WO2004000243A1

WO2004000243A1 - Foamable preparations

Info

Publication number: WO2004000243A1
Application number: PCT/EP2003/006684
Authority: WO
Inventors: Nadine Voigt; Thomas Raschke; Ilka Oelrichs; Alexander Filbry
Original assignee: Beiersdorf Ag
Priority date: 2002-06-25
Filing date: 2003-06-25
Publication date: 2003-12-31
Also published as: EP1519705A1; DE10228229A1

Abstract

The invention relates to foamable cosmetic or dermatological preparations, containing: A. at least one emulsifier selected from the group consisting of: polyglyceryl-3-methyl-glucose distearate and PEG ester and/or PEG ether having 30 to 100 ethoxy units of the following structure (n ranging from 30 to 100): R1-(CH2-CH2-0)n-R2, wherein R1 and R2, independent of one another, are selected from the group consisting of: hydrogen, alkyl radicals and acyl radicals having 12 to 40 carbon atoms; B. At least one co-emulsifier selected from the group consisting of: saturated and/or unsaturated, branched and/or unbranched fatty alcohols having a chain length ranging from 10 to 28 carbon atoms, glyceryl stearate, and; C. at least one foam-stabilizing surfactant selected from the group consisting of: N-acyl sarcosinates having a chain length ranging from 10 to 28 carbon atoms, polyglycosides having a chain length ranging from 10 to 28 carbon atoms and acylglutamates having a chain length ranging from 10 to 28 carbon atoms. The invention also relates to the use of the inventive preparations for water-sensitive, hydrophilic substances and to a method for the production thereof.

Description

description

Foamable preparations

The present invention relates to foamable cosmetic and dermatological preparations, in particular skin-care foamable cosmetic and dermatological preparations.

Foams or foam-like preparations belong to the disperse systems.

By far the most important and best-known disperse system are emulsions. Emulsions are two- or multi-phase systems of two or more liquids which are insoluble or only slightly soluble in one another. The liquids (pure or as solutions) are present in an emulsion in a more or less fine distribution, which is generally only of limited stability.

Foams are structures made of gas-filled, spherical or polyhedral cells, which are delimited by liquid, semi-liquid, highly viscous or solid cell bridges. The cell bridges, connected via so-called nodes, form a coherent framework. The foam lamellae (closed-cell foam) stretch between the cell bars. If the foam lamellae are destroyed or flow back into the cell webs at the end of foam formation, an open-cell foam is obtained. Foams, like emulsions, are also thermodynamically unstable, since surface energy can be obtained by reducing the surface area. The stability and therefore the existence of a foam depends on the extent to which it can prevent its self-destruction. Cosmetic foams are generally dispersed systems composed of liquids and gases, the liquid being the dispersant and the gas being the dispersed substance. Foams made from low-viscosity liquids are temporarily stabilized by surface-active substances (surfactants, foam stabilizers). Because of their large inner surface, such surfactant foams have a strong adsorption capacity, which is used, for example, in cleaning and washing processes. Accordingly, cosmetic foams are used in particular in the areas of cleaning, for example as shaving cream, and hair care.

To generate foam, gas is blown into suitable liquids, or the foam is formed by vigorously beating, shaking, spraying or stirring the liquid in the gas atmosphere in question, provided that the liquids contain suitable surfactants or other surfactants (so-called foaming agents) that in addition to interfacial activity, they also have a certain ability to form films.

Cosmetic foams have the advantage over other cosmetic preparations that they allow a fine distribution of the product and in particular the active ingredients contained therein on the skin.

A disadvantage of the prior art is that emulsion-based foams are often not very stable, which is why they usually collapse within about 24 hours. A requirement of cosmetic preparations, however, is that they have a stability that is as long as possible.

This problem is generally taken into account by the fact that the consumer only generates the actual foam when it is used with the aid of a suitable spray system, for which spray cans can be used, for example, in which a liquefied compressed gas serves as the propellant. When the pressure valve is opened, the blowing agent-liquid mixture escapes through a fine nozzle, the blowing agent evaporates and leaves a foam. Such systems according to the prior art develop, with the addition of propellant gas, exclusively aqueous-moist foams which break quickly after application. Post-foaming cosmetic preparations are also known per se. They are first applied to the skin in fluid form from an aerosol container and, after a short delay, develop the actual foam there, for example a shaving foam, under the influence of the post-foaming agent contained. Post-foaming preparations are often in special embodiments such as post-foaming shaving gels or the like.

Another disadvantage of the prior art is that unstable active ingredients, e.g. H. Active ingredients that are sensitive to oxidation (air) or light, for example, only in certain preparations that are difficult to formulate and in very few packaging materials - such as. B. aluminum tubes - can be presented. The skin feel of these products and the consumer acceptance of these packaging materials are often weak.

It was therefore a further object of this invention to provide a cosmetically acceptable product with high active ingredient stabilization. Interesting active ingredients in this context are ascorbic acid, green tea extracts and their main active components and flavonoids.

An object of the present invention was to enrich the prior art and to provide cosmetic or dermatological foamable preparations which do not have the disadvantages of the prior art.

It was surprising and unforeseeable for the person skilled in the art that foamable cosmetic or dermatological preparations containing A. at least one emulsifier selected from the group: polyglyceryl-3-methylglucose distearate and PEG ester and / or PEG ether with 30 to 100 Ethoxy units of the following structure (n between 30 and 100):

RMCHz-CHz-OJn-R ² , in which R1 and R2 are selected independently of one another from the group: hydrogen, alkyl and acyl radicals having 12 to 40 carbon atoms,

B. at least one co-emulsifier selected from the group: saturated and / or unsaturated, branched and / or unbranched fatty alcohols with a chain length of 10 to 28 carbon atoms, glyceryl stearate and C. at least one foam-stabilizing surfactant selected from the group: N-acyl sarcosinates with a chain length of 10 to 28 carbon atoms, polyglycosides with a chain length of 10 to 28 carbon atoms and acyl glutamates with a chain length of 10 to 28 carbon atoms the disadvantages of Remedy the state of the art.

For the purposes of the present invention, “foamable” is to be understood to mean that the preparations according to the invention form foams when they are foamed, ie when gas is blown into them, for example, or the preparations are (violently) beaten in the gas atmosphere in question, In the foams produced in this way, the gas bubbles can (arbitrarily) be distributed in one (or more) liquid phase (s), the foams not necessarily having the appearance of a foam macroscopically.

From foamable cosmetic or dermatological preparations according to the invention can by foaming z. B. macroscopically visible dispersed systems are made from gases dispersed in liquids. The foam character can, for example, only become visible under a (light) microscope. In addition, the foaming of the foamable preparations according to the invention - especially when the gas bubbles are too small to be recognized under a light microscope - can also be recognized from a large increase in volume of the system.

The preparations according to the invention are extremely satisfactory preparations in every respect. It was particularly surprising that the foams produced from the foamable preparations according to the invention are extraordinarily stable, even with an unusually high gas volume. Accordingly, preparations in the sense of the present invention are particularly suitable to serve as the basis for product forms with a variety of uses.

The preparations according to the invention and the foams obtainable therefrom have very good sensory properties, such as, for example, the distributability on the skin or the ability to be absorbed into the skin, and are furthermore distinguished by an above-average skin care. Fine-bubble, rich foams of outstanding cosmetic elegance can be obtained from compositions according to the invention. Preparations which are particularly well tolerated by the skin can furthermore be obtained from compositions according to the invention, and valuable ingredients can be distributed particularly well on the skin.

The invention further relates to the use of foamable cosmetic or dermatological preparations containing A. at least one emulsifier selected from the group: polyglyceryl-3-methylglucose distearate and PEG ester and / or PEG ether with 30 to 100 ethoxy units of following structure (n between 30 and 100):

RMCHz-CHz-OJn-R ² , in which R1 and R2 are selected independently of one another from the group: hydrogen, alkyl and acyl radicals having 12 to 40 carbon atoms, B. at least one co-emulsifier, selected from the group: saturated and / or unsaturated, branched and / or unbranched fatty alcohols with a chain length of 10 to 28 carbon atoms, glyceryl stearate and

C. at least one foam-stabilizing surfactant selected from the group: N-acyl sarcosinates with a chain length of 10 to 28 carbon atoms, polyglycosides with a chain length of 10 to 28 carbon atoms and acyl glutamates with a chain length of 10 to 28 carbon atoms as cosmetic or dermatological basis for water-sensitive, hydrophilic active substances.

