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. RandR, and/or Rs and Romay when n=3, R. Rs or R is a trivalent alkyl group: be linked together to form unsubstituted or with when n=4. R. Rs or R is a tetravalent alkyl group; and C-C alkyl Substituted pyrrolidin, piperidin, piperazin or RandR in formula (I) are not simultaneously hydrogen. morpholin; 25 Halogen is chloro, bromo, fluoro or iodo, preferably fluoro, more preferably fluoroalkyl (for example trifluorimethyl, C.C. X represents a linker, O-trifluorethyl or perfluorinated alkyl groups like heptafluo S signifies a silane-, oligosiloxane- or polysiloxane-moiety; rpropyl). the term "oligosiloxane' denotes a group of the general for Alkyl, cycloalkyl, alkenyl, alkylidene or cycloalkenyl resi mula Si(Rs).OSi(R), wherein 30 dues can be straight-chain or branched, or also monocyclic or m has a value of 0, 1 or 2, polycyclic. o has a value of 3, 2 or 1; and m+o have a value of 3 or refers Alkyl can be for example methyl, straight-chain to groups of the general formula C-C alkyl or preferably branched C-C alkyl. Alkenyl can be e.g. straight-chain C-Calkenyl or pref 35 erably branched C-Calkenyl. (1a) C-C alkyl is for example methyl, ethyl, n-propyl, isopro pyl. n-butyl, Sec.-butyl, isobutyl, tert-butyl, n-pentyl, 2-pen tyl, 3-penty1, 2,2-dimethylpropyl, n-hexyl, n-octyl, 1.1.3.3- tetramethylbutyl, 2-ethylhexyl, nonyl, decyl. n-octadecyl. 40 eicosyl, cetyl-, myristyl- or dodecyl. (1b) C-C cycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trimethylcyclohexyl, menthyl, O-Si-O-O-Si-O-Si-Rs: thuyl, bornyl, 1-adamantyloder 2-adamanty1. 45 C-Calkenyl or C-C cycloalkenyl refers to unsaturated R16 A R16 hydrocarbon residues containing one or multiple double bonds such vinyl, allyl, 2-propene-2-yl, 2-butene-1-yl, wherein 3-butene-1-yl, 1,3-butadiene-2-yl, 2-cyclobutene-1-yl, A represents a bond to the linker X; and 2-pentene-1-yl, 3-pentene-2-yl, 2-methyl-1-butene-3-yl, 50 2-methyl-3-butene-2-yl, 3-methyl-2-butene-1-yl, 1,4-penta p has a value of 1 to 9; diene-3-yl 2-cyclopentene-1-yl, 2-cyclohexene-1-yl, 3-cy the term “polysiloxane' refers in this context to groups of the clohexene-1-yl, 2.4-cyclohexadiene-1-yl, 1-p-menthene-8- general formula y1. 4(10)-thujen-10-yl, 2-norbornene-1-yl, 2.5- norbornadiene-1-yl, 7,7-dimethyl-2,4-norcaradiene-3-yl or 55 signifies different isomers of hexenyl, octenyl, nonenyl, dece (1c) nyl or dodecenyl. R16 R16 C7-Caralkyl is for example benzyl, 2-benzyl-2-propyl. 13-phenyl-ethyl, 9-fluorenyl, C.C.-dimethylbenzyl, co-phe A-li-oh- O nyl-butyl, ()-phenyl-octyl, co-phenyl-dodecyl oder 3-methyl R17 R17 60 5-(1,1',3',3'-tetramethyl-butyl)-benzyl. (1d) AC7-Caralkyl moiety can be unsubstituted or substituted R16 R16 R16 R15 at the alkyl- as well at the aryl-moiety of the aralkyl-group, "Ris-Si-O-Si-i-O-Si-i-O-Si-Ric: but preferably substituted at the aryl-moiety. (C-C)-alkylidene signifies for example methylene, ethyl R17 R17 A R17 65 1-ene, propyl-2-ene. Co-Caryl is for example phenyl, naphthyl, biphenylyl, 2-fluorenyl, phenanthryl, anthracenyl oder terphenylyl. US 8,454,940 B2 5 6 Ca-Cheteroaryl signifies a unsaturated or aromatic radi More preferably merocyanines of formula cal with 4n+2 conjugated C-electrons. Such as 2-thienyl, 2-fu ryl, 2-pyridyl, 2-thiazolyl, 2-oxazolyl, 2-imidazolyl, isothia Zolyl, triazolyl or any other ring system consisting of (2) thiophene-, furan-, pyridine, thiazol, oxazol, imidazol. 5 isothiazol, triazol, pyridine- and phenyl rings, which are unsubstituted or substituted with 1 to 6 ethyl, methyl, ethylen and/or methylen groups, such as benzotriazolyl. Cs-Cheteroaralkyl signifies for example a C-C alkyl moiety which is Substituted with a C-Csheteroaryl group. 10 Preferably merocyanines of formula (I) are used, wherein R and R independently of each other are hydrogen; or C-C alkyl, or COR are used, wherein R and Rare independently of each other CN; or COORs: R and R2, independently from each other are hydrogen; or or —SORs, or—CONRR 15 C-C alkyl, Rs is hydrogen; C-C alkyl, C-Caryl; or a radical *—X— L2 is hydrogen; S; R is COORs; or - CN: L. L or L independently of each other are hydrogen; or Ra is —CN; and C-C22alkyl, or Li and L2, Li and La L2 and L. may be Rs is C-C alkyl, linked together to form a carbocyclic ring comprising 6 to Re and R, independently from each other are hydrogen; or 10 carbon atoms, which may be further fused with other C-C alkyl. aromatic rings; and which may be further substituted by Furthermore, more preferably merocyanines of formula one or more than one C-C alkyl: X represents a linker, S refers to groups of the general formula 25 (3)
(2a)
30 are used, wherein R-i-o-, -a-. R and R2, independently from each other are hydrogen; or R17 R17 C-C alkyl, R is CN; or -COORs: wherein R is —CN; or —COOR or - SOR: R and R, independently from each other are the radical 35 Rs is C-C alkyl, —OSi(R7)((Rs) (R): R is C-C alkyl, or C-Caryl; R and R, independently of each other are C-C alkyl; Particularly preferred merocyanine compounds as used in A represents a bond to the linker X; and the present invention as component (a) are listed in the Table p has a value of 1 to 9. 1 below: TABLE 1 Examples of preferred Merocyanine compounds MC-01 O O
( ) -ClN 21 N Š
EZ-isomers
(MC-02)
scEZ-isomers US 8,454,940 B2 7 TABLE 1-continued Examples of preferred Merocyanine compounds
MC-03 O O
( ) -ClN 21 nu1 Š
EZ-isomers
(MC-04)
N
NS21N2 ---Š
EZ-isomers
(MC-05)
N |
N 2 Š
(MC-06) Nl-C O S/N-1 r /
CAS-No. 160306-22-9 US 8,454,940 B2 9 10 TABLE 1-continued
Examples of preferred Merocyanine compounds
(MC-07) -S A. V O N O N--> 1. Nales/ R Si r /S O 17
EZ-isomers
(MC-08) 's-'N-1S-1u1a-1\, N O ricl-CC CAS-No. 98835-90-6
(MC-09) -- N PSO2 On EZ-isomers (MC-10) sc EZ-isomers
(MC-11) -- O N-1 N PS21 EZ-isomers US 8,454,940 B2 11 12 TABLE 1-continued Examples of preferred Merocyanine compounds (MC-12) O O O NY O Naan 21 4. /
Examples of benzotriazole UV filters (component (b)) are disclosed in WO00/25730, WO 03070819, EP1342748, WO is (5) 9406404 A1 and EP 796613 A1. HO R Preferably benzotriazole derivatives of formula N 2 \ S. N (4) N HO 2O R R2, 21 2 N\, / x R3-- S. N 2 wherein N N =/ R. R is a random statistical mixture of at least three isomeric 25 branched secondary alkyl groups each having 8 to 30 car bon atoms and having the formula are used, wherein R is C-Coalkyl, C-Csalkoxy; C-Csalkoxycarbonyl: Cs-C,cycloalkyl, C-Caryl; aralkyl; —SOM; or a radi -CH-E: cal of formula 30 El
(4a) E is a straight-chain C-C alkyl; E is a straight-chain C-C salkyl, wherein the total number 35 of carbon atoms in E plus E, is from 7 to 29; and R is C-Csalkyl. Most preferred is the benzotriazole derivative 2-(2H-ben Zotriazol-2-yl)-6-dodecycl-4-methylphenol which corre R is hydrogen; C-Csalkyl, C-Csalkoxy; halogen, prefer 40 sponds to the formula ably Cl; or hydroxy: Ra and Rs are each independently of the other hydrogen; or C-Csalkyl; (BT-01) m is 1 or 2; HO C12H25. N n is 0 or 1; 45 e M if m=1, N R is hydrogen; unsubstituted or phenyl-substituted N / C-C2alkyl, or Co-Coaryl; N R2 is the direct bond; or -(CH2) ; and CH3 p is 1 to 3. 50 More preferably the benzotrizoles as used in the present Particularly preferred benzotriazole compounds (compo invention correspond to the formula nent (b)) are listed in Table 2 below: TABLE 2
Examples of preferred benzotriazole compounds
BT-01 HO N 2- \ N / CC N N
CAS-No.: 125304-04-3
