EP1100431A1

EP1100431A1 - Finely dispersed emulsifier-free systems of the oil-in-water and water-in-oil type

Info

Publication number: EP1100431A1
Application number: EP99936590A
Authority: EP
Inventors: Heinrich Gers-Barlag; Anja MÜLLER
Original assignee: Beiersdorf AG
Current assignee: Beiersdorf AG
Priority date: 1998-08-01
Filing date: 1999-07-22
Publication date: 2001-05-23
Also published as: JP2002522363A; DE19834819A1; US6620407B1; WO2000007548A1

Abstract

The invention relates to cosmetic or dermatological preparations constituting finely dispersed systems of the oil-in-water or water-in-oil type and containing: 1) an oil phase; 2) an aqueous phase; 3) at least one type of microfine polymer particles which (a) are present in the preparation in the form of solids and (b) have both hydrophilic and lipophilic properties and an amphiphilic character and can be dispersed in both water and oil; and 4) no more than 0.5 % by weight of one or more emulsifiers; as well as possibly other cosmetic or pharmaceutical aids, additives and/or active ingredients.

Description

description

Oil-in-water and water-in-oil type emulsifier-free finely dispersed systems

The present invention relates to emulsifier-free finely dispersed systems of the oil-in-water and water-in-oil type, preferably as cosmetic or dermatological preparations.

Emulsions are generally understood to mean heterogeneous systems which consist of two liquids which are immiscible or only miscible with one another to a limited extent and are usually referred to as phases. In an emulsion, one of the two liquids is dispersed in the other liquid in the form of very fine droplets.

If the two liquids are water and oil and oil droplets are finely distributed in water, it is an oil-in-water emulsion (O / W emulsion, e.g. milk). The basic character of an OΛ / V emulsion is characterized by the water. A water-in-oil emulsion (W / O emulsion, e.g. butter) is the opposite principle, whereby the basic character is determined by the oil.

In order to achieve permanent dispersion of one liquid in another, the addition of a surface-active substance (emulsifier) is necessary for emulsions in the conventional sense. Emulsifiers have an amphiphilic molecular structure consisting of a polar (hydrophilic) and a non-polar (lipophilic) part of the molecule, which are spatially separated from each other. In simple emulsions there are finely dispersed droplets of the second phase (water droplets in W / O or lipid vesicles in O / W emulsions) enclosed in an emulsifier shell. Emulsifiers reduce the interfacial tension between the phases by being located at the interface between the two liquids. They form at the live exclude oil / water interface films, which counteracts the irreversible confluence of the droplets. Mixtures of emulsifiers are often used to stabilize emulsions.

Conventional emulsifiers can be divided into ionic (anionic, cationic and amphoteric) and nonionic according to their hydrophilic part of the molecule:. The best-known example of an anionic emulsifier is soap, which is commonly referred to as the water-soluble sodium or potassium salts of the saturated and unsaturated higher fatty acids. . The quaternary ammonium compounds are important representatives of the cationic emulsifiers. . The hydrophilic part of the molecule of nonionic emulsifiers often consists of glycerol, polyglycerol, sorbitan, carbohydrates or polyoxyethylene glycols and is usually linked to the lipophilic part of the molecule via ester and ether bonds. This usually consists of fatty alcohols, fatty acids or isofatty acids.

By varying the structure and size of the polar and non-polar part of the molecule, lipophilicity and hydrophilicity of emulsifiers can be changed within wide limits.

The correct choice of emulsifiers is decisive for the stability of an emulsion. The characteristics of all substances contained in the system must be taken into account. Looking at z. B. skin care emulsions, polar oil components and, for example, UV filters lead to instabilities. In addition to the emulsifiers, other stabilizers are therefore used which, for example, increase the viscosity of the emulsion and / or act as a protective colloid.

Emulsions are an important product type in the field of cosmetic and / or dermatological preparations.

Cosmetic preparations are mainly used for skin care. Skin care in the cosmetic sense is primarily that the natural function of the skin as a barrier against environmental influences (eg dirt, chemicals, microorganisms) and against the loss of the body's own substances (eg water, natural fats, electrolytes) is strengthened or restored. If this function is disturbed, it can lead to stronger absorption of toxic or allergenic substances or infestation of microorganisms and, as a result, toxic or allergic skin reactions.

The aim of skin care is also to compensate for the loss of fat and water in the skin caused by daily washing. This is especially important when the natural regeneration ability is insufficient. In addition, skin care products are intended to protect against environmental influences, especially sun and wind, and to delay skin aging.

