Mixtures comprising benzotriazoles and merocyanines

Abstract

The present invention relates to the use of a stabilizing composition comprising (a) an effective stabilizing amount of at least one merocyanine derivative having an absorption maximum of 350 to 400 nm, and (b) at least one UV filter selected from benzotriazole derivatives; and optionally (c) at least one excited state quencher; for the protection of body care and household products against the deleterious effects of light, heat and oxygen.

1 . A stabilizing composition for the protection of body care and household products against the deleterious effects of light, heat and oxygen comprising
 (a) an effective stabilizing amount of at least one merocyanine derivative having an absorption maximum of 350 to 400 nm, and   (b) at least one UV filter selected from benzotriazole derivatives; and optionally   (c) at least one excited state quencher; and optionally   (d) at least one salicylate.   
     
     
         2 . A composition according to  claim 1 , wherein
 (a) corresponds to compounds of formula (1)   
       
         
           
           
               
               
           
         
         wherein 
         R 1  and R 2  independently of each other are hydrogen; C 1 -C 22 alkyl; C 2 -C 22  alkenyl, C 2 -C 22 alkinyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkenyl, C 7 -C 20 aralkyl, C 1 -C 20 heteroalkyl, C 3 -C 12 cycloheteroalkyl, C 5 -C 11 heteroaralkyl, C 6 -C 20 aryl, C 4 -C 9 heteroaryl, COR 13  or CONR 13 R 14 ; 
         R 3  is CN; —COOR 5 ; —CONHR 5 ; —COR 5 ; —SO 2 R 5 ; —CONR 5 R 6 ; C 6 -C 20 aryl; or C 4 -C 9 heteroaryl; 
         R 4  is CN; —COOR 7 ; —CONHR 7 ; —COR 7 ; —SO 2 R 7 ; —CONR 7 R 8 ; C 1 -C 22  alkyl; C 2 -C 22 alkenyl; C 2 -C 22  alkinyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; C 7 -C 20 aralkyl; C 1 -C 20 heteroalkyl; C 3 -C 12 cycloheteroalkyl; C 5 -C 11  heteroaralkyl; C 6 -C 20  aryl; or C 4 -C 9  heteroaryl; 
         R 5 , R 6 , R 7  and R 8  independently of each other are hydrogen; C 1 -C 22 alkyl; C 2 -C 22 alkenyl; C 2 -C 22  alkinyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; C 7 -C 20 aralkyl; C 1 -C 20 heteroalkyl; C 3 -C 12 cycloheteroalkyl; C 5 -C 11 heteroaralkyl; C 6 -C 20 aryl; C 4 -C 9 heteroaryl; SiR 15 R 16 R 17 ; Si(OR 15 )(OR 16 )(OR 17 ); SiR 15 (OR 16 )(OR 17 ); SiR 15 R 16 (OR 17 ); or a radical —XS; 
         L 1 , L 2  and L 3  independently of each other are hydrogen; C 1 -C 22 alkyl; C 2 -C 22 alkenyl; C 2 -C 22 alkinyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; C 7 -C 20 aralkyl; C 1 -C 20 heteroalkyl; C 3 -C 12 cycloheteroalkyl; C 5 -C 11 heteroaralkyl; C 6 -C 20  aryl; C 4 -C 9 heteroaryl; CN; OH; OR 9 ; or COOR 9 ; 
         R 9  is hydrogen; C 1 -C 22 alkyl; C 2 -C 22 alkenyl; C 2 -C 22 alkinyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; C 7 -C 20 aralkyl; C 1 -C 20 heteroalkyl; C 3 -C 12 cycloheteroalkyl; C 5 -C 11 heteroaralkyl; C 6 -C 20  aryl; or C 4 -C 9 heteroaryl; or 
         L 1  and L 2 , L 1  and L 3 , L 2  and L 3 , L 1  and R 4 , L 2  and R 4 , L 1  and R 1 , L 2  and R 1 , L 3  and R 1 , L 3  and R 5 , R 3  and R 4 , R 1  and R 2 , R 7  and R 8 , R 5  and R 6  may be linked together to form 1, 2, 3 or 4 carbocyclic or N, O and/or S-heterocyclic rings, which may be further fused with other aromatic rings; 
         R 10  represents R 13 ; COR 13 ; COOR 13 ; CONH 2 , CONHR 13 ; or CONR 13 R 14 ; 
