Photoprotecting/cosmetic compositions comprising benzotriazole and bis-resorcinyltriazine sunscreens

Abstract

Topically applicable sunscreen/cosmetic compositions suited for the improved photoprotection of human skin and/or hair against the damaging effects of UV-irradiation, particularly solar radiation, comprise an effective SPF-maintaining and water remanence-enhancing amount of intimate admixture of (a) at least one benzotriazole first sunscreen compound and (b) at least one bis-resorcinyltriazine second sunscreen compound, formulated into (c) a topically applicable, cosmetically acceptable vehicle, diluent or carrier therefor.

What is claimed is:  
     
         1 . A topically applicable sunscreen/cosmetic composition suited for the photoprotection of human skin and/or hair, comprising an effective SPF-maintaining and water remanence-enhancing amount of combinatory immixture of (a) at least one benzotriazole first sunscreen compound and (b) at least one bis-resorcinyltriazine second sunscreen compound, formulated into (c) a topically applicable, cosmetically acceptable vehicle, diluent or carrier therefor.  
     
     
         2 . A topically applicable sunscreen/cosmetic composition suited for the photoprotection of human skin and/or hair, comprising an effective SPF-maintaining and water remanence-enhancing amount of combinatory immixture of (a) at least one benzotriazole first sunscreen compound having the structural formula (I):  
       
         
           
           
               
               
           
         
       
       in which A is a hydrogen atom or a divalent radical —L—W—;  n  is 1,2, or 3; the radicals Y, which may be identical or different, are each a C 1 -C 10  alkyl radical, a halogen atom, a C 1 -C 10  alkoxy radical or a sulfonic group, with the proviso that, in the latter instance, two adjacent groups Y on the same aromatic nucleus can together form an alkylidenedioxy group in which the alkylidene moiety has 1 or 2 carbon atoms and with the further proviso that the radicals Y are other than a sulfonic group when A is other than a hydrogen atom; L is a divalent radical having the formula (II) below:  
       
         
           
           
               
               
           
         
       
       in which X is O or NH; Z is a hydrogen atom or a C 1 -C 4  alkyl radical;  n  is an integer ranging from 0 to 3, inclusive;  m  is 0 or 1;  p  is an integer ranging from 1 to 10, inclusive; W is a radical of formula (1), (2) or (3) below:  
       
         
           
           
               
               
           
         
       
       or  
       —Si(R) 3  (3)  
       in which the radicals R, which may be identical or different, are each a C 1 -C 10  alkyl, phenyl or 3,3,3-trifluoropropyl radical, at least 80%, by number of the radicals R being methyl radicals; the radicals B, which may be identical or different, are each a radical R or the radical V having the following formula:  
       
         
           
           
               
               
           
         
       
       in which Y,  n  and L are as defined above;  r  is an integer ranging from 0 to 50, inclusive, and  s  is an integer ranging from 1 to 20, inclusive, and, if  s =0, then at least one of the two radicals B is a radical V;  u  is an integer ranging from 1 to 6, inclusive, and  t  is an integer ranging from 0 to 10, inclusive, with the proviso that  t + u  is greater than or equal to 3, and (b) at least one bis-resorcinyl second sunscreen compound, formulated into (c) a topically applicable, cosmetically acceptable vehicle, diluent or carrier therefor.  
     
     
         3 . A topically applicable sunscreen/cosmetic composition suited for the photoprotection of human skin and/or hair, comprising an effective SPF-maintaining and water remanence-enhancing amount of combinatory immixture of (a) at least one benzotriazole first sunscreen compound and (b) at least one bis-resorcinyltriazine second sunscreen compound having the structural formula (III):  
       
         
           
           
               
               
           
         
       
       in which (i) the radicals R 1  and R 2 , which may be identical or different, are each a C 3 -C 18  alkyl radical, a C 2 -C 18  alkenyl radical, or a residue of formula —CH 2 —CH(OH)—CH 2 —OT 1  wherein T 1  is a hydrogen atom or a C 1 -C 8  alkyl radical; (ii) the radicals R 1  and R 2 , which may be identical or different, can also be a residue of formula (4) below:  
       
