, cationic, amphoteric and nonionic surfactants.
  • anionic surfactants are neutralized branched and / or unbranched, saturated or unsaturated fatty acids having a chain length of 10 to 40 carbon atoms.
  • Typical representatives of the cationic surfactants are
  • Typical representatives of the nonionic surfactants have a hydrophilic moiety, such as glycerol, polyglycerol, sorbitan, carbohydrates or polyoxyethylene glycols, which is linked via ester and / or ether bonds with the lipophilic moiety, which usually consists of fatty alcohols, fatty acids or iso-fatty acids.
  • the polyethoxylated fatty acid esters having chain lengths of 10 to 40 carbon atoms and having a degree of ethoxylation of 5 to 100 belong to this group.
  • conventional emulsifiers for the purposes of the present application are all amphiphilic substances with a molecular weight ⁇ 5000, which in a higher concentration micelles and / or others
  • conventional emulsifiers are all surface-active substances which, in particular at conventional storage and application temperatures, e.g. Room temperature is not present as a solid or polymer.
  • a solid emulsifier is a particulate substance which is wettable by both lipophilic and hydrophilic liquids. These may be inorganic or organic solids. The particles may also be untreated or coated. The particle size is preferably between 1 nm and 200 nm, more preferably between 5 nm and 100 nm.
  • Suitable solid emulsifiers are particulate inorganic or organic solids which are wettable by both lipophilic and hydrophilic liquids. Suitable representatives are, for example, titanium dioxide, in particular coated Titanium oxide (eg available from Merck KGaA under the name Eusolex® T-2000), zinc oxide (obtainable from BASF AG under the name Z-Cote Max) silicon dioxide, in particular highly disperse silicon dioxide, Fe 2 O 3 , Veegum, bentonite and ethylcellulose. Further, alumina, nanoparticulate precipitated calcium carbonate, carbon, magnesia, magnesium trisilicate, crystalline fatty alcohols and fatty acids, polymer latices, e.g. Polystyrenes or polymethacrylates, and polymer pseudolatices. Mixtures of the abovementioned solid emulsifiers can also be used. Coated titanium dioxide or zinc oxide are preferred.
  • the emulsions according to the invention contain more than 1% by weight of solid emulsifier, preferably more than 2% by weight of solid emulsifier, in particular from 2 to 7% by weight of solid emulsifier.
  • the emulsions according to the invention particularly preferably contain 3 to 4% by weight of the most solid ffemulgator. The data are in each case based on the total weight of the emulsion without propellant gas.
  • Suitable components which can form the oil phase can be selected from the polar and non-polar oils or mixtures thereof.
  • the oil phase of the inventive formulations is advantageously selected from the group of lecithins and fatty acid triglycerides, from the group of propylene glycols or butylene glycols, fatty acid esters, from the group of natural waxes of animal and vegetable origin, from the group of ester oils, from the group of dialkyl ethers and dialkyl carbonates, from the group of branched and unbranched hydrocarbons and waxes and from the group of cyclic and linear silicone oils.
  • Particular preference is given to triglycerides, in particular caprylic / capric triglyceride, obtainable under the name Miglyol 812 from Sasol and its blending with further oil and wax components.
  • triglycerides in particular caprylic / capric acid triglyceride, obtainable under the name Miglyol 812 from Sasol / Myritol 312 from Cognis.
  • the emulsions according to the invention preferably contain from 10 to 50% by weight of oil phase, more preferably from 25 to 35% by weight of oil phase.
  • the data are in each case based on the total weight of the emulsion without propellant gas.
  • the water phase may contain cosmetic adjuvants, e.g. lower alcohols (e.g., ethanol, isopropanol), lower diols or polyols, and their ethers (e.g., propylene glycol, glycerin, butylene glycol, hexylene glycol, and ethylene glycol), foam stabilizers, and thickeners.
  • cosmetic adjuvants e.g. lower alcohols (e.g., ethanol, isopropanol), lower diols or polyols, and their ethers (e.g., propylene glycol, glycerin, butylene glycol, hexylene glycol, and ethylene glycol), foam stabilizers, and thickeners.
  • Suitable thickeners are polymeric thickeners which are partially water soluble or at least water dispersible and form gels or viscous solutions in aqueous systems. They increase the viscosity of the water either by binding water molecules (hydration) or by absorbing and enveloping the water in their intertwined macromolecules, thereby restricting the mobility of the water.
  • Suitable polymers are:
  • Modified natural substances such as cellulose ethers (eg hydroxypropyl cellulose ethers, hydroxyethyl cellulose and hydroxypropylmethyl cellulose ethers); Natural compounds such as agar-agar, carrageenan, polyoses, starch, dextrins, gelatin, casein;
  • cellulose ethers eg hydroxypropyl cellulose ethers, hydroxyethyl cellulose and hydroxypropylmethyl cellulose ethers
  • Natural compounds such as agar-agar, carrageenan, polyoses, starch, dextrins, gelatin, casein;
  • Synthetic compounds e.g. Vinyl polymers, polyethers, polyimines, polyamides and derivatives of polyacrylic acid; and - inorganic compounds such as e.g. Polysilicic acid and clay minerals.
  • a cellulose ether is included. Particular preference is given to hydroxypropylmethylcellulose.
  • the emulsions according to the invention preferably contain from 0.2 to 1.5% by weight
  • Thickener (based on the dry weight of the thickener and the total weight of the emulsion without propellant gas). Particularly preferred are 0.5 to 0.8 wt .-% thickener.
  • the active ingredient contained can be chosen from among all surface-applied on the skin agents and mixtures thereof.
  • the active ingredient may be cosmetic or pharmaceutical. Accordingly, one obtains cosmetic or dermatological (to be used as a medical device or drug product) foam formulations. Furthermore, the formulation can be used to protect the skin from environmental influences.
  • the active substance can be purely vegetable or synthetic.
  • the group of active ingredients may also overlap with the other ingredient groups, such as the oil component, the thickeners or the solids emulsifiers.
  • some oil components can also serve as active ingredients, such as oils with polyunsaturated fatty acids, or solid emulsifiers, such as particulate titanium dioxide can serve as a UV filter.
  • the substances can be assigned to several groups.
  • Active ingredients of the formulations according to the invention are advantageously selected from the group of substances with moisturizing and barrier-strengthening properties, such as, for example, As hydro viton, a replica of NMF, Pyrrolidoncarbonklare and their salts, lactic acid and its salts, glycerol, sorbitol, propylene glycol and urea, substances from the group of proteins and protein hydrolysates such.
  • As collagen, elastin and silk protein substances from the group of glucosaminoglucans, such as. B. hyaluronic acid, from the group of carbohydrates, such as.
  • pentavidin which corresponds in composition to the carbohydrate mixture of the human horny layer, and the group of lipids and lipid precursors such as ceramides.
  • Further advantageous agents may be further selected in the context of the present invention from the group of vitamins, such as. As panthenol, niacin, ⁇ -tocopherol and its esters, vitamin A and vitamin C.
  • the active ingredients selected from the group of antioxidants z. G., Galate and polyphenols. Urea, hyaluronic acid and pentavitin are preferred substances.
  • substances with skin calming and regenerating action are used as active ingredients, such as.
  • active ingredients such as.
  • Advantageous active ingredients in the context of the present invention are also plants and plant extracts. These include e.g. Algae, aloe, arnica, beard braid, comfrey, birch, nettle, calendula, oak, ivy, witch hazel, henna, hops, chamomile, butcher's broom, peppermint, calendula, rosemary, sage, green tea, tea tree, horsetail, thyme and walnut and their extracts.
  • plants and plant extracts include e.g. Algae, aloe, arnica, beard braid, comfrey, birch, nettle, calendula, oak, ivy, witch hazel, henna, hops, chamomile, butcher's broom, peppermint, calendula, rosemary, sage, green tea, tea tree, horsetail, thyme and walnut and their extracts.
  • the preparations according to the invention may also contain as active ingredients antimycotics and antiseptics / disinfinents of synthetic or natural origin.
  • active ingredients are glucocorticoids, antibiotics, analgesics, antiphlogistics, antirheumatics, antiallergic drugs, antiparasitics, antipruriticosa, antipsoriatics, retinoids, local anesthetics, vein therapeutics, keratolytics, hyperemic substances, coronary therapeutics (nitrates / nitro compounds), antivirals, cytostatics, hormones, wound healing promoting agents, eg growth factors, enzyme preparations and insecticides.
  • the formulations may include dyes, pearlescent pigments, fragrances / perfume,
  • Light stabilizer substances preservatives, complexing agents, antioxidants and repellents.
  • Suitable propellants are z. B. N 2 O, propane, butane and i-butane, the finished
  • Foam formulation contains from 5 to 15 wt .-%, preferably about 10 wt .-% propellant gas.
  • the foam formulations according to the invention are made by providing an oil-in-water type emulsion of Pickering and filling the emulsion or Pickering emulsion and optionally propellant gas into one optionally produced pressure vessel.
  • the Pickeringemulsion can also be filled into another container, which is suitable even without propellant gas to deliver the Pickeringemulsion as a foam.
  • the Pickering emulsion is prepared in the following steps:
  • the oil phase and the water phase at a temperature of 50 to 90 0 C, preferably from 50 to 70 0 C and particularly preferably at about 60 0 C homogenized.
  • the Pickering emulsion comprises a thickening agent
  • the following steps are added: 5. Provide an aqueous thickener solution
  • the Pickeringemulsion is applied with 10 wt .-% propellant gas for the preparation of the foam formulation. 4.
  • the foam formulations of the present invention can be used for all cosmetic and dermatological (medical or pharmaceutical) purposes.
  • the formulations could be used as a skin care or skin cleanser. They can also serve as carriers for active ingredients and be used in the medical dermatological field.
  • the formulations can be used as sunscreen agents.
  • Many of the solid emulsifiers, such as titanium dioxide, are effective UVA and UVB filters.
  • composition of the primary Pickering emulsion Composition of the primary Pickering emulsion:
  • composition of the foam formulation :
  • Eusolex T2000 is weighed and transferred into a laboratory homogenizer and mixed with the heated to 60 0 C Miglyol 812 within one minute, and homogenized within 5 minutes.
  • the water is heated to 60 ° C. and added at 1000 rpm for one minute.
  • the mixture is homogenized at 3000 rpm for 5 minutes.
  • hypromellose solution 30.00 g are added to 60.00 g of the primary Pickering emulsion with stirring.
  • the hypromellose Pickeringemulsion is then applied in aluminum monoblock cans with 10.00 g of propellant gas.
  • a stable, fine-bubble cream foam is formed when removing the foam formulation from the compressed gas package by means of a suitable valve with attached foam applicator.
  • the structure of the cream foam is maintained for a period of time sufficient to evenly distribute the foam on the skin. 5.2.
  • composition of the primary Pickering emulsion Composition of the primary Pickering emulsion:
  • Myritol 318 from Cognis (caprylic acid / capric triglyceride) 30.00 g almond oil 100.00 g water
  • composition of the xanthan gum solution (1%):
  • composition of the foam formulation :
  • Eusolex T 2000 is weighed and transferred into a laboratory homogenizer and mixed with the 0 to 60 C mixture of Cetiol V, Myritol 318 and almond oil within one minute and homogenized within 5 minutes.
  • the water is heated to 60 ° C. and added at 1000 rpm for one minute.
  • the mixture is homogenized at 3000 rpm for 5 minutes.
  • Preparation of foam formulation 30.00 g of xanthan gum solution is added to 60.00 g of the primary Pickering emulsion with stirring.
  • the xanthan gum solution-containing Pickeringemulsion is then applied in aluminum monoblock cans with 10.00 g of propellant gas.
  • a stable, fine-bubble cream foam is formed when removing the foam formulation from the compressed gas package by means of a suitable valve with attached foam applicator.
  • the structure of the cream foam is maintained for a period of time sufficient to evenly distribute the foam on the skin.
  • composition of the primary Pickering emulsion Composition of the primary Pickering emulsion:
  • ZCote is weighed and transferred to a laboratory homogenizer and mixed with the mixture of Cetiol V, Myritol 318, Cetiol SN and almond oil within one minute and homogenized within 5 minutes.
  • the water is added at 1000 rpm within one minute.
  • the mixture is homogenized at 3000 rpm for 5 minutes.
  • hypromellose solution 52.00 g are added to 40.00 g of the primary Pickering emulsion with stirring.
  • the hypromellose Pickeringemulsion is then applied in aluminum monoblock cans with 8.00 g of propellant gas.
  • a stable, fine-bubble cream foam is formed when removing the foam formulation from the compressed gas package by means of a suitable valve with attached foam applicator.
  • the structure of the cream foam is maintained for a period of time sufficient to evenly distribute the foam on the skin.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Dispersion Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dermatology (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Toxicology (AREA)
  • Rheumatology (AREA)
  • Pain & Pain Management (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Cosmetics (AREA)
  • Medicinal Preparation (AREA)
  • Colloid Chemistry (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
  • Detergent Compositions (AREA)

Abstract

Foam formulation comprises an emulsifying agent-free emulsion of the type oil-in-water comprising an oil phase and a water phase. An independent claim is included for producing the foam formulation based on the pickering emulsion, comprising: producing a pickering emulsion of the type oil-in-water, filling the pickering emulsion and propulsion gas in an pressure tank or filling the pickering emulsion other than a pressure tank, which produces a foam on release of the pickering emulsion.