         R 11  represents halogen; OH; NH 2 ; NHR 15 ; NR 15 R 16 ; NR 15 OR 16 ; O—R 15 ; O—CO—R 15 ; S—R 15 ; CO—R 15 ; oxo; thiono; CN; COOH; CONH 2 ; COOR 15 ; CONHR 15 ; CONR 15 R 16 ; SO 2 NH 2 ; SO 2 NHR 15 ; SO 2 NR 15 R 16 ; SO 2 R 15 ; SO 3 R 15 ; SiR 15 R 16 R 17 ; SiOR 15 (OR 16 )(OR 17 ); SiR 15 (OR 16 )(OR 17 ); SiR 15 R 16 (OR 17 ); O—Si—R 15 R 16 R 17 ; O—Si—OR 15 (OR 16 )(OR 17 ); O—Si—R 15 R 16 (OR 17 ); O—SiR 15 (OR 16 )(OR 17 ); PO(OR 15 )(OR 16 ); or a radical *—XS; 
         R 12  represents halogen, CN, SH, OH, CHO, R 18 ; OR 18 ; SR 18 ; C(R 18 )═CR 19 R 20 ; O—CO—R 19 ; NHR 19 ; NR 18 R 19 ; CONH 2 ; CONHR 18 , CONR 18 R 19 ; SO 2 NH 2 ; SO 2 NHR 18 ; SO 2 NR 18 R 19 ; SO 2 R 18 ; COOH; COOR 18 ; OCOOR 18 ; NHCOR 18 ; NR 18 COR 19 ; NHCOOR 19 ; NR 19 COOR 20 ; SiR 15 R 16 R 17 ; SiOR 15 (OR 16 )(OR 17 ); SiR 15 (OR 16 )(OR 17 ); SiR 15 R 16 (OR 17 ); OSiR 15 R 16 R 17 ; OSiOR 15 (OR 16 )(OR 17 ); OSiR 15 R 16 (OR 17 ); OSiR 15 (OR 16 )(OR 17 ); P(═O)OR 19 OR 20 ; P(═O)R 19 OR 20 ; P(═O)R 19 R 20 ; or a radical *—XS; or is selected from the group consisting of C 1 -C 22 alkyl; C 3 -C 12 cycloalkyl; C 1 -C 12 alkenyl; C 3 -C 12 cycloalkenyl; C 1 -C 12 alkylthio; C 3 -C 12 cycloalkylthio; C 1 -C 12 alkenylthio; C 3 -C 12 cycloalkenylthio; C 1 -C 12 alkoxy; C 3 -C 12 cycloalkoxy; C 1 -C 12 alkenyloxy; and C 3 -C 12 cycloalkenyloxy, which may be unsubstituted or substituted by one or more, identical or different R 11 ; 
         R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19  and R 20  independently of each other are C 1 -C 22 alkyl; C 3 -C 12 cycloalkyl; C 2 -C 12 alkenyl; C 3 -C 12 cycloalkenyl; C 6 -C 14 aryl; C 4 -C 12 heteroaryl; C 7 -C 18 aralkyl or C 5 -C 16 heteroaralkyl; or 
         R 13  and R 14 , R 15  and R 16 , R 16  and R 17  and/or R 18  and R 19  may be linked together to form unsubstituted or C 1 -C 4 alkyl substituted pyrrolidine, piperidine, piperazine or morpholine; 
         X represents a linker; 
         S signifies a silane-, oligosiloxane- or polysiloxane-moiety; 
         the term “oligosiloxane” denotes a group of formula Si(R 15 ) m [OSi(R 16 )] o  wherein 
         m has a value of 0, 1 or 2, 
         o has a value of 3, 2 or 1; and m+o have a value of 3 or refers to groups of formula (1a) or (b) 
       
       
         
           
           
               
               
           
         
         wherein 
         A represents a bond to the linker X; and 
         p has a value of 1 to 9; 
         the term “polysiloxane” refers in this context to groups of formula (1c) or (1d) 
       
       
         
           
           
               
               
           
         
         wherein 
         A represents a bond to the linker X; 
         s has a value of 4 to 250; 
         t has a value of 5 to 250; 
         q has a value of 1 to 30; 
         n is 1 or integer; 
         n is from 1 to 6; 
         when n=2, R 1 , R 5  or R 4  is a bivalent alkyl group; or R 1  and R 2  together with the 2 nitrogen atoms linking them form a unsubstituted or alkyl-substituted 
       
       
         
           
           
               
               
           
         
       
       ring;
 v is from 1 to 4, 
 w is from 1 to 4; 
 when n=3, R 1 , R 5  or R 4  is a trivalent alkyl group; 
 when n=4, R 1 , R 5  or R 4  is a tetravalent alkyl group; and 
 R 1  and R 2  in formula (1) are not simultaneously hydrogen. 
 