The emulsifier (s) are preferably selected from the following group: PEG-9 stearate, PEG-8 distearate, PEG-20 stearate, PEG-8 stearate, PEG-8 oleate, PEG-25 glyceryl trioleate, PEG-40 -Sorbitan lanolate, PEG-15-glyceryl ricinoleate, PEG-20-glyceryl stearate, PEG-20-glyceryl isostearate, PEG-20-glyceryl oleate, PEG-20-stearate, PEG-20-methylglucose sesquistearate, PEG-30-glyceryl isostearate, PEG-20 , PEG-30 stearate, PEG-30 glyceryl stearate, PEG-40 stearate, PEG-30 glyceryl laurate, PEG-50 stearate, PEG-100 stearate, PEG-150 laurate. Polyethoxylated stearic acid esters, for example, are particularly advantageous. According to the invention, the co-emulsifier (s) are preferably selected from the following group: butyl octanol, butyl decanol, hexyl octanol, hexyl decanol, octyl dodecanol, behenyl alcohol (C ₂₂ H ₄₅ OH), cetearyl alcohol [a mixture of cetyl alcohol (C _1β H ₃₃ OH) and stearyl alcohol ( Cι ₈ H ₃₇ OH)], lanolin alcohols (wool wax alcohols, which represent the unsaponifiable alcohol fraction of the wool wax, which is obtained after the saponification of wool wax). Cetyl and cetylstearyl alcohol are particularly preferred.

For the purposes of the present invention, it is advantageous for the total amount of emulators (one or more compounds) to be in the range from 0.001 to 20% by weight, advantageously from 0.002 to 15% by weight, in particular from 0.01 to 5 % By weight, based in each case on the total weight of the formulation.

For the purposes of the present invention, it is advantageous for the total amount of co-emulsifiers (one or more compounds) to be in the range from 0.001 to 20% by weight, advantageously from 0.002 to 15% by weight, in particular from 0.01 to 5% by weight. -%, each based on the total weight of the formulation.

For the purposes of the present invention, it is advantageous for the total amount of foam-stabilizing surfactants (one or more compounds) to be in the range from 0.0001 to 20% by weight, advantageously from 0.0005 to 10% by weight, in particular from 0.001 to 2% by weight, based in each case on the total weight of the formulation.

The foamable cosmetic or dermatological agents according to the invention can, for example, be removed from aerosol containers and thereby foamed. Aerosol containers according to the invention are spray devices with a filling of the liquid or pulp-like substances which are under the pressure of a propellant (compressed gas or aerosol packs). Such containers can be equipped with valves of very different designs, which allow the contents to be removed as foam.

For the purposes of the present invention, the pressure gas containers used are primarily cylindrical vessels made of metal (aluminum, tinplate, content <1000 mL), protected or non-splintering glass or plastic (content <220 mL) or splintering glass or plastic (content <150 mL) in question, when choosing compressive strength and breaking strength, Corrosion resistance, easy fillability, possibly sterilization etc., but also aesthetic aspects, handiness, printability etc. play a role. The maximum permissible operating pressure of spray cans made of metal at 50 ° C is 12 bar and the maximum filling volume at this temperature is approx. 90% of the total volume. For glass and plastic cans, lower values for the operating pressure apply, depending on the container size and the propellant (whether liquefied, compressed or dissolved gas).

Cans made of tinplate, aluminum and glass are particularly advantageous for the purposes of the present invention. For corrosion protection reasons, metal cans can be painted inside (silver or gold painted), for which all commercially available interior protective paints are suitable. Polyester, epoxyphenol and polyamideimide lacquers are preferred for the purposes of the present invention. Foil laminations made of polyethylene (PE), polypropylene (PP) and / or polyethylene terephthalate (PET) inside the cans are also advantageous, especially for cans made of tinplate.

The compressed gas containers are usually one or two, but usually three-part cylindrical, conical or other shape. If plastics are used as spray container material, they should be resistant to chemicals and sterilization temperatures, gas-tight, impact-resistant and stable against internal pressures above 12 bar. In principle, polyacetals and polyamides are suitable for spray container purposes.

The internal structure of the spray cans and the valve construction are dependent on the intended use and the physical nature of the content - e.g. B. whether as a two- or three-phase system - very varied and can be determined by a person skilled in the art by simply trying out without inventive step. For suitable embodiments, reference is made to the “Aerosol Technology Manual for Aersosol Packaging” (Wolfgang Tauscher, Melcher Verlag GmbH Heidelberg / Munich, 1996).

Valves advantageous according to the invention can be designed with or without a riser pipe. The individual parts from which valves according to the invention are usually constructed preferably consist of the following materials:

Plate: tinplate: bright, gold or clear lacquered, foil-laminated (PE, PP or PET) Aluminum: bright, silver or gold lacquered, different lacquer variants, stoner mudge version

Sealing: natural or synthetic elastomers or thermoplastic (sleeve gaskets, film-lined from PE or PP) inner and outer seals, e.g. B. from Perbunan, Buna, neoprene, butyl, CLB, LDPE, Viton, EPDM, chlorobutyl, bromobutyl and / or various compounds

Taper: PA, POM, brass and various special materials, standard bores (e.g. 0.25 to 0.70 mm or 2 x 0.45 to 2 x 1.00 mm), various shaft diameters

Spring: metal, particularly preferably V2A, stainless steel; Plastic and also elastomer

Housing: standard and impact

VPH holes, RPT holes or slotted for overhead applications. B. polyacetal, PA, PE, POM and the like

Riser pipe: plastic (polymer resin), e.g. PE, PP, PA or polycarbonate

Advantageous spray heads in the sense of the present invention are, for example, foam heads for upright use (holding the can vertically) or foam heads for overhead use with one or more channels.

The usual "classic" volatile, liquefied propellants, such as dimethyl ether (DME) and / or linear or branched chain hydrocarbons with two to five carbon atoms (such as in particular ethane, propane, butane, isobutane and / or pentane) are suitable as blowing agents, which can be used alone or in a mixture with one another.

Compressed air and other pressurized gases such as air, oxygen, nitrogen, hydrogen, helium, krypton, xenon, radon, argon, laughing gas (N ₂ O) and coal In the context of the present invention, dioxide (CO ₂ ) can advantageously be used as propellant gases (both individually and in any mixtures with one another).

Of course, the person skilled in the art knows that there are other non-toxic propellant gases which would in principle be suitable for the implementation of the present invention in the form of aerosol preparations, but which should nevertheless be dispensed with, in particular halogenated (with, because of their harmful effects on the environment or other associated circumstances Fluorine, chlorine, bromine, iodine and / or astatine substituted) hydrocarbons such as fluorocarbons and chlorofluorocarbons (CFCs).

For the purposes of the present invention, the gases mentioned can be used individually or in any mixtures with one another.

For the purposes of the present invention, the volume fraction of propellant gas is advantageously selected from the range from 0.1 to 30% by volume, based on the total volume of filling material and propellant gas (corresponding to a volume fraction of 70 to 99.9% by volume filling material) ,

Particularly advantageous, fine creamy and rich foams can be obtained if the preparations according to the invention are foamed using linear or branched-chain, halogenated or non-halogenated hydrocarbons. Very particularly advantageous foams can be obtained by foaming the preparations according to the invention with carbon dioxide, oxygen, compressed air and / or nitrogen.

It may be advantageous, though not necessary, if the formulations according to the present invention contain further emulsifiers.

