DE19939849A1 - Emulsifier-free, finely dispersed water-in-oil systems - Google Patents

Abstract

Cosmetic or dermatological preparations representing finely dispersed water-in-oil-type systems, containing 1. an oil phase, 2. an aqueous phase, 3. at least one modified sheet silicate exhibiting hydrophilic and lipophilic properties, possessing an amphiphilic character and arranged on the oil/water interface and 4. no more than 0.5 wt. % of one or several emulsifiers, in addition to optionally containing other cosmetic or pharmaceutical adjuvants, additives and/or active substances.

Description

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

Emulsions are generally understood to be heterogeneous systems that do not consist of two or only exist to a limited extent with miscible liquids, which are usually used as Phases. One of the two liquids is in shape in an emulsion finest droplets dispersed in the other liquid.

Are the two liquids water and oil and oil droplets are finely distributed in water before, it is an oil-in-water emulsion (O / W emulsion, e.g. milk). The The basic character of an O / W emulsion is characterized by the water. With a water-in-oil Emulsion (W / O emulsion, e.g. butter) is the opposite principle, whereby the basic character here is determined by the oil.

In order to achieve the permanent dispersion of one liquid in another, at Emulsions in the conventional sense the addition of a surfactant (Emul gator) necessary. Emulsifiers have an amphiphilic molecular structure from a polar (hydrophilic) and a non-polar (lipophilic) part of the molecule, which spatially are separated from each other. In simple emulsions there are finely dispersed droplets of the second phase enclosed by an emulsifier shell (water droplets in W / O or lipid vesicles in O / W emulsions). Emulsifiers set the interfaces voltage between the phases decreases by being at the interface between the two Liquids are arranged. They form oil / water interfaces at the phase boundary  films, which counteracts the irreversible confluence of the droplets becomes. 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 the soap, as the one usually the water-soluble sodium or potassium salts of the saturated and unsaturated termed higher fatty acids.
• - The quaternary ammonium compounds are important representatives of the cationic emulsifiers fertilize.
• - The hydrophilic part of the molecule of nonionic emulsifiers often consists of glycerin, poly glycerin, sorbitans, carbohydrates or polyoxyethylene glycols and is mostly over Ester and ether linkages linked to the lipophilic part of the molecule. This is normal usually from fatty alcohols, fatty acids or isofatty acids.

Read by varying the structure and size of the polar and non-polar part of the molecule lipophilicity and hydrophilicity of emulsifiers change within wide limits.

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

Emulsions represent an important type of product in the field of cosmetic and / or derma tological preparations.

Cosmetic preparations are mainly used for skin care. Skin care in The cosmetic sense is primarily that the natural function of the skin acts as a barrier against environmental influences (e.g. dirt, chemicals, microorganisms) and against the Loss of the body's own substances (e.g. water, natural fats, electrolytes) strengthened or is restored. If this function is disturbed, increased absorption can occur toxic or allergenic substances or to infest microorganisms and as a result toxic or allergic skin reactions.  

The aim of skin care is also to reduce the fat and what caused by daily washing Compensate for skin loss. This is especially important when the natural rain generation capacity is not sufficient. In addition, skin care products are designed to protect the environment Protect rivers, especially from the sun and wind, and delay skin aging.

Cosmetic preparations are also used as deodorants. Such form stanchions serve to eliminate body odor, which arises when the smell itself loose fresh sweat is decomposed by microorganisms.

Medical topical compositions usually contain one or more medi came in effective concentration. For the sake of simplicity, it becomes a clear sub distinction between cosmetic and medical application and corresponding pro products referred to the legal provisions of the Federal Republic of Germany (e.g. cosmetics regulation, food and drug law).

The use of the usual emulsifiers in cosmetics or dermatology is in itself harmless preparations. Nevertheless, emulsifiers, like ultimately every other chemical substance, in individual cases allergic or hypersensitive to the cause wenders based reactions.

For example, it is known that certain light dermatoses are caused by certain emulsions gates, but also due to various fats and simultaneous exposure to sunlight to be triggered. Such light dermatoses are also called "Mallorca acne". It has therefore there is no lack of attempts to minimize the amount of conventional emulsifiers Ideally, to reduce it completely.

A reduction in the amount of emulsifier required can, for. B. can be achieved when out is used that finely divided solid particles ha an additional stabilizing effect ben. The solid substance accumulates at the phase boundary Oil / water in the form of a layer, which prevents the disperse phases from flowing together is changed. It is not the chemical ones that are essential, but the superiors surface properties of the solid particles.