US 8,454,940 B2 15 16 The stabilized composition of the present invention may and additionally comprise an Excited State Quencher (ESQTM) (c) hindered hydroxylamine salt compounds of formula (=component (c)). It interacts with high-energy states of mol ecules, e.g. caused by UV-radiation or visible light, and sig nificantly reduces the probability of degradation reactions 5 (6c) and Scavengers radical intermediates. This mechanism works complimentarily to that of UV light stabilizers. Examples of excited state quenchers selected from the group of hindered amine stabilizers are disclosed in the patent applications WO 01/07550, WO 2005/042828 A2 and U.S. 10 Pat. No. 6,254,724. Particularly preferred hindered amine stabilizers are (c) hindered nitroxyl compounds of formula wherein 15 G and G are independently alkyl of 1 to 4 carbon atoms or (6a) G1 G2 are together pentamethylene, Z and Z are each methyl, or Z and Z together form a Z linking moiety which may additionally be substituted by an Oo-N 2O ester, ether, hydroxy, oxy, OXO, cyanohydrin, amide, amino, Z2, carboxy or urethane group, X is an inorganic or organic anion, Such as phosphate, phos G1 G2 phonate, carbonate, bicarbonate, nitrate, chloride, bro mide, bisulfate, sulfite, bisulfate, sulfate, borate, formate, (c) hindered hydroxylamine compounds of formula 25 acetate, benzoate, citrate, oxalate, tartrate, acrylate, poly acrylate, fumarate, maleate, itaconate, glycolate, glucon ate, malate, mandelate, tiglate, ascorbate, polymethacry (6b) late, a carboxylate of nitrilotriacetic acid, G1 G2 hydroxyethylethylenediaminetriacetic acid, ethylene-di y-Z, 30 aminetetraacetic acid or of diethylenetriaminepentaacetic acid, a diethylenetriaminepentamethylenephosphonate, an HO-N alkylsulfonate or an arylsulfonate, and where the total charge of cations his equal to the total charge G1X-7, G2 of anions j. Examples of particularly preferred excited state stabilizers are listed in Table 3 below: TABLE 3
Preferred excited statestabilizers
ESS-O1 OH
ESS-O2
ESS-O3 US 8,454,940 B2 17 18 TABLE 3-continued
Preferred excited statestabilizers ESS-O4 X) ESS-OS ulO city-lO skO O
ESS-06
Octocrylene CAS 61.97-30-4
ESS-O7
CAS 5232-99-5
ESS-O8 -Oct-O C Hallbrite TQ CAS 127474-91-3
ESS-09 Polycrylene CAS 866102-82-1
ESS-10 O O HO-N o-1-cis--o
CAS #30538-92-2 US 8,454,940 B2 19 20 Combinations of excited state stabilizers like the com ture which are for example described in US 2004/047818, US pound (ESS-01) with UV absorbers like other Tinogard UV 2006/257338, US 2006/228311, US 2004/062726 and US light stabilizers show a synergistic stabilizing effect. 2004/057916. This “boosting effect allows for high demanding shelflife The stabilizing composition comprising (a) an effective stabilizing amount of at least one merocyanine enhancements as well as cost effective ingredient protection. derivative having an absorption maximum of 350 to 400 In the literature also excited state quenchers based on the nm, naphthalene structure are known. (b) at least one UV filter selected from benzotriazole deriva Particularly preferred are dialkyl naphthalates structures tives; and optionally such as disclosed US 2002/197285, US 2006/228311 and (c) at least one excited State quencher, WO 2002/087528. 10 is novel and represents a further subject matter of the present Another group of particularly preferred excited State invention. quenchers are those based on the B.f3-diphenylacrylate struc- Particularly preferred mixtures are listed in Table 4 below: TABLE 4
Preferred Combinations
Component (a) Component (b)
M1 HO C12H25 H N
N 2 Šs
CAS-No.: 125304-04-3 EZ-isomers BT-01 MC-01
M1A O O HO C12H25 H N
N 2 Šs N / CC N
CAS-No.: 125304-04-3 EZ-isomers BT-01 MC-01
M2 O O N HO C12H25 N e N N 2 N Šs N / CC N
CAS-No.: 125304-04-3 EZ-isomers BT-01 MC-09
M2A O O HO C12H25 N 2 \, N CCN
CAS-No.: 125304-04-3 EZ-isomers BT-01 MC-09
US 8,454,940 B2 31 32 TABLE 4-continued O O HO (M23) H N
N 2 2NN Š S/
CAS-No.: 125304-04-3 BT-01 EZ-isomers MC-01
and
O O H N-1
N 2 Š
EZ-isomers MC-03 Component (c)
M1
M1A OH
ck/ V citrate HO H
M2
M2A
o O-N OH
M3 M3A soOH OH
M4 OH
skM V Cl trate HO H
US 8,454,940 B2 35 36 TABLE 4-continued M11
() Octorylene CAS 6297-30-4 ESS-O2 M12 M13 (M14) (M15) (M16) (M17) (M18) (M19) (M20) (M21) (M22) (M23)
The stabilizing composition of the present invention is They preferably contain the stabilizing mixture according particularly Suitable for protecting body-care and household to the present invention and, optionally, further UV absorbers, products against photolytic degradation. sterically hindered amines, complexing agents and phenolic Personal Care Uses 30 or non-phenolic antioxidants. The stabilizing composition of the present invention may The present invention therefore also relates to a body-care be used as single component or in mixture with other stabi product comprising a stabilizing mixture according to the lizers in particular for skin-care products, bath and shower present invention. additives, preparations containing fragrances and odoriferous In the stabilizing composition the weight ratio of compo Substances, hair-care products, dentifrices, deodorizing and 35 nent (a) to component (b) is from 20:1 to 1:20 and the weight antiperspirant preparations, decorative preparations, light ratio of component (a) to component (c) is from 1:1 to 1000:1, protection formulations and preparations containing active more preferably from 10:1 to 100:1. ingredients. The stabilizing mixture according to the present invention Skin-care products are, in particular, body oils, body is present in the body care and household products in a con lotions, body gels, treatment creams, skin protection oint 40 centration of about 5 to about 50000 ppm, based on the total ments, shaving preparations, such as shaving foams or gels, formulation, preferably from about 10 to about 10000 ppm, skin powders, such as baby powder, moisturizing gels, mois and most preferably from about 100 to about 1000 ppm. turizing sprays, revitalizing body sprays, cellulite gels and The body-care products according to the present invention peeling preparations. may also contain one or one more additional compounds as Suitable bath and shower additives are shower gels, bath 45 described below. salts, bubble baths and soaps. Fatty Alcohols Preparations containing fragrances and odoriferous Sub Guerbet alcohols based on fatty alcohols having from 6 to stances are in particular scents, perfumes, toilet waters and 18, preferably from 8 to 10 carbon atoms including cetyl shaving lotions (aftershave preparations). alcohol, Stearyl alcohol, cetearylalcohol, oleyl alcohol, octyl Suitable hair-care products are, for example, shampoos for 50 dodecanol, benzoate of C-C alcohols, acetylated lanolin humans and animals, in particular dogs, hair conditioners, alcohol, etc. products for styling and treating hair, perming agents, hair Esters of Fatty Acids sprays and lacquers, hair gels, hair fixatives and hair dyeing or Esters of linear C-C fatty acids with linear C-C alco bleaching agents. hols, esters of branched C-C-carboxylic acids with linear Suitable dentifrices are in particular tooth creams, tooth 55 C-Cyfatty alcohols, esters of linear C-C fatty acids with pastes, mouth-washes, mouth rinses, anti-plaque prepara branched alcohols, especially 2-ethylhexanol, esters of tions and cleaning agents for dentures. hydroxycarboxylic acids with linear or branched C-C fatty Suitable decorative preparations are in particular lipsticks, alcohols, especially dioctyl malates, esters of linear and/or nail varnishes, eye shadows, mascaras, dry and moist make branched fatty acids with polyhydric alcohols (for example up, rouge, powders, depilatory agents and Suntan lotions. 