Sun protecting cosmetic compositions comprising derivatives of dibenzoylmethane and of benzophenone

Abstract: The present invention relates to cosmetic compositions containing sunscreens against sun radiations ranging from 280 to 380 nm and their use for the protection of the skin from UV radiations. The sunscreens of the present invention are a combination consisting of, with respect to the weight of the composition: a) from 1 to 10% of one or more derivatives of dibenzoylmethane of formula (I) wherein Q is hydrogen, straight or branched C 1 -C 4 alkoxy and G is C 1 -C 8 straight or branched alkyl; b) from 0.5 to 10% of one or more derivatives of the benzophenone of formula (II): wherein R 1 is hydrogen or a straight or branched C 1 -C 8 alkyl, R 2 is hydrogen or an SO 3 M group, wherein M is hydrogen, an alkali metal or a mono- or polyalkyl substituted ammonium group; with the condition that the weight ratio between the compounds of formula (II) and the compounds of formula (I) is at least 0.5.

Description: The present invention relates to cosmetic compositions, in the foregoing called sun-protecting formulations, useful for the protection of skin and/or hair from ultraviolet radiations containing photostable mixtures of sunscreens. Background of the invention It is well known that sun radiations ranging from 280 to 400 nm are noxious to human skin; in particular those radiations with a wavelength between 280 and 320 nm, the so-called UV-B radiations, cause erythema and cutaneous sunburns, whose severity depends on the duration of the exposition on the kind of skin. It has been ascertained that also radiations ranging from 320 to 400 nm, so-called UV-A and responsible of skin tanning, can cause alterations in the skin and damages which may not be disregarded, especially in cases of sensible skins or in case of continuous exposition to radiations. It has been demonstrated that UV-A radiation other than causing damages to elastin and collagen, whose consequence is skin ageing, can also be the cause of a number of phototoxic and photoallergic reactions. Moreover the UV-B noxious action can be enhanced by the presence of UV-A (Willis et al.: Journal of Investigative Dermatology vol. 59, 416, 1972). Some compounds derived from cinnamic acid, 4-aminobenzoic acid and benzylidencamphor are well-known and also used for the preparation of sun-protecting formulations for the protection from the UV-B radiations. These compounds, other than a more or less sufficient efficacy, do not have a satisfactory photostability . 2-Ethylhexyl-cyano-β,β'-diphenylacrylate and 2-hydroxy-4-methoxybenzophenone show good photostability, however their absorption is very low, therefore they have negligible efficacy. To date, on the contrary, sufficiently effective products for the protection from UV-A are not yet available, even if in the patent literature different compounds have been proposed; but their outcome is not satisfying in practical use. At present, the UV-A sunscreens (absorber) used in practice are limited to benzophenone derivatives and to some dibenzoylmethane derivatives. Benzophenone derivatives have a very good photostability, and can act both as UV-B filters with absorption at about 290 nm, and as UV-A filters with absorption at about 325 nm. Nonetheless, the absorptions at two different wavelengths are relatively weak, especially in the UV-A zone at 325 nm, therefore these compounds are not able to provide a sufficient protection. Among the derivatives of dibenzoylmethane, 4-methoxy-4'-ter-butyldibenzoylmethane and 4-isopropyldibenzoylmethane are those commercially known. These compounds show a good absorption at 360 nm and a fair solubility in the solvents usually employed in cosmetics. However, their use is difficult, because they are not sufficiently photostable (Int. J. Cosm. Science 10, 53, 1988). Accordingly, the formulations containing these compounds can not guarantee a sufficient protection against UV-A, since the protective filter is quickly degraded by the radiation itself. In order to avoid this quick degradation and give these UV-A filters some photostability, in the patents GB 2,198,944, WO 91/11989 and WO 94/04131 