Description

TENSIDFREIE SCHAUMFORMULIERUNGEN TENSID-FREE FOAM FORMULATIONS
Technisches Gebiet der ErfindungTechnical field of the invention
Die vorliegende Erfindung betrifft kosmetische und dermatologischeThe present invention relates to cosmetic and dermatological
Schaumformulierungen auf Basis von Emulsionen vom Typ Öl- in- Wasser, die frei sind oder im Wesentlichen frei sind von herkömmlichen Emulgatoren. Insbesondere betrifft die Erfindung die Verwendung von Pickering-Emulsionen für die Herstellung von Schäumen.Foam formulations based on emulsions of the oil-in-water type, which are free or substantially free of conventional emulsifiers. In particular, the invention relates to the use of Pickering emulsions for the production of foams.
Hintergrund der ErfindungBackground of the invention
1. Emulsionen1. Emulsions
Unter Emulsion versteht man im Allgemeinen heterogene Systeme, die aus zwei nicht oder nur begrenzt miteinander mischbaren Flüssigkeiten bestehen, die üblicherweise als Phasen bezeichnet werden. In einer Emulsion ist eine der beiden Flüssigkeiten in Form feinster Tröpfchen in der anderen Flüssigkeit dispergiert.Emulsion is generally understood to mean heterogeneous systems which consist of two liquids which are immiscible or only slightly miscible with one another, which are usually referred to as phases. In an emulsion, one of the two liquids is dispersed in the form of very fine droplets in the other liquid.
Sind die beiden Flüssigkeiten Wasser und Öl und liegen Öltröpfchen fein verteilt in Wasser vor, so handelt es sich um eine Öl-in- Wasser-Emulsion (O/W-Emulsion, z.B. Milch). Der Grundcharakter einer O/W-Emulsion ist durch das Wasser geprägt. Bei einer Wasser-in-Öl-Emulsion (W/O-Emulsion, z.B. Butter) handelt es sich um das umgekehrte Prinzip, wobei der Grundcharakter hier durch das Öl bestimmt wird.If the two liquids are water and oil and oil droplets are finely dispersed in water, then it is an oil-in-water emulsion (O / W emulsion, for example, milk). The basic character of an O / W emulsion is characterized by the water. A water-in-oil emulsion (W / O emulsion, e.g., butter) is the reverse principle, with the basic character here being determined by the oil.
Um die dauerhafte Dispergierung einer Flüssigkeit in einer anderen zu erreichen, ist bei Emulsionen im herkömmlichen Sinn der Zusatz einer grenzflächenaktiven Substanz (Emulgator) notwendig. Emulgatoren weisen einen amphiphilen Molekülaufbau auf, bestehend aus einem polaren (hydrophilen) und einem unpolaren (liphophilen) Molekülteil, die räumlich voneinander getrennt sind. In einfachen Emulsionen liegen in der einen Phase feindisperse, von einer Emulgatorhülle umschlossene Tröpfchen der zweiten Phase (Wassertröpfchen in W/O- oder Lipidvesikel in O/W-Emulsionen) vor. Emulgatoren setzen die Grenzflächenspannung zwischen den Phasen herab, indem sie an der Grenzfläche zwischen beiden Flüssigkeiten angeordnet sind. Sie bilden an der Phasengrenze Öl/Wasser Grenzflächenfϊlme aus, wodurch dem irreversiblen Zusammenfließen der Tröpfchen entgegengewirkt wird. Zur Stabilisierung von Emulsionen werden häufig Emulgatorgemische verwendet.In order to achieve the permanent dispersion of one liquid in another, emulsions in the conventional sense require the addition of a surface-active substance (emulsifier). Emulsifiers have an amphiphilic molecular structure consisting of a polar (hydrophilic) and a nonpolar (lipophilic) moiety, which are spatially separated. In simple emulsions are in one phase finely dispersed, by an emulsifier enclosed droplets of the second phase (water droplets in W / O or lipid vesicles in O / W emulsions) before. Emulsifiers reduce the interfacial tension between the phases by being located at the interface between the two liquids. They form interface surfaces at the oil / water phase interface, which counteracts irreversible coalescence of the droplets. Emulsifier mixtures are often used to stabilize emulsions.
Der Begriff „Emulgator" bzw. „herkömmlicher Emulgator" ist im Stand der Technik bekannt. Herkömmliche Emulgatoren und ihre Verwendung werden beispielsweise in den Publikationen: Pflegekosmetik, 4. Auflage, Wissenschaftliche Verlagsgesellschaft mbH Stuttgart, Seiten 151 bis 159, und Fiedler Lexikon der Hilfsstoffe, 5. Auflage Editio Cantor Verlag Aulendorf, Seiten 97 bis 121, beschrieben.The term "emulsifier" or "conventional emulsifier" is known in the art. Conventional emulsifiers and their use are described, for example, in the publications: Pflegekosmetik, 4th edition, Wissenschaftliche Verlagsgesellschaft mbH Stuttgart, pages 151 to 159, and Fiedler Lexikon der Hilfsstoffe, 5th edition Editio Cantor Verlag Aulendorf, pages 97 to 121 described.
Herkömmliche Emulgatoren können entsprechend ihrem hydrophilien Molekülteil in ionische (anionische, kationische und amphotere) und nichtionische untergliedert werden:Conventional emulsifiers can be broken down into ionic (anionic, cationic and amphoteric) and nonionic according to their hydrophilic moiety:
• Das wohl bekannteste Beispiel eines anionischen Emulgators ist die Seife, als die man gewöhnlich die wasserlöslichen Natrium- oder Kaliumsalze der gesättigten und ungesättigten höheren Fettsäuren bezeichnet.The most well-known example of an anionic emulsifier is the soap, usually referred to as the water-soluble sodium or potassium salts of the saturated and unsaturated higher fatty acids.
• Wichtige Vertreter der kationischen Emulgatoren sind die quartären Ammonium- Verbindungen.• Important representatives of the cationic emulsifiers are the quaternary ammonium compounds.
• Der hydrophile Molekülteil nichtionischer Emulgatoren besteht häufig aus Glycerin, Polyglycerin, Sorbitanen, Kohlenhydraten bzw.• The hydrophilic part of the molecule of nonionic emulsifiers often consists of glycerol, polyglycerol, sorbitans, carbohydrates or
Polyoxyethylenglykolen und ist meistens über Ester- und Etherbindungen mit dem lipophilen Molekülteil verknüpft. Dieser besteht üblicherweise aus Fettalkoholen, Fettsäuren oder Isofettsäuren. Durch Variation der Struktur und der Größe des polaren und des unpolaren Molekülteils lassen sich Lipophilie und Hydrophilie von Emulgatoren in weiten Grenzen verändern.Polyoxyethylene glycols and is usually linked via ester and ether bonds with the lipophilic moiety. This usually consists of fatty alcohols, fatty acids or iso-fatty acids. By varying the structure and size of the polar and non-polar part of the molecule, the lipophilicity and hydrophilicity of emulsifiers can be varied within wide limits.
Entscheidend für die Stabilität einer Emulsion ist die richtige Auswahl der Emulgatoren. Dabei sind die Charakteristiken aller im System enthaltenen Stoffe zu berücksichtigen. Betrachtet man z. B. Hautpflegeemulsionen, so können polare Ölkomponenten wie z. B. UV-Filter zu Instabilitäten führen. Neben den Emulgatoren werden daher noch andere Stabilisatoren verwendet, die beispielsweise die Viskosität der Emulsion erhöhen und/oder als Schutzkolloid wirken.Decisive for the stability of an emulsion is the correct choice of emulsifiers. The characteristics of all substances contained in the system must be taken into account. Looking at z. As skin care emulsions, so can polar oil components such. B. UV filters lead to instabilities. In addition to the emulsifiers therefore other stabilizers are used, for example, increase the viscosity of the emulsion and / or act as a protective colloid.
Emulsionen stellen einen wichtigen Produkttyp im Bereich kosmetischer und/oder dermatologischer Zubereitungen dar, welcher in den unterschiedlichsten Anwendungsgebieten eingesetzt wird. So stehen für die Pflege der Haut, insbesondere für die Rückfettung trockener Haut, eine Vielzahl von Produkten - wie Lotionen und Cremes - zur Verfügung. Ziel der Hautpflege ist es, den durch tägliches Waschen verursachten Fett- und Wasserverlust der Haut auszugleichen. Außerdem sollen Hautpflegeprodukte vor Umwelteinflüssen - insbesondere vor Sonne und Wind - schützen und die Hautalterung verzögern.Emulsions represent an important product type in the field of cosmetic and / or dermatological preparations, which is used in the most diverse fields of application. Thus, a variety of products - such as lotions and creams - are available for the care of the skin, in particular for the refatting of dry skin. The aim of skin care is to compensate for the loss of fat and water caused by daily washing of the skin. In addition, skin care products should protect against environmental influences - especially from sun and wind - and delay the aging of the skin.
Kosmetische Emulsionen werden auch als Desodorantien verwendet. Solche Formulierungen dienen dazu, Körpergeruch zu beseitigen, der entsteht, wenn der an sich geruchlose frische Schweiß durch Mikroorganismen zersetzt wird.Cosmetic emulsions are also used as deodorants. Such formulations serve to eliminate body odor that results when the odorless fresh sweat is decomposed by microorganisms.
Auch zur Reinigung der Haut und Hautanhangsgebilde finden Emulsionen in Form von Reinigungsemulsionen Verwendung. Sie werden meist der Gesichtsreinigung und insbesondere zur Entfernung von dekorativer Kosmetik eingesetzt. Derartige Reinigungsemulsionen haben - im Gegensatz zu anderen Reinigungszubereitungen wie beispielsweise Seife - den Vorteil, besonders hautverträglich zu sein, da sie in ihrer lipophilen Phase pflegende Öle und/oder unpolare Wirkstoffe - wie z.B. Vitamin E - enthalten können.Also for cleaning the skin and skin appendages find emulsions in the form of cleaning emulsions use. They are mostly used for facial cleansing and in particular for removing decorative cosmetics. such Cleaning emulsions have - in contrast to other cleaning preparations such as soap - the advantage of being particularly tolerated by the skin, as they may contain nourishing oils and / or non-polar active substances such as vitamin E in their lipophilic phase.
2. Emulgatorfreie Emulsionen2. Emulsifier-free emulsions
Eine besondere Form der Emulsion stellen emulgatorfreie Emulsionen dar. Diese sind frei von Emulgatoren im engeren Sinne, d.h. von amphiphilen Substanzen mit niedriger Molmasse (Molmasse < 5000), die in höherer Konzentration Mizellen und/oder andere flüssigkristalline Aggregate bilden können. Der Begriff „Emulgator" soll hier wie im Fachgebiet üblich verstanden werden. Die IUPAC definiert die Eigenschaften eines Emulgators wie folgt: Emulgatoren sind grenzflächenaktive Substanzen. Sie halten sich bevorzugt in der Grenzfläche zwischen Öl- und Wasserphase auf und senken dadurch die Grenzflächenspannung. Emulgatoren erleichtern bereits bei niedriger Konzentration die Emulsionsbildung. Darüber hinaus vermögen diese Substanzen die Stabilität von Emulsionen zu verbessern, indem sie die Geschwindigkeit der Aggregation und/oder der Koaleszenz verringern.A special form of the emulsion are emulsifier-free emulsions. These are free of emulsifiers in the strict sense, i. of low molecular weight amphiphilic substances (molecular weight <5000) which can form micelles and / or other liquid crystalline aggregates in higher concentrations. The term "emulsifier" is to be understood here as customary in the art: IUPAC defines the properties of an emulsifier as follows: Emulsifiers are surface-active substances which preferentially adhere to the interface between the oil and water phases and thus reduce the interfacial tension In addition, these substances are able to improve the stability of emulsions by reducing the rate of aggregation and / or coalescence.
