+

WO1996037187A1 - Cosmetic or dermatological preparations containing phytic acid - Google Patents

Cosmetic or dermatological preparations containing phytic acid Download PDF

Info

Publication number
WO1996037187A1
WO1996037187A1 PCT/EP1996/002197 EP9602197W WO9637187A1 WO 1996037187 A1 WO1996037187 A1 WO 1996037187A1 EP 9602197 W EP9602197 W EP 9602197W WO 9637187 A1 WO9637187 A1 WO 9637187A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
hair
skin
cosmetic
preparations
Prior art date
Application number
PCT/EP1996/002197
Other languages
German (de)
French (fr)
Inventor
Tobias Mann
Anja MÜLLER
Susann Richert
Gerhard Sauermann
Volker Schreiner
Original Assignee
Beiersdorf Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beiersdorf Ag filed Critical Beiersdorf Ag
Priority to JP8535379A priority Critical patent/JPH11505818A/en
Priority to EP96917399A priority patent/EP0827392A1/en
Publication of WO1996037187A1 publication Critical patent/WO1996037187A1/en

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/66Phosphorus compounds
    • A61K31/661Phosphorus acids or esters thereof not having P—C bonds, e.g. fosfosal, dichlorvos, malathion or mevinphos
    • A61K31/6615Compounds having two or more esterified phosphorus acid groups, e.g. inositol triphosphate, phytic acid
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/14Liposomes; Vesicles
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36Carboxylic acids; Salts or anhydrides thereof
    • A61K8/365Hydroxycarboxylic acids; Ketocarboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/55Phosphorus compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00Drugs for dermatological disorders
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P43/00Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • A61Q1/04Preparations containing skin colorants, e.g. pigments for lips
    • A61Q1/06Lipsticks
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/51Chelating agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52Stabilizers
    • A61K2800/522Antioxidants; Radical scavengers

Definitions

  • the invention relates to active ingredients and cosmetic or dermatological preparations, in particular topical preparations, which alleviate the consequential damage of substances with an oxidizing effect or acute or chronic light exposure, in particular exposure to ultraviolet light, and those which have an oxidizing effect before the consequential damage or acute or chronic light UV exposure protect, i.e. act preventively.
  • UVA radiation is also the cause of numerous phototoxic and photo-allergic reactions. It can also increase the harmful effects of UVB radiation.
  • ketoproteins result from an oxidative modification of side groups of amino acid residues of the protein. A carbonyl group is introduced into these side chains with the participation of strong oxidizing agents (for example H 2 0 2 ).
  • strong oxidizing agents for example H 2 0 2 .
  • ketoproteins also serve as markers for the UV or oxygen radical-induced damage to proteins of the epidermis. Human hair is also exposed to the damaging effects of UV light and weathered as it ages, among other things due to the oxidative splitting of stabilizing disulfide bridges.
  • high concentrations of hydrogen peroxides are used in a large number of hair dyeing processes, which may possibly cause damage to the hair substance as a side effect.
  • the photochemical reaction products are predominantly radical compounds, for example hydroxyl radicals.
  • Undefined radical photo products which arise in the skin and hair itself, can also initiate uncontrolled subsequent reactions due to their high reactivity.
  • singlet oxygen, a non-radical, excited and very reactive state of the oxygen molecule can occur with UV radiation, just as short-lived epoxies and many others.
  • UV radiation also belongs to ionizing radiation. There is therefore a risk that ionic species will also be formed on UV exposure, which in turn, e.g. can oxidatively intervene in biochemical processes of the skin
  • Typical UVB filters are derivatives of 3-benzylidene camphor, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone and 2-phenylbenzimidazole. To protect the skin from UVA radiation, certain derivatives of dibenzoylmethane are mostly used.
  • UV filters pose the following problems for the consumer: They only have a protective, but no therapeutic effect. To ensure optimal protection, the filter substances must cover the skin permanently with an even and evenly distributed film. However, these requirements can hardly be met, since wrinkles permeate the surface of the skin and the user often moves or sweats in water under sunlight. In addition, UV filters can harbor a certain risk of irritation for mucous membranes and occasionally cause a burning sensation on sensitive areas of the skin (stinging potential).
  • topical preparations are admixed with UV-reflecting or UV-scattering substances.
  • Substances such as titanium dioxide or zinc oxide fulfill this task, but give the preparations an unattractive, whitish color. In addition, it is not always possible to adequately fix these substances on the skin surface.
  • antioxidants and / or radical scavengers can also be added to cosmetic or dermatological preparations.
  • Antioxidants are substances that prevent oxidation processes in the surrounding medium (skin, hair or product).
  • Antioxidants which are used in the fields of cosmetics and pharmacy are, for example, ⁇ -tocopherol, in particular in the form of ⁇ -tocopherol acetate, butylated hydroxyanisole and butylated hydroxytoluene.
  • vitamin E a substance with a known antioxidative, that is to say oxygen radical neutralizing, effect in sunscreen formulations, but the effect achieved here still falls short of the hoped-for effect.
  • An object of the present invention was to eliminate the disadvantages of the prior art.
  • an active ingredient or preparations containing this active ingredient should be made available, the use of which can reduce or reduce the damage to the skin and / or hair due to oxidative influence, for example by reducing the formation of ketoproteins.
  • a further object of the present invention was to provide cosmetic preparations in particular which counteract the aging of the hair or before or after treatment of the hair with bleaching agents or hair dye preparations, even those with a high content of strong oxidizing agents, for example hydrogen peroxide, the harmful oxidizing effect of which.
  • the invention relates to the use of phytic acid or its salts for the prophylaxis and treatment of damaging oxidative effects on the skin or the hair.
  • the invention also relates to the use of cosmetic or dermatological preparations containing phytic acid or its salts for the prophylaxis and treatment of damaging oxidative effects on the skin or the hair.
  • Topical preparations are preferred.
  • Phytic acid (myo-inositol hexaphosphate, international free name: fytic acid) is known and described in the literature ("Römpp Chemie Lexikon", 9th edition, Georg Thieme Verlag, Stuttgart, DE, p. 3431 (1991) and "The Merck Index, 11 Edition, Merck & Co., Inc., Rahway, USA, p. 1172 (1989).
  • the invention also relates to combinations of active substances containing one or more active substances selected from the group of phytic acid and its salts in combination with one or more active substances selected from the group of chelating agents.
  • Preferred chelating agents are alpha-hydroxy fatty acids and their salts or deferoxamine and its acid addition salts.
  • active ingredients also extends to the active ingredient combinations and preparations with them.
  • cosmetic or dermatological preparations characterized by a content of an active ingredient combination containing one or more active ingredients, selected from the group of phytic acid and its salts in combination with an active ingredient or more active ingredients, selected from the group of chelating agents, are the subject of Invention.
  • Topical preparations are preferred.
  • Combinations are preferred which contain one or more alpha-hydroxy fatty acids as chelating agents and / or deferoxamine.
  • the invention also relates to the use of active substance combinations containing one or more active substances, selected from the group of phytic acid and its salts, in combination with an active substance or more active substances, selected from the group of chelating agents, for the prophylaxis and treatment of damaging oxidative effects on the skin or hair.
  • cosmetic or dermatological preparations characterized by a content of a combination of active substances, containing one or more active substances, selected from the group of phytic acid and its salts in combination with one or more active substances, selected from the group of chelating agents, for the prophylaxis and treatment of damaging oxidative effects on the skin or the hair.
  • Mixtures of alpha-hydroxy fatty acids can be formed by two, more or even a larger number of compounds and contain these compounds in different amounts by weight.
  • fractions from natural sources can have a larger number due to Have homologues or structural isomers, however, synthesized acids can consist of one compound each.
  • the alpha-hydroxy fatty acids according to the invention can be straight-chain or branched.
  • the saturated, aliphatic alpha-hydroxy fatty acids are preferred.
  • Preferred alpha-hydroxy fatty acids according to the invention contain 8 to 20 carbon atoms, but in particular 14 to 18 carbon atoms, particularly preferably 16 carbon atoms. Mixtures of the fatty acids in such areas are also advantageous.
  • alpha-hydroxy fatty acids and their salts are particularly preferred:
  • alpha-hydroxy fatty acids obtained from wool wax can also be used, e.g. Alpha-hydroxy fatty acid mixtures obtainable according to known isolation processes (DE-A-2 04 321) which are obtained from wool wax acid mixtures. They are preferably obtained as a D-enantiomer mixture. The individual compounds obtainable by known processes are also preferred.
  • alpha-hydroxy fatty acids according to the invention are known or can be obtained by known processes. Racemates obtained in the synthesis can be split into the isomers in customary processes.
  • Preferred salts of the active compounds according to the invention are compatible salts, in particular water-soluble salts, for example the sodium or potassium salts.
  • the active compounds according to the invention are preferably used in the acid form.
  • ⁇ -Hydroxy fatty acids are natural components of the lipid membranes present in the human horny layer. They are bound to the sphingosine of ceramides 4, 5 and 61 or 611 in an amide-like manner and can be released by an enzyme present in the horny layer, ceramidase. They have no UV-absorbing properties and are therefore not attributable to the filter substances.
  • ⁇ -Hydroxypalmitic acid is regarded as a particularly advantageous ⁇ -hydroxy fatty acid in the sense of the present invention.
  • the ⁇ -hydroxypalmitic acid is a natural component of the wool wax acid ⁇ of sheep, which is also a source of this active ingredient for cosmetic or dermatological preparations.
  • Deferoxamine is known from the literature and the free international short name for desferrioxamine or also 30-amino-3,14,25-trihydroxy-3,9, 14,20,25-pentaazatriacontan-2, 10, 13,21, 24-pentaon ("Römpp Chemie Lexikon", 9th edition, Georg Thieme Verlag, Stuttgart, p. 876 (1991) and "The Merck Index", 11th edition, Merck & Co., Inc., Rahway, USA, p. 449 ( 1989).
  • Preferred acid addition salts are compatible salts, especially water soluble salts, e.g. the hydrochloride.
  • oxidative action is to be understood both to mean the action of substances having an oxidizing action and also the oxidative action of radiation, namely light, in particular UV light and the secondary products caused thereby.
  • damage are meant those effects which cause undesirable changes in the skin or hair, for example aging, or ketoprotein formation but, for example, not the desired bleaching effect of hair bleaches or, for example, the desired effect of hair colors.
  • the active substances and preparations according to the invention are distinguished in that they alleviate the consequential damage of oxidizing substances or acute or chronic light exposure, in particular exposure to ultraviolet light, and protect them from the consequential damage of oxidizing substances or acute or chronic light exposure or UV exposure, i.e. preventively Act.
  • the active compounds and preparations according to the invention reduce the formation of ketoproteins in the skin and reduce or prevent the skin changes or skin damage which occur with skin aging, in particular endogenous skin aging and photoaging of the skin. They have a preventive effect, but they can also repair damage that has already occurred.
  • the active substances and preparations according to the invention for the prophylaxis and treatment of skin changes and skin damage caused by skin aging, in particular endogenous skin aging and photoaging of the skin and ketoprotein formation.
  • the active substances and preparations according to the invention can be used with UVA and / or UVB radiation.
  • the hair is also subject to a constant aging process, which is mainly based on oxidative effects.
  • the dye chromophore is formed by the reaction of precursors (phenols, aminophenols, more rarely diamines) and bases (mostly p-phenylenediami ⁇ ) with the oxidizing agent, mostly hydrogen peroxide. Hydrogen peroxide concentrations around 6% are usually used.
  • the hydrogen peroxide also has a bleaching effect.
  • oxidatively colored human hair similar to bleached hair, microscopic holes can be detected at the places where Meianingranuia was present.
  • the oxidizing agent hydrogen peroxide not only reacts with the color precursors but also with the hair substance and can cause damage to the hair.
  • Oxidative agents that can cause damage are also used for bleaching hair and shaping hair.
  • the invention particularly relates to the use of the active compounds and preparations according to the invention for the prophylaxis and treatment of hair damage caused by hair cosmetics, e.g. Bleaching agents, colorants and shaping agents.
  • hair cosmetics e.g. Bleaching agents, colorants and shaping agents.
  • Proteins better prevent ketoprotein formation in the skin, reduce the aging effect, protect the skin against photoreactions, better absorb the skin
  • the cosmetic or dermatological preparations or formulations according to the invention can be composed as usual and can be used for the treatment, care and cleaning of the skin and / or hair and as a make-up product in decorative cosmetics.
  • phytic acid or its Salt They contain e.g. 0.001 to 20 wt .-%, preferably 0.1 wt .-% to 10 wt .-%, but in particular 0.1 wt .-% to 3 wt .-%, each based on the total weight of the preparations of phytic acid or its Salt.
  • the proportion of the active compound combinations according to the invention in the preparations is, for example 0.001 to 10% by weight, preferably 0.1% to 5% by weight, but in particular 0.1% to 1% by weight, in each case based on the total weight of the preparations.
  • the weight ratio of the phytic acid or its salts to that of the chelating agent is advantageously 20: 1 to 1:20, preferably 5: 1 to 1: 5, particularly preferably approximately 2: 1 to 1: 2.
  • the cosmetic and dermatological preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics. Preparations for the treatment and care of the skin are particularly preferred.
  • Cosmetic and dermatological preparations according to the invention can be in various forms.
  • they can be a solution, an anhydrous preparation, an emulsion or microemission of the water-in-oil (W / O) or oil-in-water (O / W) type, multiple emulsions, for example of the water- in-oil-in-water (W / O / W), a gel, a solid stick, an ointment or an aerosol.
  • W / O water-in-oil
  • O / W oil-in-water
  • An advantageous embodiment of the present invention is therefore also the use of active substances according to the invention for protecting the skin and / or hair from oxidative damage, in particular this use of the active substances according to the invention in shampoos and washing formulations.
  • the cosmetic and dermatological preparations according to the invention can contain cosmetic auxiliaries as are usually used in such preparations, e.g. Preservatives, bactericides, perfumes, substances to prevent foaming, dyes, pigments that have a coloring effect, thickeners, surface-active substances, emulsifiers, 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.
  • cosmetic auxiliaries e.g. Preservatives, bactericides, perfumes, substances to prevent foaming, dyes, pigments that have a coloring effect, thickeners, surface-active substances, emulsifiers, 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 stabilizer
  • the active compounds according to the invention can also be combined with antioxidants for the effects according to the invention.
  • Such combinations are also the subject of the invention, as are the uses as have already been stated for the active compounds.
  • antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as favorable antioxidants.
  • the antioxidants are advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, Imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine,
  • D-carnosine, L-camosine and their derivatives e.g. anserine