particular combinations among UV-B filters belonging to the benzylidenecamphor and diphenylcyanoacrylate classes and the dibenzoylmethane derivatives are proposed. The results, however, still cannot be considered sufficient, because, even with large amounts of the above UV-B filters, it is not possible to give the dibenzoylmethane derivatives a satisfactory photostability. For the photoprotection of the skin a large number of sun-protecting formulations have been proposed and in this concern, a very wide patent literature exists. Therefore, the actual problem to be solved is the stabilization of sunscreens in cosmetic formulations, in particular of dibenzoylmethane derivatives. Moreover, another actual problem is the cosmetic treatment of skin when exposed to sunlight such as to allow an agreeable tanning without incurring in sunburns. Abstract of the invention It has now surprisingly been found that photostable sun-protecting formulations with protective activity against UV radiations ranging from 290 to 380 nm, i.e. UV-B and UV-A are obtained by means of combinations comprising, with respect to the total weight of the composition, as the sole UV-absorber a) from 1 to 10% of one or more compounds of formula (I) wherein Q is hydrogen, straight or branched C 1 -C 4 alkoxy group and G is straight or branched C 1 -C 8 alkyl, b) from 0.5 to 10% of one or more compounds of formula (II) wherein R 1 is a straight or branched C 1 -C 8 alkyl, R 2 is hydrogen or a SO 3 M group, wherein M is hydrogen, an alkali metal or a mono- or polyalkyl-substituted ammonium group; with the condition that the weight ratio between the compounds of formula (II) and those of formula (I) is at least 0.5. Therefore, a cosmetic composition comprising in admixture with a cosmetic substrate the components a) and b) as described above is an object of the present invention. Another object of the present invention is a method for the cosmetic treatment of human skin when exposed to sunlight, said method consisting in applying a suitable amount of a cosmetic composition as described above. A further object of the present invention is a method for the stabilization of a cosmetic composition against UV radiation comprising the addition to the cosmetic substrate a photostabilizing mixture as described in the foregoing. Detailed description of the invention Preferred compounds of formula (I) are those wherein Q is methoxy and G is ter-butyl, or Q is hydrogen and G is isopropyl. Preferred compounds of formula (II) are 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, both marketed by 3V SIGMA under the trade names of Uvasorb (R) MET and Uvasorb (R) S 5. By means of the combinations according to the present invention, particularly photostable sun-protecting formulations with protective action both in UV-A and UV-B are obtained. Notwithstanding the fact that the present inventors do not want to be bound to theoretical interpretations, it may be supposed that the compounds of formula (II) stabilize the UV-A filters of formula (I), which are per se not photostable. The weight ratio between one or more compounds of formula (II) and one or more compounds of formula (I) must be at least 0.5. Examples of straight or branched C 1 -C 8 alkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and their isomers, in particular isopropyl, ter-butyl, 2-ethylhexyl. Examples of straight or branched C 1 -C 4 alkoxy are methoxy, ethoxy, propoxy, butoxy, and their isomers. Examples of alkali metal are sodium, lithium and potassium. The derivatives of the dibenzoylmethane of formula (I), are described in the patents US 4,387,089 and US 4,489,057. The commercial compounds are Parsol (R) 1789, (4-methoxy-4'-ter-butyldibenzoylmethane) by Givaudan and Eusolex (R) 8020, (4-isopropyldibenzoylmethane) by Merck. Very often these sun-protecting formulations are in the form of oil-in-water emulsion and containing, in variable concentrations, one or more organic lipophilic and/or hydrophilic sunscreens, capable of absorbing more or less intensely UV radiations of sunlight. The kind of sunscreens and their suitable amount are selected depending on the desired sun protecting factor (SPF). SPF is an