A relatively new technical development is cosmetic or dermatological Preparations can only be stabilized by finely divided solid particles. Such "emulga  gate-free "emulsions are, according to their inventor, also known as Pickering emulsions draws.

Basic investigations have shown that a characteristic for a pic kering emulsion is that the solid particles flow at the interface between the two phases are arranged and there, so to speak, a mechanical barrier against the Form union of liquid droplets.

One way to stabilize solids in a cosmetic or dermatological According to May-Alert (Pharmacy in our time, 15th year 1986, No. 1, 1-7) for example, to use emulsifier mixtures which are both anionic and also contain cationic surfactants. Because when combining anion and cation tensi The always insoluble, electroneutral connections fail, can be done by targeted Failures of these neutral surfactants in the oil / water interface provide an additional solid achieve substance stabilization in the sense of a Pickering emulsion.

The European patent application 0 686 391 also describes "emulsions" of the water-in-oil type, which are free of surface-active substances and only through Solids are stabilized. Spherical polyalkylsilses are used for stabilization quioxane particles are used which have a diameter of 100 nm up to 20 µm, which are added to the oil phase and thicken it. That kind of preparations can therefore be called oil gels (also: oleogels) in which water is stable can be dispersed.

Furthermore, WO-publication WO-98/42301 describes emulsifier-free finely dispersed systems from Type water-in-oil, which is caused by the addition of micronized, inorganic pigments are stabilized, selected from the group of metal oxides, in particular titanium dioxide become.

However, the prior art could not point the way to the present invention.

In addition to the systems described, the prior art knows other emulsifier-free, Finely dispersed cosmetic or dermatological preparations, which are generally called Hydrodispersions are called. Hydrodispersions are one dispersions  liquid, semi-solid or solid inner (discontinuous) lipid phase in an outer aqueous (continuous) phase.

With hydrodispersions of a liquid lipid phase in an outer aqueous phase the stability can be ensured, for example, that in the aqueous phase Gel structure is built up, in which the lipid droplets are stably suspended. The 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 a Oil and a water phase one or more thickeners from the group of acrylic acid contain polymers, polysaccharides and their alkyl ethers, with a thickener for these The reduction in interfacial savings must not be measurable.

Based on similar hydrodispersions, the German Offenlegungsschrift 43 03 983 cosmetic or dermatological light protection formulations disclosed in are essentially free of emulsifiers, anor in the lipid phase of the hydrodispersion ganic micropigments are incorporated, which serve as UV filter substances.

Pickering emulsions are made according to the above through the use of suitable ones Solids or pigments stabilized. However, solids can be applied appropriate preparations on the skin a dry and partly blunt Leave an impression. Preparations with a pigment content of 1% by weight produce a dull feeling on the skin after use, that with higher Pigment concentrations are still increasing. In individual cases can therefore contain pigment Preparations may not even be marketable since they are not available from the consumer accepted or judged negatively.

The task was therefore to remedy the disadvantages of the prior art. Ins Special preparations should be made available which are on the skin do not leave a dry or dull impression.

Furthermore, it was an object of the invention, cosmetic and dermatological reason were able to develop cosmetic and dermatological preparations that stand out good skin tolerance.  

It was also an object of the present invention to provide products with the widest possible range To provide a variety of applications. For example, basic days for accessories forms of cleaning such as cleaning emulsions, face and body care preparations or Deodorants, but also very medicinal-pharmaceutical dosage forms are created, for example preparations against acne and others Skin symptoms.

Another object of the present invention was to improve the prior art to enrich metallic or dermatological preparations, in which on any Use of conventional emulsifiers can be dispensed with.

Surprisingly, all of this problem is solved by cosmetic or dermatological preparations, which are finely dispersed systems of the water-in-oil type, containing

• 1. an oil phase,
• 2. a water phase,
• 3. at least one modified layered silicate, which is both hydrophilic and shows lipophilic properties, which is amphiphilic in character arranges at the water / oil interface and
• 4. at most 0.5% by weight of one or more emulsifiers

such as
optionally containing further cosmetic or pharmaceutical auxiliaries, additives and / or active substances.

It is particularly advantageous according to the invention if the preparations are significantly less than Contain 0.5 wt .-% of one or more emulsifiers. Are very particularly preferred Preparations according to the invention which are completely free of emulsifiers in the conventional Are meaningful.

The preparations according to the invention are mixtures of oils or oil-soluble ones Substances and water or water-soluble components, which are caused by the addition of modified layered silicate particles are stabilized and no emulsifier in conventional must contain meaning.  

