# Patent

## Title
Photostable photoprotective compositions comprising dibenzoylmethane and bis-resorcinyl triazine compounds and a compound that accepts the excited triplet level energy of said dibenzoylmethane(s)

## Abstract

Topically applicable, improvedly photostabilized, photoprotective cosmetic/dermatological compositions contain (i) an effective UV-screening amount of at least one dibenzoylmethane sunscreen and an effective photostabilizing amount of (ii) at least one bis-resorcinyl triazine compound and (iii) at least one compound accepting the excited triplet level energy of said at least one dibenzoylmethane sunscreen, notably at least one 4-hydroxybenzylidenemalonate compound, 4-hydroxycinnamate compound, fluorene compound, piperidinol salt, or mixture thereof, formulated into (iv) a topically applicable, cosmetically/dermatologically acceptable support therefor.

## Background
CROSS-REFERENCE TO PRIORITY/PCT/PROVISIONAL APPLICATIONS
This application claims priority under 35 U.S.C. §119 (a)-(d) of FR 04/52368, filed Oct. 19, 2004 and claims benefit under 35 U.S.C. §119(e) of provisional application Ser. No. 60/623,580, filed Oct. 29, 2004, each hereby expressly incorporated by reference and each assigned to the assignee hereof.


CROSS-REFERENCE TO COMPANION APPLICATIONS
Copending applications Ser. No. 11/249,398 and Ser. No. 11/249,304, filed concurrently herewith and also assigned to the assignee hereof.
BACKGROUND OF THE INVENTION
1. Technical Field of the Invention
The present invention relates to photoprotective compositions for topical application containing a dibenzoylmethane derivative, a bis-resorcinyl triazine compound and a compound capable of accepting the excited triplet level energy of the said dibenzoylmethane derivative, selected from the group consisting of:

    
    
        4-hydroxybenzylidenemalonate derivatives or 4-hydroxycinnamate derivatives;
        fluorene derivatives;
        piperidinol salts;
        mixtures thereof.
    
    


The present invention also relates to a process for photostabilizing at least one dibenzoylmethane derivative against UV radiation via a combination of a bis-resorcinyl triazine compound and a compound capable of accepting the excited triplet level energy of the said dibenzoylmethane derivative, such as those indicated above.
2. Description of Background and/or Related and/or Prior Art
It is known that light radiation with wavelengths of from 280 nm to 400 nm permits tanning of the human epidermis and that light rays with wavelengths more particularly from 280 to 320 nm, known as UV-B rays, cause skin burns and erythema which can harm the development of a natural tan. For these reasons, as well as for aesthetic reasons, there is a constant demand for means of controlling this natural tanning in order thus to control the color of the skin; this UV-B radiation should thus be screened out.
It is also known that UV-A rays, with wavelengths from 320 to 400 nm, which cause tanning of the skin, are liable to induce adverse changes therein, in particular in the case of sensitive skin or skin which is continually exposed to solar radiation. UV-A rays cause in particular a loss of elasticity of the skin and the appearance of wrinkles leading to premature aging of the skin. Same promote triggering of the erythemal reaction or amplify this reaction in certain individuals and may even be the cause of phototoxic or photoallergic reactions. Thus, for aesthetic and cosmetic reasons such as the conservation of the skin's natural elasticity, for example, an increasingly large number of individuals wish to control the effect of UV-A rays on their skin. It is thus desirable also to screen out UV-A radiation.
For the purpose of protecting the skin and keratin materials against UV radiation, anti-sun compositions comprising organic screening agents that are active in the UV-A range and in the UV-B range are generally used. The majority of these screening agents are liposoluble.
In this respect, one particularly advantageous family of UV-A screening agents currently consists of dibenzoylmethane derivatives, and in particular 4-tert-butyl-4′-methoxydibenzoylmethane, which have high intrinsic absorbing power. These dibenzoylmethane derivatives, which are compounds which are now well known per se as screening agents that are active in the UV-A range, are described in particular in FR-A-2,326,405 and FR-A-2,440,933, as well as in EP-A-0,114,607; 4-tert-butyl-4′-methoxydibenzoylmethane is moreover currently marketed under the trademark “Parsol 1789” by Roche Vitamins.
Unfortunately, it has been found that dibenzoylmethane derivatives are compounds that are relatively sensitive to ultraviolet radiation (especially UV-A), i.e., more specifically, they have an annoying tendency to be degraded more or less quickly under the action of this UV. Thus, this substantial lack of photochemical stability of dibenzoylmethane derivatives towards ultraviolet radiation, to which they are by nature intended to be subjected, does not make it possible to ensure constant protection during prolonged exposure to the sun, and so the user must make repeated applications at regular and close time intervals in order to obtain effective protection of the skin against UV rays.
To solve this technical problem, it has already been proposed in the prior art to combine dibenzoylmethane derivatives with compounds capable of accepting the excited triplet level energy of the said dibenzoylmethane derivative. This is the case, for example, for the naphthalene derivatives in U.S. Pat. Nos. 5,993,789, 6,113,931, 6,126,925 and 6,284,916. This is also the case for the fluorene derivatives as described in U.S. Published Applications 2004/00579912, 2004/00579914, 2004/00579916 and 2004/06272. This is also the case for 4-hydroxybenzylidenemalonate derivatives or 4-hydroxycinnamate derivatives such as those described in WO 03/007906. However, the photochemical stability of the dibenzoylmethane derivatives obtained with these compounds is still not fully satisfactory.
WO 02/17873, DE-100,08,895 and FR-2,801,812 disclose formulations containing a combination of a dibenzoylmethane, a bis-resorcinyl triazine screening agent and a naphthalenedicarboxylic acid diester or polyester (i.e., 2,6-diethylhexyl naphthalate). These particular compounds have a tendency to present skin tolerance problems.
SUMMARY OF THE INVENTION
It has now been discovered, surprisingly, that by combining the dibenzoylmethane derivatives indicated above with an effective amount of a bis-resorcinyl triazine compound and a compound capable of accepting the excited triplet level energy of the said dibenzoylmethane derivative, selected from the group consisting of:

    
    
        4-hydroxybenzylidenemalonate derivatives or 4-hydroxycinnamate derivatives;
        fluorene derivatives;
        piperidinol salts;
        mixtures thereof,

it is possible to substantially and remarkably improve the photochemical stability (or photostability) of these same dibenzoylmethane derivatives.

    
    


This essential discovery is the focus of the present invention.
Thus, the present invention features a process for improving the stability of at least one dibenzoylmethane compound towards UV radiation, which entails combining the said dibenzoylmethane compound with at least one bis-resorcinyl triazine compound and at least one compound capable of accepting the excited triplet level energy of the said dibenzoylmethane derivative, selected from the group consisting of:

    
    
        4-hydroxybenzylidenemalonate derivatives or 4-hydroxycinnamate derivatives;
        fluorene derivatives;
        piperidinol salts;
        mixtures thereof.
    
    


The present invention also features topically applicable cosmetic or dermatological compositions comprising, formulated into a cosmetically acceptable support:

    
    
        (a) at least one dibenzoylmethane compound UV-screening agent,
        (b) at least one bis-resorcinyl triazine compound, and
        (c) at least one compound capable of accepting the excited triplet level energy of a dibenzoylmethane compound, selected from the group consisting of:
        
            4-hydroxybenzylidenemalonate derivatives or 4-hydroxycinnamate derivatives;
            fluorene derivatives;
            piperidinol salts;
            mixtures thereof.
        
        
    
    


This invention also features the combination of at least one bis-resorcinyl triazine compound and at least one compound capable of accepting the excited triplet level energy of a dibenzoylmethane derivative, such as those indicated above, in a cosmetic or dermatological composition comprising at least one dibenzoylmethane UV-screening agent to improve the stability towards UV rays of the said dibenzoylmethane derivative.
Other characteristics, aspects and advantages of the invention will be seen from the detailed description that follows.


DETAILED DESCRIPTION OF BEST MODE AND SPECIFIC/PREFERRED EMBODIMENTS OF THE INVENTION
Among the dibenzoylmethane derivatives that are representative, in a non-limiting manner, are:

    
    
        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.
    