Zur Stabilisierung pharmazeutischer und kosmetischer Emulsionen werden überwiegend sogenannte echte Emulgatoren, d.h. herkömmliche Emulgatoren im Sinne der vorliegenden Beschreibung, eingesetzt, die ihrer Struktur und ihrem physikalisch-chemischen Verhalten nach zur Stoffklasse der Tenside zählen. Sie zeichnen sich durch einen amphiphilen Aufbau und die Fähigkeit zur Mizellenassoziation aus. Auch der Begriff „emulgatorfrei" ist im Fachgebiet etabliert. Nach einer im interdisziplinären Konsens zwischen Pharmazeuten, Dermatologen und anderen Fachleuten verabschiedeten Begriffsdefinition der Gesellschaft für Dermopharmazie (http ://www. dermotopics .de/german/ausgabe_ 1 _03_d/emulgatorfrei_ 1 _2003_d.htm) kann eine Formulierung als „emulgatorfrei" bezeichnet werden, wenn sie statt mit Emulgatoren im engeren Sinne (herkömmliche Emulgatoren) mit grenzflächenaktiven Makromolekülen (Molmasse von über 5000) stabilisiert ist.For the stabilization of pharmaceutical and cosmetic emulsions predominantly so-called genuine emulsifiers, ie conventional emulsifiers in the sense of the present description, are used, which according to their structure and their physicochemical behavior belong to the substance class of the surfactants. They are characterized by an amphiphilic structure and the ability to micellar association. The term "emulsifier-free" has also been established in the field of medicine, according to a definition of the concept adopted by the Society for Dermopharmacy in an interdisciplinary consensus between pharmacists, dermatologists and other experts (http://www.dermotopics.de/de/ausgabe_ 1 _03_e / emulgatorfrei_ 1 _2003_d. htm), a formulation may be termed "emulsifier-free" if it is stabilized with surface-active macromolecules (molecular weight above 5000) instead of emulsifiers in the narrower sense (conventional emulsifiers).
3. Pickering-Emulsion3. Pickering emulsion
Eine besondere Form der emulgatorfreien Emulsion stellt die Pickering-Emulsion dar. Pickering-/feststoffstabilisierte Emulsionen sind durch feinstverteilte Feststoffteilchen stabilisiert und ermöglichen es, auf herkömmliche Emulgatoren weitestgehend zu verzichten.A special form of the emulsifier-free emulsion is the Pickering emulsion. Pickering / solids-stabilized emulsions are stabilized by finely divided solid particles and make it possible to dispense with conventional emulsifiers as far as possible.
In Pickering-Emulsionen kommt es zu einer Anreicherung des festen Stoffes an der Phasengrenze Öl/Wasser in Form einer Schicht, wodurch ein Zusammenfließen der dispersen Phasen verhindert wird. Von wesentlicher Bedeutung sind dabei insbesondere die Benetzungseigenschaften der Feststoffpartikel, welche sowohl von hydrophilen als auch lipophilen Phasen benetzt werden sollten.In Pickering emulsions, the solid substance accumulates at the phase interface oil / water in the form of a layer, which prevents the disperse phases from flowing together. Of particular importance in this case are the wetting properties of the solid particles, which should be wetted by both hydrophilic and lipophilic phases.
4, S chaumformulierungen4, foam formulations
Eine besondere Anwendungsform kosmetischer und oder dermatologischer Emulsionen ist die Applikation als Schäume. Schaumformulierungen haben denA particular application of cosmetic and / or dermatological emulsions is the application as foams. Foam formulations have the
Vorteil, sich leicht auf der Haut verteilen zu lassen. Die schaumige Konsistenz wird als angenehm empfunden und die Produkte hinterlassen in der Regel ein gutes Hautgefühl. Insbesondere wirkt sich aber auch die physikalische Struktur des Schaumes positiv auf die Hautschutzfunktion aus. Schäume sind komplizierte physikalische Gebilde, die einer besonderen Abstimmung der den Schaum bildenden Komponenten bedürfen. Schäume werden generell durch Versprühen einer Emulsionsformulierung oder einer wässrigen Tensid-(Stabilisator-)lösung erhalten. Beispielsweise wird die mit Treibgas versetzte Emulsion aus einem unter Druck stehenden Behältnis abgegeben (solche Systeme werden in der Literatur und Patentliteratur auch als Aerosolschäume bezeichnet). Dabei expandiert das unter Druck stehende Gemisch aus Emulsion und Treibgas und bildet die Schaumbläschen. Insbesondere kommt es zu einer Expansion der dispersen Ölphase, in welcher das öllösliche Gas gelöst ist. Schäume können aber auch mit Hilfe anderer Systeme erzeugt werden, wie beispielsweise Pumpsprays.The advantage of being easily distributed on the skin. The foamy consistency is perceived as pleasant and the products usually leave a good skin feeling. In particular, however, the physical structure of the Foam positive on the skin protection function. Foams are complicated physical structures that require special tuning of the foam-forming components. Foams are generally obtained by spraying an emulsion formulation or an aqueous surfactant (stabilizer) solution. For example, the propellant-added emulsion is discharged from a pressurized container (such systems are also referred to in the literature and patent literature as aerosol foams). In this case, the pressurized mixture of emulsion and propellant gas expands and forms the foam bubbles. In particular, there is an expansion of the dispersed oil phase in which the oil-soluble gas is dissolved. However, foams can also be produced using other systems, such as pump sprays.
Abgestimmte Schaumformulierungen weisen eine stabile zwei- oder mehrphasige polydisperse Struktur bei der Applikation auf, die auf der Haut eine Netzstruktur, vergleichbar mit einer Membran bildet. Solche Netzstrukturen haben den Vorteil, dass diese eine Schutzfunktion, beispielsweise vor Kontakt mit Wasser ausbilden, jedoch einen ungehinderten Gasaustausch mit der Umgebung zulassen. Bei solchen Schäumen kommt es praktisch zu keiner Behinderung der Perspiratio insensibiles und keinem entsprechenden Wärmestau. Damit werden die positiven Eigenschaften einer Schutz- und Pflegefunktion mit einer unveränderten Hautatmung verbunden.Coordinated foam formulations have a stable two- or more-phase polydisperse structure on application which forms a network structure on the skin comparable to a membrane. Such network structures have the advantage that they form a protective function, for example before contact with water, but allow unimpeded gas exchange with the environment. In such foams, there is virtually no obstruction of Perspiratio insensibiles and no corresponding heat accumulation. Thus, the positive properties of a protective and care function are associated with an unchanged skin respiration.
Bisher bekannte Schaumformulierungen enthalten herkömmliche Tenside/Emulgatoren, die für die Stabilisierung der Emulsion und für die darauf folgende Schaumstabilität sorgen.Foam formulations known heretofore include conventional surfactants / emulsifiers which provide for the stabilization of the emulsion and for the subsequent foam stability.
Herkömmliche Emulgatoren bzw. Tenside werden jedoch immer wieder als Ursache für Unverträglichkeiten bei Hautpflegeprodukten genannt, wie z.B. eine Störung der Hautbarriere oder Mallorcaakne. Auf den Zusatz geeigneter Stabilisatoren kann allerdings nicht gänzlich verzichtet werden, da disperse Systeme, wie bereits beschrieben, beispielsweise Emulsionen thermodynamisch instabil sind.However, conventional emulsifiers or surfactants are repeatedly mentioned as the cause of incompatibilities in skin care products, such as a disturbance of the skin barrier or Mallorca acne. On the addition of suitable stabilizers can However, not entirely be dispensed with, since disperse systems, as already described, for example, emulsions are thermodynamically unstable.
Die oben genannten Pickering-Emulsionen sind eine Möglichkeit, herkömmliche Emulgatoren zu vermeiden. In der EP 1 352 639 Al bzw. der DE 101 62 840 werden Pickering-Emulsionen vorgestellt, die jedoch als Emulsionen in Form von Lotionen, Cremes und Gelen zum Einsatz kommen.The above Pickering emulsions are one way to avoid conventional emulsifiers. EP 1 352 639 A1 and DE 101 62 840, respectively, present Pickering emulsions which, however, are used as emulsions in the form of lotions, creams and gels.
In der WO 2004/017930 sind weitere Pickering-Emulsionen beschrieben, die sich insbesondere durch eine niedrige Viskosität auszeichnen und damit für dermatologische Tücher geeignet sind. Solche dünnflüssigen Pickering-Emulsionen lassen sich sogar unter einer Nebelbildung versprühen.WO 2004/017930 describes further Pickering emulsions, which are distinguished, in particular, by a low viscosity and are thus suitable for dermatological wipes. Such low viscosity Pickering emulsions can even be sprayed under mist formation.
Keines der oben beschriebenen Dokumente beschreibt jedoch Schaumformulierungen auf Basis von emulgatorfreien Pickering-Emulsionen.However, none of the documents described above describes foam formulations based on emulsifier-free Pickering emulsions.
Zusammenfassung der ErfindungSummary of the invention
Die Anmelderin hat nun erkannt, dass sich Pickering-Emulsionen als Basis für Schaumformulierungen eignen. Dabei werden die positiven Eigenschaften derThe Applicant has now recognized that Pickering emulsions are suitable as the basis for foam formulations. The positive characteristics of the
Schaumformulierungen mit denen der Pickering-Emulsionen verbunden. Es lassen sich insbesondere Schaumformulierungen ohne herkömmliche Emulgatoren oder mit sehr geringen Anteilen an herkömmlichen Emulgatoren herstellen, die die positiven Eigenschaften des Schaumes, nämlich die physikalische Struktur und angenehme Anwendbarkeit, mit der guten Hautverträglichkeit verbinden. Diese Kombination der Eigenschaften macht solche Schaumformulierung insbesondere verwendbar für kosmetische und dermatologische Formulierungen für empfindliche Hauttypen. Es wird dabei Verträglichkeit und Anwendungskomfort vorteilhaft miteinander verbunden.Foam formulations associated with those of the Pickering emulsions. In particular foam formulations can be prepared without conventional emulsifiers or with very low levels of conventional emulsifiers, which combine the positive properties of the foam, namely the physical structure and pleasant applicability, with good skin tolerance. This combination of properties makes such foam formulation particularly useful for cosmetic and dermatological formulations for sensitive skin types. It Compatibility and ease of use are advantageously combined.
Dabei ist zunächst davon auszugehen, dass es nicht selbstverständlich ist, dass das Verschäumen von Feststoff-stabilisierten Pickering-Emulsionen zu stabilenIt should first be assumed that it is not self-evident that the foaming of solid-stabilized Pickering emulsions to stable
Schaumprodukten führt. Schäume werden, wie bereits erwähnt, beispielsweise durch Einarbeiten von Treibgasen in O/W-Emulsionssystemen erhalten. Verdampft bei dem Verschäumen das in der dispersen Ölphase gelöste Treibgas, bildet sich ein Schaum (Gas in Flüssigdispersion). Beim Verdampfen bzw. Expandieren des in der dispersen Ölphase gelösten Treibgases kommt es zu einer Dilatation der dispersen Ölphase. Es ist nun überraschend, dass das Feststoffnetzwerk an der Phasengrenzfläche dieser Dehnungsbelastung stand hält und es beim Verschäumen nicht zum Brechen der Zubereitung kommt.Foam products leads. As already mentioned, foams are obtained, for example, by incorporating propellant gases in O / W emulsion systems. If the propellant gas dissolved in the dispersed oil phase evaporates during foaming, a foam forms (gas in liquid dispersion). Upon evaporation or expansion of the propellant gas dissolved in the disperse oil phase, dilatation of the dispersed oil phase occurs. It is now surprising that the solids network at the phase interface of this strain load withstands and it does not break the preparation during foaming.
Die Erfindung betrifft somit Schaumformulierungen, umfassend eineThe invention thus relates to foam formulations comprising a
Pickeringemulsion vom Typ Öl in Wasser, umfassend eine Ölphase und eine Wasserphase, und gegebenenfalls Treibgas. Insbesondere betrifft die Erfindung Schaumformulierungen, die nicht mehr als 0,5 Gew.-% herkömmlicher Emulgatoren enthalten,vorzugsweise nicht mehr als 0,3 Gew.-%, mehr bevorzugt nicht mehr als 0,1 Gew. -% und mehr bevorzugt frei von herkömmlichen Emulgatoren sind. Die Abgaben werden jeweils auf das Gesamtgewicht der Emulsion ohne Treibgas bezogen.Pickering emulsion of the oil-in-water type, comprising an oil phase and a water phase, and optionally propellant gas. In particular, the invention relates to foam formulations containing not more than 0.5% by weight of conventional emulsifiers, preferably not more than 0.3% by weight, more preferably not more than 0.1% by weight, and more preferably free from conventional emulsifiers. The levies are each related to the total weight of the emulsion without propellant gas.