         
           
           
               
               
           
         
       
       in which R 6  is a covalent bond, a linear or branched C 1 -C 4  alkyl radical, or a residue of formula —C m1 H 2m1 —or —C m1 H   2m1 —O—wherein m 1  is a number ranging from 1 to 4; P 1  is a number ranging from 0 to 5; the radicals R 7 , R 8  and R 9 , which may be identical or different, are each a C 1 -C 18  alkyl radical, a C 1 -C 18  alkoxy radical, or a residue of formula:  
       
         
           
           
               
               
           
         
       
       in which R 10  is a C 1 -C 5  alkyl radical; A 1  is a residue having one of the following formulae:  
       
         
           
           
               
               
           
         
       
       in which R 3  denotes a hydrogen atom, a C 1 -C 10  alkyl radical, a radical of formula —(CH 2 CHR 5 —O) n1 R 11  wherein n 1  is a number ranging from 1 to 16, R 11  is a hydrogen atom or methyl radical or a residue of structure —CH 2 —CH(OH)—CH 2 OT 1  wherein T 1  is as defined above; R 4  is a hydrogen atom, a metal cation M, a C 1 -C 5  alkyl radical, or a residue of formula —(CH 2 )m 2 —OT 1  wherein m 2  is a number ranging from 1 to 4 and T 1  is as defined above, and Q 1  is a C 1 -C 18  alkyl radical, formulated into (c) a topically applicable, cosmetically acceptable vehicle, diluent or carrier therefor.  
     
     
         4 . A topically applicable sunscreen/cosmetic composition suited for the photoprotection of human skin and/or hair, comprising an effective SPF-maintaining and water remanence-enhancing amount of combinatory immixture of (a) at least one benzotriazole first sunscreen compound having the structural formula (I):  
       
         
           
           
               
               
           
         
       
       in which A is a hydrogen atom or a divalent radical —L—W—;  n  is 1,2, or 3; the radicals Y, which may be identical or different, are each a C 1 -C 10  alkyl radical, a halogen atom, a C 1 -C 10  alkoxy radical or a sulfonic group, with the proviso that, in the latter instance, two adjacent groups Y on the same aromatic nucleus can together form an alkylidenedioxy group in which the alkylidene moiety has 1 or 2 carbon atoms and with the further proviso that the radicals Y are other than a sulfonic group when A is other than a hydrogen atom; L is a divalent radical having the formula (II) below:  
       
         
           
           
               
               
           
         
       
       in which X is O or NH; Z is a hydrogen atom or a C 1 -C 4  alkyl radical;  n  is an integer ranging from 0 to 3, inclusive;  m  is 0 or 1;  p  is an integer ranging from 1 to 10, inclusive; W is a radical of formula (1), (2) or (3) below:  
       
         
           
           
               
               
           
         
       
       in which the radicals R, which may be identical or different, are each a C 1 -C 10  alkyl, phenyl or 3,3,3-trifluoropropyl radical, at least 80%, by number of the radicals R being methyl radicals; the radicals B, which may be identical or different, are each a radical R or the radical V having the following formula:  
       
         
           
           
               
               
           
         
       
       in which Y,  n  and L are as defined above;  r  is an integer ranging from 0 to 50, inclusive, and  s  is an integer ranging from 1 to 20, inclusive, and, if  s =0, then at least one of the two radicals B is a radical V;  u  is an integer ranging from 1 to 6, inclusive, and  t  is an integer ranging from 0 to 10, inclusive, with the proviso that  t + u  is greater than or equal to 3, and (b) at least one bis-resorcinyltriazine second sunscreen compound, having the structural formula (III):  
       
         
           
           
               
               
           
         
       
       in which (i) the radicals R 1  and R 2 , which may be identical or different, are each a C 3 -C 18  alkyl radical, a C 2 -C 18  alkenyl radical, or a residue of formula —CH 2 —CH(OH)—CH 2 —OT 1  wherein T 1  is a hydrogen atom or a C 1 -C 8  alkyl radical; (ii) the radicals R 1  and R 2 , which may be identical or different, can also be a residue of formula (4) below:  
       