    


Among the dibenzoylmethane derivatives mentioned above, 4-isopropyldibenzoylmethane will be used in particular, which is marketed under the name “Eusolex 8020” by Merck, and corresponds to the following formula:




It is most particularly preferred to use 4-(tert-butyl)-4′-methoxydibenzoylmethane or Butyl Methoxy Dibenzoylmethane, marketed under the trademark “Parsol 1789” by Roche Vitamins; this screening agent corresponds to the following formula:




The dibenzoylmethane derivative(s) may be present in the compositions in accordance with the invention in contents preferably ranging from 0.01% to 10% by weight and more preferably from 0.1% to 6% by weight relative to the total weight of the composition.
The bis-resorcinyl triazine compounds in accordance with the present invention correspond to formula (I) below:




in which:

    
    
        (i) the radicals R1 and R2, which may be identical or different, are each a C3-C18 alkyl radical; a C2-C18 alkenyl radical or a radical of formula —CH2—CH(OH)—CH2—OT1 in which T1 is a hydrogen atom or a C1-C8 alkyl radical;
        (ii) the radicals R1 and R2, which may be identical or different, may also be a radical of formula (1) below:
    
    






in which:

    
    
        R6 is a covalent bond; a linear or branched C1-C4 alkyl radical or a radical of formula —Cm1H2m1—O— in which m1 is a number ranging from 1 to 4;
        p1 is a number ranging from 0 to 5;
        the radicals R7, R8 and R9, which may be identical or different, are each a C1-C18 alkyl radical; a C1-C18 alkoxy radical or a radical of formula:
    
    






in which R10 is a C1-C5 alkyl radical;

    
    
        A1 is a radical corresponding to one of the following formulae:
    
    






in which:

    
    
        R3 is a hydrogen atom, a C1-C10 alkyl radical, a radical of formula: —(CH2CHR5—O)n1R4 in which n1 is a number ranging from 1 to 16 or a radical of structure —CH2—CH—(OH)—CH2OT1 with T1 having the same definition as indicated above,
        R4 is hydrogen, a metallic cation M, a C1-C5 alkyl radical or a radical of formula —(CH2)m2—OT1 in which m2 is a number ranging from 1 to 4 and T1 has the same definition as indicated above,
        Q1 is a C1-C18 alkyl radical.
    
    


In formulae (I) and (1) to (5) described above:

    
    
        the alkyl radicals are linear or branched and may be selected, for example, from among methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl;
        the alkenyl radicals may be selected, for example, from among allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl and n-octadec-4-enyl;
        the alkoxy radicals are linear or branched and may be selected, for example, from among methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy and tert-amyloxy;
        the C1-C5 monoalkylamino or dialkylamino radicals may be selected, for example, from among methylamino, ethylamino, propylamino, n-butylamino, sec-butylamino, tert-butylamino, pentylamino, dimethylamino, diethylamino, dibutylamino and methylethylamino;
        the metallic cations are alkali metal, alkaline-earth metal or metallic cations selected, for example, from among lithium, potassium, sodium, calcium, magnesium, copper and zinc.
    
    


The bis-resorcinyl triazine derivatives of formula (I) of the invention are screening agents that are already known per se. They are described and prepared according to the syntheses indicated in EP-A-0,775,698.
As examples of compounds of formula (I) that may be used, representative are:

    
    
        2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;
        2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;
        2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-[4-(2-methoxyethylcarboxyl)phenylamino]-1,3,5-triazine;
        2,4-bis{[4-tris(trimethylsiloxysilylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;
        2,4-bis{[4-(2′′-methylpropenyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;
        2,4-bis{[4-(1′,1′,1′,3′,5′,5′,5′-heptamethyltrisiloxy-2′′-methylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;
        2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy]-2-hydroxy]phenyl}-6-[(4-ethylcarboxyl)phenylamino]-1,3,5-triazine;
        2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(1-methylpyrrol-2-yl)-1,3,5-triazine.
    
    


The compounds derived from bis-resorcinyl triazine that are more particularly preferred according to the invention are selected from the group consisting of:

    
    
        2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;
        2,4-bis{[4-tris(trimethylsiloxysilylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;
        2,4-bis{[4-(1′,1′,1′,3′,5′,5′,5′-heptamethyltrisiloxy-2′′-methylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine.
    
    


The compound 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (INCI name), such as the product marketed under the trademark “Tinosorb S” by Ciba-Geigy, will be used more particularly.
The bis-resorcinyl triazine compound(s) of formula (I) is (are) generally present in the screening compositions according to the invention in a concentration ranging from 0.1% to 20% by weight, more preferably from 1% to 10% by weight and more particularly from 2% to 8% by weight relative to the total weight of the composition.
According to the present invention, the bis-resorcinyl triazine(s) is (are) used in combination with a compound capable of accepting the excited triplet level energy of the said dibenzoylmethane derivative so as to deactivate the excited states of the dibenzoylmethane molecule excited under the influence of UV radiation and to allow this molecule to regain its ground state.
The compounds capable of accepting the excited triplet level energy of the said dibenzoylmethane derivative are selected from among:

    
    
        (i) 4-hydroxybenzylidenemalonate compounds or 4-hydroxycinnamate compounds such as those described in WO 03/007906;
        (ii) the fluorene compounds such as described in U.S. Published Applications 2004/00579912, 2004/00579914, 2004/00579916 and 2004/062726;
        (iii) piperidinol salts such as those described in WO 03/103622;
        (iv) mixtures thereof.
    
    


According to one preferred embodiment, the compounds that accept the excited triplet level energy of the said dibenzoylmethane derivative have an excited triplet level energy ranging from 40 kcal/mol to 70 kcal/mol.
The excited triplet level energies may be determined via the techniques of oxygen perturbation or phosphorescence as described in the article by J. Gonzenbach, T. J. Hill and T. G. Truscott “The Triplet Energy Levels in UV-A and UV-B Sunscreens”, J. Photochem. Photobiol. B: Biol., Vol. 16, pages 337-379 (1992). The technique of oxygen perturbation consists in measuring the UV absorption spectrum of a compound when it is placed in an environment under a high pressure of oxygen: i.e., 2000 psi. Under these conditions, the spin selection rules are perturbed and the exposure of the compound to UV leads to the lowest excited triplet level by direct excitation of the ground state. The wavelength λ (in μm) at which the transition takes place is used to calculate the energy of the triplet level in kcal/mol via the formula E=28.635/λ, which is derived from the equation E=hv where E is the energy, h is Planck's constant and v is the frequency of the electromagnetic wave.
The technique of phosphorescence is based on the fact that many compounds emit phosphorescence during the deactivation of their excited triplet level. By measuring the wavelength of the phosphorescence, the excited triplet energy levels may be calculated as previously. The excited triplet energy levels may be determined by measuring the phosphorescence spectra of samples with a spectrophotometer equipped with a phosphorescence accessory. Such excited triplet levels have been widely reported, for example in the article by A. J. Gordon and R. A. Ford, “The Chemist Companion”, John Wiley & Sons, pages 351-355 (1992).
Among the 4-hydroxybenzylidenemalonate compounds or the 4-hydroxycinnamate compounds that will preferentially be used are those of formula (V):




in which A is a chromophoric group that absorbs UV radiation, comprising two monovalent groups containing a carbonyl function;

    
    
        R14 is hydrogen, a linear or branched C1-C8 alkyl radical or a linear or branched C1-C8 alkoxy radical,
        R15 is a linear or branched C1-C8 alkyl radical.
    
    


Among these compounds, the ones that will be used more preferentially are those of formula (Va) below:




in which:

    
    
        R14 is hydrogen, a linear or branched C1-C8 alkyl radical or a linear or branched C1-C8 alkoxy radical,
        R15 is hydrogen or a linear or branched C1-C8 alkyl radical,
        R16 is selected from —C(O)CH3, —CO2R18, —C(O)NH2, and —C(O)N(R19)2,
        X is O or NH,
        R17 is a linear or branched C1-C30 alkyl radical,
        R18 is a linear or branched C1-C20 alkyl radical,

each R19 independently is a linear or branched C1-C8 alkyl radical.