Ferner betrifft die Erfindung die Verwendung von Pickeringemulsionen, insbesondere Pickeringemulsionen, die im wesentlichen frei oder frei von herkömmlichen Emulgatoren sind, für die Herstellung von Schaumformulierungen. Ferner betrifft die Erfindung die Verwendung von Schaumformulierungen auf Basis von Pickeringemulsionen als Träger für Wirkstoffe, als Hautpflegemittel, als Hautreinigungsmittel oder als Sonnenschutzmittel. Die Schaumformulierung kann daher als Kosmetikum, Medizinprodukt oder Arzneimittel eingesetzt werden.Furthermore, the invention relates to the use of Pickering emulsions, in particular Pickering emulsions, which are substantially free or free of conventional emulsifiers, for the production of foam formulations. Furthermore, the invention relates to the use of foam formulations based on Pickering emulsions as a carrier for active ingredients, as skin care agents, as skin cleansers or as sunscreen. The foam formulation can therefore be used as a cosmetic, medical device or pharmaceutical.
Außerdem umfasst die Erfindung ein Verfahren zur Herstellung von Schaumformulierungen basierend auf Pickeringemulsionen. Das Verfahren umfasst die Schritte:In addition, the invention includes a process for the preparation of foam formulations based on Pickering emulsions. The method comprises the steps:
a) Herstellen einer Pickeringemulsion vom Typ Öl in Wasser b) Abfüllen der Pickeringemulsion und Treibgas in einen Druckbehälter, oder c) Abfüllen der Pickeringemulsion in einen anderen als einen Druckbehälter, der bei Abgabe der Pickeringemulsion einen Schaum erzeugta) Preparation of a pickering emulsion of the oil-in-water type b) filling the Pickering emulsion and propellant gas into a pressure vessel, or c) filling the Pickering emulsion into a pressure vessel other than a pressure vessel which generates a foam when the Pickering emulsion is dispensed
Detaillierte Beschreibung der ErfindungDetailed description of the invention
1. Definitionen1. Definitions
Gemäß der vorliegenden Erfindung sind Schaumformulierungen Formulierungen, insbesondere Emulsionen, die zur Erzeugung von Schaum sinnfällig hergerichtet sind. Die Formulierungen können insbesondere entweder mit Treibgas in einen Druckbehälter abgefüllt sein oder ohne Treibgas in einen anderen Behälter als einen Druckbehälter abgefüllt sein, der es ermöglicht, bei Abgabe derAccording to the present invention, foam formulations are formulations, in particular emulsions, which are prepared to produce foam. In particular, the formulations may either be filled with propellant gas into a pressure vessel or be bottled without propellant in a container other than a pressure vessel, which makes it possible, when dispensing the
Formulierung/Emulsion einen Schaum zu erzeugen. Pumpspraybehälter können beispielsweise verwendet werden. Gemäß der vorliegenden Erfindung sind im Wesentlichen emulgatorfreie Emulsionen solche Emulsionen, die nicht mehr als 0,5 Gew.-%, vorzugsweise nicht mehr als 0,3 Gew.-%, mehr bevorzugt nicht mehr als 0,1 Gew.-% herkömmlicher Emulgatoren enthalten. Gemäß der Erfindung sind emuglatorfreie Emulsionen solche, die keine herkömmlichen Emulgatoren enthalten.Formulation / emulsion to produce a foam. Pump spray containers can be used, for example. According to the present invention, substantially emulsifier-free emulsions are those emulsions which are not more than 0.5% by weight, preferably not more than 0.3% by weight, more preferably not more than 0.1% by weight of conventional emulsifiers contain. According to the invention, emulsifier-free emulsions are those which contain no conventional emulsifiers.
Gemäß der vorliegenden Erfindung ist eine Pickeringemulsion eine feststoffstabilisierte Emulsion. Insbesondere handelt es sich gemäß der Erfindung um eine feststoffstabilisierte Emulsion vom Typ Öl in Wasser (O/W Emulsion). Insbesondere umfasst eine feststoffstabilisierte Emulsion gemäß der Erfindung nicht mehr als 0,5 Gew.-%, vorzugsweise nicht mehr als 0,3 Gew.-%, mehr bevorzugt nicht mehr als 0,1 Gew.-% herkömmliche Emulgatoren. Besonders bevorzugt sind die Pickeringemulsionenen gemäß der Erfindung frei von herkömmlichen Emulgatoren.According to the present invention, a Pickering emulsion is a solids-stabilized emulsion. In particular, according to the invention, it is a solids-stabilized emulsion of the oil-in-water type (O / W emulsion). In particular, a solids-stabilized emulsion according to the invention comprises not more than 0.5% by weight, preferably not more than 0.3% by weight, more preferably not more than 0.1% by weight of conventional emulsifiers. Particularly preferred are the Pickeringemulsionenen according to the invention free of conventional emulsifiers.
Gemäß einem Aspekt sind herkömmliche Emulgatoren gemäß der vorliegenden Erfindung anionische, kationische, amphotere und nichtionische Tenside. Typische Vertreter der anionischen Tenside sind neutralisierte verzweigte und/oder unverzweigte, gesättigte oder ungesättigte Fettsäuren mit einer Kettenlänge von 10 bis 40 Kohlenstoffatomen. Typische Vertreter der kationischen Tenside sindIn one aspect, conventional emulsifiers according to the present invention are anionic, cationic, amphoteric and nonionic surfactants. Typical representatives of the anionic surfactants are neutralized branched and / or unbranched, saturated or unsaturated fatty acids having a chain length of 10 to 40 carbon atoms. Typical representatives of the cationic surfactants are
Ammoniumverbindungen. Typische Vertreter der nichtionischen Tenside haben einen hydrophilen Molekülteil, wie etwa Glycerin, Polyglycerin, Sorbitan, Kohlenhydrate bzw. Polyoxyethlenglykole, der über Ester- und/oder Etherbindungen mit dem lipophilen Molekülteil verknüpft ist, der üblicherweise aus Fettalkoholen, Fettsäuren oder Isofettsäuren besteht. Zum Beispiel zählen die polyethoxylierte Fettsäureester mit Kettenlängen von 10 bis 40 Kohlenstoffatomen und mit einem Ethoxylierungsgrad von 5 bis 100 zu dieser Gruppe. Ferner gelten gesättigte und/oder ungesättigte, verzweigte und/oder unverzweigte Fettalkohole mit einer Kettenlänge von 10 bis 40 Kohlenstoffatomen zu den nichtionischen Emulgatoren. Häufig werden herkömmliche Emulgatoren in Kombinationen eingesetzt. Herkömmliche Emulgatoren im Sinne der vorliegenden Beschreibung sind in den Publikationen: Pflegekosmetik, 4. Auflage, Wissenschaftliche Verlagsgesellschaft mbH Stuttgart, Seiten 151 bis 159 und Fiedler Lexikon der Hilfsstoffe, 5. Auflage, Editio Cantor Verlag Aulendorf, Seiten 97 bis 121, beschrieben.Ammonium compounds. Typical representatives of the nonionic surfactants have a hydrophilic moiety, such as glycerol, polyglycerol, sorbitan, carbohydrates or polyoxyethylene glycols, which is linked via ester and / or ether bonds with the lipophilic moiety, which usually consists of fatty alcohols, fatty acids or iso-fatty acids. For example, the polyethoxylated fatty acid esters having chain lengths of 10 to 40 carbon atoms and having a degree of ethoxylation of 5 to 100 belong to this group. Furthermore, saturated and / or unsaturated, branched and / or unbranched fatty alcohols with a Chain length of 10 to 40 carbon atoms to the nonionic emulsifiers. Frequently, conventional emulsifiers are used in combinations. Conventional emulsifiers for the purposes of the present description are described in the publications: Pflegekosmetik, 4th edition, Scientific Verlagsgesellschaft mbH Stuttgart, pages 151 to 159 and Fiedler Lexikon der Hilfsstoffe, 5th edition, Editio Cantor Verlag Aulendorf, pages 97 to 121 described.
Gemäß einem weiteren Aspekt der Erfindung sind herkömmliche Emulgatoren im Sinne der vorliegenden Anmeldung alle amphiphile Substanzen mit einer Molmasse < 5000, die in höherer Konzentration Mizellen und/oder andereAccording to a further aspect of the invention, conventional emulsifiers for the purposes of the present application are all amphiphilic substances with a molecular weight <5000, which in a higher concentration micelles and / or others
Flüssigkristalline Aggregate bilden können.Gemäß noch einem weiteren Aspekt sind herkömmliche Emulgatoren alle oberflächenaktiven Substanzen, die insbesondere bei üblichen Lagerungs- und Anwendungstemperaturen wie z.B. Raumtemperatur nicht als Feststoff oder Polymer vorliegen.According to yet another aspect, conventional emulsifiers are all surface-active substances which, in particular at conventional storage and application temperatures, e.g. Room temperature is not present as a solid or polymer.
Gemäß der Erfindung ist ein Feststoffemulgator eine partikuläre Substanz, die sowohl von lipophilen als auch von hydrophilen Flüssigkeiten benetzbar ist. Es kann sich hierbei um anorganische oder organische Feststoffe handeln. Die Partikel können ferner unbehandelt oder beschichtet sein. Bevorzugt liegt die Partikelgröße zwischen 1 nm und 200 nm, mehr bevorzugt zwischen 5 nm und 100 nm.According to the invention, a solid emulsifier is a particulate substance which is wettable by both lipophilic and hydrophilic liquids. These may be inorganic or organic solids. The particles may also be untreated or coated. The particle size is preferably between 1 nm and 200 nm, more preferably between 5 nm and 100 nm.
2. Zusammensetzung der Pickeringemulsionen2. Composition of Pickering Emulsions
Feststoff emulgatoren:Solid emulsifiers:
Geeignete Feststoffemulgatoren sind partikuläre anorganische oder organische Feststoffe, die sowohl von lipophilen als auch von hydrophilen Flüssigkeiten benetzbar sind. Geeignete Vertreter sind z.B. Titandioxid, insbesondere beschichtetes Titanoxid (z.B. erhältlich von Merck KGaA unter der Bezeichnung Eusolex® T- 2000), Zinkoxid (z.B. erhältlich von BASF AG unter der Bezeichnung Z-Cote Max) Siliziumdioxid, insbesondere hochdisperses Siliziumdioxid, Fe2O3, Veegum, Bentonit und Ethylcellulose. Ferner können Aluminiumoxid, nanopartikuläres gefälltes Calciumcarbonat, Kohle, Magnesiumoxid, Magnesiumtrisilikat, kristalline Fettalkohole und Fettsäuren, Polymerlatices, z. B. Polystyrole oder Polymethacrylate, und Polymer-Pseudolatices verwendet werden. Auch Mischungen der vorgenannten Feststoffemulgatoren können verwendet werden. Beschichtetes Titandioxid oder Zinkoxid werden bevorzugt.Suitable solid emulsifiers are particulate inorganic or organic solids which are wettable by both lipophilic and hydrophilic liquids. Suitable representatives are, for example, titanium dioxide, in particular coated Titanium oxide (eg available from Merck KGaA under the name Eusolex® T-2000), zinc oxide (obtainable from BASF AG under the name Z-Cote Max) silicon dioxide, in particular highly disperse silicon dioxide, Fe 2 O 3 , Veegum, bentonite and ethylcellulose. Further, alumina, nanoparticulate precipitated calcium carbonate, carbon, magnesia, magnesium trisilicate, crystalline fatty alcohols and fatty acids, polymer latices, e.g. Polystyrenes or polymethacrylates, and polymer pseudolatices. Mixtures of the abovementioned solid emulsifiers can also be used. Coated titanium dioxide or zinc oxide are preferred.
Die erfindungsgemäßen Emulsionen enthalten mehr als 1 Gew.-% Feststoff emulgator, bevorzugt mehr als 2 Gew.-% Festste ff emulgator, insbesondere von 2 bis 7 Gew.-% Feststoff emulgator. Besonders bevorzugt enthalten die erfindungsgemäßen Emulsionen 3 bis 4 Gew.-% Festste ffemulgator. Die Angaben werden jeweils auf das Gesamtgewicht der Emulsion ohne Treibgas bezogen.The emulsions according to the invention contain more than 1% by weight of solid emulsifier, preferably more than 2% by weight of solid emulsifier, in particular from 2 to 7% by weight of solid emulsifier. The emulsions according to the invention particularly preferably contain 3 to 4% by weight of the most solid ffemulgator. The data are in each case based on the total weight of the emulsion without propellant gas.
Ölphase:Oil phase:
Geeignete Komponenten, welche die Ölphase bilden können, können aus den polaren und unpolaren Ölen oder deren Mischungen gewählt werden.Suitable components which can form the oil phase can be selected from the polar and non-polar oils or mixtures thereof.