  • carotenoids e.g. carotenoids
  • Carotenes e.g. ⁇ -carotene, ⁇ -carotene, lycopene
  • Carotenes e.g. ⁇ -carotene, ⁇ -carotene, lycopene
  • Chlorogenic acid and its derivatives e.g., Chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g., Chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g., Chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g., Chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g., Chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g., Chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g., Chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g., Chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g.
  • Dihydrolipoic acid Dihydrolipoic acid
  • aurothioglucose e.g., aurothioglucose
  • propylthiouracil e.g., thioie
  • Derivatives esters, ethers, peptides, lipids, nucleotides, nucleosides and salts
  • sulfoximine compounds e.g. buthionine sulfoximines
  • Heptathioninsulfoximine in very low tolerable doses (e.g. pmol to ⁇ mol / kg), humic acid, bile acid, bile extracts, bilirubin, biliverdin,
  • Ascorbyl palmitate Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and
  • Derivatives e.g. vitamin E acetate
  • vitamin A and derivatives vitamin A palmitate
  • coniferyl benzoate of the benzin resin rutinic acid and its derivatives
  • Stilbenes and their derivatives e.g. stilbene oxide, trans-stilbene oxide
  • derivatives suitable according to the invention salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids
  • the amount of the aforementioned antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05-20% by weight, in particular 1-10% by weight, based on the total weight of the Preparation.
  • vitamin E and / or its derivatives represent the antioxidant or antioxidants, it is advantageous to have their respective concentrations in the range of 0.001-10% by weight, based on the total weight of the formulation.
  • vitamin A or vitamin A derivatives or carotenes or their derivatives represent the antioxidant or antioxidants, it is advantageous to use their respective concentrations in the range from 0.001-10% by weight, based on the total weight of the formulation, to choose.
  • Emulsions according to the invention are advantageous and contain e.g. the said fats, oils, waxes and other fat bodies, as well as water and an emulsifier, as is usually used for such a type of formulation.
  • oils such as triglycerides of capric or caprylic acid, but preferably castor oil;
  • Fats, waxes and other natural synthetic and / or partially synthetic fat bodies preferably esters of fatty acids with alcohols of low C number, e.g. with isopropanol, propylene glycol or glycerin, or esters of fatty alcohols with low C number alkanoic acids or with fatty acids;
  • Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.
  • saturated compounds such as hydrocarbons of natural or synthetic origin (petroleum jelly, squalane)
  • the aqueous phase of the preparations according to the invention advantageously advantageously contains alcohols, diols or polyols of low C number, and also their ethers, preferably ethanol, isopropanol, 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 analogous products, furthermore alcohols of low carbon number, for example ethanol, isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickeners, which one or more can advantageously be selected from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, e.g.
  • hyaluronic acid, xanthan gum, hydroxypropylmethyl cellulose particularly advantageously from the group of the polyacrylates, preferably a polyacrylate from the group of the so-called carbopoles, for example carbopoles of types 980, 981, 1382, 2984, 5984, or also of types ETD ( Easy-to-disperse) 2001, 2020, 2050, each individually or in any combination with each other.
  • carbopoles for example carbopoles of types 980, 981, 1382, 2984, 5984, or also of types ETD ( Easy-to-disperse) 2001, 2020, 2050, each individually or in any combination with each other.
  • Water can also be a component of alcoholic solvents.
  • Emulsions according to the invention are advantageous and contain e.g. the fats, oils, waxes and other fat bodies mentioned, as well as water and an emulsifier, as is usually used for such a type of formulation.
  • Gels according to the invention usually contain alcohols of low carbon number, for example ethanol, isopropanol, 1, 2-propanediol, glycerin, and water or an 'abovementioned oil in the presence of a thickener, preferably in oily-alcoholic gels is silicon dioxide or an aluminum silicate, in the case of aqueous-alcoholic or alcoholic gels is preferably a polyacrylate.
  • alcohols of low carbon number for example ethanol, isopropanol, 1, 2-propanediol, glycerin, and water or an 'abovementioned oil in the presence of a thickener, preferably in oily-alcoholic gels is silicon dioxide or an aluminum silicate, in the case of aqueous-alcoholic or alcoholic gels is preferably a polyacrylate.
  • Suitable propellants for preparations according to the invention which can be sprayed from aerosol containers are the customary, known volatile, liquefied propellants, for example hydrocarbons (propane, butane, isobutane), which can be used alone or in a mixture with one another. Compressed air can also be used advantageously.
  • hydrocarbons propane, butane, isobutane
  • Preparations according to the invention can also advantageously contain substances which absorb UV radiation in the UVB range, the Total amount of the filter substances is, for example, 0.1% to 30% by weight, preferably 0.5 to 10% by weight, in particular 1.0 to 6.0% by weight, based on the total weight of the preparations, to provide cosmetic preparations that protect the hair or skin from the entire range of ultraviolet radiation. They can also serve as a sunscreen for the hair or skin.
  • the emulsions according to the invention contain UVB filter substances, they can be oil-soluble or water-soluble.
  • Oil-soluble UVB filters which are advantageous according to the invention are, for example:
  • 3-benzylidene camphor derivatives preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;
  • 4-aminobenzoic acid derivatives preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;
  • Esters of cinnamic acid preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;
  • esters of salicylic acid preferably salicylic acid (2-ethylhexyl) ester, salicylic acid (4-isopropylbenzyl) ester, salicylic acid homomethyl ester;
  • benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
  • Esters of benzalmalonic acid preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) ester, 2,4,6-trianiiino- (p-carbo-2'-ethyl-1 '- hexyloxy) -1, 3,5-triazine.
  • Salts of 2-phenylbenzimidazole-5-sulfonic acid such as its sodium, potassium or triethanolammonium salt, and also the sulfonic acid itself;
  • Sulfonic acid derivatives of benzophenones preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;
  • Sulfonic acid derivatives of 3-benzylidene camphor e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene methyl) sulfonic acid and their salts.
  • UVB filters mentioned, which can be used in combination with the active compounds according to the invention, should of course not be limiting.
  • the invention also relates to the use of the active compounds according to the invention with at least one UVB filter as an antioxidant or the use of the active compounds according to the invention with at least one UVB filter in a cosmetic or dermatological preparation.
  • UVA filters can also be advantageous to combine active ingredients according to the invention with UVA filters.
  • suitable are those which have hitherto usually been contained in cosmetic preparations.
  • These substances are preferably derivatives of dibenzoylmethane, in particular 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione and 1-phenyl-3- (4 '-isopropylphenyl) propane-1,3-dione.
  • These combinations or preparations containing these combinations are also the subject of the invention.
  • the quantities used for the UVB combination can be used.
  • the invention also relates to the use of a combination of the active compounds according to the invention with at least one UVA filter or the use of a combination of the active compounds according to the invention with at least one UVA filter in a cosmetic or dermatological preparation.
  • the invention also relates to the use of a combination of the active compounds according to the invention with at least one UVA filter and at least one UVB filter or the use of a combination of Active substances according to the invention with at least one UVA filter and at least one UVB filter in a cosmetic or dermatological preparation.
  • Cosmetic and dermatological preparations with an effective content of active substances according to the invention can also contain inorganic pigments which are usually used in cosmetics to protect the skin from UV rays. These are oxides of titanium, zinc, iron, zirconium, silicon, manganese, aluminum, cerium and mixtures thereof, as well as modifications in which the oxides are the active agents. It is particularly preferred to use pigments based on titanium dioxide.
  • UVA filter and pigment or preparations containing this combination are also the subject of the invention.
  • the amounts given for the above combinations can be used.
  • Cosmetic and dermatological preparations for protecting the hair from UV rays according to the invention are, for example, shampooing agents, preparations which are used when rinsing the hair before or after the shampooing, before or after the permanent wave treatment, before or after the coloring or discoloration of the Hair is applied to preparations for blow-drying or pickling hair, preparations for coloring or decolouring, to a styling and treatment lotion, a hair lacquer or to permanent waving agents.
  • the combinations with UV filters and UV protective substances have the effects described for the active substances and can be used in the same way.
  • the cosmetic and dermatological preparations contain active substances and auxiliaries as are usually used for this type of preparations for hair care and hair treatment.
  • auxiliaries Preservatives, surface-active substances, substances to prevent foaming, thickening agents, emulsifiers, fats, oils, waxes, organic solvents, bactericides, perfumes, dyes or pigments, the task of which is to dye the hair or the cosmetic or dermatological preparation itself, electrophoresis , Substances against greasy hair.
  • Electrolytes for the purposes of the present invention are water-soluble alkali metal, ammonium, alkaline earth metal (including magnesium) and zinc salts of inorganic anions and any mixtures of such salts, it being necessary to ensure that these salts are pharmaceutically or cosmetically harmless award.
  • the anions according to the invention are preferably selected from the group of chlorides, sulfates and hydrogen sulfates, phosphates, hydrogen phosphates and linear and cyclic oligophosphates as well as carbonates and hydrogen carbonates.
  • Cosmetic preparations which are a skin cleansing agent or shampooing agent preferably contain at least one anionic, non-ionic or amphoteric surface-active substance, or else mixtures of such substances, active substance combinations according to the invention in an aqueous medium and auxiliaries as are usually used therefor.
  • the surface-active substance or the mixtures of these substances can be present in the shampoo in a concentration of between 1% and 50% by weight.
  • the cosmetic or dermatological preparations are in the form of a lotion which is rinsed out and used, for example, before or after decolorization, before or after shampooing, between two shampooing steps, before or after permanent wave treatment, these are, for example, aqueous or aqueous alcoholic solutions, which may contain surface-active substances, the concentration of which may be between 0.1 and 10% by weight, preferably between 0.2 and 5% by weight.
  • aqueous or aqueous alcoholic solutions which may contain surface-active substances, the concentration of which may be between 0.1 and 10% by weight, preferably between 0.2 and 5% by weight.
  • These cosmetic or dermatological preparations can also be aerosols with the auxiliaries usually used for them.
  • a cosmetic preparation in the form of a lotion that is not rinsed out, in particular a lotion for inlaying the hair, a lotion used for blow-drying the hair, a styling and treatment lotion generally provides an aqueous, alcoholic or aqueous-alcoholic solution represents and contains at least one cationic, anionic, non-ionic or amphoteric polymer or mixtures thereof, as well as active ingredient combinations according to the invention in effective concentration.
  • the amount of the polymers used is e.g. between 0.1 and 10% by weight, preferably between 0.1 and 3% by weight.
  • Cosmetic preparations for the treatment and care of the hair which contain active ingredients according to the invention, can be present as emulsions which are of the non-ionic or anionic type.
  • non-ionic emulsions contain oils or fatty alcohols, which can also be polyethoxylated or polypropoxylated, for example, or also mixtures of the two organic components.
  • These emulsions may contain cationic surface-active substances.
  • cosmetic preparations for the treatment and care of the hair can be in the form of gels which, in addition to an effective content of active compound combinations according to the invention and the solvents usually used for them, preferably water, and also organic thickeners, for example gum arabic, xanthan gum, sodium alginate, cellulose derivatives, preferably methyl cellulose, hydroxymethyl cellulose , Hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose or inorganic thickeners, for example aluminum silicates such as bentonites, or a mixture of polyethylene glycol and polyethylene glycol stearate or distearate.
  • organic thickeners for example gum arabic, xanthan gum, sodium alginate, cellulose derivatives, preferably methyl cellulose, hydroxymethyl cellulose , Hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose or inorganic thickeners, for example aluminum silicates such as bentonites, or a mixture of
  • the thickener is contained in the gel, for example, in an amount between 0.1 and 30% by weight, preferably between 0.5 and 15% by weight.
  • the amount of the active compounds according to the invention in an agent intended for the hair is preferably 0.05% by weight to 10% by weight, in particular 0.5% by weight to 5% by weight, based on the total weight of the agent.
  • Aqueous cosmetic cleaning agents according to the invention or water-free or anhydrous cleaning agent concentrates intended for aqueous cleaning can contain anionic, nonionic and / or amphoteric surfactants, for example
  • Cosmetic preparations which are cosmetic cleaning preparations for the skin, can be in liquid or solid form.
  • they preferably contain at least one anionic, nonionic or amphoteric surface-active substance or mixtures thereof, if desired one or more electrolytes and auxiliaries of the kind usually used for this purpose.
  • the surface-active substance can be present in the cleaning preparations in a concentration between 1 and 94% by weight, based on the total weight of the preparations.
  • Cosmetic preparations which are a shampooing agent preferably contain, in addition to an effective content of active ingredients according to the invention, at least one anionic, nonionic or amphoteric surface-active substance or mixtures thereof, optionally an electrolyte and auxiliary according to the invention, as are usually used therefor.
  • the surface-active substance can be present in the shampoo in a concentration between 1% by weight and 94% by weight.
  • compositions according to the invention contain water and, if appropriate, the additives customary in cosmetics, for example perfume, thickeners, dyes, deodorants, antimicrobial substances, lipid-replenishing agents, complexing and sequestering agents, pearlescent agents, plant extracts, vitamins, active ingredients and the like.
  • the additives customary in cosmetics for example perfume, thickeners, dyes, deodorants, antimicrobial substances, lipid-replenishing agents, complexing and sequestering agents, pearlescent agents, plant extracts, vitamins, active ingredients and the like.
  • the present invention also encompasses a cosmetic or dermatological method for protecting the skin and hair from oxidative or photooxidative processes, which is characterized in that a cosmetic agent which contains an effective concentration of active compound combinations according to the invention is sufficient Apply a lot to the skin or hair.
  • the active substances according to the invention can be used individually or as a mixture of several active substances and can also be contained individually or as a mixture in the preparations.
  • the invention also relates to the process for the preparation of the cosmetic compositions according to the invention, which is characterized in that active ingredients according to the invention are incorporated into cosmetic and dermatological formulations in a manner known per se. This can e.g. done by stirring or emulsifying.
  • Vitamin E acetate 2.00
  • Titanium dioxide 1.00
  • Paraffin oil, pigments and dyes ad 100.00
  • Vitamin E acetate 2.00
  • Titanium dioxide 1.00
  • Paraffin oil, pigments and dyes ad 100.00
  • Titanium dioxide 1.00