The preparations according to the invention are extremely satisfactory in every respect Preparations that surprisingly show excellent cosmetic properties the skin does not leave a dry or dull impression and is distinguish excellent skin tolerance.

Modified layered silicates

Silicates are salts and esters (silicic acid esters) of orthosilicic acid [Si (OH) ₄ ] and their condensation products. The silicates are not only the most species-rich class of minerals, but also extremely important geologically and technically. Over 80% of the earth's crust consists of silicates. Layered silicates (phyllosilicates, leaf silicates) are (ideally) silicate structures with two-dimensionally infinite layers of [SiO ₄ ] ⁴ tetrahedra, each tetrahedron being connected to neighboring tetrahedra via 3 bridging oxygen.

Chemical formulas can only be approximated for layered silicates because they have a large ion exchange capacity and silicon can be exchanged for aluminum and this in turn for magnesium, Fe ²⁺ , Fe ³⁺ , Zn and the like. The resulting negative charge on the layers is generally compensated for by cations, in particular by Na ⁺ and Ca ²⁺ in interlayer positions.

Layered silicates can be made by reversible storage of water (in the 2- to 7-fold Amount) and other substances such. B. alcohols, glycols and the like swell. Their use as a thickener in cosmetic products is demented speaking known per se. However, the state of the art could not pave the way to present invention.

Advantageous sheet silicates for the purposes of the present invention are, for example, the greatest direction of expansion in the unmodified and unswollen state in Has an average length of less than 10 microns. For example, the middle ones Expansions of the modified layered silicate particles used at 1000 nm × 100 nm × 1 nm and below. The effective size of the modified layered silicate particles in A cosmetic or dermatological formulation naturally depends on the Amount of stored substances.  

Advantageously modified layered silicates in the sense of the present invention are, for example, modified smectites (smectites). Smectites are always very fine-grained (mostly <2 mm), predominantly lamellar, moss-like or spherical aggregates three-layer clay minerals (2: 1 layer silicates), in which a central layer of octahedrally coordinated cations sandwiched by 2 layers of [(Si, Al) O ₄ ] tetrahedra is surrounded. Smectites are idealized by the following structural formula, in which white circles filled with silicon and / or aluminum atoms, light gray circles filled with oxygen atoms, dark gray circles filled with hydrogen atoms and black circles filled with aluminum, magnesium, iron atoms and / or other exchange cations:

Advantageous modified smectites are e.g. B. modified Montmorillonite. Montmorillonites are described by the approximate chemical formula Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] .n H ₂ O or Al ₂ O ₃ .4 SiO ₂ .H ₂ On H ₂ O and represent dioctahedral smectites Clay minerals.

Modified hectorites, for example, are also particularly advantageous for the purposes of the present invention. Hectorites are smectites and have the approximate chemical formula M ⁺ _0.3 (Mg _2.7 Li _0.3 ) [Si ₄ O ₁₀ (OH) ₂ ], in which M ⁺ mostly represents Na ⁺ .

Modified bentonites are also advantageous for the purposes of the present invention. Ben tonites are clays and rocks, the smectites, especially montmorillonite, as the main minerals contain. The "raw" bentonites are either calcium bentonites (in the UK as Fuller earths) or sodium bentonite (also: Wyoming bentonite).

Modified layered silicates in the sense of the present invention are layered silicates, especially the sheet silicate types already mentioned, their organophilicity (also: Li pophilie) - for example by reaction with quaternary ammonium compounds - was increased. Layered silicates of this type are also known as organophilic layered silicates draws.  

So-called bentones, ie. H. organic derivatives of montmorillonites (or bentonites) and / or hectorites, which by Ion exchange reactions with alkylammonium bases are prepared.

Advantageously modified layered silicates in the sense of the present invention can be obtained, for example, by reacting layered silicates with quaternium-18. Qua temium-18 is a mixture of quaternary ammonium chloride salts, which are described by the following structural formula:

wherein
the radicals R ¹ are selected independently of one another from the group methyl and hydrogenated valley residues with a chain length of 12 to 20 carbon atoms.

According to the invention, stearalkonium hectorite, a reaction product, is particularly preferred from hectorite and stearalkonium chloride (benzyldimethylstearylammonium chloride), and Quaternium-18 hectorite, a reaction product of hectorite and quaternium-18, which e.g. B. under the trade names Bentone 27 and Bentone 38 from Nordmann & Rassmann are available.

The total amount of one or more modified layered silicates in the finished Cosmetic or dermatological preparations are advantageous from the range of 0.05 to 20.0 wt .-%, preferably 0.1 to 5.0 wt .-% selected, based on the total Ge importance of the preparations.

