DE19830004B4 - Cosmetic preparation with high radical protection factor and their use - Google Patents

Abstract

Cosmetic preparation with high radical protection factor, characterized by a content of
(a) a product obtained by extraction of the bark of Quebracho blanco and subsequent enzymatic hydrolysis containing at least 90% by weight of proanthocyanidin oligomers and at most 10% by weight of gallic acid, the content of (a) being that of a microcapsule-bound Active ingredient concentration of 2% by weight, is in the range of 1 to 10% by weight;
(b) a silkworm extract obtained by extraction, which contains the peptide cecropins, amino acids and a vitamin mixture, the content of (b) being in the range of 0.1 to 10% by weight;
(c) a nonionic, cationic or anionic hydrogel or mixture of hydrogels containing (c) in the range 0.1 to 5% by weight;
(d) one or more phospholipids in an amount of 0.1 to 30% by weight; and
(e) water;
in each case based on the total weight of the active compound preparation.

Description

The cosmetic active ingredient preparation according to the invention protects in a particularly effective manner against the attack of free radicals the skin both alone and in combination with other active ingredients.

As you know, free radicals, such as superoxide ions, hydroxy radicals, oxides for tissue degradation and thus for the Appearance of aging of the skin responsible. The proteins and Cell membrane lipids are destroyed, DNA damaged and damaged a key substance the skin, hyaluronic acid, will also be dismantled. Under normal biological conditions is there an equilibrium ratio? between occurring free radicals and their containment by endogenous chemical or enzymatic systems. Due to additional stress factors from the outside, like agressive atmosphere, Tobacco smoke, ultraviolet radiation, etc. are these endogenous Defense systems overwhelmed and disturbed the balance in favor of free radicals. It kick inflammatory or aging of the skin, and a balance by cosmetic Products is displayed.

A number of products have been proposed for this purpose, which often contain vitamin mixtures with vitamins A, C and E, or additives of superoxide dismutase or extracts from certain plant or animal organisms. So is out of the US-A-5,629,185 a cosmetic composition containing ultrasonic disruption products of yeasts or other cell dispersions. From WO96 / 29048 a cosmetic is known which contains condensed degradation products of plant or animal origin.

Furthermore, there are a variety of Publications, in which the use of pure plant extracts for cosmetic Purpose is described, for example, in WO97 / 45100 with a mixture of seven different extracts to combat Cellulite.

The search for more effective Substance is an essential element of cosmetic research. Farther problematic with many of these products is that the against Free radicals effective substances their catcher potential within the often do not permanently maintain the cosmetic composition, i. e. Special formulations are required to increase effectiveness the radical scavenger maintained in the long term.

On the other hand, in the cosmetic industry the knowledge does not seem to have prevailed until now that it is possible to measure the antioxidative potential of the skin ( DE 4328639 ) and, more recently, with the help of a relatively simple method to determine the radical protection factor of a cosmetic preparation and thus specifically include materials in such a preparation.

It is an object of the present invention to provide a cosmetic active ingredient preparation which is a particularly has high radical protection potential.

Another object of the invention is the provision of an active compound preparation that its radical protection potential over a long period stops.

Another object of the invention is the provision of special cosmetic compositions, containing this preparation of active compound.

From the DE 19655736A1 is a cosmetic preparation containing α-MSH-derived peptide derivatives and SOD-containing vitamin / enzyme digestion products with antioxidant activity.

The DE 3403476A1 describes compositions for human nails containing quebracho and / or mimosa extracts.

The EP-A-507 272 relates to hair cosmetics with a chitin derivative and a polyphenol, wherein the polyphenol may also be a tannin-containing plant extract of quebracho.

• (a) einem durch Extraktion der Rinde von Quebracho blanco und nachfolgender enzymatischer Hydrolyse gewonnenem Produkt, das wenigstens 90 Gew- % Proanthocyanidin-Oligomere und höchstens 10 Gew- % Gallussäure enthält, wobei der Gehalt von (a), das in einer an Mikrokapseln gebundenen Wirkstoffkonzentration von 2 Gew- % vorliegt, im Bereich von 1 bis 10 Gew- % liegt;
• (b) einem durch Extraktion gewonnenen Seidenraupenextrakt, der das Peptid Cecropine, Aminosäuren und ein Vitamingemisch enthält, wobei der Gehalt von (b) im Bereich von 0,1 bis 10 Gew- % liegt;
• (c) einem nichtionischen, kationischen oder anionischen Hydro-Gel oder Gemisch von Hydro-Gelen mit einem Gehalt von (c) im Bereich von 0,1 bis 5 Gew-%;
• (d) einem oder mehreren Phospholipiden mit einem Anteil von 0,1 bis 30 Gew-%; und
• (e) Wasser; jeweils bezogen auf das Gesamtgewicht der Wirkstoffzubereitung.