Cosmetic preparations are also used as deodorants. Such formulations serve to eliminate body odor that arises when the odorless fresh sweat is decomposed by microorganisms.

Medical topical compositions usually contain one or more drugs in effective concentration. For the sake of simplicity, reference is made to the legal provisions of the Federal Republic of Germany for a clear distinction between cosmetic and medical use and corresponding products (e.g. cosmetics ordinance, food and drug law).

As such, the use of the customary emulsifiers in cosmetic or dermatological preparations is harmless. Nevertheless, emulsifiers, like any chemical substance, can cause allergic or hypersensitive reactions in individual cases.

For example, it is known that certain light dermatoses are triggered by certain emulsifiers, but also by various fats and simultaneous exposure to sunlight. Such light dermatoses are also called "Mallorca acne". There has been no shortage of attempts to reduce the amount of conventional emulsifiers to a minimum, ideally even completely.

A reduction in the amount of emulsifier required can, for. B. can be achieved if it is used that finely divided solid particles have an additional stabilizing effect. The solid material accumulates at the oil / water phase boundary in the form of a layer, which causes the disperse phases to flow together. is prevented. It is not the chemical, but the surface properties of the solid particles that are essential.

Around 1910, Pickering produced paraffin-water emulsions that were only stabilized by adding various solids such as basic copper sulfate, basic iron sulfate or other metal sulfates. This type of emulsions is therefore also called a Pickering emulsion. Pickering postulated the following conditions for this form of emulsions:

(1) The solid particles are only suitable for stabilization if they are significantly smaller than the droplets of the inner phase and do not tend to form agglomerates.

(2) Another important property of an emulsion-stabilizing solid is its wettability. That To stabilize an OΛΛ / emulsion, the solid must, for example, be wettable more easily by water than by oil.

So to speak, the original forms of Pickering emulsions first appeared as undesirable side effects in various technical processes, such as. B. in the secondary oil production, the extraction of bitumen from tar sand and other separation processes, in which two immiscible liquids and fine, dispersed solid particles are involved. In general, these are W / O emulsions that are stabilized by mineral solids. Accordingly, the investigation of corresponding systems, such. B. the systems oil-water-soot or oil-water-slate dust initially in the focus of the research activities.

Basic investigations have shown that a characteristic of a Pickering emulsion is that the solid particles are arranged at the interface between the two liquid phases and form, so to speak, a mechanical barrier against the unification of the liquid droplets.

A relatively new technical development is to use Pickering emulsions as the basis for cosmetic or dermatological preparations. According to May-Alert (Pharmacy in our Time, 15th year 1986, No. 1, 1-7), one way of stabilizing the solids in a cosmetic or dermatological preparation is to use emulsifier mixtures which are both anionic and cationic Contain surfactants. Since insoluble, electroneutral compounds always fail when anion and cationic surfactants are combined, specific precipitation of these neutral surfactants in the oil / water interface can achieve additional solid stabilization in the sense of a Pickering emulsion.

European laid-open specification 0 686 391 describes water-in-oil emulsions which are free of surface-active substances and are only stabilized by solids. Spherical polyalkylsilsesquioxane particles with a diameter of 100 nm to 20 μm are used for stabilization. These emulsions can be referred to as Pickering emulsions after the above.

In addition to the Pickering emulsions described, the prior art knows other emulsifier-free, finely dispersed cosmetic or dermatological preparations which are generally referred to as hydrodispersions. Hydrodispersions are dispersions of a liquid, semisolid or solid inner (discontinuous) lipid phase in an outer aqueous (continuous) phase.

In the case of hydrodispersions of a liquid lipid phase in an outer aqueous phase, the stability can be ensured, for example, by building a gel structure in the aqueous phase in which the lipid droplets are stably suspended. German Offenlegungsschrift 44 25 268 describes stable, finely dispersed, emulsifier-free cosmetic or dermatological preparations of the oil-in-water type which, in addition to an oil and a water phase, contain one or more thickeners from the group of acrylic acid polymers, polysaccharides and their alkyl ethers, and for these Thickener an interfacial tension reduction must not be measurable.

Based on similar hydrodispersions, German Offenlegungsschrift 43 03 983 discloses cosmetic or dermatological light protection formulations which are essentially free from emulsifiers, the hydrochloride being inorganic micropigments are incorporated, which serve as UV filter substances.

The object of the present invention was to enrich the prior art with cosmetic or dermatological preparations, in which any use of conventional emulsifiers can be dispensed with.