Die Ölphase der erfmdungsgemäßen Formulierungen wird vorteilhaft gewählt aus der Gruppe der Lecithine und der Fettsäuretriglyceride, aus der Gruppe der Propylenglykole oder Butylenglykole, Fettsäureester, aus der Gruppe der natürlichen Wachse, tierischen und pflanzlichen Ursprungs, aus der Gruppe der Esteröle, aus der Gruppe der Dialkylether und Dialkylcarbonate, aus der Gruppe der verzweigten und unverzweigten Kohlenwasserstoffe und Wachse sowie aus der Gruppe der zyklischen und linearen Silikonöle. Besonders bevorzugt sind Triglyceride insbesondere Caprylsäure-/Caprinsäure- triglycerid erhältlich unter der Bezeichnung Miglyol 812 der Firma Sasol und dessen Abmischung mit weiteren Öl- und Wachskomponenten.The oil phase of the inventive formulations is advantageously selected from the group of lecithins and fatty acid triglycerides, from the group of propylene glycols or butylene glycols, fatty acid esters, from the group of natural waxes of animal and vegetable origin, from the group of ester oils, from the group of dialkyl ethers and dialkyl carbonates, from the group of branched and unbranched hydrocarbons and waxes and from the group of cyclic and linear silicone oils. Particular preference is given to triglycerides, in particular caprylic / capric triglyceride, obtainable under the name Miglyol 812 from Sasol and its blending with further oil and wax components.
Besonders bevorzugt sind weiterhin Triglyceride, insbesondere Caprylsäure-/Caprin- säuretriglycerid, erhältlich unter der Bezeichnung Miglyol 812 der Firma Sasol/Myritol 312 der Fa. Cognis.Particular preference is furthermore given to triglycerides, in particular caprylic / capric acid triglyceride, obtainable under the name Miglyol 812 from Sasol / Myritol 312 from Cognis.
Die erfϊndungsgemäßen Emulsionen enthalten bevorzugt von 10 bis 50 Gew.-% Ölphase, besonders bevorzugt 25 bis 35 Gew.-% Ölphase. Die Angaben werden jeweils auf das Gesamtgewicht der Emulsion ohne Treibgas bezogen.The emulsions according to the invention preferably contain from 10 to 50% by weight of oil phase, more preferably from 25 to 35% by weight of oil phase. The data are in each case based on the total weight of the emulsion without propellant gas.
Wasserphase:Water phase:
Die Wasserphase kann kosmetische Hilfsstoffe enthalten, z.B. niedere Alkohole (z.B. Ethanol, Isopropanol), niedere Diole oder Polyole sowie deren Ether (z.B. Propylenglycol, Glycerin, Butylenglykol, Hexylenglykol und Ethylenglykol), Schaumstabilisatoren und Verdickungsmittel.The water phase may contain cosmetic adjuvants, e.g. lower alcohols (e.g., ethanol, isopropanol), lower diols or polyols, and their ethers (e.g., propylene glycol, glycerin, butylene glycol, hexylene glycol, and ethylene glycol), foam stabilizers, and thickeners.
Geeignete Verdickungsmittel sind polymere Verdickungsmittel, die teilweise wasserlöslich oder zumindest in Wasser disperierbar sind und in wässrigen Systemen Gele oder viskose Lösungen bilden. Sie erhöhen die Viskosität des Wassers, indem sie entweder Wassermoleküle binden (Hydratation) oder aber das Wasser in ihre unter sich verflochtenen Makromoleküle aufnehmen und einhüllen, wobei sie die Beweglichkeit des Wassers einschränken. Geeignete Polymere sind:Suitable thickeners are polymeric thickeners which are partially water soluble or at least water dispersible and form gels or viscous solutions in aqueous systems. They increase the viscosity of the water either by binding water molecules (hydration) or by absorbing and enveloping the water in their intertwined macromolecules, thereby restricting the mobility of the water. Suitable polymers are:
- Abgewandelte Naturstoffe, wie Celluloseether (z.B. Hydroxypropylcelluloseether, Hydroxyethlylcellulose und Hydroxypropylmethylcelluloseether); - Natürliche Verbindungen, wie z.B. Agar-Agar, Carrageen, Polyosen, Stärke, Dextrine, Gelatine, Casein;Modified natural substances, such as cellulose ethers (eg hydroxypropyl cellulose ethers, hydroxyethyl cellulose and hydroxypropylmethyl cellulose ethers); Natural compounds such as agar-agar, carrageenan, polyoses, starch, dextrins, gelatin, casein;
- Synthetische Verbindungen wie z.B. Vinylpolymere, Polyether, Polyimine, Polyamide und Derivate der Polyacrylsäure; und - Anorganische Verbindungen wie z.B. Polykieselsäure und Tonmineralien.Synthetic compounds, e.g. Vinyl polymers, polyethers, polyimines, polyamides and derivatives of polyacrylic acid; and - inorganic compounds such as e.g. Polysilicic acid and clay minerals.
Bevorzugt ist ein Celluloseether enthalten. Besonderes bevorzugt ist Hydroxypropylmethylcellulose.Preferably, a cellulose ether is included. Particular preference is given to hydroxypropylmethylcellulose.
Die erfϊndungsgemäßen Emulsionen enthalten bevorzugt von 0,2 bis 1,5 Gew.-%The emulsions according to the invention preferably contain from 0.2 to 1.5% by weight
Verdickungsmittel (bezogen auf das Trockengewicht des Verdickungsmittels und das Gesamtgewicht der Emulsion ohne Treibgas). Besonders bevorzugt sind 0,5 bis 0,8 Gew.-% Verdickungsmittel.Thickener (based on the dry weight of the thickener and the total weight of the emulsion without propellant gas). Particularly preferred are 0.5 to 0.8 wt .-% thickener.
Wirkstoffe:active ingredients:
Der enthaltene Wirkstoff kann unter allen oberflächig auf der Haut applizierbaren Wirkstoffen und Mischungen dieser gewählt werden. Der Wirkstoff kann kosmetisch oder pharmazeutisch wirken. Entsprechend erhält man kosmetische oder dermatologische (als Medizinprodukt oder Arzneimittelprodukt einzusetzende) Schaumformulierungen. Ferner kann die Formulierung zum Schutz der Haut vor Umwelteinflüssen dienen. Der Wirkstoff kann rein pflanzlich oder synthetisch sein. Die Gruppe der Wirkstoffe kann sich auch mit den anderen Inhaltstoffgruppen, wie z.B. der Ölkomponente, den Verdickungsmitteln oder den Feststoffemulgatoren, überschneiden. Beispielsweise können manche Ölkomponenten auch als Wirkstoffe dienen, wie z.B. Öle mit mehrfach ungesättigten Fettsäuren, oder Feststoffemulgatoren, wie z.B. partikuläres Titandioxid als UV-Filter dienen kann. Je nach Eigenschaftspro fil sind die Substanzen mehreren Gruppen zuzuordnen. Wirkstoffe der erfϊndungsgemäßen Formulierungen werden vorteilhaft gewählt aus der Gruppe der Substanzen mit feuchtigkeitspendenden und barrierestärkenden Eigenschaften, wie z. B. Hydro viton, eine Nachbildung des NMF, Pyrrolidoncarbonsäure und deren Salze, Milchsäure und deren Salze, Glycerol, Sorbitol, Propylenglykol und Harnstoff, Substanzen aus der Gruppe der Proteine und Proteinhydrolysate wie z. B. Collagen, Elastin sowie Seidenprotein, Substanzen aus der Gruppe der Glucosaminoglucane, wie z. B. Hyaluronsäure, aus der Gruppe der Kohlenhydrate, wie z. B. Pentavitin, das in seiner Zusammensetzung dem Kohlehydratgemisch der menschlichen Hornschicht entspricht, und der Gruppe der Lipide und Lipidvorstufen wie beispielsweise die Ceramide. Weitere vorteilhafte Wirkstoffe können im Sinne der vorliegenden Erfindung ferner gewählt werden aus der Gruppe der Vitamine, wie z. B. Panthenol, Niacin, α-Tocopherol und seine Ester, Vitamin A sowie Vitamin C. Außerdem können die Wirkstoffe, gewählt aus der Gruppe der Antioxidantien z. B. Galate und Polyphenole, verwendet werden. Harnstoff, Hyaluronsäure und Pentavitin sind bevorzugte Substanzen.The active ingredient contained can be chosen from among all surface-applied on the skin agents and mixtures thereof. The active ingredient may be cosmetic or pharmaceutical. Accordingly, one obtains cosmetic or dermatological (to be used as a medical device or drug product) foam formulations. Furthermore, the formulation can be used to protect the skin from environmental influences. The active substance can be purely vegetable or synthetic. The group of active ingredients may also overlap with the other ingredient groups, such as the oil component, the thickeners or the solids emulsifiers. For example, some oil components can also serve as active ingredients, such as oils with polyunsaturated fatty acids, or solid emulsifiers, such as particulate titanium dioxide can serve as a UV filter. Depending on the property profile, the substances can be assigned to several groups. Active ingredients of the formulations according to the invention are advantageously selected from the group of substances with moisturizing and barrier-strengthening properties, such as, for example, As hydro viton, a replica of NMF, Pyrrolidoncarbonsäure and their salts, lactic acid and its salts, glycerol, sorbitol, propylene glycol and urea, substances from the group of proteins and protein hydrolysates such. As collagen, elastin and silk protein, substances from the group of glucosaminoglucans, such as. B. hyaluronic acid, from the group of carbohydrates, such as. As pentavidin, which corresponds in composition to the carbohydrate mixture of the human horny layer, and the group of lipids and lipid precursors such as ceramides. Further advantageous agents may be further selected in the context of the present invention from the group of vitamins, such as. As panthenol, niacin, α-tocopherol and its esters, vitamin A and vitamin C. In addition, the active ingredients selected from the group of antioxidants z. G., Galate and polyphenols. Urea, hyaluronic acid and pentavitin are preferred substances.
Es ist ferner bevorzugt, dass als Wirkstoffe Substanzen mit hautberuhigender und regenerierender Wirkung eingesetzt werden, wie z. B. Panthenol, Bisabo lol und Phytosterole.It is further preferred that substances with skin calming and regenerating action are used as active ingredients, such as. As panthenol, Bisabo lol and phytosterols.
Vorteilhafte Wirkstoffe im Sinne der vorliegenden Erfindung sind auch Pflanzen und Pflanzenextrakte. Hierzu gehören z.B. Algen, Aloe, Arnika, Bartflechten, Beinwell, Birke, Brennessel, Calendula, Eiche, Efeu, Hamamelis, Henna, Hopfen, Kamille, Mäusedorn, Pfefferminze, Ringelblume, Rosmarin, Salbei, grüner Tee, Teebaum, Schachtelhalm, Thymian und Walnuss sowie deren Extrakte.Advantageous active ingredients in the context of the present invention are also plants and plant extracts. These include e.g. Algae, aloe, arnica, beard braid, comfrey, birch, nettle, calendula, oak, ivy, witch hazel, henna, hops, chamomile, butcher's broom, peppermint, calendula, rosemary, sage, green tea, tea tree, horsetail, thyme and walnut and their extracts.
Die erfindungsgemäßen Zubereitungen können ferner als Wirkstoffe Antimykotika und Antiseptika/Desinfizientia synthetischen oder natürlichen Ursprungs enthalten. Weitere Wirkstoffe sind Glucocortikoide, Antibiotika, Analgetika, Antiphlogistika, Antirheumatika, Antiallergika, Antiparasitika, Antipruriginosa, Antipsoriatika, Retinoide, Lokalanästhetika, Venentherapeutika, Keratolytika, Hyperämisierende Substanzen, Koronartherapeutika (Nitrate/Nitro-Verbindungen), Virusstatika, Zytostatika, Hormone, Wundheilungsfördernde Wirkstoffe, zB Wachstumsfaktoren, Enzympräparate und Insektizide.The preparations according to the invention may also contain as active ingredients antimycotics and antiseptics / disinfinents of synthetic or natural origin. Other active ingredients are glucocorticoids, antibiotics, analgesics, antiphlogistics, antirheumatics, antiallergic drugs, antiparasitics, antipruriticosa, antipsoriatics, retinoids, local anesthetics, vein therapeutics, keratolytics, hyperemic substances, coronary therapeutics (nitrates / nitro compounds), antivirals, cytostatics, hormones, wound healing promoting agents, eg growth factors, enzyme preparations and insecticides.
Weitere Bestandteile der Pickeringemulsion:Other components of the Pickering emulsion:
Die Formulierungen können Farbstoffe, Perlglanzpigmente, Duftstoffe/Parfum,The formulations may include dyes, pearlescent pigments, fragrances / perfume,
Lichtschutzfϊltersubstanzen, Konservierungsmittel, Komplexbildner, Antioxidantien und Repellenten enthalten.Light stabilizer substances, preservatives, complexing agents, antioxidants and repellents.
Die obige Aufzählung der einzelnen Bestandteile der Pickeringemulsion soll so verstanden werden, dass einzelne Beispielkomponenten aufgrund ihrer verschiedenen Eigenschaften auch mehreren Gruppen zugeordnet werden können.The above listing of the individual components of the Pickeringemulsion should be understood so that individual example components can be assigned to several groups due to their different properties.
Treibgase:Propellants:
Geeignete Treibgase sind z. B. N2O, Propan, Butan und i-Butan, Die fertigeSuitable propellants are z. B. N 2 O, propane, butane and i-butane, the finished