60 propylene glycol, dimer diol or trimer triol) and/or Guerbet Suitable cosmetic formulations containing active ingredi alcohols, for example caproic acid, caprylic acid, 2-ethylhex ents are in particular hormone preparations, vitamin prepara anoic acid, capric acid, lauric acid, isotridecanoic acid, myris tions, vegetable extract preparations and antibacterial prepa tic acid, palmitic acid, palmitoleic acid, Stearic acid, isos rations. tearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic The mentioned body-care products may be in the form of 65 acid, linolenic acid, elaeoStearic acid, arachidic acid, gadoleic creams, ointments, pastes, foams, gels, lotions, powders, acid, behenic acid and erucic acid and technical-grade mix make-ups, sprays, Sticks or aerosols. tures thereof (obtained, for example, in the pressure removal US 8,454,940 B2 37 38 of natural fats and oils, in the reduction of aldehydes from decenes and polybutene, hydrogenated polyisobutene, Roelen's oxosynthesis or in the dimerisation of unsaturated squalane, isohexadecane, isododecane and others from plant fatty acids) with alcohols, for example, isopropyl alcohol, and animal kingdom. caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric Silicones or Siloxanes (Organosubstituted Polysiloxanes) alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, Dimethylpolysiloxanes, methylphenylpolysiloxanes, cetyl alcohol, palmoleyl alcohol, Stearyl alcohol, isostearyl cyclic silicones, and also amino-, fatty acid-, alcohol-, poly alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, ether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified linoyl alcohol, linolenyl alcohol, elaeoStearyl alcohol, silicone compounds, which at room temperature may be in arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl either liquid or resinous form, linear polysiloxanes, dimethi 10 cone (Dow Corning 200 fluid, Rhodia Mirasil DM), dimethi alcohol and brassidyl alcohol and technical-grade mixtures conol, cyclic silicone fluids, cyclopentasiloxanes Volatiles thereof (obtained, for example, in the high-pressure hydroge (Dow Corning 345 fluid), phenyltrimethicone (Dow Corning nation of technical-grade methyl esters based on fats and oils 556 fluid). Also suitable are simethicones, which are mixtures or aldehydes from Roelen's oxosynthesis and as monomer of dimethicones having an average chain length of from 200 fractions in the dimerisation of unsaturated fatty alcohols). 15 to 300 dimethylsiloxane units with hydrogenated silicates. Examples of Suchester oils are isopropylmyristate, isopro A detailed survey by Todd et al. of suitable volatile sili pylpalmitate, isopropylstearate, isopropyl isostearate, isopro cones may in addition be found in Cosm. Toil. 91, 27 (1976). pyloleate, n-butylstearate, n-hexyllaurate, n-decyloleate, iso Fluorinated or Perfluorinated Oils octylstearate, iso-nonylstearate, isononyl isononanoate, Perfluorhexane, dimethylcyclohexane, ethylcyclopentane, 2-ethylhexylpalmitate, 2-hexyllaurate, 2-hexyldecylstearate, polyperfluoromethylisopropyl ether. 2-octyldodecylpalmitate, oleyloleate, oleylerucate, erucy Emulsifiers loleate, erucylerucate, cetearyl octanoate, cetyl palmitate, Any conventionally usable emulsifier can be used for the cetyl Stearate, cetyl oleate, cetyl behenate, cetylacetate, myri compositions. Emulsifier systems may comprise for styl myristate, myristyl behenate, myristyl oleate, myristyl example: carbocyclic acids and their salts: alkaline Soap of Stearate, myristyl palmitate, myristyl lactate, propylene gly 25 Sodium, potassium and ammonium, metallic Soap of calcium col dicaprylate/caprate, Stearyl heptanoate, diisoStearyl or magnesium, organic basis soap Such as Lauric, palmitic, malate, octyl hydroxyStearate, etc. Stearic and oleic acid etc., alkyl phosphates or phosphoric Natural or Synthetic Triglycerides Including Glyceryl Esters acid esters, acid phosphate, diethanolamine phosphate, potas and Derivatives sium cetyl phosphate, ethoxylated carboxylic acids or poly Di- or tri-glycerides, based on C-Cs fatty acids, modified 30 ethyleneglycol esters, PEG-n acrylates, linear fatty alcohols by reaction with other alcohols (caprylic/capric triglyceride, having from 8 to 22 carbonatoms, branched from 2 to 30 mol wheat germ glycerides, etc.). Fatty acid esters of polyglycerin of ethylene oxide and/or from 0 to 5 mol propylene oxide with (polyglyceryl-n Such as polyglyceryl-4 caprate, polyglyc fatty acids having from 12 to 22 carbon atoms and with eryl-2 isostearate, etc. or castor oil, hydrogenated vegetable alkyl-phenols having from 8 to 15 carbon atoms in the alkyl oil, Sweet almond oil, wheat germ oil, sesame oil, hydroge 35 group, fatty alcohol polyglycolether Such as laureth-n, cet nated cottonseed oil, coconut oil, avocado oil, corn oil, hydro eareth-n, Steareth-n, oleth-n, fatty acid polyglycolether Such genated castor oil, sheabutter, cocoa butter, soybean oil, mink as PEG-n stearate, PEG-noleate, PEG-in cocoate. Monoglyc oil, Sunflower oil, safflower oil, macadamia nut oil, olive oil, erides and polyol esters. C-C fatty acid mono- and di hydrogenated tallow, apricot kernel oil, hazelnut oil, borago esters of addition products of from 1 to 30 mol of ethylene oil, etc. 40 oxide with polyols. Waxes Fatty acid and polyglycerol ester Such as monostearate Including esters of long-chain acids and alcohols as well as glycerol, diisostearoyl polyglyceryl-3-diisoStearates, polyg compounds having wax-like properties, e.g., carnauba wax, lyceryl-3-diisoStearates, triglyceryl disostearates, polyglyc beeswax (white or yellow), lanolin wax, candellila wax, oZo eryl-2-sesqui-isostearates or polyglyceryl dimerates (mix kerite, japan wax, paraffin wax, microcrystalline wax, cer 45 tures of compounds from a plurality of those Substance esin, cetearyl esters wax, synthetic beeswax, etc. Also, hydro classes are also suitable); fatty acid polyglycolesters such as philic waxes as Cetearyl Alcohol or partial glycerides. monostearate diethylene glycol, fatty acid and polyethylene Pearlescent Waxes glycol esters, fatty acid and Saccharose esters such as Sucro Alkylene glycol esters, especially ethylene glycol distear esters, glycerol and saccharose esters such as Sucroglycer ate; fatty acid alkanolamides, especially coco fatty acid 50 ides, Sorbitol and Sorbitan, Sorbitan mono- and di-esters of diethanolamide; partial glycerides, especially Stearic acid saturated and unsaturated fatty acids having from 6 to 22 monoglyceride; esters of polyvalent, unsubstituted or carbon atoms and ethylene oxide addition products, polysor hydroxy-substituted carboxylic acids with fatty alcohols hav bate-n series, Sorbitan esters such as sesquiisoStearate, Sorbi ing from 6 to 22 carbonatoms, especially long-chained esters tan, PEG-(6)-isostearate sorbitan, PEG-(10)-sorbitan laurate, of tartaric acid; fatty Substances, for example fatty alcohols, 55 PEG-17-dioleate sorbitan, glucose derivatives, C-C alkyl fatty ketones, fatty aldehydes, fatty ethers and fatty carbon mono and oligo-glycosides and ethoxylated analogues with ates, which in total have at least 24 carbon atoms, especially glucose being preferred as the Sugar component, O/W emul laurone and distearyl ether, fatty acids, such as Stearic acid, sifiers such as methyl gluceth-20 sesquistearate, Sorbitan hydroxy Stearic acid or behenic acid, ring-opening products of Stearate/Sucrose cocoate, methylglucose sesquistearate, cet olefin epoxides having from 12 to 22 carbon atoms with fatty 60 earyl alcohol/cetearyl glucoside, W/O emulsifiers such as alcohols having from 12 to 22 carbon atoms and/or polyols methyl glucose dioleate/methyl glucose isostearate, Sulfates having from 2 to 15 carbon atoms and from 2 to 10 hydroxy and Sulfonated derivatives, dialkylsulfoSuccinates, dioctyl groups, and mixtures thereof. Succinate, alkyl lauryl Sulfonate, linear Sulfonated parafins, Hydrocarbon Oils Sulfonated tetraproplyne Sulfonate, sodium lauryl Sulfates, Mineral oil (light or heavy), petrolatum (yellow or white), 65 amonium and ethanolamine lauryl Sulfates, lauyl ether Sul microcrystalline wax, paraffinic and isoparaffinic com fates, Sodium laureth Sulfates, Sulfo Succinates, aceyl pounds, hydrogenated isoparaffinic molecules as poly isothionates, alkanolamide Sulfates, taurines, methyl tau US 8,454,940 B2 39 40 rines, imidazole Sulfates, amine derivatives, amine salts, Super-Fatting Agents ethoxylated amines, oxide amine with chains containing an Substances suitable for use as Super-fatting agents are, for heterocycle Such as alkyl imidazolines, pyridine derivatives, example, lanolin and lecithin and also polyethoxylated or isoquinoteines, cetyl pyridinium chlorure, cetyl pyridinium acrylated lanolin and lecithin derivatives, polyol fatty acid bromide, quaternary ammonium Such ascetyltrimethylbroide esters, monoglycerides and fatty acid alkanolamides, the lat amonium broide (CTBA), stearylalkonium, amide deriva ter simultaneously