Amazingly, this problem is solved by

containing cosmetic or dermatological preparations which are finely dispersed systems of the oil-in-water or water-in-oil type

1. an oil phase,

2. a water phase,

3. at least one type of microfine polymer particles which (a) are present in the preparation in the form of solids and which

(b) show both hydrophilic and lipophilic properties, which therefore have amphiphilic character and are dispersible in both water and oil, and

4. containing at most 0.5% by weight of one or more emulsifiers and, if appropriate, further cosmetic or pharmaceutical auxiliaries, additives and / or active ingredients.

It is particularly advantageous according to the invention if the preparations contain significantly less than 0.5% by weight of one or more emulsifiers or are even completely emulsifier-free.

The preparations according to the invention are mixtures of oils or oil-soluble substances and water or water-soluble components which are stabilized by the addition of the microfine polymer particles and do not have to contain an emulsifier in the conventional sense. The stabilization is achieved in that the microfine polymer particles attach to the droplets of the disperse phase and form, so to speak, a mechanical barrier that prevents the coalescing, ie the confluence of the droplets. The preparations according to the invention are extremely satisfactory preparations in every respect, which are surprisingly highly variable in their water-fat phase ratio and also offer the advantage over the prior art that large amounts of oils can be incorporated stably in water. It was also surprising that if the teaching on technical action disclosed herewith is followed, both Pickering emulsions of the water-in-oil type and Pickering emulsions of the oil-in-water type can be produced.

Advantageous microfine polymer particles for the purposes of the present invention are, for example, polycarbonates, polyethers, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamides, polyacrylates and the like.

According to the invention, for example, microfine polyamide particles which are available under the trade name SP-500 from TORAY are advantageous. Polyamide 6 (also: nylon 6) or polyamide 12 (also: nylon 12) particles are also advantageous. Polyamide 6 is the polyamide [poly (ε-caprolactam)] composed of ε-aminocaproic acid (6-aminohexanoic acid) or ε-caprolactam, and polyamide 12 is a poly (ε-lauric lactam) made of ε-laurolactam. Advantageous for the purposes of the present invention are, for example Orgasol ^® 1002 (polyamide 6) and Orgasol ^® 2002 (polyamide 12) from ELF ATOCHEM.

Microfine polymethacrylates are further advantageous polymer particles. Such particles are available, for example, under the trade name POLYTRAP ^® from DOW CHEMICAL.

It is particularly advantageous, although not essential, if the microfine polymer particles used are coated on the surface. This surface treatment can consist in that the pigments are provided with a thin hydrophilic layer by methods known per se. Advantageous coatings consist, for example, of TiO ₂ , ZrO ₂ or other polymers, such as polymethyl methacrylate. Particularly advantageous microfine polymer particles for the purposes of the present invention are also obtainable by the process for the hydrophilic coating of hydrophobic polymer particles described in US Pat. No. 4,898,913.

In all of the aforementioned cases, it is advantageous to choose the average particle diameter of the microfine polymer particles used to be less than 100 μm, particularly advantageously less than 50 μm. It is essentially irrelevant in which form (platelets, rods, beads, etc.) the polymer particles used are present.

It is also advantageous, although not essential, to combine the amphiphilic, microfine polymer particles according to the invention with further amphiphilic pigments, which may also contribute to stabilizing the Pickering emulsions.

Such pigments are, for example, micronized, inorganic pigments which are selected from the group of amphiphilic metal oxides, in particular from the group titanium dioxide, zinc oxide, silicon dioxide or silicates (for example talcum), where the metal oxides can be present either individually or in a mixture . It is essentially irrelevant in which of the possibly naturally occurring modifications the amphiphilic metal oxides used are present.

The average particle diameter of the amphiphilic metal oxides used for combination with polymer particles according to the invention is preferably selected between 1 nm and 200 nm, particularly advantageously between 5 nm and 100 nm.

For the purposes of the present invention, it is advantageous to combine the amphiphilic microfine polymer particles according to the invention with untreated, almost pure, amphiphilic metal oxide particles, in particular with those which are also used as a dye in the food industry and / or as an absorber of UV radiation in sunscreen agents can be. Advantageous are, for example, the zinc oxide pigments available from Merck and those that are available under the trade names zinc oxide neutral from Haarmann & Reimer or NanoX from the Harcros Chemical Group. Another advantageous, untreated pigment is boron nitride. According to the invention, the microfine polymer particle or particles are preferably combined with the boron nitrides listed below:

Trade name available from

Boron Nitride Powder Advanced Ceramics Boron Nitride Powder Sintec Ceramics Ceram Blanche Kawasaki

HCST Boron Nitride Stark

Tres BN ^® Carborundum

Wacker boron nitride BNP Wacker-Chemie

The average particle diameter of the boron nitride particles used is preferably chosen to be less than 20 μm, in particular less than 15 μm.