The oil phase of the formulations according to the invention is advantageously selected from the group of polar oils, for example from the group of lecithins and fatty acid triglycerides, especially the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24 , in particular 12 to 18 carbon atoms. The fatty acid triglycerides can for example be advantageously selected from the group of synthetic, semi-synthetic and natural oils, such as. B. cocoglyceride, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, Palm oil, coconut oil, castor oil, wheat germ oil, grape seed oil, safflower oil, evening primrose oil, macadamia nut oil and the like.

According to the invention, z. B. natural waxes of animal and vegetable origin, such as beeswax and other insect waxes, and berry wax, shea butter and / or lanolin (wool wax).

For the purposes of the present invention, further advantageous polar oil components can also be selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms and from the group of esters from aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms. Such ester oils can then advantageously be selected from the group octyl palmitate, octyl co-coat, octyl isostearate, octyl dodeceyl myristate, octyl dodecanol, cetearyl isononanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-stonolate, n-stonolate, n-stonyl-n-stonate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, stearyl heptanoate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate, tridecyl stearate, tridecyltrimetic halosynthesis, as well as synthetic, such as. B. Jojoba oil.

Furthermore, the oil phase can advantageously be selected from the group of dialkyl ethers and dialkyl carbonates. B. dicaprylyl ether (Cetiol OE) and / or dicaprylyl carbonate, for example that available under the trade name Cetiol CC from Cognis.

It is further preferred that the oil component (s) from the group isoeikosan, neopentyl glycol diheptanoate, propylene glycol dicaprylate / dicaprate, caprylic / capric / diglyceryl succinate, butylene glycol dicaprylate / dicaprate, Cι ₂ . ₁₃ alkyl lactate, di- ₂ . _13- alkyl tartrate, triisostearin, dipentaerythrityl hexacaprylate / hexacaprate, propylene glycol monoisostearate, tri-caprylin, dimethyl isosorbide. It is particularly advantageous if the oil phase of the invented Formulations according to the invention have a content of C ₁₂ -is alkyl benzoate or consist entirely of this.

Advantageous oil components are also z. B. butyl octyl salicylate (for example that available under the trade name Hallbrite BHB from CP Hall), hexadecyl benzoate and butyl octyl benzoate and mixtures thereof {Hallstar AB) and / or diethyl hexyl naphthalate {Hallbrite TQ or Corapan TQ from H&R).

Any mixtures of such oil and wax components can also be used advantageously for the purposes of the present invention.

The oil phase can also advantageously also contain non-polar oils, for example those selected from the group of branched and unbranched hydrocarbons and waxes, in particular mineral oil, petroleum jelly (petrolatum), paraffin oil, squalane and squalene, polyolefins, hydrogenated polyisobutenes and isohexa- decane. Among the polyolefins, polydecenes are the preferred substances.

The oil phase can advantageously also have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or the silicone oils.

Silicone oils are high-molecular synthetic polymeric compounds in which silicon atoms are linked in a chain and / or network-like manner via oxygen atoms and the remaining valences of silicon by hydrocarbon residues (mostly methyl, more rarely ethyl, propyl, phenyl) Groups, etc.) are saturated. The silicone oils are systematically referred to as polyorganosiloxanes. The methyl-substituted polyorganosiloxanes, which are the most important compounds of this group in terms of quantity and are characterized by the following structural formula

are also known as polydimethylsiloxane or dimethicone (INCI). Dimethicone is available in different chain lengths or with different molecular weights.

Particularly advantageous polyorganosiloxanes for the purposes of the present invention are, for example, dimethylpolysiloxanes [poly (dimethylsiloxane)], which are available, for example, from Th. Goldschmidt under the trade names Abil 10 to 10,000. Also advantageous are phenylmethylpolysiloxanes (INCI: phenyl dimethicone, phenyl trimethicone), cyclic silicones (octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane), which according to INCI are also called cyclomethicones, amino-modified silicones (INCI: amodimethicone and silicone). B. polysiloxane-polyalkylene copolymers (INCI: stearyl dimethicone and cetyl dimethicone) and dialkoxydimethyl polysiloxanes (stearoxy dimethicone and behenoxy stearyl dimethicone), which are available as different Abil-Wax types from Th. Goldschmidt. However, other silicone oils can also be used advantageously for the purposes of the present invention, for example cetyldimethicone, hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).

The cosmetic and / or dermatological preparations according to the invention and foams obtainable therefrom can be composed as usual. Preparations for skin care are particularly advantageous for the purposes of the present invention: they can be used for cosmetic and / or dermatological light protection, for treating the skin and / or hair and as a make-up product in decorative cosmetics. Another advantageous embodiment of the present invention consists of after-sun products.

Depending on their structure, cosmetic or topical dermatological compositions can be used for the purposes of the present invention, for example as a skin protection cream, day or night cream, etc. It may be possible and advantageous to use the compositions according to the invention as the basis for pharmaceutical formulations.

Just as emulsions of liquid and solid consistency are used as cosmetic cleaning lotions or cleaning creams, the foams obtainable from preparations according to the invention can also represent “cleaning foams” which for example to remove make-up and / or make-up or as a mild wash foam - possibly also for impure skin. Such cleaning foams can advantageously also be used as so-called “rinse off” preparations which are rinsed off the skin after use

Foams obtainable from cosmetic and / or dermatological preparations according to the invention can also advantageously be in the form of a foam for the care of the hair or the scalp, in particular a foam for inserting the hair, a foam which is used when the hair is blow-dried, a hairdressing and Treatment foam.

For use, the cosmetic and dermatological preparations according to the invention and / or foams obtainable therefrom are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.

The cosmetic and dermatological preparations according to the invention can contain cosmetic auxiliaries as are usually used in such preparations, e.g. B. preservatives, preservation aids, bactericides, perfumes, dyes, pigments that have a coloring effect, moisturizing and / or moisturizing substances, fillers that improve the feeling on the skin, 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.

Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde releasers (such as, for example, DMDM hydantoin), iodopropyl butyl carbamates (for example those available under the trade names Koncyl-L, Koncyl-S and Konkaben LMB from Lonza), parabens, Phenoxyethanol, ethanol, benzoic acid and the like. Usually, the preservation system according to the invention advantageously also includes preservation aids, such as, for example, octoxyglycerol, glycine soya, etc.

Particularly advantageous preparations are also obtained if antioxidants are used as additives or active ingredients. According to the invention, the preparations contain gene advantageously one or more antioxidants. All of the antioxidants which are suitable or customary for cosmetic and / or dermatological applications can be used as inexpensive but nevertheless optional antioxidants.

The antioxidants are 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-camosine, D-carnosine, L-camosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, ß-carotene, lycopene) and their derivatives, lipoic acid and their 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, dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleotides and salts) and sulfoximine Compounds (e.g. Buthioninsulfoximine, Homocysteinsulfoximin, Buthioninsulfone, Penta-, Hexa-, Heptat hioninsulfoximine) in very low tolerable dosages (e.g. B. pmol to μmol / kg), further (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, biliverdin, 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, vitamin C and derivatives (e.g. B. ascorbyl palmitate, Mg - ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) as well as konyferyl benzoate of benzoin, rutinic acid and its derivatives, ferroic acid and their derivatives, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg Znö, ZnSÜ4) selenium and its derivative ate (e.g. selenium methionine), stilbene and their derivatives (e.g. B. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances.

For the purposes of the present invention, water-soluble antioxidants, such as vitamins, e.g. B. ascorbic acid and its 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, preferred active ingredients being antioxidants which can protect the skin against oxidative stress. It was particularly surprising that the cosmetic or dermatological preparations according to the invention stabilize water-sensitive, hydrophilic active substances - in particular ascorbic acid - better against decay than the preparations of the prior art and that they are also excellent cosmetic and dermatological transport agents for ascorbic acid and / or ascorbyl compounds.

The amount of the antioxidants (one or more compounds) in the preparations is preferably 0.0001 to 30% by weight, particularly preferably 0.0005 to 10% by weight, in particular 0.001 to 5% by weight, based on the total weight the preparation.

