PHOTOPROTECTIVE COMPOSITIONS COMPRISING A DIBENZOYLMETHANE DERIVATIVE, A MEROCYANINE COMPOUND AND A COMPOUND CAPABLE OF ACCEPTING THE TRIPLET EXCITED LEVEL ENERGY OF THE DIBENZOYLMETHANE COMPOUND

Abstract

Photoprotective compositions comprising a dibenzoylmethane derivative, a merocyanine compound and a compound capable of accepting the triplet excited level energy of the dibenzoylmethane compound

The present invention relates to a photoprotective composition for topical use comprising, in a cosmetically acceptable medium, at least one dibenzoylmethane derivative compound, at least one merocyanine compound and at least one compound capable of accepting the triplet excited level energy of said dibenzoylmethane derivative compound(s).

The invention also relates to the use of at least one compound capable of accepting the triplet excited level energy of said dibenzoylmethane derivative compound(s), for photostabilizing with respect to UV radiation a composition comprising at least one dibenzoylmethane derivative compound and at least one merocyanine compound.

Claims

1. Photoprotective composition for topical use, characterized in that it comprises, in a cosmetically acceptable medium: (i) one or more dibenzoylmethane derivative compounds chosen from those of formula (I) below, and/or mixtures thereof: ##STR00029## in which formula (I): R.sub.1, R.sub.4, R.sub.5 and R.sub.6 represent, independently of one another, a hydrogen atom, a hydroxyl radical, a linear or branched C.sub.1-C.sub.4 alkyl radical or a linear or branched C.sub.1-C.sub.4 alkoxy radical, and R.sub.2 and R.sub.3 represent, independently of one another, a hydrogen atom, a hydroxyl radical, a linear or branched C.sub.1-C.sub.4 alkyl radical or a linear or branched C.sub.1-C.sub.4 alkoxy radical, or form, with the 2 carbon atoms of the covalent bonds C—R.sub.2 and C—R.sub.3, a 5- or 6-membered heterocycle optionally substituted with a linear or branched C.sub.1-C.sub.4 hydrocarbon-based chain; (ii) one or more merocyanine compounds chosen from those of formula (II) below, the tautomeric forms thereof, the geometric isomers E/E or E/Z thereof; and/or mixtures thereof: ##STR00030## in which formula (II), R represents a linear or branched C.sub.1-C.sub.22 alkyl, C.sub.2-C.sub.22 alkenyl or C.sub.2-C.sub.22 alkynyl radical, a C.sub.3-C.sub.22 cycloalkyl radical or a C.sub.3-C.sub.22 cycloalkenyl radical, said radicals possibly being interrupted with one or more oxygen atoms; and (iii) one or more compounds capable of accepting the triplet excited level energy of said dibenzoylmethane derivative compound(s) (i).

2. Composition according to claim 1, characterized in that the dibenzoylmethane derivative compound(s) are chosen, alone or as a mixture, from 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4′-diisopropyldibenzoylmethane, 4,4′-dimethoxydibenzoylmethane, 4-tert-butyl-4′-methoxydibenzoylmethane, 2-methyl-5-isopropyl-4′-methoxydibenzoylmethane, 2-methyl-5-tert-butyl-4′-methoxydibenzoylmethane, 2,4-dimethyl-4′-methoxydibenzoylmethane, 2,6-dimethyl-4-tert-butyl-4′-methoxydibenzoylmethane, 1-(4-tert-butylphenyl)-3-(2-hydroxyphenyl)propane-1,3-dione, 1-(4-methoxy-1-benzofuran-5-yl)-3-phenylpropane-1,3-dione; preferably chosen, alone or as a mixture, from 4-tert-butyl-4′-methoxydibenzoylmethane and/or 4-isopropyldibenzoylmethane; preferentially chosen from 4-tert-butyl-4′-methoxydibenzoylmethane.