    
    


Among these compounds, the ones that will be used more preferentially are those of formula (Vb) or (Vc) below:




in which:

    
    
        R16 is —CO2R18,
        R17 is a linear or branched C1-C8 alkyl radical,
        R18 is a linear or branched C1-C8 alkyl radical,
        X is O.
    
    


The compound that will be used in particular is diethylhexyl syringylidenemalonate (INCI name) having the following formula:




such as the commercial product marketed under the trademark Oxynex ST by Merck.

Among the fluorene derivatives in accordance with the invention, use will preferably be made of those corresponding to one of the formulae (VI), (VII), (VIII), (IX), (X), (XI), (XII) and (XIII) below, such as those described in U.S. Published Applications. 2004/00579912, 2004/00579914, 2004/00579916 and 2004/062726:







in which:

    
    
        the radicals R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30 R32, R33, R34, R35, R36, R37 and R38, which may be identical or different, are each an optionally substituted linear or branched C1-C30 alkyl radical; an optionally substituted C3-C8 cycloalkyl radical; an optionally substituted monocyclic, bicyclic or tricyclic aryl radical; an optionally substituted monocyclic, bicyclic or tricyclic heteroaryl radical; an optionally substituted C3-C14 heterocycloalkyl radical; an amino or cyano group; an ester group of formula:
    
    






in which R is an optionally substituted linear or branched C1-C30 alkyl radical or an optionally substituted C3-C8 cycloalkyl radical;

    
    
        the radicals R39 and R44, which may be identical or different, are each substituted or unsubstituted diphenylmethylene; substituted or unsubstituted 9H-fluorene;
        the radical R45 is an optionally substituted linear or branched C1-C30 alkyl radical; an optionally substituted linear or branched C1-C30 hydroxyalkyl radical; an optionally substituted C3-C8 cycloalkyl radical; an optionally substituted monocyclic, bicyclic or tricyclic aryl radical; an optionally substituted monocyclic, bicyclic or tricyclic heteroaryl radical; an optionally substituted C3-C14 heterocycloalkyl radical; an optionally substituted ether; an amino group;
        the radicals R46 and R47 are each, independently of each other, hydrogen, an optionally substituted linear or branched C1-C30 alkyl radical; an optionally substituted linear or branched C1-C30 hydroxyalkyl radical; an optionally substituted C3-C8 cycloalkyl radical; an optionally substituted monocyclic, bicyclic or tricyclic aryl radical; an optionally substituted monocyclic, bicyclic or tricyclic heteroaryl radical; an optionally substituted C3-C14 heterocycloalkyl radical; an amino group, a cyano, hydroxyl, amide or imide, a halogen, an optionally substituted ether, an ester or a urethane;
        g, r, s and t are numbers ranging from 1 to 100;
        a, b, c, d, e and f are numbers ranging from 0 to 4,
        u is a number ranging from 0 to 100,
        and also mixtures of these compounds.
    
    


Among the compounds of formula (VI) that will be used more particularly are the compounds for which the radicals R20 and R21 are each branched C1-C15 alkyl radicals and more particularly simultaneously are 2-ethylhexyl (i.e.,: the compound 2-ethylhexyl (9H-fluoren-9-ylidene)acetate).
Among the compounds of formula (VII) that will be used more particularly are the compounds for which the radicals R22 and R23 are branched C1-C15 alkyl radicals and more particularly are compounds for which the radicals R22 and R23 simultaneously are isopropyl or 2-ethylhexyl.
Mention may be made in particular of the compounds diisopropyl fluorenemalonate (or diisopropyl 9H-fluoren-9-ylidenemalonate) and bis(2-ethylhexyl) fluorenemalonate (or bis(2-ethylhexyl) 9H-fluoren-9-ylidenemalonate).
Among the compounds of formula (VIII) that will be used more particularly are the compounds for which the radicals R24 and R25 are branched C3-C20 alkyl radicals and more particularly simultaneously are 2-ethylhexyl.
Among the compounds of formula (X) that will be used more particularly are the compounds for which the radicals R28, R29 and R30 are branched C1-C15 alkyl radicals and more particularly are compounds for which R28 and R30 are simultaneously 2-ethylhexyl.
Among the compounds of formula (XI) that will be used more particularly are the compounds for which the radicals R31, R32 and R33 are branched C1-C15 alkyl radicals and more particularly are compounds for which R31 and R33 are simultaneously 2-ethylhexyl.
Among the compounds of formula (XII) that will be used more particularly are the compounds for which the radicals R40 and R42 are C1-C15 alkyl radicals, in particular 2-methylpropyl, R41 is a linear C1-C15 alkyl and especially n-butyl; the radicals R38 and R43 simultaneously are cyano and the radicals R39 and R44 are diphenylmethylene.
Use will be made more particularly of the polymer having the following structure:




in which t=1 and u is a number ranging from 2 to 10.

Among the compounds of formula (XIII) that will preferably be used are the compounds for which e and f are equal to 0 and the radical R45 is a branched C3-C20 alkyl radical or a C1-C15 hydroxyalkyl radical.
Use will be made in particular of the compounds of formula (XIII) for which the radical R45 is a hydroxyalkyl selected from hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxy-n-butyl; 1-hydroxy-1-methylpropyl, 1-hydroxy-2,2-dimethylpropyl and 2-hydroxy-2-methylpropyl.
Use will be made more particularly of the compound of formula (XIV) for which e and f are equal to 0 and the radical R39 is 2-ethylhexyl, i.e., the compound 2-ethylhexyl cyano(9H-fluoren-9-ylidene)acetate or octofluorene.
Among the piperidinol salts in accordance with the invention, the ones that may preferably be used are those of formula (XIV) below:




in which:

    
    
        R1 is hydrogen or methyl,
        x is 1 or 2,
    
    
    1) when x is equal to 1:
    
        R2 is a hydrogen; a C1-C18 alkyl radical; a C2-C18 alkenyl radical; a propargyl radical; a glycidyl group; a C2-C50 alkyl radical interrupted with 1 to 20 oxygen atoms, the said alkyl being substituted with 1 to 10 hydroxyl groups or alternatively simultaneously interrupted with the said oxygen atoms and substituted with the said hydroxyl groups; a C1-C4 alkyl radical substituted with a carboxyl group or a group —COOZ in which Z is hydrogen, a C1-C4 alkyl radical, phenyl, a C1-C4 alkyl radical substituted with a group (COO−)p Mp+ wherein p is an integer ranging from 1 to 3 and M is a metal ion from Groups 1, 2 and 3 of the Periodic Table or Zn, Cu, Ni or Co, or alternatively M is a group Np+(R′′)4 wherein R′′ is a C1-C8 alkyl or a benzyl radical;
    
    
    2) when x is 2:
    
        R′ is a C1-C12 alkylene radical; a C4-C12 alkenylene radical; a xylylene group; a C1-C50 alkylene radical interrupted with 1 to 20 oxygen atoms, the said alkyl being substituted with 1 to 10 hydroxyl groups or alternatively simultaneously interrupted with the said oxygen atoms and substituted with the said hydroxyl groups;
        Y is an organic or mineral anion;
        the total charge of cations y being equal to the total charge of anions z.
    
    


Among the anions Y that may be mentioned are phosphate, phosphonate, carbonate, bicarbonate, nitrate, chloride, bromide, bisulfite, sulfite, bisulfate, borate, formate, acetate, benzoate, citrate, oxalate, tartrate, acrylate, polyacrylate, fumarate, maleate, itaconate, glycolate, gluconate, malate, mandelate, tiglate, ascorbate, polymethacrylate, a carboxylate of nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenediaminepentaacetic acid, diethylenetriaminepentamethylene phosphonate, an alkylsulfonate or an arylsulfonate.
Use will be made in particular of the compounds of formula (XV) for which R1 and R2 are hydrogen, x=1 and Y is a citrate anion, and even more particularly the compound tris(tetramethylhydroxypiperidinol) citrate of structure:




with y=3, such as the commercial product marketed under the name Tinoguard Q or Tinoguard S-FX by Ciba-Geigy.

