WO2009027538A2 - Stabilised pickering emulsion - Google Patents

Abstract

The invention relates to a cosmetic or pharmaceutical agent, an agent for the cleaning, care, finishing, brightening and/or conditioning of textiles or an agent for treating, in particular cleaning hard surfaces. The agent contains a Pickering emulsion that is packaged in a container and is coated, at least on the inner surface, with a metal oxide layer and/or a semi-metal oxide layer.

Description

 Stabilized Pickering emulsion

The present application relates to a cosmetic or pharmaceutical agent, a cleaning, care, finishing, softening and / or conditioning agent for textiles or a treatment agent, in particular for cleaning hard surfaces, comprising a Pickering emulsion for stabilization the Pickering emulsion against coalescence is packaged in a container which is coated at least on the inner surface with a metal oxide layer and / or with a Halbmetalloxidschicht.

Preparations of two immiscible phases which have an oily phase and an aqueous phase are known, in particular from the cosmetic field, whereby the oily phase is generally above the aqueous phase due to its lower density. At the time of use, an emulsion is obtained by stirring or shaking. A preparation with completely separate aqueous and oily phase is useful if the preparation contains active ingredients which can be stored stably either only in the aqueous phase or only in the oily phase. However, a preparation of two superimposed phases can be completely homogenized only with great effort, which usually sets in the practical application of the tendency that the upper oily layer is consumed in greater amount than the aqueous sub-layer.

In this context, emulsifiers enable or facilitate the uniform distribution of two or more immiscible phases and at the same time prevent their segregation. They are therefore used to stabilize water-lipid mixtures in the form of emulsions. Emulsifiers reduce interfacial tension between phases by forming interfacial films at the oil / water interface, counteracting irreversible coalescence of the droplets (coalescence). As a rule cloudy emulsions with a droplet size in the micrometer range are formed. As emulsifiers surfactants are usually used.

A Pickering emulsion is understood as meaning emulsions which are solid particles, eg. Colloidal silica particles stabilized at the interface between the two phases (hydrophilic and lipophilic phase) and prevent the droplets of the emulsified phase in the outer phase from coalescing. The hydrophobicity, shape and size of the solid particles affect the emulsion stability. The contact angle between the particle and the droplet surface is a measure of the hydrophobicity of the particles. When the contact angle between the particle and the droplet surface is small, the particle is wetted predominantly by the droplet phase, which can easily lead to coalescence of the droplets. Particles that are both hydrophobic and hydrophilic are more suitable as emulsion stabilizers because they are derived from Both phases wets and adsorb better on the droplet surface. Particularly preferred are those particles which form a contact angle of about 90 °, that is, which are wetted by about the same extent of both phases. The phase which predominates in the wetting of the particles normally forms the continuous phase of the emulsion system. Pickering emulsion contained as emulsifying components instead of surfactants or optionally in addition to surfactants finely divided powdered solids. The use of these finely divided powdery solids with emulsifying properties has the advantage that it is possible to dispense with the use of (short-chain) surfactants having irritative properties. This is particularly interesting for the formulation of sunscreen emulsions. In order to avoid the so-called Mallorca acne, it is attempted to formulate sunscreen emulsions which are used on the skin under strong sunlight with as low an emulsifier concentration as possible. Such sunscreen emulsions based on Pickering emulsions are known, for example, from WO 98/42300 A1. Such emulsions have a number-average particle size of the emulsified (lipophilic) phase in the usual range for emulsions of 100 nm to 2 microns and are stabilized by Pickering emulsifiers having a number average particle size of 1 to 200 nm, preferably 5 to 100 nm. However, emulsions can also be prepared by Pickering emulsifiers in which the dispersed phase forms large spherical structures which are visible visually, ie with the naked eye. This can be achieved by using larger solid particles, as disclosed, for example, in US Pat. Nos. 3,920,883 and 4,767,741. These optically visible sphere structures also allow the stabilization of lipophilic drugs that would be unstable in an aqueous environment.

Fine particle W / O emulsions with oil droplets in the micrometer range, which are free of surfactants and stabilized only by solids, are described in EP 686391. To stabilize spherical polyalkylsilsesquioxane particles are used here, which have a diameter of 100 nm up to 20 microns. EP 870495 describes finely divided O / W emulsions with oil droplets in the micrometer range, surfactants also being used here as emulsifiers in addition to finely divided solids having a diameter of up to 200 nm.

US Pat. No. 3,920,883 and US Pat. No. 4,767,741 disclose surfactant-free, drop-shaped O / W macroemulsions having a particle diameter of the oil droplets in the range from 0.1 millimeter to several centimeters, in which finely divided solid particles are also used as the emulsifier.

With regard to a possible commercial use of these Pickering emulsions, it has turned out to be a problem that the Pickering emulsions can not be stably stored in the plastic containers intended for cost, weight and safety aspects, but the structure of the Pickering emulsion disintegrated, since the oil phase wetted the plastic surface better than the aqueous phase.

According to the invention, it has now surprisingly been found that containers coated on the inner surface with a metal oxide layer and / or with a Halbmetalloxidschicht are excellent for storage of the Pickering emulsions are suitable because the Pickering emulsions can be stored in these without causing destabilization and coalescence of the Pickering emulsion.

A first subject of the present application is therefore a cosmetic or pharmaceutical agent, a cleaning, care, finishing, softening and / or conditioning agent for textiles or an agent for treatment, in particular for cleaning hard surfaces, comprising a Pickering packaged in a container Emulsion, characterized in that the container is coated at least on the inner surface with a metal oxide layer and / or with a Halbmetalloxidschicht.

The semimetal oxide layer is preferably selected from silicon oxides and aluminum oxides, more preferably selected from silicon oxides with the formula SiO _x and aluminum oxides with the formula Al ₂ O _x .

In a further preferred embodiment of the invention, the container coated at least on the inner surface with a metal oxide layer and / or with a semimetal oxide layer is a plastic container.

In a further preferred embodiment of the invention, the plastic vessel is made of polyethylene terephthalate (PET) and / or polyethylene naphthalate (PEN) and / or polymer blends containing polyethylene terephthalate and / or polyethylene naphthalate. In principle, however, all plastics from which bottles and similar containers can be formed, and which are suitable for coating with a metal oxide layer and / or with a semimetal oxide layer, are also suitable for the compositions according to the invention.

The silicon oxide-coated container according to the invention is preferably a plastic container which is coated with silicon oxide at least in the interior. The plastic is preferably polyethylene terephthalate (PET). Preference is also given to a biodegradable plastic, for example polylactides (PLA). Preferred layer thicknesses are 0.001 to 1 μm, preferably 0.01 to 0.1 μm, very preferably 0.02 μm, 0.03 μm, 0.04 μm, 0.05 μm, 0.06 μm, 0.07 μm, 0.08 μm and 0.09 μm.

The coating of the container with a metal oxide layer and / or with a Halbmetalloxidschicht can be carried out by methods, as disclosed for example in DE 10042333 A1, DE 4305856 C1, etc. A method as disclosed in EP 1375570 is particularly preferred according to the invention because the internally coated plastic containers thus obtained are transparent. The coating of the container with a silicon oxide such as SiO _x via the decomposition of siloxanes in a plasma, see, for example, DE 4313136 A1. The SiO _x vapor deposition can be carried out, for example, by electron beam evaporation or by conventional evaporation in a high vacuum, as in conventional metallization. In the electron beam evaporation, SiO, which is in the form of granules or pieces, is brought to red-hot by means of a directed electron beam and evaporated, which takes place in a very short time due to the high energy of the beams.

In conventional vapor deposition in a high vacuum, the SiO is brought to a high temperature in a melting tank. The temperature is about 1400 ⁰ C. In both methods, the SiO sublimates and condenses on the film surface - depending on the O ₂ content of the atmosphere - as SiO _x .

The container is preferably injection-stretch blown. The container can have any shape. Particularly preferred are bottle and bottle forms, as are customary for cosmetic products or products for the treatment of hard surfaces.

Pickering emulsions according to the invention preferably comprise a) as the first phase water, a hydrophilic organic solvent or water in combination with at least one hydrophilic organic solvent or a mixture of different anhydrous hydrophilic organic solvents, b) as second phase at least one fatty substance and c) as emulsifier at least a finely divided, powdery solid which is at least partially localized in the interface between first and second phases.

Pickering emulsions preferred according to the invention are characterized in that the dispersed, preferably lipophilic, phase of the Pickering emulsion has a number-average particle diameter of 10 nm to 10 μm, preferably 50 nm to 2 μm, particularly preferably 100 nm to 1.5 μm, exceptionally preferably 200 nm to 1 μm.

In another, likewise preferred embodiment, the Pickering emulsion is characterized in that the dispersed, preferably lipophilic (fatty substance-containing), phase in the form of visually (with the naked eye) visible and distinguishable from each other spherical particles having a number average particle diameter of at least 0.5 mm, preferably 1 to 20 mm, more preferably 2 to 10 mm and most preferably 3 to 8 mm. With the formation of optically highly visible and distinguishable spherical particles having a particle diameter of at least 0.5 mm is compared to finely dispersed emulsions (with number average particle diameter of 10 nm to 10 microns) due to the larger particle diameter, a significant reduction of the contact area between the first and second phase. This achieves an encapsulation effect that makes it possible to separate non-compatible ingredients more effectively and more sustainably. Especially with long storage times are thus to achieve decisive advantages in terms of stability and the constant composition of the preparation.

In a further preferred embodiment, these macroemulsions are distinguished by the fact that the emulsion formed is not milky or turbid, but has a high transparency. possesses, since the visible and distinguishable spherical particles in the preferably colorless first phase are emulsified as clearly distinguishable objects. This offers the advantage that, for example, by the use of pigment particles of the preparation, a special aesthetic effect with a high optical brilliance can be imparted. Other preferred macroemulsions can be converted to virtually homogeneous mixtures by mere shaking by hand before use. In a further preferred embodiment of the invention, the second phase emulsified in the form of spherical particles in the first phase forms after the homogenization within a period of 10 seconds to 100 minutes, preferably from 20 seconds to 100 minutes, particularly preferably from 30 seconds to 30 minutes , most preferably from 1 to 10 minutes, the original emulsion or macroemulsion having a particle diameter of 0.5 to 20 mm back. For the purposes of the invention, homogenization is understood to mean the fine distribution of the second phase in the first phase caused by an external action, such as shaking or stirring, so that the particle diameter of the emulsified second phase is at most 100 μm and the individual droplets are optical, that is to say , with the naked eye, as such are imperceptible or distinguishable.