Although it is particularly preferred to use the preparations according to the invention only by The addition of one or more modified layered silicates can stabilize it be furthermore advantageous, the modified layered silicate particles with other amphiphiles To combine pigments, which may also be used to stabilize the Pickering Emulsions can contribute.  

Examples of such pigments are micronized, inorganic pigments are from the group of amphiphilic metal oxides, in particular from the group titanium di oxide, zinc oxide, silicon dioxide or silicates (e.g. talcum), the metal oxides being both a individual as well as in a mixture. It is essentially irrelevant in which of the naturally occurring modifications the used on phiphile metal oxides are present.

It is advantageous to determine the average particle diameter for combination with modified Layered silicates used pigments between 1 nm and 200 nm, particularly advantageous choose between 5 nm and 100 nm.

For the purposes of the present invention, it is advantageous to use the modified inventive To combine layered silicates with untreated, almost pure pigment particles, ins especially with those that are also used as colorants in the food industry and / or Absorbers of UV radiation can be used in sunscreens. Advantageous Examples include the zinc oxide pigments available from Merck and those those under the trade names zinc oxide neutral from Haarmann & Reimer or NanoX are available from the Harcros Chemical Group.

The combination of modified phyllosilicates is also advantageous according to the invention with inorganic pigments that have a water-repellent finish ("coated") are, at the same time an amphiphilic character of these pigments is formed or should be preserved. This surface treatment can consist in that the Pigments according to known methods with a thin hydrophobic layer be provided.

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

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

is produced. 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 dimethyl poly siloxane (also: Dimethicone), a mixture of fully methylated, linear siloxane polymers, the are terminally blocked with trimethylsiloxy units. Particularly advantageous in the sense of The present invention is the combination of modified layered silicates with zinc oxide Pigments coated in this way.

It is also advantageous if the anor used in addition to modified layered silicates ganic pigments with a mixture of dimethylpolysiloxane, especially dimethyl polysiloxane with an average chain length of 200 to 350 dimethylsiloxane Units, and silica gel are coated, which is also called Simethicone. It is particularly advantageous if the inorganic pigments are also included Aluminum hydroxide or aluminum oxide hydrate (also: alumina, CAS no .: 1333-84-2) are coated. Particularly advantageous combination partners are titanium dioxide, which with Si methicone and alumina are coated, the coating also containing water can. An example of this is that under the trade name Eusolex T2000 at the company Titanium dioxide available from Merck.

The combination of modified is also advantageous in the sense of the present invention Layered silicates with a mixture of various inorganic, amphiphilic Pigment types both within a crystal, for example as iron mixed oxide or Talc (magnesium silicate), as well as by mixing several types of metal oxides within a preparation. Particularly advantageous combination partners are magnesium silicates for example the one under the trade name Talkum Micron from the company Grolmann er available.

The modified layered silicates according to the invention can also advantageously be used with other Pigments are combined, for example with titanium dioxide pigments, with octylsilanol are coated, and / or with silicon dioxide particles that are water-repellent on the surface are treated. Silicon dioxide particles suitable for combination are, for example, spherical nical polyalkylsilsesquioxane particles as described in the European patent application 0 686 391 may be mentioned. Such polyalkylsilsesquioxane particles are, for example, under  receives the trade names Aerosil R972 and Aerosil 200 V from Degussa Lich.

The modified layered silicates with microfine polymer particles are further advantageous combined, which are present in the preparation in the form of solids. Cheap Combination partners in the sense of the present invention are, for example, polycarbo nate, polyether, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamides, Polyacrylates and the like.

Combination partners suitable according to the invention are, for example, microfine polyamide Particles, especially those under the trade name SP-500 from TORAY available. Polyamide 6 (also: nylon 6) or polyamide 12- (also: Nylon 12) particles. Polyamide 6 is made of ε-aminocaproic acid (6-aminohexanoic acid) or ε-caprolactam built polyamide [poly (ε-caprolactam)], and polyamide 12 is a poly (ε- laurin lactam) from ε-laurolactam. Are advantageous in the sense of the present invention for example Orgasol® 1002 (polyamide 6) and Orgasol® 2002 (polyamide 12) from the company ELF ATOCHEM.

Further advantageous microfine polymer particles, which can be combined with the he modified layered silicates according to the invention are microfine polymethacrylates. Such particles are for example under the trade name POLYTRAP® DOW CHEMICAL available.