3. Composition according to claim 1, characterized in that the total content of the dibenzoylmethane derivative compound(s) (i) is between 0.1% and 15% by weight, preferably between 0.2% and 10% by weight, more preferentially between 0.3% and 5% by weight, relative to the total weight of the composition.

4. Composition according to claim 1, characterized in that it comprises at least one merocyanine compound (ii) of formula (II) in which R represents a linear or branched C.sub.1-C.sub.22 alkyl radical which may be interrupted with one or more oxygen atoms.

5. Composition according to claim 1, characterized in that it comprises at least one merocyanine compound (ii) chosen from the compounds (1′) to (6′) below, and also the tautomeric forms thereof, the geometric isomers E/E or E/Z thereof; and/or mixtures thereof: ##STR00031## ##STR00032##

6. Composition according to claim 5, characterized in that it comprises at least one merocyanine compound (ii) chosen from 2-ethoxyethyl 2-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate (2′) in its geometric configuration E/Z having the structure below: ##STR00033## and/or in its geometric configuration E/E having the structure below: ##STR00034## and also the tantomeric forms thereof; and mixtures thereof.

7. Composition according to claim 1, characterized in that the total content of the merocyanine compound(s) (ii) is between 0.1% and 10% by weight, preferably between 0.2% and 10% by weight, more preferentially between 0.3% and 5% by weight, relative to the total weight of the composition.

8. Composition according to claim 1, characterized in that the compound(s) (iii) capable of accepting the triplet excited level energy of said dibenzoylmethane derivative compound(s) have a triplet excited level energy ranging from 40 kcal/mol to 70 kcal/mol.

9. Composition according to claim 1, characterized in that the compound(s) (iii) capable of accepting the triplet excited level energy of said dibenzoylmethane derivative compound(s) are chosen, alone or as a mixture, from: (A) the compounds of formula (III) and/or (IIIbis) below, and also the tautomeric forms thereof, the optical isomers thereof, the geometric isomers thereof; and/or mixtures thereof, ##STR00035## in which: A represents a chromophore group which absorbs UV radiation, comprising two monovalent groups having a carbonyl function; R.sub.14 represents a hydrogen atom, a linear or branched C.sub.1-C.sub.8 alkyl radical, or a linear or branched C.sub.1-C.sub.8 alkoxy radical; and R.sub.15 denotes a linear or branched C.sub.1-C.sub.8 alkyl radical; (B) piperidinol salts of formula (V) below, and also the optical isomers thereof, the geometric isomers thereof, and/or mixtures thereof, ##STR00036## in whichw: R and R.sup.1, which may be identical or different, denote a hydrogen atom or a methyl group, y is 1, 2 or 4; z is 1, 2, 3 or 4; x is 1 or 2; 1) when x is equal to 1: R.sup.2 denotes a hydrogen atom; a C.sub.1-C.sub.18 alkyl radical; a C.sub.2-C.sub.18 alkenyl radical; a propargyl radical; a glycidyl group; a C.sub.2-C.sub.50 alkyl radical interrupted with 1 to 20 oxygen atoms and substituted with 1 to 10 hydroxyl groups; a C.sub.1-C.sub.4 alkyl radical substituted with a carboxy group or a group —COOZ where Z represents a hydrogen atom, a C.sub.1-C.sub.4 alkyl, a phenyl, a C.sub.1-C.sub.4 alkyl substituted with a group (COO.sup.−).sub.p M.sup.p+ where p is an integer from 1 to 3 and M is a metal ion of groups 1, 2 and 3 of the periodic table, or Zn, Cu, Ni or Co or else M is a group N.sup.p+(R″).sub.4 where R″ is a C.sub.1-C.sub.8 alkyl or a benzyl; 2) when X is 2: R.sup.2 is a C.sub.1-C.sub.12 alkylene radical; a C.sub.4-C.sub.12 alkenylene radical; a xylylene group; a C.sub.1-C.sub.50 alkylene radical interrupted with 1 to 20 oxygen atoms and substituted with 1 to 10 hydroxyl groups; Y denotes an organic or inorganic anion; the total charge of cations y being equal to the total charge of anions z; (D) the compounds of formula (X) below, and also the optical isomers thereof, the geometric isomers thereof, and/or mixtures thereof, ##STR00037## in which: R.sub.1 represents a hydrogen atom or a linear or branched C.sub.1-C.sub.8 alkyl radical, R.sub.2 represents a linear or branched C.sub.1-C.sub.20, preferably C.sub.1-C.sub.8, alkyl radical.