For the purposes of the invention, the particle diameter of the spherically visible particles, which are clearly visible and distinguishable from each other, is the average particle diameter. This can be determined by visual, imaging and / or microscopic methods by determining the diameter of a statistically significant amount of spherical particles. The mean particle diameter is then the quotient of the sum of the individual particle diameters and the number of particles (number-average particle diameter).

Preferred agents according to the invention are characterized in that the continuous phase of the Pickering emulsion is hydrophilic and the dispersed phase is lipophilic.

At least part of the finely divided, pulverulent solid contained in the Pickering emulsion contained in the agent according to the invention is adsorbed on the phase interface between the first and second phase and thereby exerts an emulsion-stabilizing effect. Preferably, the majority, that is, more than 50%, particularly preferably the entire finely divided, powdery solid is adsorbed between the first and second phases. The Pickering emulsion contained in the composition according to the invention is characterized in a further preferred embodiment according to the invention characterized in that the second phase is emulsified in the first phase in the form of spherical particles having a particle diameter of 0.5 to 20 mm and at least part of the finely divided , powdered solid, preferably the majority, more preferably the complete finely divided powdery solid is located at the interface of the two phases. The finely divided, pulverulent solids which stabilize the Pickering emulsions according to the invention are also known to the person skilled in the art as Pickering emulsifiers and are preferably selected from polyalkylsilsesquioxane, iron oxide, titanium oxide, cerium oxide, antimony oxide, magnesium oxide, chromium oxide, aluminum oxide, zinc oxide, zinc peroxide, calcium aluminate, Silicic acid, magnesium silicoaluminate, magnesium metasilicate aluminate, talc, mica, zirconia, colloidal kaolin, bentonite, glass, zinc laurate, polyvinyl chloride, nylon, microcrystalline cellulose, mother of pearl, carbon black, calcium carbonate, barium carbonate, manganese oxide, bismuth oxychloride, interference pigments, lanolin and mixtures thereof.

To obtain color and / or pearlescent effects, the finely divided, pulverulent solid may preferably contain color pigments and / or pearlescent pigments and / or interference pigments, in particular those based on mica.

In a further embodiment preferred according to the invention, the Pickering emulsion is stabilized by at least one finely divided, pulverulent, optionally coated, solid which is non-spherical, preferably platelet-shaped.

In a particularly preferred embodiment of the invention, the finely divided, pulverulent solid is a mica coated with a metal oxide, wherein the metal oxide is preferably selected from iron oxide or titanium oxide or mixtures thereof.

In a very particularly preferred embodiment of the invention, Colorona pigments (Merck, Darmstadt, Germany) are used as finely divided, pulverulent solid, in particular Colorona Light Blue, Colorona Patina Silver, Colorona Bright Gold, Colorona Blackstar Gold, Colorona Majestic Green, Colorona Aborigine Amber, Colorona Bronze, Colorona Bordeaux, Colorona Oriental Beige, Colorona Dark Blue, Colorona Red Gold, Colorona Sienna, Colorona Copper, Colorona Blackstar Green, Colorona Russet, Colorona Patagonian Purple, Colorona Carmine Red, Colorona Passion Orange, Colorona Blackstar Blue, Colorona Red Brown , Colorona Chameleon, Colorona Imperial Red and / or Colorona Magenta and their mixtures.

In a further preferred embodiment of the invention, the Pickering emulsion is stabilized by at least one finely divided, powdery solid having a particle diameter of 1 nm to 100 .mu.m, preferably from more than 200 nm to 50 .mu.m, more preferably 1 .mu.m to 25 .mu.m, most preferably 2 μm to 5 μm.

The particle diameter of the finely divided, pulverulent solid in a particularly preferred embodiment of the invention is more than 200 nm. Particularly preferred particle diameters according to the invention are 1 to 100 μm, preferably 2 μm to 50 μm and especially 5 to 25 μm. Particles of these particle diameters are particularly preferred for the stabilization of Pickering emulsions whose dispersed phase has visible ball structures visible to the naked eye.

In another preferred embodiment of the invention, the Pickering emulsion is stabilized by at least one finely divided, powdery solid having a particle diameter of 1 nm to 200 nm, preferably 5 nm to 100 nm, more preferably 50 nm to 80 nm.

The particle diameter in the sense of the invention means the average particle diameter. This can easily be determined by a person skilled in the art by means of the laser diffraction method using suitable measuring devices (eg Mastersizer 2000 from Malvern, LA-920 from Horiba). The mean particle diameter is preferably the median particle diameter d _z . This separates the area of the particle size distribution curve into two equal halves, ie there are as many particles with a diameter larger than d _z than particles with a diameter smaller than d _z .

The amount used of the finely divided, pulverulent solid according to the invention is preferably from 0.001 to 10% by weight, based on the weight of the Pickering emulsion (without container). For the embodiment according to the invention which comprises the spherical structures visible to the naked eye, the total amount used of the finely divided, pulverulent solid according to the invention is preferably 0.01 to 1% by weight, particularly preferably 0.01 to 2% by weight or 0, 01 to 3 wt .-% and very preferably 0.01 to 0.1 wt .-%, in particular 0.04, 0.05 or 0.06 wt .-%, each based on the weight of the Pickering emulsion (without Container).

For the inventive embodiment with particle sizes of the dispersed phase of 10 nm to 10 .mu.m, the total amount used of finely divided powdered solid according to the invention is preferably 0.1 to 10 wt .-%, particularly preferably 0.5 to 5 wt .-% or 1 to 4 wt .-% and most preferably 2 to 3 wt .-%, in particular 1, 5, 1, 8, or 2.5 wt .-%, each based on the weight of the Pickering emulsion (without container).

The solvent of the first phase according to the invention is water, a hydrophilic organic solvent or water in combination with at least one hydrophilic organic solvent or a mixture of different anhydrous hydrophilic organic solvents.

Particularly suitable hydrophilic organic solvents are monohydric branched or unbranched alcohols having preferably 1 to 4 carbon atoms and polyhydric alcohols having preferably 1 to 4 carbon atoms or mixtures of said solvents. Preferred monohydric alcohols are, for example, ethanol, n-propanol and isopropanol. Preferred polyhydric alcohols are polyols, such as water-soluble diols, triols and higher alcohols and polyethylene glycols. Among the diols are C ₂ -C ₂ -DbIe, in particular 1, 2-propylene glycol, 2-methyl-1, 3 propanediol, glycerol, butylene glycols such as 1, 2-butylene glycol, 1, 3-butylene glycol and 1, 4-butylene glycol, pentylene glycols such as 1, 2-pentanediol and 1, 5-pentanediol, hexanediols such as 1, 2-hexanediol and 1, 6-hexanediol, hexanetriols such as 1, 2,6-hexanetriol, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 1, 2-octanediol, 1, 8-octanediol, dipropylene glycol, tripropylene glycol, diglycerol, triglycerol, erythritol, Sorbitol, as well as the polyethylene glycols (PEG) PEG-3, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG- 18 and PEG-20 PEG-400, PEG-600, PEG-1000, PEG-1550, PEG-3000 and PEG-4000, and mixtures of the aforementioned substances.

In the context of the invention, the first phase is particularly preferably water: ethanol mixtures, the ratio of the two components preferably being between 10: 1 and 1:10, particularly preferably between 5: 1 and 1: 5. Highly preferred mixing ratios of water to ethanol are between 4: 1 and 1: 4, between 3: 1 and 1: 3, between 2: 1 and 1: 2, in particular the mixing ratio is between 1.6: 1 and 1: 1, in each case based on the wt .-% ratio of the components used.

The proportion of the first phase in the total amount of the preparation is preferably 20 to 95 wt .-%, preferably 30 to 94 wt .-%, most preferably 50 to 93 wt .-%, and most preferably 70 to 92 wt .-% , in particular 80 to 91 wt .-% and 85 to 90 wt .-%.

The second phase of the preparation contains at least one fatty substance. Fatty substances are to be understood as meaning fatty acids, fatty alcohols, natural and synthetic cosmetic oil components as well as natural and synthetic waxes, which can be in solid or liquid form in aqueous or oily dispersion.

In particular, the fatty substance may be a nonpolar or polar liquid oil, which may be natural or synthetic, or any mixtures thereof. The oil component may in particular be selected from

- Vegetable oils, in particular sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach kernel oil and the liquid portions of coconut oil. Also suitable, however, are other triglyceride oils such as the liquid portions of beef tallow as well as synthetic triglyceride oils.

liquid paraffin oils, isoparaffin oils, e.g. Isohexadecane and isoeicosane, from hydrogenated polyalkenes, especially poly-1-decenes (commercially available as Nexbase 2004, 2006 or 2008 FG (Fortum, Belgium)), from synthetic hydrocarbons, e.g. 1,3-di- (2-ethyl-hexyl) -cyclohexane (Cetiol® S)

volatile and nonvolatile silicone oils which are cyclic, e.g. As decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane, or may be linear, for. B. linear dimethylpolysiloxane, in Trade available for. Example under the name Dow Corning 190, 200, 244, 245, 344, 345 or 350 and Baysilon ^® 350 M.

Dialkyl ethers, in particular di-n-alkyl ethers having a total of from 12 to 36 carbon atoms, particularly preferably having 12 to 24 carbon atoms, such as, for example, di-n-octyl ether (commercially available as Cetiol® OE), di-n- decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-undecyl-n- dodecyl ether and n-hexyl-n-undecyl ether and di-tert-butyl ether, di-iso-pentyl ether, di-3-ethyldecyl ether, tert-butyl n-octyl ether, iso-pentyl-n-octyl ether and 2-methyl-pentyl n-octyl ether.