Also advantageous according to the invention is the combination of microfine polymer particles with amphiphilic inorganic pigments which have been surface-treated ("coated") in a water-repellent manner, and at the same time an amphiphilic character of these pigments is to be formed or maintained. This surface treatment can consist in that the Pigments are provided with a thin hydrophobic layer by methods known per se.

One such method, which is described below using the example of titanium dioxide, consists, for example, in that the hydrophobic surface layer after a reaction according to

n TiO ₂ + m (RO) ₃ Si-R '→ n TiO ₂ (surface)

is generated, n and m are stoichiometric parameters to be used at will, R and R 'are the desired organic radicals. Particularly advantageous combination partners are TiO ₂ pigments, for example those coated with aluminum stearate, available under the trade name MT 100 T from TAYCA. Another advantageous coating of the combination partners consists of dimethylpolysiloxane (also: Dimethicone), a mixture of fully methylated, linear siloxane polymers which are blocked at the end with trimethylsiloxy units. The combination of microfine polymer particles with zinc oxide pigments, which are coated in this way, is particularly advantageous in the sense of the present invention. Advantageous combination partners are also available from Carborundum under the trade name Tres BN ^® UHP 1106, boron nitride particles treated with dimethicone.

Advantageous, coated boron nitride particles are also those which have been treated with polymethylhydrogensiloxane, a linear polysiloxane, which is also referred to as methicone. Advantageous boron nitride particles treated with methicone are, for example, those available from Carborundum under the trade name Tres ^BN® UHP 1107.

It is also advantageous in the sense of the present invention if the inorganic amphiphilic pigments used in addition to microfine polymer particles are coated with a mixture of dimethylpolysiloxane, in particular dimethylpolysiloxane with an average chain length of 200 to 350 dimethylsiloxane units, and silica gel, which is also referred to as simethicone. It is particularly advantageous if the inorganic pigments are additionally coated with aluminum hydroxide or aluminum oxide hydrate (also: alumina, CAS no .: 1333-84-2). Particularly advantageous combination partners are titanium dioxides which are coated with simethicone and alumina, the coating also being able to contain water. An example of this is the titanium dioxide available from Merck under the trade name Eusolex T2000.

Another advantage of the present invention is the combination of microfine polymer particles with a mixture of different inorganic, amphiphilic pigment types both within a crystal, for example as iron mixed oxide or talc (magnesium silicate), as well as by mixing several metal oxide types within one preparation. Particularly advantageous combination partners are magnesium silicates, for example those available from Grolmann under the trade name Talkum Micron. The amphiphilic microfine polymer particles according to the invention can furthermore advantageously be combined with other pigments, for example with titanium dioxide pigments which are coated with octylsilanol, and / or with silicon dioxide particles which have been treated to be water-repellent on the surface. Silicon dioxide particles suitable for combination are, for example, spherical polyalkylsilsesquioxane particles as mentioned in European laid-open specification 0 686 391. Such polyalkylsilsesquioxane particles are available, for example, from Degussa under the trade names Aerosil R972 and Aerosil 200V.

The amphiphilic microfine polymer particles according to the invention are furthermore preferably combined with amphiphilic modified polysaccharides which do not show any thickening properties.

Such amphiphilic polysaccharides can be obtained, for example, by reacting starch with mono-, bi- or polyfunctional reagents or oxidizing agents in reactions which are largely polymer-analogous.

These reactions are essentially based on conversions of the hydroxyl groups of the polyglucans by etherification, esterification or selective oxidation. This creates z. B. so-called starch ethers and starch esters of the general structural formula

Structural formula (I) in which R can represent, for example, a hydrogen and / or an alkyl and / or aralkyl radical (in the case of starch ethers) or a hydrogen and / or an organic and / or inorganic acid radical (in the case of starch esters). Starch ethers and starch esters are advantageous combination partners in the sense of the present invention. It is particularly advantageous to combine the polymer particles of the invention with starch ethers, e.g. B. with those which are obtainable by etherification of starch with tetramethylolacetylene diurea and which are referred to as Amylum non mucilaginosum (non-swelling starch). ,

Also particularly advantageous is the combination of polymer particles with starch esters and / or their salts, for example with sodium and / or aluminum salts of low-substituted half-esters of starch, in particular with sodium starch n-octenyl succinate of structural formula (I), in which R is the following Structure distinguished

and which z. B. is available under the trade name Amiogum ^® 23 from CERESTAR and with aluminum starch octenyl succinate, in particular with those available under the trade names Dry Flo ^® Elite LL and Dry Flo ^® PC from CERESTAR.