acting as foam stabilisers. tives, alkanolamides Such as acylamide DEA, ethoxylated Surfactants amides Such as PEG-nacylamide, Oxydeamide, polysiloxane/ Examples of suitable mild Surfactants, that is to say Surfac polyalkyl/polyether copolymers and derivatives, dimethi tants especially well tolerated by the skin, include fatty alco cone, copolyols, silicone polyethylene oxide copolymer, sili 10 hol polyglycol ether sulfates, monoglyceride Sulfates, mono cone glycol copolymer, propoxylated or POE-n ethers and/or di-alkyl Sulfo Succinates, fatty acid isethionates, fatty (Meroxapols), polaxamers or poly(oxyethylene)m-block acid sarcosinates, fatty acid taurides, fatty acid glutamates, poly(oxypropylene)n-block(Oxyethylene), Zwitterionic Sur C-olefin Sulfonates, ethercarboxylic acids, alkyl oligogluco factants that carry at least one quaternary ammonium group sides, fatty acid glucamides, alkylamidobetaines and/or pro and at least one carboxylate and/or Sulfonate group in the 15 tein fatty acid condensation products, the latter preferably molecule, Zwitterionic Surfactants that are especially suitable being based on wheat proteins. are betaines, such as N-alkyl-N,N dimethylammonium gly Consistency Regulators/Thickeners and Rheology Modifiers cinates, cocoalkyldimethylammonium glycinate, N-acylami Silicon dioxide, magnesium silicates, aluminium silicates, nopropyl-N,N-dimethylammonium glycinates, cocoacy polysaccharides or derivatives thereof for example hyalu laminopropyldimethylammonium glycinate and 2-alkyl-3- ronic acid, Xanthan gum, guar-guar, agar-agar, alginates, car carboxymethyl-3-hydroxyethylimidazolines each having raghenan, gellan, pectines, or modified cellulose such as from 8 to 18 carbon atoms in the alkyl or acyl group and also hydroxycellulose, hydroxypropylmethylcellulose. In addi cocoacylaminoethylhydroxyethylcarboxymethylglycinate, tion polyacrylates or homopolymer of reticulated acrylic N-alkylbetaine, N-alkylaminobetaines, alkylimidazolines, acids and polyacrylamides, carbomer (carbopol types 980, alkylopeptides, lipoaminoacides, self emulsifying bases and 25 981, 1382, ETD2001, ETD2020, Ultrez. 10) or Salcare range the compounds as described in K. F. DePolo. A short textbook such as Salcare SC80(steareth-10 alkyl ether/acrylates of cosmetology, Chapter 8, Table 8-7, p 250-251. copolymer), Salcare SC81 (acrylates copolymer), Salcare Nonionic emulsifiers such as PEG-6 beeswax (and)PEG-6 SC91 and Salcare AST (sodium acrylates copolymer/PPG-1 Stearate (and) polyglyceryl-2-isostearate Apifac, glyceryl trideceth-6), sepigel 305(polyacrylamide/laureth-7), Simul stearate (and) PEG-100 stearate. Arlacel 165, PEG-5 glyc 30 gel NS and Simulgel EG (hydroxyethyl acrylate/sodium eryl Stearate Iarlatone983 S, sorbitan oleate (and) polyglyc acryloyldimethyl taurate copolymer), Stabilen 30 (acrylates/ eryl-3 ricinoleate. Arlacel 1689), sorbitan stearate and vinyl isodecanoate crosspolymer), Pemulen TR-1 (acrylates/ Sucrose cocoate arlatone 2121, glyceryl Stearate and lau C10-30 alkyl acrylate crosspolymer), Luvigel EM (sodium reth-23 Cerasynth945, cetearyl alcohol and ceteth-20 Ce acrylates copolymer), Aculyn 28 (acrylates/beheneth-25 tomacrogol Wax, cetearyl alcohol and colysorbate 60 and 35 methacrylate copolymer), etc. PEG-150 and stearate-20 Polawax GP 200, Polawax NF, Polymers cetearyl alcohol and cetearyl polyglucoside Emulgade PL Suitable cationic polymers are, for example, cationic cel 1618), cetearyl alcohol and ceteareth-20 Emulgade 1000NI, lulose derivatives, for example a quaternised hydroxymethyl Cosmowax, cetearyl alcohol and PEG-40 castor oil Emul cellulose obtainable under the name Polymer JR 400 from gade F Special, cetearyl alcohol and PEG-40 castor oil and 40 Amerchol, cationic starches, copolymers of diallylammo Sodium cetearyl Sulfate Emulgade F. Stearyl alcohol and nium salts and acrylamides, quaternised vinylpyrrolidone? steareth-7 and steareth-10Emulgator E2155, cetearyl alco vinyl imidazole polymers, for example Luviduata (BASF), hol and Szeareth-7 and steareth-10 Emulsifying wax condensation products of polyglycols and amines, quater U.S.N.F. glyceryl Stearate and PEG-75 stearate Gelot 64. nised collagen polypeptides, for example lauryldimonium propylene glycol ceteth-3 acetate. Hetester PCS, propylene 45 hydroxypropyl hydrolyzed collagen (LamequataL/Grünau). glycol isoceth-3 acetate Hetester PHA), cetearyl alcohol and quaternised wheat polypeptides, polyethyleneimine, cationic ceteth-12 and oleth-12 Lanbritol Wax N21, PEG-6 stearate silicone polymers, for example amidomethicones, copoly and PEG-32 stearate Tefose 1500, PEG-6 stearate and cet mers of adipic acid and dimethylaminohydroxypropyldi eth-20 and steareth-20 Tefose 2000, PEG-6 stearate and ethylenetriamine (Cartaretin/SandoZ), copolymers of acrylic ceteth-20 and glyceryl Stearate and steareth-20 Tefose 2561. 50 acid with dimethyldiallylammonium chloride (Merquat 550/ glyceryl Stearate and ceteareth-20 Teginacid H, C, X. Chemviron), polyaminopolyamides, as described, for Anionic emulsifiers such as PEG-2 stearate SE, glyceryl example, in FR-A-2 252 840, and the crosslinked water stearate SE Monelgine, Cutina KD), propylene glycol stear soluble polymers thereof, cationic chitin derivatives, for ate Tegin P. cetearyl Alcohol and Sodium cetearyl sulfate example of quaternised chitosan, optionally distributed as Lanette N. Cutina LE, Crodacol GP, cetearyl alcohol and 55 microcrystals; condensation products of dihaloalkyls, for sodium lauryl sulfate Lanette W. trilaneth-4 phopshate and example dibromobutane, with bisdialkylamines, for example glycol stearate and PEG-2 stearate Sedefos 75, glyceryl bisdimethylamino-1,3-propane, cationic guar gum, for stearate and sodium lauryl Sulfate Teginacid Special. Cat example Jaguar C-17, Jaguar C-16 from Celanese, quater ionic acid bases such as cetearyl alcohol and cetrimonium nised ammonium salt polymers, for example Mirapol A-15, bromide. 60 Mirapol AD-1, MirapolAZ-1 from Miranol. As anionic, Zwit The emulsifiers may be used in an amount of for example, terionic, amphoteric and non-ionic polymers there come into from 1 to 30% by weight, especially from 4 to 20% by weight consideration, for example, vinyl acetate/crotonic acid and preferably from 5 to 10% by weight, based on the total copolymers, vinylpyrrolidone/vinyl acrylate copolymers, weight of the composition. vinyl acetate/butyl maleate/isobornyl acrylate copolymers, When formulated in O/W emulsions, the preferably 65 methyl vinyl ether/maleic anhydride copolymers and esters amount of such emulsifier system could represent 5% to 20% thereof, uncrosslinked polyacrylic acids and polyacrylic of the oil phase. acids crosslinked with polyols, acrylamidopropyl-trimethy US 8,454,940 B2 41 42 lammonium chloride? acrylate copolymers, octyl acrylamide/ rolidone/vinyl acetate copolymers, polymers of quaternary methyl methacrylatetert. butylaminoethyl methacrylate/2- cellulose derivatives containing a high proportion of acrylic hydroxypropyl methacrylate copolymers, acid, collagen, hyaluronic acid and salts thereof and similar polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate compounds. copolymers, vinylpyrrolidone/dimethylaminoethyl meth Hydrotropic Agents acrylate/vinyl caprolactam terpolymers and also optionally For improvement of the flow behaviour it is also possible to derivatised cellulose ethers and silicones. Furthermore the employ hydrotropic agents, for example ethoxylated or non polymers as described in EP 1093.796 (pages 3-8, paragraphs ethoxylated mono-alcohols, diols or polyols with a low num 17-68) may be used. ber of carbonatoms or their ethers (e.g. ethanol, isopropanol, Cationic Surfactants 10 1.2-dipropanediol, propyleneglycol, glyerin, ethylene glycol, cetyl trimethyl ammonium bromide (CTAB), dimethicone ethylene glycol monoethylether, ethylene glycol monobu copolyols, amidomethicones, acrylamidopropyltrimonium tylether, propylene glycol monomethylether, propylene gly chloride/Acrylamide copolymer, guar hydroxypropyl