GB2202146A - Skin-regenerating cosmetic composition - Google Patents

Description

or 1 1 1 2202146 SKIN-REGEINERATING COSMETIC COMPOSITION AND PROCESS FOR

PREPARING SAME This invention relates to skin-regenerating cosmetic compositions as well as to their preparation.

The skin is one of the most important organs of the living organism which is in a continuous contact with the outside world and is exposed to a wide variety of influences.

It is known that C 18-22 CA,-3 unsaturated fatty acids possess advantageous biological properties. Of these compounds eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) are outstanding. Oyerberg et al. /-The Lancet 15, 117 (1978)7 pointed at the importance and multifold biological effects of both acids.

The stabilization of polyunsaturated fatty acids by glutathione in compositions used for various alimentary and cosmetical purposes was described in the published Japanese patent application No. 61.23599.

The ability of EPA and DHA to be incorporated in the fibroblasts of the human skin was described by Baherjee et al. /-Biochim. et Biophys. Acta 835, 533 (1985)7.

The active ingredients of the fish-oil, e.g. EPA and DHA, are precursors of the biosynthesis of the PG-3 series and inhibit the formation of harmful metabolites such as UA 2 and UB 2 arising from the so-called "arachidonic acid cascade" which is a chain of complicated biochemical - 2 processes starting from arachidonic acid.

A further advantage of the fi5h-oil is that it contains in a native form vitamins such as vitamins A and D which are most important for the skin.

An extraordinarily high number of publications and patent specifications have been devoted to the biological effect of polyunsaturated acids, especially EPA and DHA, such as the effects on the platelet aggregation, tumour cells, arteriosclerotic diseases and oxido-reductive steps of several biochemical processes.

It is further known that algae have from time immemorial been used by the mankind for the purpose of nutrition and feeding. Recently, the scope of using algae has significantly been extended since the algae contain innumerable in- dispensable bioactive substances such as essential fatty acids, vitamins, provitamins, mucoproteins, and polysaccharides. In the last decades the algae even represent an important basic material in several industrial fields such as the food, pharmaceutical and cosmetical industries.

The possibilities of using marine algae for the last purpose, which are available in large amounts, were mainly reported by De Roeek and Holtzhauer /-La France et ses Parfums 68, 166 (198127. A number of cosmetic compositions have been prepared by using algae. Such a solution was described in the French patent specifications Nos. 2,242,990 and 2,426, 404 as well as in the published Japanese patent applications Nos. 52. 003835 and 60.013700.

Investigations on the biological effects of micro- k I, 6 -8.

k elements and trace elements have been started in the last decades. Thus, it became known that selenium is one of the most important and indispensable substances of life. The beneficial action of selenium is mainly based on its activating effect directed to the glutathione-peroxidase enzyme as selenium is an indispensable constituent of the prosthetic group of this enzyme which is the most important endogenic inhibitor of the harmful peroxidation processes. Selenium is not accumulated in the organism, thus it should continuously be supplemented. Hitherto, selenium has mainly been introduced to the organism in the form of inorganic compounds, e.g. selenium dioxide and sodium 5elenite. A comprehensive report on the biological effects of selenium was published by Thressa et al. /- Nutrition Review 35, 7 (1977)7, Shamberger /-J. of Env. Path. and Tox. 4, 305 (1980)7 as well as Masukawa /_Experientia 39, 405 (1983j.

The aim of the present invention is to provide a novel cosmetic composition combining the advantageous effects of C4X-3-polyunsaturated fatty acids, particularly EPA and DHA, as well as of algae and of selenium.

The invention is based on the recognition that the above aim can be fully achieved by using selenium-containing algae together with polyunsaturated fatty acids.

The invention is further based on the recognition that the selenium content of the algae, used together with unsaturated fatty acids and applied onto the skin, is given off whereby the ageing process of the skin is inhibited.

Based on the above, the invention relates to a skin- i 1 i C, - 4 -regenerating cosmetic composition, which comprises as active ingredients 0.5 to 40% by mass of selenium-contain ing alga as well as 99.5 to 605. by M2SS of polyunsaturated fatty acids in admixture with carriers and/or additives, commonly used in the cosmetic industry, and possibly with antioxidants.