index of protection and is expressed as the ratio between the time of irradiation necessary to reach the erythematogenic threshold in the presence of the UV filter and the time necessary to reach the erythematogenic threshold in the absence of the UV filter. SPF can be determined according to the method described by B. Diffey and J. Robson in J. Soc. Cosmet. Chem. 40, 127-133 (1989). It is thus possible to prepare sun-protecting formulations with high SPF, suitable to guarantee a continuous protection of the skin also during prolonged expositions to sunlight, so avoiding frequent and repeated applications necessary for an effective protection. According to the present invention, the photostable cosmetic compositions suitable to skin protection from UV radiations with wavelength between 290 and 380 nm comprise a cosmetic substrate containing, with respect to the weight of the composition, from 1 to 10% of one or more compounds of formula (I), from 0.5 to 10% of one or more compounds of formula (II) and from 1 to 10% of one or more compounds of formula (III), with the condition that the weight ratio between the compounds of formula (II) and those of formula (I) is at least 0.5. The sun-protecting formulations according to the present invention, once applied on epidermis, exert a protecting action against the noxious effects of UV radiation, thus avoiding the formation of erythema or sunburns or an early skin ageing. The compositions of the invention can also be useful for the treatment, then the protection, of hair or of make-up in decorative cosmetic. According to the present invention the cosmetic formulations can be solutions, lotions, emulsions of the water-in-oil or oil-in-water type; or can also be in the form of gels, lipsticks, aerosol. The compositions according to the present invention are prepared by formulating the ingredients usually employed, such as for example oils, fats, emulsifiers, moisturizing agents, humectants, emollients, preservatives, surfactants, thickening agents, perfumes, pigments, dyes and other else such as alcohols, polyols, electrolytes, siliconic derivatives. The more commonly used solvents are triglycerides of caprinic or caprilic acid, castor oil, esters of fatty acids with isopropanol, propylene glycol, glycerin, propylene glycol monomethyl- or monoethyl- or monobutylether. The sun-protecting formulations according to the present invention can also contain inorganic pigments commonly used in cosmetics; such as for example titanium dioxide, zinc oxide, silica or aluminium oxide. The present invention comprises also the protection of the cosmetic compositions themselves from UV radiation by means of the addition of from 1 to 5% by weight with respect to the composition of a compound of formula (I) and from 0.5 to 5% of a compound of formula (II). In this case it is a matter of compositions whose components can undergo unwanted light-induced degradation or colouring, as for example shampoos and hair lacquers, hair dressing lotions, hair-dyeing compositions, make-up formulations, as nail lacquers, foundation, lipstick. Preferred cosmetic formulations are the ones for the protection of skin from sun radiations. Therefore, it is another object of the present invention a photostabilizing mixture consisting of: a) at least a compound of formula (I) wherein Q is hydrogen, straight or branched C 1 -C 4 alkoxy group and G is straight or branched C 1 -C 8 alkyl, b) at least a compound of formula (II) wherein R 1 is a straight or branched C 1 -C 8 alkyl, R 2 is hydrogen or an SO 3 M group, wherein M is hydrogen, an alkali metal or a mono- or polyalkyl-substituted ammonium group; with the condition that the weight ratio between the compounds of formula (II) and those of formula (I) is at least 0.5. This mixture can be used for the preparation of a medicament useful for the protection of human skin when exposed to sunlight. The following examples further illustrate the invention. Example A - Photostability A solution of the sunscreens or their combinations in a solvent mixture consisting of 70% ethyl alcohol and 30% isopropyl myristate was prepared. From each solution 2 samples of 20 microliters were withdrawn