According to the invention, the cosmetic active substance preparation with a high radical protection factor is characterized by a content

• (a) a product obtained by extraction of the bark of Quebracho blanco and subsequent enzymatic hydrolysis containing at least 90% by weight of proanthocyanidin oligomers and at most 10% by weight of gallic acid, the content of (a) being that of a microcapsule-bound Active ingredient concentration of 2% by weight, is in the range of 1 to 10% by weight;
• (b) a silkworm extract obtained by extraction, which contains the peptide cecropins, amino acids and a vitamin mixture, the content of (b) being in the range of 0.1 to 10% by weight;
• (c) a nonionic, cationic or anionic hydrogel or mixture of hydrogels containing (c) in the range 0.1 to 5% by weight;
• (d) one or more phospholipids in an amount of 0.1 to 30% by weight; and
• (e) water; in each case based on the total weight of the active compound preparation.

In addition, the active ingredient preparation may contain (f) at least 150 units of superoxide dismut tase per ml containing ultrasonic digestion product of a yeast, wherein the content of the digestion product (e) is in the range of 0 to 4% by weight; and (g) an extract of acerola fruit Malpighia punidifolia, wherein the content (f) is in the range of 0 to 20% by weight; in each case based on the total weight of the active compound preparation.

The quebracho bark extract according to the invention or its hydrolysis product contains a very high proportion Proanthocyanidins, which are condensed tannins. This in Form of oligomers occurring compounds and the low Proportion of gallic acid shows in this combination and in concentrations between 1 and 10 wt% a clear radical protection effect, the effect of Superoxide dismutase (SOD) far surpasses. The activity against free radicals were compared with that of SOD and were at one 1% by weight solution of the Extract at 42% (SOD 4%), a 2.5 wt% solution at 83% (SOD 15%) and a 5% by weight solution at 100% (SOD 38%).

The extract preferably contains (a) at least 95% by weight of proanthocyanidin oligomers and at most 5% by weight of gallic acid, in particular at least 99% by weight of proanthocyanidin oligomers and at most 1% by weight of gallic acid.

The content of (a) is 1 to 10% by weight, wherein the active ingredient from the Quebrachorinde in microcapsules is included. The microcapsules are e.g. from petrolatum, Sodium tristearate, agar, phenonip and water.

The silkworm extract (b) becomes obtained by extraction of the silkworm (Bombyx mori) with propylene glycol and contains Vitamins, amino acids and the peptide Cecropine, which has a special antibacterial activity having. In recent years have a number of investigations at the hemolymph and the cutural matrix of the silk worm have shown that not only antibacterial peptides but also inhibitors of especially fungal proteases are contained therein. Farther such extracts show oxygen-consuming properties, whereby they activate cell metabolism, and they have moisture-retaining properties Properties that have a significant healing effect on skin lesions shortening the healing time as well as a smoothing Effect on the skin.

The extract (b) preferably contains the amino acids aspartic acid, asparagine, Threonine, serine, glutamic acid, Proline, glycine, alanine, valine, cysteine, methionine, isoleucine, leucine, Tyrosine, phenylalanine, lysine, histidine, arginine.

The extract (b) furthermore preferably contains a vitamin mixture with the vitamins B ₁ , B ₂ , B ₅ , B ₆ , B ₈ , B ₉ , B ₁₂ , PP, A, E and C.

The components (a) and (b) are preferably in concentrations of 0.1 to 3% by weight in each case Preparation of active ingredient.

The gel containing the invention, also A mixture of different gels can be a hydrogel that water soluble is higher at temperatures as about 40 to 50 ° C and the gel structure at lower temperatures between 10 and 30 ° C forms. examples for such gels are nonionic polymers such as polyvinyl alcohol, Polyvinyl pyrrolidone modified corn starch and hydroxyethyl cellulose; cationic polymers such as cationic guar, cationic cellulose, synthetic cationic polymers; or gels such as gelatin, carrageenan, Bentonite gels, copolymer gels such as Carbomer.

The phospholipids according to the invention are selected from phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, phosphatidic acid and lysolecithins and mixtures thereof. Known products include Phoslipon ^®. The proportion of phospholipids is in the range of 0.1 to 30% by weight, preferably 0.5 to 20% by weight.

The components (a) and (b) of the preparation of active compound probably form associative with the phospholipids (d) Structures of different molecules, in turn in the forming structure of the gel (c) + (e) in a largely uniform distribution which are collectively referred to as the "association of associations". Integrated in it can also portions of the SOD-containing yeast digestion product and the acerola extract and certain plant extracts.

The preparation of active ingredient in the form of the association complex may additionally contain a mixture of the vitamins A, B and C and in addition SOD and / or extracts of acerola fruits. It can, however, too Vitamins as well as other antioxidants in the overall composition be included in the cosmetic preparation.