The compositon contains preferably (.4.r-3 fatty acids having,18-22 carbon atoms, advantageously 5,8,11,14,17-eicosapentaenoic acid (EPA) and 4,7,10,13,16,19-docosa- hexaenoic acid (DHA) or their derivatives, preferably esters, alkali metal salts or amine salts, as unsaturated fatty acids.

The composition according to the invention is suitably prepared in such a way that the fat phase and the aqueous phase are separately made up by heating the fat-soluble components up to the melting, keeping the watersoluble components in an aqueous solution at 80 0 C for 30 minutes and then combining both phases. Just at the moment before mixing, vitamins A and E are added to the fat phase and Hygroplex (manufacturer: CLR, WestBerlin, Friedenau) is mixed to the aqueous phase. The mixing is carried out by pouring the aqueous phase to the fat phase under vigorous stirring, then mechanically stirring the mixture cooled to 50 OC for additional 1 to 2 minutes. The fragrance and camomile extract are blended to the ointment while rapid stirring at 40 0 C. Thereafter, the mass is cooled to room temperature under continuous stirring.

W C - 5 As raw materials of the unsaturated fatty acids, oils obtained from various marine and fresh-water fish, e.g. the oil of mackerel, cod-fish, herring, sardine and squid can be used. In addition, the oils obtained from the liver of fish such as cod-liver oil can preferably be used.

The selenium-containing algae can be prepared by cultivating algae on or in an aqueous medium containing 10-7 to 2 x 10-3 moles per litre of a soluble organic and/or inorganic selenium compound; preferably the algae used for cultivation is selected by treating a strain of algae with N-nethyl-N'-nitro-N-nitrosoguarnidine and propagating the strain on a selenium-containing propagation medium and selecting for further cultivation those individuals that both -Lnccrporate selenium, readily and have a high growth rate. Preferred algae species include unicellular blue or green algae, e.g. Chlorella sp., Scenedesmus sp., or Sp.Lrulina sp., and in particular Apha-nocapsa thernalis, Chlorella minitissima, Chlorella fusca, Scenedesmus obtisjusculus, Scenedesmus obliquus or Nostoc commune (as described in our co-pending application corresponding to HU 575/88). In this way, selenium accumulates in the organism of the growing algae.

As cosmetic additives, among others stearoyl monoglyceride, Chremofor 'W' and "0" (manufacturer of both: BASF, Ludwigshafen, German Federal Republic), cetylalcohol, octylstearate, vitamins A and E, glycerol, Hygroplex (manufacturer: CLR),fragrances and camomile extract are used.

As antioxidant e.g. butylhydroxy-toluene can be p referably used.

1 1 i G The main advantages of the composition according to the invention can be summarized as follows: a) The preferred properties of EPA and DHA as well as of selenium and algae are combined by the components of the composition. b) It contains selenium as a natural substance enriched with the alga; the selenium administered together with the C 7 alga is better resorbed and exerts more preferably its favourable effects.

c) The compositions containing alga enriched with selenium can be very preferably used to care the skin and to delay or avoid, respectively, the ageing of the skin tissue.

d) The composition exerts its effect directly on the skin, without any internal treatment.

e) In. the course of use, the alga contained in the composi tion gives off its selenium content through the human skin and protects the skin against the harmful effects of malondialdehyde which arises from the radical peroxidation reactions proceeding in the skin.

The invention is illustrated in detail by the following non-limiting Examples.

The components used as basic materials are prepared according to Examples 1, 2 and 3. The preparation of the compositions according to the invention is described in the further Examples.

Example 1

2 kg of sodium hydroxide are dissolved in 70 litres of 95% ethanol and while keeping as hot, 10 kg of sardine-oil are added. The mixture is refluxed under nitrogen for 2 hours, then cooled to 10 OC while stirring. The sodium salts of the saturated fatty acids are precipitated. The crystals are filtered and washed with a little ethanol. The ethanclic filtrate is evaporated and 20 litres of boiled- -out water.are added to the residue. The nonhydrolyzable compounds such as cholesterol are completely removed by extraction with 5 litres of hexane. The aqeuous phase is acidified to pH 2 by adding dilute sulfuric acid and it is again extracted with 15 litres of hexane. The organic phase is washed with water, dried over anhydrous sodium sulfate and evaporated to give 3.2 kg of a concentrated oil with a DHA content of 36.8% and EPA content of 31.8%. This oil is brown and smells of fish. Thus, it is mixed with Fuller's earth, heated under nitrogen at 105 OC for 10 minutes and filtered as hot. The deodourization is achieved by steam distillation under vacuum at 170 0 C/1.3 bar for 3 hours to give 1.6 kg of a light yellow, tasteless, practically odourless fatty acid mixture with virtually unchanged composition.

