EP1746972A1

EP1746972A1 - Cosmetic method for treating skin with sun products and sun product combination

Info

Publication number: EP1746972A1
Application number: EP05730919A
Authority: EP
Inventors: Karin Golz-Berner; Leonhard Zastrow
Original assignee: Coty BV
Current assignee: Coty BV
Priority date: 2004-04-20
Filing date: 2005-04-14
Publication date: 2007-01-31
Also published as: WO2005102260A1; DE102004020060B3; US20090117060A1; US7892523B2; CN1942169A; JP2007533690A

Abstract

The invention relates to a cosmetic method, whereby skin is treated with various sun products, and to a sun product combination. The inventive method is characterized by applying, prior to intensive exposure of the skin to UV radiation, a pre-sun product, then a sun product and finally repeatedly applying an after-sun product. The pre-sun product comprises a radical interceptor, the combination caffeine/complex amino acid salt, the combination photolyase/UV endonuclease and an algae extract of Corallina officinalis. The sun product comprises a UV filter combination of UVA and UVB filters having at least 3 % by weight of UVA filter. The after-sun product comprises components similar to those used for the pre-sun product, the content of the radical interceptor and the enzyme photolyase being by 50 to 90 % by weight lower, the content of the enzyme UV endonuclease being by 50 to 90 % by weight higher, and the algae extract being replaced by a cooling plant extract.

Description

Cosmetic procedure for treating the skin with sun products and sun product combination

The invention relates to a cosmetic method in which the skin is treated with different sun products, and a combination of sun products. A large number of sun protection preparations in cosmetics are known which contain sun protection filters in different compositions, which are often also only aimed at adequate UVB protection. Furthermore, products with a self-tanning effect are known, as are products which are applied to the skin after the end of the sun exposure, e.g. After-sun spray. A formulation with a skin-care effect and certain UV filter combinations is known from EP-Ar 1380279. The invention has for its object to provide a new sun product combination with improved sun protection, with improved tanning success and at the same time skin care effect and a cosmetic method for treating the skin with this sun product combination. According to the invention, the method for treating the skin with sun products is that

(a) apply a pre-sun product to the skin one to several times a day for 2 to 7 days before intensive UV radiation, comprising as essential components a radical scavenger, a combination of caffeine and complex amino acid salts, a combination of liposomally enclosed enzyme photolyase and UV endonuclease and an algae extract from Corallina officinalis,

(b) applying a Sun product to the skin in the event of intensive UV radiation, comprising a UV filter combination of UVA filters and UVB filters, at least 3.0% by weight of UVA filter being present, based on the total weight of the Sun product, and one