The compounds capable of accepting the triplet state energy of the dibenzoylmethane derivatives in accordance with the invention may be present in the compositions in accordance with the invention in contents ranging from 0.1% to 25% by weight, more preferentially from 0.2% to 10% by weight and even more preferentially from 0.2% to 7% by weight relative to the total weight of the composition.
According to the present invention, the photostabilizing mixture of compound capable of accepting the triplet state energy of the dibenzoylmethane derivatives/bis-resorcinyl triazine will be used in a sufficient amount for obtaining an appreciable and significant improvement in the photostability of the dibenzoylmethane derivative in a given composition. This minimum amount of photostabilizer to be used may vary according to the amount of dibenzoylmethane present at the start in the composition and according to the nature of the cosmetically acceptable support adopted for the composition. It may be determined without any difficulty by means of a standard test for measuring photostability.
The compositions in accordance with the invention may also comprise other additional UV-A-active and/or UV-B-active organic or mineral photoprotective agents that are water-soluble or liposoluble or insoluble in the cosmetic solvents commonly used.
The additional organic photoprotective agents are selected especially from among anthranilates; salicylic derivatives; camphor derivatives; benzophenone derivatives; β,β-diphenylacrylate derivatives; triazine derivatives other than those of the bis-resorcinyl triazine type; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis-benzazolyl derivatives as described in EP-669,323 and U.S. Pat. No. 2,463,264; p-aminobenzoic acid (PABA) derivatives; methylenebis(hydroxyphenylbenzotriazole) derivatives as described in U.S. Pat. Nos. 5,237,071, 5,166,355, GB-2,303,549, DE-197,26,184 and EP-893,119; benzoxazole derivatives such as those described in EP-0,832,642; EP-1,027,883, EP-1,300,137 and DE-101,62,844; screening polymers and screening silicones such as those described especially in WO 93/04665; dimers derived from α-alkylstyrene, such as those described in DE-198,55,649; 4,4-diarylbutadienes such as those described in EP-0,967,200, DE-197,46,654, DE-197,55,649, EP-A-1,008,586, EP-1,133,980 and EP-133,981, and mixtures thereof.
As examples of additional organic photoprotective agents, representative are those denoted hereinbelow under their INCI name:
para-Aminobenzoic acid Derivatives:

    PABA,
    Ethyl PABA,
    Ethyl dihydroxypropyl PABA,
    Ethylhexyl dimethyl PABA marketed in particular under the name “Escalol 507” by ISP,
    Glyceryl PABA,
    PEG-25 PABA marketed under the name “Uvinul P25” by BASF.


Salicylic Derivatives:

    Homosalate marketed under the name “Eusolex HMS” by Rona/EM Industries,
    Ethylhexyl salicylate marketed under the name “Neo Heliopan OS” by Haarmann and Reimer,
    Dipropylene glycol salicylate marketed under the name “Dipsal” by Scher,
    TEA salicylate marketed under the name “Neo Heliopan TS” by Haarmann and Reimer.


β,β-Diphenylacrylate Derivatives:

    Octocrylene marketed in particular under the trademark “Uvinul N539” by BASF,
    Etocrylene marketed in particular under the trademark “Uvinul N35” by BASF.


Benzophenone Derivatives:

    Benzophenone-1 marketed under the trademark “Uvinul 400” by BASF,
    Benzophenone-2 marketed under the trademark “Uvinul D50” by BASF,
    Benzophenone-3 or Oxybenzone marketed under the trademark “Uvinul M40” by BASF,
    Benzophenone-4 marketed under the trademark “Uvinul MS40” by BASF,
    Benzophenone-5,
    Benzophenone-6 marketed under the trademark “Helisorb 11” by Norquay,
    Benzophenone-8 marketed under the trademark “Spectra-Sorb UV-24” by American Cyanamid,
    Benzophenone-9 marketed under the trademark “Uvinul DS-49” by BASF,
    Benzophenone-12
    n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate.


Benzylidenecamphor Derivatives:

    3-Benzylidenecamphor manufactured under the name “Mexoryl SD” by Chimex,
    4-Methylbenzylidenecamphor marketed under the name “Eusolex 6300” by Merck,
    Benzylidenecamphorsulfonic acid manufactured under the name “Mexoryl SL” by Chimex,
    Camphor benzalkonium methosulfate manufactured under the name “Mexoryl SO” by Chimex,
    Terephthalylidenedicamphorsulfonic acid manufactured under the name “Mexoryl SX” by Chimex,
    Polyacrylamidomethylbenzylidenecamphor manufactured under the name “Mexoryl SW” by Chimex.


Phenylbenzimidazole Derivatives:

    Phenylbenzimidazolesulfonic acid marketed in particular under the trademark “Eusolex 232” by Merck,
    Disodium phenyl dibenzimidazole tetrasulfonate marketed under the trademark “Neo Heliopan AP” by Haarmann and Reimer.


Phenylbenzotriazole Derivatives:

    Drometrizole trisiloxane marketed under the name “Silatrizole” by Rhodia Chimie,
    Methylenebis(benzotriazolyl)tetramethylbutylphenol marketed in solid form under the trademark “MIXXIM BB/100” by Fairmount Chemical, or in micronized form as an aqueous dispersion under the trademark “Tinosorb M” by Ciba Specialty Chemicals.


Triazine Derivatives:

    Ethylhexyltriazone marketed in particular under the trademark “Uvinul T150” by BASF,
    Diethylhexylbutamidotriazone marketed under the trademark “Uvasorb HEB” by Sigma 3V,
    2,4,6-tris(diisobutyl 4′-aminobenzalmalonate)-s-triazine.


Anthranilic Derivatives:
Menthyl anthranilate marketed under the trademark “Neo Heliopan MA” by Haarmann and Reimer.
Imidazoline Derivatives:

    Ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.


Benzalmalonate Derivatives:

    Polyorganosiloxane containing benzalmalonate functions, for instance
    Polysilicone-15, marketed under the trademark “Parsol SLX” by Hoffmann LaRoche.


4,4-Diarylbutadiene Derivatives:

    1,1-Dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene.


Benzoxazole Derivatives:

    2,4-bis[5-(1-dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine marketed under the name Uvasorb K2A by Sigma 3V

and mixtures thereof.



The preferred additional organic photoprotective agents are selected from among:

    Homosalate,
    Ethylhexyl salicylate,
    Octocrylene,
    Phenylbenzimidazolesulfonic acid,
    Benzophenone-3,
    Benzophenone-4,
    Benzophenone-5,
    n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,
    4-Methylbenzylidenecamphor,
    Terephthalylidenedicamphorsulfonic acid,
    Disodium phenyldibenzimidazoletetrasulfonate,
    Methylenebis(benzotriazolyl)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.



The additional mineral photoprotective agents are selected from among pigments and even more preferably nanopigments (mean size of the primary particles: generally from 5 nm to 100 nm and preferably from 10 nm to 50 nm) of treated or untreated metal oxides such as, for example, nanopigments of titanium oxide (amorphous or crystallized in rutile and/or anatase form), of iron oxide, of zinc oxide, of zirconium oxide or of cerium oxide.
The treated nanopigments are pigments that have undergone one or more surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds as described, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal (titanium or aluminum) alkoxides, polyethylene, silicones, proteins (collagen or elastin), alkanolamines, silicon oxides, metal oxides, sodium hexametaphosphate, alumina or glycerol.
The treated nanopigments may more particularly be titanium oxides treated with:

    
    
        silica and alumina, such as the products “Microtitanium Dioxide MT 500 SA” and “Microtitanium Dioxide MT 100 SA” from the company Tayca, and the products “Tioveil Fin”, “Tioveil OP”, “Tioveil MOTG” and “Tioveil IPM” from the company Tioxide,
        alumina and aluminum stearate, such as the product “Microtitanium Dioxide MT 100 T” from the company Tayca,
        alumina and aluminum laurate, such as the product “Microtitanium Dioxide MT 100 S” from the company Tayca,
        iron oxides and iron stearate, such as the product “Microtitanium Dioxide MT 100 F” from the company Tayca,
        silica, alumina and silicone, such as the products “Microtitanium Dioxide MT 100 SAS”, “Microtitanium Dioxide MT 600 SAS” and “Microtitanium Dioxide MT 500 SAS” from the company Tayca,
        sodium hexametaphosphate, such as the product “Microtitanium Dioxide MT 150 W” from the company Tayca,
        octyltrimethoxysilane, such as the product “T-805” from the company Degussa,
        alumina and stearic acid, such as the product “UVT-M160” from the company Kemira,
        alumina and glycerol, such as the product “UVT-M212” from the company Kemira,
        alumina and silicone, such as the product “UVT-M262” from the company Kemira.
    