Further preferred antioxidants are vitamin E and its derivatives and vitamin A and its derivatives. If vitamin E and / or its derivatives represent the antioxidant (s), it is advantageous to choose their respective concentrations from the range from 0.001 to 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 add their respective concentrations in the range from 0.001 to 10% by weight, based on the total weight of the formulation 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, e.g. B. hydrocortisone-17-valerate, vitamins of the B and D series, very cheap the vitamin B ^ the vitamin B ₁₂ the vitamin D ₍ but also bisabolol, unsaturated fatty acids, especially the essential fatty acids (often 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 plant and animal origin, e.g. B. 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 active ingredient (s) are particularly advantageously selected from the group of NO synthase inhibitors, in particular if the preparations according to the invention are intended for the treatment and prophylaxis of the symptoms of intrinsic and / or extrinsic skin aging and for the treatment and prophylaxis of the harmful effects of ultraviolet radiation on the skin ,

The preferred NO synthase inhibitor is nitroarginine.

The active ingredient (s) are also advantageously selected from the group comprising catechins and bile esters of catechins and aqueous or organic extracts from plants or parts of plants which contain catechins or bile esters of catechins, such as, for example, the leaves of Plant family Theaceae, especially the species Camellia sinensis (green tea). Their typical ingredients (such as polyphenols or catechins, caffeine, vitamins, sugar, minerals, amino acids, lipids) are particularly advantageous.

Catechins are a group of compounds which are to be understood as hydrogenated flavones or anthocyanidins and derivatives of "catechins" (catechol, 3,3 ', 4', 5,7-flavanpentaol, 2- (3,4- Dihydroxyphenyl) -chroman-3,5,7-triol) Also epicatechin ((2R, 3R) -3,3 ', 4', 5,7-flavanpentaol) is an advantageous active substance in the sense of the present invention.

Plant extracts containing catechins, in particular extracts of green tea, such as. B. Extracts from leaves of the plants of the species Camellia spec, especially the teas Camellia sinenis, C. assamica, C. talien- sis or C. irrawadiensis and crosses of these with, for example, Camellia japonica.

Preferred active ingredients are also polyphenols or catechins from the group (-) - catechol, (+) - catechin, (-) - catechin gallate, (-) - gallocatechin gallate, (+) - epicatechin, (-) - epicatechin , (-) - epicatechin gallate, (-) - epigallocatechin, (-) - epigallocatechin gallate.

Flavon and its derivatives (often also collectively called "flavones") are advantageous active substances in the sense of the present invention. They are characterized by the following basic structure (substitution positions specified):

Some of the more important flavones, which can also preferably be used in preparations according to the invention, are listed in the table below:

In nature, flavones usually occur in glycosidated form.

According to the invention, the flavonoids are preferably chosen from the group of substances of the generic structural formula

where Zi to Z _{7 are} independently selected from the group H, OH, alkoxy and hydroxyalkoxy, where the alkoxy or hydroxyalkoxy groups can be branched and unbranched and can have 1 to 18 carbon atoms, and wherein Gly is selected from the Group of the mono- and oligoglycoside residues.

According to the invention, the flavonoids can also be advantageously selected from the group of substances of the generic structural formula

where Z to Ze are independently selected from the group H, OH, alkoxy and hydroxyalkoxy, where the alkoxy or hydroxyalkoxy groups are branched and unbranched and can have 1 to 18 carbon atoms, and wherein Gly is selected from the group the mono- and oligoglycoside residues. Such structures can preferably be selected from the group of substances of the generic structural formula

.

wherein Gly Gly ₂ and Gly ₃ independently of one another represent monoglycoside residues or. Gly ₂ or Gly ₃ can also represent, individually or together, saturations by hydrogen atoms.

Gly, Gly ₂ and Gly ₃ are preferably selected independently of one another from the group of the hexosyl radicals, in particular the rhamnosyl radicals and glucosyl radicals. However, other hexosyl radicals, for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be used advantageously. It can also be advantageous according to the invention to use pentosyl residues.

Become an asset

to Z ₅ independently selected from the group H, OH, methoxy, ethoxy and 2-hydroxyethoxy, and the flavone glycosides have the structure

The flavone glycosides according to the invention from the group which are represented by the following structure are particularly advantageous:

where Gly ^ Gly ₂ and Gly ₃ independently of one another represent monoglycoside residues or. Gly ₂ or Gly ₃ can also represent, individually or together, saturations by hydrogen atoms.

Glyi, Gly ₂ and Gly ₃ are preferably selected independently of one another from the group of the hexosyl radicals, in particular the rhamnosyl radicals and glucosyl radicals. However, other hexosyl radicals, for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be used advantageously. It can also be advantageous according to the invention to use pentosyl residues.

For the purposes of the present invention, it is particularly advantageous to choose the flavone glycosides from the group α-glucosyl rutin, α-glucosyl myrcetin, α-glucosyl iso-quercitrin, α-glucosyl iso-quercetin and α-glucosyl-quercitrin.

According to the invention, α-glucosylrutin is particularly preferred.

Also advantageous according to the invention are naringin (aurantiin, naringenin-7-rhamnoglucosid), hesperidin (3 ', 5,7-trihydroxy-4'-methoxyflavanon-7-rutinoside, hesperidoside, hesperetin-7-O-rutinoside). Rutin (3,3 ', 4', 5,7-pentahydroxyflyvon-3-rutinosid, quercetin-3-rutinosid, Sopho n, Birutan, Rutabion, taurutin, phytomelin, Melin), troxerutin (3,5-dihydroxy- ^3,, 4 ', 7-tris (2-hydroxyethoxy) flavone-3- (6-0- (6-deoxy-α-L-mannopyranosyl) -beta-D-glucopy- ranosid)), monoxerutin (3, 3 ', 4', 5-tetrahydroxy-7- (2-hydroxyethoxy) flavon-3- (6-O- (6-deoxy-α-L-mannopyranosyl) -ß-D-glucopyranoside)), dihydrorobinetin (3,3 ', 4', 5 ', 7-pentahydroxyflavanone), taxifolin (3,3', 4 ', 5,7-pentahydroxyflavanone), eriodictyol-7-glucoside (3', 4 ', 5, 7-tetrahydroxyflavanone-7-glucoside), Flavanomareϊn (3 ', 4', 7,8-tetrahydroxyflava- non-7-glucoside) and isoquercetin (3,3 ', 4', 5,7-pentahydroxyflavanon-3- (ß-D-glucopyranosid).

It is also advantageous to choose the active ingredient (s) from the group of ubiquinones and plastoquinones.

Ubiquinones are characterized by the structural formula

and represent the most widespread and thus best studied biochinones. Depending on the number of isoprene units linked in the side chain, ubiquinones are classified as Q-1, Q-2, Q-3 etc. or according to the number of C- Atoms referred to as U-5, U-10, U-15, etc. They preferably occur with certain chain lengths, e.g. B. in some microorganisms and yeasts with n = 6. Q10 predominates in most mammals, including humans.

Coenzyme Q10, which is characterized by the following structural formula, is particularly advantageous:

Plastoquinones have the general structural formula

on. Plastoquinones differ in the number n of isoprene residues and are named accordingly, e.g. B. PQ-9 (n = 9). There are also other plastoquinones with different substituents on the quinone ring.

Creatine and / or creatine derivatives are also preferred active substances for the purposes of the present invention. Creatine is characterized by the following structure:

Preferred derivatives are creatine phosphate and creatine sulfate, creatine acetate, creatine ascorbate and the derivatives esterified on the carboxyl group with mono- or polyfunctional alcohols.

Another advantageous active ingredient is L-camitin [3-hydroxy-4- (trimethylammonio) -butter-acid-betaine]. Also acyl-camitines, which are selected from the group of substances of the following general structural formula

^'

where R is selected from the group of branched and unbranched alkyl radicals having up to 10 carbon atoms are advantageous active ingredients in the sense of the present invention. Propionylcarnitine and in particular acetylcarnitine are preferred. Both enantiomers (D- and L-form) can be used advantageously for the purposes of the present invention. the. It can also be advantageous to use any mixture of enantiomers, for example a racemate of D and L form.