Schaumformulierung enthält von 5 bis 15 Gew.-%, bevorzugt etwa 10 Gew.-% Treibgas.Foam formulation contains from 5 to 15 wt .-%, preferably about 10 wt .-% propellant gas.
3. Herstellungsverfahren3. Manufacturing process
Die Schaumformulierungen gemäß der Erfindung werden durch Bereitstellen einer Emulsion bzw. Pickeringemulsion vom Typ Öl in Wasser und Abfüllen der Emulsion bzw. Pickeringemulsion und gegebenenfalls Treibgas in einen gegebenenfalls Druckbehälter hergestellt. Alternativ zum Treibgas und Druckbehälter kann die Pickeringemulsion auch in einen anderen Behälter abgefüllt werden, der auch ohne Treibgas dafür geeignet ist, die Pickeringemulsion als Schaum abzugeben.The foam formulations according to the invention are made by providing an oil-in-water type emulsion of Pickering and filling the emulsion or Pickering emulsion and optionally propellant gas into one optionally produced pressure vessel. As an alternative to the propellant gas and pressure vessel, the Pickeringemulsion can also be filled into another container, which is suitable even without propellant gas to deliver the Pickeringemulsion as a foam.
Insbesondere wird die Pickeringemulsion in folgenden Schritten hergestellt:In particular, the Pickering emulsion is prepared in the following steps:
1. Bereitstellen einer liquiden Ölphase1. Provide a liquid oil phase
2. Suspendieren der oder des Festste ff emulgators in der Ölphase, um eine Feststoffemulgatorsuspension zu erhalten 3. Bereitstellen einer Wasserphase2. Suspend the or the solid state emulsifier in the oil phase to obtain a solid emulsifier suspension. 3. Provide a water phase
4. Homogenisieren der Wasserphase mit der Feststoffemulgatorsuspension, um eine Pickeringemulsion zu erhalten.4. Homogenize the water phase with the solids emulsifier suspension to obtain a Pickering emulsion.
Bevorzugt wird die Ölphase und die Wasserphase bei einer Temperatur von 50 bis 900C, bevorzugt von 50 bis 700C und besonders bevorzugt bei ca. 600C homogenisiert.Preferably, the oil phase and the water phase at a temperature of 50 to 90 0 C, preferably from 50 to 70 0 C and particularly preferably at about 60 0 C homogenized.
Wenn die Pickeringemulsion ein Verdickungsmittel umfasst, kommen vorteilhaft ferner die folgenden Schritte hinzu: 5. Bereitstellen einer wässrigen VerdickungsmittellösungFurther, if the Pickering emulsion comprises a thickening agent, the following steps are added: 5. Provide an aqueous thickener solution
6. Mischen der Verdickungsmittellösung mit der Pickeringemulsion.6. Mix the thickener solution with the Pickering emulsion.
Bevorzugt wird die Pickeringemulsion mit 10 Gew.-% Treibgas zur Herstellung der Schaumformulierung beaufschlagt. 4. VerwendungenPreferably, the Pickeringemulsion is applied with 10 wt .-% propellant gas for the preparation of the foam formulation. 4. Uses
Die Schaumformulierungen der vorliegenden Erfindung können für alle kosmetischen und dermatologischen (als Medizinprodukt oder Arzneimittel) Zwecke eingesetzt werden. Zum Beispiel könne die Formulierungen als Hautpflegemittel oder Hautreinigungsmittel eingesetzt werden. Sie können ferner als Träger für Wirkstoffe dienen und im medizinisch dermatologischen Bereich eingesetzt werden. Insbesondere können die Formulierungen als Sonnenschutzmittel eingesetzt werden. Viele der Feststoffemulgatoren, wie beispielsweise Titandioxid, sind wirksame UVA und UVB Filter.The foam formulations of the present invention can be used for all cosmetic and dermatological (medical or pharmaceutical) purposes. For example, the formulations could be used as a skin care or skin cleanser. They can also serve as carriers for active ingredients and be used in the medical dermatological field. In particular, the formulations can be used as sunscreen agents. Many of the solid emulsifiers, such as titanium dioxide, are effective UVA and UVB filters.
5. Beispiele5. Examples
5.1. Beispiel 15.1. example 1
Zusammensetzung der primären Pickeringemulsion:Composition of the primary Pickering emulsion:
10,00 g Eusolex T 2000 der Firma Merck KGaA (Alumina/Simethicone beschichtetes Titandioxid) 95,00 g Miglyol 812 der Firma Sasol (Caprylsäure/Caprinsäuretriglycerid) 95,00 g Wasser 10.00 g Eusolex T 2000 from Merck KGaA (Alumina / simethicone coated titanium dioxide) 95.00 g Miglyol 812 from Sasol (caprylic acid / capric triglyceride) 95.00 g water
Zusammensetzung der Schaumformulierung:Composition of the foam formulation:
60,00 g primäre Pickeringemulsion 30,00 g wässrige Hypromelloselösung (2 %) 10,00 g Treibgas60.00 g primary Pickering emulsion 30.00 g aqueous Hypromellose solution (2%) 10.00 g propellant gas
Herstellung der primären Pickeringemulsion:Preparation of the Primary Pickering Emulsion:
Eusolex T2000 wird abgewogen und in einen Laborhomogenisator überführt und mit dem auf 600C erwärmten Miglyol 812 innerhalb von einer Minute gemischt sowie innerhalb von 5 Minuten homogenisiert. Das Wasser wird auf 600C erwärmt und bei 1000 U/min innerhalb von einer Minute zugegeben. Die Mischung wird bei 3000 U/Min für 5 Minuten homogenisiert.Eusolex T2000 is weighed and transferred into a laboratory homogenizer and mixed with the heated to 60 0 C Miglyol 812 within one minute, and homogenized within 5 minutes. The water is heated to 60 ° C. and added at 1000 rpm for one minute. The mixture is homogenized at 3000 rpm for 5 minutes.
Herstellung der Schaumformulierung:Preparation of foam formulation:
30,00 g Hypromellose-Lösung werden zu 60,00 g der primären Pickeringemulsion unter Rühren zugegeben. Die hypromellosehaltige Pickeringemulsion wird dann in Aluminiummonoblockdosen mit 10,00 g Treibgas beaufschlagt.30.00 g of hypromellose solution are added to 60.00 g of the primary Pickering emulsion with stirring. The hypromellose Pickeringemulsion is then applied in aluminum monoblock cans with 10.00 g of propellant gas.
S chaumerzeugung :Growth:
Ein stabiler, feinblasiger Cremeschaum entsteht bei der Entnahme der Schaumformulierung aus der Druckgaspackung mittels eines geeigneten Ventils mit aufgesetztem Schaumapplikator. Die Struktur des Cremeschaumes bleibt für einen Zeitraum erhalten, der ausreicht den Schaum auf der Haut gleichmäßig zu verteilen. 5.2. Beispiel 2A stable, fine-bubble cream foam is formed when removing the foam formulation from the compressed gas package by means of a suitable valve with attached foam applicator. The structure of the cream foam is maintained for a period of time sufficient to evenly distribute the foam on the skin. 5.2. Example 2
Zusammensetzung der primären Pickeringemulsion:Composition of the primary Pickering emulsion:
10,00 g Eusolex T 2000 der Firma Merck KGaA (Alumina/Simethicone beschichtetes Titandioxid) 30,00 g Cetiol V der Firma Cognis (Decyloleat)10.00 g Eusolex T 2000 from Merck KGaA (Alumina / simethicone coated titanium dioxide) 30.00 g Cetiol V from Cognis (decyl oleate)
30,00 g Myritol 318 der Firma Cognis (Caprylsäure/Caprinsäuretriglycerid) 30,00 g Mandelöl 100,00 g Wasser30.00 g Myritol 318 from Cognis (caprylic acid / capric triglyceride) 30.00 g almond oil 100.00 g water
Zusammensetzung der Xanthan Gum-Lösung (1%):Composition of the xanthan gum solution (1%):
1,0 g Xanthan Gum 99,00 g Wasser1.0 g of xanthan gum 99.00 g of water
Zusammensetzung der Schaumformulierung:Composition of the foam formulation:
60,00 g primäre Pickeringemulsion 30,00 g wässrige Xanthan Gum-Lösung (1%) 10,00 g Treibgas60.00 g Primary Pickering Emulsion 30.00 g Aqueous Xanthan Gum Solution (1%) 10.00 g Propellant
Herstellung der primären Pickeringemulsion:Preparation of the Primary Pickering Emulsion:
Eusolex T 2000 wird abgewogen und in einen Laborhomogenisator überführt und mit der auf 600C Mischung aus Cetiol V, Myritol 318 und Mandelöl innerhalb von einer Minute gemischt sowie innerhalb von 5 Minuten homogenisiert. Das Wasser wird auf 600C erwärmt und bei 1000 U/min innerhalb von einer Minute zugegeben. Die Mischung wird bei 3000 U/Min für 5 Minuten homogenisiert. Herstellung der Schaumformulierung: 30,00 g Xanthan Gum-Lösung werden zu 60,00 g der primären Pickeringemulsion unter Rühren zugegeben. Die Xanthan Gum-Lösung-haltige Pickeringemulsion wird dann in Aluminiummonoblockdosen mit 10,00 g Treibgas beaufschlagt.Eusolex T 2000 is weighed and transferred into a laboratory homogenizer and mixed with the 0 to 60 C mixture of Cetiol V, Myritol 318 and almond oil within one minute and homogenized within 5 minutes. The water is heated to 60 ° C. and added at 1000 rpm for one minute. The mixture is homogenized at 3000 rpm for 5 minutes. Preparation of foam formulation: 30.00 g of xanthan gum solution is added to 60.00 g of the primary Pickering emulsion with stirring. The xanthan gum solution-containing Pickeringemulsion is then applied in aluminum monoblock cans with 10.00 g of propellant gas.
Schaumerzeugung:Foam generation:
Ein stabiler, feinblasiger Cremeschaum entsteht bei der Entnahme der Schaumformulierung aus der Druckgaspackung mittels eines geeigneten Ventils mit aufgesetztem Schaumapplikator. Die Struktur des Cremeschaumes bleibt für einen Zeitraum erhalten, der ausreicht den Schaum auf der Haut gleichmäßig zu verteilen.A stable, fine-bubble cream foam is formed when removing the foam formulation from the compressed gas package by means of a suitable valve with attached foam applicator. The structure of the cream foam is maintained for a period of time sufficient to evenly distribute the foam on the skin.
5.3 Beispiel 35.3 Example 3
Zusammensetzung der primären Pickeringemulsion:Composition of the primary Pickering emulsion:
10,00 g ZCote der Firma BASF (Zinkoxid)10.00 g ZCote from BASF (zinc oxide)
20,00 g Myritol 318 der Firma Cognis (Caprylsäure/Caprinsäuretriglycerid) 10,00 g Cetiol V der Firma Cognis (Decyloleat) 20,00 g Cetiol SN der Firma Cognis (Cetylstearylisononnanoat) 20,00 g Mandelöl 120,00 g Wasser20.00 g Myritol 318 from Cognis (caprylic acid / capric triglyceride) 10.00 g Cetiol V from Cognis (decyl oleate) 20.00 g Cetiol SN from Cognis (cetylstearyl isone nanoanoate) 20.00 g almond oil 120.00 g water
Zusammensetzung der Hypromellose-Lösung (2%):Composition of the hypromellose solution (2%):
2,00 g Hypromellose 5,00 g Glycerol 5,00 g Harnstoff 88,00 g Wasser Zusammensetzung der Schaumformulierung:2.00 g hypromellose 5.00 g glycerol 5.00 g urea 88.00 g water Composition of the foam formulation:
40,00 g primäre Pickeringemulsion 52,00 g wässrige Hypromelloselösung (2 %) 8,00 g Treibgas40.00 g primary Pickering emulsion 52.00 g aqueous Hypromellose solution (2%) 8.00 g propellant gas
Herstellung der primären Pickeringemulsion:Preparation of the Primary Pickering Emulsion:
ZCote wird abgewogen und in einen Laborhomogenisator überführt und mit der Mischung aus Cetiol V, Myritol 318, Cetiol SN und Mandelöl innerhalb von einer Minute gemischt sowie innerhalb von 5 Minuten homogenisiert. Das Wasser wird bei 1000 U/min innerhalb von einer Minute zugegeben. Die Mischung wird bei 3000 U/Min für 5 Minuten homogenisiert.ZCote is weighed and transferred to a laboratory homogenizer and mixed with the mixture of Cetiol V, Myritol 318, Cetiol SN and almond oil within one minute and homogenized within 5 minutes. The water is added at 1000 rpm within one minute. The mixture is homogenized at 3000 rpm for 5 minutes.
Herstellung der Schaumformulierung:Preparation of foam formulation:
52,00 g Hypromellose-Lösung werden zu 40,00 g der primären Pickeringemulsion unter Rühren zugegeben. Die hypromellosehaltige Pickeringemulsion wird dann in Aluminiummonoblockdosen mit 8,00 g Treibgas beaufschlagt.52.00 g of hypromellose solution are added to 40.00 g of the primary Pickering emulsion with stirring. The hypromellose Pickeringemulsion is then applied in aluminum monoblock cans with 8.00 g of propellant gas.
S chaumerzeugung :Growth:
Ein stabiler, feinblasiger Cremeschaum entsteht bei der Entnahme der Schaumformulierung aus der Druckgaspackung mittels eines geeigneten Ventils mit aufgesetztem Schaumapplikator. Die Struktur des Cremeschaumes bleibt für einen Zeitraum erhalten, der ausreicht den Schaum auf der Haut gleichmäßig zu verteilen. A stable, fine-bubble cream foam is formed when removing the foam formulation from the compressed gas package by means of a suitable valve with attached foam applicator. The structure of the cream foam is maintained for a period of time sufficient to evenly distribute the foam on the skin.