trimo col monoethylether, propylene glycol monobutylether, dieth nium chloride, hydroxycetyl hydroxyethyl dimonium chlo ylene glycol monomethylether, diethylene glycol ride quaternium compounds as listed in International Cos 15 monoethylether, diethylene glycol monobutylether and simi metic Ingredient Dictionary and Handbook, 7" Edition 1997, lar products). The polyols for that purpose comprise prefer for example Quaternium-80, polyduaternium compounds, as ably 2 to 15 carbon atoms and at least two hydroxy groups. listed in International Cosmetic Ingredient Dictionary and The polyols may also contain further functional groups, espe Handbook, 7" Edition 1997, for example polyguaternium-5, cially amino groups, and/or may be modified with nitrogen. polyduaternium-6, polyduaternium-7. polyduaternium-10, Typical examples are as follows: glycerol, alkylene glycols, polyduaternium-11, polyduaternium-17, polyduaternium for example ethylene glycol, diethylene glycol, propylene 18, polyduaternium-24 or polyduaternium-27, polyduater glycol, butylene glycol, hexylene glycol and also polyethyl nium-28, polyduaternium-32, polycuaternium-37. ene glycols having an average molecular weight of from 100 Biogenic Active Ingredients to 1000 Dalton; technical oligo-glycerol mixtures having an Biogenic active ingredients are to be understood as mean 25 intrinsic degree of condensation of from 1.5 to 10, for ing, for example, tocopherol, tocopherol acetate, tocopherol example technical diglycerol mixtures having a diglycerol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bis content of from 40 to 50% by weight; methylol compounds, abolol, allantoin, phytantriol, panthenol. AHA acids, amino Such as, especially, trimethylolethane, trimethylolpropane, acids, ceramides, pseudoceramides, essential oils, plant trimethyl-olbutane, pentaerythritol and dipentaerythritol; extracts and vitamin complexes. 30 lower alkyl-glucosides, especially those having from 1 to 8 Deodorising Active Ingredients carbon atoms in the alkyl radical, for example methyl and As deodorising active ingredients are for example, antiper butyl glucoside: Sugar alcohols having from 5 to 12 carbon spirants, for example aluminium chlorohydrates (see J. Soc. atoms, for example Sorbitol or mannitol; Sugars having from Cosm. Chem. 24, 281 (1973)). Under the trade mark Locrona 5 to 12 carbon atoms, for example glucose or saccharose; of Hoechst AG, Frankfurt (FRG), there is available commer 35 amino Sugars, for example glucamine; dialcohol amines, such cially, for example, an aluminium chlorohydrate correspond as diethanolamine or 2-amino-1,3-propanediol. ing to formula Al2(OH)5C1x2.5H2O, the use of which is Preservatives especially preferred (see J. Pharm. Pharmacol. 26, 531 Suitable preservatives include, for example methyl-, (1975)). Besides the chlorohydrates, it is also possible to use ethyl-, propyl-, butyl-parabens, benzalkonium chloride, aluminium hydroxyacetates and acidic aluminium/zirconium 40 2-bromo-2-nitro-propane-1,3-diol, dehydroacetic acid, dia salts. Esterase inhibitors may be added as further deodorising Zolidinyl urea, 2-dichloro-benzyl alcohol, dimdim hydantoin, active ingredients. Such inhibitors are preferably trialkyl cit formaldehyde solution, methyldibromoglutanitrile, phe rates, such as trimethyl citrate, tripropyl citrate, triisopropyl noxyethanol, Sodium hydroxymethylglycinate, imidazolidi citrate, tributyl citrate and especially triethylcitrate (Hydagen nyl urea, triclosan and further substance classes listed in the CAT, Henkel), which inhibit enzyme activity and hence 45 following reference: K. F. Depolo—A Short Textbook Of reduce odour formation. Further substances that come into Cosmetology, Chapter 7, Table 7-2, 7-3, 7-4 And 7-5, P210 consideration as esterase inhibitors are sterol Sulfates orphos 219. phates, for example lanosterol, cholesterol, campesterol, Stig Bacteria-Inhibiting Agents masterol and sitosterol Sulfate or phosphate, dicarboxylic Typical examples of bacteria-inhibiting agents are preser acids and esters thereof, for example glutaric acid, glutaric 50 Vatives that have a specific action against gram-positive bac acid monoethyl ester, glutaric acid diethyl ester, adipic acid, teria, such as 2,4,4-trichloro-2'-hydroxydiphenyl ether, chlo adipic acid monoethyl ester, adipic acid diethyl ester, malonic rhexidine (1,6-di(4-chlorophenyl-biguanido)hexane) or TCC acid and malonic acid diethyl ester and hydroxycarboxylic (3,4,4-trichlorocarbanilide). A large number of aromatic sub acids and esters thereof, for example citric acid, malic acid, stances and ethereal oils also have antimicrobial properties. tartaric acid or tartaric acid diethyl ester. Antibacterial active 55 Typical examples are the active ingredients eugenol, menthol ingredients that influence the germ flora and kill or inhibit the and thymol in clove oil, mint oil and thyme oil. A natural growth of Sweat-decomposing bacteria can likewise be deodorising agent of interest is the terpene alcohol farnesol present in the preparations (especially in Stick preparations). (3.7, 11-trimethyl-2,6,10-dodecatrien-1-ol), which is present Examples include chitosan, phenoxyethanol and chlorhexi in lime blossom oil. Glycerol monolaurate has also proved to dine gluconate. 5-chloro-2-(2,4-dichlorophenoxy)phenol 60 be a bacteriostatic agent. The amount of the additional bac (Triclosan, Irgasan, Ciba Specialty Chemicals Inc.) has also teria-inhibiting agents present is usually from 0.1 to 2% by proved especially effective. weight, based on the Solids content of the preparations. Anti-Dandruff Agents Perfume Oils As anti-dandruff agents there may be used, for example, Mixtures of natural and/or synthetic aromatic Substances. climbazole, octopiroX and Zinc pyrithione. Customary film 65 Natural aromatic Substances are, for example, extracts from formers include, for example, chitosan, microcrystalline chi blossom (lilies, lavender, roses, jasmine, neroli, ylang-ylang), tosan, quaternised chitosan, polyvinylpyrrolidone, vinylpyr from stems and leaves (geranium, patchouli, petitgrain), from US 8,454,940 B2 43 44 fruit (aniseed, coriander, carraway, juniper), from fruit peel skin-care preparations, e.g. skin-washing and cleansing (bergamot, lemons, oranges), from roots (mace, angelica, preparations in the form of tablet-form or liquid Soaps, celery, cardamom, costus, iris, calmus), from wood (pin Soapless detergents or washing pastes, ewood, sandalwood, guaiacum wood, cedarwood, rose bath preparations, e.g. liquid (foam baths, milks, shower wood), from herbs and grasses (tarragon, lemon grass, sage, preparations) or Solid bath preparations, e.g. bath cubes thyme), from needles and twigs (spruce, pine, Scots pine, and bath salts; mountain pine), from resins and balsams (galbanum, elemi, skin-care preparations, e.g. skin emulsions, multi-emul benzoin, myrrh, olibanum, opoponax). Animal raw materials sions or skin oils; body oils, body lotions, body gels; skin also come into consideration, for example civet and cas protection ointments; toreum. Typical synthetic aromatic Substances are, for 10 cosmetic personal care preparations, e.g. facial make-up in example, products of the ester, ether, aldehyde, ketone, alco the form of day creams or powder creams, face powder hol or hydrocarbon type. Aromatic Substance compounds of (loose or pressed), rouge or cream make-up, eye-care the ester type are, for example, benzyl acetate, phenoxyethyl preparations, e.g. eyeshadow preparations, mascara, isobutyrate, p-tert-butylcyclohexyl acetate, linallyl acetate, eyeliner, eye creams or eye-fix creams; lip-care prepa dimethylbenzylcarbinyl acetate, phenylethyl acetate, linallyl 15 rations, e.g. lipsticks, lip gloss, lip contour pencils, nail benzoate, benzyl formate, ethylmethylphenyl glycinate, care preparations, such as nail varnish, nail varnish allylcyclohexyl propionate, Styrallyl propionate and benzyl removers, nail hardeners or cuticle removers; salicylate. The ethers include, for example, benzyl ethyl foot-care