(c) after intensive UV radiation at least once or once to several times for 1 to 7 Days, an after-sun product is applied to the skin which comprises essentially the same constituents as the pre-sun product, the proportion of the radical scavenger and of the enzyme photolyase being 50-90% by weight lower, the proportion of the enzyme UV endonuclease is 50-90% by weight, based in each case on its total weight, and instead of the algae extract, a cooling plant extract or a plant extract mixture is contained. The pre-sun product is preferably applied two to three times a day for 5 to 7 days, and the after-sun product is preferably applied two to three times a day for 3 to 6 days. In a preferred embodiment of the invention, a Sun product is applied which contains at least 3.5% by weight of organic UVA filters, of which 0.3 to 0.7% by weight is a photostable, organic UVA filter and 2.8 up to 3.2% by weight is a photo-unstable, organic UVA filter, based on the total weight of the sun product. A Sun product with a sun protection factor (SPF) in the range from SPF 8 to SPF 30 is preferably applied. Intensive solar radiation is understood as an amount of radiation that is either achieved by exposing the skin to direct natural sunlight on a bright sandy beach for more than 30 minutes, or by artificial radiation using a sun simulator (xenon lamp XBO 450 W / 20FR) with EU _A = 8.4 mW / cm ² and EU _B = 0.18 mW / cm ^{2 for} more than 20 minutes, this process being continued for at least 3 to 6 days. Another object of the invention is a sun product combination, which consists of a pre-sun product, a sun product and an after-sun product, the pre-sun product as essential components a radical scavenger, a combination of caffeine and complex amino acid salts, a combination of liposomally encapsulated enzyme photolyase and UV endonuclease and an algae extract from Corallina officinalis, the Sύn product comprises a UV filter combination of UVA filters and UVB filters, with at least 3.0% by weight UVA Filters are included, based on the total weight of the sun product, and the after-sun product comprises essentially the same components as the pre-sun product, the proportion of the radical scavenger and the enzyme photolyase being 50-90% by weight lower the proportion of the enzyme UV endonuclease is 50-90% by weight higher, in each case based on their total weight, and instead of the algae extract, a cooling plant extract or plant extract mixture is contained. In a further embodiment of the invention, the sun product according to the invention is present as a set of a pre-sun product, a sun product and an after-sun product in a weight ratio of 1: 0.5-2: 0.8-1. The following proportions are preferred: radical scavenger 0.1-2% by weight; Combination of caffeine / complex amino acid salts 0.01 - 3.0% by weight at a ratio of 1: 10-300, with a maximum of 0.5% caffeine; Photolyase and UV endonuclease together in the range of 0.1-1.5% by weight; Algae extract 0.2 to 2.5% by weight; and plant extract 0.1 to 2.5% by weight, all proportions being based on the total weight of the respective sun product. Water- and / or oil-soluble UVA and UVB filters can be added. Benzophenone-3 and Benzophenone-4 can be used for advantageous broadband filters with effects both in the UVA range and in the UVB range. Advantageous UVB filters include 4-aminobenzoic acid derivatives such as 4- (dimethylamino) benzoic acid (2-ethyl-hexyl) ester; Esters of cinnamic acid such as 4-methoxy-cinnamic acid (2-ethylhexyl) ester, 3-benzylidene camphor derivatives such as 3-benzylidene camphor or its sulfonic acid derivatives, octyl methoxycinnamate, isoamyl p-methoxycinnamate, - ethylhexyl methoxycinnamate, octyl-methylbenzylate, 4-methylbenzene , Homosalate and octyl dimethyl PABA, sulfonic acid derivatives of benzophenone or salts such as the Na or K salt of 2-phenylbenzimidazole-5-sulfonic acid or salicylic acid derivatives such as ethylhexyl salicylates. Preferred UVA filters are butyl methoxybenzoylmethane, 1-phenyl-4- (4'-isopropylphenyl) propane-1, 3-dione, menthyl anthranilates and bis-ethylhexyloxyphenol / methoxyphenyl triazines. UVA / UVB filters can also be used, such as UV pearls (Merck, Germany). Other UVA filters also include 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 in a mixture. Particularly preferred as inorganic filters are agglomerated substrates of TiO ₂ and / or ZnO which have a content of spherical and porous SiO ₂ particles, the SiO ₂ particles having a particle size in the range from 0.05 μm to 1.5 μm , and In addition to the SiO ₂ particles, there are other inorganic particulate substances with a spherical structure, the spherical SiO ₂ particles forming defined agglomerates with a particle size in the range from 0.06 μm to 5 μm (according to WO99 / 06Ö12). During UVB rays of the wavelength range 290-320. nm only in the

If the epidermis penetrates to a depth of approximately 50 μm, UVA rays penetrate into the lower dermis layer to a depth of approximately 3 mm. Therefore, free radicals in the skin are mainly generated by the UVA range of the solar spectrum. However, the UVA range is frequently not adequately covered by filters in known sunscreens, so that the occurrence of free radicals can take place unchecked, and corresponding tissue damage is therefore often only recognized late. In the present invention, the proportion of organic UVA filters is therefore a minimum content of 3%, preferably 3.5%, and is increased even further by physical filters, in particular in the case of higher SPFs. A preferred combination of organic UVA filters is e.g. butyl

Methoxydibenzoylmethane (Parsol® 1789) with a proportion of 3.0% by weight and bis-ethylhexyloxyphenol / methoxyphenyl triazine (Tinosorb® S) with a proportion of 0.5% by weight. Surprisingly, it was found that a photostable UVA filter, such as, for example, bis-ethylhexyloxyphenol / methoxyphenyl triazine, can have a stabilizing effect compared to a photoinstable filter, such as butyl methoxybenzoyimethane or Tinosorb® M, so that overall a relatively stable UVA filter mixture is present. This also results in the above-mentioned special preferred ratio of UVA filters to one another. In addition, 0.3 - 0.7% by weight UV-Pearis® (Merck, Germany) can be added as a broadband filter, consisting of water, ethylhexyl methoxycinnamate, silica, PVP, ethanol, sodium citrate, chlorphenesin, centrimonium chloride. Complex amino acid salts are preferably mixtures of histidine-HCl, arginine-HCl, omithine-HCl, tyrosine and glutathione, preferably in a mixture with a polysaccharide such as sorbitol; for example, this is Phototan® LS2261 E from Laboratoires Serobioiogiques, Pulnoy, FR. It is also necessary to add radical scavengers that can eliminate free radicals that may occur. The proportion is 0.1-2% by weight, based on the Total weight of the product. A known and particularly effective free radical scavenger for the preparation according to the invention is an active ingredient with a high radical protection factor, comprising a content of a product obtained by extraction of the bark of quebracho blanco and subsequent enzymatic hydrolysis, which contains at least 90% by weight of proanthocyanidin oligomers and at most 10% by weight. % Contains gallic acid, in microcapsules, and a content of silkworm extract obtained by extraction, which contains the peptide cecropine, amino acids and a vitamin mixture, and a nonionic, cationic or anionic hydrogel or mixture of hydrogels, and one or more phospholipids, and water (RPF complex). Reference is made to WO99 / 66881, for example, active ingredient complex according to Example 1 or 2, or WO01 / 26617, for example active ingredient complex according to Example 1. This complex, which is referred to here as RPF complex, can be supplemented by adding the digestion product previously mentioned as a further active ingredient of yeasts and an orange extract obtained by extracting fruits with propylglycol. The cosmetic sun product according to the invention advantageously contains 0.1-1% by weight of the aforementioned RPF complex with a high radical protection factor, has an RPF for the pre-sun product in the range from 60 to 2000 × 10 ¹⁴ radicals / mg and is therefore higher as usual cosmetic formulations with declared radical scavengers, which reach values of about 10 to 40. The proportion of the radical scavenger in the Sun product and in the after-sun product is advantageously 80-90% below the proportion in the pre-sun product. The radical protection factor (RPF) determines the activity for binding free radicals by an antioxidant against a test substance. This test substance consists of a very reactive, semi-stable radical such as DMPO (5,5'-dimethyl-1-purrolin-N-oxide) or PBN (phenyl-tert-butyl-nitron), which is compatible with all known