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

The average particle diameter of the microfine used as a combination partner Polymer particles are preferably smaller than 100 μm, particularly advantageously smaller than  50 µm selected. It is essentially irrelevant in what form (platelets, Rods, beads, etc.) the polymer particles used are present.

The modified layered silicates according to the invention are also preferably am combined phiphile modified polysaccharides, which have no thickening properties show.

Such amphiphilic polysaccharides are, for example, by reacting starch with monofunctional, bifunctional or polyfunctional reagents or oxidizing agents in largely poly reactions similar to that available.

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

where R is, for example, a hydrogen and / or an alkyl and / or aralkyl radical (in the case the starch ether) or a hydrogen and / or an organic and / or inorganic Acid residue (in the case of starch esters). Starch ether and starch ester are in front partial combination partner in the sense of the present invention.

It is particularly advantageous to also use the modified layered silicates according to the invention Combine starch ethers, e.g. B. with those by etherification of starch with tetra methylolacetylene diurea are available and which as Amylum non mucilaginosum (non-swelling starch).

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

and which z. B. under the trade name Amiogum® 23 from CERESTAR is available as well as with aluminum starch octenyl succinate, especially with the under the Trade names Dry Flo® Elite LL and Dry Flo® PC obtained from CERESTAR lichen.

It is advantageous to determine the average particle diameter for combination with the inventions modified polysaccharides used in accordance with the invention to be smaller than 20 µm, particularly advantageously to be smaller than 15 µm.

The list of the modified polysaccharides mentioned with the modified layer silicates can be combined should of course not be limiting. Modes fected polysaccharides, the advantageous combination in the sense of the present invention partner, are in numerous, known ways, both chemical and also available in physical form. There are also new ones for the production of such polysaccharides In principle, possible paths. It is essential that the modified polysaccharides amphi show phile properties and that they do not have a thickening effect.

In all of the above cases it is advantageous to increase the total concentration of all pigments ßer than 0.05 wt .-%, particularly advantageously between 0.05 wt .-% and 30 wt .-% based to choose the total weight of the preparations, the concentration of modified layered silicates - also based on the total weight of the accessories riding - in the sense of the present invention preferably from the field 0.05% by weight to 30% by weight, advantageously 0.1% by weight to 10% by weight is to be selected.

The Pickering emulsions according to the invention can be used as the basis for cosmetic or serve 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 Deoproduct and as a make-up or make-up removal product in decorative cosmetics or as  Serve sunscreen. The cosmetic according to the invention are used and dermatological preparations in the manner customary for cosmetics in the skin sufficient amount applied.

Accordingly, cosmetic or topical dermatological compositions in the For the purposes of the present invention, depending on its structure, for example as skin protection cream, cleansing milk, sun protection lotion, nutrient cream, daily or Night cream, etc. It may be possible and advantageous to add the inventive to use compositions as the basis for pharmaceutical formulations.

The cosmetic and dermatological preparations according to the invention can be kos contain metallic auxiliaries, as they are usually used in such preparations be, e.g. B. preservatives, bactericides, perfumes, substances to prevent the Foaming, dyes, pigments that 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 amazing property of the preparations according to the invention is that they are very are good vehicles for cosmetic or dermatological agents in the skin, being before Partial active ingredients are antioxidants that protect the skin from oxidative stress can protect.

According to the invention, the preparations advantageously contain one or more antioxidants tien. As cheap, yet optional antioxidants all can be used for cosmetic and / or dermatological applications suitable or customary Antioxidants are used. It is beneficial to have antioxidants as the only ones Active ingredient class to be used, for example, if a cosmetic or dermatological Application is in the foreground, such as. B. combating oxidative stress of the skin. However, it is also favorable to use the stick preparations according to the invention with a Provide content of one or more antioxidants when the preparations serve another purpose, e.g. B. as deodorants or sunscreens.  

The antioxidants are particularly advantageously selected from the group consisting of amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D. -Carnosine, L-carosene and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives ( e.g. 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-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (e.g. Buthioninsulfoximine, Homocy stone sulfoximine, B uthioninsulfones, penta-, hexa-, heptathioninsulfoximine) in very low tolerable doses (e.g. B. pmol to µmol / kg), also (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, Bile acid, bile extracts, bilirubin, bili verdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and their derivatives, ubiquinone and ubiquinol and their derivatives, vitamins C and Derivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin, ferulic acid, furfurylidene glucitol , Carnosine, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (e.g. ZnO, ZnSO ₄ ), selenium and its derivatives (e.g. selenium methion n), stilbene and their derivatives (e.g. B. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, zuc ker, nucleotides, nucleosides, peptides and lipids) of these active ingredients.