     
     
         3 . A composition according to  claim 2 , wherein in formula (1)
 R 1  and R 2  independently of each other are hydrogen; COR 13 ; or C 1 -C 22 alkyl;   R 3  is CN; —COOR 5 ; or —SO 2 R 5 ;   R 5  is hydrogen; C 1 -C 22 alkyl; C 6 -C 20 aryl; or the radical *—X—S;   L 1 , L 2  and L 3  independently of each other are hydrogen; or C 1 -C 22 alkyl; or   L 1  and L 2 , L 1  and L 3 , L 2  and L 3 , may be linked together to form a carbocyclic ring comprising 6 to 10 carbon atoms, which may be further fused with other aromatic rings; and which may be further substituted by one or more than one C 1 -C 4 alkyl;   X represents a linker;   S refers to groups of formula (2a)   
       
         
           
           
               
               
           
         
         wherein 
         R 15 , R 16  and R 17  independently from each other are C 1 -C 22 alkyl; or the radical *—OSi(R 18 )((R 19 )(R 20 ); 
         R 18 , R 19  and R 20  independently of each other are C 1 -C 22 alkyl; 
         A represents a bond to the linker X; and 
         p has a value of 1 to 9. 
       
     
     
         4 . A composition according to  claim 1 , wherein component (a) corresponds to at least one compound of formula (2) 
       
         
           
           
               
               
           
         
         wherein 
         R 1  and R 2 , independently from each other are hydrogen; or C 1 -C 12 alkyl; 
         R 3  is COOR 5 ; or —CN; 
         R 4  is —CN; and 
         R 6  and R 7  independently from each other are hydrogen; or C 1 -C 3 alkyl. 
       
     
     
         5 . A composition according to  claim 1 , wherein component (a) corresponds to at least one compound of formula (3) 
       
         
           
           
               
               
           
         
         wherein 
         R 1  and R 2 , independently from each other are hydrogen; or C 1 -C 12 alkyl; 
         R 3  is —CN; or COOR 5 ; 
         R 4  and R 5 , independently from each other are C 1 -C 22 alkyl; or a radical *—X—S; 
         X represents a linker; 
         S refers to groups of formula (1a) 
       
       
         
           
           
               
               
           
         
         wherein 
         R 15 , R 16  and R 17  independently of each other are C 1 -C 22 alkyl; 
         A represents a bond to the linker X; and 
         p has a value of 1 to 9. 
       
     
     
         6 . A composition according to  claim 1 , wherein component (a) corresponds to a compound of formula (MC-03) 
       
         
           
           
               
               
           
         
       
     
     
         7 . A composition according to  claim 1 , wherein component (a) corresponds to a compound of formula (MC-08) 
       
         
           
           
               
               
           
         
       
     
     
         8 . A composition according to  claim 1 , wherein component (b) is at least one benzotriazole of formula (4) 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is C 1 -C 30 alkyl; C 1 -C 5 alkoxy; C 1 -C 5 alkoxycarbonyl; C 5 -C 7 cycloalkyl; C 6 -C 10 aryl; aralkyl; —SO 3 M; or a radical of formula (4a); 
       
       
         
           
           
               
               
           
         
         R 3  is hydrogen; C 1 -C 5 alkyl; C 1 -C 5 alkoxy; halogen; or hydroxy; 
         R 4  and R 5  each independently of the other are hydrogen; or C 1 -C 5 alkyl; 
         m is 1 or 2; 
         n is 0 or 1; 
         if m=1, 
         R 2  is hydrogen; unsubstituted or phenyl-substituted C 1 -C 12 alkyl; or C 6 -C 10 aryl; 
         if m=2, 
         R 2  is the direct bond; or —(CH 2 ) p —; and 
         p is 1 to 3. 
       
     
     
         9 . A composition according to  claim 1 , wherein component (b) is at least one benzotriazole of formula (5) 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is a random statistical mixture of at least three isomeric branched secondary alkyl groups each having 8 to 30 carbon atoms of the radical 
       
       
         
           
           
               
               
           
         
         E 1  is a straight-chain C 1 -C 14 alkyl; 
         E 2  is a straight-chain C 4 -C 15 alkyl; wherein the total number of carbon atoms in E 1  plus E 2  is from 7 to 29; and 
         R 2  is C 1 -C 5 alkyl. 
       