10. Composition according to claim 1, characterized in that the compound(s) (iii) capable of accepting the triplet excited level energy of said dibenzoylmethane derivative compound(s) are chosen, alone or as a mixture, from the diethylhexyl syringylidenemalonate of formula (IV) below and also the tautomeric forms thereof, the optical isomers thereof, and/or mixtures thereof, the bisethylhexylhydroxydimethoxy benzylmalonate of formula (IVbis) below and also the tautomeric forms thereof, the optical isomers thereof, and/or mixtures thereof; the tris(tetramethylhydroxypiperidinol) citrate of formula (VI) below and also the optical isomers thereof, and/or mixtures thereof; diethylhexyl 2,6-naphthalate and also the optical isomers thereof, and the ethylhexyl methoxycrylene of formula (Xbis) below and also the tautomeric forms thereof, the optical ##STR00038##

11. Composition according to claim 1, characterized in that the total content of the compound(s) (iii) capable of accepting the triplet excited level energy of said dibenzoylmethane derivative compound(s) is between 0.001% and 15% by weight, preferably between 0.003% and 10% by weight, and more preferentially between 0.005% and 5% by weight, relative to the total weight of the composition.

12. Composition according to claim 1, characterized in that the ratio of the weight content of the compound(s) (iii) capable of accepting the triplet excited level energy of said dibenzoylmethane derivative compound(s) to the sum of the weight contents of the dibenzoylmethane derivative compound(s) (i) and of the merocyanine compound(s) (ii), is between 0.01 and 20, preferably between 0.1 and 15, and more preferentially between 0.5 and 10.

13. Composition according to claim 1, characterized in that it also comprises one or more additional UV-screening agents chosen from hydrophilic, lipophilic or insoluble organic UV-screening agents and/or one or more mineral pigments; preferably chosen, alone or as a mixture, from anthranilates; salicylic derivatives; benzylidenecamphor derivatives; benzophenone derivatives; β,β-diphenylacrylate compounds different from ethylhexyl methoxycrylene derivatives; triazine derivatives such as derivatives of bisresorcinyl triazine type; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bisbenzoazolyl derivatives; p-aminobenzoic acid (PABA) derivatives; methylenebis(hydroxyphenyl benzotriazole) derivatives; benzoxazole derivatives; screening polymers and screening silicones; α-alkylstyrene-based dimers; 4,4-diarylbutadienes; and/or treated or untreated metal oxide pigments or nanopigments, such as titanium oxides, zinc oxides, iron oxides, zirconium oxides, cerium oxides and mixtures thereof, preferably chosen, alone or as a mixture, from titanium oxides.

14. Composition according to claim 13, in which the additional UV-screening agents are chosen, alone or as a mixture, from the following UV-screening agents: ethylhexyl salicylate, octocrylene, phenylbenzimidazole sulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate, 4-methylbenzylidenecamphor, terephthalylidenedicamphorsulfonic acid, disodium phenyldibenzimidazole tetrasulfonate, methylenebisbenzotriazolyl tetramethylbutylphenol, ethylhexyl triazone, diethylhexyl butamido triazone, drometrizole trisiloxane, polysilicone-15, 1,1-dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene, 2,4-bis[5-1-(dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine, and mixtures thereof.

15. Composition according to claim 1, characterized in that it comprises at least one oil, preferably chosen from hydrocarbon-based oils, silicone oils, fluoro oils, and/or mixtures thereof.