The amount of the aforementioned antioxidants (one or more compounds) in the inventions Preparations according to the invention are preferably 0.001 to 30% by weight, particularly be preferably 0.05 to 20 wt .-%, in particular 0.1 to 10 wt .-%, based on the Ge total weight of the preparation.

If vitamin E and / or its derivatives represent the antioxidant (s), there is some, whose respective concentrations from the range of 0.001 to 10 wt .-%, be drew on the total weight of the formulation to choose.  

If vitamin A, or vitamin A derivatives, or carotenes or their derivatives, the or the Antioxidants are beneficial, their respective concentrations out of the range from 0.001 to 10% by weight, based on the total weight of the formulation.

According to the invention, the active compounds (one or more compounds) can also be selected very advantageously from the group of lipophilic active compounds, in particular from the following group:
Acetylsalicylic acid, atropine, azulene, hydrocortisone and its derivatives, e.g. B. Hydrocor tison-17-valerate, vitamins, e.g. B. ascorbic acid and its derivatives, vitamins of the B and D series, very cheap vitamin B ₁ , vitamin B _12, vitamin D ₁ , but also bisabolol, unsaturated fatty acids, especially the essential fatty acids (often called vitamin F) , in particular gamma-linolenic acid, oleic acid, eicosapentaenoic acid, docosa hexaenoic acid and its derivatives, chloramphenicol, caffeine, prostaglandins, thymol, camphor, extracts or other products of plant and animal origin, e.g. B. Nachtker zenöl, 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 add the active ingredients from the group of refatting substances choose, for example Purcellinöl, Eucerit® and Neocerit®.

The list of active substances or combinations of active substances mentioned in the Invention Pickering emulsions can of course not be used be acting.

Those cosmetic and dermatological preparations which are in the Form of a sunscreen. In addition to the inventions, these preferably contain active ingredient combinations according to the invention additionally at least one UV-A filter substance and / or at least one UV-B filter substance. Such formulations, though not necessary, if necessary also one or more inorganic pigments as UV Filter substances included.

Inorganic pigments based on metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water are preferred, in particular the oxides of titanium (TiO ₂ ), zinc (ZnO), iron (e.g. Fe ₂ Q ₃ ), zirconium (ZrO ₂ ), silicon (SiO ₂ ), manganese (e.g. MnO), aluminum (Al ₂ O ₃ ), cerium (e.g. Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures of such oxides.

Also an additional content of stabilizing titanium dioxide and / or zinc oxide Particles can of course be advantageous, but is in the sense of the present Er not necessary.

It is also advantageous in the sense of the present invention, such cosmetic and to create dermatological preparations, the main purpose of which is not the Protection against sunlight is, but which nevertheless contains UV protection substances hold. So z. B. in day creams usually UV-A or UV-B filter substances incorporated.

UV protection substances, as well as antioxidants and, if desired, con preservatives, an effective protection of the preparations themselves against spoilage.

Preparations according to the invention advantageously contain substances which emit UV radiation Absorb UV-A and / or UV-B range, the total amount of filter substances e.g. B. 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 20 wt .-%, in particular 1.0 to 15.0% by weight, based on the total weight of the preparations, is cosmetic To provide preparations that cover the hair or skin before the whole Protect the area of ultraviolet radiation. You can also use it as a sunscreen Serving hair or skin.

Advantageous UV-A filter substances in the sense of the present invention are dibenzoyl methane derivatives, especially the 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS no. 70356-09-1), which is sold by Givaudan under the Parsol® 1789 brand and by Merck under the Trade name Eusolex® 9020 is sold.

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 triethanolamium salts, in particular the phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid-bis-sodium salt :

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

Advantageous UV filter substances in the sense of the present invention are also so-called called broadband filters, d. H. Filter substances that contain both UV-A and UV-B radiation absorb.

Advantageous broadband filters or UV-B filter substances are, for example, bis-resorcinyl triazine derivatives with the following structure:

where R ¹ , R ² and R ^{3 are} independently selected from the group of ver branched and unbranched alkyl groups having 1 to 10 carbon atoms or a single hydrogen atom. Particularly preferred are the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (INCI: Aniso triazine) , which is available under the trade name Tinosorb® S from CIBA-Chemicals GmbH, and the 4,4 ', 4 "- (1,3,5-trin-2,4,6-triyltriimino) -tris-benzoic acid tris (2-ethyl hexyl ester), synonym: 2,4,6-tris [anilino- (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine (INCI: octyl triazone) , which is sold by BASF Aktiengesellschaft under the trade name UVINUL® T 150.