by means of a microsiringe and put on 2 x 5 cm microscope slides. The samples so prepared were left in the air at room temperature for 30 minutes, as to allow ethanol evaporation. Subsequently, one of the two samples was exposed to UV irradiation for 2 and 4 hours in a Suntest Heraeus CPS + apparatus, fitted with a Xenon lamp and a filter system in order to cut off UV radiation lower than 290 nm and IR radiation. After exposition, the slides were washed with 50 or 100 ml of ethanol, as to quantitatively solubilize the deposed material. In the so obtained ethanolic solutions, without further dilution, absorbance was measured in quartz cuvettes with 1 cm optical path by means of a spectrophotometer Perkin-Elmer Lambda 2. Photostability F was calculated as the percent ratio between absorbance at the wavelength of maximum absorption of the exposed sample and the one of the not exposed sample. For the combinations, photostability was calculated only for the filter of formula (I). The results are shown in the following Table. Sunscreens g/100 ml solvent F F 2 hours 4 hours A 5 23 14 B 5 94 86 C 5 75 68 D 5 91 84 A + B 5 + 5 89 78 A + C 5 + 5 78 65 A + D 5 + 5 81 69 A + B 4 + 2 91 85 A + C 4 + 2 81 63 A + D 4 + 2 87 72 A = 4-methoxy-4'-ter-butyldibenzoylmethane B = 2-hydroxy-4-methoxybenzophenone C = 4-methylbenzylydencamphor D = 2-ethylhexyl-α-cyano-β,β'-diphenylacrilate Example 1 - Sun milk Fatty acid triglyceride 20.0 g Cetyl alcohol 2.0 g Cetylstearyl alcohol 2.0 g Lanoline 4.0 g Silicon oil 0.4 g 4-methoxy-4'-ter-butyldibenzoylmethane 3.0 g 2-hydroxy-4-methoxybenzophenone 2.5 g Abiol (Preservative of 3V SIGMA) 0.2 g Synthalen M (thickening agent 3V SIGMA) 0.1 g Triethanolamine 0.15 g Perfume 0.3 g Water up to 100.0 g Fatty phase was warmed to 80-90°C, sunscreen were added, then the mixture was added to water, containing the hydrosoluble compounds, heated to 80-90°C. Warm stirring was continued for 15-20 minutes. The mixture was slowly cooled and perfume was added.

Claims: A photostabilizing mixture consisting of: a) at least a compound of formula I wherein Q is hydrogen, straight or branched C 1 -C 4 alkoxy group and G is straight or branched C 1 -C 8 alkyl, b) at least a compound of formula (II) wherein R 1 is a straight or branched C 1 -C 8 alkyl, R 2 is hydrogen or a SO 3 M group, wherein M is hydrogen, an alkali metal or a mono- or polyalkyl-substituted ammonium group; with the condition that the weight ratio between the compounds of formula (II) and those of formula (I) is at least 0.5. A photostabilizing mixture according to claim 1, in which in the formula (I) Q is methoxy and G is ter-butyl. A photostabilizing mixture according to claim 1, in which in the formula (I) Q is hydrogen and G is isopropyl. A photostabilizing mixture according to anyone of claims 1-3, in which in the formula (II), R 1 is methyl, R 2 is hydrogen. A photostabilizing mixture according to anyone of claims 1-3, in which in the formula (II), R 1 is methyl, R 2 is SO 3 M, wherein M is hydrogen. A cosmetic composition containing as the sole absorber: a) from 1 to 10% of one or more compounds of formula I wherein Q is hydrogen, straight or branched C 1 -C 4 alkoxy group and G is straight or branched C 1 -C 8 alkyl, b) from 0,5 to 10% of one or more compounds of formula (II) wherein R 1 is a straight or branched C 1 -C 8 alkyl, R 2 is hydrogen or a SO 3 M group, wherein M is hydrogen, an alkali metal or a mono- or polyalkyl-substituted ammonium group; with the condition that the weight ratio between the compounds of formula (II) and those of formula (I) is at least 0.5. A cosmetic composition according to claim 6, containing also zinc oxide. A cosmetic composition according to anyone of claims 6-7, containing also titanium dioxide. A cosmetic composition accordirig to anyone of claims 6-8, containing as adjuvant one or more components selected from the group consisting of: thickening agents, emollients, hydrating agents, preservative, perfume.

Inventors: MALPEDE ALVERIO, RASPANTI GIUSEPPE, MALPEDE, ALVERIO, RASPANTI, GIUSEPPE
Applicants: 3V SIGMA SPA, 3V SIGMA S.P.A
Application year: 1997
Main classification: A61K7
IPC codes: A61K8, A61Q19, A61Q17