Antioxidant reacts. The RPF is measured in such a way that the signal amplitude of the test radical is measured by electron spin resonance (ESR / EPR) before and after mixing with an antioxidant, and the RPF is calculated therefrom. The RPF is known for a number of standard antioxidants; it is 827 for all-trans-retinol and 196 for all-trans-retinol acetate; for DL-α-tocopherol at 41200 and for "-Tocopherolacetät at 48, each x 10 ¹⁴ radicals / mg. The exact measuring procedure is described by Herrling, Groth, Fuchs and Zastrow in Conference Materials "Modern Challenges To The Cosmetic Formulation" 5.5.-7.5.97, Düsseldorf, pp. 150-155, publisher f. Formerly Ind. 1997. Based on the known concentration of the test radical or the number of free radicals (radicals per ml), a signal amplitude S ^ _{t is} measured by means of an ESR spectrometer. The test radical, like the antioxidant, is dissolved in a water / alcohol solution. Then the signal amplitude S _{2 of} the anti-oxidant is measured. The normalized difference between the two signal amplitudes is the reduction factor RF. RF = (S-, - Sa) / St The result of the test radical reduction RC x RF is normalized to the amount of product input Pl (mg / ml). The radical protection factor is calculated according to the following equation RC [Rarlikalf./ml] x RF RPF = Pl [mg / ml]

The result is RPF = N x 10 ¹⁴ [radicals per mg], where N is a positive real number that is generally given without the potency number.

(See also WO99 / 66881) The combination of caffeine / complex amino acid salts surprisingly leads to an increased microcirculation. It also enhances the tanning effect caused by UV radiation in the skin. Reinforcement means a particularly long-lasting tanning effect, which can last up to 8 days. The complex amino acid salt consists of sorbitol, arginine HCI, ornithine HCI, tyrosine and SiO ₂ . A preferred combination is Caffein / Phototan® LS2261 E.

The combination of caffeine / complex amino acid salts in the sun product according to the invention is preferred in a proportion of 0.01-3.0% by weight, the ratio of caffeine to the complex amino acid salts being 1:10-300. However, it contains a maximum of 0.5% by weight of caffeine. In the sun product combination according to the invention, the sun product can additionally contain an active ingredient with a wrinkle-smoothing effect, such as, for example, colhibin and hydrolyzed rice proteins, which protect collagen from the harmful effects of collagenases and their collagenase inhibitory activity in not less than 20 collagenase inhibitor units lies. The algae extract of. Used according to the invention in the pre-sun product Corallina officinalis enhances the radical-catching effect of the RPF complex that is preferably used by an enzymatic catalytic activity and a large variety of trace elements such as iron, copper, iodine, cobalt, manganese. A preferred product is Oligophycocorail (from Semca, Pontrieux, France). The extract is preferably used in propylene glycol. The preparation according to the invention further contains cosmetic auxiliaries and carriers, as are usually used in such preparations, for example water, preservatives, dyes, pigments with a coloring effect, thickeners, fragrances, alcohols, polyols, esters, electrolytes, gelling agents, polar and non-polar oils, polymers, copolymers, emulsifiers, waxes, stabilizers. It can also contain other active ingredients. These include e.g. B. humectants, skin softeners, antioxidants, vitamins, enzymes, herbal agents, polymers, antioxidants, anti-inflammatory natural agents, oxygen-loaded asymmetric lamellar aggregates according to WO 94/00109; Digestion products of yeast or vegetable substances, produced by a gentle ultrasonic digestion process according to WO 94/13783, kaolin and kaolin modified with SiO ₂ according to WO94 / 17588. To be used as additional active antioxidants include vitamins such as vitamin C and derivatives thereof, eg ascorbyl acetate, phosphate and palmitate ^■; Vitamin A and derivatives thereof; Folic acid and its derivatives, vitamin E and its derivatives, such as tocopheryl acetate; Flavones or flavonoids; Amino acids such as histidine, glycine, tyrosine, tryptophan and derivatives thereof; Carotenoids and carotenes, such as, for example, α-carotene, β-carotene; Uric acid and derivatives thereof; α-hydroxy acids such as citric acid, lactic acid, malic acid; Stilbene and its derivatives; as well as various plant extracts. A plankton extract is introduced as an active ingredient via liposomes, for example one obtained from cyanobacteria of the genus Anacystes nidulans and containing an effective amount of the enzyme photolyase. This enzyme contributes to the fact that cyclobutaripyrimidine dimers formed as a result of UV radiation are split up again with the inclusion of daylight, thus achieving a repair effect for the skin. The encapsulation of the plankton extract in special liposomes which are formed from three types of phospholipids is particularly advantageous: from phosphatidylethanolamine, phosphatidylcholine / oleic acid and cholesterylhemisuccinate. Such lipo some show a high penetration power in keratinocytes and suddenly release their content depending on a pH reduction from eg pH 6 to pH 4. A preferred product that contains the plankton extract is Photosomes® from Barnet Products Corp., NJ / USA. A micrococcus lysate with the enzyme UV-