    


Other titanium oxide nanopigments treated with a silicone are preferably TiO2 treated with octyltrimethylsilane and for which the mean size of the elementary particles is from 25 to 40 nm, such as the product marketed under the trademark “T805” by Degussa Silices, TiO2 treated with a polydimethylsiloxane and for which the mean size of the elementary particles is 21 nm, such as the product marketed under the trademark “70250 Cardre UF TiO2SI3” by Cardre, anatase/rutile TiO2 treated with a polydimethylhydrogenosiloxane and for which the mean size of the elementary particles is 25 nm, such as the product marketed under the trademark “Microtitanium Dioxide USP Grade Hydrophobic” by Color Techniques.
The uncoated titanium oxide nanopigments are marketed, for example, by Tayca under the trademarks “Microtitanium Dioxide MT 500 B” or “Microtitanium Dioxide MT 600 B”, by Degussa under the name “P 25”, by Wacker under the name “Oxyde de titane transparent PW”, by Myoshi Kasei under the name “UFTR”, by Tomen under the name “ITS” and by Tioxide under the name “Tioveil AQ”.
The uncoated zinc oxide nanopigments are, for example:

    
    
        those marketed under the name “Z-Cote” by Sunsmart;
        those marketed under the name “Nanox” by Elementis;
        those marketed under the name “Nanogard WCD 2025” by Nanophase Technologies.
    
    


The coated zinc oxide nanopigments are, for example:

    
    
        those marketed under the name “Zinc Oxide CS-5” by Toshibi (ZnO coated with polymethylhydrogenosiloxane);
        those marketed under the name “Nanogard Zinc Oxide FN” by Nanophase Technologies (as a 40% dispersion in Finsolv TN, C12-C15 alkyl benzoate);
        those marketed under the name “Daitopersion ZN-30” and “Daitopersion ZN-50” by Daito (dispersions in cyclopolymethylsiloxane/oxyethylenated polydimethylsiloxane, containing 30% or 50% of nanozinc oxides coated with silica and polymethylhydrogenosiloxane);
        those marketed under the name “NFD Ultrafine ZNO” by Daikin (ZnO coated with perfluoroalkyl phosphate and copolymer based on perfluoroalkylethyl as a dispersion in cyclopentasiloxane);
        those marketed under the name “SPD-Z1” by Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane);
        those marketed under the name “Escalol Z100” by ISP (alumina-treated ZnO dispersed in an ethylhexyl methoxycinnamate/PVP-hexadecene/methicone copolymer mixture);
        those marketed under the name “Fuji ZNO-SMS-10” by Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane);
        those marketed under the name “Nanox Gel TN” by Elementis (ZnO dispersed at a concentration of 55% in C12-C15 alkyl benzoate with hydroxystearic acid polycondensate).
    
    


The uncoated cerium oxide nanopigments are marketed under the name “Colloidal Cerium Oxide” by Rhone-Poulenc.
The uncoated iron oxide nanopigments are marketed, for example, by Arnaud under the names “Nanogard WCD 2002 (FE 45B)”, “Nanogard Iron FE 45 BL AQ”, “Nanogard FE 45R AQ” and “Nanogard WCD 2006 (FE 45R)” or by Mitsubishi under the name “TY-220”,
The coated iron oxide nanopigments are marketed, for example, by Arnaud under the names “Nanogard WCD 2008 (FE 45B FN)”, “Nanogard WCD 2009 (FE 45B 556)”, “Nanogard FE 45 BL 345” and “Nanogard FE 45 BL” or by BASF under the name “Transparent Iron Oxide”.
Also exemplary are the mixtures of metal oxides, especially of titanium dioxide and of cerium dioxide, including the silica-coated equal-weight mixture of titanium dioxide and of cerium dioxide, marketed by Ikeda under the name “Sunveil A”, and also the alumina, silica and silicone-coated mixture of titanium dioxide and of zinc dioxide, such as the product “M 261” marketed by Kemira, or the alumina, silica and glycerol-coated mixture of titanium dioxide and of zinc dioxide, such as the product “M 211” marketed by Kemira.
The nanopigments may be introduced into the compositions according to the invention in unmodified form or in the form of pigmentary paste, i.e., as a mixture with a dispersant, as described, for example, in GB-A-2,206,339.
The additional photoprotective agents are generally present in the compositions according to the invention in proportions ranging from 0.01% to 20% by weight relative to the total weight of the composition and preferably ranging from 0.1% to 10% by weight relative to the total weight of the composition.
The compositions according to the invention may also contain agents for artificially tanning and/or browning the skin (self-tanning agents) and more particularly dihydroxyacetone (DHA). They are preferably present in amounts ranging from 0.1% to 10% by weight relative to the total weight of the composition.
The compositions in accordance with the present invention may also comprise standard cosmetic adjuvants selected especially from among fatty substances, organic solvents, ionic or nonionic, hydrophilic or lipophilic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, anti-foams, fragrances, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, active agents, fillers, polymers, propellants, acidifying or basifying agents or any other ingredient usually used in cosmetics and/or dermatology.
The fatty substances may be an oil or a wax or mixtures thereof. The term “oil” means a compound that is liquid at room temperature. The term “wax” means a compound that is solid or substantially solid at room temperature and whose melting point is generally greater than 35° C.
Oils that may be mentioned include mineral oils (paraffin); plant oils (sweet almond oil, macadamia oil, grapeseed oil or jojoba oil); synthetic oils, for instance perhydrosqualene, fatty alcohols, fatty acids or fatty esters (for instance the C12-C15 alkyl benzoate marketed under the trademark “Finsolv TN” by Witco, octyl palmitate, isopropyl lanolate and triglycerides, including capric/caprylic acid triglycerides), oxyethylenated or oxypropylenated fatty esters and ethers; silicone oils (cyclomethicone and polydimethylsiloxanes, or PDMS) or fluoro oils, and polyalkylenes.
Waxy compounds that may be mentioned include paraffin, carnauba wax, beeswax and hydrogenated castor oil.
Among the organic solvents that may be mentioned are lower alcohols and polyols. These polyols may be selected from glycols and glycol ethers, for instance ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.
Hydrophilic thickeners that may be mentioned include carboxyvinyl polymers such as the Carbopol products (carbomers) and the Pemulen products (acrylate/C10-C30-alkylacrylate copolymer); polyacrylamides, for instance the crosslinked copolymers marketed under the names Sepigel 305 (CTFA name: polyacrylamide/C13-14 isoparaffin/Laureth 7) or Simulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyltaurate copolymer/isohexadecane/polysorbate 80) by SEPPIC; 2-acrylamido-2-methylpropanesulfonic acid polymers and copolymers, which are optionally crosslinked and/or neutralized, for instance the poly(2-acrylamido-2-methylpropanesulfonic acid) marketed by Hoechst under the trademark “Hostacerin AMPS” (CTFA name: ammonium polyacryldimethyltauramide); cellulose-based derivatives such as hydroxyethylcellulose; polysaccharides and especially gums such as xanthan gum; and mixtures thereof.
Lipophilic thickeners that may be mentioned include modified clays such as hectorite and its derivatives, for instance the products marketed under the name bentone.
Among the active agents that are representative are:

    
    
        anti-pollution agents and/or free-radical scavengers;
        depigmenting agents and/or propigmenting agents;
        anti-glycation agents;
        NO-synthase inhibitors;
        agents for stimulating the synthesis of dermal or epidermal macromolecules and/or for preventing their degradation;
        agents for stimulating fibroblast proliferation;
        agents for stimulating keratinocyte proliferation;
        muscle relaxants;
        tensioning agents;
        desquamating agents;
        moisturizers;
        anti-inflammatory agents;
        agents acting on the energy metabolism of cells;
        insect repellants;
        substance P or CGRP antagonists.
    