preparations, e.g. foot baths, foot powders, foot ether; the aldehydes include, for example, the linear alkanals creams or footbalsams, special deodorants and antiper having from 8 to 18 hydrocarbon atoms, citral, citronellal, spirants or callus-removing preparations; citronellyl oxyacetaldehyde, cyclamen aldehyde, hydroxy light-protective preparations, such as Sun milks, lotions, citronellal, lilial and bourgeonal; the ketones include, for creams or oils, Sunblocks or tropicals, pre-tanning example, the ionones, isomethylionone and methyl cedryl preparations or after-Sun preparations; ketone; the alcohols include, for example, anethol, cit 25 skin-tanning preparations, e.g. Self-tanning creams: ronellol, eugenol, isoeugenol, geraniol, linalool, phenyl ethyl depigmenting preparations, e.g. preparations for bleaching alcohol and terpinol; and the hydrocarbons include mainly the skin or skin-lightening preparations; the terpenes and balsams. It is preferable, however, to use insect-repellents, e.g. insect-repellent oils, lotions, sprays mixtures of various aromatic Substances that together pro or sticks; duce an attractive scent. Ethereal oils of relatively low vola 30 deodorants, such as deodorant sprays, pump-action sprays, tility, which are chiefly used as aroma components, are also deodorant gels, Sticks or roll-ons; Suitable as perfume oils, e.g. sage oil, camomile oil, clove oil, antiperspirants, e.g. antiperspirant Sticks, creams or roll OnS, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper preparations for cleansing and caring for blemished skin, berry oil, Vetiver oil, olibanum oil, galbanum oil, labolanum 35 e.g. synthetic detergents (solid or liquid), peeling or oil and lavandin oil. Preference is given to the use ofbergamot Scrub preparations or peeling masks; oil, dihydromyrcenol, lilial, lyral, citronellol, phenyl ethyl hair-removal preparations in chemical form (depilation), alcohol, hexyl cinnamaldehyde, geraniol, benzyl acetone, e.g. hair-removing powders, liquid hair-removing cyclamen aldehyde, linalool, boisambrene forte, ambroxan, preparations, cream- or paste-form hair-removing indole, hedione, Sandelice, lemon oil, tangerine oil, orange 40 preparations, hair-removing preparations in gel form or oil, allyl amylglycolate, cyclovertal, lavandin oil, muscatel aerosol foams; sage oil, damascone, bourbon geranium oil, cyclohexyl sali shaving preparations, e.g. shaving Soap, foaming shaving cylate, vertofix coeur, iso-E-Super, Fixolide NP, evernyl, iral creams, non-foaming shaving creams, foams and gels, dein gamma, phenylacetic acid, geranyl acetate, benzyl preshave preparations for dry shaving, aftershaves or acetate, rose oxide, romillat, irotyl and floramat alone or in 45 aftershave lotions; admixture with one another. fragrance preparations, e.g. fragrances and odoriferous Other Adjuvants Substances containing preparations (scents, eau de It is furthermore possible for the cosmetic preparations to Cologne, eau de toilette, eau de parfum, parfum de toi contain, as adjuvants, anti-foams, such as silicones, struc lette, perfume), perfume oils or perfume creams; turants, such as maleic acid, solubilisers, such as ethylene 50 cosmetic hair-treatment preparations, e.g. hair-washing glycol, propylene glycol, glycerol or diethylene glycol, preparations in the form of shampoos and conditioners, opacifiers, such as latex, styrene/PVP or styrene/acrylamide hair-care preparations, e.g. pretreatment preparations, copolymers, propellants, such as propane?butane mixtures, hair tonics, styling creams, styling gels, pomades, hair N2O, dimethyl ether, CO2, N2 or air, so-called coupler and rinses, treatment packs, intensive hair treatments, hair developer components as oxidation dye precursors, reducing 55 structuring preparations, e.g. hair-waving preparations agents, such as thioglycolic acid and derivatives thereof, thi for permanent waves (hot wave, mild wave, cold wave), olactic acid, cysteamine, thiomalic acid or mercaptoethane hair-straightening preparations, liquid hair-setting Sulfonic acid, or oxidising agents, such as hydrogen peroxide, preparations, hair foams, hairsprays, bleaching prepara potassium bromate or Sodium bromate. tions, e.g. hydrogen peroxide solutions, lightening Suitable insect repellents are, for example, N,N-diethyl-m- 60 shampoos, bleaching creams, bleaching powders, toluamide, 1.2-pentanediolor insect repellent 3535; suitable bleaching pastes or oils, temporary, semi-permanent or self-tanning agents are, for example, dihydroxyacetone and/ permanent hair colourants, preparations containing self or erythrulose or dihydroxy acetone and/or dihydroxy oxidising dyes, or natural hair colourants, such as henna acetone precursors as described in WO 01/85124 and/or or camomile; erythrulose. 65 dentifrices, in particular tooth creams, toothpastes, mouth The present stabilized compositions are particularly Suit washes, mouth rinses, anti-plaque preparations and able for stabilizing body care products, in particular: cleaning agents for dentures; US 8,454,940 B2 45 46 decorative preparations, in particular lipsticks, nail var c) mixtures or solutions comprising the compound stabilized nishes, eye shadows, mascaras, dry and moist make-up, composition of the present invention with alkylpyrroli rouge, powders, depilatory agents and Suntan lotions done; and optionally another stabilizer. cosmetic formulations containing active ingredients, in Examples of body care products of the present invention particular hormone preparations, vitamin preparations, 5 are listed in the Table below: Vegetable extract preparations and antibacterial prepa rations. Suitable cosmetic formulations containing active ingredi Body care ents are in particular hormone preparations, vitamin prepara product Ingredients tions, vegetable extract preparations and antibacterial prepa 10 rations. Sun screen Oils, emulsifers, water, UV absorbers, thickeners, antioxidants, stabilizer according to invention Presentation Forms moisturising vegetable oil, emulsifier, thickener, perfume, water, The final formulations listed may exist in a wide variety of Ce:8 antioxidant, stabilizer according to invention presentation forms, for example: Hair or body Surfactant, emulsifier, colorant, preservatives, perfume, 15 shampoo antioxidant, stabilizer according to invention in the form of liquid preparations as a W/O, O/W, O/W/O, Hair Surfactant, cationic polymers, emulsifier, colorant, WIO/W or PIT emulsion and all kinds of microemul conditioner preservatives, perfume, antioxidant, stabilizer according Sions, to invention Toothpaste cleaning agent, abbrasives, water, thickener, Sweetener, in the form of a gel, flavor, colorant, antioxidant, stabilizer according to in the form of an oil, a cream, milk or lotion, invention in the form of a stick, lip-care stick vegetable oil, wax, TiO2, pigments, antioxidant, in the form of a spray (spray with propellent gas or pump stabilizer according to invention action spray) or an aerosol, in the form of a foam, or Household Products in the form of a paste. 