It is advantageous to choose the mean particle diameter of the modified polysaccharides used for combination with the polymer particles according to the invention to be less than 20 μm, particularly advantageously less than 15 μm.

The list of the modified polysaccharides mentioned, which can be combined with the polymer particles according to the invention, is of course not intended to be limiting. Modified polysaccharides, which are advantageous combination partners for the purposes of the present invention, are obtainable in numerous ways known per se, both chemical and physical. In principle, new ways of producing such polysaccharides are also conceivable. It is essential that the modified polysaccharides show amphiphilic properties and that they do not have a thickening effect.

It is advantageous in all of the aforementioned cases that the total concentration of all pigments is greater than 0.1% by weight, particularly advantageously between 0.1% by weight and 30% by weight. to choose based on the total weight of the preparations, the concentration of amphiphilic microfine polymer particles according to the invention - likewise based on the total weight of the preparations - in the sense of the present invention preferably from the range 0.1% by weight to 30% by weight, advantageously 0, 5% to 10% by weight is to be selected

The Pickering emulsions according to the invention can serve as the basis for cosmetic or dermatological formulations. These can be composed as usual and for example for the treatment and care of the skin, as a lip care product, as a demo product and as a make-up or make-up removal product in decorative cosmetics or as a light protection preparation For use, the cosmetic and dermatological preparations according to the invention are applied to the skin in a sufficient amount in the manner customary for cosmetics

Accordingly, cosmetic or topical dermatological compositions in the sense of the present invention, depending on their structure, can be used, for example, as skin protection cream, cleansing milk, sunscreen lotion, nutritional cream, day or night cream, etc. It is possible and advantageous, if appropriate, to use the compositions according to the invention as the basis for pharmaceutical formulations - to use gene

The cosmetic and dermatological preparations according to the invention can contain cosmetic auxiliaries, as are usually used in such preparations, for example preservatives, bactericides, perfumes, substances for preventing foaming, dyes, pigments which have a coloring effect, thickeners, softening, moisturizing and / or moisturizing substances, fats, oils, waxes or other usual components of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives

An astonishing property of the preparations according to the invention is that they are very good vehicles for cosmetic or dermatological active ingredients in the skin, advantageous active ingredients being antioxidants which can protect the skin against oxidative stress According to the invention, the preparations advantageously contain one or more antioxidants. All the antioxidants suitable or useful for cosmetic and / or dermatological applications can be used as cheap but nevertheless optional antioxidants. It is advantageous to use antioxidants as the only class of active ingredient, for example then , if a cosmetic or dermatological application is in the foreground, such as combating the oxidative stress on the skin. However, it is also advantageous to provide the stick preparations according to the invention with one or more antioxidants if the preparations are different To serve the purpose, for example as deodorants or sunscreens

The antioxidants are particularly advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L -Carnosine and its derivatives (eg Anseπn), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and its derivatives (eg dihydroliponic acid), aurothioglucose, Propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N, acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ, unoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thio dipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (eg buthiomn-sulfoxmsulfone, homocysteine sulfone sulfone, homocysteine sulfone sulfate, homocysteine sulfone sulfate, homocysteine sulfone sulfate, homocysteine sulfone sulfate, homocysteine sulfone sulfate, homocysteine sulfone sulfate, homocysteine sulfone sulfate, homocysteine sulfone sulfate, homocysteine sulfone sulfone, homocysteine sulfone sulfone, homocysteine sulfone sulfone, homocysteine sulfone sulfone, nta-, hexa-, heptathione-sulfoximine) in very low contractual doses (e.g. pmol to μmol / kg), furthermore (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferπn) α-hydroxy acids (e.g. Citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinone and ubiquinone and ubiquinone and ubiquinone their derivatives, vitamin C and derivatives (e.g. ascorbyl paimitat, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of the benzoic resin rutmate and their Derivatives, -Glycosylrutin, Ferulasaure Furfurylidenglucitol, Carnosin Butylhydroxytoluol, Butylhydroxyanisol, Nordihydroguajakh resin acid, Nordihydroguajaretsäure, trihydroxybutyrophenon, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (e.g. ZnO, ZnSO ₄ ), selenium and its derivatives (e.g. selenomethionine), stilbenes and their derivatives (e.g. stilbene oxide and trans-stilbene oxide) the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances.