The active ingredient preparation according to the invention may further contain, in addition to the basic components (a) to (e), various plant extracts, such as citrus peel or leaf extracts (Citrus bigaradia, Citrus hystrix, Citrus aurantifolia, Citrofurtunella microcarpa, Citrus aurantium, Citrus reticulata), bitter orange extract (Peel or fruit), Cherry Cherry Cherry Extract, Kiwi Extract (Actinidia chinensis), Papaya Fruit Extract (Caricae papayae), Tea Extract [leaves of green or black tea, leaves or bark of New Jersey Tea ( Ceanthus velutinas)], bean extract (INCI name: Coffee Bean Extract, from green or roasted beans), Prunus extract (Prunus armeniaca, Prunus dulcis, Prunus persica, Prunus domestica, Prunus spinosa, Prunus serotina, Prunus virginiana), Extracts of the bark of the Mexican skin tree (Mimosa tenuiflora), Angelica root extract (Angelica archangelica). Such plant extracts are sin commercially available, eg from DRAGOCO, Holzminden, Germany.

The content of these plant extracts may be between 0 and 20% by weight, with mixtures of these Extracts and mixtures with the components (f) and (g) of the active ingredient preparation may be included.

The addition of the above plant extracts can the radical protection factor depending on the plant and appropriately added Increase quantity several times, presumably synergistic interactions occur whose relationships not yet complete clarified could become.

To be used in the invention Antioxidants include Vitamins such as Vitamin C and derivatives thereof, for example ascorbyl acetates, phosphates and palmitates; Vitamin A and derivatives thereof; Folic acid and their derivatives, vitamin E and their derivatives, such as tocopheryl acetate; Flavones or flavonoids; Amino acids, such as histidine, glycine, tyrosine, tryptophan and derivatives thereof; carotenoids and carotenes such as α-carotene, β-carotene; uric acid and derivatives thereof; α-hydroxy acids such as citric acid, Lactic acid, Malic acid; Stilbenes and their derivatives, etc.

Vitamins can also be mixed with enzymes as a further proportion in the preparation of active ingredient or in the cosmetic Composition may be included in addition to the preparation of active ingredient. Of the Content may be at least 0.5% by weight of a mixture of enzymes and Vitamins amounting to at least 150 units / ml (U / ml) superoxide dismutase Contains (SOD).

The mixture of enzymes and vitamins used is preferably a digestion product of a yeast prepared by sonication, the digestion product containing SOD, protease, vitamin B ₂ , vitamin B ₆ , vitamin B ₁₂ , vitamin D ₂ and vitamin E. Preferably, it contains at least 150 U / ml SOD, protease and vitamins B and D, with the SOD: protease ratio as international units being at least in the range of 3: 1 to 8: 1.

Particularly advantageous for the preparation of the enzyme / vitamin mixture is a digestion process by means of ultrasound, which in the DE 4241154C1 is described and in which in a ultrasonic flow cell, a cell dispersion or suspension is passed through a sound space in which the sonotrode protrudes to half to two-thirds of its length in the flow cell and immersed in the medium to be sonicated. The sonotrode has an angle of 80.5 to 88.5 °, and the ratio of the immersion length of the sonotrode in mm to the sound volume in ml is set to a value of 1: 1.1 to 1:20. The solids content in the medium to be sonicated is in the range of 1: 0.02 to 1: 2.2 (in% by weight).

As a cell dispersion, yeasts, like bakers' yeast, Brewer's yeast, wine yeast and specially treated yeasts, e.g. SOD-enriched yeasts are used. An advantageous to be used Cell dispersion contains z. B. Saccharomyces cerevisiae.

The addition of e.g. 1% by weight of one such yeast digestion product from bakers yeast as an optional component of the association complex can the already high radical protection factor of e.g. 1620 about twice increase to 3150. For the radical protection factor, further details are given below.

The preparation of active ingredient in the form of the association complex may be in addition to the above components also an extract of acerola fruits (Malpighia punidifolia). Acerola is a small in West Indies, in the north South America, tree native to Central America, Florida and Texas and rich of vitamin C and other active ingredients such as vitamin A, thiamine, riboflavin and niacin, along with various other ingredients, how phosphorus, iron, calcium can have a complex effect. The aqueous acerola extract is usually present as a powdered product.