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dermatology (AREA)
  • Organic Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Emergency Medicine (AREA)
  • Cosmetics (AREA)

Abstract

The object of the invention comprises the use of phytic acid or its salts for the prevention and treatment of damaging oxidative effects on the skin or hair and also combinations containing one or more active agents selected from the group of phytic acid and its salts in combination with one or more agents selected from the chelating agent group.

Description

Beschreibung description
Kosmetische oder dermatologische Zubereitungen mit einem Gehalt an PhytinsäureCosmetic or dermatological preparations containing phytic acid
Die Erfindung betrifft Wirkstoffe und kosmetische oder dermatologische Zubereitungen, insbesondere topische Zubereitungen, die die Folgeschäden oxidierend wirkender Substanzen oder einer akuten oder chronischen Lichtexposition, insbesondere einer Ultraviolettlichtexposition, lindern und die vor den Folgeschäden oxidierend wirkender Substanzen oder einer akuten oder chronischen Licht-UV-Exposition schützen, also präventiv wirken.The invention relates to active ingredients and cosmetic or dermatological preparations, in particular topical preparations, which alleviate the consequential damage of substances with an oxidizing effect or acute or chronic light exposure, in particular exposure to ultraviolet light, and those which have an oxidizing effect before the consequential damage or acute or chronic light UV exposure protect, i.e. act preventively.
Die schädigenden Effekte des Sonnenlichtes sind gut beschrieben. Dabei verursachen Strahlen im Bereich zwischen 290 nm und 320 nm, dem sogenannten UVB-Bereich, akut bei Überschreitung einer minimalen Dosis ein Erythem, einen einfachen Sonnenbrand. Als ein Maximum der Erythemwirksamkeit wird der engere Bereich um 308 nm angegeben.The damaging effects of sunlight are well described. Rays in the range between 290 nm and 320 nm, the so-called UVB range, cause an erythema, a simple sunburn, when a minimum dose is exceeded. The narrower range around 308 nm is given as a maximum of the erythema effectiveness.
Über diesen Akutschaden hinaus kann Sonnenlicht, irisbesondere im UVA- Bereich von 320 nm bis 400 nm, bei wiederholter, also chronischer Exposition kumulativ schädigend wirksam sein und eine Schädigung der elastischen und kollagenen Fasern der Haut verursachen. Dieser Prozeß wird als Photoalterung der Haut bezeichnet. Er überlagert und beschleunigt den natürlichen Alterungsprozess der Haut und bedingt deren zunehmende Schlaffheit und Faltigkeit. Darüberhinaus gehören die sichtbare Gefäßerweiterung (Couperosis), lokale Fehlpigmentierungen (z.B. Altersflecken), die vergrößerte Anfälligkeit gegenüber mechanischem Streß (z.B. Rissigkeit) zum Symptomkomplex der photogealterten, also chronisch UVA-exponierten Haut. Alle diese Phänomene sind detailliert im Handbook of Nonprescription Drugs, 7th Ed. Chapter 26, pp: 499-511 (Am. Pharmaceutical Association, Washington, D.C., 1982) beschrieben.In addition to this acute damage, sunlight, in particular in the UVA range from 320 nm to 400 nm, can be cumulatively damaging in repeated, ie chronic, exposure and can damage the elastic and collagen fibers of the skin. This process is called Called photoaging of the skin. It overlays and accelerates the natural aging process of the skin and causes its increasing flaccidity and wrinkles. In addition, visible vasodilation (couperosis), local incorrect pigmentation (e.g. age spots), increased susceptibility to mechanical stress (e.g. cracking) are part of the symptom complex of photo-aged, i.e. chronically exposed to UVA. All of these phenomena are detailed in the Handbook of Nonprescription Drugs, 7th Ed. Chapter 26, pp: 499-511 (Am. Pharmaceutical Association, Washington, DC, 1982).
UVA-Strahlung ist auch die Ursache zahlreicher phototoxischer und photo¬ allergischer Reaktionen. Ferner kann sie den schädigenden Einfluß der UVB- Strahlung verstärken.UVA radiation is also the cause of numerous phototoxic and photo-allergic reactions. It can also increase the harmful effects of UVB radiation.
Letztlich liegt ein großer Teil der Ursachen für die zuvor aufgeführten makroskopischen Phänomene der Photoalterung in Funktionsstörungen der Hautzellen begründet, deren enzym- also proteinkatalysierte, biochemische Aktivität (Hautmetabolismus) durch den Photoalterungsprozess signifikant eingeschränkt ist. Zum anderen sind von der Schädigung durch chronische UV- Exposition Gerüst- und Strukturproteine (z.B. Keratine, Mikrofilamente) in- und außerhalb der Zellen betroffen, die beispielsweise die mechanischen Eigenschaften des Zellverbandes Haut ausmachen. Dabei kann die UV- Strahlung zu photochemischen Reaktionen führen, wobei die photochemischen Reaktionsprodukte in alle Ebenen des Hautmetabolismus eingreifen.Ultimately, a large part of the causes of the macroscopic phenomena of photoaging mentioned above are due to functional disorders of the skin cells, whose enzyme-catalyzed biochemical activity (skin metabolism) is significantly restricted by the photoaging process. On the other hand, damage caused by chronic UV exposure affects scaffolding and structural proteins (e.g. keratins, microfilaments) inside and outside the cells, which, for example, make up the mechanical properties of the skin cell structure. UV radiation can lead to photochemical reactions, with the photochemical reaction products intervening in all levels of skin metabolism.
Eine Ursache des endogenen und durch äußere Einflüsse beschleunigten Hautalterungsprozesses ist eine Zunahme des Gehaltes an Ketoproteinen in der Homschicht. Ketoproteine entstehen durch eine oxidative Modifikation von Seitengruppen von Aminosäureresten des Proteins. In diese Seitenketten wird eine Carbonylgruppe unter Mitwirkung von starken Oxidationsmitteln (z.B. H202) eingeführt. Ketoproteine dienen aber auch als Marker für den UV- bzw. Sauerstoffradikal-induzierten Schaden an Proteinen der Epidermis. Auch menschliches Haar ist dem schädigenden Effekten des UV-Lichtes ausgesetzt und verwittert im Verlauf seiner Alterung u.a. durch oxidative Aufspaltung von stabilisierenden Disulfidbrücken. Weiterhin werden bei einer Vielzahl von Haarfärbeprozessen hohe Konzentrationen an Wasserstoffperoxiden eingesetzt, die möglicherweise als Nebenwirkung eine Schädigung der Haarsubstanz bedingen können.One cause of the endogenous skin aging process, which is accelerated by external influences, is an increase in the content of ketoproteins in the homolayer. Ketoproteins result from an oxidative modification of side groups of amino acid residues of the protein. A carbonyl group is introduced into these side chains with the participation of strong oxidizing agents (for example H 2 0 2 ). However, ketoproteins also serve as markers for the UV or oxygen radical-induced damage to proteins of the epidermis. Human hair is also exposed to the damaging effects of UV light and weathered as it ages, among other things due to the oxidative splitting of stabilizing disulfide bridges. Furthermore, high concentrations of hydrogen peroxides are used in a large number of hair dyeing processes, which may possibly cause damage to the hair substance as a side effect.
Vorwiegend handelt es sich bei den photochemischen Reaktionsprodukten um radikalische Verbindungen, beispielsweise Hydroxyradikale. Auch Undefinierte radikalische Photoprodukte, weiche in der Haut und Haaren selbst entstehen, können aufgrund ihrer hohen Reaktivität unkontrollierte Folgereaktionen initiieren. Aber auch Singulettsauerstoff, ein nichtradikalischer, angeregter und sehr reaktiver Zustand des Sauerstoffmoleküls kann bei UV-Bestrahlung auftreten, ebenso kurzlebige Epoxide und viele andere.The photochemical reaction products are predominantly radical compounds, for example hydroxyl radicals. Undefined radical photo products, which arise in the skin and hair itself, can also initiate uncontrolled subsequent reactions due to their high reactivity. But also singlet oxygen, a non-radical, excited and very reactive state of the oxygen molecule can occur with UV radiation, just as short-lived epoxies and many others.
Ferner zählt UV-Strahlung zur ionisierenden Strahlung. Es besteht also das Risiko, daß auch ionische Spezies bei UV-Exposition entstehen, welche dann ihrerseits z.B. oxidativ in biochemische Prozesse der Haut eingreifen können.UV radiation also belongs to ionizing radiation. There is therefore a risk that ionic species will also be formed on UV exposure, which in turn, e.g. can oxidatively intervene in biochemical processes of the skin
Um diesen Reaktionen vorzubeugen und den Schutz der Haut vor UV- Strahlung zu gewährleisten, werden zahlreiche Verbindungen in topischen Präparaten eingesetzt, die die UVB- und/oder UVA-Strahlung absorbieren, also filtern.In order to prevent these reactions and to protect the skin from UV radiation, numerous compounds are used in topical preparations which absorb, ie filter, the UVB and / or UVA radiation.
Typische UVB-Filter sind Derivate des 3-Benzylidencamphers, der 4- Aminobenzoesäure, der Zimtsäure, der Salicylsäure, des Benzophenons sowie des 2-Phenylbenzimidazols. Zum Schutz der Haut vor UVA-Strahlung kommen zumeist gewisse Derivate des Dibenzoylmethans zum Einsatz.Typical UVB filters are derivatives of 3-benzylidene camphor, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone and 2-phenylbenzimidazole. To protect the skin from UVA radiation, certain derivatives of dibenzoylmethane are mostly used.
UV-Filter bergen jedoch folgende Probleme für den Verbraucher in sich: Sie entfalten lediglich einen schützenden, jedoch keinen therapeutischen Effekt. Um einen optimalen Schutz zu gewährleisten, müssen die Filtersubstanzen die Haut dauerhaft mit einen gleichmäßigen und gleichverteilten Film überziehen. Diese Voraussetzungen sind jedoch kaum zu erfüllen, da die Hautoberfläche von Fältchen durchsetzt ist und der Anwender sich bei Sonnenlicht häufig auch im Wasser bewegt bzw. schwitzt. Darüberhinaus können UV-Filter ein gewisses Irritatioπsrisiko für Schleimhäute in sich bergen und gelegentlich ein Brenngefühl an empfindlichen Hautpartien verursachen (Stinging-Potential).However, UV filters pose the following problems for the consumer: They only have a protective, but no therapeutic effect. To ensure optimal protection, the filter substances must cover the skin permanently with an even and evenly distributed film. However, these requirements can hardly be met, since wrinkles permeate the surface of the skin and the user often moves or sweats in water under sunlight. In addition, UV filters can harbor a certain risk of irritation for mucous membranes and occasionally cause a burning sensation on sensitive areas of the skin (stinging potential).
Als weiterer, rein physikalischer Schutz werden topischen Zubereitungen UV- reflektierende bzw. UV-streuende Substanzen beigemischt. Stoffe wie Titandioxid bzw. Zinkoxid erfüllen diese Aufgabe, verleihen den Zubereitungen jedoch eine unattraktive, weißliche Farbe. Außerdem gelingt es nicht immer, gerade diese Substanzen auf der Hautoberfläche ausreichend zu fixieren.As a further, purely physical protection, topical preparations are admixed with UV-reflecting or UV-scattering substances. Substances such as titanium dioxide or zinc oxide fulfill this task, but give the preparations an unattractive, whitish color. In addition, it is not always possible to adequately fix these substances on the skin surface.
Um den photochemischen Reaktionen vorzubeugen, können kosmetischen bzw. dermatologischen Zubereitungen auch Antioxidantien und/oder Radikalfänger zugesetzt werden. Antioxidantien sind Substanzen, welche Oxidationsprozesse in dem sie umgebenden Medium (Haut, Haare oder Produkt) verhindern. Antioxidantien, welche auf den Gebieten der Kosmetik und Pharmazie Verwendung finden, sind beispielsweise α-Tocopherol, insbesondere in Form des α-Tocopherolacetats, Butylhydroxyanisols und Butylhydroxytoluol.In order to prevent the photochemical reactions, antioxidants and / or radical scavengers can also be added to cosmetic or dermatological preparations. Antioxidants are substances that prevent oxidation processes in the surrounding medium (skin, hair or product). Antioxidants which are used in the fields of cosmetics and pharmacy are, for example, α-tocopherol, in particular in the form of α-tocopherol acetate, butylated hydroxyanisole and butylated hydroxytoluene.
In den US-Patentschriften 4.144.325 und 4.248.861 sowie zahlreichen anderen Dokumenten ist vorgeschlagen worden, Vitamin E, eine Substanz mit bekannter antioxidativer, sprich sauerstoffradikalneutralisierenden Wirkung in Lichtschutzformulierungen einzusetzen, dennoch bleibt auch hier die erzielte Wirkung hinter der erhofften zurück.In US Pat. Nos. 4,144,325 and 4,248,861 as well as numerous other documents, it has been proposed to use vitamin E, a substance with a known antioxidative, that is to say oxygen radical neutralizing, effect in sunscreen formulations, but the effect achieved here still falls short of the hoped-for effect.
Eine Aufgabe der vorliegenden Erfindung war es, die Nachteile des Standes der Technik zu beseitigen. Insbesondere sollte ein Wirkstoff bzw. Zubereitungen, diesen Wirkstoff enthaltend, zur Verfügung gestellt werden, bei deren Verwendung die Schädigungen der Haut und/oder Haare durch oxidativen Einfluß gemindert oder verringert werden können, z.B. indem die Ketoproteinbildung verringert wird. Eine weitere Aufgabe der vorliegenden Erfindung bestand darin, insbesondere kosmetische Zubereitungen zur Verfügung zu stellen, welche der Haaralterung oder vor oder nach Behandlung des Haares mit Bleichmitteln oder Haarfärbezubereitungen, selbst solcher mit einem hohen Gehalt an starken Oxidationsmitteln, z.B. Wasserstoffperoxid, deren schädigender Oxidationswirkung entgegenwirken.An object of the present invention was to eliminate the disadvantages of the prior art. In particular, an active ingredient or preparations containing this active ingredient should be made available, the use of which can reduce or reduce the damage to the skin and / or hair due to oxidative influence, for example by reducing the formation of ketoproteins. A further object of the present invention was to provide cosmetic preparations in particular which counteract the aging of the hair or before or after treatment of the hair with bleaching agents or hair dye preparations, even those with a high content of strong oxidizing agents, for example hydrogen peroxide, the harmful oxidizing effect of which.
Diese Aufgaben werden gemäß der vorliegenden Erfindung gelöst.These objects are achieved in accordance with the present invention.
Gegenstand der Erfindung ist die Verwendung von Phytinsäure oder deren Salzen zur Prophylaxe und Behandlung von schädigenden oxidativen Einwirkungen auf die Haut oder die Haare.The invention relates to the use of phytic acid or its salts for the prophylaxis and treatment of damaging oxidative effects on the skin or the hair.
Gegenstand der Erfindung ist auch die Verwendung von kosmetischen oder dermatologischen Zubereitungen mit einem Gehalt an Phytinsäure oder deren Salzen zur Prophylaxe und Behandlung von schädigenden oxidativen Einwirkungen auf die Haut oder die Haare.The invention also relates to the use of cosmetic or dermatological preparations containing phytic acid or its salts for the prophylaxis and treatment of damaging oxidative effects on the skin or the hair.
Bevorzugt werden topische Zubereitungen.Topical preparations are preferred.
Phytinsäure (myo-lnosithexaphosphat, internationaler Freiname: Fytinsäure) ist bekannt und in der Literatur beschrieben („Römpp Chemie Lexikon", 9. Auflage, Georg Thieme Verlag, Stuttgart, DE, S. 3431 (1991) und „The Merck Index, 11. Auflage, Merck & Co., Inc., Rahway, USA, S. 1172 (1989).Phytic acid (myo-inositol hexaphosphate, international free name: fytic acid) is known and described in the literature ("Römpp Chemie Lexikon", 9th edition, Georg Thieme Verlag, Stuttgart, DE, p. 3431 (1991) and "The Merck Index, 11 Edition, Merck & Co., Inc., Rahway, USA, p. 1172 (1989).
Gegenstand der Erfindung sind auch Wirkstoffkombinationen, enthaltend einen Wirkstoff oder mehrere Wirkstoffe, ausgewählt aus der Gruppe der Phytinsäure und deren Salzen in Kombination mit einem Wirkstoff oder mehreren Wirkstoffen, ausgewählt aus der Gruppe der Chelatbildner.The invention also relates to combinations of active substances containing one or more active substances selected from the group of phytic acid and its salts in combination with one or more active substances selected from the group of chelating agents.
Bevorzugte Chelatbildner sind alpha-Hydroxyfettsäuren und deren Salze oder Deferoxamin und dessen Säureadditionssalze.Preferred chelating agents are alpha-hydroxy fatty acids and their salts or deferoxamine and its acid addition salts.
