USOO8454.940B2 (12) United States Patent (10) Patent No.: US 8.454,940 B2 Wagner et al. (45) Date of Patent: Jun. 4, 2013 (54) MIXTURES COMPRISING (58) Field of Classification Search BENZOTRAZOLES AND MEROCYANNES None See application file for complete search history. (75) Inventors: Barbara Wagner, Lörrach (DE); Oliver Reich, Grenzach-Wyhlen (DE); (56) References Cited Alexander Mantler, U.S. PATENT DOCUMENTS Rheinfelden-Karsau (DE); Michael Schork, Riehen (CH) 2006, O2573.38 A1 11, 2006 Bonda FOREIGN PATENT DOCUMENTS (73) Assignee: BASF SE. Ludwigshafen (DE) EP 1649.902 A 4/2006 GB 2409203 A 6, 2005 (*) Notice: Subject to any disclaimer, the term of this WO OO,25730 A 5, 2000 patent is extended or adjusted under 35 WO 2004/006878 A 1, 2004 WO 2006/032741 A 3, 2006 U.S.C. 154(b) by 219 days. WO 2007/014848 A 2, 2007 WO WO 2007O 14848 A2 * 2/2007 (21) Appl. No.: 12/674,172 OTHER PUBLICATIONS (22) PCT Fled: Aug. 18, 2008 Printout from Scifinder for CAS registry No. 23328-53-2, 2-(2H benzotriazol-2-yl)-6-dodecyl-4-methylphenol. Printed Apr. 18, (86) PCT NO.: PCT/EP2008/060797 2012.* “stabilized body care products, household products, textiles and fab S371 (c)(1), rics' Nov. 5, 2003. (2), (4) Date: Feb. 19, 2010 English Language Abstract of EP 1649.902. (87) PCT Pub. No.: WO2009/027258 * cited by examiner PCT Pub. Date: Mar. 5, 2009 Primary Examiner — Frederick Krass (65) Prior Publication Data Assistant Examiner — Michael P Cohen US 2011 FO2OO540 A1 Aug. 18, 2011 (74) Attorney, Agent, or Firm — Shiela A. Loggins (30) Foreign Application Priority Data (57) ABSTRACT The present invention relates to the use of a stabilizing com Aug. 24, 2007 (EP) ..................................... O7114913 position comprising (a) an effective stabilizing amount of at least one merocyanine (51) Int. C. derivative having an absorption maximum of 350 to 400 A61O 1704 (2006.01) nm, and A6 IK 8/4I (2006.01) (b) at least one UV filter selected from benzotriazole deriva A6 IK S/37 (2006.01) tives; and optionally A 6LX3L/275 (2006.01) (c) at least one excited State quencher, A6 IK 8/3 (2006.01) for the protection of body care and household products (52) U.S. C. against the deleterious effects of light, heat and oxygen. USPC ............ 424/59: 424/70.9; 514/506; 514/579; 252/589 20 Claims, No Drawings US 8,454,940 B2 1. 2 MIXTURES COMPRISING The merocyanine compounds of component (a) preferably BENZOTRAZOLES AND MEROCYANNES correspond to the compounds of formula The present invention relates to the use of merocyanine compounds having an absorption maximum of 350 to 400 nm (1) and 2-hydroxyphenylbenzotriazole UV filters for the protec tion of body care and household products against the delete rious effects of light, heat and oxygen. The present invention also relates to a mixture of at least one merocyanine having an absorption maximum of 350 to 10 400 nm and of at least one 2-hydroxyphenyl benzotriazole UV filter and optionally at least one excited state quencher. Since consumers can choose from a large variety of Home wherein & Personal Care products, producers need to communicate R and R independently of each other are hydrogen; clearly how their brands are unique. Sophisticated products 15 C-C alkyl, C2-C22 alkenyl, C-Calkinyl, containing new fragrances and actives in many colourful C-C2cycloalkyl, Ca-Cacycloalkenyl, C7-Coaralkyl, formulations, displayed in transparent and translucent pack C-Coheteroalkyl, C-C cycloheteroalkyl, aging are very common. Cs-Cheteroaralkyl, C-Caryl, Ca-Cheteroaryl, It is mandatory for commercial Success that the pleasant COR or CONRR, appearance, product efficacy and the fresh Smell of a con R is CN; -COOR: -CONHRs – COR; or -SOR: Sumer product will last during its whole product life cycle —CONRSRs: Co-Caryl or C-Coheteroaryl; even when exposed heavily to UV-light. This exposure can R is CN: -COOR; CONHR; COR: -SOR: result in decomposition processes and strong color fading —CONR,Rs: C-C alkyl: C-Calkenyl: C-C alki destroying the product appearance, active ingredients and nyl: C-Cacycloalkyl, C-Cacycloalkenyl: fragrances. 25 C7-Coaralkyl, C-Coheteroalkyl, Various stabilization techniques of clear packaged prod C-C cycloheteroalkyl, Cs-C heteroaralkyl, Co-Co ucts by absorption of UV light are commonly used and well aryl; or C-C heteroaryl; known. For example broad-band UV light stabilizers of the Rs. R. R., and Rs independently of each other are hydrogen: benzotriazole class enhance products stability and shelf live C-C22alkyl, C2-C22alkenyl: C2-C22 alkinyl: due to their very good UV-A and UV-Babsorption properties. 