25 The stabilized compositions of the present invention are Of special importance as cosmetic preparations for the skin also used in household cleaning and treatment agents, for are light-protective preparations, such as Sun milks, lotions, example in laundry products and fabric softeners, liquid creams, oils, Sunblocks or tropicals, pretanning preparations cleansing and Scouring agents, glass detergents, neutral or after-Sun preparations, also skin-tanning preparations, for cleaners (all-purpose cleaners), acid household cleaners example self-tanning creams. Of particular interest are Sun 30 (bath), bathroom cleaners, WC cleaners, for instance inwash protection creams, Sun protection lotions, Sun protection milk ing, rinsing and dishwashing agents, kitchen and oven clean and sun protection preparations in the form of a spray. ers, clear rinsing agents, dishwasher detergents, shoe pol Of special importance as cosmetic preparations for the hair ishes, polishing waxes, floor detergents and polishes, metal, are the above-mentioned preparations for hair treatment, glass and ceramic cleaners, textile-care products, rug cleaners especially hair-washing preparations in the form of sham 35 and carpet shampoos, agents for removing rust, color and poos, hair conditioners, hair-care preparations, e.g. pretreat stains (stain remover salt), furniture and multipurpose pol ment preparations, hair tonics, styling creams, styling gels, ishes and leather and vinyl dressing agents (leather and vinyl pomades, hair rinses, treatment packs, intensive hair treat sprays) and air fresheners. ments, hair-straightening preparations, liquid hair-setting Household cleaning agents are aqueous or alcoholic (etha preparations, hair foams and hairsprays. Of special interest 40 nol or isopropyl alcohol) solutions of one or more of the are hair-washing preparations in the form of shampoos. following components: A shampoo has, for example, the following composition: anionic, nonionic, amphoteric and/or cationic Surfactants 0.01 to 5% by weight of the stabilized composition of the Soaps, prepared by Saponification of animal and vegetable present invention, greases 12.0% by weight of sodium laureth-2-sulfate, 45 organic acids, like hydrochloric acid, phosphoric acid, or 4.0% by weight of cocamidopropyl betaine, Sulfuric acid, 3.0% by weight of sodium chloride, for basic products inorganic (NaOH or KOH) or organic and water ad 100%. bases; For example, especially the following hair-cosmetic for abrasives for improved cleaning of Surfaces, mulations may be used: 50 waxes and/or silicones for maintenance and protection of a1) spontaneously emulsifying stock formulation, compris Surfaces, ing stabilized composition of the present invention, option polyphosphates, ally another stabilizer, PEG-6-C10oxoalcohol and sorbitan Substances which eliminate hypochlorite or halogens: sesquioleate, to which water and any desired quaternary peroxides comprising bleaching activators like TAED, for ammonium compound, for example 4% minkamidopropyl 55 example sodium perborate or H2O: dimethyl-2-hydroxyethylammonium chloride or Quater enzymes; nium 80 is added; in washing detergents discoloration inhibitors, Soil-release a2) spontaneously emulsifying stock formulation comprising compounds, grey Scale inhibitors, foam inhibitors, fluo the stabilized composition of the present invention, option rescent whitening agents; ally another stabilizer, tributyl citrate and PEG-20-sorbitan 60 cleaning agents based on wax may comprise solvents monooleate, to which water and any desired quaternary Selected from benzine, turpentine and/or paraffines and ammonium compound, for example 4% minkamidopropyl emulsifiers based on waX; dimethyl-2-hydroxyethylammonium chloride or Quater filling agents like silicates, polyphosphates, Zeolithes for nium 80 is added; powdery cleaning agents: b) quat-doped solutions comprising the stabilized composi 65 pigments, lakes or soluble dyes; tion of the present invention in butyl triglycol and tributyl perfumes; and citrate; and optionally another stabilizer, light stabilizers, antioxidants and chelating agents. US 8,454,940 B2 47 48 Colored cleaning agents and decorative cosmetic products all other hair dyes listed in International Cosmetic Ingre can comprise the following dyes: dient Dictionary and Handbook, 7th edition 19997) or inorganic pigments, for example iron oxide (Iron Oxide listed in Color Index International or Society of Dyers Red, Iron Oxide Yellow, Iron Oxide Black, etc.), Ultra and Colourists; marines, Chromium Oxide Green or Carbon Black; 5 color lakes (insoluble salts of soluble dyes, like many Ca-, natural or synthetic orgnic pigments; Ba- or Al-Salts of anionic dyes); disperse dyes which may be solubilzed in solvents like soluble anionic or cationic dyes, like acid dyes (anionic), direct hair dyes of the HC type, for example HC Red No. basic dyes (cationic), direct dyes, reactive dyes or sol 3, HC Blue No. 2 and all other hair dyes listed in Inter vent dyes. national Cosmetic Ingredient Dictionary and Handbook, 10 Generally, for the coloration of household- and body care 7th edition 19997) or the dispersion dyes listed in Color products all Substances are Suitable which have an absorption Index International or Society of Dyers and Colourists; in the visible light of electromagnetic radiation (wave length color varnishes (insoluble salts of soluble dyes, like many of ca. 4000 to 700 nm). The absorption is often caused by the Ca-, Ba- or Al-salts of anionic dyes); following chromophores: Soluble anionic or cationic dyes, like acid dyes (anionic), 15 AZO- (mono-, di, tris-, or poly-)stilbene-, carotenoide-, dia basic dyes (cationic), direct dyes, reactive dyes or sol rylmethan-, triarylmethan-, Xanthen-, acridin-, quinoline, vent dyes. methin- (also polymethin-), thiazol-, indamin-, indophenol-, Generally, for the coloration of household- and body care azin-, oxazin, thiazin-, anthraquinone-, indigoid-, phtalocya products all Substances are suitable which have an absorption nine- and further synthetic, natural and/or inorganic chro in the visible light of electromagnetic radiation (wave length mophores. of ca. 4000 to 700 nm). The absorption is often caused by the The stabilized composition of the present invention are for following chromophores: example incorporated by dissolution in an oil phase or alco AZO- (mono-, di, tris-, or poly-)stilbene-, carotenoide-, dia holic or water phase, where required at elevated temperature. rylmethan-, triarylmethan-, Xanthen-, acridin-, quinoline, The present body care products and household products methin- (also polymethin-), thiazol-, indamin-, indophenol-, 25 have high stability towards color changes and chemical deg azin-, oxazin, thiazin-, anthraquinone-, indigoid-, phtalocya radation of the ingredients present in these products. For nine- and further synthetic, natural and/or inorganic chro example, present compositions that comprise a dye are found mophores. to have excellent color stability. The present invention also relates to home care and fabric The following Examples illustrate the invention. care products such as drain cleaners, disinfectant Solutions, 30 upholstery cleaners, automotive care products (e.g., to clean A. PREPARATION EXAMPLES and/or polish and protect paint, tires, chrome, vinyl, leather, fabric, rubber, plastic and fabric), degreasers, polishes (glass, Example A1 wood, leather, plastic, marble, granite, and tile, etc.), and metal polishes and cleaners. The present invention also 35 Preparation of Merocyanine of Formula (MC-01) relates to home care products Such as candles, gel candles, air fresheners and fragrance oils (for the home). 40.13 g dimethylsulfate is added dropwise to 75.43 g3-(2- Typical examples of household cleaning and treating ethylhexyl)amino-5,5-dimethyl-2-cyclohexen-1-one (CAS: agents are listed in the table below: 110186-59-9). 