- Alkanecarboxylic acid esters. Alkanecarboxylic acid esters are to be understood as meaning the esters of C ₆ -C ₃₀ -, in particular C ₆ -C ₂₂ -fatty acids, with C ₂ -C ₃₀ -, in particular C ₂ -C ₂₄ -fatty alcohols. Examples of fatty acid components used in the esters are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeo stearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures which are obtained, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxo synthesis or the dimerization of unsaturated fatty acids. Examples of the fatty alcohol components in the ester oils are isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, Elaeostearylalkohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and Brassi-dylalkohol and their technical mixtures, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols , Particularly suitable for use according to the invention are isopropyl myristate (Rilanit® IPM), isononanoic C 16-18 alkyl ester (Cetiol® SN), 2-ethylhexyl palmitate (Cegesoft® 24), stearic acid 2-ethylhexyl ester (Cetiol® 868), cetyl oleate (CetioKDV), glycerol tricaprylate , Coconut fatty alcohol caprinate / caprylate (Cetiol® LC), n-butyl stearate, oleyl erucate (Cetiol® J 600), isopropyl palmitate (Rilanit® IPP), oleyl oleate (Cetiol®), lauryl hexyl ester (Cetiol® A), n-butyl adipate (Cetiol® B), myristyl myristate (Cetiol® MM), cetearyl isononanoate (Cetiol® SN), oleic acid decyl ester (Cetiol® V),

Dicarboxylic acid esters such as di-n-butyl adipate, di (2-ethylhexyl) adipate, di- (2-ethylhexyl) succinate and diisotridecyl acelate and diol esters such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di (2-ethylhexanoate), Propylene glycol diisostearate, propylene glycol dipelargonate, butanediol diisostearate, neopentyl glycol dicaprylate,

symmetrical, unsymmetrical or cyclic esters of carbonic acid with fatty alcohols, for example described in DE-OS 197 56 454, glycerol carbonate or dicaprylyl carbonate (Cetiol® CC), - Mono-, di- and Trifettsäureestern, in particular Trifettsäureestern, of saturated and / or unsaturated linear and / or branched fatty acids, in particular C ₆ -C ₂₂ fatty acids, with glycerol, such as triglycerides of capric acid and / or caprylic acid, glycerol mono-oleate (eg, available as Monomuls® 90-018), glycerol monolaurate (eg, available as Monomuls® 90-L12 or glycerol mono-, distearate (eg, available as Cutina® MD).

The oil component may be further selected from vaselines, polyolefins, mineral oils, branched alkanols, for. B. Guerbet alcohols having a single branch on the carbon atom 2 such as 2-hexyldecanol, 2-octyldodecanol, isotridecanol and isohexadecanol, from alkanediols, eg. B. from Epoxyalkanen with 12 - 24 carbon atoms by ring opening with water available vicinal diols, from ether alcohols, eg. As the monoalkyl ethers of glycerol, ethylene glycol, 1, 2-propylene glycol or 1, 2-butanediol, from dialkyl ethers each having 12 - 24 carbon atoms, z. Example, the alkyl methyl ethers or di-n-alkyl ethers, each having a total of 12 to 24 carbon atoms, in particular di-n-octyl ether (Cetiol ^® OE ex Cognis), as well as adducts of ethylene oxide and / or propylene oxide to mono- or polyvalent C ₃ . ₂ o-alkanols such as butanol and glycerol, z. PPG-3-Myris- tylether (Witconol APM ^®), PPG-14 butyl ether (Ucon Fluid ^® AP) PPG-15 stearyl ether (Arlamol ^® E), PPG-9-butyl ether (Breox B25 ^®) and PPG -10-butanediol (Macol ^® 57).

Suitable fatty acids may be linear and / or branched, saturated and / or unsaturated C ₈ - ₃ o-fatty acids are used. ₂₂ fatty acids - ₁₀ C are preferred. Examples are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidonic acid, gadoleic acid, behenic acid and erucic acid and their technical properties mixtures. The fatty acids used can carry one or more hydroxyl groups. Preferred examples of these are the α-hydroxy-C ₈ -C ₈ -carboxylic acids and 12-hydroxystearic acid.

As fatty alcohols it is possible to use saturated, mono- or polyunsaturated, branched or unbranched fatty alcohols having 6 to 30, preferably 10 to 22 and very particularly preferably 12 to 22 carbon atoms. Applicable according to the invention are e.g. Decanol, octanol, dodecadienol, decadienol, oleyl alcohol, eruca alcohol, ricinoleic alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, capryl alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, and the like Guerbet.

As natural or synthetic waxes can be used according to the invention are solid paraffins or isoparaffins, plant waxes such as candelilla wax, carnauba wax, Espartogras wax, Japan wax, cork wax, sugarcane wax, ouricury wax, montan wax, sunflower wax, fruit waxes and animal waxes such. Beeswax and other insects waxes, spermaceti, shellac wax, wool wax and raffia fat, continue to mineral waxes such. As ceresin and ozokerite or the petrochemical waxes such. As petrolatum, paraffin waxes, Microwachse of polyethylene or polypropylene and polyethylene glycol waxes. It may be advantageous to use hydrogenated or hardened waxes. Furthermore, chemically modified waxes, especially the hard waxes, z. As montan ester waxes, Sasol waxes and hydrogenated jojoba waxes, can be used.

Also suitable are the triglycerides of saturated and optionally hydroxylated Ci ₆ - ₃ o-fatty acids, such as. B. hydrogenated triglyceride fats (hydrogenated palm oil, hydrogenated coconut oil, hydrogenated castor oil), glyceryl tribehenate or glyceryl tri-12-hydroxystearate, further synthetic Vollester of fatty acids and glycols (eg Syncrowachs ^®.) Or polyols having 2 - 6 carbon atoms, fatty acid alkanolamides with an d _2-22 acyl group and a C _2-4 alkanol, esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 1 to 80 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 1 to 80 carbon atoms, including z. Example, synthetic fatty acid fatty alcohol esters such as stearyl or cetyl palmitate, esters of aromatic carboxylic acids, dicarboxylic acids or hydroxycarboxylic acids (eg., 12-hydroxystearic) and saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 1 to 80 C atoms, lactides of long-chain hydroxycarboxylic acids and full esters of fatty alcohols and di- and tricarboxylic acids, eg. As dicetylsuccinate or dicetyl / stearyl adipate, and mixtures of these substances.

It is particularly preferred to choose the wax components from the group of esters of saturated, unbranched alkanecarboxylic acids having a chain length of 14 to 44 carbon atoms and saturated, unbranched alcohols of a chain length of 14 to 44 carbon atoms, provided the wax component or the entirety of the wax components are solid at room temperature. Particularly advantageously, the wax components from the group of Ci ₆ can - ₃₆ alkyl stearates, C _10-40 - alkyl stearates, C ₂ ^ ₀ -Alkylisostearate, the C ₂₀ - ₄₀ dialkyl esters of dimer acids, C-ι _8-38 - Alkylhydroxystearoylstearates, the C ₂₀ - ₄₀ -Alkylerucate be selected, also C ₃₀ - ₅₀ -alkylbienwax and cetearyl behenate can be used. Silicone waxes, for example stearyltrimethylsilane / stearyl alcohol, may also be advantageous. Particularly preferred wax components are the esters of saturated, monohydric C ₂₀ -C ₆₀ alcohols and saturated Cs-Cso-monocarboxylic acids, in particular a C ₂₀ -C ₄₀ alkyl preferred that Inc. under the name ^® Kesterwachs K82H from Koster Keunen is available. The wax or the wax components should be solid at 25 ° C, but in the range of 35 - 95 ° C to melt, with a range from 45 to 85 ⁰ C is preferred.

Natural, chemically modified and synthetic waxes may be used alone or in combination. According to the invention, any combination of the aforementioned fatty substances can be used. In a preferred embodiment according to the invention, the lipophilic phase of the Pickering emulsion comprises as fatty substance at least one of the abovementioned non-polar or polar oils.

Preferred oils here are ester oils, fatty acid triglycerides, silicone oils or cosmetic oils and mixtures thereof. Very particularly preferred oils are polydimethylsiloxanes (eg Dow Corning DC 200), decamethylcyclopentasiloxanes (Dow Corning DC 245), propylene glycol dicaprylates (eg Cognis Myritol PC), cetylstearyl isononanoates (eg Cognis Cetiol SN) and / or dibutyl adipates (eg Cetiol B) and any mixtures thereof ,

In a particularly preferred embodiment of the invention, the proportion of the fatty substance or of the mixture of different fatty substances, based on the total amount of the Pickering emulsion (without container), is between 0.01 and 80% by weight, preferably between 0.1 and 65% by weight %, more preferably between 0.1 and 50% by weight, and most preferably between 0.1 and 30% by weight, in particular between 1 and 25% by weight, between 2 and 20% by weight and between 5 and 15% by weight.

As a further component, the preparation according to the invention may preferably contain a density compensation agent. In the context of the invention, density compensation means are to be understood as meaning all substances which are suitable for varying the relative density of the first and second phases relative to one another. The function of the density balance agent is either to increase the density of a phase by increasing the mass of the respective phase without practically changing the volume, or to decrease the density of a phase by increasing the volume without the respective mass to change decisively. The density compensation agent is selected from the group of substances soluble in the first or second phase as well as their mixtures.

As an example of a density-balancing agent that is soluble in the second phase, oils, especially adipates such as dioctyl adipate, myristates such as isopropyl myristate, palmitates such as Octylpa Imitat, stearates such as isopropyl stearate, vitamins such as vitamin A, vitamin E, vitamin F, oils such as sunflower oil , Fish oil, pentaerythrityl tetra-2-ethylhexanoate and their mixtures or similar products.

As a density balance agent which is soluble in the first phase, mineral and / or organic water-soluble salts such as tri-, di-, monosodium phosphate, sodium metabisulfite, magnesium sulfate, sodium sulfate, mono-, di-, tripotassium phosphate, sodium chloride, potassium chloride, mono-, Call di- and trisodium citrate and generally water-soluble mineral salts or mixtures thereof. As the density-balancing agent which is soluble in the first phase, one may also cite a cosmetic ingredient such as a preservative, ultraviolet filter cloth, a buffering agent and a complexionener, and more generally any water-soluble compound or mixtures thereof which are suitable To change the density of the water. It is also possible to use one or more density balance agents that are soluble in both the first and second phases.

In a further preferred embodiment of the invention, the density of the second phase of the Pickering emulsion emulsified in the form of spherical particles is greater than the density of the first, continuous phase or the density of the second, emulsified phase corresponds to the density of the first, continuous phase. This ensures that the second phase emulsified in the form of spherical particles in the first phase floats in the first phase or settles at the bottom. A contact of the second phase with the atmospheric oxygen is thus excluded, so that in the oil component (2nd phase) dissolved or dispersed sensitive active substances are effectively protected from contact with the atmospheric oxygen during storage and application.

In a further preferred embodiment, the agent according to the invention is characterized in that the Pickering emulsion contains at least one surfactant. In a further particularly preferred embodiment, the composition according to the invention is characterized in that the Pickering emulsion containing the dispersed, preferably lipophilic, phase of the Pickering emulsion in the form of optically (with the naked eye) visible and distinguishable spherical particles having a number average particle diameter from 0.5 mm to 20 mm, containing at least one surfactant.

The fact that the addition of surfactants would be possible in the production of the Pickering emulsions according to the invention, in particular those having a particle diameter of the dispersed phase of 0.5 to 20 mm, was surprising to the person skilled in that it was to be expected that by competing micelle formation the disperse phase is split into small droplets so that they are no longer perceptible or distinguishable with the naked eye. The inventive formation of a macroscopic drop structure in the presence of surfactants was thus surprising and unpredictable.