Im folgenden erstreckt sich die Bezeichnung „Wirkstoffe'' auch auf die Wirkstoffkombinationen und Zubereitungen damit. Außerdem sind auch kosmetische oder dermatologische Zubereitungen, gekennzeichnet durch einen Gehalt an einer Wirkstoffkombination, enthaltend einen Wirkstoff oder mehrere Wirkstoffe, ausgewählt aus der Gruppe der Phytinsäure und deren Salzen in Kombination mit einem Wirkstoff oder mehreren Wirkstoffen, ausgewählt aus der Gruppe der Chelatbildner, Gegenstand der Erfindung.In the following, the term “active ingredients” also extends to the active ingredient combinations and preparations with them. In addition, cosmetic or dermatological preparations, characterized by a content of an active ingredient combination containing one or more active ingredients, selected from the group of phytic acid and its salts in combination with an active ingredient or more active ingredients, selected from the group of chelating agents, are the subject of Invention.
Bevorzugt werden topische Zubereitungen.Topical preparations are preferred.
Weiterhin werden Kombinationen bevorzugt, die eine oder mehrere alpha- Hydroxyfettsäuren als Chelatbildner und/oder Deferoxamin enthalten.Combinations are preferred which contain one or more alpha-hydroxy fatty acids as chelating agents and / or deferoxamine.
Gegenstand der Erfindung ist auch die Verwendung von Wirkstoffkombinationen, enthaltend einen Wirkstoff oder mehrere Wirkstoffe, ausgewählt aus der Gruppe der Phytinsäure und deren Salzen in Kombination mit einem Wirkstoff oder mehreren Wirkstoffen, ausgewählt aus der Gruppe der Chelatbildner, zur Prophylaxe und Behandlung von schädigenden oxidativen Einwirkungen auf die Haut oder die Haare.The invention also relates to the use of active substance combinations containing one or more active substances, selected from the group of phytic acid and its salts, in combination with an active substance or more active substances, selected from the group of chelating agents, for the prophylaxis and treatment of damaging oxidative effects on the skin or hair.
Außerdem ist auch die Verwendung kosmetischer oder dermatologischer Zubereitungen, gekennzeichnet durch einen Gehalt an einer Wirkstoffkombination, enthaltend einen Wirkstoff oder mehrere Wirkstoffe, ausgewählt aus der Gruppe der Phytinsäure und deren Salzen in Kombination mit einem Wirkstoff oder mehreren Wirkstoffen, ausgewählt aus der Gruppe der Chelatbildner, zur Prophylaxe und Behandlung von schädigenden oxidativen Einwirkungen auf die Haut oder die Haare Gegenstand der Erfindung.In addition, the use of cosmetic or dermatological preparations, characterized by a content of a combination of active substances, containing one or more active substances, selected from the group of phytic acid and its salts in combination with one or more active substances, selected from the group of chelating agents, for the prophylaxis and treatment of damaging oxidative effects on the skin or the hair. Object of the invention.
Gemische von alpha-Hydroxyfettsäuren können von zwei, mehreren aber auch einer größeren Anzahl von Verbindungen gebildet werden und diese Verbindungen in unterschiedlichen Gewichtsmengen enthalten. So können aus natürlichen Quellen stammende Fraktionen eine größere Zahl aufgrund von Homologen oder Strukturisomeren aufweisen, synthetisierte Säuren können dagegen aus jeweils einer Verbindung bestehen.Mixtures of alpha-hydroxy fatty acids can be formed by two, more or even a larger number of compounds and contain these compounds in different amounts by weight. For example, fractions from natural sources can have a larger number due to Have homologues or structural isomers, however, synthesized acids can consist of one compound each.
Die erfindungsgemäßen alpha-Hydroxyfettsäuren können geradkettig oder verzweigt sein. Bevorzugt werden die gesättigten, aliphatischen alpha- Hydroxyfettsäuren.The alpha-hydroxy fatty acids according to the invention can be straight-chain or branched. The saturated, aliphatic alpha-hydroxy fatty acids are preferred.
Bevorzugte erfindungsgemäße alpha-Hydroxyfettsäuren enthalten 8 bis 20 Kohlenstoffatome, insbesondere aber 14 bis 18 Kohlenstoffatome, besonders bevorzugt 16 Kohlenstoffatome. Vorteilhaft sind auch Gemische der in solchen Bereichen liegenden Fettsäuren.Preferred alpha-hydroxy fatty acids according to the invention contain 8 to 20 carbon atoms, but in particular 14 to 18 carbon atoms, particularly preferably 16 carbon atoms. Mixtures of the fatty acids in such areas are also advantageous.
Besonders bevorzugt sind die folgenden alpha-Hydroxyfettsäuren und ihre Salze, insbesondere in der D-Form:The following alpha-hydroxy fatty acids and their salts, in particular in the D form, are particularly preferred:
alpha-Hydroxy-hexadecansäurealpha-hydroxy hexadecanoic acid
(alpha-Hydroxy-palmitinsäure).(alpha-hydroxy-palmitic acid).
Erfindungsgemäß können auch aus Wollwachs gewonnene alpha- Hydroxyfettsäuren eingesetzt werden, z.B. gemäß bekannten Isolierungsverfahren erhältliche alpha-Hydroxy-Fettsäuregemische (DE-A- 2 04 321) die aus Wollwachssäuregemischen gewonnen werden. Sie fallen vorzugsweise als D-Enantiomeren-Gemisch an. Auch die nach bekannten Verfahren erhältlichen Einzelverbindungen sind bevorzugt.According to the invention, alpha-hydroxy fatty acids obtained from wool wax can also be used, e.g. Alpha-hydroxy fatty acid mixtures obtainable according to known isolation processes (DE-A-2 04 321) which are obtained from wool wax acid mixtures. They are preferably obtained as a D-enantiomer mixture. The individual compounds obtainable by known processes are also preferred.
Die erfindungsgemäßen alpha-Hydroxyfettsäuren sind bekannt oder nach bekannten Verfahren erhältlich. In der Synthese anfallende Racemate lassen sich in üblichen Verfahren in die Isomeren aufspalten.The alpha-hydroxy fatty acids according to the invention are known or can be obtained by known processes. Racemates obtained in the synthesis can be split into the isomers in customary processes.
Bevorzugte Salze der erfindungsgemäßen Wirkstoffe sind verträgliche Salze, insbesondere wasserlösliche Salze, z.B. die Natrium- -oder Kaliumsalze. Vorzugsweise werden die erfindungsgemäßen Wirkstoffe in der Säureform eingesetzt. α-Hydroxyfettsäuren sind natürliche Bestandteile der in der menschlichen Hornschicht vorhandenen Lipidmembranen. Sie sind hier amidartig an das Sphingosin der Ceramide 4,5 und 61 bzw. 611 gebunden und können durch ein in der Hornschicht vorhandenes Enzym, die Ceramidase, freigesetzt werden. Sie besitzen keine UV-absorbierenden Eigenschaften und sind somit nicht den Filtersubstanzen zuzurechnen.Preferred salts of the active compounds according to the invention are compatible salts, in particular water-soluble salts, for example the sodium or potassium salts. The active compounds according to the invention are preferably used in the acid form. α-Hydroxy fatty acids are natural components of the lipid membranes present in the human horny layer. They are bound to the sphingosine of ceramides 4, 5 and 61 or 611 in an amide-like manner and can be released by an enzyme present in the horny layer, ceramidase. They have no UV-absorbing properties and are therefore not attributable to the filter substances.
Als besonders vorteilhafte α-Hydroxyfettsäure im Sinne der vorliegenden Erfindung wird die α-Hydroxypalmitinsäure angesehen. Die α- Hydroxypalmitinsäure ist ein natürlicher Bestandteil der Wollwachsäureπ des Schafes, womit zugleich eine Quelle dieses Wirkstoffes für kosmetische oder dermatologische Zubereitungen bezeichnet ist.Α-Hydroxypalmitic acid is regarded as a particularly advantageous α-hydroxy fatty acid in the sense of the present invention. The α-hydroxypalmitic acid is a natural component of the wool wax acid π of sheep, which is also a source of this active ingredient for cosmetic or dermatological preparations.
Die Offenlegungsschrift DE-A- 4204321 beschreibt zwar die desodorierenden Eigenschaften, die Fähigkeit als Konservierungshelfer zu dienen oder Ionen zu binden. Es war aber für den Fachmann nicht vorauszusehen oder der Schrift zu entnehmen, das die erfindungsgemäße Wirkstoffgruppe in den Kombinationen die erfindungsgemäßen Eigenschaften entfalten würde.The published patent application DE-A-4204321 describes the deodorising properties, the ability to serve as preservation aids or to bind ions. However, it was not foreseeable for the person skilled in the art or it could be gathered from the document that the active ingredient group according to the invention in the combinations would develop the properties according to the invention.
Deferoxamin ist aus der Literatur bekannt und die freie internationale Kurzbezeichnung für Desferrioxamin oder auch 30-Amino-3,14,25-trihydroxy- 3,9, 14,20,25-pentaazatriacontan-2, 10, 13,21 ,24-pentaon („Römpp Chemie Lexikon", 9. Auflage, Georg Thieme Verlag, Stuttgart, S. 876 (1991) und „The Merck Index", 11. Auflage, Merck & Co., Inc., Rahway, USA, S. 449 (1989).Deferoxamine is known from the literature and the free international short name for desferrioxamine or also 30-amino-3,14,25-trihydroxy-3,9, 14,20,25-pentaazatriacontan-2, 10, 13,21, 24-pentaon ("Römpp Chemie Lexikon", 9th edition, Georg Thieme Verlag, Stuttgart, p. 876 (1991) and "The Merck Index", 11th edition, Merck & Co., Inc., Rahway, USA, p. 449 ( 1989).
Bevorzugte Säureadditionssalze sind verträgliche Salze, insbesondere wasserlösliche Salze, z.B. das Hydrochlorid.Preferred acid addition salts are compatible salts, especially water soluble salts, e.g. the hydrochloride.
Unter dem Begriff „oxidativer Einwirkung" ist sowohl die Wirkung von oxidierend wirkenden Substanzen zu verstehen als auch die oxidative Wirkung von Strahlung, namentlich Licht, insbesondere UV-Licht und den dadurch hervorgerufenen Folgeprodukten. Mit „schädigend" sind solche Einwirkungen gemeint, die unerwünschte Veränderungen der Haut oder der Haare hervorrufen, z.B. die Alterung, oder Ketoproteinbildung aber z.B. nicht die gewünschte Bleichwirkung von Haarbleichmitteln oder z.B. die gewünschte Wirkung von Haarfarben.The term “oxidative action” is to be understood both to mean the action of substances having an oxidizing action and also the oxidative action of radiation, namely light, in particular UV light and the secondary products caused thereby. By "damaging" are meant those effects which cause undesirable changes in the skin or hair, for example aging, or ketoprotein formation but, for example, not the desired bleaching effect of hair bleaches or, for example, the desired effect of hair colors.
Die erfindungsgemäßen Wirkstoffe und Zubereitungen zeichnen sich dadurch aus, daß sie die Folgeschäden oxidierend wirkender Substanzen oder einer akuten oder chronischen Lichtexposition, insbesondere einer Ultraviolettlichtexposition, lindern und vor den Folgeschäden oxidierend wirkender Substanzen oder einer akuten oder chronischen Lichtexposition oder UV-Exposition schützen, also präventiv wirken.The active substances and preparations according to the invention are distinguished in that they alleviate the consequential damage of oxidizing substances or acute or chronic light exposure, in particular exposure to ultraviolet light, and protect them from the consequential damage of oxidizing substances or acute or chronic light exposure or UV exposure, i.e. preventively Act.
Überraschenderweise wurde auch gefunden, daß die erfindungsgemäßen Wirkstoffe und Zubereitungen die Bildung von Ketoproteinen in der Haut reduzieren und die Hautveränderungen oder Hautschäden, die mit der Hautalterung, insbesondere der endogenen Hautalterung und der Photoalterung der Haut auftreten, verringern oder verhindern. Sie wirken dabei präventiv, aber sie können auch bereits entstandene Schäden beheben.Surprisingly, it has also been found that the active compounds and preparations according to the invention reduce the formation of ketoproteins in the skin and reduce or prevent the skin changes or skin damage which occur with skin aging, in particular endogenous skin aging and photoaging of the skin. They have a preventive effect, but they can also repair damage that has already occurred.
Besonders bevorzugt ist die Verwendung der erfindungsgemäßen Wirkstoffe und Zubereitungen zur Prophylaxe und Behandlung von Hautveränderungen und Hautschäden der Hautalterung, insbesondere der endogenen Hautalterung und der Photoalterung der Haut und der Ketoproteinbildung.It is particularly preferred to use the active substances and preparations according to the invention for the prophylaxis and treatment of skin changes and skin damage caused by skin aging, in particular endogenous skin aging and photoaging of the skin and ketoprotein formation.
Bei der Photoalterung können die erfindungsgemäßen Wirkstoffe und Zubereitungen bei UVA- und/oder UVB-Bestrahlung verwendet werden.In photoaging, the active substances and preparations according to the invention can be used with UVA and / or UVB radiation.
Auch die Haare unterliegen einem ständigen Alterungsprozeß, der überwiegend auf oxidativen Einwirkungen beruht.The hair is also subject to a constant aging process, which is mainly based on oxidative effects.
Soll menschliches Haar dauerhaft gefärbt werden, kommen in der Praxis lediglich oxidierende Haarfärbeverfahren in Betracht. Beim oxidativen Haarfärben erfolgt die Ausbildung des Farbstoffchromophoren durch Reaktion von Präkursoren (Phenole, Aminophenole, seltener auch Diamine) und Basen (meistens p-Phenylendiamiπ) mit dem Oxidationsmittel, zumeist Wasserstoffperoxid. Wasserstoffperoxidkonzentrationen um 6% werden dabei gewöhnlich verwendet.If human hair is to be dyed permanently, in practice only oxidizing hair dyeing processes can be considered. In oxidative hair dyeing, the dye chromophore is formed by the reaction of precursors (phenols, aminophenols, more rarely diamines) and bases (mostly p-phenylenediamiπ) with the oxidizing agent, mostly hydrogen peroxide. Hydrogen peroxide concentrations around 6% are usually used.
Üblicherweise wird davon ausgegangen, daß neben der Färbewirkung auch eine Bleichwirkung durch das Wasserstoffperoxid erfolgt. In oxidativ gefärbtem menschlichem Haar sind, ähnlich wie bei gebleichtem Haar, mikroskopische Löcher an den Stellen, an denen Meianingranuia vorlagen, nachweisbar.It is usually assumed that, in addition to the coloring effect, the hydrogen peroxide also has a bleaching effect. In oxidatively colored human hair, similar to bleached hair, microscopic holes can be detected at the places where Meianingranuia was present.
Es ist nicht auszuschließen, daß das Oxidationsmittel Wasserstoffperoxid nicht nur mit den Farbvorstufen, sondern auch mit der Haarsubstanz reagieren und dabei unter Umständen eine Schädigung des Haares bewirken kann.It cannot be ruled out that the oxidizing agent hydrogen peroxide not only reacts with the color precursors but also with the hair substance and can cause damage to the hair.
Auch zum Bleichen von Haaren und beim Formen der Haare werden oxidativ wirkende Mittel verwendet, die Schäden bewirken können.Oxidative agents that can cause damage are also used for bleaching hair and shaping hair.
Gegenstand der Erfindung ist insbesondere auch die Verwendung der erfindungsgemäßen Wirkstoffe und Zubereitungen zur Prophylaxe und Behandlung von Haarschäden durch Haarkosmetika, z.B. Bleichmittel, Färbemittel und formgebende Mittel.The invention particularly relates to the use of the active compounds and preparations according to the invention for the prophylaxis and treatment of hair damage caused by hair cosmetics, e.g. Bleaching agents, colorants and shaping agents.
Es war für den Fachmann daher nicht vorauszusehen gewesen, daß die erfindungsgemäßen Wirkstoffe bzw. Zubereitungen, diese enthaltendIt was therefore not foreseen by the expert that the active compounds or compositions of the invention comprising these
besser reduzierend auf die Entstehung von Radikalen wirken besser die Bindung von schädlichen Photoprodukten an Lipide, DNS undthe binding of harmful photoproducts to lipids, DNA and has a better reducing effect on the formation of radicals
Proteine verhindern besser die Ketoproteinbildung in der Haut reduzieren besser gegen die Hautalterung wirken besser die Haut gegen Photoreaktionen schützen besser auf die Haut aufziehenProteins better prevent ketoprotein formation in the skin, reduce the aging effect, protect the skin against photoreactions, better absorb the skin
als die Wirkstoffe, Wirkstoffkombinationen und Zubereitungen des Standes der Technik. Die erfindungsgemäßen kosmetischen oder dermatologischen Zubereitungen oder Formulierungen können wie üblich zusammengesetzt sein und zur Behandlung, der Pflege und der Reinigung der Haut und/oder der Haare und als Schminkprodukt in der dekorativen Kosmetik dienen.as the active ingredients, combinations of active ingredients and preparations of the prior art. The cosmetic or dermatological preparations or formulations according to the invention can be composed as usual and can be used for the treatment, care and cleaning of the skin and / or hair and as a make-up product in decorative cosmetics.
Sie enthalten z.B. 0,001 bis 20 Gew.-%, bevorzugt 0,1 Gew.-% bis 10 Gew.-%, insbesondere aber 0,1 Gew.-% bis 3 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zubereitungen an Phytinsäure oder deren Salzen.They contain e.g. 0.001 to 20 wt .-%, preferably 0.1 wt .-% to 10 wt .-%, but in particular 0.1 wt .-% to 3 wt .-%, each based on the total weight of the preparations of phytic acid or its Salt.