Endonuclease introduced, which has long-lasting, skin-repairing effects. The liposomes can have the advantageous embodiment described for the plankton extract. A preferred product is Ultrasomes® from Barnet Products Corp., NJ / USA. The proportion of photolyase and UV endonuclease in the form of the commercial products mentioned is 0.1-1.5% by weight. The proportion of the enzyme photolyase in the after-sun product is advantageously 75-90% below the proportion of photolyase in the pre-sun product. It is also advantageous to add a revitalizing active complex to the sun product or after-sun product according to the invention or to both. This complex consists of 1 to 9% by weight of creatine or a creatine derivative, 0.1 to 40% by weight of water-soluble glyeogen, 1 to 10% by weight of a phospholipid, 0.1 to 5% by weight of a cosmetically acceptable gel and the rest 100% by weight of water (according to WO02 / 060394). The active complex reduces the release of LDH (LDH = lactodehydrogenase, a stress enzyme that is released by the cells under UVB radiation). Furthermore, when the cells are treated with the complex, oxygen consumption as a sign of cell vitality increases and cell repair takes place, which makes the cells appear younger and in better shape. The effect occurring in this sense is a synergistic effect, since the total individual effects of glycogen and creatine are clearly exceeded both in the anti-UV test (up to +153%) and in the oxygen consumption test (up to +174%). 0.5-5% by weight, based on the weight of the preparation, of this complex can be added. The overall effect of the sun product according to the invention, due to an increased proportion of UVA filters, has a significantly reduced risk of free radical formation and combines these very good UV protective properties with skin-care properties in the form of the pre-sun and after-sun products. While with common products even with the presence of UVA and UVB

If the ratio between them is not more than 1: 3, the present invention increases this to about 1: 1.8-2.2. In addition, the combination of photostable and photoinstable UVA filters according to the invention in the appropriate conditions as particularly effective to protect the skin from damage caused by UVA rays. The pretreatment of the skin with the pre-sun product also achieves a special care effect in the combination of the components, which when used in the suggested time frame is an excellent basis for the subsequent sun exposure. The skin also proves to be very well cared for, even with prolonged intensive exposure to the sun's rays, essentially without DNA damage and negative wrinkle changes, and shows a healthy brown tone over a long period of time. Surprisingly, the relatively small addition of plant extract in the after-sun product, in particular in the form of a watermelon extract as a humectant, together with the other components of the product and the corresponding pretreatment, has a particularly long-lasting effect. In comparative experiments, it was found that the expected moisturizing effect was exceeded by 1.5-1.8 times in interaction with the other necessary components of the preparation. The watermelon extract (Citrullus vulgaris) is a water glycerin extract that contains at least -2% fruit components. The extract content is 0.1-2.0% by weight, in particular 0.1-0.5% by weight, based on the total weight of the after-sun product. A rose flower extract and a jasmine flower extract (each with water / glycerol) or mixtures of such plant extracts are also advantageous with the same direction of action. A particularly advantageous extract mixture consists of watermelon, rose and jasmine and is contained in a total proportion of 1.5-2.5% by weight. Overall, an improved supply of skin through protective and

Building materials achieved with the sun protection combination, which significantly increases the skin's resistance to UV radiation, ensures a healthy appearance of the skin and largely prevents damage. The method according to the invention and the sun product combination are also of particular importance in the case of artificial skin tanning in tanning salons in the low-light condition