The surfactants are preferably contained in the aqueous phase of the Pickering emulsions. At least 50%, preferably at least 80%, of the surfactants are particularly preferably contained in the aqueous phase of the Pickering emulsions.

Surfactants preferred according to the invention are selected from the group of anionic, cationic, amphoteric and / or nonionic surfactants or mixtures thereof.

Suitable anionic surfactants in the compositions according to the invention are all anionic surfactants suitable for use on the human body or on technical surfaces. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or poly- be contained glycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable foaming anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 carbon atoms in the alkanol group,

Acylglutamates of the formula (I),

XOOC-CH ₂ CH ₂ CH-COOX (I)

HN-COR ¹

in which R ¹ CO is a linear or branched acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and X is hydrogen, an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, for example acylglutamates, which are derived from fatty acids having 6 to 22, preferably 12 to 18 carbon atoms, such as, for example, C _12/14 or C _12/18 coconut fatty acid, lauric acid, myristic acid, palmitic acid and / or stearic acid, in particular sodium N-cocoyl and Sodium N-stearoyl-L-glutamate, esters of a hydroxy-substituted di- or tricarboxylic acid of the general formula (II),

X

HO - C - COOR ¹ (II)

Y - CH - COOR ²

wherein X is H or a -CH ₂ COOR group, Y is H or -OH is under the condition that Y is H when X is -CH ₂ COOR, R, R ¹ and R ^{2 are} independently a hydrogen atom, an alkali or alkaline earth metal cation, an ammonium group, the cation of an ammonium organic base or a radical Z derived from a polyhydroxylated organic compound selected from the group of etherified (C ₆ -C ₈ ) alkyl polysaccharides having 1 to 6 monomeric saccharide units and / or the etherified aliphatic (C ₆ -C ₁₆ ) -hydroxyalkylpolyols having 2 to 16 hydroxyl radicals, with the proviso that at least one of the groups R, R ¹ or R ^{2 is} a radical Z, esters of Sulfosuccinic acid salt of the general formula (III),

H ₂ C - COOR ¹ (IM)

O ₃ S - CH - COOR ²

in the R ¹ and R ^{2 are} independently a hydrogen atom, an alkali or alkaline earth metal cation, an ammonium group, the cation of an ammonium organic base or a Radical Z derived from a polyhydroxylated organic compound selected from the group consisting of the etherified (C ₆ -C ₁₈ ) -alkyl polysaccharides having 1 to 6 monomeric saccharide units and / or the etherified aliphatic (C ₆ -C ₁₆ ) -hydroxyalkylpolyols with 2 to 16 hydroxyl radicals, with the proviso that at least one of the groups R ¹ or R ^{2 is} a radical Z,

Sulfosuccinic acid mono- and dialkyl esters having 8 to 24 C atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethyl esters having 8 to 24 C atoms in the alkyl group and 1 to 6 ethoxy groups,

Esters of tartaric acid and citric acid with alcohols which are addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide onto fatty alcohols having 8 to 22 C atoms, linear and branched fatty acids having 8 to 30 C atoms (soaps),

Ethercarbonsäuren the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 8 to 30 carbon atoms and x = 0 or 1 to 16,

Acylsarcosinates having a linear or branched acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds,

Acyl taurates having a linear or branched acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds,

Acyl isethionates having a linear or branched acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, linear alkanesulfonates having 8 to 24 carbon atoms, linear alpha-olefin sulfonates having 8 to 24 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids with 8 to 30 C atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _Z -SO ₃ X, in which R is a preferably linear alkyl group having 8 to 30 C atoms, particularly preferably 8-18 C Atoms, z = 0 or 1 to 12, more preferably 3, and X is a sodium, potassium, magnesium, zinc, ammonium or a monoalkanol, dialkanol or trialkanolammonium ion having 2 to 4 carbon atoms in the alkanol group, wherein a particularly preferred example is zinc cocoyl ether sulfate having a degree of ethoxylation of z = 3, mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE 3723354,

Sulfonates of unsaturated fatty acids having 8 to 24 carbon atoms and 1 to 6 double bonds according to DE 3926344, alkyl and / or alkenyl ether phosphates of the formula (IV)

O

IL R ¹ - (OCH ₂ CH ₂ ) _n - OPO-R ² (IV)

OX in the R ^{1 is} preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R ^{2 is} hydrogen, a radical (CH ₂ CH ₂ O) _n R ¹ or X, n is from 1 to 10 and X is hydrogen, an alkali metal radical or alkaline earth metal or NR ³ R ⁴ R ⁵ R ⁶ , where R ³ to R ⁶ independently of one another represent a C ¹ to C ₄ hydrocarbon radical, is a sulfated fatty acid alkylene glycol ester of the formula R ⁷ CO (Al k O) _n SO ₃ M, in the R ⁷ CO- represents a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 C atoms, Alk represents CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ , n represents numbers from 0, 5 to 5 and M is a cation, as described in DE 19736906, monoglyceride sulfates and monoglyceride ether sulfates of the formula (V),

CH ₂ O (CH ₂ CH ₂ O) _x - COR ⁸ CH ₂ O (CH ₂ CH ₂ O) _y H (V)

CH ₂ O (CH ₂ CH ₂ O) ₂ - SO ₃ X

in which R ⁸ CO is a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z are in total 0 or numbers of 1 to 30, preferably 2 to 10, and X is an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. Preferably, monoglyceride sulfates of the formula (V) are used in which R ⁸ CO is a linear acyl radical having 8 to 18 carbon atoms.

Suitable cationic surfactants in the compositions according to the invention are all cationic surfactants suitable for use on the human body or on technical surfaces.

Cationic surfactants are distinguished in cosmetic application areas in that, like amphoteric and zwitterionic surfactants, they contribute to a significantly improved cosmetic appearance of the skin and hair. The cationic charge ensures a good bond to the rather negatively charged surfaces, especially of damaged hair or stressed skin. On the long fat residues of these molecular structures, in turn, more hydrophobically structured active ingredients can accumulate. As a result, an overall increased deposition of care substances on the surface of skin and hair is effected. For example, the hair is easier to comb, easier to style both in the dry and in the wet state and shows more shine and a pleasant grip. Cationic surfactants are generally derived from ammonium ions and have a structure (NR ¹ R ² R ³ R ⁴ ) ⁺ with a correspondingly negatively charged counterion. Such cationic ammonium compounds are well known to those skilled in the art. Further cationic surfactants are, for example, the esterquats or the imidazolium compounds. Cationic surfactants of the quaternary ammonium compound type, the esterquats, the imidazolines and the amidoamines are particularly preferably usable according to the invention. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 8 to 30 carbon atoms. Typical examples of cationic surfactants are quaternary ammonium compounds and esterquats, in particular quaternized fatty acid trialkanolamine ester salts.

According to the invention, cationic compounds with behenyl residues, in particular those known under the name of behentrimonium chloride or bromide (docosanyltrimethylammonium chloride or bromide), can be used with particular preference. Other preferred QAVs have at least two behenyl residues. Commercially available, these substances are, for example, under the designations Genamin ^® KDMP (Clariant).

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® L80 and Dehyquart ^® AU-35 are examples of such esterquats.

As further cationic surfactants, the agents according to the invention may contain at least one quaternary imidazoline compound, ie a compound which has a positively charged imidazoline ring. The formula (VI) shown below shows the structure of these compounds.

Suitable amphoteric / zwitterionic surfactants are surface-active compounds which are suitable for use on the human body or on technical surfaces and which carry at least one quaternary ammonium group and at least one -COO ^" or -SO ₃ ^" group in the molecule. Particularly suitable amphoteric surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinates, for example the Kokosalkyldimethylammoniumglyci- nat, N-acyl-aminopropyl-N, N-dimethylammoniumglycinate, for example Kokosacylaminopropyldimethylammoniumglycinat, and 2-alkyl-3 carboxymethyl-3-hydroxyethyl imidazolines having in each case 8 to 18 C atoms in the alkyl or acyl group, and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Suitable surface-active compounds which can be used according to the invention are also all nonionic surfactants which are suitable for use on the human body or on technical surfaces, for example, without being limited to:

Nonionic surfactants in the context of the invention are alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also suitable are block polymers of ethylene oxide and propylene oxide as well as fatty acid alkanolamides and fatty acid polyglycol ethers. Important classes of nonionic surfactants according to the invention are furthermore the amine oxides and the sugar surfactants, in particular the alkyl polyglucosides.

fatty alcohol polyglycol ethers

According to the invention, fatty alcohol polyglycol ethers are to be understood as meaning ethylene oxide (EO) and / or propylene oxide (PO) alkoxylated, unbranched or branched, saturated or unsaturated C ₂₂ alcohols having an alkoxylation degree of up to 30, preferably ethoxylated C ₁₈ fatty alcohols having a degree of ethoxylation of less than 30, preferably with a degree of ethoxylation of 1 to 20, in particular from 1 to 12, more preferably from 1 to 8, most preferably from 2 to 5, for example Ci ₂ -i ₄ -Fettalkoholethoxylate with 2, 3 or 4 EO or a mixture of the C ₁₂ - ₁₄ - Fatty alcohol ethoxylates with 3 and 4 EO in a weight ratio of 1 to 1 or isotridecyl alcohol ethoxylate with 5, 8 or 12 EO.

amine oxides

The amine oxides suitable according to the invention include alkylamine oxides, in particular alkyl dimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides. Preferred amine oxides satisfy formula VII,

R ⁶ R ⁷ R ⁸ N ⁺ -O ^" (VII)

R ⁶ - [CO-NH- (CH ₂ ) _W ] _Z -N ⁺ (R ⁷ ) (R ⁸ ) -O ^" (VII)

in which R ⁶ is a saturated or unsaturated C _6-22 -alkyl radical, preferably C ₈ -i ₈ -alkyl radical, preferably a saturated C ₁₀ -i ₆ alkyl radical, for example a saturated C ₂ - ₁₄ alkyl group, the above in the alkylamidoamine oxides a carbonylamidoalkylene group -CO-NH- (CH ₂ ) _Z - and in the alkoxyalkylamine oxides via an oxaalkylene group -O- (CH ₂ ) _Z - is bonded to the nitrogen atom N, where z is in each case from 1 to 10 , preferably 2 to 5, in particular 3,

R ^7, R, ^8, independently, a CI_ ₄ alkyl optionally hydroxysubstituted such as a hydroxyethyl group, in particular a methyl radical.