Der Anteil der erfindungsgemäßen Wirkstoffkombinationen in den Zubereitungen beträgt z.B. 0.001 bis 10 Gew.-%, bevorzugt 0,1 Gew.-% bis 5 Gew.-%, insbesondere aber 0,1 Gew.-% bis 1 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zubereitungen.The proportion of the active compound combinations according to the invention in the preparations is, for example 0.001 to 10% by weight, preferably 0.1% to 5% by weight, but in particular 0.1% to 1% by weight, in each case based on the total weight of the preparations.
In der Kombination beträgt das Gewichtsverhältnis der Phytinsäure bzw. ihrer Salze zu dem der Chelatbildner vorteilhaft 20 : 1 bis 1 : 20, bevorzugt 5 : 1 bis 1 : 5, insbesondere bevorzugt etwa 2 : 1 bis 1 : 2.In combination, the weight ratio of the phytic acid or its salts to that of the chelating agent is advantageously 20: 1 to 1:20, preferably 5: 1 to 1: 5, particularly preferably approximately 2: 1 to 1: 2.
Zubereitungen zur Prophylaxe, Behandlung und Pflege der Haut werden besonders bevorzugt.Preparations for the prophylaxis, treatment and care of the skin are particularly preferred.
Zur Anwendung werden die erfindungsgemäßen kosmetischen und dermatolo¬ gischen Zubereitungen in der für Kosmetika üblichen Weise auf die Haut und/oder die Haare in ausreichender Menge aufgebracht. Zubereitungen zur Behandlung und Pflege der Haut werden besonders bevorzugt.For use, the cosmetic and dermatological preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics. Preparations for the treatment and care of the skin are particularly preferred.
Erfindungsgemäße kosmetische und dermatologische Zubereitungen können in verschiedenen Formen vorliegen. So können sie z.B. eine Lösung, eine wasserfreie Zubereitung, eine Emulsion oder Mikroemuision vom Typ Wasser¬ in-Öl (W/O) oder vom Typ Öl-in-Wasser (O/W), eine multiple Emulsionen, beispielsweise vom Typ Wasser-in-ÖI-in-Wasser (W/O/W), ein Gel, einen festen Stift, eine Salbe oder auch ein Aerosol darstellen. Es ist auch vorteilhaft, die erfindungsgemäßen Wirkstoffe in verkapselter Form darzureichen, z.B. in Kollagenmatrices und anderen üblichen Verkapselungsmaterialien, z.B. als Celluloseverkapselungen, in Gelatine, Wachsmatrices oder liposomal verkapselt. Insbesondere Wachsmatrices wie sie in der DE-OS 43 08 282 beschrieben werden, haben sich als günstig herausgestellt.Cosmetic and dermatological preparations according to the invention can be in various forms. For example, they can be a solution, an anhydrous preparation, an emulsion or microemission of the water-in-oil (W / O) or oil-in-water (O / W) type, multiple emulsions, for example of the water- in-oil-in-water (W / O / W), a gel, a solid stick, an ointment or an aerosol. It is also advantageous to present the active compounds according to the invention in encapsulated form, for example in collagen matrices and other customary encapsulation materials, for example in the form of cellulose encapsulations, in gelatin, wax matrices or liposomally encapsulated. In particular, wax matrices as described in DE-OS 43 08 282 have been found to be favorable.
Es ist auch möglich und vorteilhaft im Sinne der vorliegenden Erfindung, die erfindungsgemäßen Wirkstoffe in wäßrige Systeme bzw. Tensidzubereitungen zur Reinigung der Haut und der Haare einzufügen.For the purposes of the present invention, it is also possible and advantageous to insert the active compounds according to the invention into aqueous systems or surfactant preparations for cleaning the skin and hair.
Als vorteilhafte Verkörperung der vorliegenden Erfindung wird daher auch die Verwendung erfindungsgemäßer Wirkstoffe zum Schütze der Haut und/oder der Haare vor oxidativer Schädigung angesehen, insbesondere diese Ver¬ wendung der erfindungsgemäßen Wirkstoffe in Shampoos und Wasch- formulierungeπ.An advantageous embodiment of the present invention is therefore also the use of active substances according to the invention for protecting the skin and / or hair from oxidative damage, in particular this use of the active substances according to the invention in shampoos and washing formulations.
Die erfindungsgemäßen kosmetischen und dermatologischen Zubereitungen können kosmetische Hilfsstoffe enthalten, wie sie üblicherweise in solchen Zubereitungen verwendet werden, z.B. Konservierungsmittel, Bakterizide, Parfüme, Substanzen zum Verhindern des Schäumens, Farbstoffe, Pigmente, die eine färbende Wirkung haben, Verdickungsmittel, oberflächenaktive Substanzen, Emulgatoren, weichmachende, anfeuchtende und/oder feuchhaltende Substanzen, Fette, Öle, Wachse oder andere übliche Bestandteile einer kosmetischen oder dermatologischen Formulierung wie Alkohole, Polyole, Polymere, Schaumstabilisatoren, Elektrolyte, organische Lösemittel oder Silikonderivate.The cosmetic and dermatological preparations according to the invention can contain cosmetic auxiliaries as are usually used in such preparations, e.g. Preservatives, bactericides, perfumes, substances to prevent foaming, dyes, pigments that have a coloring effect, thickeners, surface-active substances, emulsifiers, 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.
Insbesondere können die erfindungsgemäßen Wirkstoffe für die erfindungsgemäßen Wirkungen auch mit Antioxidantien kombiniert werden. Auch solche Kombinationen sind Gegenstand der Erfindung wie auch die Verwendungen, wie sie schon für die Wirkstoffe angegeben wurden.In particular, the active compounds according to the invention can also be combined with antioxidants for the effects according to the invention. Such combinations are also the subject of the invention, as are the uses as have already been stated for the active compounds.
Erfindungsgemäß können als günstige Antioxidantien alle für kosmetische und/oder dermatologische Anwendungen geeigneten oder gebräuchlichen Antioxidantien verwendet werden.According to the invention, all the antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as favorable antioxidants.
Vorteilhaft werden die Antioxidantien gewählt aus der Gruppe bestehend aus Aminosäuren (z.B. Glycin, Histidin, Tyrosin, Tryptophan) und deren Derivate, Imidazole (z.B. Urocaninsäure) und deren Derivate, Peptide wie D,L-Carnosin,The antioxidants are advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, Imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine,
D-Carnosin, L-Camosin und deren Derivate (z.B. Anserin), Carotinoide,D-carnosine, L-camosine and their derivatives (e.g. anserine), carotenoids,
Carotine (z.B. α-Carotin, ß-Carotin, Lycopin) und deren Derivate,Carotenes (e.g. α-carotene, β-carotene, lycopene) and their derivatives,
Chlorogensäure und deren Derivate, Liponsäure und deren Derivate (z.B.Chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g.
Dihydroliponsäure), Aurothioglucose, Propylthiouracil und andere Thioie (z.B.Dihydrolipoic acid), aurothioglucose, propylthiouracil and other thioie (e.g.
Thioredoxin, Glutathion, Cystein, Cystin, Cystamin und deren Glycosyl-,Thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl,
N-Acetyl-, Methyl-, Ethyl-, Propyl-, Amyl-, Butyl- und Lauryl-, Palmitoyl-, Oleyl-, γ-Linoleyl-, Cholesteryl- und Glycerylester) sowie deren Salze,N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts,
Dilaurylthiodipropionat, Distearylthiodipropionat, Thiodipropionsäure und derenDilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their
Derivate (Ester, Ether, Peptide, Lipide, Nukleotide, Nukleoside und Salze) sowie Sulfoximinverbindungen (z.B. Buthioninsulfoximine,Derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. buthionine sulfoximines,
Homocysteinsulfoximin, Buthioninsulfone, Penta-, Hexa-,Homocysteine sulfoximine, buthionine sulfones, penta-, hexa-,
Heptathioninsulfoximin) in sehr geringen verträglichen Dosierungen (z.B. pmol bis μmol/kg), Huminsäure, Gallensäure, Gallenextrakte, Bilirubin, Biliverdin,Heptathioninsulfoximine) in very low tolerable doses (e.g. pmol to μmol / kg), humic acid, bile acid, bile extracts, bilirubin, biliverdin,
EDTA, EGTA und deren Derivate, ungesättigte Fettsäuren und deren DerivateEDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives
(z.B. γ-Linolensäure, Linolsäure, Ölsäure), Folsäure und deren Derivate,(e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives,
Ubichinon und Ubichinol und deren Derivate, Vitamin C und Derivate (z.B.Ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g.
Ascorbylpalmitat, Mg-Ascorbylphosphat, Ascorbylacetat), Tocopherole undAscorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and
Derivate (z.B. Vitamin-E-acetat), Vitamin A und Derivate (Vitamin-A-palmitat) sowie Koniferylbenzoat des Beπzoeharzes, Rutinsäure und deren Derivate,Derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) as well as coniferyl benzoate of the benzin resin, rutinic acid and its derivatives,
Butylhydroxytoluol, Butylhydroxyanisol, Nordihydroguajakharzsäure,Butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguanay resin acid,
Nordihydroguajaretsäure, Trihydroxybutyrophenon, Harnsäure und deren' Nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and their '
Derivate, Mannose und deren Derivate, Sesamol, Sesamolin, Zink und dessen Derivate (z.B. ZnO, ZnS04) Selen und dessen Derivate (z.B. Selenmethionin),Derivatives, mannose and their derivatives, sesamol, sesamolin, zinc and their derivatives (e.g. ZnO, ZnS04) selenium and their derivatives (e.g. selenium methionine),
Stilbene und deren Derivate (z.B. Stilbenoxid, Trans-Stilbenoxid) und die erfindungsgemäß geeigneten Derivate (Salze, Ester, Ether, Zucker, Nukleotide, Nukleoside, Peptide und Lipide) dieser genannten Wirkstoffe.Stilbenes and their derivatives (e.g. 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.
Die Menge der vorgenannten Antioxidantien (eine oder mehrere Verbindungen) in den Zubereitungen beträgt vorzugsweise 0,001 bis 30 Gew.- %, besonders bevorzugt 0,05 - 20 Gew.-%, insbesondere 1 - 10 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung.The amount of the aforementioned antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05-20% by weight, in particular 1-10% by weight, based on the total weight of the Preparation.
Sofern Vitamin E und/oder dessen Derivate das oder die Antioxidantien darstellen, ist vorteilhaft, deren jeweilige Konzentrationen aus dem Bereich von 0,001 - 10 Gew.-%, bezogen auf das Gesamtgewicht der Formulierung, zu wählen.If vitamin E and / or its derivatives represent the antioxidant or antioxidants, it is advantageous to have their respective concentrations in the range of 0.001-10% by weight, based on the total weight of the formulation.
Sofern Vitamin A, bzw. Vitamin-A-Derivate, bzw. Carotine bzw. deren Derivate das oder die Antioxidantien darstellen, ist vorteilhaft, deren jeweilige Konzentrationen aus dem Bereich von 0,001 - 10 Gew.-%, bezogen auf das Gesamtgewicht der Formulierung, zu wählen.If vitamin A or vitamin A derivatives or carotenes or their derivatives represent the antioxidant or antioxidants, it is advantageous to use their respective concentrations in the range from 0.001-10% by weight, based on the total weight of the formulation, to choose.
Erfindungsgemäße Emulsionen sind vorteilhaft und enthalten z.B. die ge¬ nannten Fette, Öle, Wachse und anderen Fettkörper, sowie Wasser und einen Emulgator, wie er üblicherweise für einen solchen Typ der Formulierung ver¬ wendet wird.Emulsions according to the invention are advantageous and contain e.g. the said fats, oils, waxes and other fat bodies, as well as water and an emulsifier, as is usually used for such a type of formulation.
Die Lipidphase kann dabei vorteilhaft gewählt werden aus folgender Substanzgruppe:The lipid phase can advantageously be selected from the following group of substances:
natürliche, synthetische und/oder partialsynthetische Öle, wie Trigiyceride der Caprin- oder der Caprylsäure, vorzugsweise aber Rizinusöl;natural, synthetic and / or partially synthetic oils, such as triglycerides of capric or caprylic acid, but preferably castor oil;
Fette, Wachse und andere natürliche synthetische und/oder partialsynthetische Fettkörper, vorzugsweise Ester von Fettsäuren mit Alkoholen niedriger C-Zahl, z.B. mit Isopropanol, Propylenglykol oder Glycerin, oder Ester von Fettalkoholen mit Alkansäuren niedriger C-Zahl oder mit Fettsäuren;Fats, waxes and other natural synthetic and / or partially synthetic fat bodies, preferably esters of fatty acids with alcohols of low C number, e.g. with isopropanol, propylene glycol or glycerin, or esters of fatty alcohols with low C number alkanoic acids or with fatty acids;
Silikonöle wie Dimethylpolysiloxane, Diethylpolysiloxane, Diphenylpolysiloxane sowie Mischformen daraus.Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.
gesättigte Verbindungen wie Kohlenwasserstoffe natürlichen oder synthetischen Ursprungs (Vaseline, Squalan)saturated compounds such as hydrocarbons of natural or synthetic origin (petroleum jelly, squalane)
Die wäßrige Phase der erfindungsgemäßen Zubereitungen enthält gegebenenfalls vorteilhaft Alkohole, Diole oder Polyole niedriger C-Zahl, sowie deren Ether, vorzugsweise Ethanol, Isopropanol, Propylenglykol, Glycerin, Ethylenglykol, Ethylenglykolmonoethyl- oder -monobutylether, Propylenglykolmonomethyl, -monoethyl- oder -monobutylether, Diethylenglykolmonomethyl- oder -monoethylether und analoge Produkte, ferner Alkohole niedriger C-Zahl, z.B. Ethanol, Isopropanol, 1 ,2-Propandiol, Glycerin sowie insbesondere ein oder mehrere Verdickungsmittel, welches oder welche vorteilhaft gewählt werden können aus der Gruppe Siliciumdioxid, Aiuminiumsilikate, Polysaccharide bzw. deren Derivate, z.B. Hyaluronsäure, Xanthangummi, Hydroxypropylmethylcellulose, besonders vorteilhaft aus der Gruppe der Polyacrylate, bevorzugt ein Polyacrylat aus der Gruppe der sogenannten Carbopole, beispielsweise Carbopole der Typen 980, 981 , 1382, 2984, 5984, oder auch der Typen ETD (Easy-to-disperse) 2001 , 2020, 2050, jeweils einzeln oder in beliebigen Kombinationen untereinander.Kombination.The aqueous phase of the preparations according to the invention advantageously advantageously contains alcohols, diols or polyols of low C number, and also their ethers, preferably ethanol, isopropanol, 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 analogous products, furthermore alcohols of low carbon number, for example ethanol, isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickeners, which one or more can advantageously be selected from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, e.g. hyaluronic acid, xanthan gum, hydroxypropylmethyl cellulose, particularly advantageously from the group of the polyacrylates, preferably a polyacrylate from the group of the so-called carbopoles, for example carbopoles of types 980, 981, 1382, 2984, 5984, or also of types ETD ( Easy-to-disperse) 2001, 2020, 2050, each individually or in any combination with each other.
Insbesondere werden Gemische der vorstehend genannten Lösemittel verwendet. Bei alkoholischen Lösemitteln kann Wasser ein weiterer Bestandteil sein.Mixtures of the abovementioned solvents are used in particular. Water can also be a component of alcoholic solvents.
Erfindungsgemäße Emulsionen sind vorteilhaft und enthalten z.B. die genannten Fette, Öle, Wachse und anderen Fettkörper, sowie Wasser und einen Emulgator, wie er üblicherweise für einen solchen Typ der Formulierung verwendet wird.Emulsions according to the invention are advantageous and contain e.g. the fats, oils, waxes and other fat bodies mentioned, as well as water and an emulsifier, as is usually used for such a type of formulation.
Gele gemäß der Erfindung enthalten üblicherweise Alkohole niedriger C-Zahl, z.B. Ethanol, Isopropanol, 1 ,2-Propandiol, Glycerin und Wasser bzw. ein ' vorstehend genanntes Öl in Gegenwart eines Verdickungsmittels, das bei ölig¬ alkoholischen Gelen vorzugsweise Siliciumdioxid oder ein Aluminiumsilikat, bei wäßrig-alkoholischen oder alkoholischen Gelen vorzugweise ein Polyacrylat ist.Gels according to the invention usually contain alcohols of low carbon number, for example ethanol, isopropanol, 1, 2-propanediol, glycerin, and water or an 'abovementioned oil in the presence of a thickener, preferably in oily-alcoholic gels is silicon dioxide or an aluminum silicate, in the case of aqueous-alcoholic or alcoholic gels is preferably a polyacrylate.
Als Treibmittel für erfindungsgemäße, aus Aerosolbehältern versprühbare Zubereitungen sind die üblichen bekannten leichtflüchtigen, verflüssigten Treibmittel, beispielsweise Kohlenwasserstoffe (Propan, Butan, Isobutan) geeignet, die allein oder in Mischung miteinander eingesetzt werden können. Auch Druckluft ist vorteilhaft zu verwenden.Suitable propellants for preparations according to the invention which can be sprayed from aerosol containers are the customary, known volatile, liquefied propellants, for example hydrocarbons (propane, butane, isobutane), which can be used alone or in a mixture with one another. Compressed air can also be used advantageously.