The amount of the aforementioned antioxidants (one or more compounds) in the preparations according to the invention is preferably 0.001 to 30% by weight, particularly preferably 0.05-20% by weight, in particular 1-10% by weight, based on the total weight of the preparation.

If vitamin E and / or its derivatives represent the antioxidant (s), it is advantageous to choose their respective concentrations from the range of 0.001-10% by weight, based on the total weight of the formulation.

If vitamin A or vitamin A derivatives or carotenes or their derivatives represent the antioxidant or antioxidants, it is advantageous to use their respective concentrations in the range from 0.001-10% by weight, based on the total weight of the formulation, to choose.

According to the invention, the active ingredients (one or more compounds) can also be selected very advantageously from the group of lipophilic active ingredients, in particular from the following group:

Acetylsalicylic acid, atropine, azulene, hydrocortisone and its derivatives, for example hydrocortisone 17-valerate, vitamins, for example ascorbic acid and its derivatives, vitamins of the B and D series, very cheap the vitamin Bi, the vitamin Bι ₂ the vitamin D. _L but also bisabolol, unsaturated fatty acids, especially the essential fatty acids (often also called vitamin F), especially gamma-linolenic acid, oleic acid, eicosapentaenoic acid, docosahexaenoic acid and its derivatives, chloramphenicol, caffeine, prostaglandins, thymol, camphor, extracts or other products of vegetable and animal origin, for example evening primrose oil, borage oil or currant seed oil, fish oils, cod liver oil but also ceramides and ceramide-like compounds and so on. It is also advantageous to select the active substances from the group of refatting substances, for example purcellin oil, Eucerit and Neocerit.

The list of the active substances or combinations of active substances mentioned which can be used in the Pickering emulsions according to the invention is of course not intended to be limiting.

Cosmetic and dermatological preparations in the form of a sunscreen are also favorable. These preferably contain at least one UV-A filter substance and / or at least one UV-B filter substance and / or at least one further inorganic pigment from the group of the oxides of iron, zirconium, silicon, manganese, aluminum, cerium and mixtures thereof, and modifications where the oxides are the active agents.

However, it is also advantageous in the sense of the present inventions to create cosmetic and dermatological preparations whose main purpose is not protection against sunlight, but which nevertheless contain UV protection substances. For example, UV-A or UV-B filter substances are usually incorporated into day creams.

Preparations according to the invention can advantageously contain substances which absorb UV radiation in the UV-B range, the total amount of filter substances, for. B. 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 15 wt .-%, based on the total weight of the preparations to provide cosmetic preparations that the hair or the skin before protect the entire range of ultraviolet radiation.

If the emulsions according to the invention contain UV-B filter substances, they can be oil-soluble or water-soluble. Oil-soluble UV-B filters which are advantageous according to the invention are, for example:

, 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor; , 4-aminobenzoic acid, preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) amyl benzoate,

. Esters of cinnamic acid, preferably 4-methoxycinnamate (2-ethylhexyl) ester, 4-methoxycinnamate isopentyl ester, • esters of salicylic acid, preferably salicyl acid (2-ethylhexyl) ester, salicyl acid (4-isopropylbenzyl) ester, salicyl ester,

. Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone,

. Esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid (2-ethylhexyl) ester,

, Tπazindenπvate symmetrically or asymmetrically substituted with respect to the C ₃ axis of the basic tnazine body, preferably 4,4 ', 4 "- (1, 3,5-trιazιn-2,4,6-tπyltπιmιno) - tπs-benzoic acid trιs (2-ethylhexyl ester ) (symmetrical) and 2,4-Bιs - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-tπazιn, 2,4 -Bιs - {[4- (3-sulfonato) -2-hydroxy-propyioxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-trιazιn

Sodium salt, 2,4-bιs - {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6-

(4-methoxyphenyl) -1,3,5-trιazιn, 2,4-Bιs - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6-

[4- (2-methoxyethyl-carboxyl) phenylamine] -1, 3,5-tπazιn, 2,4-Bιs - {[4- (3- (2-propyloxy) -