Examples of suitable amine oxides are the following compounds designated as INCI: almond amidopropylamine oxides, babassuamidopropylamine oxides, behenamine oxides, cocamidopropyl amine oxides, cocamidopropylamine oxides, cocamine oxides, coco-morpholine oxides, decylamine oxides, decyltetradecylamines oxides, diaminopyrimidines oxides, dihydroxyethyl C8-10 Alkoxypropylamines oxides, dihydroxyethyl C9-11 alkoxypropylamines oxides, dihydroxyethyl C12-15 alkoxypropylamines oxides, dihydroxyethyl cocamines oxides, dihydroxyethyl lauramine oxides, dihydroxyethyl stearamines oxides, dihydroxyethyl tallowamine oxides, hydrogenated palm kernel amines oxides, hydrogenated tallowamine oxides, hydroxyethyl hydroxypropyl C12 -15 Alkoxypropylamines Oxides, Isostearamidopropylamines Oxides, Isostearamidopropyl Morpholine Oxides, Lauramidopropylamines Oxides, Lauramine Oxides, Methyl Morpholine Oxides, Milk Amidopropyl Amines Oxides, Mincamidopro- pylamines Oxides, Myristamidopropylamines Oxides, Myristamines Oxides, Myristyl / Cetyl Am Oxide, Oleamidopropylamine Oxide, Oleamine Oxide, Olivamidopropylamine Oxide, Palmitamidopropylamine Oxide, Palmitamine Oxide, PEG-3 Lauramine Oxide, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Trisphosphonomethylamine Oxide, Sesamidopropylamine Oxide, Soyamidopropylamine Oxide, Stearamidopropylamine Oxide, Stearamine Oxide, Tallowamidoproxide pylamine oxides, tallowamine oxides, undecylenamidopropylamine oxides and wheat germamidopropylamides oxides. A preferred amine oxide is, for example, cocamidopropylamine oxides (cocoamidopropylamine oxide). sugar surfactants

Sugar surfactants are known surface-active compounds, which include, for example, the sugar surfactant classes of alkyl glucose esters, aldobionamides, gluconamides (sugar acid amides), glycerol amides, glycerol glycolipids, polyhydroxy fatty acid amide sugar surfactants (sugar amides) and alkylpolyglycosides. Preferred sugar surfactants within the scope of the teaching according to the invention are the alkylpolyglycosides and the sugar amides and their derivatives, in particular their ethers and esters. The ethers are the products of the reaction of one or more, preferably one, sugar hydroxy group with a compound containing one or more hydroxy groups, for example C 1. ₂₂ -alcohols or glycols such as ethylene and / or propylene glycol, wherein the sugar hydroxy group can also carry polyethylene glycol and / or polypropylene glycol. The esters are the reaction products of one or more, preferably one, sugar with a carboxylic acid, especially a C _6-22 fatty acid.

sugar amides

Particularly preferred sugar amides satisfy the formula R'C (O) N (R ") [Z], in which R 'is a linear or branched, saturated or unsaturated acyl radical, preferably a linear unsaturated acyl radical, having 5 to 21, preferably 5 to 17, in particular 7 to 15, particularly preferably 7 to 13 carbon atoms, R "is a linear or branched, saturated or unsaturated alkyl radical, preferably a linear unsaturated alkyl radical, having 6 to 22, preferably 6 to 18, in particular 8 to 16, particularly preferred 8 to 14 carbon atoms, a C |. ₅ alkyl, in particular a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or n-pentyl rest, or hydrogen and Z is a sugar residue, ie a Monosaccharidrest stand , Particularly preferred sugar amides are the amides of glucose, the glucamides, for example lauroyl methyl glucamide.

alkylpolyglycosides

The alkyl polyglycosides (APG) are particularly preferred sugar surfactants within the scope of the teaching according to the invention and preferably satisfy the general formula R ^{Errors! The text mark nιcht defines} O (AO) _a [G] _x , in which R ^{errors! Textmarke undefined} - for a linear or branched, saturated or unsaturated alkyl radical having 6 to 22, preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, [G] for a glycosidically linked sugar residue and x for a number of 1 to 10 and AO for an alkyleneoxy group, for example an ethyleneoxy or Propylenoxygruppe, and a for the average degree of alkoxylation of 0 to 20. Here, the group (AO) _{3 may} also contain different alkyleneoxy, for example ethyleneoxy or propyleneoxy, where it is a to the average Gesamtalkoxylierungsgrad, ie the sum of Ethoxylierungs- and Propoxylierungsgrad acts. Unless otherwise stated below, the alkyl radicals R ^{1 of} the APG are linear unsaturated radicals having the stated number of carbon atoms. APG are non-ionic surfactants and are known substances that can be obtained by the relevant methods of preparative organic chemistry. The index number x indicates the C ¹ degree of gyration (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While x must always be an integer in a given compound, and here especially If the values x = 1 to 6 can be assumed, the value x for a particular alkyl glycoside is an analytically determined arithmetic variable, which usually represents a fractional number. Alkyl glycosides having an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6 are preferred. The glycosidic sugar used is preferably xylose, but in particular glucose.

The alkyl or alkenyl radical R ^{Error! Bookmark not defined} - can be derived from primary alcohols having 8 to 18, preferably 8 to 14 carbon atoms. Typical examples are caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, such as those obtained in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelene's oxosynthesis.

The alkyl or alkenyl radical R is preferably derived. ^{Error! Bookmark not defined} - but from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Also to be mentioned are elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof.

Particularly preferred APG are not alkoxylated (a = 0) and satisfy the formula RO [G] _x , in which R is as previously described for a linear or branched, saturated or unsaturated alkyl radical having 4 to 22 carbon atoms, [G] for a glycosidically linked sugar radical, preferably glucose residue, and x is a number from 1 to 10, preferably 1, 1 to 3, in particular 1, 2 to 1, 6, stand. Accordingly, preferred alkyl polyglycosides are, for example C -io- ₈ and a ₁₂ C -i ₄ alkyl polyglucoside with an average degree of 1, 4 or 1, 5, in particular C ₈ -io- alkyl-1, 5-glucoside and C ₁₂ - i ₄ -alkyl-1,4-glucoside.

Within the meaning of the present invention, the Pickering emulsion may particularly advantageously contain one or more surfactants from the groups of anionic surfactants. It is also advantageous to use a combination of anionic with one or more amphoteric surfactants and / or one or more nonionic surfactants.

Very particularly preferred surfactants are sodium alkylbenzenesulfonic acids (eg Unger Tensid Service GmbH: Ufaryl DL85), sodium lauryl ether sulfates (eg Cognis: Texapon NSO), sodium lauryl sulfates (eg Cognis: Texapon K12), betaines (eg Clariant: Genagen CAB), amine oxides (eg Clariant : Genaminox CSL), alkyl polyglycosides (eg Cognis: Plantacare 1200 UP), cetyltrimethyl ammonium chlorides (eg Cognis: Dehyquart A CA) and / or PEG-60 hydrogenated castor oils (eg BASF: Cremophor CO 60) and any mixtures thereof.

In a particularly preferred embodiment of the invention, the proportion of one or more surfactants, if used, based on the total amount of the Pickering emulsion is at least 0.5 wt .-%, preferably 0.5 to 20 wt .-%, particularly preferably 0, 6 to 10 wt .-%, more preferably 0.7 to 8 wt .-% and in particular 0.8 to 6 wt .-%, 0.9 to 4 wt .-% or 1 to 2 wt .-%. In a very particularly preferred embodiment of the invention, the proportion of one or more surfactants in the total amount of Pickering emulsion is 1 wt .-%, 1, 3 wt .-%, 1, 6 wt .-% and 1, 9 parts by weight. %.

In a further preferred embodiment, the agent according to the invention is characterized in that the Pickering emulsion is free of surfactants.

In a further particularly preferred embodiment, the composition according to the invention is characterized in that the Pickering emulsion, which contains the dispersed, preferably lipophilic, phase of the Pickering emulsion in the form of particles having a number average particle diameter of 10 nm to 10 .mu.m, is surfactant-free ,

The Pickering emulsion may optionally contain at least one further component, in particular selected from the group of cosmetic active ingredients, vitamins, UV filter substances, fragrances, conditioning agents, thickeners, preservatives, antioxidants, colorants, buffering agents, the sequestration products, the antiperspirant active ingredients, the tanning substances, the moisturizer for the skin or the brightener.

In this case, the cosmetic active ingredient in a proportion of 0.0001 to 38 wt .-%, based on the total amount of the Pickering emulsion, preferably selected from the following active ingredients or mixtures thereof:

• antiperspirant active ingredients

• deodorizing agents

Monomers, oligomers and polymers of amino acids, NC ₂ -C ₂₄ -acylamino acids, the esters and / or the physiologically acceptable salts of these substances

• DNA or RNA oligonucleotides

• natural betaine compounds

Α-hydroxycarboxylic acids, α-ketocarboxylic acids, β-hydroxycarboxylic acids and their ester, lactone or salt form,

• Flavonoids and flavonoid-rich plant extracts

Isoflavonoids and isoflavonoid-rich plant extracts Polyphenols and polyphenol rich plants are extra kten

• ubiquinone and ubiquinol and their derivatives

• Silymarin

• Ectoin

• repellents

• self-tanning active ingredients

• skin lightening agents

• soothing agents

• moisturizing ingredients

• sebum-regulating agents

In a preferred embodiment, the inventive Pickering emulsions contain at least one vitamin, provitamin or a compound called vitamin precursor from the vitamin groups A, B, C, E, H and K and the esters of the aforementioned substances.

The group of substances called vitamin A includes retinol (vitamin A ₁ ) and 3,4-didehydroretinol (vitamin A ₂ ). The ß-carotene is the provitamin of retinol. As vitamin A component according to the invention, for example, vitamin A acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters, such as retinyl palmitate and retinyl acetate into consideration. The Pickering emulsions of the invention contain the vitamin A component preferably in amounts of 0.05 to 1 wt .-%, based on the total composition.

The vitamin B group or the vitamin B complex include, among others

Vitamin B _1, thiamine trivial name, chemical designation 3 - [(4 ^'-amino-2' -methyl-5 ^'- pyrimidinyl) methyl] -5- (2-hydroxyethyl) -4-methylthiazolium chloride. Thiamine hydrochloride is preferably used in amounts of from 0.05 to 1% by weight, based on the total agent. Vitamin B ₂ , common name riboflavin, chemical name 7,8-dimethyl-10- (1-D-ribityl) - benzo [g] pteridine-2,4 (3H, 10H) -dione. Riboflavin or its derivatives are preferably used in amounts of from 0.05 to 1% by weight, based on the total agent. Vitamin B ₃ . Under this name, the compounds nicotinic acid and nicotinamide (niacinamide) are performed. Preferred according to the invention is the nicotinic acid amide, which is preferably present in the agents according to the invention in amounts of from 0.05 to 1% by weight, based on the total agent.