Other UV filter substances which describe the structural motif are also described

are advantageous UV filter substances for the purposes of the present invention, for example the s-triazine derivatives described in European patent application EP 570 838 A1, the chemical structure of which is given by the generic formula

is reproduced, whereby
R represents a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ alkyl groups,
X represents an oxygen atom or an NH group,
R _{1 is} a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted with one or more C ₁ -C ₄ alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of formula

means in which
A represents a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl or aryl radical, optionally substituted by one or more C ₁ -C ₄ alkyl groups,
R _{3 represents} a hydrogen atom or a methyl group,
n represents a number from 1 to 10,
R _{2 represents} a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted with one or more C ₁ -C ₄ alkyl groups, when X represents the NH group, and
a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted with one or more C ₁ -C ₄ alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula

means in which
A represents a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl or aryl radical, optionally substituted by one or more C ₁ -C ₄ alkyl groups,
R _{3 represents} a hydrogen atom or a methyl group,
n represents a number from 1 to 10,
when X represents an oxygen atom.

A particularly preferred UV filter substance in the sense of the present invention is also an asymmetrically substituted s-triazine, the chemical structure of which is represented by the formula

is reproduced, which is also called dioctylbutylamidotriazon (INCI: Dioctylbutamidotriazone) is called and under the trade name UVASORB HEB is available from Sigma 3 V.

European laid-open specification 775 698 also describes bis-resorcinyltriazine derivatives which are preferably to be used and whose chemical structure is represented by the generic formula

is reproduced, wherein R ₁ , R ₂ and A _{1 represent a} wide variety of organic radicals.

Also advantageous in the sense of the present invention are the 2,4-bis - {[4- (3-sulfonato) -2- hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine sodium salt, the 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) - 1,3,5-triazine, the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- [4- (2-methoxyethyl carboxyl) phenylamino] -1,3,5-triazine, the 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) - 2-hydroxy] phenyl} -6- [4- (2-ethylcarboxyl) phenylamino] -1,3,5-triazine, the 2,4-bis - {[4- (2- ethyl-hexyloxy) -2-hydroxy] phenyl} -6- (1-methyl-pyrrol-2-yl) -1,3,5-triazine, the 2,4-bis - {[4- tris (trimethylsiloxysilylpropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, the 2,4-bis - {[4- (2 "-methylpropenyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine and the 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.

An advantageous broadband filter in the sense of the present invention is the 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol), which through the chemical structural formula

and is marketed under the trade name Tinosorb® M by CIBA-Che mikalien GmbH is available.  

Another advantageous broadband filter for the purposes of the present invention is 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1 - [( trimethylsilyl) oxy] disiloxa nyl] propyl] phenol (CAS no .: 155633-54-8) with the INCI name Drometrizole Trisiloxane, which is characterized by the chemical structural formula

is marked.

The UV-B filters can be oil-soluble or water-soluble. Advantageous oil-soluble UV-B filter substances are e.g. B .:

• - 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzy lidencampher;
• - 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2-ethyl hexyl ester, 4- (dimethylamino) benzoic acid amyl ester;
• - 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine;
• - Esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhe xyl) ester;
• - Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxy isopentyl cinnamate;
• Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2- Hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone
• - As well as UV filters bound to polymers.

Advantageous water-soluble UV-B filter substances are e.g. B .:

• - Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or tri ethanolammonium salt, as well as the sulfonic acid itself;
• - Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-Oxo-3-bornylidenme thyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidenemethyl) sulfonic acid and their Salts.

Another light protection filter substance which can advantageously be used according to the invention is ethylhexyl-2-cyano-3,3-diphenylacrylate (octocrylene), which is available from BASF under the name Uvinul® N 539 and is distinguished by the following structure:

It can also be of considerable advantage to use polymer-bound or polymeric UV filters to use substances in preparations according to the present invention, esp in particular those as described in WO-A-92/20690.

Furthermore, it may be advantageous to add further UV-A and / or Incorporate UV-B filters in cosmetic or dermatological preparations for example certain salicylic acid derivatives such as 4-isopropylbenzyl salicylate, 2-ethylhexyl salicylate (= octyl salicylate), homomenthyl salicylate.

The list of UV filters mentioned, used in the sense of the present invention of course, should not be limiting.

Preparations according to the invention can also advantageously be used as the basis for cosmetics cal deodorants or antiperspirants are used, so that the present Er invention in a special embodiment Pickering emulsions as the basis for kos concerns metallic deodorants.