2-hydroxy-propyloxy) -2-hydroxy] phenyl} -6- [4- (2-ethyl-carboxyl) phenylamine] -1, 3,5-tnazine, 2,4-bιs - {[4- ( 2-ethyl-hexyloxy) -2-hydroxy] phenyl} -6- (1-methyl-pyrrol-2-yl) -1, 3,5-tπazm, 2,4-Bιs - {[4-trιs (tπmethyisιloxy -sιlylpropyloxy) -2-hydroxy] -phenyl} -6- (4-methoxy-phenyl) -1, 3,5-tπazιn, 2,4-Bιs - {[4- (2 "-methylpropenyloxy) -2-hydroxy ] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-tπazιn, 2,4-Bιs - {[4- (1 ', 1', 1 ', 3', 5 ', 5', 5'-heptamethylsιloxy-2-methyl-propyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-trιazιn (asymmetrical),

. Benzotπazoldeπvate, preferably 2,2'-methylene-bιs- (6- (2H-benzotπazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyl) phenol)

. as well as UV filters bound to polymers

Advantageous water-soluble UV-B filter substances are, for example

, Salts of 2-phenylbenzιmιdazol-5-sulfonic acid, such as its sodium, potassium or Tπ-ethanolammonium salt, and the sulfonic acid itself, , Sulfonic acid derivatives of 3-benzylidene camphor, such as 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene methyl) sulfonic acid and their salts.

The list of the UV-B filters mentioned, which can be used in the Pickering emulsions according to the invention, is of course not intended to be limiting.

It can also be advantageous to use UV-A filters in Pickering emulsions according to the invention which have hitherto usually been contained in cosmetic preparations. These substances are preferably derivatives of dibenzoyl methane, in particular 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione and 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione.

Other advantageous UV-A filter substances are phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid:

and their salts, especially the corresponding sodium, potassium or triethanolammonium salts, especially the phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt :

as well as the 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene and its salts (especially the corresponding 10-sulfato compounds, especially the corresponding sodium, potassium or triethanolammonium salt), the is also referred to as benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) and is characterized by the following structure:

Advantageous UV filter substances are also so-called broadband filters, i.e. Filter substances that absorb both UV-A and UV-B radiation.

An example of a broadband filter which can be used advantageously is ethylhexyl-2-cyano-3,3-diphenyl acrylate (octocrylene), which is available from BASF under the name Uvinul ^® N 539 and is characterized by the following structure:

Preparations which contain UV-A filters or so-called broadband filters are also the subject of the invention. The quantities used for the UV-B combination can be used.

Preparations according to the invention can also advantageously be used as the basis for cosmetic deodorants or antiperspirants, so that in a particular embodiment the present invention relates to Pickering emulsions as the basis for cosmetic deodorants.

Cosmetic deodorants are used to eliminate body odor that arises when the fresh, odorless sweat is decomposed by microorganisms. The usual cosmetic deodorants are based on different active principles. In so-called antiperspirants, astringents - primarily aluminum salts such as aluminum hydroxychloride (aluminum chlorohydrate) - can reduce the formation of sweat.

The use of antimicrobial substances in cosmetic deodorants can reduce the bacterial flora on the skin. Ideally, only the odor-causing microorganisms should be effectively reduced. The sweat flow itself is not affected by this, in the ideal case only the microbial decomposition of the sweat is temporarily stopped.

The combination of astringents with antimicrobial substances in one and the same composition is also common.

All active ingredients for deodorants or antiperspirants can be used advantageously, for example odor maskers such as the common perfume components, odor absorbers, for example the layered silicates described in patent application DE-P 40 09 347, of which in particular montmorillonite, kaolinite, llite, beidellite, nontronite, saponite , Hectorite, bentonite, smectite, furthermore, for example, zinc salts of ricinoleic acid. Germ-inhibiting agents are also suitable for being incorporated into the W / O emulsion sticks according to the invention. Advantageous substances are, for example, 2,4,4'-trichloro-2'-hydroxydiphenyl ether (irgasane), 1,6-di- (4-chlorophenylbiganido) hexane (chlorhexidine), 3,4,4'-trichlorocarbanilide, quaternary ammonium compounds, clove oil, mint oil, thyme oil, triethyl citrate, farnesol (3,7,11-trimethyl-2,6, 10-dodecatrien-1-ol) and those described in patent publications DE-37 40 186, DE-39 38 140, DE-42 04 321, DE-42 29 707, DE-43 09 372, DE-44 11 664, DE-195 41 967, DE-195 43 695, DE-195 43 696, DE-195 47 160, DE- 196 02 108, DE-196 02 110, DE-196 02 111, DE-196 31 003, DE-196 31 004 and DE-196 34 019 and the patents DE-42 29 737, DE-42 37 081, DE- 43 24 219, DE-44 29 467, DE-44 23 410 and DE-195 16 705 described active ingredients or combinations of active ingredients. Sodium hydrogen carbonate can also be used advantageously. The list of the active substances or combinations of active substances mentioned which can be used in the Pickering emulsions according to the invention is of course not intended to be limiting.