    


Needless to say, one skilled in this art will take care to select the optional additional compound(s) mentioned above and/or the amounts thereof such that the advantageous properties intrinsically associated with the compositions in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).
The compositions according to the invention may be formulated according to techniques that are well known to those skilled in the art, in particular those suited for the preparation of emulsions of oil-in-water or water-in-oil type. They may be in particular in the form of a simple or complex emulsion (O/W, W/O, O/W/O or W/O/W emulsion) such as a cream or a milk, in the form of a gel or a cream-gel, or in the form of a lotion, a powder or a solid tube, and may optionally be packaged as an aerosol and may be in the form of a mousse or a spray.
The compositions according to the invention are preferably in the form of an oil-in-water or water-in-oil emulsion.
The emulsions generally contain at least one emulsifier selected from among amphoteric, anionic, cationic and nonionic emulsifiers, which are used alone or as a mixture. The emulsifiers are appropriately selected according to the emulsion to be obtained (W/O or O/W).
As emulsifying surfactants that may be used for the preparation of the W/O emulsions, examples that may be mentioned include sorbitan, glycerol or sugar alkyl esters or ethers; silicone surfactants, for instance dimethicone copolyols, such as the mixture of cyclomethicone and of dimethicone copolyol, marketed under the name “DC 5225 C” by Dow Corning, and alkyldimethicone copolyols such as laurylmethicone copolyol marketed under the name “Dow Corning 5200 Formulation Aid” by Dow Corning; cetyidimethicone copolyol, such as the product marketed under the name Abil EM 90R by Goldschmidt, and the mixture of cetyidimethicone copolyol, of polyglyceryl isostearate (4 mol) and of hexyl laurate, marketed under the name Abil WE 09 by Goldschmidt. One or more co-emulsifiers may also be added thereto, which may be selected advantageously from the group comprising polyol alkyl esters. Polyol alkyl esters that may especially be mentioned include glycerol and/or sorbitan esters, for example polyglyceryl isostearate, such as the product marketed under the name Isolan GI 34 by Goldschmidt, sorbitan isostearate, such as the product marketed under the name Arlacel 987 by ICI, sorbitan glyceryl isostearate, such as the product marketed under the name Arlacel 986 by ICI, and mixtures thereof.
For the O/W emulsions, examples of emulsifiers that may be mentioned include nonionic emulsifiers such as oxyalkylenated (more particularly polyoxyethylenated) fatty acid esters of glycerol; oxyalkylenated fatty acid esters of sorbitan; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty acid esters; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty alkyl ethers; sugar esters, for instance sucrose stearate; fatty alkyl ethers of sugars, especially polyalkylglucosides (APG) such as decylglucoside and laurylglucoside marketed, for example, by Henkel under the respective names Plantaren 2000 and Plantaren 1200, cetostearyl glucoside optionally as a mixture with cetostearyl alcohol, marketed, for example, under the name Montanov 68 by SEPPIC, under the name Tegocare CG90 by Goldschmidt and under the name Emulgade KE3302 by Henkel, and also arachidyl glucoside, for example in the form of a mixture of arachidyl alcohol, behenyl alcohol and arachidyl glucoside, marketed under the name Montanov 202 by SEPPIC. According to one particular embodiment of the invention, the mixture of the alkylpolyglucoside as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition as described, for example, in WO-A-92/06778.
When it is an emulsion, the aqueous phase of this emulsion may comprise a nonionic vesicular dispersion prepared according to known processes (Bangham, Standish and Watkins, J. Mol. Biol., 13, 238 (1965), FR-2,315,991 and FR-2,416,008).
The compositions according to the invention find application in a large number of treatments, especially cosmetic treatments, of the skin, the lips and the hair, including the scalp, especially for protecting and/or caring for the skin, the lips and/or the hair, and/or for making up the skin and/or the lips.
The present invention also features the use of the subject compositions as defined above for the manufacture of cosmetic products for treating the skin, the lips, the nails, the hair, the eyelashes, the eyebrows and/or the scalp, especially care products and makeup products.
The cosmetic compositions according to the invention may be administered (regime or regimen), for example, as care products and/or anti-sun products for the face and/or the body, of liquid to semi-liquid consistency, such as milks, more or less rich creams, cream-gels and pastes. They may optionally be packaged as an aerosol and may be in the form of mousses or sprays.
The compositions according to the invention in the form of vaporizable fluid lotions are applied to the skin or the hair in the form of fine particles by means of pressurization devices. The devices in accordance with the invention are well known to those skilled in the art and include non-aerosol pumps or “atomizers”, aerosol containers comprising a propellant and also aerosol pumps using compressed air as propellant. The latter pumps are described in U.S. Pat. Nos. 4,077,441 and 4,850,517.
The compositions packaged in aerosol form in accordance with the invention generally contain conventional propellants, for instance hydrofluoro compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane or trichlorofluoromethane. They are preferably present in amounts ranging from 15% to 50% by weight relative to the total weight of the composition.
In order to further illustrate the present invention and the advantages thereof, the following specific examples are given, it being understood that same are intended only as illustrative and in nowise limitative. In said examples to follow, all parts and percentages are given by weight, unless otherwise indicated.
COMPOSITION EXAMPLES 1 AND 2
The following compositions were prepared, the amounts being expressed as weight percentages.













FOR-
FOR-


COMPOSITION
MULA 1
MULA 2

















Phase A:




Polydimethylsiloxane
0.5
0.5


Preservatives
1
1


Stearic acid
1.5
1.5


Glyceryl monostearate/PEG
1
1


stearate mixture (100 EO)


Mixture of cetylstearyl glucoside,
2
2


cetyl alcohol and stearyl alcohol


Cetyl alcohol
0.5
0.5


4 tert-Butyl-4′-methoxydibenzoylmethane
2
2


C12-C13 alkyl benzoate
10
5


Bis(ethylhexyloxyphenol)methoxyphenyltriazine
3
3


(Tinosorb S from Ciba-Geigy)


N-Lauroyl isopropyl sarcosinate
20
20


Diethylhexyl syringylidenemalonate
1
—


(Oxynex ST from Merck)


Tris(tetramethylhydroxypiperidinol)
—
2 (AM)*


citrate (Tinoguard Q from Ciba-Geigy)


Phase B:


Deionized water
qs 100
qs 100


Complexing agent
0.1
0.1


Glycerol
5
5


Xanthan gum
0.2
0.2


Monocetyl phosphate
1
1


Phase C:


Isohexadecane
1
1


Acrylic acid/stearyl methacrylate copolymer
0.2
0.2


Triethanolamine
qs pH
qs pH





*AM = active material






Method:
The aqueous phase (Phase B) containing all of its ingredients is heated to 80° C. on a water bath. The fatty phase (Phase A) containing all of its ingredients is heated to 80° C. on a water bath. A is emulsified in B with stirring of rotor-stator type (machine from the company Moritz). Phase C is incorporated and the mixture is allowed to cool to room temperature with moderate stirring. The triethanolamine is introduced so as to adjust the pH to the desired value at the end of manufacture.
Each patent, patent application, publication and literature article/report cited or indicated herein is hereby expressly incorporated by reference.
While the invention has been described in terms of various specific and preferred embodiments, the skilled artisan will appreciate that various modifications, substitutions, omissions, and changes may be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the present invention be limited solely by the scope of the following claims, including equivalents thereof.