     
     
         10 . A composition according to  claim 1 , wherein component (b) is 2-(2H-benzotriazol-2-yl)-6-dodecycl-4-methyl-phenol, (BT-01) 
       
         
           
           
               
               
           
         
       
     
     
         11 . A composition according to  claim 1 , wherein component (a) corresponds a compound of formula (MC-03) 
       
         
           
           
               
               
           
         
         and 
         component (b) corresponds to a compound of formula (BT-01) 
       
       
         
           
           
               
               
           
         
       
     
     
         12 . A composition according to  claim 1 , comprising component (c) which is at least one quencher selected from
 (c 1 ) hindered nitroxyl compounds of formula (6a);   
       
         
           
           
               
               
           
         
         (c 2 ) hindered hydroxylamine compounds of formula (6b) 
       
       
         
           
           
               
               
           
         
         and 
         (c 3 ) hindered hydroxylamine salt compounds of formula (6c) 
       
       
         
           
           
               
               
           
         
         wherein 
         G 1  and G 2  independently from each other are C 1 -C 4 alkyl alkyl; or are together pentamethylene, 
         Z 1  and Z 2  are each methyl; or Z 1  and Z 2  together form a linking moiety which may additionally be substituted by an ester, ether, hydroxy, oxo, cyanohydrine, amide, amino, carboxy or urethane group; 
         X is an inorganic or organic anion selected from phosphate, phosphonate, carbonate, bicarbonate, nitrate, chloride, bromide, bisulfite, sulfite, bisulfate, sulfate, borate, formate, acetate, benzoate, citrate, oxalate, tartrate, acrylate, polyacrylate, fumarate, maleate, itaconate, glycolate, gluconate, malate, mandelate, tiglate, ascorbate, polymethacrylate, a carboxylate of nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylene-diaminetetraacetic acid or of diethylenetriaminepentaacetic acid, a diethylenetriaminepentamethylenephosphonate, an alkylsulfonate or an arylsulfonate; and 
         where the total charge of cations h is equal to the total charge of anions j. 
       
     
     
         13 . A composition according to  claim 12 , wherein component (c) corresponds to a compound of formula (ESS-01) 
       
         
           
           
               
               
           
         
       
     
     
         14 . A composition according to  claim 1 , comprising component (d), which is at least one salicylate selected from salicylic acid, homosalate, 2-ethylhexyl salicylate, benzyl salicylate, ethyl salicylate, methyl salicylate, isoamyl salicylate, acetylsalicylic acid and isobutyl salicylate. 
     
     
         15 . A composition according to  claim 1 , wherein the component (a) corresponds to a compound of formula (MC-03); 
       
         
           
           
               
               
           
         
         component (b) corresponds to a compound of formula (BT-01) 
       
       
         
           
           
               
               
           
         
         and 
         component (c) corresponds to a compound of formula (ESS-01) 
       
       
         
           
           
               
               
           
         
       
     
     
         16 . A composition according to  claim 1 , wherein component (a) corresponds a compound of formula (MC-03); 
       
         
           
           
               
               
           
         
         component (b) corresponds to a compound of formula (BT-01) 
       
       
         
           
           
               
               
           
         
         and 
         component (d) corresponds to a compound of formula 
       
       
         
           
           
               
               
           
         
       
     
     
         17 . A body-care or a household product comprising a stabilizing composition according to  claim 1 , wherein the stabilizing composition is present in the body-care or household product in a concentration of about 5 to about 50000 ppm. 
     
     
         18 . A stabilizing composition according to  claim 1 , wherein the weight ratio of component (a) to component (b) is from 20:1 to 1:20. 
     
     
         19 . A stabilizing composition according to  claim 1 , wherein the weight ratio of component (a) to component (c) is from 1:1 to 1000:1. 
     
     
         20 . A product according to  claim 17 ,
 wherein the body-care product is selected from skin-care products, bath or shower additives, preparations containing fragrances or odoriferous substances, hair-care products, dentifrices, deodorizing or antiperspirant preparations, decorative preparations, light protection formulations and preparations containing active ingredients and   wherein the household product is selected from washing, rinsing or dishwashing agents, shoe polishes, polishing waxes, floor detergents or polishes, all purpose cleaners, bath or toilet cleaners, kitchen cleaners, car shampoos or waxes, neutral, acidic or alkaline cleaners, metal, glass or ceramic cleaners, textile care agents, agents for removing rust, color or stains (stain remover salt), bleaches, furniture or multipurpose polishes, surface protecting formulations, film forming formulations, air care formulations and candles.