16. Composition according to claim 1, characterized in that it is in the form of an oil-in-water or water-in-oil emulsion.

17. Cosmetic method for treating the skin, in particular human skin, against UV radiation, comprising at least one step of applying to the skin a composition as defined in claim 1.

18. Use of at least one compound capable of accepting the triplet excited level energy of said dibenzoylmethane derivative compound(s) as defined in claim 1, for photostabilizing, with respect to UV radiation, a composition comprising at least one dibenzoylmethane derivative compound (i), and at least one merocyanine compound (ii).

Description

EXAMPLES

[0459] The compositions 1, 2 and 3 are prepared from the ingredients shown in the table below, the amounts of which are expressed as weight percentages of active material (AM).

TABLE-US-00001 Composition Composition Composition 1 2 3 Phases Ingredients (Comparative) (Invention) (Invention) A Water qs qs qs Glycerol 5 5 5 Triethanolamine 0.45 0.45 0.45 Disodium EDTA 0.1 0.1 0.1 Preservative qs qs qs Ammonium acryloyldimethyltaurate/ 0.5 0.5 0.5 Steareth-8 Methacrylate Copolymer (ARISTOFLEX SNC ®) B Isopropyl Lauroyl Sarcosinate 30 30 30 4-tert-butyl-4′-methoxydibenzoylmethane 2 2 2 2-ethoxyethyl 2-cyano{3-[(3- 1 1 1 methoxypropyl)amino]cyclohex-2-en-1- ylidene}ethanoate Diethylhexyl syringylidenemalonate + — 2 — 90/10 Caprylic/Capric Triglyceride (OXYNEX ST LIQUID) Tris(Tetramethylhydroxypiperidinol) — — 0.01 Citrate (TINOGARD QS) Stearyl Alcohol 1 1 1 Glyceryl Isostearate 0.5 0.5 0.5 C Isohexadecane 1 1 1 Xanthan gum 0.2 0.2 0.2 Ammonium Polyacryloyldimethyl 0.4 0.4 0.4 Taurate (HOSTACERIN AMPS ®)

[0460] Composition Preparation Method:

[0461] The aqueous phase A and the oily phase B were prepared by mixing the starting materials with mechanical stirring at 80° C. Once the aqueous phase A and the oily phase B are macroscopically homogeneous, the emulsion is prepared by introducing the phase B into the phase A with stirring by means of a rotor-stator homogenizer at a stirring speed of 4500 revolutions per minute for 20 minutes. The phase C is then added, and the composition is called to ambient temperature (25° C.).

[0462] Results:

[0463] Once the compositions 1 to 3 have been prepared, these are then irradiated under a UV-A sun lamp at 21.6 J/cm.sup.2, for one hour.

[0464] After irradiation, the residual contents of the compounds 4-tert-butyl-4′-methoxydibenzoylmethane and 2-ethoxyethyl 2-cyano{3-[(3-methoxypropyl)amino]-cyclohex-2-en-1-ylidene}ethanoate in each of the compositions were measured by conventional HPLC chromatography methods.

[0465] The residual content of the ingredient corresponds to the weight ratio of the content of the ingredient after UV irradiation to the content of the ingredient before UV irradiation. The residual contents are expressed as percentages.

[0466] The results obtained are collated in the table below:

TABLE-US-00002 Composition 1 Composition 2 Composition 3 Residual contents after irradiation (Comparative) (Invention) (Invention) 4-tert-butyl-4′- 72% 86% 87% methoxydibenzoylmethane 2-ethoxyethyl 2-cyano{3-[(3- 46% 72% 71% methoxypropyl)amino]cyclohex- 2-en-1-ylidene}ethanoate

[0467] These results show that the compositions 2 and 3 according to the invention exhibit residual contents of the dibenzoylmethane derivative and of the merocyanine compound that are substantially higher compared with the comparative composition 1, and thus exhibit better photostability with respect to UV radiation.