## Claims

1. A topically applicable, photostabilized, photoprotective cosmetic/dermatological composition, comprising (i) an effective UV-screening amount of at least one dibenzoylmethane sunscreen and an effective photostabilizing amount of (ii) at least one bis-resorcinyl triazine compound and (iii) at least one compound accepting the excited triplet level energy of said at least one dibenzoylmethane sunscreen, formulated into (iv) a topically applicable, cosmetically/dermatologically acceptable support therefor.

2. The photostable photoprotective cosmetic/dermatological composition as defined by claim 1, said at least one compound accepting the excited triplet level energy of said at least one dibenzoylmethane sunscreen being selected from the group consisting of 4-hydroxybenzylidenemalonate compounds, 4-hydroxycinnamate compounds, fluorene compounds, piperidinol salts, and mixtures thereof.

3. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, said at least one dibenzoylmethane sunscreen being selected from the group consisting of:
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, and mixtures thereof.

4. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, said at least one dibenzoylmethane sunscreen comprising 4-(tert-butyl)-4′-methoxydibenzoylmethane (Butyl Methoxy Dibenzoylmethane).

5. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, said at least one bis-resorcinyl triazine compound having the formula (I) below:




in which:
(i) the radicals R1 and R2, which may be identical or different, are each a C3-C18 alkyl radical; a C2-C18 alkenyl radical or a residue of formula —CH2—CH(OH)—CH2—OT1 in which T1 is a hydrogen atom or a C1-C8 alkyl radical;
(ii) the radicals R1 and R2, which may be identical or different, may also be a residue of formula (1) below:





in which:
R6 is a covalent bond; a linear or branched C1-C4 alkyl radical or a residue of formula —Cm1H2m1—O— in which m1 is a number ranging from 1 to 4;
p1 is a number ranging from 0 to 5;
the radicals R7, R8 and R9, which may be identical or different, are each a C1-C18 alkyl radical; a C1-C18 alkoxy radical or a residue of formula:





in which R10 is a C1-C5 alkyl radical;
A1 is a radical having one of the following formulae:





in which:
R3 is a hydrogen atom, a C1-C10 alkyl radical, a radical of formula: —(CH2CHR5—O)n1R4 in which n1 is a number ranging from 1 to 16 or a residue of structure —CH2—CH—(OH)—CH2OT1 wherein T1 is as defined above;
R4 is hydrogen, a metallic cation M, a C1-C5 alkyl radical or a residue of formula —(CH2)m2—OT1 in which m2 is a number ranging from 1 to 4 and T1 is as defined above; and
Q1 is a C1-C18 alkyl radical.

6. The photostable photoprotective cosmetic/dermatological composition as defined by claim 5, said at least one bis-resorcinyl triazine compound of formula (I) being selected from the group consisting of:
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;
2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-4-(2-methoxyethylcarboxyl)phenylamino]-1,3,5-triazine;
2,4-bis{[4-tris(trimethylsiloxysilylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;
2,4-bis{[4-(2′′-methylpropenyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;
2,4-bis{[4-(1′,1′,1′,3′,5′,5′,5′-heptamethyltrisiloxy-2′-methylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;
2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy]-2-hydroxy]phenyl}-6-[(4-ethylcarboxyl)phenylamino]-1,3,5-triazine;
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(1-methylpyrrol-2-yl)-1,3,5-triazine, and mixtures thereof.

7. The photostable photoprotective cosmetic/dermatological composition as defined by claim 6, said at least one bis-resorcinyl triazine compound of formula (II) comprising 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine).

8. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, said at least one bis-resorcinyl triazine compound ranging from 0.1% to 20% by weight, relative to the total weight of the composition.

9. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, said at least one dibenzoylmethane sunscreen ranging from 0.01% to 10% by weight relative to the total weight of the composition.

10. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, said at least one compound accepting the excited triplet level energy of said at least one dibenzoylmethane sunscreen having an excited triplet level energy ranging from 40 kcal/mol to 70 kcal/mol.

11. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, said at least one compound accepting the excited triplet level energy of said at least one dibenzoylmethane sunscreen comprising a 4-hydroxybenzylidenemalonate compound or a 4-hydroxycinnamate compound of formula (V):




in which A is a chromophoric group that absorbs UV radiation, including two monovalent groups containing a carbonyl function;
R14 is hydrogen, a linear or branched C1-C8 alkyl radical or a linear or branched C1-C8 alkoxy radical, and
R15 is a linear or branched C1-C8 alkyl radical.

12. The photostable photoprotective cosmetic/dermatological composition as defined by claim 11, comprising at least one compound of formula (Va) below:




in which:
R14 is hydrogen, a linear or branched C1-C8 alkyl radical or a linear or branched C1-C8 alkoxy radical;
R15 is hydrogen or a linear or branched C1-C8 alkyl radical;
R16 is —C(O)CH3, —C2R18, —C(O)NH2, or —C(O)N(R19)2;
X is O or NH,
R17 is a linear or branched C1-C30 alkyl radical;
R18 is a linear or branched C1-C20 alkyl radical; and each R19 independently is a linear or branched C1-C8 alkyl radical.

13. The photostable photoprotective cosmetic/dermatological composition as defined by claim 11, comprising at least one compound of formula (Vb) or (Vc) below:




in which:
R16 is —CO2R18;
R17 is a linear or branched C1-C8 alkyl;
R18 is a linear or branched C1-C8 alkyl radical; and
X is O.

14. The photostable photoprotective cosmetic/dermatological composition as defined by claim 13, comprising diethylhexyl syringylidenemalonate having the following formula:

15. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, said at least one compound accepting the excited triplet level energy of said at least one dibenzoylmethane sunscreen comprising at least one fluorene compound having one of the formulae (VI), (VII), (VIII), (IX), (X), (XI), (XII) and (XIII) below:







in which:
the radicals R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37 and R38, which may be identical or different, are each an optionally substituted linear or branched C1-C30 alkyl radical; an optionally substituted C3-C8 cycloalkyl radical; an optionally substituted monocyclic, bicyclic or tricyclic aryl radical; an optionally substituted monocyclic, bicyclic or tricyclic heteroaryl radical; an optionally substituted C3-C14 heterocycloalkyl radical; an amino or cyano group; an ester group of formula:





in which R is an optionally substituted linear or branched C1-C30 alkyl group or an optionally substituted C3-C8 cycloalkyl radical;
the radicals R39 and R44, which may be identical or different, are each substituted or unsubstituted diphenylmethylene; substituted or unsubstituted 9H-fluorene;
the radical R45 is an optionally substituted linear or branched C1-C30 alkyl radical; an optionally substituted linear or branched C1-C30 hydroxyalkyl radical; an optionally substituted C3-C8 cycloalkyl radical; an optionally substituted monocyclic, bicyclic or tricyclic aryl radical; an optionally substituted monocyclic, bicyclic or tricyclic heteroaryl radical; an optionally substituted C3-C14 heterocycloalkyl radical; an optionally substituted ether; an amino group;
the radicals R46 and R47 are each, independently of each other, hydrogen, an optionally substituted linear or branched C1-C30 alkyl radical; an optionally substituted linear or branched C1-C30 hydroxyalkyl radical; an optionally substituted C3-C8 cycloalkyl radical; an optionally substituted monocyclic, bicyclic or tricyclic aryl radical; an optionally substituted monocyclic, bicyclic or tricyclic heteroaryl radical; an optionally substituted C3-C14 heterocycloalkyl radical; an amino group, a cyano, hydroxyl, amide or imide, a halogen, an optionally substituted ether, an ester or a urethane;
q, r, s and t are numbers ranging from 1 to 100;
a, b, c, d, e and f are numbers ranging from 0 to 4;
u is a number ranging from 0 to 100, and also mixtures of these compounds.

16. The photostable photoprotective cosmetic/dermatological composition as defined by claim 15, comprising at least one compound of formula (VI) wherein the radicals R20 and R21 are each branched C1-C15 alkyl radicals.