Season. Both contribute to a significant improvement in the combination of UV protection and skin care, particularly in this form of application. In this context, the term “solar radiation” or “UV radiation” as used here means the radiation from lamps in tanning salons etc. that simulate solar radiation. The oils used for the invention can be conventional cosmetic oils, such as a mineral oil, hydrogenated polyisobutene, synthetic or squalane or natural products, cosmetic esters or ethers, which can be branched or unbranched, saturated or unsaturated; vegetable oils; or mixtures of two or more of them. Particularly suitable oils are, for example, silicone oils and vegetable oils, such as calendula oil, jojoba oil, avocado oil, macadamia nut oil, castor oil, cocoa butter, coconut oil, corn oil etc. The preparation according to the invention can also be formulated with gelling agents. Suitable gelling agents include carbomers, xanthan gum, carrageenan, acacia, guar gum, agar agar, alginates and tyloses, carboxymethyl cellulose, hydroxyethyl cellulose, quaternized cellulose, quaternized guar, certain polyacrylates, polyvinyl alcohol, polyvinyl pyrrolidone, montmorillonite. Carbomer is preferred. Pigments, pigment mixtures or powders with a pigment-like effect can also be added, including those with a pearlescent effect. These can include, for example, iron oxides, natural aluminum silicates such as ocher, titanium dioxide, mica, kaolin / manganese-containing clays, calcium carbonate, talc, mica-titanium oxide, mica-titanium oxide-iron oxide, bismuth oxychloride, nylon beads,

Ceramic balls, expanded and unexpanded synthetic polymer powders, powdery natural organic compounds such as ground solid algae, ground plant parts, encapsulated and unencapsulated cereal starch and mica titanium oxide organic dye. Polyols are also possible components of the invention

Sun product. Polyols are, for example, propylene glycol, dipropylene glycol, ethylene glycol, isoprene glycol, glycerin, butylene glycols, sorbitol and mixtures thereof. The proportion of the polyol is in the range from 2 to 10% by weight, preferably from about 2 to about 7% by weight, based on the total weight of the product. The invention will be explained in more detail below by examples. All information is given in percent by weight, unless stated otherwise. In the accompanying drawing, Fig. 1 shows electron micrographs for wrinkling of the skin. Example 1 Cream I SPF * ² 8 Phase A

Water q.s. ad 100, propylene glycol 2.0, xanthan gum 0.25, acrylate cross polymer 0.5,

Caffeine 0.5.

Phase B isoamyl p-methoxycinnamate 6.0, ethylhexyl salicylate 4.0, butyl

Methoxydibenzene methane 3.0, bis-ethylhexyloxyphenol / methoxyphenyl triazine 0.5,

Ethylhexyl methoxycinnamate 5.0, dicaprylyl carbonate 5.0, UV-Pearls® 0.5.

Phase C

Ethanol 3.0, RPF complex * 0.5, preservative 1, 5, Photosomes® 0.6, Ultrasomes® 0.1, vitamin E and Micrococcus lysate in liposomes 0.1,

Hydrolyzed rice protein 0.5, soy protein 0.5, Phototan® 0.5, perfume 0.8.

* Quebracho blanco bark extract enzymatically hydrolyzed and microencapsulated,

Silkworm extract with phospholipids and water in gel, WO99 / 66881

Active ingredient complex according to Example 1. * ² SPF = Sun Protection Factor (e.g. Cole, C. in Photoderm. Photoimmun. Photomed. 17: 2-

10.2001). Phases A and B are prepared separately, heated to 75 ° C and combined with stirring. After longer homogenization for about 1-20 minutes at 2800-3200

U / min the mixture is cooled to 40 ° C. Phase G is added with stirring and stirring is continued for a few minutes.

Example 2 Cream II SPF 8

Phase A

Water q.s. ad 100, propylene glycol 2.0, xanthan gum 0.25, acrylates crosspolymer

0.5, caffeine 0.5. Phase B

TiO ₂ 5.0, ZnO 2.0, ethylhexyl salicylate 4.0, bis-ethylhexyloxyphenol / methoxyphenyl

Triazine 0.5, Methylene Bis-BenzotriazIyl Tetramethylbutyl-phenol / Decyl Glycosine / PPG / -

Xanthan Gum / Water (Tinosorb M®) 2.0, ethylhexyl methoxycinnamate 5.0, dicaprylyl

Carbonate 5.0, UV-Pearls® 0.5. Phase C

Ethanol 3.0, RPF complex * 0.5, preservative 1.0, Photosomes® 0.6,

Ultrasomes® 0.1, vitamin E and micrococcus lysate in liposomes 0.1,

Hydrolyzed rice protein 0.5, soy protein 0.5, Phototan® 0.5, perfume 0.8. The procedure was as in Example 1. * see example 1