         
           
           
               
               
           
         
       
       in which R 6  is a covalent bond, a linear or branched C 1 -C 4  alkyl radical, or a residue of formula —C m1 H 2m1 —or —C m1 H   2m1 —O—wherein ml is a number ranging from 1 to 4; P 1  is a number ranging from 0 to 5; the radicals R 7 , R 8  and R 9 , which may be identical or different, are each a C 1 -C 18  alkyl radical, a C 1 -C 18  alkoxy radical, or a residue of formula:  
       
         
           
           
               
               
           
         
       
       in which R 10  is a C 1 -C 5  alkyl radical; A 1  is a residue having one of the following formulae:  
       
         
           
           
               
               
           
         
       
       in which R 3  denotes a hydrogen atom, a C 1 -C 10  alkyl radical, a radical of formula —(CH 2 CHR 5 —O) n1 R 11  wherein n 1  is a number ranging from 1 to 16, R 11  is a hydrogen atom or methyl radical or a residue of structure —CH 2 —CH(OH)—CH 2 OT 1  wherein T 1  is as defined above; R 4  is a hydrogen atom, a metal cation M, a C 1 -C 5  alkyl radical, or a residue of formula —(CH 2 )m 2 —OT 1  wherein m 2  is a number ranging from 1 to 4 and T 1  is as defined above, and Q 1  is a C 1 -C 18  alkyl radical, formulated into (c) a topically applicable, cosmetically acceptable vehicle, diluent or carrier therefor.  
     
     
         5 . The topically applicable sunscreen/cosmetic composition as defined by  claim 2 , said at least one benzotriazole first sunscreen compound (a) comprising 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-3′-butyl-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-5′-t-octylphenyl)benzotriazole, or 2-(2′-hydroxy-3′-sec-butyl-5′-benzenesulfonato)benzotriazole.  
     
     
         6 . The topically applicable sunscreen/cosmetic composition as defined by  claim 2 , wherein formula (I), A is a divalent radical —L—W—and W has the formula (I), at least one of the following conditions being satisfied: 
 R is an alkyl radical,  
   r  ranges from 0 to 15, inclusive;  s  ranges from 1 to 5, inclusive,  
   n  is other than zero and Y is a methyl, tert-butyl or C 1 -C 4  alkoxy radical,  
 Z is a hydrogen atom or methyl,  
   m =0 or [m=1 and X=0],  
   p  is equal to 1.  
 
     
     
         7 . The topically applicable sunscreen/cosmetic composition as defined by  claim 6 , each of said conditions being satisfied.  
     
     
         8 . The topically applicable sunscreen/cosmetic composition as defined by  claim 2 , said at least one benzotriazole first sunscreen compound (a) having the structural formula (I′):  
       
         
           
           
               
               
           
         
       
       in which: 0 ≦ r ≦15,  
       1≦ s ≦5,  
       and D is the divalent radical:  
       
         
           
           
               
               
           
         
       
     
     
         9 . The topically applicable sunscreen/cosmetic composition as defined by  claim 8 , wherein formula (I′)  r =0 s =1 and  
       
         
           
           
               
               
           
         
       
     
     
         10 . The topically applicable sunscreen/cosmetic composition as defined by  claim 1 , comprising from 0.1% to 15% by weight of said at least one benzotriazole first sunscreen compound (a).  
     
     
         11 . The topically applicable sunscreen/cosmetic composition as defined by  claim 10 , comprising from 0.2% to 10% by weight of said at least one benzotriazole first sunscreen compound (a).  
     
     
         12 . The topically applicable sunscreen/cosmetic composition as defined by  claim 3 , said at least one bis-resorcinyl second sunscreen compound (b) comprising 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(trimethylsiloxy)silylpropyloxy)-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-(ethoxycarbonyl)phenylamino]-1,3,5-triazine; or 2,4-bis}[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-( 1-methylpyrrol-2-yl)-1,3,5-triazine.  
     
     
         13 . The topically applicable sunscreen/cosmetic composition as defined by  claim 3 , said at least one bis-resorcinyl second sunscreen compound (b) comprising 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(tris(trimethylsiloxy)silylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; or 2,4-bis{[4-(1″,1″,1″,3″,5″,5″,5″-heptamethyltrisiloxy-2″-methylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine.  
     