17. The photostable photoprotective cosmetic/dermatological composition as defined by claim 16, comprising the compound 2-ethylhexyl (9H-fluoren-9-ylidene)acetate.

18. The photostable photoprotective cosmetic/dermatological composition as defined by claim 15, comprising at least one compound of formula (VII) wherein the radicals R22 and R23 are each branched C1-C15 alkyl radicals.

19. The photostable photoprotective cosmetic/dermatological composition as defined by claim 18, comprising the compounds diisopropyl fluorenemalonate and bis(2-ethylhexyl) fluorenemalonate.

20. The photostable photoprotective cosmetic/dermatological composition as defined by claim 15, comprising at least one compound of formula (VIII) wherein the radicals R24 and R25 are each branched C3-C20 alkyl radicals and more particularly simultaneously are 2-ethylhexyl.

21. The photostable photoprotective cosmetic/dermatological composition as defined by claim 15, comprising at least one compound of formula (X) wherein the radicals R28, R29 and R30 are each branched C1-C15 alkyl radicals and more particularly compounds for which R28 and R30 are simultaneously 2-ethylhexyl.

22. The photostable photoprotective cosmetic/dermatological composition as defined by claim 15, comprising at least one compound of formula (XI) wherein the radicals R31, R32 and R33 are each branched C1-C15 alkyl radicals and more particularly are compounds for which R31 and R33 are simultaneously 2-ethylhexyl.

23. The photostable photoprotective cosmetic/dermatological composition as defined by claim 15, comprising at least one compound of formula (XII) wherein the radicals R40 and R42 are each C1-C15 alkyl radicals, R41 is a linear C1-C15 alkyl radical, the radicals R38 and R43 simultaneously are cyano, and the radicals R39 and R44 are each diphenylmethylene.

24. The photostable photoprotective cosmetic/dermatological composition as defined by claim 23, said at least one fluorene compound of formula (XII) comprising the polymer having the following structure:




in which t=1 and u is a number ranging from 2 to 10.

25. The photostable photoprotective cosmetic/dermatological composition as defined by claim 15, comprising at least one compound of formula (XIII) wherein e and f are equal to 0; and the radical R45 is a branched C3-C20 alkyl radical or a C1-C15 hydroxyalkyl radical.

26. The photostable photoprotective cosmetic/dermatological composition as defined by claim 25, wherein formula (XIII) is hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxy-n-butyl, 1-hydroxy-1-methylpropyl, 1-hydroxy-2,2-dimethylpropyl or 2-hydroxy-2-methylpropyl.

27. The photostable photoprotective cosmetic/dermatological composition as defined by claim 25, comprising the compound 2-ethylhexyl cyano(9H-fluoren-9-ylidene)acetate (or octofluorene).

28. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, said at least one compound accepting the excited triplet level energy of said at least one dibenzoylmethane sunscreen comprising at least one piperidinol salt having the formula (XIV) below:




in which:
R1 is hydrogen or methyl;
x is 1 or 2;

1) when x is equal to 1:
R2 is hydrogen; a C1-C18 alkyl radical; a C2-C18 alkenyl radical; a propargyl radical; a glycidyl group; a C2-C50 alkyl radical interrupted with 1 to 20 oxygen atoms, the said alkyl being substituted with 1 to 10 hydroxyl groups or alternatively simultaneously interrupted with the said oxygen atoms and substituted with the said hydroxyl groups; a C1-C4 alkyl radical substituted with a carboxyl group or a group —COOZ in which Z is hydrogen, a C1-C4 alkyl, phenyl, a C1-C4 alkyl radical substituted with a group (COO−)p Mp+ wherein p is an integer ranging from 1 to 3 and M is a metal ion from Groups 1, 2 and 3 of the Periodic Table or Zn, Cu, Ni or Co, or alternatively M is a group Np+(R′′)4 wherein R′′ is a C1-C8 alkyl or a benzyl;

2) when x is 2:
R′ is a C1-C12 alkylene radical; a C4-C12 alkenylene radical, a xylylene radical; a C1-C50 alkylene radical interrupted with 1 to 20 oxygen atoms, the said alkyl being substituted with 1 to 10 hydroxyl groups or alternatively simultaneously interrupted with the said oxygen atoms and substituted with the said hydroxyl groups;
Y is an organic or mineral anion; and the total charge of cations y being equal to the total charge of anions z.

29. The photostable photoprotective cosmetic/dermatological composition as defined by claim 28, comprising at least one compound of formula (XIV) wherein R1 and R2 are each hydrogen, x=1 and Y is a citrate anion.

30. The photostable photoprotective cosmetic/dermatological composition as defined by claim 29, comprising tris(tetramethylhydroxypiperidinol) citrate of structure:




with y=3.

31. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, said at least one compound accepting the energy of the triplet state of the dibenzoylmethane sunscreen(s) ranging from 0.1% to 25% by weight, relative to the total weight of the composition.

32. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, further comprising other UV-A-active and/or UV-B-active organic or mineral photoprotective agents that are water-soluble or liposoluble or insoluble in the cosmetic solvents commonly used.

33. The photostable photoprotective cosmetic/dermatological composition as defined by claim 32, comprising additional organic photoprotective agents are selected from among anthranilates; salicylic derivatives, camphor derivatives; benzophenone derivatives; β,β-diphenylacrylate derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis-benzazolyl derivatives; p-aminobenzoic acid (PABA) derivatives; methylenebis(hydroxyphenylbenzotriazole) derivatives; benzoxazole derivatives; screening polymers and screening silicones, α-alkylstyrene-based dimers derivatives; 4,4-diarylbutadienes, and mixtures thereof.

34. The photostable photoprotective cosmetic/dermatological composition as defined by claim 33, said additional organic UV-screening agent(s) being selected from among the following compounds:
Ethylhexyl salicylate,
Octocrylene,
Phenylbenzimidazolesulfonic acid,
Benzophenone-3,
Benzophenone-4,
Benzophenone-5,
n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,
4-Methylbenzylidenecamphor,
Terephthalylidenedicamphorsulfonic acid,
Disodium phenyldibenzimidazoletetrasulfonate,
Methylenebis(benzotriazolyl)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.

35. The photostable photoprotective cosmetic/dermatological composition as defined by claim 32, comprising additional mineral photoprotective agents are treated or untreated metal oxide pigments or nanopigments.

36. The photostable photoprotective cosmetic/dermatological composition as defined by claim 35, said additional pigments or nanopigments being selected from among titanium oxide, zinc oxide, iron oxide, zirconium oxide and cerium oxide, and mixtures thereof, which are treated or untreated.

37. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, further comprising at least one agent for artificially tanning and/or browning the skin.

38. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, further comprising at least one adjuvant selected from among fatty substances, organic solvents, ionic or nonionic, hydrophilic or lipophilic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, anti-foams, fragrances, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, active agents, fillers, polymers, propellants and acidifying or basifying agents.

39. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, formulated for the cosmetic treatment of the skin, the lips, the nails, the hair, the eyelashes, the eyebrows and/or the scalp.

40. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, formulated as a care product for the skin, the lips, the nails, the hair and/or the scalp.

41. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, formulated as a makeup product.

42. A process for photostabilizing a dibenzoylmethane sunscreen against UV-radiation, comprising combining same with at least one arylalkyl benzoate compound and at least one compound accepting the excited triplet level energy of said dibenzoylmethane sunscreen.

43. A regime or regimen for photoprotecting the skin, the lips, the nails, the hair, the eyelashes, the eyebrows, and/or the scalp against the damaging effects of UV-radiation, comprising topically applying thereon a photostabilized photoprotective cosmetic/dermatological composition containing (i) an effective UV-screening amount of at least one dibenzoylmethane sunscreen and an effective photostabilizing amount of (ii) at least one bis-resorcinyl triazine compound and (iii) at least one compound accepting the excited triplet level energy of said at least one dibenzoylmethane sunscreen, formulated into (iv) a topically applicable, cosmetically/dermatologically acceptable support therefor.

44. The photostable photoprotective cosmetic/dermatological composition as defined by claim 2, formulated as a water-in-oil or oil-in-water emulsion.