(VIII) Vitamin B ₆ , which is understood hereunder no uniform substance, but the known under the common names pyridoxine, pyridoxamine and pyridoxal derivatives of 5-hydroxymethyl-2-methylpyridin-3-ols. Vitamin B ₆ is contained in the agents according to the invention preferably in amounts of 0.0001 to 1, 0 wt .-%, in particular in amounts of 0.001 to 0.01 wt .-%.

Vitamin B ₇ (biotin), also known as vitamin H or "skin vitamin". Biotin is (3aS, 4S, 6aR) -2-oxohexahydrothienol [3,4-d] imidazole-4-valeric acid. Biotin is preferably present in the compositions according to the invention in amounts of from 0.0001 to 1.0% by weight, in particular in amounts of from 0.001 to 0.01% by weight.

- Folic acid (Vitamin B ₉ , Vitamin B _c ). International generic name for N- [4- (2-amino-3,4-dihydro-4-oxo-6-pteridinylmethylamino) -benzoyl] -L-glutamic acid (N-pteroyl-L-glutamic acid, PteGlu). Folate is used synonymously with pteroylglutamate. Folate is the generic term for all acid-active compounds and refers to a class of substances containing a pteridine ring linked to 4-aminobenzoic acid and L-glutamic acid. Folic acid is a growth factor for various microorganisms and a compound of vitamin character, which is usually found in nature as polyglutamate and in reduced form (7,8-dihydrofolic acid, H ₂ folate, DHF, tetrahydrofolic acid, H ₄ folate, THF, 5'-methyl). Tetrahydrofolic acid, CH ₃ -H ₄ folate, MeTHF). Pickering emulsions which are particularly preferred according to the invention are characterized in that they contain at least one component selected from folic acid, folates and their esters, in a total amount of 0.0001 to 1.0% by weight, in particular 0.01 to 0.5% by weight .-%, based on the Pickering emulsion included.

- Orotic acid (vitamin B ₁₃ , 1, 2,3,6-tetrahydro-2,6-dioxo-4-pyrimidine-carboxylic acid, uracil-6-carboxylic acid, molar acid). Orotic acid, its choline ester or orotic acid metal salts (orotates of Ca, Cr, Fe, K, Co, Cu, Li, Mg, Mn, Na, Zn, Sn) are particularly preferred according to the invention. Pickering emulsions which are particularly preferred according to the invention are characterized in that they contain at least one component selected from orotic acid, orotates and their esters, in a total amount of 0.0001-1.0% by weight, in particular 0.01-0.5% by weight .-%, based on the Pickering emulsion included.

Vitamin C (ascorbic acid) is preferably used in amounts of 0.1 to 3 wt .-%, based on the total Pickering emulsion. The use of the derivatives ascorbyl palmitate, stearate, dipalmitate, acetate, Mg ascorbyl phosphate, Na ascorbyl phosphate, sodium and magnesium ascorbate, disodium ascorbyl phosphate and sulfate, potassium ascorbyl tocopheryl phosphate, chitosan ascorbate or ascorbyl glucoside may be preferred. The use in combination with tocopherols may also be preferred.

The vitamin E group includes tocopherol, especially α-tocopherol, and its derivatives. Preferred derivatives are in particular the esters, such as tocopheryl acetate, nicotinate, phosphate, succinate, linoleate, oleate, tocophereth-5, tocophereth-10, tocophereth-12, tocophereth-18, tocophereth-50 and tocopherol. Tocopherol and its derivatives are preferably present in amounts of from 0.05 to 1% by weight, based on the total composition.

Vitamin F is usually understood as meaning essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid.

Vitamin H is another name for biotin or vitamin B ₇ (see above).

The fat-soluble vitamins of the vitamin K group, which are based on the basic structure of 2-methyl-1,4-naphthoquinone, include phylloquinone (vitamin K ₁ ), farnoquinone or menaquinone.

7 (vitamin K2) and menadione (vitamin K _3). Vitamin K is preferred in amounts of from 0.0001 to 1.0

Wt .-%, in particular 0.01 to 0.5 wt .-%, each based on the total composition.

Vitamin A palmitate (retinyl palmitate), panthenol, folic acid, nicotinic acid amide, pyridoxine, pyridoxamine, pyridoxal, biotin, ascorbyl palmitate, acetate, Mg ascorbyl phosphate, Na ascorbyl phosphate,

Sodium and magnesium ascorbate and the tocopherol esters, especially tocopheryl acetate, are especially preferred according to the invention.

In a further extraordinarily preferred embodiment, the inventive Pickering emulsion contains at least one inorganic and / or at least one organic UV filter substance. The UV filter substances are substances which are liquid or crystalline at room temperature and which are capable of absorbing ultraviolet rays and of absorbing the absorbed energy in the form of longer-wave radiation, eg. B. to give off heat again. One differentiates between UVA filters and UVB filters. The UVA and UVB filters can be used individually or in mixtures. The use of filter mixtures is preferred according to the invention.

The organic UV filters preferred according to the invention are selected from the derivatives of dibenzoylmethane, cinnamic acid esters, diphenylacrylic acid esters, benzophenone, camphor, p-aminobenzoic acid esters, o-aminobenzoic acid esters, salicylic acid esters, benzimidazoles, symmetrically or unsymmetrically substituted 1,3,5-triazines, monomers and oligomeric 4,4-diarylbutadienecarboxylic acid esters and carboxamides, ketotricyclo (5.2.1.0) decane, benzalmalonic acid esters, benzoxazole and any mixtures of the stated components. The organic UV filters can be oil-soluble or water-soluble. The benzoxazole derivatives are advantageously present in dissolved form in the cosmetic preparations according to the invention. If appropriate, it may be particularly preferred for the benzoxazole derivatives to be present in a pigmentary, ie undissolved form, for example in particle sizes of from 10 nm to 300 nm. Oil-soluble UV filters which are particularly preferred according to the invention are 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione (Parsol® 1789), 1-phenyl-3- (4'-dichloro) isopropylphenyl) -propane-1, 3-dione, 3- (4 ^{methylbenzylidene)} - D, L-camphor, 4- (dimethylamino) benzoic acid 2-ethylhexyl ester, 4- (dimethylamino) benzoic acid 2-octyl ester, 4 Ethyl (dimethylamino) benzoate, 2-ethylhexyl 4-methoxycinnamate, Propyl 4-methoxycinnamate, isopentyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene), 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomethyl salicylate (SSS-trimethylcyclohexylsalicylate), 2- Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (4'-diethylamino-2'-hydroxybenzoyl) -benzoic acid hexyl ester ( also: aminobenzophenone, available under the name Uvinul A Plus from BASF), 4-Methoxybenzmalonsäuredi- 2-ethylhexylester, bound to polymers UV filters, eg. For example, the 3- (4- (2,2-bis-ethoxycarbonylvinyl) phenoxy) propenyl) -methoxysiloxane / dimethylsiloxane copolymer having the INCI name Dimethicodiethylbenzal malonate (CAS No. 207574-74-1, Parsol® SLX), triazine derivatives, such as. B. 2,4-bis {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine (INCI: bis-ethylhexyl) oxyphenol methoxyphenyl triazine, available under the name Tinosorb S from CIBA), dioctylbutyl amidotriazone (INCI: diethylhexyl butamido triazone, available under the name Uvasorb® HEB from Sigma 3V), 2,4,6-trianilino- (p-carbo-2 '-ethyl-1'-hexyloxy) -1, 3,5-triazine (ethylhexyl triazone, Uvinul® T 150), 2- [4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine -2-yl] -5- (octyloxy) phenol (CAS No .: 2725-22-6), 2,4-bis [5-1 (di-methylpropyl) benzoxazol-2-yl (4-phenyl) -imino] -6- (2-ethylhexyl) -imino-1,3,5-triazine (CAS No. 288254-16-0, Uvasorb® K2A from 3V Sigma), the benzotriazole derivatives 2,2'-methylene-bis- (6- (2H-Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -phenol) [Tinosorb M (Ciba)], 2,2'-methyl-bis- [6 (2H benzotriazol-2-yl) -4- (methyl) phenol] (MIXXIM BB / 200 from Fairmount Chemical), 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole (CAS). No .: 025973-551), 2- (2'-hydroxy-5'-octylp henyl) benzotriazole (CAS no. 003147-75-9), 2- (2'-hydroxy-5'-methylphenyl) benzotriazole (CAS No. 2440-22-4), 2- (2H-benzotriazol-2-yl) -4-methyl- 6- [2-methyl-3- [1,3,3,3-tetramethyl-1 - ((trimethylsilyl) oxy] disiloxanyl) propyl] phenol (CAS No .: 155633-54-8) with the INCI name drometrizole trisiloxanes, 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine ( INCI: bis-ethylhexyloxyphenol methoxyphenyl triazine or aniso triazine, available as Tinosorb® S from CIBA), 2,4-bis - {[4- (3-sulfonato) -2-hydroxy-propyloxy) -2-hydroxy] -phenyl } -6- (4-methoxyphenyl) -1, 3,5-triazine sodium salt, 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxy-propyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine, 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- [4 - (2-methoxyethylcarboxyl) -phenylamino] -1, 3,5-triazine, 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxy-propyloxy) -2-hydroxy] -phenyl } -6- [4- (ethylcarboxyl) -phenylamino] -1, 3,5-triazine, 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- ( 1-methyl-pyr rol-2-yl) -1, 3,5-triazine, 2,4-bis - {[4-tris (trimethylsiloxy-silylpropyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine, 2,4-bis - {[4- (2-methylpropenyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine, 2,4- Bis - {[4- (1 ', 1', 1 ', 3', 5 ', 5', 5'-heptamethylsiloxy-2-methyl-propyloxy) -2-hydroxy] -phenyl} -6- (4- methoxyphenyl) -1,3,5-triazine and mixtures of said components.

Preferred water-soluble UV filters are 2-phenylbenzimidazole-5-sulfonic acid, phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and their alkali metal, alkaline earth metal, ammonium, Alkylammonium, alkanolammonium and Glucammoniumsalze, in particular the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (CAS No. 27503-81-7), which is available, for example, under the trade name Eusolex 232 from Merck or from Neo Heliopan Hydro from Symrise, and the phenylene 1,4-bis (2-one) benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name Disodium Phenyl Dibenzimidazole Tetrasulfonate (CAS No .: 180898-37- 7), for example, under the trade name Neo Heliopan AP at Symrise is available, sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts, sulfonic acid derivatives of 3-Benzylidencamphers, such as. B. 4- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and its salts with the INCI name Terephthalydene Dicampher Sulfonic Acid (CAS. 90457-82-2, available as Mexoryl SX from Chimex).