• (1) Extrakte oder behandelte Extrakte von freie Radikale bindenden oder feuchtigkeitsbindenden Pflanzen, ausgewählt unter Acerolafrüchten (Malpighia punidifolia), Camellia oleifera, Colunsonia canadensis und Hibiscus sabdariffa;
• (2) Extrakte oder behandelte Extrakte von freie Radikale bindenden oder feuchtigkeitsbindenden Algen, ausgewählt unter Omegaplankton mit hohem Anteil an Cerebrosid-Stimulantien, Mikro-Algen der Gattung Chlorella und mit Byssus (Muschelseide) assoziierten Makro-Algen der Gattung Ulva als biotechnologische Proteinfraktion und nachfolgender Assoziierung mit Dextrin, wobei das Produkt im Gemisch mit Peptiderivaten vorliegt, die von α-MSH abgeleitet und mit Xanthin assoziiert sind;
• (3) natürliche und synthetische Polymere, ausgewählt unter Chitosanglycolat, Kondensationsprodukte von Milchpulver und aktivierten Fettsäuren;
• (4) hartmagnetische Einkristalle aus Bariumhexaferrit mit einer Koerzitivfeldstärke von 3000-5000 0e und einer Korngröße von 50-1200 nm eingelagert in oder im Gemisch mit asymmetrischen lamellaren Aggregaten aus Phospholipiden und Fluorcarbonen; sowie
• (5) weitere Wirk- und Trägerstoffe, ausgewählt unter Hyaluronsäure, Omega CH Aktivator, Behentrimoniumchlorid, Passionsblumenöl sowie modifizierter Kaolin.

As a further active ingredient in the overall composition of the cosmetic preparation and in addition to the abovementioned active ingredient complex, in a particularly preferred embodiment it may contain one or more of the following constituents:

• (1) extracts or treated extracts of free radical binding or moisture binding plants selected from acerola fruits (Malpighia punidifolia), Camellia oleifera, Colunsonia canadensis and Hibiscus sabdariffa;
• (2) Extracts or treated extracts of free radical binding or moisture binding algae selected from Omegaplankton high in cerebroside stimulants, Micro algae of the genus Chlorella and Byssus (mussel silk) associated macro-algae of the genus Ulva as a biotechnological protein fraction and the following Association with dextrin, which product is in admixture with peptide derivatives derived from α-MSH and associated with xanthine;
• (3) natural and synthetic polymers selected from chitosan glycolate, condensation products of milk powder and activated fatty acids;
• (4) hard-magnetic single crystals of barium hexaferrite with a coercive field strength of 3000-5000 0e and a grain size of 50-1200 nm incorporated in or in admixture with asymmetric lamellar aggregates of phospholipids and fluorocarbons; such as
• (5) other active ingredients and excipients selected from hyaluronic acid, omega CH activator, behentrimonium chloride, passion flower oil and modified kaolin.

Said modified kaolin is contained according to WO96 / 17588 and is modified with spherical TiO ₂ or SiO ₂ particles having a particle size <5 μm, the spherical particles having a proportion of the kaolin mixture of 0.5 to 10% by weight. The preparation thus receives a very soft skin feeling and an additional anti-inflammatory activity. The modified kaolin may have a content of 0.1 to 6% by weight based on the total amount of the cosmetic.

The said hard magnetic particles to promote the circulation can be such as those described in WO95 / 03061 or such with smaller particle sizes and in mixture with asymmetric lamellar aggregates, which are up to saturation pressure are charged with oxygen, the proportion of magnetic particles, based on the total composition of the cosmetic in the area from 0.01 to 10% by weight.

The mentioned asymmetric lamellar Aggregates are known from WO94 / 00098 and consist of phospholipids and oxygen-loaded fluorocarbon or fluorocarbon mixture. The content of fluorocarbon is in the range of 0.2 to 100% weight / volume, wherein the phospholipid has a phosphatidylcholine content of more than 30 to 99% by weight, and wherein these aggregates are a skin penetration dependent on from the critical solubility temperature possess the fluorocarbons.

The aggregates can also be used alone only loaded with oxygen in the cosmetic preparation. The proportion can be between 2.5 and 20% by weight, based on the overall composition of the cosmetic.

These aggregates are oxygen carriers and enable a penetration of the oxygen into the skin and thus a better one Supply the skin with oxygen.

The preparation according to the invention also contains cosmetic auxiliary and carriers, as they usually do used in such preparations, e.g. Water, glycerine, Propylene glycol, preservatives, dyes, pigments with coloring Effect, thickener, softening substances, moisturizing Substances, fragrances, alcohols, polyols, electrolytes, polar and nonpolar oils, Polymers, copolymers, emulsifiers, waxes, stabilizers, colored plant extracts, like fat-soluble Gardenia extract, fat-soluble Carrot extract, paprika LS extract, β-carotene, Lithospermum extract as well as active deodorants.

It is also advantageous that Compositions of the invention corresponding water and / or oil-soluble UVA or UVB filters or add both. Advantageous oil-soluble UVB filters include 4-aminobenzoic acid derivatives such as the 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester; ester the cinnamic acid such as the 4-methoxycinnamic acid (2-ethylhexyl) ester, Benzophenone derivatives such as 2-hydroxy-4-methoxybenzophenone; 3-benzylidenecamphor derivatives such as 3-benzylidene camphor.

Water-soluble UVB filters are e.g. sulfonic acid derivatives benzophenone or 3-benzylidene camphor or salts like that Na or K salt of 2-phenylbenzimidazole-5-sulfonic acid.

UVA filters include dibenzoylmethane derivatives such as 1-phenyl-4- (4'-isopropylphenyl) propane-1,3-dione.