     
         14 . The topically applicable sunscreen/cosmetic composition as defined by  claim 8 , wherein formula (I′), r=0, s=1 and D= 
       
         
           
           
               
               
           
         
       
     
     
         15 . The topically applicable sunscreen/cosmetic composition as defined by  claim 10 , comprising from 0.1 % to 15% by weight of said at least one bis-resorcinyltriazine second sunscreen compound (b).  
     
     
         16 . The topically applicable sunscreen/cosmetic composition as defined by  claim 11 , comprising from 0.2% to 10% by weight of said at least one bis-resorcinyltriazine second sunscreen compound (b).  
     
     
         17 . The topically applicable sunscreen/cosmetic composition as defined by  claim 1 , formulated as an oil-in-water emulsion.  
     
     
         18 . The topically applicable sunscreen/cosmetic composition as defined by  claim 1 , further comprising at least one additional hydrophilic or lipophilic organic UV-A and/or UV-B sunscreen.  
     
     
         19 . The topically applicable sunscreen/cosmetic composition as defined by  claim 18 , further comprising at least one cinnamic derivative, salicylic derivative, camphor derivative, triazine derivative, benzophenone derivative, dibenzoylmethane derivative, benzimidazole derivative, β-β-diphenylacrylate derivative, p-aminobenzoic acid derivative, sunscreen polymer, or sunscreen silicone.  
     
     
         20 . The topically applicable sunscreen/cosmetic composition as defined by  claim 1 , further comprising a photoprotecting effective amount of particulates of at least one coated or uncoated inorganic pigment or nanopigment.  
     
     
         21 . The topically applicable sunscreen/cosmetic composition as defined by  claim 20 , said at least one pigment or nanopigment comprising titanium dioxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide, or mixture thereof.  
     
     
         22 . The topically applicable sunscreen/cosmetic composition as defined by  claim 1 , further comprising at least one active agent for the artificially tanning and/or browning of human skin.  
     
     
         23 . The topically applicable sunscreen/cosmetic composition as defined by  claim 1 , further comprising at least one cosmetically acceptable adjuvant or additive.  
     
     
         24 . The topically applicable sunscreen/cosmetic composition as defined by  claim 23 , said at least one adjuvant or additive comprising a fat, organic solvent, thickening agent, softener, antioxidant, opacifying agent, stabilizing agent, emollient, hydroxy acid, anti-foaming agent, hydrating agent, vitamin, fragrance, preservative, surfactant, filler, sequestering agent, polymer, propellant, basifying or acidifying agent, dye, colorant, or mixture thereof.  
     
     
         25 . The topically applicable sunscreen/cosmetic composition as defined by  claim 1 , comprising a nonionic vesicular dispersion, emulsion, cream, milk, gel, cream gel, ointment, suspension, dispersion, powder, solid stick or tube, foam or spray.  
     
     
         26 . The topically applicable sunscreen/cosmetic composition as defined by  claim 1 , comprising a makeup.  
     
     
         27 . The topically applicable sunscreen/cosmetic composition as defined by  claim 26 , comprising an anhydrous or aqueous solid or paste, emulsion, suspension or dispersion.  
     
     
         28 . The topically applicable sunscreen/cosmetic composition as defined by  claim 1 , comprising a shampoo, lotion, gel, nonionic vesicular dispersion, hair lacquer, or rinse.  
     
     
         29 . The topically applicable sunscreen/cosmetic composition as defined by  claim 1 , having a sun protection factor of at least 2.  
     
     
         30 . A regime/regimen for protecting human skin and/or hair against the deleterious effects of ultraviolet irradiation, comprising topically applying thereto an effective amount of the topically applicable sunscreen/cosmetic composition as defined by  claim 1 .  
     
     
         31 . A regime/regimen for protecting human skin and/or hair against the deleterious effects of solar radiation, comprising topically applying thereto a effective amount of the topically applicable sunscreen/cosmetic composition as defined by  claim 1.