Some of the oil-soluble UV filters can themselves serve as solvents or solubilizers for other UV filters. For example, solutions of the UV-A filter 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione (eg Parsol® 1789) in different UV-B Make filters. Therefore, in a further preferred embodiment, the compositions according to the invention contain 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione in combination with at least one UV-B filter selected from 4 2-ethylhexyl 2-ethoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate, 2-ethylhexyl salicylate and 3,3,5-trimethylcyclohexylsalicylate. In these combinations, the weight ratio of UV-B filter to 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione is between 1: 1 and 10: 1, preferably between 2 : 1 and 8: 1, the molar ratio is between 0.3 and 3.8, preferably between 0.7 and 3.0.

The inventively preferred inorganic photoprotective pigments are finely dispersed or colloidally disperse metal oxides and metal salts, for example titanium dioxide, zinc oxide, iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (talc) and barium sulfate. The particles should preferably have an average diameter of less than 100 nm, more preferably between 5 and 50 nm and in particular between 15 and 30 nm, so-called nanopigments. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments can also be surface treated, i. hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Particularly preferred are titanium dioxide and zinc oxide.

The inorganic sunscreen pigments can also function as Pickering emulsifier. In a particularly preferred embodiment according to the invention, the Pickering emulsion is stabilized by at least one inorganic sunscreen pigment. As already explained above, organic sunscreen filters, in particular benzoxazole derivatives, in pigmentary, ie undissolved form - for example, in particle sizes of 10 nm up to 300 nm - are present. In a further particularly preferred embodiment according to the invention, the Pickering emulsion is therefore stabilized by at least one organic photoprotective pigment.

Preferred agents of the invention are characterized in that the Pickering emulsion at least one organic UV filter substance in a total amount of 0.1 to 30 wt .-%, preferably 0.5 to 20 wt .-%, particularly preferably 1, 0 - 10th % By weight and most preferably 2 or 3 to 7% by weight, based in each case on the entire Pickering emulsion (without container).

Preferred agents of the invention are characterized in that the Pickering emulsion at least one inorganic UV filter substance in a total amount of 0.1 to 15 wt .-%, preferably 0.5 to 10 wt .-%, particularly preferably 1-5 wt. -% and most preferably 2 - 4 wt .-%, each based on the total Pickering emulsion (without container) contains.

In a further preferred embodiment, the inventive Pickering emulsion contains at least one perfume. Perfume components, perfume oils or perfume oil components can be used as perfume component. Perfume oils or fragrances can according to the invention individual fragrance compounds, eg. As the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethylacetate, benzylacetate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzylsalicylate, cyclohexylsalicylate, floramate, melusate and jasmecyclate. The ethers include, for example, benzyl ethyl ether and ambroxane, to the aldehydes e.g. the linear alkanals of 8 - 18 C atoms, citral, citronellal, citronellyloxy-acetaldehyde, cyclamen aldehyde, lilial and bourgeonal, to the ketones e.g. the ionones, alpha-isomethylionone and methylcedryl ketone; the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.

Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muskateller sage oil, camomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and laudanum oil and orange blossom oil, neroli oil, orange peel oil and sandalwood oil.

To be perceptible, an odoriferous substance must be volatile, and besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role plays. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note or body" As the smell perception is based to a large extent on the odor intensity, the top note of a perfume or fragrance consists not only of volatile compounds, while the base note for the most part from less volatile In the composition of perfumes, for example, volatile fragrances can be bound to certain fixatives, which prevents them from evaporating too quickly the odor impression and on whether the corresponding end fragrance is perceived as the head or middle note, nothing said.

Adhesive-resistant fragrances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamot oil, champacilla oil, noble-pine oil, pinecone oil, elemi oil, eucalyptus oil, fennel oil, spruce alder oil, galbanum oil, geranium oil, Gingergrass oil, guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine needle oil, copaϊva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, Lime oil, Tangerine oil, Melissa oil, Musk grain oil, Myrrh oil, Clove oil, Neroli oil, Niaouli oil, Olibanum oil, Orange oil, Origanum oil, Palmarosa oil, Patchouli oil, Peru balsam oil, Petitgrain oil, Pepper oil, Peppermint oil, Pimento oil, Pine oil, Rose oil, Rosemary oil, Sandalwood oil, Celery oil, Spiked oil, star aniseed oil, turpentine oil, thuja oil, thymia oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon oil, lemon oil, lemon oil and cypress oil.

But also the higher-boiling or solid fragrances of natural or synthetic origin can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances. These compounds include the following compounds and mixtures thereof: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol , Bornyl acetate, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptincarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole , Iron, isoeugenol, isoeugenol methyl ether, isosapril, jasmone, camphor, karvakrol, karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilate, p-methylacetophenone, methylchavikol, p-methylquinoline, methyl β-naphthyl ketone, methyl n-nonyl acetaldehyde, methyl n-nonyl ketone, Musko n, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol l, n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, β-phenylethylalcohol, phenylacetaldehyde-dimethylacetal, phenylacetic acid, pulegone, safrole, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, cyclohexyl salicylate, santalol, skatole, terpineol, thymene, thymol, γ-undelactone, vaniline, veratrum aldehyde, cinnamaldehyde, cimat alcohol, cinnamic acid, cinnamic acid ethyl ester, cinnamic acid benzyl ester.

The more volatile fragrances include in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more readily volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butadione, citral, citronellal, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde and terpinyl acetate.

Particularly preferred agents according to the invention are characterized in that at least one perfume component in a total amount of 0.00001 to 4 wt .-%, preferably 0.5 to 2 wt .-%, particularly preferably 1-1, 5 wt .-%, respectively based on the Pickering emulsion (without container) is included.

In a further preferred embodiment, the inventive Pickering emulsions comprise conditioning agents. Examples of conditioning agents which may be mentioned are cationic as well as amphoteric and / or non-ionogenic polymers and / or mixtures thereof or copolymers. For the purposes of the invention, polymers are understood to mean both natural and synthetic polymers.

Cationic polymers are to be understood as meaning polymers which have a group in the main and / or side chain which may be "temporary" or "permanent" cationic. According to the invention, "permanently cationic" refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C 1-4 hydrocarbon group to a polymer main chain constructed from acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.

Further cationic polymers according to the invention are the so-called "temporary cationic" polymers, which usually contain an amino group which, at certain pH values, is present as a quaternary ammonium group and thus cationically.

These two groups of polymers share a potentially cationic charge. Both cationic and amphoteric or zwitterionic polymers can therefore be characterized by their cationic charge density. The polymers of the invention are characterized by a charge density of at least 1 to 7 meq / g. A charge density of at least 2 to 7 meq / g is preferred. Particularly preferred is a charge density of at least equal to 3meq / g to 7 meq / g.

Another characteristic feature of the polymers according to the invention is their molecular weight. The molecular weight of the particular polymer is understood to mean the molecular weight which the manufacturer indicates in the corresponding data sheets by its method. For the selection of a suitable polymer, a molecular weight of at least 50,000 g / mol has proven to be suitable according to the invention. Polymers with a molecular weight of more than 100,000 g / mol have proven to be particularly suitable. Polymers with a molecular weight of more than 1000,000 g / mol are very particularly suitable.

Furthermore, amphoteric polymers can be used as polymers. The term "amphoteric polymers" includes both those polymers which contain both free amino groups and free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, as well as zwitterionic polymers which have quaternary ammonium groups in the molecule Contain -COO - or - SO ₃ ^~ groups, and those polymers comprising -COOH or SO ₃ H groups and quaternary ammonium groups.

Amphoteric polymers, like the cationic polymers, are most preferred polymers.

The Pickering emulsions according to the invention may also contain nonionic polymers in a further preferred embodiment.

Suitable polymers are known to those skilled in the art and can be readily determined from this without undue experimentation.

Other preferred polymers are polymers in the "International Cosmetic Ingredient Dictionary and Handbook" (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 ^th Street, NW, Suite 300, Washington, DC 20036-4702) as polymers in one of the chapters on polymers and are commercially available, reference is made to this document and the sections cited therefrom.

The polymers are preferably contained in the Pickering emulsions according to the invention in amounts of from 0.01 to 30% by weight, based on the total Pickering emulsion (without container). Amounts of 0.01 to 25 wt .-%, in particular from 0.01 to 15 wt .-%, from 0.01 to 10 wt .-%, from 0.01 to 5 wt .-% and from 0.01 to 1 wt .-% are particularly preferred. The inventive Pickering emulsion may further contain thickening agents in a preferred embodiment, e.g. Cellulose ethers, such as hydroxypropylcellulose, hydroxyethylcellulose and methylhydroxypropylcellulose, furthermore gelatine, plant gums such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum or locust bean gum, and thickening polymers based on polyacrylates, which may be crosslinked if desired, or based on polyacrylamides or sulfonic acid-containing polyacrylates, eg. B Sepigel ^® 305 or Simulgel® ^® EG, also inorganic thickeners such. B. natural and synthetic clays and phyllosilicates, z. As bentonite, hectorite, montmorillonite or Laponite ^® , as well as fully synthetic hydrocolloids such. As polyvinyl alcohol, and also Ca, Mg or Zn soaps of fatty acids.

Suitable preservatives according to the invention are, for example, phenoxyethanol, formaldehyde solution, parabens, in particular methyl or propylparaben, pentanediol or sorbic acid, and the further classes of substances listed in Appendix 6, Parts A and B of the Cosmetics Regulation.

The Pickering emulsions according to the invention may further contain antioxidants, for example imidazoles (eg urocanic acid) and derivatives thereof, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), Chlorogenic acid and its derivatives, lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, Ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, Peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg buthionine sulfoximines, homocysteine sulfoximine, bithine sulfones, penta, hexa, heptathionine sulfoximine) in very low tolerated dosages (eg pmol to μmol / kg), furthermore (metal) -Chel ator (eg, α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), humic acid, bile acid, biliary extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. Gamma-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and derivatives thereof, the benzylic resin, rutinic acid and its derivatives, α-glycosylrutin, ferulic acid, furfurylideneglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacetic acid , Nordihydroguajaretsäure, trihydroxybutyrophenone, uric acid and its derivatives, catalase, superoxide dismutase, zinc and its derivatives (eg ZnO, ZnSO ₄ ), selenium and its derivatives (eg selenium methionine), stilbenes and their Derivatives (eg stilbene oxide, trans-stilbene oxide) and the antioxidant suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these drugs.

Suitable colorants, buffers, sequestering products, anti-dandruff agents, tanning agents, skin moisturizers and brighteners are known to those skilled in the art.