Preferred sunscreen filters are inorganic pigments based on metal oxides, such as TiO ₂ , SiO ₂ , ZnO, Fe ₂ O ₃ , ZrO ₂ , MnO, Al ₂ O ₃ , which can also be used mixed with one another or with organic filters.

Particularly preferred as inorganic pigments are agglomerated substrates of TiO ₂ and / or ZnO, which have a content of spherical and porous SiO ₂ particles, wherein the SiO ₂ particles have a particle size in the range of 0.05 .mu.m to 1.5 .mu.m , and in addition to the SiO ₂ particles other inorganic particulate matter having a spherical structure are present, wherein the spherical SiO ₂ particles with the other inorganic substances defined agglomerates having a particle size in the range of 0.06 microns to 5 microns.

Particularly advantageous SiO ₂ particles are highly monodisperse, non-porous, spherical SiO ₂ particles according to DE 3616133 , which are produced by hydrolytic polycondensation of tetraalkoxysilane in aqueous-alcoholic-ammoniacal medium, wherein a sol of primary particles is produced and then by a continuous, controlled in accordance with the Abreagierens metered addition of tetraalkoxysilane, the resulting SiO ₂ particles to the desired particle size of about 0.05 to 10 microns brings.

Pigments, pigment mixtures or powders with pigmentary effect, including those with pearlescent effect can be understood For example, mica, kaolin, talc, mica-titania, Mica titanium oxide iron oxide, bismuth oxychloride, nylon beads, Ceramic beads, expanded and unexpanded synthetic polymer powder, powdered natural organic Compounds such as ground algae, encapsulated and unencapsulated cereal starches and mica-titania-organic dye.

As a softener can normally a variety of compounds are used, such as stearyl alcohol, Glyceryl monoricinoleate, glyceryl monostearate, propane-1,2-diol, butane-l, 3-diol, Cetyl alcohol, isopropyl isostearate, stearic acid, isobutyl palmitate, oleyl alcohol, Isopropyl laurate, decyl oleate, octadecan-2-ol, isocetyl alcohol, cetyl palmitate, silicone oils such as dimethylpolysiloxane, isopropyl myristate, isopropyl palmitate, polyethylene glycol, Lanolin, cocoa butter, vegetable oils such as corn oil, cottonseed oil, olive oil, mineral oils, butyl myristate, palmitic etc.

Cosmetic compositions containing the active compound preparation according to the invention can be present as O / W or W / O emulsions. Suitable emulsifiers for O / W emulsions are, for example, adducts of 2-30 moles of ethylene oxide with linear C ₈ -C ₂₂ -fatty alcohols, with C ₁₂ -C ₂₂ -fatty acids and with C ₈ -C ₁₅ -alkylphenols; C ₁₂ -C ₂₂ fatty acid mono- and diesters of addition products of 1-30 moles of ethylene oxide with glycerol; Glycerol mono- and diesters and sorbitan mono- and diesters of C ₆ -C ₂₂ fatty acids; Polyol and polyglycerol esters; Addition products of ethylene oxide with castor oil; Betaines such as Kokosalkyldimethylammoniumglycinat or Kokosacylaminoethylhydroxyethylcarboxymethylglycinat (CTFA: Cocamidopropyl Betaine) and ampholytic surfactants.

Suitable emulsifiers for O / W emulsions are, for example, addition products of 2-15 mol of ethylene oxide with castor oil; Esters of C ₁₂ -C ₂₂ fatty acids and glycerol, polyglycerol, pentaerythritol, sugar alcohols (eg sorbitol), polyglucosides (eg cellulose); polyalkylene glycols; Lanolin alcohol; Copolymers of polysiloxane-polyalkylpolyethers.

The cosmetic active ingredient preparation according to the invention protects in a particularly effective manner against the attack of free radicals on the skin both alone and in combination with other active ingredients. It has a high radical protection factor between 100 and 3500 × 10 ¹⁴ radicals / mg.

The radical protection factor (RPF) determined the activity a substance for binding free radicals to a test substance. This Test substance consists of a very reactive, semi-stable radical, which reacts with all known antioxidants. To such Radicals belong Nitroxides, such as Proxo (2,2,5,5-tetramethyl-1-dihydropyrroline-oxy-nitroxide), Tempol (2,2,6,6-tetramethyl-1-piperidinoxy-4-ol-nitroxide), DTBN (di-tert-butyl-nitroxide or preferably DPPH (1,1-diphenyl-2-picryl-hydrazyl).

The measurement of the RPF is made by measuring the signal amplitude of the test radical by electron spin resonance (ESR / EPR) before and after mixing with an antioxidant and calculating the RPF therefrom. RPF is known for a number of standard antioxidants, for all-trans retinol at 827, all-trans retinol acetate at 196; for DL-α-tocopherol at 41200 and for α-tocopherol acetate at 48, respectively × 10 ¹⁴ radicals / mg.