Other advantageous active ingredients are sericoside, pyridoxol, vitamin K, biotin and flavorings.

The list of the active substances or combinations of active substances mentioned which can be used in the preparations according to the invention is of course not intended to be limiting. The active ingredients can be used individually or in any combination with one another.

Skin aging is e.g. B. caused by endogenous, genetically determined factors. In the epidermis and dermis it occurs due to aging e.g. B. the following structural damage and malfunctions, which may also fall under the term "senile xerosis":

a) dryness, roughness and formation of (dryness) wrinkles, b) itching and c) reduced regreasing by sebum glands (e.g. after washing).

Exogenous factors, such as UV light and chemical pollutants, can be cumulatively effective and e.g. B. accelerate or complement the endogenous aging processes. In the epidermis and dermis, it is caused in particular by exogenous factors, e.g. B. the following structural damage and functional disorders in the skin, which go beyond the extent and quality of the damage with chronological aging:

d) visible vasodilation (telangiectasia, cuperosis); e) flaccidity and wrinkling; f) local hyper, hypo and incorrect pigmentation (e.g. age spots) and g) increased susceptibility to mechanical stress (e.g. cracking).

Surprisingly, selected formulations according to the invention can also have an anti-wrinkle effect or considerably increase the effect of known anti-wrinkle active ingredients. Accordingly, formulations within the meaning of the present invention are particularly advantageous for the prophylaxis and treatment of cosmetic or dermatological tological skin changes, such as z. B. occur during skin aging. They are also advantageous against the appearance of dry or rough skin.

In a particular embodiment, the present invention therefore relates to products for the care of the naturally aged skin and for the treatment of the consequential damage caused by photoaging, in particular the phenomena listed under a) to g).

The water phase of the preparations according to the invention can advantageously contain customary cosmetic auxiliaries, such as, for example, alcohols, in particular those having a low C number, preferably ethanol and / or isopropanol, diols or polyols having a low C number, and their ethers, preferably propylene glycol, glycerol, ethylene glycol, Ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analog products, polymers, foam stabilizers, electrolytes and moisturizers.

Moisturizers are substances or mixtures of substances that give cosmetic or dermatological preparations the property of reducing the release of moisture from the horny layer (also known as trans-epidermal water loss (TEWL)) and / or hydrating the skin after application or distribution on the skin surface To influence the horny layer positively.

Advantageous moisturizers for the purposes of the present invention are, for example, glycerol, lactic acid, pyrrolidone carboxylic acid and urea. Furthermore, it is particularly advantageous to use polymeric moisturizers from the group of water-soluble and / or water-swellable and / or water-gelable polysaccharides. Particularly advantageous are, for example, hyaluronic acid, chitosan and / or a fucose-rich polysaccharide, which is filed in the Chemical Abstracts under the registration number 178463-23-5 and z. B. under the name Fucogel®1000 from the company SOLABIA S.A. is available.

The cosmetic and dermatological preparations according to the invention can contain dyes and / or color pigments, in particular if they are in the form of decorative cosmetics. The dyes and pigments can be found in the corresponding positive list of the Cosmetics Regulation or the EC list of cosmetic colorants to be selected. In most cases, they are identical to the colorants approved for food. Advantageous color pigments are, for example, titanium dioxide, mica, iron oxides (eg Fe ₂ 0 ₃ , Fe ₃ 0 ₄ , FeO (OH)) and / or tin oxide. Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramarine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the Rowe Color Index, 3rd edition, Society of Dyers and Colorists, Bradford, England, 1971.

If the formulations according to the invention are in the form of products which are used on the face, it is advantageous to choose one or more substances from the following group as the dye: 2,4-dihydroxyazobenzene, 1- (2'-chloro-4'- nitro-1'-phenylazo) -2-hydroxynaphthalene, ceres red, 2- (sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid, calcium salt of 2-hydroxy-1, 2'-azonaphthalene-1'- sulfonic acid, calcium and barium salts of 1- (2-sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid, calcium salt of 1- (2-sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid, aluminum salt 1- (4-sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid, aluminum salt of 1- (4-sulfo-1-naphthyl-azo) -2-naphthol-3,6-disulfonic acid, 1 - ( 4-sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid, aluminum salt of 4- (4-sulfo-1-phenylazo) -1 - (4-sulfophenyl) -5-hydroxy-pyrazolon-3-car - bonic acid, aluminum and zirconium salts of 4,5-dibromofluorescein, aluminum and zirconium salts of 2,4,5,7-tetrabromofluor escein, S '^'. δ'.β'-tetrachlor ^^. S -tetrabromo-fluorescein and its aluminum salt, aluminum salt of 2,4,5,7-tetraiodofluorescein, aluminum salt of quinophthalone disulfonic acid, aluminum salt of indigo disulfonic acid, red and black iron oxide (CIN: 77491 (red) and 77499 (black)), iron oxide hydrate (CIN: 77 492), manganese ammonium diphosphate and titanium dioxide.

Also advantageous are oil-soluble natural dyes, such as. B. paprika extracts, ß-carotene or cochineal.

Formulations containing pearlescent pigments are also advantageous for the purposes of the present invention. The types of pearlescent pigments listed below are particularly preferred: 1. Natural pearlescent pigments, such as. B.

■ "fish silver" (guanine / hypoxanthine mixed crystals from fish scales) and

■ "mother-of-pearl" (ground mussel shells) 2. Monocrystalline pearlescent pigments such as B. Bismuth oxychloride (BiOCI)

3. Layer-substrate pigments: e.g. B. mica / metal oxide

Pearlescent pigments are based, for example, on powdered pigments or castor oil dispersions of bismuth oxychloride and / or titanium dioxide and bismuth oxychloride and / or titanium dioxide on mica. Particularly advantageous is e.g. B. the gloss pigment listed under CIN 77163.

The following pearlescent pigment types based on mica / metal oxide are also advantageous:

Z are particularly preferred. B. the pearlescent pigments available from Merck under the trade names Timiron, Colorona or Dichrona.

The list of the pearlescent pigments mentioned is of course not intended to be limiting. Pearlescent pigments which are advantageous in the sense of the present invention are obtainable in numerous ways known per se. For example, other substrates besides mica can be coated with other metal oxides, such as. B. silica and the like. Are advantageous for. B. with Ti0 ₂ and Fe ₂ 0 ₃ coated Si0 ₂ particles ("Ronasphe- ren "), which are sold by Merck and are particularly suitable for the optical reduction of fine wrinkles.

It can also be advantageous to completely move to a substrate such as mica. Iron pearlescent pigments which are produced without the use of mica are particularly preferred. Such pigments are e.g. B. available under the trade name Sicopearl copper 1000 from BASF.

Also particularly advantageous are effect pigments which are available from Flora Tech under the trade name Metasomes Standard / Glitter in various colors (yello, red, green, blue). The glitter particles are present in mixtures with various auxiliaries and dyes (such as, for example, the dyes with the Color Index (Cl) numbers 19140, 77007, 77289, 77491).

The dyes and pigments can be present both individually and in a mixture and can be mutually coated, different color effects generally being produced by different coating thicknesses. The total amount of dyes and coloring pigments is advantageously from the range of z. B. 0.1% by weight to 30% by weight, preferably from 0.5 to 15% by weight, in particular from 1.0 to 10% by weight, in each case based on the total weight of the preparations ,

It is also advantageous for the purposes of the present invention to produce cosmetic and dermatological preparations, the main purpose of which is not protection from sunlight, but which nevertheless contain UV protection substances. So z. For example, UV-A or UV-B filter substances are usually incorporated into day creams or makeup products. UV protection substances, like antioxidants and, if desired, preservatives, also provide effective protection of the preparations themselves against spoilage. Cosmetic and dermatological preparations which are in the form of a sunscreen are also favorable.