Claims

Patentansprüche Patent claims
1. Schaumformulierung umfassend, eine im Wesentlichen emulgatorfreie Emulsion vom Typ Öl in Wasser, umfassend eine Ölphase und eine Wasserphase.1. Foam formulation comprising a substantially emulsifier-free oil-in-water type emulsion comprising an oil phase and a water phase.
2. Schaumformulierung gemäß Anspruch 1, wobei die Emulsion nicht mehr als 0,5 Gew.-%, bevorzugt nicht mehr als 0,3 Gew.-%, mehr bevorzugt nicht mehr als 0,1 Gew.-% herkömmlicher Emulgatoren enthält.2. Foam formulation according to claim 1, wherein the emulsion contains not more than 0.5% by weight, preferably not more than 0.3% by weight, more preferably not more than 0.1% by weight of conventional emulsifiers.
3. Schaumformulierung gemäß Anspruch 1 oder 2, umfassend eine emulgatorfreie Emulsion, die keine herkömmlichen Emulgatoren enthält.3. Foam formulation according to claim 1 or 2, comprising an emulsifier-free emulsion which does not contain any conventional emulsifiers.
4. Schaumformulierung gemäß einem der Ansprüche 1 bis 3, wobei die Emulsion eine Pickeringemulsion ist.4. Foam formulation according to one of claims 1 to 3, wherein the emulsion is a Pickering emulsion.
5. Schaumformulierung gemäß Anspruch 4, wobei die Pickeringemulsion mindestens einen partikulären5. Foam formulation according to claim 4, wherein the Pickering emulsion contains at least one particulate
Feststoffemulgator, ausgewählt aus der Gruppe, bestehend aus Titandioxid, Siliziumdioxid, Fe2O3, Zinkoxid, Veegum, Bentonit und Ethylcellulose, Aluminiumoxid, nanopartikuläres gefälltes Calciumcarbonat, Kohle, Magnesiumoxid, Magnesiumtrisilikat, kristalline Fettalkohole und Fettsäuren, Polymerlatices, wie etwaSolid emulsifier selected from the group consisting of titanium dioxide, silicon dioxide, Fe 2 O 3 , zinc oxide, Veegum, bentonite and ethyl cellulose, aluminum oxide, nanoparticulate precipitated calcium carbonate, carbon, magnesium oxide, magnesium trisilicate, crystalline fatty alcohols and fatty acids, polymer latices, such as
Polystyrole oder Polymethacrylate, und Polymer-Pseudolatices oder Mischungen davon umfasst. Polystyrenes or polymethacrylates, and polymer pseudolactics or mixtures thereof.
6. Schaumformulierung gemäß Anspruch 4, wobei die Pickeringemulsion beschichtetes Titandioxid oder Zinkoxid umfasst.6. Foam formulation according to claim 4, wherein the Pickering emulsion comprises coated titanium dioxide or zinc oxide.
7. Schaumformulierung gemäß einem der vorangegangen Ansprüche, wobei die Ölphase mindestens ein Triglycerid umfasst.7. Foam formulation according to one of the preceding claims, wherein the oil phase comprises at least one triglyceride.
8. Schaumformulierung gemäß Anspruch 7, wobei das Triglycerid Caprylsäure/Caprinsäuretriglycerid umfasst.8. Foam formulation according to claim 7, wherein the triglyceride comprises caprylic acid/capric acid triglyceride.
9. Schaumformulierung gemäß einem der vorangegangen Ansprüche, wobei die Emulsion mindestens ein Verdickungsmittel umfasst.9. Foam formulation according to one of the preceding claims, wherein the emulsion comprises at least one thickener.
10. Schaumformulierung gemäß Anspruch 9, wobei das Verdickungsmittel Hydroxypropylmethylcellulose umfasst.10. The foam formulation according to claim 9, wherein the thickener comprises hydroxypropylmethylcellulose.
11. Schaumformulierung gemäß einem der voran stehenden Ansprüche, wobei die Emulsion mindestens einen Wirkstoff enthält.11. Foam formulation according to one of the preceding claims, wherein the emulsion contains at least one active ingredient.
12. Schaumformulierung gemäß Anspruch 11, wobei der Wirkstoff aus der Gruppe bestehend aus Hydroviton, Pyrrolidoncarbonsäure und deren Salze, Milchsäure und deren Salze, Glycerol, Sorbitol, Propylenglykol, Harnstoff, Collagen, Elastin, Seidenprotein, Hyaluronsäure, Pentavitin, Ceramide, Panthenol, Niacin, α-Tocopherol und seine Ester, Vitamin A, Vitamin C, Galate,12. Foam formulation according to claim 11, wherein the active ingredient is selected from the group consisting of hydroviton, pyrrolidonecarboxylic acid and its salts, lactic acid and its salts, glycerol, sorbitol, propylene glycol, urea, collagen, elastin, silk protein, hyaluronic acid, pentavitin, ceramides, panthenol, niacin , α-tocopherol and its esters, vitamin A, vitamin C, galates,
Polyphenole, Panthenol, Bisabo Io 1, Phytosterole, Glucocortikoide, Antibiotika, Analgetika, Antiphlogistika, Antirheumatika, Antiallergika, Antiparasitika, Antipruriginosa, Antipsoriatika, Retinoide, Lokalanästhetika, Venentherapeutika, Keratolytika, Hyperämisierende Substanzen, Koronartherapeutika (Nitrate/Nitro- Verbindungen), Virusstatika, Zytostatika, Hormone, Wundheilungsfördernde Wirkstoffe, Wachstumsfaktoren, Enzympräparate, Insektizide und Pflanzenmaterial wie bzw.Polyphenols, panthenol, Bisabo Io 1, phytosterols, glucocorticoids, antibiotics, analgesics, anti-inflammatory drugs, anti-rheumatic drugs, anti-allergics, anti-parasitic drugs, antipruriginosa, antipsoriatic drugs, Retinoids, local anesthetics, venous therapeutics, keratolytics, hyperaemic substances, coronary therapeutics (nitrates/nitro compounds), antivirals, cytostatics, hormones, active ingredients that promote wound healing, growth factors, enzyme preparations, insecticides and plant material such as or
Pflanzenextrakte von Algen, Aloe, Arnika, Bartflechten, Beinwell, Birke, Brennnessel, Calendula, Eiche, Efeu, Hamamelis, Henna, Hopfen, Kamille, Mäusedorn, Pfefferminze, Ringelblume, Rosmarin, Salbei, grüner Tee, Teebaum, Schachtelhalm, Thymian und Walnuss oder Mischungen davon, ausgewählt ist.Plant extracts of algae, aloe, arnica, beard lichen, comfrey, birch, nettle, calendula, oak, ivy, witch hazel, henna, hops, chamomile, butcher's broom, peppermint, marigold, rosemary, sage, green tea, tea tree, horsetail, thyme and walnut or mixtures thereof is selected.
13. Verwendung einer Pickeringemulsion für die Herstellung einer13. Using a Pickering emulsion to make a
S chaumformulierung .Foam formulation.
14. Verwendung gemäß Anspruch 13 für die Herstellung einer14. Use according to claim 13 for the production of a
Schaumformulierung gemäß einem der Ansprüche 1 bis 11.Foam formulation according to one of claims 1 to 11.
15. Verwendung einer Schaumformulierung gemäß einem der Ansprüche 1 bis 12 als Träger für einen Wirkstoff.15. Use of a foam formulation according to one of claims 1 to 12 as a carrier for an active ingredient.
16. Verwendung einer Schaumformulierung gemäß einem der Ansprüche 1 bis 12 als Hautpflegemittel.16. Use of a foam formulation according to one of claims 1 to 12 as a skin care product.
17. Verwendung einer Schaumformulierung gemäß einem der Ansprüche 1 bis 12 als Hautreinigungsmittel.17. Use of a foam formulation according to one of claims 1 to 12 as a skin cleansing agent.
18. Verwendung einer Schaumformulierung gemäß einem der Ansprüche 1 bis 12 als Sonnenschutzmittel. 18. Use of a foam formulation according to one of claims 1 to 12 as a sunscreen.
19. Verwendung einer Schaumformulierung gemäß einem der Ansprüche 1 bis 12 zur Herstellung eines Kosmetikums, Medizinprodukts oder Arzneimittels.19. Use of a foam formulation according to one of claims 1 to 12 for producing a cosmetic, medical product or drug.
20. Verfahren zur Herstellung einer Schaumformulierung basierend auf einer Pickeringemulsion, umfassend die Schritte:20. Process for producing a foam formulation based on a Pickering emulsion, comprising the steps:
a) Herstellen einer Pickeringemulsion vom Typ Öl in Wasser b) Abfüllen der Pickeringemulsion und Treibgas in einena) Producing a Pickering emulsion of the oil in water type b) Filling the Pickering emulsion and propellant gas into one
Druckbehälter, oder c) Abfüllen der Pickeringemulsion in einen anderen als einenpressure vessel, or c) filling the Pickering emulsion into something other than one
Druckbehälter, der bei Abgabe der Pickeringemulsion einen Schaum erzeugt.Pressure vessel that produces a foam when the Pickering emulsion is dispensed.
21. Verfahren gemäß Anspruch 20 zur Herstellung einer Schaumformulierung nach einem der Ansprüche 1 bis 12.21. The method according to claim 20 for producing a foam formulation according to one of claims 1 to 12.
22. Verfahren gemäß Anspruch 21, wobei das Herstellen der Pickeringemulsion die Schritte22. The method according to claim 21, wherein producing the Pickering emulsion comprises the steps
1. Bereitstellen einer liquiden Ölphase1. Providing a liquid oil phase
2. Suspendieren der oder des Festste ff emulgators in der Ölphase, um eine Feststoffemulgatorsuspension zu erhalten2. Suspending the solid emulsifier in the oil phase to obtain a solid emulsifier suspension
3. Bereitstellen einer Wasserphase 4. Homogenisieren der Wasserphase mit der Feststoffemulgatorsuspension, um eine Pickeringemulsion zu erhalten, umfasst. 3. Providing a water phase 4. Homogenizing the water phase with the solid emulsifier suspension to obtain a Pickering emulsion.
23. Verfahren gemäß Anspruch 22, wobei die Ölphase und die23. The method according to claim 22, wherein the oil phase and the
Wasserphase bei einer Temperatur zwischen 50 und 90 0C homogenisiert werden.Water phase is homogenized at a temperature between 50 and 90 0 C.
24. Verfahren gemäß Anspruch 22 oder 23, wobei die Pickeringemulsion ein Verdickungsmittel umfasst, ferner umfassend die Schritte:24. The method according to claim 22 or 23, wherein the Pickering emulsion comprises a thickener, further comprising the steps:
5. Bereitstellen einer wässrigen Verdickungsmittellösung5. Provide an aqueous thickener solution
6. Mischen der Verdickungsmittellösung mit der Pickeringemulsion.6. Mix the thickener solution with the Pickering emulsion.
25. Verfahren gemäß einem der Ansprüche 20 bis 24, wobei die25. The method according to any one of claims 20 to 24, wherein the
Schaumformulierung 10 Gew.- Treibgas enthält. Foam formulation contains 10% by weight of propellant gas.
EP08759493A 2007-05-10 2008-05-09 Surfactant-free foam formulations Ceased EP2155148A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08759493A EP2155148A2 (en) 2007-05-10 2008-05-09 Surfactant-free foam formulations

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07107950A EP1992323B1 (en) 2007-05-10 2007-05-10 Tenside-free foam formulae
PCT/EP2008/055760 WO2008138894A2 (en) 2007-05-10 2008-05-09 Surfactant-free foam formulations
EP08759493A EP2155148A2 (en) 2007-05-10 2008-05-09 Surfactant-free foam formulations

Publications (1)

Publication Number Publication Date
EP2155148A2 true EP2155148A2 (en) 2010-02-24

Family

ID=38788222

Family Applications (2)

Application Number Title Priority Date Filing Date
EP07107950A Active EP1992323B1 (en) 2007-05-10 2007-05-10 Tenside-free foam formulae
EP08759493A Ceased EP2155148A2 (en) 2007-05-10 2008-05-09 Surfactant-free foam formulations

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP07107950A Active EP1992323B1 (en) 2007-05-10 2007-05-10 Tenside-free foam formulae

Country Status (23)

Country Link
US (4) US20100316684A1 (en)
EP (2) EP1992323B1 (en)
JP (1) JP2010527332A (en)
KR (1) KR101604776B1 (en)
CN (1) CN101677913B (en)
AT (1) ATE544441T1 (en)
AU (1) AU2008250298B2 (en)
CA (1) CA2683869C (en)
CO (1) CO6361888A2 (en)
DK (1) DK1992323T3 (en)
EA (1) EA023887B1 (en)
EC (1) ECSP10010396A (en)
ES (1) ES2382110T3 (en)
HK (1) HK1126126A1 (en)
HR (1) HRP20120371T1 (en)
IL (1) IL201972A (en)
MX (1) MX2009011708A (en)
PL (1) PL1992323T3 (en)
PT (1) PT1992323E (en)
RS (1) RS52336B (en)
UA (1) UA98960C2 (en)
WO (1) WO2008138894A2 (en)
ZA (1) ZA200906927B (en)