The cosmetic deodorants according to the invention can be in the form of water-containing cosmetic preparations which can be applied from normal containers.

The amount of the antiperspirant active ingredients or deodorants (one or more compounds) in the preparations is preferably 0.01 to 30% by weight, particularly preferably 0.1-20% by weight, in particular 1-10% by weight, based on the total weight of the preparation.

The pens according to the invention are also excellent vehicles for dermatological active ingredients. They are particularly suitable as carriers for substances active against acne. Acne is a skin disease with various forms and causes, characterized by non-inflammatory and inflammatory nodules, starting from blocked hair follicles (comedones), which can lead to pustules, abscesses and scars. The most common is acne vulgaris, which mainly occurs during puberty. Causal conditions for acne vulgaris are cornification and constipation of the hair follicle mouth, the production of taig depending on the blood level of the male sex hormones and the production of free fatty acids and tissue-damaging enzymes by bacteria {Propionibacterium acnes).

It is therefore advantageous to add substances which are active against acne to the preparations according to the invention and are active, for example, against Propionibacterium acnes (for example those described in DE-OS 42 29 707, DE-OS 43 05 069, DE-OS 43 07 976, DE- OS 43 37 711, DE-OS 43 29 379), but also other substances active against acne, for example all-trans-retinoic acid, 13-cis-retinoic acid and related substances) or anti-inflammatory agents, for example batyl alcohol (α-octa- decylglyceryl ether), selachyl alcohol (α-9-octadecenylglyceryl ether), chimyl alcohol (α-hexadecylglyceryl ether) and / or bisabolol as well as antibiotics and / or keratolytics. Keratolytics are substances that soften horny skin (such as warts, corns, calluses and the like) so that they can be removed more easily, so that they fall off or dissolve.

All common acne-active substances can be used to advantage, especially benzoyl peroxide, bituminosulfonates (ammonium, sodium and calcium salts of shale oil sulfonic acids), salicylic acid (2-hydroxybenzoic acid), miconazole (1- [2- (2,4- Dichlorobenzyloxy) -2- (2,4-dichlorophenyl) ethyl] imidazole) and derivatives, adapalene (6- [3- (1-adamantyl) -4-methoxyphenyl] -2-naphthoic acid), azelaic acid (nonandioic acid) , Mesulfen (2,7-dimethylthianthrene, C ₁ Hι ₂ S ₂ ) and aluminum oxide, zinc oxide and / or finely divided sulfur.

The amount of the anti-acne agent (one or more compounds) in the preparations is preferably 0.01 to 30% by weight, particularly preferably 0.1-20% by weight, in particular 1-10% by weight, based on the total weight of the preparation.

The following examples are intended to illustrate the present invention without restricting it. The numerical values in the examples mean percentages by weight, based on the total weight of the respective preparations.

Examples:

Claims

claims

1. Cosmetic or dermatological preparations which are finely dispersed systems of the oil-in-water or water-in-oil type, comprising 1. an oil phase,

2. a water phase,

3. at least one type of microfine polymer particles, which

(a) are present in the preparation in the form of solids and which

4. at most 0.5% by weight of one or more emulsifiers.

2. Preparations according to claim 1, characterized in that they are emulsifier-free.

3. Preparations according to one of the preceding claims, characterized in that further cosmetic or pharmaceutical auxiliaries, additives and / or active ingredients are included.

4. Preparations according to one of the preceding claims, characterized in that the content of one or more microfine polymer particles is between 0.1 wt .-% and 30 wt .-%, based on the total weight of the preparations.

5. Preparations according to one of the preceding claims, characterized in that the average particle diameter of the microfine polymer particles used is less than 00 microns, particularly advantageously less than 50 microns.

6. Preparations according to one of the preceding claims, characterized in that, in addition to microfine polymeφarticles, further amphiphilic pigments are contained, in particular boron nitride and / or modified polysaccharides and / or micronized, inorganic pigments which are selected from the group of amphiphilic metal oxides, in particular from the Group titanium dioxide, zinc oxide, Iron oxides or mixed iron oxides, silicon dioxide or silicates, where these pigments can be present either individually or in a mixture.

7. Preparations according to one of the preceding claims, containing one or more additives or active ingredients selected from the group of antioxidants and / or UV protection agents.

8. Preparations according to one of the preceding claims, containing one or more additives or active substances selected from the group of astringents and / or antimicrobial substances and / or substances active against acne.