The cosmetic active ingredient preparation according to the invention, which, when called the "association complex" of the components (a) to (e) is present at a concentration of (a) and (b) each of 10% by weight alone has an RPF of 1255 and is thus very much high above usual Active ingredients in cosmetic formulations with declared radical scavengers Reach values of about 4 to 40. Here are the actual active ingredients in (a) and (b) only in a concentration of not more than 2% by weight.

Under "high radical protection factor" is used in the present Invention understood a value of 100 or higher, preferably 1000 or higher. This value can be used in certain combinations of plant extracts according to the invention and the actual association complex increased to 10,000 and higher become.

The exact measuring method for the radical protection factor is described by Herrling, Groth, Fuchs and Zastrow in Conference Materials "Modern Challenges To The Cosmetic Formulation" 5.5.-7-5.97, Dusseldorf, pp. 150-155, Verlag f. chem. Ind. 1997. Here, starting from the known concentration of the test substance (here: DPPH) or the number of its free radicals (radicals per ml), a signal amplitude S _{1 is} measured by means of an ESR spectrometer. The test radical, like the antioxidant, is dissolved in a (eg 0.1 M) water / alcohol solution. Then the signal amplitude S _{2 of} the antioxidant is measured. The normalized difference between the two signal amplitudes is the reduction factor RF. RF = (S. 1 - p 2 ) / S 1

The result of the radical reduction of the test substance RC × RF is normalized to the amount of product input PI (mg / ml). Here, RC is the amount of the test substance, ie the known number of radicals of the test substance. The radical protection factor is calculated according to the following equation

The result is RPF = N × 10 14 [Radicals per mg], where N is a positive real number, and the RPF can be shortened to the numerical value of N in a simplified manner.

The radical protection factor can be determined using a handy and very simply constructed ESR spectrometer (GALENUS GmbH, Berlin, Germany) and is a new size for labeling cosmetic products in terms of their ability to bind free radicals. The method is an in vitro method in which no individual properties of the cosmetic user affect the antioxidants sen.

Further advantageous effects of Products with the active compound preparation according to the invention along with other active ingredients and carriers are a long-lasting Improvement of the overall condition of the skin, delaying the aging process the skin, sustained improved moisturizing and smoothing of the skin Skin. The above-described particularly advantageous embodiment with an additional Algae-peptide product and hard-magnetic barium hexaferrite monocrystals shows a particularly allergy-reduced risk of allergies and dermatological testing.

The use of the cosmetic according to the invention preparation can e.g. take place in sun creams, sun gels, aftersun products, Day creams, night creams, masks, body lotions, cleansing milk, Make up's, lipsticks, Eye cosmetics, hair masks, hair conditioners, hair shampoos, shower gels, shower oils, bath oils and further usual Products. The production of such products takes place in a manner as known to those skilled in the art. It can at Choice of entspechender carriers also corresponding pharmaceutical preparations are produced.

The invention further relates a cosmetic preparation according to claim 1 or 10 the one Content of plant extracts selected from the group consisting from citrus extract, bitter orange extract, cherry extract of the Spanish Cherry cherry, papaya extract, tea extract, coffee bean extract, Prunus extract, H extract, Angelica extract and mixtures thereof, closer as you can see above have been defined, with a proportion of 0.5 to 40% by weight, and 99.5 to 60% by weight of further active ingredients or carriers or mixtures of Active ingredients and carriers, in each case based on the total composition. As active ingredients and carriers can the previously mentioned substances are used.

The invention will be understood by Examples closer explained become. All information is given in weight percent, if nothing another is indicated.

manufacturing of the active substance complex

For the preparation of the gel base Gel powder, such as carbomer, in water was homogenized therein and subsequently e.g. neutralized with triethanolamine. After that, an encore was done of ethanol and glycerol for better incorporation, the Mixture well stirred has been.

To this gel base a mixture of phospholipids (Phoslipon ^®), quebracho extract and silkworm extract was added and mixed at a temperature not exceeding 45 ° C so. This was followed by the addition of another part of the above gel or a second gel, such as guar Propyltriammoniumchlorid, which was stirred well with the overall mixture at elevated temperature but below 45 ° C. This gave the active compound preparation according to the invention.

In the case where the active ingredient preparation contained other ingredients such as yeast digestion product, acerola extract or extracts of tea, coffee, kiwi, citrus, cherry, papaya or skin tree, this extract was added to the phospholipid mixture and then mixed with the gel. Example 1 Day Cream Phase A Carbomer 0.2 glycerin 2.0 propylene glycol 1.0 least. water qs ad 100 Phase B C ₁₂ -C ₁₅ alkyl cetyl alcohol 3.7 Stearath 0.5 jojoba oil 1.0 Phase C triethanolamine 0.2 Phase D Active substance complex with (a) - (e) 3.5 Perfume 0.5 preservative 0.3

The phases A and B were heated with stirring to 65 ± 2 ° C and the phase B in phase A homogenized. This was followed by the addition of phase C and corresponding homogenization. It was then cooled with stirring to about 35 ° C and the phase D added with thorough mixing. The active ingredient complex contained 1.0% from baker's yeast and after the ultrasound method of DE 4241154C1 recovered SOD-containing enzyme / vitamin product.