Vorteilhaft können erfindungsgemäße Zubereitungen außerdem Substanzen enthalten, die UV-Strahlung im UVB-Bereich absorbieren, wobei die Gesamtmenge der Filtersubstanzen z.B. 0,1 Gew.-% bis 30 Gew.-%, vorzugsweise 0,5 bis 10 Gew.-%, insbesondere 1 ,0 bis 6,0 Gew.-% beträgt, bezogen auf das Gesamtgewicht der Zubereitungen, um kosmetische Zubereitungen zur Verfügung zu stellen, die das Haar bzw. die Haut vor dem gesamten Bereich der ultravioletten Strahlung schützen. Sie können auch als Sonnenschutzmittel fürs Haar oder die Haut dienen.Preparations according to the invention can also advantageously contain substances which absorb UV radiation in the UVB range, the Total amount of the filter substances is, for example, 0.1% to 30% by weight, preferably 0.5 to 10% by weight, in particular 1.0 to 6.0% by weight, based on the total weight of the preparations, to provide cosmetic preparations that protect the hair or skin from the entire range of ultraviolet radiation. They can also serve as a sunscreen for the hair or skin.
Enthalten die erfindungsgemäßen Emulsionen UVB-Filtersubstanzen, können diese öllöslich oder wasserlöslich sein. Erfindungsgemäß vorteilhafte öllösliche UVB-Filter sind z.B.:If the emulsions according to the invention contain UVB filter substances, they can be oil-soluble or water-soluble. Oil-soluble UVB filters which are advantageous according to the invention are, for example:
3-Benzylidencampher-Derivate, vorzugsweise 3-(4-Methylben- zyliden)camρher, 3-Benzylidencamρher;3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;
4-Aminobenzoesäure-Derivate, vorzugsweise 4-(Dimethylamino)-benzoe- säure(2-ethylhexyl)ester, 4-(Dimethylamino)benzoesäureamylester;4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;
Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure(2- ethylhexyl)ester, 4-Methoxyzimtsäureisopentylester;Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;
Ester der Salicylsäure, vorzugsweise Salicylsäure(2-ethylhexyl)ester, Salicylsäure(4-isopropylbenzyl)ester, Salicylsäurehomomenthylester;Esters of salicylic acid, preferably salicylic acid (2-ethylhexyl) ester, salicylic acid (4-isopropylbenzyl) ester, salicylic acid homomethyl ester;
Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzo- phenon, 2-Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4- methoxybenzophenon;Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzal- malonsäuredi(2-ethylhexyl)ester, - 2,4,6-Trianiiino-(p-carbo-2'-ethyl-1 '- hexyloxy) -1 ,3,5-triazin.Esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) ester, 2,4,6-trianiiino- (p-carbo-2'-ethyl-1 '- hexyloxy) -1, 3,5-triazine.
Vorteilhafte wasserlösliche UVB-Filter sind z.B.:Advantageous water-soluble UVB filters include:
Salze der 2-Phenylbenzimidazol-5-sulfonsäure wie ihr Natrium-, Kalium¬ oder ihr Triethanolammonium-Salz, sowie die Sulfonsäure selbst; Sulfonsäure-Derivate von Benzophenonen, vorzugsweise 2-Hydroxy-4- methoxybenzophenon-5-sulfonsäure und ihre Salze;Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and also the sulfonic acid itself; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;
Sulfonsäure-Derivate des 3-Benzylidencamphers, wie z.B. 4-(2-Oxo-3- bornylidenmethyl)benzolsulfonsäure, 2-Methyl-5-(2-oxo-3-bornylidenme- thyl)sulfonsäure und ihre Salze.Sulfonic acid derivatives of 3-benzylidene camphor, e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene methyl) sulfonic acid and their salts.
Die Liste der genannten UVB-Filter, die in Kombination mit den erfindungsgemäßen Wirkstoffen verwendet werden können, soll selbst¬ verständlich nicht limitierend sein.The list of the UVB filters mentioned, which can be used in combination with the active compounds according to the invention, should of course not be limiting.
Gegenstand der Erfindung ist auch die Verwendung der erfindungsgemäßen Wirkstoffe mit mindestens einem UVB-Filter als Antioxidans bzw. die Verwendung der erfindungsgemäßen Wirkstoffe mit mindestens einem UVB-Filter in einer kosmetischen oder dermatologischen Zubereitung.The invention also relates to the use of the active compounds according to the invention with at least one UVB filter as an antioxidant or the use of the active compounds according to the invention with at least one UVB filter in a cosmetic or dermatological preparation.
Es kann auch von Vorteil sein, erfindungsgemäße Wirkstoffe mit UVA-Fiitern zu kombinieren. Beispielsweise sind solche geeignet, die bisher üblicherweise in kosmetischen Zubereitungen enthalten sind. Bei diesen Substanzen handelt es sich vorzugsweise um Derivate des Dibenzoylmethans, insbesondere um 1- (4'-tert.Butylphenyl)-3-(4'-methoxyphenyl)propan-1 ,3-dion und um 1 -Phenyl-3- (4'-isopropylphenyl)propan-1 ,3-dion. Auch diese Kombinationen bzw. Zubereitungen, die diese Kombinationen enthalten, sind Gegenstand der Erfindung. Es können die für die UVB-Kombination verwendeten Mengen eingesetzt werden.It can also be advantageous to combine active ingredients according to the invention with UVA filters. For example, suitable are those which have hitherto usually been contained in cosmetic preparations. These substances are preferably derivatives of dibenzoylmethane, in particular 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione and 1-phenyl-3- (4 '-isopropylphenyl) propane-1,3-dione. These combinations or preparations containing these combinations are also the subject of the invention. The quantities used for the UVB combination can be used.
Gegenstand der Erfindung ist auch die Verwendung einer Kombination der erfindungsgemäßen Wirkstoffe mit mindestens einem UVA-Filter bzw. die Verwendung einer Kombination der erfindungsgemäßen Wirkstoffe mit mindestens einem UVA-Filter in einer kosmetischen oder dermatologischen Zubereitung.The invention also relates to the use of a combination of the active compounds according to the invention with at least one UVA filter or the use of a combination of the active compounds according to the invention with at least one UVA filter in a cosmetic or dermatological preparation.
Gegenstand der Erfindung ist auch die Verwendung einer Kombination der erfindungsgemäßen Wirkstoffe mit mindestens einem UVA-Filter und mindestens einem UVB-Filter bzw. die Verwendung einer Kombination der erfindungsgemäßen Wirkstoffe mit mindestens einem UVA-Filter und mindestens einem UVB-Filter in einer kosmetischen oder dermatologischen Zubereitung.The invention also relates to the use of a combination of the active compounds according to the invention with at least one UVA filter and at least one UVB filter or the use of a combination of Active substances according to the invention with at least one UVA filter and at least one UVB filter in a cosmetic or dermatological preparation.
Kosmetische und dermatologische Zubereitungen mit einem wirksamen Gehalt an erfindungsgemäßen Wirkstoffen können auch anorganische Pigmente enthalten, die üblicherweise in der Kosmetik zum Schütze der Haut vor UV- Strahlen verwendet werden. Dabei handelt es sich um Oxide des Titans, Zinks, Eisens, Zirkoniums, Siliciums, Mangans, Aluminiums, Cers und Mischungen davon, sowie Abwandlungen, bei denen die Oxide die aktiven Agentien sind. Besonders bevorzugt handelt es sich um Pigmente auf der Basis von Titandioxid.Cosmetic and dermatological preparations with an effective content of active substances according to the invention can also contain inorganic pigments which are usually used in cosmetics to protect the skin from UV rays. These are oxides of titanium, zinc, iron, zirconium, silicon, manganese, aluminum, cerium and mixtures thereof, as well as modifications in which the oxides are the active agents. It is particularly preferred to use pigments based on titanium dioxide.
Auch diese Kombinationen von UVA-Filter und Pigment bzw. Zubereitungen, die diese Kombination enthalten, sind Gegenstand der Erfindung. Es können die für die vorstehenden Kombinationen genannten Mengen verwendet werden.These combinations of UVA filter and pigment or preparations containing this combination are also the subject of the invention. The amounts given for the above combinations can be used.
Bei kosmetischen und dermatologischen Zubereitungen zum Schütze der Haare vor UV-Strahlen gemäß der Erfindung handelt es sich beispielsweise um Shampoonierungsmittel, Zubereitungen, die beim Spülen der Haare vor oder nach der Shampoonierung, vor oder nach der Dauerwellbehandlung, vor oder nach der Färbung oder Entfärbung der Haare angewendet werden, um Zubereitungen zum Fönen oder Einlegen der Haare, Zubereitungen zum Färben oder Entfärben, um eine Frisier- und Behandlungslotion, einen Haarlack oder um Dauerwellmittel.Cosmetic and dermatological preparations for protecting the hair from UV rays according to the invention are, for example, shampooing agents, preparations which are used when rinsing the hair before or after the shampooing, before or after the permanent wave treatment, before or after the coloring or discoloration of the Hair is applied to preparations for blow-drying or pickling hair, preparations for coloring or decolouring, to a styling and treatment lotion, a hair lacquer or to permanent waving agents.
Die Kombinationen mit UV-Filtern und UV-Schutzstoffen haben die für die Wirkstoffe beschriebenen Wirkungen und können in gleicher Weise verwendet werden.The combinations with UV filters and UV protective substances have the effects described for the active substances and can be used in the same way.
Die kosmetischen und dermatologischen Zubereitungen enthalten Wirkstoffe und Hilfsstoffe, wie sie üblicherweise für diesen Typ von Zubereitungen zur Haarpflege und Haarbehandlung verwendet werden. Als Hilfsstoffe dienen Konservierungsmittel, oberflächenaktive Substanzen, Substanzen zum Verhindern des Schäumens, Verdickungsmittel, Emulgatoren, Fette, Öle, Wachse, organische Lösungsmittel, Bakterizide, Parfüme, Farbstoffe oder Pigmente, deren Aufgabe es ist, die Haare oder die kosmetische oder dermatologische Zubereitung selbst zu färben, Elektroyte, Substanzen gegen das Fetten der Haare.The cosmetic and dermatological preparations contain active substances and auxiliaries as are usually used for this type of preparations for hair care and hair treatment. Serve as auxiliaries Preservatives, surface-active substances, substances to prevent foaming, thickening agents, emulsifiers, fats, oils, waxes, organic solvents, bactericides, perfumes, dyes or pigments, the task of which is to dye the hair or the cosmetic or dermatological preparation itself, electrophoresis , Substances against greasy hair.
Unter Elektrolyten im Sinne der vorliegenden Erfindung sind wasserlösliche Alkali-, Ammonium-, Erdalkali- (unter Einbeziehung des Magnesiums) und Zinksalze anorganischer Anionen und beliebige Gemische aus solchen Salzen zu verstehen, wobei gewährleistet sein muß, daß sich diese Salze durch pharmazeutische oder kosmetische Unbedenklichkeit auszeichnen.Electrolytes for the purposes of the present invention are water-soluble alkali metal, ammonium, alkaline earth metal (including magnesium) and zinc salts of inorganic anions and any mixtures of such salts, it being necessary to ensure that these salts are pharmaceutically or cosmetically harmless award.
Die erfindungsgemäßen Anionen werden bevorzugt gewählt aus der Gruppe der Chloride, der Sulfate und Hydrogensulfate, der Phosphate, Hydrogenphosphate und der linearen und cyclischen Oligophosphate sowie der Carbonate und Hydrogencarbonate.The anions according to the invention are preferably selected from the group of chlorides, sulfates and hydrogen sulfates, phosphates, hydrogen phosphates and linear and cyclic oligophosphates as well as carbonates and hydrogen carbonates.
Kosmetische Zubereitungen, die ein Hautreinigungsmittel oder Shampoonierungsmittel darstellen, enthalten vorzugsweise mindestens eine anionische, nicht-ionische oder amphotere oberflächenaktive Substanz, oder auch Gemische aus solchen Substanzen, erfindungsgemäße Wirkstoffkombinationen im wäßrigen Medium und Hilfsmittel, wie sie üblicherweise dafür verwendet werden. Die oberflächenaktive Substanz bzw. die Gemische aus diesen Substanzen können in einer Konzentration zwischen 1 Gew.-% und 50 Gew.-% in dem Shampoonierungsmittel vorliegen.Cosmetic preparations which are a skin cleansing agent or shampooing agent preferably contain at least one anionic, non-ionic or amphoteric surface-active substance, or else mixtures of such substances, active substance combinations according to the invention in an aqueous medium and auxiliaries as are usually used therefor. The surface-active substance or the mixtures of these substances can be present in the shampoo in a concentration of between 1% and 50% by weight.
Liegen die kosmetischen oder dermatologischen Zubereitungen in Form einer Lotion vor, die ausgespült und z.B. vor oder nach der Entfärbung, vor oder nach der Shampoonierung, zwischen zwei Shampoonierungsschritten, vor oder nach der Dauerwellbehandlung angewendet wird, so handelt es sich dabei z.B. um wäßrige oder wäßrig-alkoholische Lösungen, die gegebenenfalls oberflächenaktive Substanzen enthalten, deren Konzentration zwischen 0,1 und 10 Gew.-%, vorzugsweise zwischen 0,2 und 5 Gew.-%, liegen kann. Diese kosmetischen oder dermatologischen Zubereitungen können auch Aerosole mit den üblicherweise dafür verwendeten Hilfsmitteln darstellen.If the cosmetic or dermatological preparations are in the form of a lotion which is rinsed out and used, for example, before or after decolorization, before or after shampooing, between two shampooing steps, before or after permanent wave treatment, these are, for example, aqueous or aqueous alcoholic solutions, which may contain surface-active substances, the concentration of which may be between 0.1 and 10% by weight, preferably between 0.2 and 5% by weight. These cosmetic or dermatological preparations can also be aerosols with the auxiliaries usually used for them.
Eine kosmetische Zubereitung in Form einer Lotion, die nicht ausgespült wird, insbesondere eine Lotion zum Einlegen der Haare, eine Lotion, die beim Fönen der Haare verwendet wird, eine Frisier- und Behandlungslotion, stellt im allgemeinen eine wäßrige, alkoholische oder wäßrig-alkoholische Lösung dar und enthält mindestens ein kationisches, anionisches, nicht-ionisches oder amphoteres Polymer oder auch Gemische derselben, sowie erfindungsgemäße Wirkstoffkombinatonen in wirksamer Konzentration. Die Menge der verwendeten Polymeren liegt z.B. zwischen 0,1 und 10 Gew.-%, bevorzugt zwischen 0,1 und 3 Gew.-%.A cosmetic preparation in the form of a lotion that is not rinsed out, in particular a lotion for inlaying the hair, a lotion used for blow-drying the hair, a styling and treatment lotion, generally provides an aqueous, alcoholic or aqueous-alcoholic solution represents and contains at least one cationic, anionic, non-ionic or amphoteric polymer or mixtures thereof, as well as active ingredient combinations according to the invention in effective concentration. The amount of the polymers used is e.g. between 0.1 and 10% by weight, preferably between 0.1 and 3% by weight.
Kosmetische Zubereitungen zur Behandlung und Pflege der Haare, die erfindungsgemäße Wirkstoffe enthalten, können als Emulsionen vorliegen, die vom nicht-ionischen oder anionischen Typ sind. Nicht-ionische Emulsionen enthalten neben Wasser Öle oder Fettalkohole, die beispielsweise auch polyethoxyliert oder polypropoxyliert sein können, oder auch Gemische aus den beiden organischen Komponenten. Diese Emulsionen enthalten gegebenenfalls kationische oberflächenaktive Substanzen.Cosmetic preparations for the treatment and care of the hair, which contain active ingredients according to the invention, can be present as emulsions which are of the non-ionic or anionic type. In addition to water, non-ionic emulsions contain oils or fatty alcohols, which can also be polyethoxylated or polypropoxylated, for example, or also mixtures of the two organic components. These emulsions may contain cationic surface-active substances.
Erfindungsgemäß können kosmetische Zubereitungen zur Behandlung und Pflege der Haare als Gele vorliegen, die neben einem wirksamen Gehalt an erfindungsgemäßen Wirkstoffkombinationen und dafür üblicherweise verwendeten Lösungsmitteln, bevorzugt Wasser, noch organische Verdickungsmittel, z.B. Gummiarabikum, Xanthangummi, Natriumalginat, Cellulose-Derivate, vorzugsweise Methylcellulose, Hydroxymethylcellulose, Hydroxyethylcellulose, Hydroxypropylcellulose, Hydroxypropylmethylcellulose oder anorganische Verdickungsmittel, z.B. Aluminiumsilikate wie beispielsweise Bentonite, oder ein Gemisch aus Polyethylenglykol und Polyethylenglycolstearat oder -distearat, enthalten. Das Verdickungsmittel ist in dem Gel z.B. in einer Menge zwischen 0,1 und 30 Gew.-%, bevorzugt zwischen 0,5 und 15 Gew.-%, enthalten. Vorzugsweise beträgt die Menge der erfindungsgemäßen Wirkstoffe in einem für die Haare bestimmten Mittel 0,05 Gew.-% bis 10 Gew.-%, insbesondere 0,5 Gew.-% bis 5 Gew.-%, bezogen auf das Gesamtgewicht des Mittels.According to the invention, cosmetic preparations for the treatment and care of the hair can be in the form of gels which, in addition to an effective content of active compound combinations according to the invention and the solvents usually used for them, preferably water, and also organic thickeners, for example gum arabic, xanthan gum, sodium alginate, cellulose derivatives, preferably methyl cellulose, hydroxymethyl cellulose , Hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose or inorganic thickeners, for example aluminum silicates such as bentonites, or a mixture of polyethylene glycol and polyethylene glycol stearate or distearate. The thickener is contained in the gel, for example, in an amount between 0.1 and 30% by weight, preferably between 0.5 and 15% by weight. The amount of the active compounds according to the invention in an agent intended for the hair is preferably 0.05% by weight to 10% by weight, in particular 0.5% by weight to 5% by weight, based on the total weight of the agent.