Accordingly, in the sense of the present invention, the preparations preferably contain, in addition to one or more UV filter substances according to the invention, at least one further UV-A and / or UV-B filter substance. The wording may, although not necessary, optionally also contain one or more organic and / or inorganic pigments as UV filter substances, which may be present in the water and / or oil phase.

The preparations according to the present invention can furthermore advantageously also be in the form of so-called oil-free cosmetic or dermatological emulsions which contain a water phase and at least one UV filter substance which is liquid at room temperature as a further phase and which, in particular, can advantageously also be free of further oil components.

Particularly advantageous UV filter substances which are liquid at room temperature for the purposes of the present invention are homomenthyl salicylate (INCI: homosalate), 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (INCI: octocrylene), 2-ethylhexyl-2-hydroxybenzoate (2- Ethyl hexyl salicylate, octyl salicylate, INCI: Ethylhexyl salicylate) and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl-4-methoxycinnamate, INCI: Ethylhexyl methoxycinnamate) and 4-methopentyl acetate - methoxycinnamate, INCI: Isoamyl p-methoxycinnamate), 3- (4- (2,2-bis-ethoxycarbonylvinyl) -phenoxy) propenyl) methoxysiloxane / dimethylsiloxane - copolymer which is available, for example, from Hoffmann La Röche under the trade name Parsol® SLX is.

Preferred inorganic pigments are metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular oxides of titanium (Ti0 ₂ ), zinc (ZnO), iron (e.g. Fe ₂ 0 ₃ ), zirconium (Zr0 ₂ ), silicon ( Si0 ₂ ), manganese (e.g. MnO), aluminum (Al ₂ 0 ₃ ), cerium (e.g. Ce ₂ 0 ₃ ), mixed oxides of the corresponding metals as well as mixtures of such oxides and the sulfate of barium (BaSO ₄ ).

For the purposes of the present invention, the pigments can also advantageously be used in the form of commercially available oily or aqueous predispersions. Dispersing aids and / or solubilizing agents can advantageously be added to these predispersions.

According to the invention, the pigments can advantageously be surface-treated (“coated”), for example a hydrophilic, amphiphilic or hydrophobic character should be formed or retained. This surface treatment can best hen that the pigments are provided with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer by methods known per se. For the purposes of the present invention, the various surface coatings can also contain water.

Inorganic surface coatings in the sense of the present invention can consist of aluminum oxide (Al ₂ 0 ₃ ), aluminum hydroxide Al (OH) ₃ , or aluminum oxide hydrate (also: alumina, CAS no .: 1333-84-2), sodium hexametaphosphate (NaP0 ₃ ) _β , sodium metaphosphate (NaP0 ₃ ) _n , silicon dioxide (Si0 ₂ ) (also: silica, CAS No .: 7631-86-9), or iron oxide (Fe ₂ 0 ₃ ). These inorganic surface coatings can occur alone, in combination and / or in combination with organic coating materials.

Organic surface coatings in the sense of the present invention can consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane (also: dimethicone), methylpolysiloxane (methicone), simethicone (a mixture of dimethylpolysiloxane with an average chain length of 200 to 350 dimethylsiloxane Units and silica gel) or alginic acid. These organic surface coatings can occur alone, in combination and / or in combination with inorganic coating materials.

Zinc oxide particles and predispersions of zinc oxide particles suitable according to the invention are available under the following trade names from the companies listed:

Suitable titanium dioxide particles and predispersions of titanium dioxide particles are available under the following trade names from the companies listed:

Other advantageous pigments are latex particles. Latex particles which are advantageous according to the invention are those described in the following documents: US Pat. No. 5,663,213 and EP 0 761 201. Particularly advantageous latex particles are those which are formed from water and styrene / acrylate copolymers and, for. B. are available under the trade name "Alliance SunSphere" from Rohm & Haas.

Advantageous UV-A filter substances for the purposes of the present invention are dibenzoyl methane dehvate, in particular 4- (tert-butyl) -4'-methoxydibenzoyl methane (CAS No. 70356-09-1), which is available from Givaudan under the Parsol brand ^® 1789 and is sold by Merck under the trade name Eusolex® 9020.

Advantageous further UV filter substances in the sense of the present invention are sulfonated, water-soluble UV filters, such as. For example: • phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its 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 with the INCI name Disodium Phenyl Dibenzimidazole Tetrasulfonate (CAS No .: 180898-37-7) , which is available, for example, from Haarmann & Reimer under the trade name Neo Heliopan AP;

• Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (CAS No. 27503-81-7), which is available, for example, under the trade name Eusolex 232 from Merck or under Neo Heliopan Hydro from Haarmann &Reimer; 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene (also: 3,3 '- (1,4-phenylenedimethylene)) -bis- (7,7-dimethyl-2-oxo -bicyclo- [2.2.1] hept-1-ylmethane sulfonic acid) and its salts (especially the corresponding 10-sulfato compounds, especially the corresponding sodium, potassium or triethanolammonium salt), which is also called benzene-1,4 -di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) Benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) has the INCI name Terephthalic Dicampher Sulfonic Acid (CAS No .: 90457-82-2) and is available, for example, under the trade name Mexoryl SX from Chimex; sulfonic acid derivatives of 3-benzylidene camphor, such as 4- (2-oxo-3-bomylidene) methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidenemethyl) sulfonic acid and their salts.

Advantageous UV filter substances for the purposes of the present invention are also benzoxazole derivatives, which are distinguished by the following structural formula,

wherein R ¹ , R ² and R ^{3 are} independently selected from the group of branched or unbranched, saturated or unsaturated alkyl radicals having 1 to 10 carbon atoms. It is particularly advantageous according to the invention to choose the radicals R ¹ and R ^{2 the} same, in particular from the group of the branched alkyl radicals having 3 to 5 carbon atoms. It is furthermore particularly advantageous for the purposes of the present invention if R ^{3 is} an unbranched or branched alkyl radical having 8 carbon atoms, in particular the 2-ethylhexyl radical. Benzoxazole derivative which is particularly preferred according to the invention is 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylhexyl) -imino-1, 3,5-triazine with CAS No. 288254-16-0, which is characterized by the structural formula

distinguished and is available from 3V Sigma under the trade name Uvasorb® K2A.

The benzoxazole derivative (s) are advantageously present in dissolved form in the cosmetic preparations according to the invention. However, it may also be advantageous if the benzoxazole derivative or derivatives in pigmentary, ie. H. undissolved form - for example in particle sizes from 10 nm to 300 nm.

Advantageous UV filter substances in the sense of the present invention are also so-called hydroxybenzophenones. Hydroxybenzophenones are characterized by the following structural formula:

wherein • R ¹ and R ^{2 are} independently hydrogen, dC d-alkyl, C ₃ -C ₁₀ cycloalkyl or C ₃ -Cι ₀ cycloalkenyl, the substituents R ¹ and R ² together with the nitrogen atom to which they are attached , can form a 5- or 6-ring and

• R ^{3 represents} a CrC ^ alkyl radical.

A particularly advantageous hydroxybenzophenone for the purposes of the present invention is 2- (4'-diethylamino-2'-hydoxybenzoyl) benzoic acid hexyl ester (also: aminobenzophenone), which is distinguished by the following structure:

and is available under the Uvinul A Plus from BASF.

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

Advantageous broadband filters or UV-B filter substances are, for example, triazine derivatives, such as. B.

• 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (INCI: bis-ethylhexyloxyphenol methoxyphenyl triazine ), which is available under the trade name Tinosorb® S from CIBA-Chemicals GmbH;

• Dioctylbutylamidotriazon (INCI: Diethylhexyl Butamido Triazone), which is available under the trade name UVASORB HEB from Sigma 3V;

• 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester), also: 2,4,6-tris [anilino - (p-carbo-2'-ethyl-r-hexyloxy)] - 1,3,5-triazine (INCI: ethylhexyl

Triazone), which is sold by BASF Aktiengesellschaft under the trade name UVINUL® T 150;

• 2- [4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazin-2-yl] -5- (octyloxy) phenol (CAS No .: 2725-22-6). An advantageous broadband filter in the sense of the present invention is also the 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol ) (INCI: Methylene Bis-Benztriazolyl Tetramethylbutylphenol), which is available, for example, under the trade name Tinosorb® M from CIBA-Chemicals GmbH.