Example 2

8 kg of 40% sodium hydroxide solution are dropped at 50 to 60 OC to 24 kg of cod-liver oil dissolved at 60 0 C in 16 litres of methanol. under stirring. Then the mixture is stirred at 60 0 C for additional 45 minutes.

kg of 15% hydrochloric acid are added to the.solution at about 60 OC. After separating the phases the organic layer is washed with 10 kg of 15% hydrochloric acid and then with 180 litres of hot tap water until neutral. The phases are again separated, 100 litres of acetone are added to the oily phase which is then heated to about 45 0 C and a solution of 3.8 kg of lithium hydroxide monohydrate in 1 -q- litres of water is added. After stirring for 30 minutes the mixture is left to stand overnight, then filtered and the acetone filtrate is evaporated. The residue is acidified by adding about 8 kg of 15% hydrochloric acid, extracted 3 times with hexane and evaporated. During the whole purifying operation nitrogen atmosphere is used.

Thus, 6.4 9 of purified fish-oil are obtained with an iodine number of 258 and an acid number of 160.

One kg of the cod-liver oil purified as described above is dropped at 60 0 C to a solution containing 3 kg of urea in 9 litres of methanol. The mixture is stirred at the same temperature for 2 hours and then cooled. It is left to stand at -10 OC overnight, then filtered and the filtrate is evaporated. 2.5 litres of 1:1 hydrochloric acid are added to the residue and the mixture is stirred C for 15 minutes. After extracting with hexane, the hexane phase is washed with water until neutral, dried over anhydrous sodium sulfate and evaporated to give 0.34 kg of C4X -3 unsaturated fatty acids with an iodine number of 315,' EPA content of 24% and DHA content of 42%.

Example 3 40 mg of sodium selenite are added to 8 litres of KnopPringsheimls culture medium filled in an alga-cultivat- ing glass bottle of 10 litres volume. The thus-obtained culture medium is sterilized at 121 0 C under an overpressure of 1 bar for 30 minutes. The sterile' solution is inoculated with a pure alga culture of selenium- resistant i i 1 ( - M - Scenedesmus obtisiusculus. Sterile air containing.5% by volume of carbon dioxide is bubbled through the culture medium at 25 OC while the system is illuminated by an electric discharge tube working with 4000 lux at a wavelength of 440.to 520 /um and 640 to 700 /um. After a cultivation period of 14 days the alga is separated from the culture medium. The thusobtained alga mass is decomposed by supersound and carefully dried at a temperature below 65 OC to give an alga powder with a selenium content of 1200 /ug/9.

Example 4 100 9 of a selenium-containing alga powder (selenium con.tent: 260 /ug/g) are added to 150 g of 65% enriched cod-liver oil (containing 22% of EPA a-nd 43% 6f DHA).

After homogenizing, 0.5% of vitamin E is. added. The thus-obtained homogenizate is used as active ingredient for the preparation of hydrating and skin-regenerating evening and morning ointments as well as eye wrinkle cream.

Example 5 The homogenizate prepared as described in Example 4 is mixed with the following components: Homogenizate according to Example 4 2.00 5.00 2.00 2.00 2.00 Stearoyl monoglyceride Cremophor A (BASO Cremophor 0 (BASO Cetylalcohol 1 Y cl Cetylstearate Vitamins A + E Water Glycerol Phenonip (NIP Laboratorien, West-Berl Schbneberg) Hygroplex (CLR) Camomile extract 60% 10.00 1.00 65.60 4.00 0.20 5.00 1.00 Fragrance 0.30 From the above components a cream is prepared in a manner known from the cosmetic practice as follows:

a) Preparation of the fat phase The mixture of stearyl monoglyceride, Cremophor A, Cremophor 0, Alfol and Cetiol 868 is heated at 76 to 8U OC until the complete melting of the components. Before mixing the fat phase with the aqueous phase, vitamins A and E are added.