Families Citing this family (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL152486A0 (en) 2002-10-25 2003-05-29 Meir Eini Alcohol-free cosmetic and pharmaceutical foam carrier
US8636982B2 (en) 2007-08-07 2014-01-28 Foamix Ltd. Wax foamable vehicle and pharmaceutical compositions thereof
JP4994397B2 (en) * 2009-01-05 2012-08-08 富士フイルム株式会社 Astaxanthin-containing dispersion and method for producing the same
ES2576691T3 (en) 2009-01-29 2016-07-08 L'oréal Cosmetic composition in foam form
WO2011013009A2 (en) 2009-07-29 2011-02-03 Foamix Ltd. Non surfactant hydro-alcoholic foamable compositions, breakable foams and their uses
US20110054058A1 (en) * 2009-08-31 2011-03-03 William Crooker Emulsified polyol and resultant foam therefrom
CA2683258C (en) * 2009-10-20 2011-08-09 Asa Bullion Investment Limited Lotion for cleaning human anorectal area
PL2335675T3 (en) * 2009-12-10 2015-08-31 Neubourg Skin Care Gmbh & Co Kg Emulsifier-free, polymer stabilised foam formulas
PL2363108T3 (en) 2010-03-02 2018-04-30 Neubourg Skin Care Gmbh & Co. Kg Foam formulation containing at least one triterpenoid
FR2962662B1 (en) * 2010-07-19 2012-08-24 Agronomique Inst Nat Rech EMULSION-FORMING COMPOSITION COMPRISING A DISPERSE HYDROPHOBIC PHASE IN AQUEOUS PHASE
BR112013014574B1 (en) * 2010-12-15 2019-10-15 Speximo Ab EMULSION OR FOAM STABILIZED BY PARTICULATE, USE OF A PARTICULATED EMULSION AND FORMULATION
CN102085162B (en) * 2011-01-13 2013-04-03 广州环亚化妆品科技有限公司 Face cleansing emulsion without surfactant and preparation method thereof
CN102772318A (en) * 2011-05-09 2012-11-14 深圳市中航健身时尚股份有限公司 Weak membrane cleaning type cutin-removing composition and preparation method thereof
DE202011100483U1 (en) 2011-05-10 2011-07-13 Neubourg Skin Care Gmbh & Co. Kg Application system for care products with sponge applicator
CN102488638A (en) * 2011-12-16 2012-06-13 江南大学 Cosmetic with no or less emulsifier and preservative
WO2014001033A1 (en) * 2012-06-27 2014-01-03 Unilever N.V. Sheet-like particulates comprising an alkylated cellulose ether and method for making these
KR101435161B1 (en) * 2012-08-17 2014-08-29 주식회사 엔에프씨 Skin cleaning cosmetic compositions and cleanser manufactured by using the same
AU2013323808A1 (en) 2012-09-27 2015-04-30 Bayer Consumer Care Ag Foaming skincare formulations
KR102007800B1 (en) 2012-11-09 2019-08-07 (주)아모레퍼시픽 Sunscreen cosmetic composition of mousse type
US9655821B2 (en) 2013-04-05 2017-05-23 The Procter & Gamble Company Personal care composition comprising a pre-emulsified formulation
FR3008617B1 (en) * 2013-07-18 2016-09-23 Oreal OIL / OIL PICKERING EMULSIONS INCLUDING CURVED BREAKING PARTICLES, COMPOSITIONS COMPRISING THE SAME, AND USE OF THE PARTICLES FOR STABILIZING PICKERING H / H EMULSIONS
WO2015089750A1 (en) * 2013-12-18 2015-06-25 L'oreal Composition of pickering emulsion comprising low amount of alcohol
DE102013114572A1 (en) 2013-12-19 2015-06-25 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Process for producing structured metallic coatings
EP2907823A1 (en) 2014-02-14 2015-08-19 Gene Signal International SA Polypeptide fragments of 168A-T2 and compositions comprising them for use in treating cancer
SG11201605920PA (en) 2014-02-21 2016-09-29 Amorepacific Corp Mousse-type cosmetic composition with waterproof property
CN104013955B (en) * 2014-06-18 2016-02-24 中国科学院过程工程研究所 A kind of not containing O/w emulsion and uses thereof of surfactant
US10639249B2 (en) 2014-09-25 2020-05-05 Eiko Kinoshita Reduction treatment agent, reduction cosmetic, reduction food and method for producing reduction treatment agent
CN104233802B (en) * 2014-09-28 2016-06-22 苏州印丝特纺织数码科技有限公司 A kind of preparation method of the silk fabric with photonic crystal structure color
US10806688B2 (en) 2014-10-03 2020-10-20 The Procter And Gamble Company Method of achieving improved volume and combability using an anti-dandruff personal care composition comprising a pre-emulsified formulation
US9993404B2 (en) 2015-01-15 2018-06-12 The Procter & Gamble Company Translucent hair conditioning composition
KR101757245B1 (en) 2015-07-28 2017-07-13 한국과학기술원 Pickering emulsion and method for preparation thereof
US20170079892A1 (en) * 2015-09-18 2017-03-23 Johnson & Johnson Consumer Inc. Foaming sunscreen composition containing an ultraviolet radiation-absorbing compound and a superhydrophilic amphiphilic copolymer
WO2017127344A1 (en) 2016-01-20 2017-07-27 The Procter & Gamble Company Hair conditioning composition comprising monoalkyl glyceryl ether
CN106726675A (en) * 2016-02-13 2017-05-31 顾银凤 A kind of cosmetics with anti-aging, whitening, moisture-keeping efficacy
CN107312179B (en) * 2016-04-26 2020-08-25 中国科学院理化技术研究所 Preparation method of tobacco mosaic virus-poly (N-isopropylacrylamide) block copolymer Pickering emulsion
ES2951675T3 (en) * 2016-07-12 2023-10-24 Oreal Pickering emulsion composition
US10398641B2 (en) 2016-09-08 2019-09-03 Foamix Pharmaceuticals Ltd. Compositions and methods for treating rosacea and acne
KR101971658B1 (en) 2016-10-20 2019-04-24 한국과학기술원 porous polymers which have particles on the pores surface, preparing method thereof and usages thereof
JP6884574B2 (en) * 2016-12-28 2021-06-09 ポーラ化成工業株式会社 Method of modifying the surface of powder particles
CN106731925A (en) * 2017-01-06 2017-05-31 宁波大学 Solid phase dispersion co-emulsifier method
DE102017204709A1 (en) 2017-03-21 2018-09-27 Beiersdorf Ag Cosmetic foam containing waxes and polyacrylic acid polymers
KR101981853B1 (en) 2017-06-19 2019-05-23 연세대학교 원주산학협력단 Pickering emulsion composition using polyimide particles and preparation method thereof
CN107970230B (en) * 2017-11-10 2020-04-28 华南理工大学 Pickering emulsion capable of collapsing and inhibiting generation of bacterial biofilm and preparation and application thereof
WO2019239526A1 (en) * 2018-06-13 2019-12-19 三菱ケミカルフーズ株式会社 Oil-in-water pickering emulsion
DE102018212458A1 (en) 2018-07-26 2020-01-30 Beiersdorf Ag Mineral oil and emulsifier free preparation
WO2020130035A1 (en) * 2018-12-19 2020-06-25 日東メディック株式会社 Foamable topical composition
JP7429504B2 (en) * 2019-06-28 2024-02-08 リンテック株式会社 Injection device, composition injection method, and composition for injection
CN110354027A (en) * 2019-08-28 2019-10-22 重庆医科大学 A kind of multi-functional lotion and preparation method thereof
CN111116975B (en) * 2019-12-30 2021-01-08 浙江大学 Pickering emulsion gel based on mutual attraction of liquid drops and preparation method thereof
CN111205479B (en) * 2020-01-14 2022-11-18 陕西师范大学 High internal phase Pickering emulsion with stable modified bacterial cellulose nanofiber and preparation method thereof
CN111296840B (en) * 2020-03-27 2022-08-23 重庆市中药研究院 A lotion containing rhizoma Zingiberis recens and fructus Jujubae for regulating gastrointestinal health, and its preparation method
EP4138785A1 (en) 2020-04-21 2023-03-01 Yissum Research Development Company of the Hebrew University of Jerusalem Ltd. Solid dispersions and particles and methods for controlled-release of lipid-soluble or dispesible actives
US20230166229A1 (en) 2020-05-14 2023-06-01 Fukuoka University Method for producing cellulose nanofiber capsule
DE202021004246U1 (en) 2020-06-12 2023-04-25 Mary Kay Inc. Topical composition
KR102489312B1 (en) * 2020-08-13 2023-01-17 명지대학교 산학협력단 Phase transition emulsion and preparation method thereof
DE102020127308A1 (en) 2020-10-16 2022-04-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Cosmetic agent to reduce wrinkles
CN115414262B (en) * 2022-07-19 2023-09-22 江苏诺兴生物科技有限公司 Epsilon-polylysine Pickering emulsion and preparation method and application thereof

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3330730A (en) * 1962-08-03 1967-07-11 Colgate Palmolive Co Pressurized emulsion quick breaking foam compositions
US4515810A (en) * 1983-10-06 1985-05-07 American Cyanamid Company Composition of matter
JP3432979B2 (en) * 1995-11-17 2003-08-04 花王株式会社 Cosmetics
FR2754451B1 (en) * 1996-10-14 1998-11-06 Oreal SELF-FOAMING CREAM
JPH11222417A (en) * 1998-01-30 1999-08-17 Kose Corp Aerosol type hair treatment composition
FR2783171B1 (en) * 1998-09-16 2000-11-17 Oreal EMULSION CONSISTING OF A HYDROPHILIC THICKENING COMPOUND AND A POLYSACCHARIDE ALKYLETHER, COMPOSITIONS CONSISTING OF THE SAID EMULSION, AND USES
FR2783159B1 (en) * 1998-09-16 2000-11-17 Oreal EMULSION CONSISTING OF A HYDROPHILIC THICKENING COMPOUND AND A THICKNING COPOLYMER, COMPOSITIONS CONSISTING OF THE SAID EMULSION, AND USES
DE19842730A1 (en) * 1998-09-18 2000-03-23 Beiersdorf Ag Emulsifier-free finely dispersed systems of the oil-in-water and water-in-oil type
DE10033414B4 (en) * 2000-07-08 2004-02-19 Wella Aktiengesellschaft Clear, two-phase, foam-forming aerosol hair care product
DE10148392A1 (en) * 2001-09-29 2003-04-30 Beiersdorf Ag Cosmetic cleaning foams
DE10161171A1 (en) * 2001-12-13 2003-06-18 Beiersdorf Ag Cosmetic cleaning emulsions containing talc
DE10162840A1 (en) * 2001-12-20 2003-07-03 Beiersdorf Ag Cosmetic and dermatological light protection formulations containing water-soluble UV filter substances and benzoxazole derivatives
US20030129213A1 (en) * 2001-12-26 2003-07-10 Gonzalez Anthony D. Meta-stable insect repellent emulsion composition and method of use
US6517816B1 (en) 2001-12-26 2003-02-11 Avon Products, Inc. Sunscreen emulsion composition and method of use
DE10238649A1 (en) * 2002-08-23 2004-03-11 Beiersdorf Ag Low-viscosity cosmetic or dermatological preparations of the oil-in-water type
US7700076B2 (en) * 2002-10-25 2010-04-20 Foamix, Ltd. Penetrating pharmaceutical foam
JP2006036763A (en) * 2004-06-25 2006-02-09 Kao Corp Water-in-oil emulsion composition
DE102004039212A1 (en) * 2004-08-12 2006-03-02 Wacker-Chemie Gmbh Rheology control of Pickering emulsion by electrolytes
BRPI0607038A2 (en) * 2005-01-28 2009-12-01 Basf Ag use of polymers cosmetic compositions for hair and skin and dermatological composition
DE102005034685A1 (en) * 2005-07-25 2007-02-08 Langhals, Heinz, Prof. Dr. Naphthalenamidinimides and piperazino-bisimides
US9089493B2 (en) * 2005-09-16 2015-07-28 The Procter & Gamble Company Skin care composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008138894A2 *

Also Published As

Publication number Publication date
KR101604776B1 (en) 2016-03-18
AU2008250298A1 (en) 2008-11-20
US20200276458A1 (en) 2020-09-03
EA200971042A1 (en) 2010-04-30
HRP20120371T1 (en) 2012-06-30
US20220193460A1 (en) 2022-06-23
CA2683869A1 (en) 2008-11-20
WO2008138894A2 (en) 2008-11-20
UA98960C2 (en) 2012-07-10
HK1126126A1 (en) 2009-08-28
CA2683869C (en) 2017-02-28
WO2008138894A3 (en) 2009-05-22
CN101677913B (en) 2016-04-20
US20100316684A1 (en) 2010-12-16
EP1992323B1 (en) 2012-02-08
ATE544441T1 (en) 2012-02-15
DK1992323T3 (en) 2012-05-21
IL201972A0 (en) 2010-06-16
KR20100031097A (en) 2010-03-19
PT1992323E (en) 2012-05-15
MX2009011708A (en) 2009-11-10
PL1992323T3 (en) 2012-07-31
ECSP10010396A (en) 2010-09-30
IL201972A (en) 2014-08-31
EP1992323A1 (en) 2008-11-19
CO6361888A2 (en) 2012-01-20
RS52336B (en) 2012-12-31
ES2382110T3 (en) 2012-06-05
CN101677913A (en) 2010-03-24
EA023887B1 (en) 2016-07-29
AU2008250298B2 (en) 2011-12-22
ZA200906927B (en) 2010-05-26
US20180078794A1 (en) 2018-03-22
JP2010527332A (en) 2010-08-12

Similar Documents

Publication Publication Date Title
EP1992323B1 (en) Tenside-free foam formulae
EP2020221B1 (en) DMS (Derma Membrane Structure) in foaming creams
EP2335675B1 (en) Emulsifier-free, polymer stabilised foam formulas
EP2363108B1 (en) Foam formulation containing at least one triterpenoid
KR20130051705A (en) O/w nano-emulsion with high emulsion stability, preparation method thereof, and cosmetic composition comprising the same
EP4346770A1 (en) Compositions containing membrane-forming substances for the preparation of a pumping foam

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20091209

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

17Q First examination report despatched

Effective date: 20100226

REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1137948

Country of ref document: HK

RAX Requested extension states of the european patent have changed

Extension state: MK

Payment date: 20091209

Extension state: RS

Payment date: 20091209

Extension state: BA

Payment date: 20091209

APBK Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNE

APBN Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2E

APBR Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3E

APAF Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R003

APBT Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9E

APAM Information on closure of appeal procedure modified

Free format text: ORIGINAL CODE: EPIDOSCNOA9E

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20151027

REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1137948

Country of ref document: HK