The added active substance complex contained 1% of dry gel, 7% phospholipids 2% quebracho extract (Radikalys ^® from Greentech SA, Saint Beauzire, France), 1% silkworm extract, 1% SOD from yeast decomposition. The radical protection factor of the active substance complex was 1925; the formulation had a factor of 49. Example 2 Special Cream Phase A glycerin 3.0 least. water qs ad 100 Phase B vaseline 22.5 jojoba oil 5.0 Phase C Complex of Active Compounds with (a) - (f) Asymmetric Lamellar Aggregates (AOCS) 5.5 according to Example 2 of WO94 / 00109 AOCS with Ba hexaferrite single crystals 10.5 according to Example 1 of WO95 / 03061 Modified kaolin according to Example 1 2.0 from W096 / 17588 0.3

Phases A and B were added with stirring 65 ± 2 C ° heated and phase B is homogenized in phase A. Thereafter, it was stirred up about 35 ° C chilled and phase C under careful Mixing added.

The active substance complex contained 1.0% from wine yeast and after the ultrasonic procedure of DE 4241154C1 0.5% vitamin E and 0.5% vitamin C were added as basic constituents of the active ingredient complex. 0.5% dry gel, 10% phospholipids, 1% quebracho extract, 2% silkworms Extract. The radical protection factor of the Wirkstoffkomppees was 2120; the formulation had a factor of 41.5. Example 3 Sonnengel Phase A Carbomer 1.5 glycerin 3.0 propylene glycol 2.5 least. water qs ad 100 Phase B Triethanolamine 1.5 Phase C Peptide preparation MAP-X ^® according to PCT / DE97 / 02941 1.0 ZnO 2.0 TiO ₂ 5, 0 SiO ₂ 1, 0 Shellac (20% aqueous solution) 1.0 Phase D Active substance complex with (a) - (f) 3.5 Phase E Perfume 0,5; preservative 0.3

Phase A was stirred up 60 ± 2 C ° heated and homogenized and at 45 ° C cooled. The Phase B was homogenized in phase A. After cooling to about 40 ° C the addition of phase C and good homogenization took place. Then it became with stirring at about 35 ° C chilled and phases D and E with thorough mixing and further stir added.

The active substance complex contained 1.0% of brewer's yeast and after the ultrasound method of DE 4241154C1 in each case 0.5% vitamin E, vitamin C and vitamin A. The basic constituents of the active substance complex were 0.15% dry gel, 20% phospholipids, 5% quebracho extract, 3% silkworms -Extract.

The radical protection factor of the active substance complex was 3050.

Example 4 day cream

It became a composition according to example 1, wherein the drug complex instead of 1% SOD Yeast digestion 20% Tea extract of black tea contained. The radical protection factor of the active substance complex was 3100.

Example 5 sun cream

A composition was prepared according to Example 1, wherein in phase A additionally 3% TiO ₂ and 7.5% Benzophenone-3 were included. The drug complex contained 5% coffee bean extract of roasted coffee beans and 2% kiwi extract instead of 1% SOD from yeast digest. The radical protection factor of the active substance complex was 3200.

Example 6 day cream

In a composition according to example 1, 1% TiO ₂ and 0.5% ZnO were additionally added in phase A. Instead of 1% SOD from yeast digest, the active ingredient complex contained 1% tea extract of green tea, 2% coffee bean extract of green coffee beans, 1% vitamin C and 1% vitamin E (tocopherol acetate). The radical protection factor of the active substance complex was 5600.

Example 7 Comparative Example 1

The following constituents of an active substance complex were mixed together: 0.15% Guar propyl triammonium chloride (gel) 20% phospholipids 0.1% triethanolamine 79.75% Water.

The measured radical protection factor was zero.

Example 8 Comparative Example 2

The ingredients of Example 7 at a water content of 78.65% 1% vitamin E and 0.1% Vitamin C added. The mixture had a radical protection factor from 2.