Erfindungsgemäße wäßrige kosmetische Reinigungsmittel oder für die wäßrige Reinigung bestimmte wasserarme oder wasserfreie Reinigungsmittelkonzentrate können anionische, nichtionische und/oder amphotere Tenside enthalten, beispielsweiseAqueous cosmetic cleaning agents according to the invention or water-free or anhydrous cleaning agent concentrates intended for aqueous cleaning can contain anionic, nonionic and / or amphoteric surfactants, for example
herkömmliche Seifen, z.B. Fettsäuresaize des Natriumsconventional soaps, e.g. Fatty acid salts of sodium
Alkylsulfate, Alkylethersuifate, Alkan- und AlkylbenzolsulfonateAlkyl sulfates, alkyl ether sulfates, alkane and alkyl benzene sulfonates
SulfoacetateSulfoacetates
SulfobetaineSulfobetaines
SarcosinateSarcosinate
AmidosulfobetaineAmidosulfobetaines
SulfosuccinateSulfosuccinates
SulfobernsteinsäurehalbesterSulfosuccinic acid semiesters
AlkylethercarboxylateAlkyl ether carboxylates
Eiweiß-Fettsäure-KondensateProtein fatty acid condensates
Alkylbetaine und AmidobetaineAlkyl betaines and amido betaines
FettsäurealkanolamideFatty acid alkanolamides
Polyglycolether-DerivatePolyglycol ether derivatives
Kosmetische Zubereitungen, die kosmetische Reinigungszubereitungen für die Haut darstellen, können in flüssiger oder fester Form vorliegen. Sie enthalten neben erfindungsgemäßen Wirkstoffkombinationen vorzugsweise mindestens eine anionische, nicht-ionische oder amphotere oberflächenaktive Substanz oder Gemische daraus, gewünschtenfalls einen oder mehrere Elektrolyten und Hilfsmittel, wie sie üblicherweise dafür verwendet werden. Die oberflächenaktive Substanz kann in einer Konzentration zwischen 1 und 94 Gew.-% in den Reinigungszubereitungen vorliegen, bezogen auf das Gesamtgewicht der Zubereitungen.Cosmetic preparations, which are cosmetic cleaning preparations for the skin, can be in liquid or solid form. In addition to the active ingredient combinations according to the invention, they preferably contain at least one anionic, nonionic or amphoteric surface-active substance or mixtures thereof, if desired one or more electrolytes and auxiliaries of the kind usually used for this purpose. The surface-active substance can be present in the cleaning preparations in a concentration between 1 and 94% by weight, based on the total weight of the preparations.
Kosmetische Zubereitungen, die ein Shampoonierungsmittel darstellen, enthalten neben einem wirksamen Gehalt an erfindungsgemäßen Wirkstoffen vorzugsweise mindestens eine anionische, nicht-ionische oder amphotere oberflächenaktive Substanz oder Gemische daraus, gegebenenfalls einen erfindungsgemäßes Elektrolyten und Hilfsmittel, wie sie üblicherweise dafür verwendet werden. Die oberflächenaktive Substanz kann in einer Konzentration zwischen 1 Gew.-% und 94 Gew.-% in dem Shampoonierungsmittel vorliegen.Cosmetic preparations which are a shampooing agent preferably contain, in addition to an effective content of active ingredients according to the invention, at least one anionic, nonionic or amphoteric surface-active substance or mixtures thereof, optionally an electrolyte and auxiliary according to the invention, as are usually used therefor. The surface-active substance can be present in the shampoo in a concentration between 1% by weight and 94% by weight.
Die erfindungsgemäßen Zusammensetzungen enthalten außer den vorgenannten Tensiden Wasser und gegebenenfalls die in der Kosmetik üblichen Zusatzstoffe, beispielsweise Parfüm, Verdicker, Farbstoffe, Desodorantien, antimikrobielle Stoffe, rückfettende Agentien, Komplexierungs- und Sequestrierungsagentien, Perlglanzagentien, Pflanzenextrakte, Vitamine, Wirkstoffe und dergleichen.In addition to the aforementioned surfactants, the compositions according to the invention contain water and, if appropriate, the additives customary in cosmetics, for example perfume, thickeners, dyes, deodorants, antimicrobial substances, lipid-replenishing agents, complexing and sequestering agents, pearlescent agents, plant extracts, vitamins, active ingredients and the like.
Die vorliegende Erfindung umfaßt auch ein kosmetisches oder dermatologisches Verfahren zum Schütze der Haut und der Haare vor oxidati¬ ven bzw. photooxidativen Prozessen, das dadurch gekennzeichnet ist, daß man ein kosmetisches Mittel, welches eine wirksame Konzentration an erfin¬ dungsgemäßen Wirkstoffkombinationen enthält, in ausreichender Menge auf die Haut oder Haare aufbringt.The present invention also encompasses a cosmetic or dermatological method for protecting the skin and hair from oxidative or photooxidative processes, which is characterized in that a cosmetic agent which contains an effective concentration of active compound combinations according to the invention is sufficient Apply a lot to the skin or hair.
Die erfindungsgemäßen Wirkstoffe können einzeln oder als Gemisch mehrerer Wirkstoffe verwendet werden und auch einzeln oder als Gemisch in den Zubereitungen enthalten sein.The active substances according to the invention can be used individually or as a mixture of several active substances and can also be contained individually or as a mixture in the preparations.
Als zweckmäßig hat es sich erwiesen, den pH-Wert der erfindungsgemäßen Zubereitungen z.B. im Bereich von 4 bis 9 einzustellen, insbesondere aber im Bereich pH5 bis pH7.It has proven to be advantageous to adjust the pH of the preparations according to the invention e.g. to be set in the range from 4 to 9, but in particular in the range from pH5 to pH7.
Gegenstand der Erfindung ist auch das Verfahren zur Herstellung der erfindungsgemäßen kosmetischen Mittel, das dadurch gekennzeichnet ist, daß man in an sich bekannter Weise erfindungsgemäße Wirkstoffe in kosmetische und dermatologische Formulierungen einarbeitet. Dies kann z.B. durch Rühren oder Emulgieren geschehen.The invention also relates to the process for the preparation of the cosmetic compositions according to the invention, which is characterized in that active ingredients according to the invention are incorporated into cosmetic and dermatological formulations in a manner known per se. This can e.g. done by stirring or emulsifying.
Die nachfolgenden Beispiele sollen die vorliegende Erfindung verdeutlichen, ohne sie einzuschränken. Alle Mengenangaben, Anteile und Prozentanteile sind, soweit nicht anders angegeben, auf das Gewicht und die Gesamtmenge bzw. auf das Gesamtgewicht der Zubereitungen oder der jeweiligen Mischung bezogen. Die Herstellung der Zubereitungen erfolgt in an sich bekannter Weise.The following examples are intended to illustrate the present invention without restricting it. All quantities, proportions and percentages unless otherwise stated, are based on the weight and the total amount or on the total weight of the preparations or the respective mixture. The preparations are prepared in a manner known per se.
Beispiel 1example 1
W/O CremeW / O cream
Gew.-%% By weight
Paraffinöl 10 ,00Paraffin oil 10.00
Petrolatum 4 ,00Petrolatum 4, 00
Wollwachsalkohol 1,00%Wool wax alcohol 1.00%
PEG-7 Hydriertes Rizinusöl 3,00PEG-7 hydrogenated castor oil 3.00
Aluminumstearat 0,40Aluminum stearate 0.40
Phytinsäure 1,0Phytic acid 1.0
Glycerin 2,00Glycerin 2.00
Wasser, Konservierungsmittel und Parfüm ad 100,00Water, preservatives and perfume ad 100.00
Beispiel 2Example 2
W/O LotionW / O lotion
Gew.-%% By weight
Paraffinöl 20,00Paraffin oil 20.00
Petrolatum 4,00Petrolatum 4.00
Glucosesesqiisostearat 2,00Glucose Seqiisostearate 2.00
Aluminumstearat 0,40Aluminum stearate 0.40
Phytinsäure 1 ,5Phytic acid 1, 5
Vitamin E Acetat 2,00Vitamin E acetate 2.00
Vitamin C Palmitat 0,20Vitamin C palmitate 0.20
Glycerin 5.Q0Glycerin 5.Q0
Wasser, Konservierungsmittel und Parfüm ad 100,00 24Water, preservatives and perfume ad 100.00 24
Beispiel 3Example 3
O/W LotionO / W lotion
Gew.-%% By weight
Paraffinöl 8,00Paraffin oil 8.00
Isopropylpalmitat 3,00Isopropyl palmitate 3.00
Petrolatum 4,00,Petrolatum 4.00,
Cetearylalkohol 2,00Cetearyl alcohol 2.00
PEG-40 Rizinusöl 0,50PEG-40 castor oil 0.50
Natriumcetearylsulfat 0,50Sodium cetearyl sulfate 0.50
Natrium Carbomer 0,40Sodium carbomer 0.40
Phytinsäure 0,7Phytic acid 0.7
Glycerin 3,00 α-Tocopherol 0,20Glycerin 3.00 α-tocopherol 0.20
Octylmethoxycinnamat 5,00Octyl methoxycinnamate 5.00
Butylmethoxydibenzoylmethan 1 ,00Butyl methoxydibenzoyl methane 1.00
Wasser, Konservierungsmittel und Parfüm ad 100,00Water, preservatives and perfume ad 100.00
Beispiel 4Example 4
O/W CremeO / W cream
Gew.-%% By weight
Paraffinöl 7,00Paraffin oil 7.00
Avocadoöl 4,00Avocado oil 4.00
Glycerylmonostearat 2,00Glyceryl monostearate 2.00
Natriumstearat 1 ,00Sodium stearate 1, 00
Phytinsäure 0,8Phytic acid 0.8
Natriumphytat 1 ,Q0Sodium phytate 1, Q0
Titandioxid 1 ,00Titanium dioxide 1.00
Natriumlactat 3,00Sodium lactate 3.00
Glycerin 3,00 Wasser, Konservierungsmittel und Parfüm ad 100,00Glycerin 3.00 Water, preservatives and perfume ad 100.00
Beispiel 5Example 5
LippenpflegestiftLip balm
Gew.-%% By weight
Hydriertes Rizinusöl 4,00Hydrogenated castor oil 4.00
Ceresin 8,00Ceresin 8.00
Bienenwachs 4,00Beeswax 4.00
Carnaubawachs 2,00Carnauba wax 2.00
Petrolatum 40,00Petrolatum 40.00
Phytinsäure 2,0 ß-Carotin 0,10Phytic acid 2.0 ß-carotene 0.10
Paraffinöl, Pigmente und Farbstoffe ad 100,00Paraffin oil, pigments and dyes ad 100.00
Beispiel 6Example 6
Liposomenhaltiges GelGel containing liposomes
Gew.-%% By weight
Lecithin 6,00Lecithin 6.00
Schibutter 3,00Ski butter 3.00
Phytinsäure 2,0Phytic acid 2.0
Vitamin A Palmitat 0,20Vitamin A palmitate 0.20
Biotin 0,08Biotin 0.08
Natriumeitrat 0,50Sodium citrate 0.50
Glycin 0,20Glycine 0.20
Harnstoff 0,20Urea 0.20
Natrium PCA 0,50Sodium PCA 0.50
Hydrolysiert.es Kollagen 2,00Hydrolyzed collagen 2.00
Xanthan Gummi 1 ,40Xanthan gum 1, 40
Sorbitol 3,00Sorbitol 3.00
Wasser, Konservierungsmittel und Parfüm ad 100,00 Beispiel 7Water, preservatives and perfume ad 100.00 Example 7
HaarkurHair treatment
Gew.-%% By weight
Paraffinöl 3,00Paraffin oil 3.00
Mandelöl 3,00Almond oil 3.00
Cetostearylalcohol 5,00Cetostearyl alcohol 5.00
PEG - 40 Rizinusöl 1 ,00PEG - 40 castor oil 1, 00
Natriumcetearylsurfate 0,50Sodium cetearyl surfate 0.50
Sorbitol 5,00Sorbitol 5.00
Glycerin 5,00Glycerin 5.00
Phytinsäure 1,3Phytic acid 1.3
Dilaurylthiodipropionat 0,05Dilauryl thiodipropionate 0.05
Wasser, Konservierungsmittel und Parfüm ad 100,00Water, preservatives and perfume ad 100.00
Beispiel 8Example 8
MassagecremeMassage cream
Gew.-%% By weight
Stearylalkohol 2,00Stearyl alcohol 2.00
Petrolatum 4,00Petrolatum 4.00
Dimethicon 2,00Dimethicone 2.00
Isopropylpalmitat 6,00Isopropyl palmitate 6.00
Cetearylalkohol 4,00Cetearyl alcohol 4.00
PEG- 40 Hydriertes Rizinusöl 2,00PEG-40 hydrogenated castor oil 2.00
Phytinsäure 0,7Phytic acid 0.7
Glycerin 3,00Glycerin 3.00
Wasser, Konservierungsmittel und Parfüm ad 100,00 Beispiel 9Water, preservatives and perfume ad 100.00 Example 9
W/O CremeW / O cream
Gew.-%% By weight
Paraffinöl 10 ,00Paraffin oil 10.00
Petrolatum 4 ,00Petrolatum 4, 00
Wollwachsalkohol 1 ,00%Wool wax alcohol 1.00%
PEG-7 Hydriertes Rizinusöl 3,00PEG-7 hydrogenated castor oil 3.00
Aluminumstearat 0,40Aluminum stearate 0.40
Phytinsäure 0,5 alpha-Hydroxypaimitinsäure 0,5Phytic acid 0.5 alpha-hydroxypaimitic acid 0.5
Glycerin 2,00Glycerin 2.00
Wasser, Konservierungsmittel und Parfüm ad 100,00Water, preservatives and perfume ad 100.00
Beispiel 10Example 10
W/O LotionW / O lotion
Gew.-%% By weight
Paraffinöl 20,00Paraffin oil 20.00
Petrolatum 4,00Petrolatum 4.00
Glucosesesqiisostearat 2,00Glucose Seqiisostearate 2.00
Aluminiumstearat 0,40Aluminum stearate 0.40
Phytinsäure 1,0 alpha-Hydroxypalmitinsäure 0,3Phytic acid 1.0 alpha-hydroxypalmitic acid 0.3
Vitamin E Acetat 2,00Vitamin E acetate 2.00
Vitamin C Palmitat 0,20Vitamin C palmitate 0.20
Glycerin 5,00Glycerin 5.00
Wasser, Konservierungsmittel und Parfüm ad 100,00Water, preservatives and perfume ad 100.00
Beispiel 11Example 11
O/W Lotion Gew.-%O / W lotion % By weight
Paraffinöl 8,00Paraffin oil 8.00
Isopropylpalmitat 3,00Isopropyl palmitate 3.00
Petrolatum 4,00,Petrolatum 4.00,
Cetearylalkohol 2,00Cetearyl alcohol 2.00
PEG-40 Rizinusöl 0,50PEG-40 castor oil 0.50
Natriumcetearyisulfat 0,50Sodium ceteary sulfate 0.50
Natrium Carbomer 0,40Sodium carbomer 0.40
Phytinsäure 2,0 alpha-Hydroxypalmitinsäure 0,5Phytic acid 2.0 alpha-hydroxypalmitic acid 0.5
Glycerin 3,00 α-Tocopherol 0,20Glycerin 3.00 α-tocopherol 0.20
Octylmethoxycinnamat 5,00Octyl methoxycinnamate 5.00
Butylmethoxydibenzoylmethan 1,00Butyl methoxydibenzoyl methane 1.00
Wasser, Konservierungsmittel und Parfüm ad 100,00Water, preservatives and perfume ad 100.00
Beispiel 12Example 12
O/W CremeO / W cream
Gew.-%% By weight
Paraffinöl 7,00Paraffin oil 7.00
Avocadoöl 4,00Avocado oil 4.00
Glycerylmonostearat 2,00Glyceryl monostearate 2.00
Natriumstearat 1 ,00Sodium stearate 1, 00
Phytinsäure 0,8 alpha-Hydroxypalmitinsäure 0,2Phytic acid 0.8 alpha-hydroxypalmitic acid 0.2
Titandioxid 1,00Titanium dioxide 1.00
Natriumlactat 3,00Sodium lactate 3.00
Glycerin 3,00Glycerin 3.00
Wasser, Konservierungsmittel und Parfüm ad 100,00 Beispiel 13Water, preservatives and perfume ad 100.00 Example 13
LippenpfiegestiftLip care stick
Gew.-%% By weight
Hydriertes Rizinusöl 4,00Hydrogenated castor oil 4.00
Ceresin 8,00Ceresin 8.00
Bienenwachs 4,00Beeswax 4.00
Camaubawachs 2,00Camauba wax 2.00
Petrolatum 40,00Petrolatum 40.00
Phytinsäure 1.5 alpha-Hydroxypalmitinsäure 0,2 ß-Carotin 0,10Phytic acid 1.5 alpha-hydroxypalmitic acid 0.2 ß-carotene 0.10
Paraffinöl, Pigmente und Farbstoffe ad 100,00Paraffin oil, pigments and dyes ad 100.00
Beisoiel 14Example 14
Liposomenhaltiges GelGel containing liposomes
Gew.-%% By weight
Lecithin 6,00Lecithin 6.00
Schibutter 3,00Ski butter 3.00
Phytinsäure 1,0 alpha-Hydroxypalmitinsäure 0,1Phytic acid 1.0 alpha-hydroxypalmitic acid 0.1
Vitamin A Palmitat 0,20Vitamin A palmitate 0.20
Biotin 0,08Biotin 0.08
Natriumeitrat 0,50Sodium citrate 0.50
Glycin 0,20Glycine 0.20
Harnstoff 0,20Urea 0.20
Natrium PCA 0,50Sodium PCA 0.50
Hydrolysiertes Kollagen 2,00Hydrolyzed collagen 2.00
Xanthan Gummi 1 ,40Xanthan gum 1, 40
Sorbitol 3,00Sorbitol 3.00
Wasser, Konservierungsmittel und Parfüm ad 100,00 Beispiel 15Water, preservatives and perfume ad 100.00 Example 15
HaarkurHair treatment
Gew.-%% By weight
Paraffinöl 3,00Paraffin oil 3.00
Mandelöl 3,00Almond oil 3.00
Cetostearylalcohol 5,00Cetostearyl alcohol 5.00
PEG - 40 Rizinusöl 1,00PEG - 40 castor oil 1.00
Natriumcetearylsulfate 0,50Sodium cetearyl sulfate 0.50
Sorbitol 5,00Sorbitol 5.00
Glycerin 5,00Glycerin 5.00
Phytinsäure 0,5 alpha-Hydroxypalmitinsäure 1,00Phytic acid 0.5 alpha-hydroxypalmitic acid 1.00
Dilaurylthiodipropionat 0,05Dilauryl thiodipropionate 0.05
Wasser, Konservierungsmittel und Parfüm ad 100,00Water, preservatives and perfume ad 100.00
Beispiel 16Example 16
MassagecremeMassage cream
Stearylalkohol 2,00Stearyl alcohol 2.00
Gew.-%% By weight
Petrolatum 4,00Petrolatum 4.00
Dimethicon 2,00Dimethicone 2.00
Isopropylpalmitat 6,00Isopropyl palmitate 6.00
Cetearylalkohol 4,00Cetearyl alcohol 4.00
PEG- 40 Hydriertes Rizinusöl 2,00PEG-40 hydrogenated castor oil 2.00
Phytinsäure 0,5 alpha-Hydroxypalmitinsäure 0,3Phytic acid 0.5 alpha-hydroxypalmitic acid 0.3
Glycerin 3,00Glycerin 3.00
Wasser, Konservierungsmittel und Parfüm ad 100,00 Beispiel 17Water, preservatives and perfume ad 100.00 Example 17
O/W LotionO / W lotion
Gew.-%% By weight
Paraffinöl 8,00Paraffin oil 8.00
Isopropylpalmitat 3,00Isopropyl palmitate 3.00
Petrolatum 4,00Petrolatum 4.00
Cetearylalkohol 2,00Cetearyl alcohol 2.00
PEG-40 Rizinusöl 0,50PEG-40 castor oil 0.50
Natriumcetearylsulfat 0,50Sodium cetearyl sulfate 0.50
Natrium Carbomer 0,40Sodium carbomer 0.40
Phytinsäure 2,0Phytic acid 2.0
Deferoxamin 0,5Deferoxamine 0.5
Glycerin 3,00 aipha-Tocopherol 0,20Glycerin 3.00 aipha-tocopherol 0.20
Octylmethoxycinnamat 5,00Octyl methoxycinnamate 5.00
Butylmethoxydibenzoylmethan 1 ,00Butyl methoxydibenzoyl methane 1.00
Wasser, Konservierungsmittel und Partüm ad 100,00Water, preservatives and particles ad 100.00
Beispiel 18Example 18
O/W CremeO / W cream
Gew.-%% By weight
Paraffinöl 7,00Paraffin oil 7.00
Avocadoöl 4,00Avocado oil 4.00
Glycerylmonostearat 2,00Glyceryl monostearate 2.00
Natriumstearat 1 ,00Sodium stearate 1, 00
Phytinsäure 0,8Phytic acid 0.8
Deferoxamin 0,2Deferoxamine 0.2
Natriumphytat 1 ,00 alpha-Hydroxypalmitinsäure 0,3Sodium phytate 1.00 alpha-hydroxypalmitic acid 0.3
Titandioxid 1 ,00Titanium dioxide 1.00
Natriumlactat 3,00Sodium lactate 3.00
Glycerin 3,00Glycerin 3.00
Wasser, Konservierungsmittel und Parfüm ad 100,00 Water, preservatives and perfume ad 100.00