30 C-C cycloalkyl: C-C cycloalkenyl: C7-Caralkyl: The most effective stabilizers known as of today to prevent C-Coheteroalkyl, C-C cycloheteroalkyl, or delay light induced fading of transparent packaged prod Cs-Cheteroaralkyl; Co-Coaryl; or C-Coheteroaryl; ucts are e.g. benzotriazoles like known under the trade names SiRRR, Si(ORs)(OR)(OR7); SiR (ORs) Ciba TINOGARD HS or Ciba TINOGARD TL. These (OR7); SiRR(OR7); or a radical —XS, proved to be very effective, due to their broadband absorption 35 L. L or L independently of each other are hydrogen, properties and strong extinction in the UV-A range. C-C22alkyl, C2-C22alkenyl, C2-C22alkinyl: WO 2004/006878, WO 2005/058269, WO 2006/016806 C-C cycloalkyl, C-C cycloalkenyl; C7-Caralkyl, A1, WO 2006/009451, WO 2006/125676 A1 and WO 2006/ C-Coheteroalkyl; C-C cycloheteroalkyl, 032741 A1 disclose merocyanine UV-A absorbers and their Cs-Cheteroaralkyl; Co-Co aryl; Ca-Coheteroaryl; CN: use for protecting human and animal hair and skin from UV 40 OH: OR: or COOR: radiation as well as their application in cosmetic and derma Ro is hydrogen; C-C22alkyl, C2-C22alkenyl, C2-C2alkinyl: tological formulations. C-C cycloalkyl: C-C cycloalkenyl: C7-Caralkyl: WO 2007/014848 discloses various merocyanine struc C-Coheteroalkyl; C-C cycloheteroalkyl, tures which have Superior properties in stabilizing cosmetic C-C heteroaralkyl; Co-Co aryl; or C-C heteroaryl; and dermatological formulations and household products. 45 Li and L2, Li and La L2 and L3, Li and R4. L2 and R4, Li and These references also describe that the merocyanine UV R. L2 and R. L. and R. L. and Rs. Rs and R, R and R2, absorbers can be mixed with any other UV filter substance. R, and Rs. Rs and R may be linked together to form 1, 2. It was now Surprisingly found that the combination of 3 or 4 carbocyclic or N, O and/or S-heterocyclic rings, specific merocyanine derivatives which have an absorption which may be further fused with other aromatic rings. Each maximum in the range of 350 to 400 nm with benzotriazole 50 N in a N-heterocyclic ring can be unsubstituted or substi UV-B filters and optionally with at least one excited state tuted by Ro; each alkyl, alkenyl, alkinyl, cycloalkyl or quencher have outstanding stabilizing properties. cycloalkylen group may be unsubstituted or Substituted Therefore, the present invention relates to the use of stabi independently of one another by one or more R, and each lizing composition comprising aryl, heteroaryl, aralkyl, arylen, heteroarylen or aralkylen (a) an effective stabilizing amount of at least one merocyanine 55 may be unsubstituted or Substituted by one or more R. derivative having an absorption maximum of 350 to 400 wherein nm, and Ro represents R. COR, COOR, CONH; CONHR: (b) at least one UV filter selected from benzotriazole deriva or CONRR: tives; and optionally R represents halogen, OH: NH; NHRs, NRSR; (c) at least one excited State quencher; 60 NROR: O—Rs; C CO—Rs. S-Rs; CO-Ro: for the protection of body care and household products oxo; thiono; CN: COOH: CONH; COOR CONHRs: against the deleterious effects of light, heat and oxygen. CONRR: SONH; SONHRs, SONRR: Examples of merocyanine compounds which correspond SORs; SORs, SiRRR, SiORs (OR)(OR7); to component (a) are disclosed in WO 2004/006878, WO SiRs (OR)(OR7); SiRR (OR7), O Si 2005/058269, WO 2006/016806A1, WO 2006/009451, WO 65 RisRF17. O Si OR (OR)(OR7): O—S1— 2006/125676 A1, WO 2006/032741 A1 and WO 2007/ Risk (OR7), O SiRs (OR)(OR7); PO(ORs) O81209. (OR); or a radical XS: US 8,454,940 B2 3 4 R represents halogen, CN, SH, OH, CHO, Rs: ORs, SRs: wherein C(Rs)—CRR: O—CO R. NHR: NRRo: A represents a bond to the linker X: CONH; CONHRs: CONRsR; SONH; SONHRs: s has a value of 4 to 250; SONRsR; SORs: COOH: COOR: OCOOR: thas a value of 5 to 250; NHCORs: NR COR: NHCOOR: NRCOOR: q has a value of 1 to 30: SiRRR.: SiOR(OR)(OR7); SiRs (OR)(OR7); n is 1 or integer, SiRR(OR7); OSiRRR: OSiORs (OR)(OR7); when n=2, R. Rs or R is a bivalent alkyl group; or RandR OSiRR(OR7); OSiRs (OR)(OR7); P(=O) together with the 2 nitrogen atoms linking them form a OROR: P(=O)ROR: P(=O)RoRo; or a radical unsubstituted or alkyl-substituted —XS, or is selected from the group consisting of 10 C-C alkyl, C-Cacycloalkyl, C-Calkenyl: C-C cycloalkenyl: C-C alkylthio; C-C cycloalkylthio; C-Calkenylthio; ( (CH), ) C-C cycloalkenylthio; C-C alkoxy: N N C-C cycloalkoxy; C-Calkenyloxy; O 15 C-C cycloalkenyloxy, which may be unsubstituted or Sci substituted by one or more, identical or different R; R. R. Rs. R. R.17, Rs. Rio and R29 are independently of -ring: each other C-C alkyl: C-C cycloalkyl: C-Calkenyl: C-C cycloalkenyl; Co-Caryl, Ca-Cheteroaryl; V is from 1 to 4, C7-Caralkyl or Cs-Cheteroaralkyl, or w is from 1 to 4; RandR R5 and R.