Cosmetic deodorants are used to eliminate body odor that arises when the odorless fresh 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) - who reduces the formation of sweat the.  

By using antimicrobial substances in cosmetic deodorants, the Bak flora on the skin can be reduced. Ideally, only the smell should be the cause relevant microorganisms can be effectively reduced. The sweat flow itself becomes there not affected by, ideally only the microbial decomposition of the sweat time stopped for a while.

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

All active ingredients common to deodorants or antiperspirants can advantageously be used are used, for example odor maskers such as the common perfume ingredients, Ge odor absorber, for example that in the patent application DE-P 40 09 347 be layered silicates, of which in particular montmorillonite, kaolinite, ilite, beidellite, Nontronite, saponite, hectorite, bentonite, smectite, and furthermore, for example, zinc salts of ricinol acid. Germ-inhibiting agents are also suitable in the W / O- Emulsion pens to be incorporated. Examples of advantageous substances are 2,4,4'- Trichloro-2'-hydroxydiphenyl ether (irgasane), 1,6-di- (4-chlorophenylbiguanido) hexane (chlorhe xidin), 3,4,4'-trichlorocarbonilide, quaternary ammonium compounds, clove oil, mint oil, Thyme oil, triethyl citrate, farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol) and the in the 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 drug combinations. Sodium hydrogen carbonate can also be used advantageously.

The list of active substances or combinations of active substances mentioned in the Invention Pickering emulsions can of course not be used be acting.

The cosmetic deodorants according to the invention can be in the form of normal Containable water-containing cosmetic preparations.

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

The pens according to the invention are also excellent vehicles for dermatological activity fabrics. They are particularly suitable as carriers for substances active against acne. Acne is a skin condition with various forms and causes from non-inflammatory and inflammatory nodules, starting from blocked hair follicles celestial (comedones), which can lead to the formation of pustules, abscesses and scars. Most frequently is the acne vulgaris, which mainly occurs during puberty. Causal conditions for the acne vulgaris are the cornification and constipation of the hair follicle mouth caused by the Blood levels of male sex hormones dependent on sebum production and production free fatty acids and tissue-damaging enzymes caused by bacteria (Propionibacterium acnes).

It is therefore advantageous to use the preparations according to the invention against acne to add stamps that are effective, for example, against Propionibacterium acnes (e.g. 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 effective against acne zen, for example all-trans retinoic acid, 13-cis retinoic acid and related substances) or anti inflammatory agents, for example batyl alcohol (α-octadecylglyceryl 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 cause keratinized skin (such as warts, corns, calluses) and the like) soften so that it is easier to remove or so that it falls off or dissolves.

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 ₁₄ H ₁₂ S ₂ ) as well as aluminum oxide, zinc oxide and / or finely divided sulfur.

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

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

Examples

Claims (8)

1. Containing cosmetic or dermatological preparations which represent finely dispersed systems of the water-in-oil type

• 1. an oil phase,
• 2. a water phase,
• 3. at least one modified layered silicate which shows both hydrophilic and lipophilic properties, which therefore has an amphiphilic character and is arranged at the water / oil interface and
• 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 that further cosmetic or pharmaceutical auxiliaries, additives and / or active ingredients ent are holding. 4. Preparations according to one of the preceding claims, characterized in that that the content of one or more modified layered silicates between 0.05% by weight and 10% by weight, advantageously between 0.1 and 2% by weight, based on the total weight of the preparations. 5. Preparations according to one of the preceding claims, characterized in that in addition to one or more modified layered silicates, other pigments are contained, in particular modified polysaccharides and / or microfine polymer Particles and / or micronized, inorganic pigments that 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, the Pigments can be present both individually and in a mixture. 6. Preparation according to one of the preceding claims, characterized in that that they selected from the UV filter substances (one or more compounds) Group of asymmetrically substituted s-triazine derivatives, especially 2,4-bis - {[4- (2- Ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine and / or dioctyl butylamidotriazon, contains.   7. Preparation according to one of the preceding claims, characterized in that that it contains sulfonated UV filters, which are selected from the group phenylene 1,4-bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, benzene-1,4-di (2- oxo-3-bornylidenemethyl-10-sulfonic acid) and its salts, 2-phenylbenzimidazole-5- sulfonic acid and its salts and sulfonic acid derivatives of 3-benzylidene camphor and their salts. 8. Preparations according to one of the preceding claims, containing one or several additives or active ingredients, selected from the group of astringents and / or the antimicrobial substances and / or the substances against acne.