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-tetramethyl-1- [(trimethylsilyl) oxy] disiloxanyl] propyl] phenol (CAS No .: 155633-54-8) with the INCI name Drometrizole Trisiloxane.

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

• 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;

4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;

2,4,6-Thanilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine;

• esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) ester;

• esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;

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

• UV filters bound to polymers.

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

Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bomylidene methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene methyl) sulfonic acid and salts thereof. A further light protection filter substance according to the invention to be used advantageously is ethylhexyl-2-cyano-3,3-diphenyl acrylate, sold under the name Uvinul ^® N 539 T is available (octocrylene) from BASF.

Particularly advantageous preparations in the sense of the present invention, which are distinguished by a high or very high UV-A protection, preferably contain, in addition to the filter substance (s) according to the invention, further UV-A and / or broadband filters, in particular dibenzoylmethane dehvate [ for example the 4- (tert-butyl) -4'-methoxydibenzoylmethane] and / or the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine and / or phenylene-1,4, bis (2-benzimidazyl) -3,3'-5,5'-tetrasuifonic acid bis-sodium salt in each case individually or in any Combinations with each other.

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

The preparations according to the present invention advantageously contain the substances which absorb UV radiation in the UV-A and / or UV-B range in a total amount of, for. B. 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 20 wt .-%, in particular 1, 0 to 15.0 wt .-%, each based on the total weight of the preparations to cosmetic To provide preparations that protect the hair or skin from the entire range of ultraviolet radiation.

The preparations according to the present invention can furthermore advantageously also contain self-tanning substances, such as, for example, dihydroxyacteon and / or melanin derivatives in concentrations of 0.1% by weight to 5% by weight, in particular 0.5 to 3% by weight, in each case based on the total weight of the preparation.

The following examples are intended to illustrate the present invention without restricting it. Unless otherwise stated, all quantities, parts and percentages are based on the weight and the total amount or on the total weight of the preparations. Example 1 (foam-shaped O / W cream):

Emulsion I% by weight

PEG-100 stearate 1, 00

Cetheareth-20 2.00

Steareth-2 0.80

Glyceryl stearate 1, 00

Cetylstearyl alcohol 2.00

Hydrogenated coconut glycerides 1, 00

Caprylic / Capric Triglyceride 3.00

Lauroyl sarcosinate, sodium salt 1.00

Cyclomethicone 4.00

Glycerin 5.00

Ascorbic acid 3.00

EDTA 0.20

Xanthan gum 0.20

Sodium hydroxide q.s.

Conservation q.s.

Perfume q.s.

Water demineralizes Ad 100 pH adjusted to 6.5-7.0

To produce the foam, 90% by volume of the emulsion is foamed with 10% by volume of a propellant gas mixture of propane and butane *. ^a The foaming can e.g. B. done by blowing gas into the preparations or beating, shaking, spraying or stirring in the relevant gas atmosphere (violently).

Example 2 (foam-shaped O / W cream)

Emulsion 1% by weight

PEG-100 stearate 0.80

Cetheareth-20 2.00

Steareth-2 0.80

Cetylstearyl alcohol 2.00

Hydrogenated coconut glycerides 1, 00

Caprylic / Capric Triglyceride 3.00

Octyldodecanol 2.00

Lauroyl sarcosinate, sodium salt 1.00

Cyclomethicone 4.00

Glycerin 5.00

Panthenol 1.00

Xanthan gum 0.10

Sodium hydroxide q.s.

Conservation q.s.

Perfume q.s.

Water demineralizes Ad 100 pH adjusted to 6.0-7.0

To produce the foam, 95% by volume of the emulsion is foamed with 5% by volume of a propellant gas mixture of propane and butane in an aluminum aerosol can.

Example 3 (OW emulsion make-up):

Emulsion 1 wt%

PEG-100 stearate 1, 00

Cetheareth-20 2.00

Steareth-2 0.80

Cetylstearyl alcohol 2.00

Glyceryl stearate 1, 50

Hydrogenated coconut glycerides 1, 00

Caprylic / Capric Triglyceride 3.00

Mica 1, 00

Iron oxide 1.00

Titanium dioxide 4.00

Lauroyl sarcosinate, sodium salt 1.00

Cyclomethicone 4.00

Glycerin 7.50

Panthenol 1, 00

Xanthan gum 0.10

Sodium hydroxide q.s.

Conservation q.s.

Perfume q.s.

Water demineralizes Ad 100 pH adjusted to 6.0-7.0

Example 4 (foam-shaped O / W sun protection cream):

Emulsion 1% by weight

PEG-100 stearate 0.80

Cetheareth-20 2.00

Steareth-2 0.80

Glyceryl stearate 2.00

Cetylstearyl alcohol 2.00

Myristyl myristate 1, 00

Caprylic / Capric Triglycehde 2.00

Lauroyl sarcosinate, sodium salt 1.00

Cyclomethicone 3.00

Ethyl hexyl methoxycinnamate 5.00

Bis-ethylhexyloxyphenol-methoxyphenyl-1, 00 triazines

Glycerin 5.00

Ascorbic acid 1, 00

Xanthan gum 0.20

EDTA 0.20

Sodium hydroxide q.s.

Conservation q.s.

Perfume q.s.

Water demineralizes Ad 100 pH adjusted to 6.5-7.0

To produce the foam, 90% by volume of the emulsion is foamed with 10% by volume of a propellant gas mixture of propane and butane ^* .

⁸ The foaming can e.g. B. done by blowing gas into the preparations or beating, shaking, spraying or stirring in the relevant gas atmosphere (violently). Example 5 (foam-shaped O / W sun protection cream):

Emulsion 1% by weight

PEG-100 stearate 0.80

Cetheareth-20 2.00

Steareth-2 0.70

Glyceryl stearate 1, 00

Cetylstearyl alcohol 1.00

Myristyl myristate 2.00

Caprylic / Capric Triglyceride 2.00

Dicaprylyl ether 1, 00

Cyclomethicone 3.00

2-ethylhexyl-2-cyano-3-diphenyl acrylate 5.00

(Octocrylene)

Butyl methoxydibenzoyl methane 2.00

Glycerin 7.00

Alpha glycosyl rutin 0.10

Panthenol 1, 00

EDTA 0.20

Xanthan gum 0.10

Sodium hydroxide q.s.

Conservation q.s.

Perfume q.s.

Water demineralizes Ad 100 pH adjusted to 5.0-6.0

To produce the foam, 90% by volume of the emulsion is foamed with 10% by volume of a propellant gas mixture of propane and butane *. ^a The foaming can e.g. B. done by blowing gas into the preparations or beating, shaking, spraying or stirring in the relevant gas atmosphere (violently). Example 6 (foam-like OW cream)

Emulsion II% by weight

Polyglyceryl-3-methyl glucose distearate 2.00

Sorbitan stearate 2.00

Cetylstearyl alcohol 2.00

Hydrogenated coconut glycerides 1, 00

Mineral oil 2.00

Octyldodecanol 1.00

Lauroyl sarcosinate, sodium salt 1.00

Cyclomethicone 4.00

Glycerin 5.00

Ascorbic acid 1, 00

EDTA 0.20

Xanthan gum 0.10

Sodium hydroxide q.s.

Conservation q.s.

Perfume q.s.

Water demineralizes Ad 100 pH adjusted to 6.5-7.0

Example 7 (Foam O / W Cream)

Emulsion II% by weight

Polyglyceryl-3-methylglucose distearate 2.50

Sorbitan stearate 1.50

Cetyl alcohol 1.00

Myristyl myristate 2.00

Caprylic / Capric Triglyceride 2.00

Octyldodecanol 1.00

Cyclomethicone 3.00

Glycerin 7.00

Panthenol 0.50

Coenzyme Q10 0.05

Xanthan gum 0.10

Sodium hydroxide q.s.