Example 3 Cream I SPF 15

Phase A

Water q.s. ad 100, glycerin 3.0, xanthan gum 0.4, caffeine 0.5. Phase B

Tribehenin PEG20 Esters 1.0, Stearic Acid 1.5, PEG 100 Stearate Glyceryl Stearate 3.0,

Dicaprylyl Carbonate 6.5m, Cyclohexasiloxane 3.0, Butyl Methoxydibenzolmethane 3.0,

Bis-ethylhexyloxyphenol / methoxyphenyl triazine 0.5, 4-methyl benzylidene camphor 4.0,

Tinosorb M® 3.0, ethylhexyl methoxy cinnamate 7.5, ethylhexyl salicylate 5.0. Phase C

RPF complex ^* 0.15, UV-Pearls® 0.1, Colhibin® 0.5, preservative 1.0,

Photosomes® 0.6, Ultrasomes® 0.1, soy protein 0.5, Phototan® 0.5, perfume 0.8.

The procedure was as in Example 1.

Example 4 Cream II SPF 15 Instead of butyl methoxydibenzolmethane and bis-ethylhexyloxyphenol / meth-oxyphenyl

Triazines 3% ZnO and 5% TiO _{2 were} used, and both were combined with the

Phase A processed. The proportion of ethylhexyl salicylate was reduced to 1%. Otherwise the procedure was as in Example 1.

Example 5 Cream I SPF 30 Phase A

Water qs ad 100, propylene glycol 2.5, EDTA 0.1, caffeine 0.5, TiO ₂ 2.0.

Phase B

Isoamyl p-methoxycinnamate 7.5, butyl methoxydibenzolmethane 3.0, Parsol MCX® 4.0,

Bis-ethylhexyloxyphenol / methoxyphenyl triazine 2.0, 4-methyl benzylidene camphor 2.0, Tinosorb M® 4.0, powder 2.0, dimethicone 2.0, isopropyl palmitate 3.0, cetyl ricinoleate

2.0.

Phase C

Ethanol 3.0, Colhibin® 0.5, RPF complex * 0.1, preservative 1.0, Photosomes®

0.6, Ultrasomes® 0.1, soy protein 0.5, Phototan® 0.5, perfume 0.9. The procedure was as in Example 1.

Example 6 Cream II SPF 30

Instead of butyl methoxydibenzene methane, 1% ZnO and 7% TiO _{2 were} used, and both were processed together with phase A. Example 7 Pre-sun Cream Phase A

Water q.s. ad 100, propylene glycol 2.0, glycerin 4.0, carbomers 0.2, caffeine 0.5.

Phase B Cetearyl Alcohol 3.0, Beheneth-25 3.5, Dicaprylyl Carbonate 10.0, Dimethicone 5.0.

Phase C

Triethanolamine 0.2,

Phase D

Ethanol 5.0, algae extract Oligophycocorail 0.7, RPF complex * 1, 0, preservative, 0,

Photosomes® 0.6, Ultrasomes® 0.1, soy protein 1.0, Phototan® 0.5, perfume 0.8.

The procedure was as in Example 1, with phase C after the merger of the

Phases A and B are added at 60 ° C.

Example 8 Pre-sun Lotion Phase A

Water q.s. ad 100, propylene glycol 1.0, glycerol 7.0, carbomers 0.08, caffeine 0.5.

Phase B

Cetearyl alcohol 5.0, Beheneth-25 4.0, dicaprylyl carbonate 12.0, dimethicone 6.0.

Phase C triethanolamine 0.08.

Phase D

Ethanol 6.0, oligophycocorail 0.5, RPF complex * 1.0, preservative 1.0,

The procedure was as in Example 7. Example 9 After-sun Cream

Phase A

Water q.s. ad 100, butylene glycol 3.0, glycerin 4.0, EDTA 0.1, caffeine 0.5

Phase B

Cetearyl alcohol 3.0, Beheneth-25 3.5, Dicaprylyl Carbonate 8.5, Dimethicone 2.0, Shea Butter 7.0.

Phase C

Ethanol 3.0, RPF complex * 0.1, watermelon extract 0.1, preservative 1, 0,

Photosomes® 0.1, Ultrasomes® 0.6, soy protein 1.0, Phototan® 0.8, Rose Extract 1.0, Jasminum Off. Extract 1.0, perfume oil 0.5.

The procedure was as in Example 1.

Example 10 After-sun Lotion

Phase A water q.s. ad 100, butylene glycol 2.0, glycerin 2.0, EDTA 0.1, caffeine 0.5.

Phase B

Cetearyl alcohol 1, 0, beheneth-25 3.5, dicaprylyl carbonate 10.0, dimethicone 3.0, Shea

Butter 5.0.