Claims (12)

Cosmetic preparation with high radical protection factor, characterized by a content (a) one by extraction the bark of Quebracho blanco and subsequent enzymatic hydrolysis recovered product containing at least 90% by weight of proanthocyanidin oligomers and at most 10% by weight of gallic acid contains wherein the content of (a), that in a bound to microcapsules Active ingredient concentration of 2% by weight, in the range of 1 to 10% by weight; (b) a silkworm extract obtained by extraction, the peptide Cecropine, amino acids and contains a vitamin mixture, wherein the content of (b) is in the range of 0.1 to 10% by weight; (C) a nonionic, cationic or anionic hydrogel or mixture of hydro-gels containing (c) in the range of 0.1 to 5% by weight; (d) one or more phospholipids in one portion from 0.1 to 30% by weight; and (e) water; each related on the total weight of the active compound preparation. Preparation according to claim 1, characterized by a radical protection factor in the range of 100 to 3500, measured by determining the number of free radicals of a solution of a test substance (S ₁ ) by means of electron spin resonance (ESR) in comparison with the ESA measurement result of the cosmetic active substance preparation according to the relation RPF = (RC × RF) / PI where RF = (S ₁ -S ₂ ) / S ₁ ; RC = concentration of the test substance (radicals / ml); PI = concentration of active ingredient preparation (mg / ml). Preparation according to claim 1, characterized in that that the Extract (a) at least 99% by weight of proanthocyanidin oligomers and at the most 1% by weight of gallic acid contains. Preparation according to claim 1, characterized in that that the in (b) contained amino acids Aspertinsäure, Asparagine, threonine, serine, glutamic acid, proline, glycine, alanine, Valine, cysteine, methionine, isoleucine, leucine, tyrosine, phenylalanine, Lysine, histidine, arginine include. Composition according to Claim 1, characterized in that the vitamin mixture containing (b) comprises vitamins B ₁ , B ₂ , B ₅ , B ₆ , B ₈ , B ₉ , B ₁₂ , PP, A, E and C. Preparation according to claim 1, characterized in that that the Active ingredient preparation in addition contains a mixture of vitamins A, E and C or the vitamins individually. Preparation according to claim 1, characterized in that that she as an association complex exists between the phospholipids (d), which partially include components (a) and (b), and the gel (c) with the water (e). Preparation according to claim 1, characterized in that that she additionally contains (F) containing at least 150 units of superoxide dismutase per ml Ultrasonic decomposition product a yeast, wherein the content of the digestion product (e) in the range of 0 to 4% by weight; and (g) an extract of Acerola Malpighia punidifolia, wherein the content (f) is in the range of 0 to 30% by weight; in each case based on the total weight of the active compound preparation. Preparation according to claim 1, characterized in that that the Active ingredient preparation is present in a cosmetic composition, which still has one or more of the following components includes: (1) Extracts or treated free radical binding or extracts hygroscopic (1.1) Plants selected under acerola (Malpighia punidifolia), Camellia oleifera, Colunsonia canadensis and Hibiscus sabdariffa, or (1.2) Algae selected under Omegaplanktone with high content of cerebroside-stimulants, micro-algae of the genus Chlorella and associated with byssus (mussel silk) Macro-algae of the genus Ulva as a biotechnological protein fraction and subsequent association with dextrin, the product being in the Mixture with peptide derivatives derived from α-MSH and with xanthine are associated; (2) Yeast digestion products selected under baker's yeast, Brewer's yeast and wine yeast and produced after a gentle Sonication of the aqueous yeasts; (3) natural and synthetic polymers selected from chitosan glycolate, Condensation products of milk powder and activated fatty acids; (4) hard magnetic single crystals of barium hexaferrite with a coercive field strength of 3000-5000 0e and a grain size of 50-1200 nm embedded in or in admixture with asymmetric lamellars Aggregates of phospholipids and fluorocarbons; and (5) others Active ingredients selected Chitosanglycolate, hyaluronic acid, Omega CH activator, Behentrimoniumchlorid, Passion flower oil, as well as carriers. Preparation according to claim 1, characterized in that that the Components (a) and (b) in concentrations of 0.1 to 3% by weight in the preparation of active ingredient. Preparation according to claim 1 or 10, characterized that she additionally has a content of 0.1 to 20% by weight of plant extracts selected from of the group consisting of citrus peel or leaf extracts (Citrus bigaradia, Citrus hystrix, Citrus aurantifolia, Citrofurtunella microcarpa, Citrus aurantium, Citrus reticulata), bitter orange extract (Peel or fruit), Cherry cherry cherry extract, Kiwi Extract (Actinidia chinensis), Papaya Fruit Extract (Caricae papayae), tea extract [leaves from green or black tea, leaves or bark of New Jersey tea (Ceanthus velutinas)], coffee bean extract (INCI name: Coffee Bean Extract, of green or roasted beans), Prunus extract (Prunus armeniaca, Prunus dulcis, Prunus persica, Prunus domestica, Prunus spinosa, Prunus serotina, Prunus virginiana), Extracts of the bark of the Mexican skin tree (Mimosa tenuiflora), Angelica root extract (Angelica archangelica). Use of the cosmetic active substance preparation with high radical protection factor according to one of claims 1 to 11 together with other cosmetic substances, such as other active substances, Excipients and carriers in cosmetic preparations such as creams, gels, lotions, masks, Make-up's, shampoos, pencils, oils, mascara and appropriate sunscreen preparations.