Conservation q.s.

Perfume q.s.

Water demineralizes Ad 100 pH adjusted to 6.5-7.0

To produce the foam, 90% by volume of the emulsion is foamed with 10% by volume of a propellant gas mixture of propane and butane *.

⁸ The foaming can e.g. B. done by blowing gas into the preparations or beating, shaking, spraying or stirring in the relevant gas atmosphere (violently).

Example 8 (foam-shaped O / W sun protection cream):

Emulsion II% by weight

Polyglyceryl-3-methyl glucose distearate 2.00

Sorbitan stearate 1, 00

Cetylstearyl alcohol 3.00

Hydrogenated coconut glycerides 1, 00

Ethyl hexyl methoxycinnamate 5.00

Bis-ethylhexyloxyphenol-methoxyphenyl-1, 00 triazines

Ethylhexyltriazon 1.00

Octyldodecanol 1.00

Tocopheryl acetate 1.00

Lauroyl sarcosinate, sodium salt 1.00

Cyclomethicone 4.00

Glycerin 5.00

Ascorbic acid 1, 00

EDTA 0.20

Xanthan gum 0.20

Sodium hydroxide q.s.

Conservation q.s.

Perfume q.s.

Water demineralizes Ad 100 pH adjusted to 6.5-7.0

⁸ The foaming can e.g. B. done by blowing gas into the preparations or beating, shaking, spraying or stirring in the relevant gas atmosphere (violently). Example 9 (foam-shaped O / W cream):

Emulsion II% by weight

Polyglyceryl-3-methyl glucose distearate 2.00

Sorbitan stearate 1, 50

Cetyl alcohol 1, 50

Myristyl myristate 1, 00

Caprylic / Capric Triglyceride 2.00

Octyldodecanol 2.00

Cyclomethicone 2.00

Butyl methoxydibenzoyl methane 1.00

Ethyl hexyl methoxycinnamate 5.00

Glycerin 5.00

Panthenol 0.50

Alpha glycosyl rutin 0.10

Xanthan gum 0.10

Sodium hydroxide q.s.

Conservation q.s.

Perfume q.s.

Water demineralizes Ad 100 pH adjusted to 5.0-6.0

Claims

claims:

1. Foamable cosmetic or dermatological preparations containing

A) at least one emulsifier selected from the group: polyglyceryl-3-methylglucose distearate and PEG ester and / or PEG ether with 30 to 100 ethoxy units of the following structure (n between 30 and 100):

R ¹ - (CH ₂ -CH ₂ -0) _n -R ² , in which R1 and R2 are selected independently of one another from the group: hydrogen, alkyl and acyl radicals having 12 to 40 carbon atoms, B) at least one coemulsifier selected from the Group: saturated and / or unsaturated, branched and / or unbranched fatty alcohols with a chain length of 10 to 28 carbon atoms, glyceryl stearate and C) at least one foam-stabilizing surfactant, selected from the group: N-acyl sarcosinates with a chain length of 10 to 28 carbon atoms,

Polyglycosides with a chain length of 10 to 28 carbon atoms and acylglutamates with a chain length of 10 to 28 carbon atoms.

2. Preparation according to one of the preceding claims, characterized in that the emulsifier or emulsifiers (A) are selected from the group:

PEG-9 stearate, PEG-8 distearate, PEG-20 stearate, PEG-8 stearate, PEG-8 oleate, PEG-25 glyceryl trioleate, PEG-40 sorbitan lanolate, PEG-15 glyceryl ricinoleate, PEG-20 Glyceryl stearate, PEG-20 glyceryl isostearate, PEG-20 glyceryl oleate, PEG-20 stearate, PEG-20 methylglucose sesquistearate, PEG-30 glyceryl isostearate, PEG-20 glyceryl laurate, PEG-30 stearate, PEG-30 glyceryl , PEG-40 stearate, PEG-30-

Glyceryl laurate, PEG-50 stearate, PEG-100 stearate, PEG-150 laurate.

3. Preparation according to one of the preceding claims, characterized in that the or the co-emulsifiers (B) are selected from the group: butyl octanol, butyl decanol, hexyl octanol, hexyl decanol, octyl dodecanol, behenyl alcohol (C ₂₂ H ₄₅ OH), cetearyl alcohol [a Mixture of cetyl alcohol (C ₁₆ H ₃₃ OH) and stearyl alcohol (C ₁₈ H ₃₇ OH)], lanolin alcohols (wool wax alcohols, which represent the unsaponifiable alcohol fraction of the wool wax that is obtained after the saponification of wool wax)

4. Preparation according to one of the preceding claims, characterized in that it contains at least one water-soluble active ingredient.

5. Preparation according to claim 4, characterized in that the or the water-soluble active ingredients are selected from the group ascorbic acid and derivatives, extracts of green tea, proteases, lipases, flavonoids, isoflavonoids, creatine and derivatives, panthenol and amino acids or their derivatives.

6. Preparation according to one of claims 4 or 5, characterized in that the or the water-soluble active ingredients are selected from the group ascorbic acid and / or flavonoids.

7. Preparation according to one of claims 4 to 6, characterized in that the or the water-soluble active ingredients are present in a concentration of 0.001 to 5 wt .-%, based on the total weight of the preparations.

8. Preparation according to one of the preceding claims, characterized in that a) as an emulsifier, a combination of an ester of polyethylene glycol with one or more polyethylene glycol alkyl ethers, b) as co-emulsifiers, glyceryl monostearate in combination with one or more fatty alcohols, c) as a foam-stabilizing surfactant, an N -Acyl sarcosinate, d) as a water-soluble active ingredient ascorbic acid, extract of green tea and / or

Flavonoids can be chosen.

9. Preparation according to one of the preceding claims, characterized in that a) as an emulsifier, an alkyl polyglycoside, b) as a coemulsifier, sorbitan stearate in combination with one or more fatty alcohols, c) as a foam-stabilizing surfactant, an N-acyl sarcosinate, d) ascorbic acid, creatine and / or isoflavonoids are chosen as the water-soluble active ingredient.

10. Preparation according to one of the preceding claims, characterized in that the total amount of emulsifiers (one or more compounds) from the

Range from 0.5 to 20 wt .-%, based on the total weight of the formulation can be selected.

11. Preparation according to one of the preceding claims, characterized in that it contains one or more substances selected from the group of moisturizers.

12. A process for the production of foams, characterized in that preparations according to one of claims 1 to 11 when removed from a pressurized gas container with the aid of a) linear and / or branched-chain, halogenated and / or non-halogenated hydrocarbons, b) carbon dioxide, Oxygen, compressed air and / or nitrogen and / or c) dimethyl ether are foamed.

13. The method according to claim 12, characterized in that the compressed gas containers are in the form of cylindrical vessels.

14. The method according to claim 12, characterized in that the compressed gas containers consist of metal or non-splintering glass or plastic.

15. The method according to claim 12, characterized in that the compressed gas container consist of protected, splintering glass or protected, splintering plastic.

16. Use of foamable cosmetic or dermatological preparations containing A. at least one emulsifier selected from the group: polyglyceryl-3-methylglucose distearate and PEG ester and / or PEG ether with 30 to 100 ethoxy units of the following structure (n between 30 and 100):

R - (CH ₂ -CH ₂ -O) _n -R ² , in which R1 and R2 are selected independently of one another from the group:

Hydrogen, alkyl and acyl radicals with 12 to 40 carbon atoms,

B. at least one co-emulsifier selected from the group: saturated and / or unsaturated, branched and / or unbranched fatty alcohols with a chain length of 10 to 28 carbon atoms, glyceryl stearate and

C. at least one foam-stabilizing surfactant, selected from the group: N-acyl sarcosinates with a chain length of 10 to 28 carbon atoms, polyglycosides with a chain length of 10 to 28 carbon atoms and acyl glutamates with a chain length of 10 to 28 carbon atoms as cosmetic or dermatological basis for water-sensitive, hydrophilic active substances.