Phase C ethanol 4.0, RPF complex * 0, 1, watermelon extract 0.5, preservative 1, 0,

Photosomes® 0.1, Ultrasomes® 0.6, soy protein 1, 0, Phototan® 0.8, Rose Extract 1, 0,

Jasminum off. Extract 1, 0, perfume oil 0.5.

The procedure was as in Example 1.

Example 11 The composition corresponded to that of Example 3 with an additional 1% creatine.

Example 12 Comparative Example Skin moisture measurements were made with the corneometer at 12

Subjects with dry combination skin performed. A corneometer was used

CM 825 (Courage & Khazaka, Germany) at 23 ° C and 52% rel. Humidity. ^• 2 hours after a previous skin cleansing, the different creams were applied to the

Facial skin (cheeks) applied.

Cream A: Composition according to Example 10, but without caffeine / complex amino acid salt (Phototan®)

Cream B: Composition according to Example 10, but without watermelon extract

Cream C: composition according to Example 10

Time cream A cream B cream C to 120 98 119 after 4h 79 74 98 after 8h 54 49 88 after 12h 46 41 81 after 12h 46 41 81 after 24h 45 39 72

The comparison experiment shows that a content of 1.0% watermelon extract in cream C together with the caffeine / complex amino acid salt show a clearly superior binding of skin moisture compared to cream A, which contained only the watermelon extract. Such an effect after 24 hours can be seen as a long-term effect. Example 13 User test A user test was carried out with 100 test subjects aged 35 to 56 years. In test phase 1, the test subjects received three commercially available creams / lotions, which had been advertised by well-known manufacturers as a pre-sun product, as a sun product with SPF 15 and as an after-sun product. The products were used once a day for 14 days. This was followed by a break of four weeks. In the subsequent test phase 2, the test subjects received creams / lotions according to Examples 3, 8 and 10 of the invention. The products of the invention were rated significantly better by the test subjects without exception. In detail, the following positive opinions were obtained regarding the product combination according to the invention (in%): refreshing 90 soothing 90 reddening 91 soothing sunburn 85 immediately soothing 85 long-lasting soothing 94

Skin well-being 96 beautiful skin 87 soft skin 99 • firm skin 79 regenerated skin 93 supple skin 96 golden tan 86 more intensive tanning 70 long-lasting tanning 81 even tanning 89 radiant tanning 85 pleasant coloring 74 pleasant texture 97

Example 14 DNA repair / damage in vitro In vitro tests (with Comet Assay = Single Cell Electrophoresis Assay;

J.of Chromatography B 722 (1999) 225-247) on normal human keratinocytes. At SPF levels 8 and 30 there was a DNA repair effect of treated and irradiated keratinocytes compared to untreated and irradiated by +52%. The reduction in DNA damage at SPF levels 8, 15 and 30 was approximately -83% in each case.

Example 15 Dermis repair / fiber protection in vitro In vitro tests (ELISA immunoassay) were carried out on normal human fibroblasts. At SPF levels 8, 15 and 30 there was a dermis repair effect of treated fibroblasts compared to untreated fibroblasts of +20%. The dermis fiber protection of untreated and UV-irradiated fibroblasts and treated and UV-irradiated fibroblasts was -38%. The proportion of metal proteinase matrix was measured.

Example 16 Skin Tanning in Vitro In vitro tests were carried out on normal human melanocytes. In SPF stages 8, 15 and 30, the amount of melanin increased by + 45% for the treated melanocytes compared to the untreated ones after UVB irradiation. Example 17 Skin protection / wrinkling

The product according to the invention according to Examples 5, 7 and 9 was used in a clinical test with 20 test persons of Caucasian skin type. The product according to Example 5 was applied once a day four days before UV irradiation, the product according to Example 9 was applied three days after UV irradiation. Then the evaluation took place. 1 shows electron micrographs of unprotected and unirradiated skin (A) and of unprotected and UV-irradiated skin (B) as well as protected and UV-irradiated skin (C). Compared to B, the depth of wrinkles at C is significantly reduced, and C shows the clearly better skin appearance. Example 18 UV Protection Cell investigations on the influence of the protection of the filter combination on SPF 8, 15 and 30 showed the following result SPF 8 SPF 15 SPF 30

% UVA stopped 74 85 89% UVB stopped 87 93 97

% UVA + B stopped 88 91 94

Claims

claims

1. Cosmetic process for treating the skin with sun products, characterized in that a pre-sun product is applied to the skin one to several times a day for 2 to 7 days before intensive UV radiation, comprising a radical scavenger, a combination, as essential constituents from caffeine and complex amino acid salts, a combination of liposomally encapsulated enzyme photolyase and UV endonuclease and an algae extract from Corallina officinalis, apply a Sun product to the skin in the event of intense UV radiation, comprising a UV filter combination of UVA filters and UVB Filter, whereby at least 3.0% by weight UVA filter is contained, based on the total weight of the sun product, and after intensive UV radiation, an after-sun product is applied at least once or once to several times for 1 to 7 days Applies skin that comprises essentially the same components as the Pre-sun product, with the Antei compared to the Pre-sun product l of the radical scavenger and of the enzyme photolyase is 50-90% by weight lower, the proportion of the enzyme UV-endonuclease is 50-90% by weight, based in each case on their total weight, and a cooling plant extract or a instead of the algae extract

Plant extract mixture is included.