A particularly preferred Pickering emulsion according to the invention contains, in each case based on the total amount of the preparation: From 0.5 to 8% by weight of an anionic surfactant or of a mixture of different anionic surfactants,

From 0.03 to 0.10% by weight of a finely divided, pulverulent solid having a particle diameter of from 1 to 30 μm,

5 to 15% by weight of one or more fatty acid triglycerides as the second phase,

- A water / ethanol mixture as the first phase.

An extremely preferred Pickering emulsion according to the invention contains, in each case based on the total amount of the preparation:

From 1 to 2% by weight of an anionic surfactant or a mixture of different anionic surfactants,

From 0.03 to 0.06% by weight of a finely divided, pulverulent solid having a particle diameter of from 5 to 25 μm,

5 to 15% by weight of one or more fatty acid triglycerides as the second phase,

- A water / ethanol mixture with a mixing ratio between 1, 5: 1 and 1: 1, 5 based on the wt .-% ratio of the components used as the first phase.

Another object of the present invention is an agent for the treatment, in particular for cleaning, hard surfaces, in particular of wood, glass, plastic and / or metal surfaces, comprising one in a container according to one of claims 2 to 5, the at least the inner surface is coated with a metal oxide layer and / or with a Halbmetalloxidschicht, packaged Pickering emulsion according to any one of claims 6 - 18. The hard surfaces are surfaces of the interior, of wet rooms and / or the outside, preferably in order

(a) glassware and articles, such as preferably windows, drinking glasses, glass showcases,

(b) wood and products, such as preferably furniture, floorboards, parquet,

(c) sanitary ware, such as preferably sanitary basin and furniture, bathtubs and wash basins, shower curtains, bathroom fixtures, tiles,

(d) kitchen furnishings and utensils, such as, preferably, ovens, ceramic hobs, hobs, kitchen furniture, kitchen fittings, porcelain items, ceramics, grills (including garden grilles),

(e) structure and building material such as preferably masonry, wallpapered, painted, painted walls and / or ceilings, bricks, bricks, plaster, floor slabs, joints, preferably cement and silicone joints, laminate, plastic surfaces, garage doors, plasterboard,

(f) outdoor furnishings and garden accessories, preferably garden furniture, stair treads, swimming pools, walkway fixtures of wood and stone, e.g. Path plates, garden sheds, wooden fences,

(d) paints, windowpanes and fittings of vehicles. Another object of the present invention is a means for cleaning, care, equipment, conditioning and / or conditioning of textiles, comprising in a container according to one of claims 2 to 5, which at least on the inner surface with a metal oxide layer and / or with a semimetal oxide layer is coated, packaged Pickering emulsion according to any one of claims 6-18.

A further subject of the present invention is a cosmetic or pharmaceutical composition comprising in a container according to one of claims 2 to 5, which is coated on at least the inner surface with a metal oxide layer and / or with a Halbmetalloxidschicht, packaged Pickering emulsion according to a A further subject matter of the present invention is a cosmetic or pharmaceutical sunscreen composition comprising in a container according to one of claims 2 to 5, which is coated on at least the inner surface with a metal oxide layer and / or with a semimetal oxide layer, A packaged Pickering emulsion according to any of claims 6-19, wherein the Pickering emulsion is a cosmetic or pharmaceutical sunscreen composition.

Cosmetic and pharmaceutical agents preferred according to the invention are agents for the cosmetic and / or dermatological treatment and / or purification of the skin, in particular of the human skin.

According to the invention, the term "skin" is generally understood to mean the skin itself, the mucous membrane and the skin appendages, insofar as they comprise living cells, in particular hair follicles, hair roots, hair bulbs, the anterior epithelium of the nail bed (lectorulus) as well as sebaceous glands and sweat glands.

The cosmetic and pharmaceutical compositions according to the invention can be used in particular for the treatment of sensitive or dry skin, for the treatment of mature skin and / or for the treatment of stressed, in particular UV-stressed skin. The cosmetic and pharmaceutical compositions according to the invention can be used in particular to avoid sensitive or dry skin and / or to prevent skin reddening and skin irritation.

The cosmetic and pharmaceutical compositions according to the invention can be used in particular for the care, conditioning and maintenance of the natural lipid coat of keratinic materials, in particular keratinous fibers, wherein the Pickering emulsion is particularly preferably applied to the keratinic material, in particular the skin or the keratinic fiber is rinsed again after a contact time of 5 seconds to 45 minutes.

In a preferred embodiment of the invention, the Pickering emulsion is a sunscreen composition, a washing and cleansing lotion, a skin care and / or skin protection agent or a hair conditioner. The following exemplary embodiments are intended to explain the invention in more detail, without limiting it thereto.

embodiments

a) washing and cleaning lotion

[a] All data in% by weight refers to active substance proportions

In all the example formulations listed, the DC 245 or myritol PC is present as a second, lipophilic phase in the form of optically highly visible and distinguishable spherical particles having a particle diameter of at least 0.5 mm, emulsified in the first, hydrophilic phase. b) hair conditioning (dry hair conditioner, rinse-off product)

[a] All data in% by weight refers to active substance proportions

In the example recipe listed, the mixture of DC 245 and Myritol PC is in the form of optically highly visible and distinguishable spherical particles having a particle diameter of at least 0.5 mm, emulsified in the first phase before.

c) sunscreens (surfactant-free)

[a] All data in% by weight refers to active substance proportions

In the example recipe listed, the DC 200 is present as a second phase in the form of optically highly visible and distinguishable spherical particles having a particle diameter of at least 0.5 mm, emulsified in the first phase.

Comparison of storage stability (at 25 ^° C.)

All of the example formulations were filled in glass bottles, in uncoated PET plastic bottles and in SiO _x coated PET plastic bottles.

When stored in uncoated PET plastic bottles, the spherical structure was partially lost after 24 hours, after 4 weeks of storage no balls were visible.

When stored in glass bottles and when stored according to the invention in SiO _x coated

PET plastic bottles, the ball structure was preserved unchanged even after 12 weeks of storage.

Glass bottles are disadvantageous for safety reasons and because of the high weight compared to plastic bottles for cosmetic and cleaning products.

Claims

claims

1. Cosmetic or pharmaceutical composition, agent for cleaning, care, equipment, conditioning and / or conditioning of textiles or means for treatment, in particular for cleaning, hard surfaces, comprising a packaged in a container Pickering emulsion, characterized in that the container is coated at least on the inner surface with a metal oxide layer and / or with a Halbmetalloxidschicht.

2. Composition according to claim 1, characterized in that the Halbmetalloxidschicht is selected from silicon oxides and aluminum oxides, preferably selected from silicon oxides with the formula SiO _x and aluminum oxides with the formula AI ₂ O _x .

3. Composition according to claim 1 or 2, characterized in that the coated at least on the inner surface with a metal oxide layer and / or with a Halbmetalloxidschicht container is transparent.

4. Composition according to claim 1, 2 or 3, characterized in that it is the at least on the inner surface with a metal oxide layer and / or coated with a Halbmetalloxidschicht container is a plastic vessel.

5. Composition according to claim 1, 2, 3 or 4, characterized in that the plastic vessel made of polyethylene terephthalate and / or polyethylene naphthalate and / or polymer blends containing polyethylene terephthalate and / or polyethylene naphthalate, is made.

6. Composition according to claim 1, 2, 3, 4 or 5, characterized in that the dispersed, preferably lipophilic, phase of the Pickering emulsion has a number average particle diameter of 10 nm to 10 .mu.m, preferably 50 nm to 2 .mu.m, particularly preferably 100 nm to 1, 5 microns, exceptionally preferably 200 nm to 1 micron having.

7. Composition according to claim 1, 2, 3, 4, 5 or 6, characterized in that the dispersed, preferably lipophilic, phase of the Pickering emulsion in the form of optically (naked eye) visible and distinguishable from each other spherical particles which have a number-average particle diameter of at least 0.5 mm, preferably 1 to 20 mm, more preferably 2 to 10 mm and most preferably 3 to 8 mm.

8. Composition according to claim 7, characterized in that the continuous, preferably hydrophilic, phase of the Pickering emulsion has a high light transmittance and is preferably transparent.

9. Composition according to claim 1, 2, 3, 4, 5, 6, 7 or 8, characterized in that the continuous phase of the Pickering emulsion is hydrophilic and the dispersed phase is lipophilic.

10. Composition according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9, characterized in that the Pickering emulsion is stabilized by at least one finely divided, powdery, optionally coated, solid, which is selected from Polyalkylsilsesquioxan , Iron oxide, titanium oxide, cerium oxide, antimony oxide, magnesium oxide, chromium oxide, aluminum oxide, zinc oxide, zinc peroxide, calcium aluminate, silicic acid, magnesium silicoaluminate, magnesium metasilicate aluminate, talc, mica, zirconium oxide, colloidal kaolin, bentonite, glass, zinc laurate, polyvinyl chloride, nylon, microcrystalline cellulose , Mother of pearl, carbon black, calcium carbonate, barium carbonate, manganese oxide, bismuth oxychloride, interference pigments, lanolin and mixtures thereof.

11. Composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, characterized in that the Pickering emulsion is stabilized by at least one finely divided, powdery, optionally coated, solid, the non- spherical, preferably platelike.

12. Composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, characterized in that the Pickering emulsion is stabilized by a coated with a metal oxide mica, wherein the metal oxide is preferably selected is made of iron oxide or titanium oxide or mixtures thereof.

13. Composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, characterized in that the particle diameter of the finely divided, powdery solid 1 nm to 100 .mu.m, preferably more than 200 nm to 50 microns, more preferably 1 micron to 25 microns, exceptionally preferably 2 microns to 5 microns, is.

14. Composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, characterized in that the at least one of the Pickering emulsion stabilizing finely divided, powdery, optionally coated, solid in a total amount of 0.001 to 10 wt .-%, based on the weight of the Pickering emulsion (without container) is included.

15. Composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, characterized in that the hydrophilic phase of the Pickering emulsion contains water and ethanol, preferably in a weight ratio of water: ethanol between 10: 1 and 1:10, especially preferably between 5: 1 and 1: 5, even more preferably between 4: 1 and 1: 4, between 3: 1 and 1: 3, between 2: 1 and 1: 2, in particular between 1, 6: 1 and 1: 1.

16. Composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, characterized in that the density of the emulsified in the form of spherical particles second phase the Pickering emulsion is at least equal to or greater than the density of the first, continuous phase.

17. Composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, characterized in that the Pickering emulsion is free of surfactants.

18. Composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, characterized in that the Pickering emulsion contains at least one surfactant.

19. Composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18, characterized in that the Pickering emulsion a cosmetic or pharmaceutical sunscreen composition.