b) Preparation of the aqueous phase Glycerol is heated together with Phenonip, alga concentrate and water at 80 OC for 30 minutes and Hygroplex is added to the mixture before mixing the fat phase with the aqueous phase.

c) The aqueous phase is poured to the fat phase while rapid stirring, the mixture is mechanically stirred for 2 minutes and then further stirred manually.

d) The mixture is again mechanically stirred at 50 OC for 1 to 2 minutes.

i a -1 (P e) The fragrance and the camomile extract are added at 40 OC to the mixture which is then subjected to vigorous stirring.

f) The thus-obtained cream is slowly cooled to room temperature while stirring.

Example 6

The process described in Example 4 is followed, except that the homogenizate (amounting to 2.0 parts by mass of the final product) is mixed with the following components:

Mixture of mono-, di- and tri(alkyltetraglycolether)-o-phosphonic acid ester C 12-14 (Hostaphat KL 340 N; HOECHST, Frankfurt a.M., FRG) 4.00 parts by mass Decylester of oleic acid 4.00 parts by mass White oil (vaseline oil) 6.00 parts by mass Water q.s. ad 100.00 parts by mass Sodium salt of a copolymerisate on acrylic acid/acrylamide basis (Hostacerin PN 73; HOECHST) 0.60 parts by mass Phenonip (NIP Laboratorien) 0.30 parts by mass Fragrance 0.30 parts by mass From the above components, a body-caring cosmetic composition is prepared in a manner known in the cosmetic Practice and described in Example 5.

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Claims (11)

C 1 a i m S

1. A skin-regenerating cosmetic composition, which c o m p r i s e s 0.5 to 40% by mass of selenium-containing algae and 99.5 to 60% by mass of unsaturated fatty acids or their derivatives in admixture with carriers and/or additives,commonly used in the cosmetic industryand optionally with antioxidants.

2. A composition as claimed in claim 1, which c o m p r i s e s c 16-22 CAJM-3 fatty acids as unsaturated fatty acids.

3. A composition as claimed in claim 2, which c o m p r i s e s 5,8,11,14, 17-eicosapentaenoic acid (EPA) and 4,7,10,13,16,19-docosahexaenoic acid (DHA) as unsaturated fatty acids.

4. A composition as claimed in claim 1, which comprises esters, alkali metal salts or amine salts as fatty acid derivatives.

5. A process for the preparation of a skin-regenerat- ing cosmetic composition as claimed in claim 1, which c c m p r i s e s mixing 0.5 to 40% by mass of selenium-containing algae and 99.5 to 60% by mass of'unsaturated fatty acids or their derivatives with carriers and/or additives,commonly used in the cosmetic industryand optionally with an antioxidant, in a manner commonly known in the cosmetic industry.

-1k-

6. A skin-regenerating cosmetic composition comprising a seleniumcontaining algae and one or more unsaturated fatty acids or derivatives thereof in admixtures with carriers and/or additives commonly used in the cosmetic industry, optionally 5 together with antioxidants.

7. A composition as claimed in claim 6 ' which contains, based on the combined weight of the selenium-containing algae and the unsaturated fatty acid(s) or derivatives thereof, 0.5 to 4WIG of the selenium- containing algae and/or 60 to 99.5% of the unsaturated fatty acid(s) or derivatives thereof.

8. A process of preparing a skin-regenerating cosmetic composition as claimed in claim 6 or claim 7, whichcomprises mixing together the components thereof.

9. A skin-regenerating cosmetic composition substantially as hereinbefore described in Example 5 or Example 6.

10. A composition as claImed in claim 1 or 6, wherein the fatty acid(s) and/or the algae are prepared by a process substantially as hereinbefore described in Example 1 or 2 or in Example 3 respectively.

11. A process as claimed in claim 8, substantially as hereinbefore described in Example 5 or Example 6.

Published 1988 at The Patent Ofnce, State House, 66171 HIgh Holborn, London WC1R 4TP. Further copies may be obtained from The Patent Ofnee, Sales Branch, St Mary Cray, Orpington, Kent BR5 3RD. Printed by Multiplex techniques ltd, St Mary Cray, Kent. Con. 1187.

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