2. The method according to claim 1, characterized in that the pre-sun product is applied two to three times a day for 5 to 7 days.

3. The method according to claim 1, characterized in that the after-sun product is applied two to three times a day for 3 to 6 days.

4. The method according to claim 1, characterized in that a Sun product is applied which contains at least 3.5% by weight of organic UVA filters, of which 0.3 to 0.7% by weight.

% is a photo-stable, organic UVA filter and 2.8 to 3.2% by weight is a photo-unstable, organic UVA filter, based on the total weight of the sun product. lf

5. The method according to claim 4, characterized in that a Sun product with a sun protection factor (SPF) in the range of SPF 8 to SPF 30 is applied.

6. Cosmetic sun product combination, characterized in that it consists of a pre-sun product, a sun product and an after-sun product, the pre-sun product as essential components a radical scavenger, a combination of caffeine and complex amino acid salts, a combination of liposomally encapsulated enzyme photolyase and UV endonuclease and an algae extract from Corallina officinalis, the Sun product comprises a UV filter combination of UVA filters and UVB filters, with at least 3.0% by weight UVA Filters are included, based on the total weight of the sun product, and the after-sun product comprises essentially the same components as the pre-sun product, the proportion of the radical scavenger and the enzyme photolyase being 50-90% by weight lower is, the proportion of the enzyme UV-endonuclease is 50-90% by weight higher, based in each case on their total weight, and instead of the algae extract a cooling plant extract or Plant extract mixture is included.

7. Sun product according to claim 6, characterized in that it is a set of a pre-sun product, a sun product and an after-sun product in a weight ratio of 1: 0.5-2: 0.8-1.

8. Sun product according to claim 6, characterized in that the pre-sun product and the after-sun product each contain an active substance complex as a radical scavenger, consisting of a microencapsulated bark extract from Quebracho blanco, which was subsequently enzymatically hydrolyzed, a silkworm extract with the Peptide cecropine, amino acids and vitamins, together with phospholipids and an ionic or nonionic gel and water.

9. Sun product according to claim 6, characterized in that the proportion of the radical scavenger is in the range of 0.1-2% by weight, the proportion of the combination

Caffeine / complex amino acid salts in the range of 0.01-3.0% by weight is in a ratio of 1: 10-300, with a maximum of 0.5% caffeine, the proportion of photolyase and UV endonuclease together in the range of 0, 1 - 1.5% by weight, the proportion Algae extract is in the range of 0.2 to 2.5% by weight and the proportion of plant extract is in the range of 0.1 to 2.5% by weight, all proportions being based on the total weight of the respective sun product.

10. Sun product according to claim 6, characterized in. that the

Plant extract in the after-sun product is a watermelon extract with a share of 0.1 - 2.0% by weight, based on the total weight of the after-sun product.

11. Sun product according to claim 6, characterized in that it contains as a plant extract mixture in the after-sun product watermelon, rose flower and jasmine flower extract in a proportion of 1.5-2.5% by weight.

12. Sun product according to claim 6, characterized in that it contains in the Sun product or in the after-sun product or in both products as an additional active ingredient 0.5-3.0% by weight of an active complex which consists of 1 to 9% by weight % Creatine or a creatine derivative, 0.1 to 40% by weight of water-soluble glyeogen, 1 to 10% by weight of a phospholipid, 0.1 to 5% by weight of a cosmetically acceptable gel and the rest 100% by weight consisting of water , these percentages based on the total weight of the complex, and wherein the mixture of Kreätiri, - - glycogen and phospholipid is present in the aqueous gel in a homogeneous distribution.

13. Sun product according to claim 6, characterized in that each part of the combination contains additional auxiliaries, carriers or other active ingredients.

14. Sun product according to claim 6, characterized in that the pre-sun product has a radical protection factor of 60-2000 x 10 ¹⁴ radicals / mg

15. Soήnen product according to claim 6, characterized in that the proportion of the radical scavenger in the Sun product and in the after-sun product is 80-90% below the proportion in the pre-sun product.

16. Sun product according to claim 6, characterized in that the proportion of the enzyme photolyase in the after-sun product is 75-90% below the proportion in the pre-sun product.