Claims

Patentansprüche claims
1. Verwendung von Phytinsäure oder deren Salzen zur Prophylaxe und Behandlung von schädigenden oxidativen Einwirkungen auf die Haut oder die Haare.1. Use of phytic acid or its salts for the prophylaxis and treatment of damaging oxidative effects on the skin or hair.
2. Verwendung von kosmetischen oder dermatologischen Zubereitungen mit einem Gehalt an Phytinsäure oder deren Salzen zur Prophylaxe und Behandlung von schädigenden oxidativen Einwirkungen auf die Haut oder die Haare.2. Use of cosmetic or dermatological preparations containing phytic acid or its salts for the prophylaxis and treatment of damaging oxidative effects on the skin or hair.
3. Wirkstoffkombinationen, enthaltend einen Wirkstoff oder mehrere Wirkstoffe, ausgewählt aus der Gruppe der Phytinsäure und deren Salzen in Kombination mit einem Wirkstoff oder mehreren Wirkstoffen, ausgewählt aus der Gruppe der Chelatbildner.3. Active substance combinations containing one or more active substances selected from the group of phytic acid and its salts in combination with one or more active substances selected from the group of chelating agents.
4. Kosmetische oder dermatologische Zubereitungen mit einem Gehalt an einer Wirkstoffkombination gemäß Anspruch 3.4. Cosmetic or dermatological preparations containing an active ingredient combination according to claim 3.
5. Verwendung von Wirkstoffkombinationen gemäß Anspruch 3 zur Prophylaxe und Behandlung von schädigenden oxidativen Einwirkungen auf die Haut oder die Haare.5. Use of active substance combinations according to claim 3 for the prophylaxis and treatment of damaging oxidative effects on the skin or the hair.
6. Verwendung kosmetischer oder dermatologischer Zubereitungen, gekennzeichnet durch einen Gehalt an einer Wirkstoffkombination gemäß Anspruch 3 zur Prophylaxe und Behandlung von schädigenden oxidativen Einwirkungen auf die Haut oder die Haare.6. Use of cosmetic or dermatological preparations, characterized by a content of an active ingredient combination according to claim 3 for the prophylaxis and treatment of damaging oxidative effects on the skin or the hair.
7. Wirkstoffkombination gemäß Anspruch 3, dadurch gekennzeichnet, daß sie alpha-Hydroxypalmitinsäure und/oder Deferoxamin enthält.7. Active ingredient combination according to claim 3, characterized in that it contains alpha-hydroxypalmitic acid and / or deferoxamine.
8. Verwendung gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Phytinsäure oder ihre Salze mit Antioxidantien kombiniert werden. 8. Use according to claim 1 or 2, characterized in that the phytic acid or its salts are combined with antioxidants.
9. Verwendung gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Phytinsäure oder ihre Salze mit mindestens einem UVA-Filter und/oder mindestens einem UVB-Filter kombiniert werden.9. Use according to claim 1 or 2, characterized in that the phytic acid or its salts are combined with at least one UVA filter and / or at least one UVB filter.
10. Wirkstoffkombinationen gemäß Anspruch 3, dadurch gekennzeichnet, daß sie mit Antioxidantien kombiniert sind.10. Active substance combinations according to claim 3, characterized in that they are combined with antioxidants.
11. Wirkstoffkombinationen gemäß Anspruch 3, dadurch gekennzeichnet, daß sie mit mindestens einem UVA-Filter und/oder mindestens einem UVB- Filter kombiniert werden. 11. Active ingredient combinations according to claim 3, characterized in that they are combined with at least one UVA filter and / or at least one UVB filter.
PCT/EP1996/002197 1995-05-23 1996-05-22 Cosmetic or dermatological preparations containing phytic acid WO1996037187A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP8535379A JPH11505818A (en) 1995-05-23 1996-05-22 Cosmetic or dermatological preparations containing phytic acid
EP96917399A EP0827392A1 (en) 1995-05-23 1996-05-22 Cosmetic or dermatological preparations containing phytic acid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19518845A DE19518845A1 (en) 1995-05-23 1995-05-23 Cosmetic or dermatological preparations containing phytic acid
DE19518845.4 1995-05-23

Publications (1)

Publication Number Publication Date
WO1996037187A1 true WO1996037187A1 (en) 1996-11-28

Family

ID=7762628

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/002197 WO1996037187A1 (en) 1995-05-23 1996-05-22 Cosmetic or dermatological preparations containing phytic acid

Country Status (4)

Country Link
EP (1) EP0827392A1 (en)
JP (1) JPH11505818A (en)
DE (1) DE19518845A1 (en)
WO (1) WO1996037187A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101076316B (en) * 2004-12-17 2011-11-09 株式会社资生堂 Composition and method for accelerating fibulin-5 production and/or enhancing fibulin-5 activity
CN103338746A (en) * 2011-01-27 2013-10-02 太阳星光齿磨公司 Composition containing polyunsaturated fatty acid
US20210236398A1 (en) * 2020-01-31 2021-08-05 L'oreal Compositions and methods for hair
US20220362128A1 (en) * 2019-06-27 2022-11-17 L'oreal Composition comprising ingredients for dic-gel and polyol
WO2023034283A1 (en) * 2021-08-30 2023-03-09 Living Proof, Inc. Methods for strengthening and repairing hair

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10050155A1 (en) * 2000-10-11 2002-04-18 Beiersdorf Ag Stabilization of cosmetic or dermatological emulsions, hydrogels or oleogels useful eg as skin-care or make-up compositions is by addition of desferrioxamine
JP2005325034A (en) * 2004-05-12 2005-11-24 Okuno Chem Ind Co Ltd Singlet oxygen eliminator
JP4502903B2 (en) * 2005-08-01 2010-07-14 中野製薬株式会社 Two-component oxidative hair dye / bleaching agent composition
JP4502904B2 (en) * 2005-08-01 2010-07-14 中野製薬株式会社 Two-component oxidative hair dye / bleaching agent composition
WO2007039057A1 (en) * 2005-09-23 2007-04-12 Dsm Ip Assets B.V. Cosmetic compositions comprising hydroxyfatty acids
JP5279209B2 (en) * 2006-06-27 2013-09-04 ロート製薬株式会社 Topical skin preparation
JP6824823B2 (en) * 2017-06-06 2021-02-03 株式会社マンダム Nrf2 gene expression promoter, catalase gene expression promoter, and glutathione peroxidase gene expression promoter
WO2024132679A1 (en) * 2022-12-21 2024-06-27 Evonik Dr. Straetmans Gmbh Compositions containing biosurfactants and desferrioxamines

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4328871A1 (en) * 1993-08-27 1995-03-02 Beiersdorf Ag Means against sensitive, hyper-reactive skin conditions, atopic dermatitis, pruritus, psoriasis prurigo, photodermatoses and ichthyosis
EP0650720A1 (en) * 1993-10-28 1995-05-03 Sanwa Kagaku Kenkyusho Co., Ltd. Skin care and deodorant compositions
US5434144A (en) * 1994-03-04 1995-07-18 The Procter & Gamble Company Methods of using cyclic polyanionic polyol derivatives for regulating skin wrinkles
JPH08104635A (en) * 1994-10-06 1996-04-23 Ichimaru Pharcos Co Ltd External pharmaceutical preparation containing zinc phytate as active ingredient

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2610626B1 (en) * 1987-02-09 1989-05-19 Oreal NOVEL ANTI-OXIDIZER SYSTEM BASED ON A STABILIZED ASCORBYL ESTER, COMPRISING AT LEAST ONE COMPLEXING AGENT AND AT LEAST ONE THIOL, AND COMPOSITIONS CONTAINING SUCH ANTI-OXIDIZING SYSTEM
IL88961A (en) * 1988-01-29 1992-07-15 Basf Ag Stable mixtures containing oxidation-sensitive compounds
JPH0348625A (en) * 1989-07-14 1991-03-01 Sanwa Kagaku Kenkyusho Co Ltd Phytic acid-stabilized composition and body smell-and-urine smell removing agent with the same as active ingredient
FR2651125B1 (en) * 1989-08-23 1992-10-02 Roussel Uclaf PHARMACEUTICAL COMPOSITIONS OF THE "WATER PASTE" TYPE.
FR2674748B1 (en) * 1991-04-03 1995-01-13 Oreal USE OF SPHINGOLIPIDS IN THE PREPARATION OF A COSMETIC OR DERMOPHARMACEUTICAL COMPOSITION PROTECTING THE SKIN AND HAIR FROM THE HARMFUL EFFECTS OF ATMOSPHERIC POLLUTION.
CA2123211C (en) * 1991-11-12 2008-09-16 Colin L. Masters A method for assaying and treating alzheimer's disease
FR2697161B1 (en) * 1992-10-26 1995-01-13 Jouvance Daniel Cosmetic product with stabilized redox potential.
DE4242876C2 (en) * 1992-12-18 1997-11-27 Beiersdorf Ag Cosmetic and / or dermatological preparations for the cosmetic and / or dermatological care of the skin and / or the skin appendages
FR2710527B1 (en) * 1993-09-30 1995-12-08 Roussel Uclaf New cosmetic and dermatological compositions combining ceramides and linoleic acid, their preparation.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4328871A1 (en) * 1993-08-27 1995-03-02 Beiersdorf Ag Means against sensitive, hyper-reactive skin conditions, atopic dermatitis, pruritus, psoriasis prurigo, photodermatoses and ichthyosis
EP0650720A1 (en) * 1993-10-28 1995-05-03 Sanwa Kagaku Kenkyusho Co., Ltd. Skin care and deodorant compositions
US5434144A (en) * 1994-03-04 1995-07-18 The Procter & Gamble Company Methods of using cyclic polyanionic polyol derivatives for regulating skin wrinkles
JPH08104635A (en) * 1994-10-06 1996-04-23 Ichimaru Pharcos Co Ltd External pharmaceutical preparation containing zinc phytate as active ingredient

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9626, Derwent World Patents Index; AN 96-255077, XP002010765, "New external prepn. phytic acid zinc salt - used as inhibitor of lipid peroxidase" *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101076316B (en) * 2004-12-17 2011-11-09 株式会社资生堂 Composition and method for accelerating fibulin-5 production and/or enhancing fibulin-5 activity
CN103338746A (en) * 2011-01-27 2013-10-02 太阳星光齿磨公司 Composition containing polyunsaturated fatty acid
CN103338746B (en) * 2011-01-27 2015-12-23 太阳星光齿磨公司 Compositions containing polyunsaturated fatty acid
US20220362128A1 (en) * 2019-06-27 2022-11-17 L'oreal Composition comprising ingredients for dic-gel and polyol
US20210236398A1 (en) * 2020-01-31 2021-08-05 L'oreal Compositions and methods for hair
WO2023034283A1 (en) * 2021-08-30 2023-03-09 Living Proof, Inc. Methods for strengthening and repairing hair

Also Published As

Publication number Publication date
JPH11505818A (en) 1999-05-25
EP0827392A1 (en) 1998-03-11
DE19518845A1 (en) 1996-11-28

Similar Documents

Publication Publication Date Title
EP0945128B1 (en) Use of flavones, flavanones, or flavonoides for the protection of ascorbic acid and/or ascorbylbonds against oxidation
EP1194115B1 (en) Topically applied idebenone-containing agent with protective and regenerative effect
EP0716847A1 (en) Cosmetic or dermatologic compositions containing cinnamic acid derivatives and a flavonoid
EP0824915B1 (en) Use of glycoglycerolipids as surfactants and cosmetic or dermatological compositions containing them
EP0770378A1 (en) Cosmetic preparations with an effective amount of glycosylglycerides
DE19933460A1 (en) Cosmetic or dermatological dispersions having radical scavenging and antioxidant activity, useful e.g. for preventing skin aging and inflammatory reactions
WO1994004129A2 (en) Cosmetic and dermatological sunscreen compositions containing thiols and/or thiol derivates
WO1994018942A1 (en) Synergistic combinations of sunscreening substances, cosmetic and dermatological compositions containing such combinations
DE10064818A1 (en) Use of chroman derivatives in cosmetic or dermatological preparations
EP0827392A1 (en) Cosmetic or dermatological preparations containing phytic acid
EP1214927A1 (en) Use of folic acid and/or its derivatives for the manufacture of topical compositions
DE19720339A1 (en) Treatment or prevention of undesired skin pigmentation
EP1166780A2 (en) Use of physiologically acceptable sulfinic acid as antioxidant or radical scavenger in cosmetic or dermatologic preparations
EP0744175A2 (en) Cosmetic or dermatological compositions containing alpha-hydroxy fatty acids
WO2005048970A1 (en) Use of lignans in cosmetic or dermatological preparations
DE19545107A1 (en) Use of adenosine
EP1397119A2 (en) Use of sodium polystyrene sulfonate for tightening skin
DE4436270C1 (en) Use of chlorogenic acid as an antioxidant in hair cosmetic preparations
DE19739349A1 (en) Use of troxerutin as antioxidant and/or radical scavenger
WO2010121676A2 (en) Use of glycyrrhetic acid and/or derivatives thereof for the production of cosmetic or dermatological preparations for the prophylaxis of damage to skin dna and/or for repairing previously incurred damaged to skin dna
DE10121069A1 (en) Use of tetrahydrocurcumin, tetrahydrodemethoxycurcumin and/or tetrahydrobisdemethoxycurcumin to prepare a cosmetic or dermatological composition for treating or preventing skin aging
DE19615576A1 (en) New mono: and di:glucoside of glabridin
DE19739044A1 (en) Use of di:hydro-robinetin as antioxidant and/or radical scavenger
EP1080716A1 (en) Annelated benzene derivatives as antioxidants and radical scavengers in cosmetic preparations
DE19753983A1 (en) Cosmetic or dermatological preparation containing isoquercitrin as antioxidant and radical scavenger, useful for protection of skin or hair

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1996917399

Country of ref document: EP

ENP Entry into the national phase

Ref country code: JP

Ref document number: 1996 535379

Kind code of ref document: A

Format of ref document f/p: F

WWP Wipo information: published in national office

Ref document number: 1996917399

Country of ref document: EP

WWR Wipo information: refused in national office

Ref document number: 1996917399

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1996917399

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务,不要输入任何密码和下载