40 The mixture is heated under stirring for 40 min at 90-100° C. After cooling down the reaction mixture to 60° C. first Household 31.33 g methylcyanoacetate and then Subsequently 33.21 g cleaners household triethylamine are added. treating agents Ingredients 45 The resulting mixture is then stirred at 100-110° C. for about 70 min. detergent Surfactant mixture, builders, water, ethanol, pH concentrate adjuster, antioxidant, antioxidants, stabilizer After cooling to room temperature the mixture is diluted according to invention with 240 ml toluene. Cleaner Surfactant mixture, water, pH adjuster, colorant, The toluene solution is washed with 240 ml water and then stabilizer according to invention 50 extracted with 120 ml of an aqueous HCl solution (5%) and Bleaches Hypochlorite or peroxide bleach, water, pH adjuster, 3-times with 120 ml of water. EDTA, stabilizer according to invention shoe polish wax wax emulsifier, antioxidant, water, preservative, The organic phase is then washed with 120 ml aqueous antioxidants, stabilizer according to invention NaOH solution (5%) and three times with 120 ml water. wax-containing emulsifier, wax, sodium chloride, water, preservative, The organic phase is then filtered over a silica gel pad and floor cleaning antioxidant, stabilizer according to invention 55 eluted with 51 toluene in total. agent After distilling off the solvent 76 g of the product is obtained as an orange oil. Colored cleaning agents, personal care and decorative cos The product can be dissolved in methanol and precipitated metic products can comprise the following dyes and pig by the addition of water yielding yellowish crystals (melting ments: 60 point: 78-81° C.). inorganic pigments, for example iron oxide (Iron Oxide Red, Iron Oxide Yellow, Iron Oxide Black, etc.), Ultra B. APPLICATION EXAMPLES marines, Chromium Oxide Green or Carbon Black; natural or synthetic organic pigments; Example B1 dispersed dyes which may be solubilzed in solvents like 65 direct hair dyes of the HC type, for example HC Red No. The following colored basic shampoo formulation was 3, HC Blue No. 2 prepared: US 8,454,940 B2 49 50 (8) basic shampoo formulation plus 0.02% of the compound (BT-01) and 0.01% of the compound (ESS-01): Sodium Laureth Ether Sulfate 10 (ww)% Cocamidopropylbetaine 3 (ww)% (9) basic shampoo formulation plus 0.03% of a 1:3 (w Citric Acid to pH 5 %)-mixture of compound (MC-03) and of the compound FD&C Blue No. 1 0.001 (w?w)% 5 (BT-01); Aqua ad. 100 (ww)% (10) basic shampoo formulation plus 0.03% of a 1:4 (w Stabilizer C.a. %)-mixture of compound (MC-03) and of the compound (BT-01); The following stabilized and unstabilized samples of this (11) basic shampoo formulation plus 0.02% of a 1:3 (w formulation are prepared for light stability testing: 10 %)-mixture of compound (MC-03) and of the compound (1) unstabilized basic shampoo formulation (BT-01) plus additional 0.01% of the compound (ESS-01); (2) basic shampoo formulation plus 0.03% of the compound (12) basic shampoo formulation plus 0.02% of a 1:4 (w (BT-01) %)-mixture of compound (MC-03) and of the compound (3) basic shampoo formulation plus 0.003% of compound 15 (BT-01) plus additional 0.01% of the compound (ESS-01). (MC-03) The formulations are filled into 30 ml glass bottles and (4) basic shampoo formulation plus 0.003% of compound irradiated in an ATLAS Suntest XLS+ Xenon Lamp (light (MC-03) and 0.027% of the compound (BT-01) intensity 500 W/m2, spectrum of light adjusted to indoor (5) basic shampoo formulation plus 0.0075% of compound conditions, sample chamber temperature: 32° C.). (MC-03) and 0.0225% of the compound (BT-01) (corre sponds to 0.03% of a 1:3 (w %)-mixture of compound (MC-03) and of the compound (BT-01)). The formulations are filled into 30 ml glass bottles and Results irradiated in an ATLAS Suntest XLS+ Xenon Lamp (light Sample Irradiation Time until samples were significantly faded intensity 500 W/m2, spectrum of light adjusted to indoor 25 (6) 9 hours (nearly colorless) conditions, sample chamber temperature: 32° C.). (7) 9 hours (faded), 24 hours (colorless) Results: (8) 39 hours (strongly faded, but still colored) (9) 31 hours (faded, but still colored) (10) 31 hours (faded, but still colored) 30 (11) 63 hours (still no fading observed) Sample Irradiation Time until samples were significantly faded (12) 63 hours (still no fading observed) (1) 2 hours (colorless) (2) 8 hours (colorless) Samples 9 and 10, stabilized by the synergistic combina (3) 6 hours (faded, but still colored), 8 hours (colorless) tion of the compound (BT-01) with (MC-03), exhibited sig (4) 18 hours (colorless) 35 nificantly better light stability compared to the samples when (5) 24 hours (colorless) the compound (BT-01) (Sample (7)) is used alone. Best performance is shown by a combination of the com Samples (4) and (5), stabilized by the synergistic combi pound (BT-01) and (MC-03) with the compound (ESS-01). nation of the compound (BT-01) with (MC-03), exhibit sig Even after 63 hours of irradiation no fading is observed in the nificantly better light stability compared to the samples when 40 samples (11) and (12). the compound (BT-01) (Sample (2)) or the merocyanine UV filter (MC-03) (Sample (3)) are used alone. Example B3-B17 Sample (2), stabilized with 0.03% of the compound (BT Preparation of Body-Care and Household 01), is totally faded after 8 hours. Formulations In Sample (5), where 25% of the compound (BT-01) are 45 replaced by the merocyanine (MC-03), the fading time is more than doubled to 18 hours.
Example B2 Example B3: Preparation of a sprayable hair styling gel: 50 The following colored basic shampoo formulation is pre Phase Ingredients (wfw)% pared: A carbomer (1% dispersion) O.30 water, demin. 3O.OO B glycerol 2.OO 55 methylparaben O.2O Texapon NSO 30 (ww)% C water, demin. ad 100 Dehyton K 10 (ww)% PVP/VA copolymer 8.OO Aqua 60 (ww)% triethanolamine (88%) O.12 Citric Acid to pH 5 EDTA, disodium salt O.O1 PURICOLOR. Blue ABL9 0.001 (w?w)% (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) O.08 Aqua ad. 100 (ww)% 60 Merocyanine (MC-01) O.O2 Stabilizer C.a. Preparation: The following stabilized and unstabilized samples of this The components (A) are dispersed at room temperature. formulation were prepared for light stability testing: (B) is mixed under heating until the paraben is completely (6) unstabilized basic shampoo formulation 65 dissolved and then (B) is added with gentle stirring to (A). (7) basic shampoo formulation plus 0.03% of the compound (C) is blended until it is completely dissolved and is slowly (BT-01); added under stirring to the mixture of (A) and (B). US 8,454,940 B2 51 52 The transparency of the gel can be increased by adding small amounts of triethanolamine (pH 5.6-5.75). Example B7: Preparation of a floor wax
Example B4. Preparation of a baby shampoo Ingredients (wfw)% Ingredients (wfw)% wax mixture 12 white spirit ad 100 cocoamidopropylbetaine 3S.OO d-limonene 4.OO water, demin. ad...100 10 citric acid q.S. (pH) Merocyanine (MC-03) O.O2S polycuaternium-15 O.15 Compound (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) 0.075 perfume oil O.30 chlorophyll O.20 Merocyanine (MC-03) O.O2 Compound (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) O.O2 15 Preparation: colorant (D&C Yellow No. 5) O.O2 The components are stirred in the indicated sequence until Sodium chloride O.30 a homogeneous mixture is obtained. Preparation: Surfactant and water are blended until a homogeneous Example B8. Preparation of a lipstick, non-greasy solution is obtained. The pH is adjusted to 6.0–6.5 with citric acid and the other components are added in the indicated Ingredients (wfw)% sequence. The mixture is stirred until it is completely dis Carnauba wax 2.5 solved. 25 Beeswax, white 2O.O Ozekerite 1O.O Lanoline, anhydrous S.O Cetyl alcohol 2.0 Liquid paraffin 3.0 Example B5: Preparation of a perfumed toilet water Isopropyl Myristate 3.0 Propylene glycol recinoleate 4.0 Ingredients (wfw)% 30 CI Pigment Red 4 9.0 CI Pigment Blue 15 1.O ethanol, 96% 60 Merocyanine (MC-03) 0.025 d-limonene 5 Compound (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) 0.075 cedrene 1.5 Castor Oil ad 100 citronellol O.S savin O.S 35 Merocyanine (MC-03) O.OS Compound (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) O.OS Compound (ESS-01) (INCI: Tris O.O3 (tetramethylhydroxypiperidinol) citrate) Tinogard TS (CAS number: 2082-79-3) O.O2 Example B9: Preparation of a lipstick, transfer resistant S.S.-EDDS O.O1 40 colorant (D&C Yellow No. 5) O.1 Ingredients (wfw)% Water ad. 100 Cyclomethicone 41.50 Isodecane 1O.OO D&C Red No. 7 8.OO Preparation: Synthetic wax 6.OO 45 Isostearyltrimethylpropane siloxysilicate S.OO The components are thoroughly mixed in the indicated Cetylstearatefacetylated lanolin, 90:10 S.OO sequence at 50° C. A clear homogeneous solution is obtained. Ceresin 4.OO Paraffin 3.00 Preparation of Formulations of Household Products Titanium dioxide 2.OO Methylparaben O.30 50 Propylparaben O.10 Tinogard AS (INCI Bumetrizole) O.10 Example B6: Preparation of a green-colored glass detergent Merocyanine (MC-03) O.O2 Compound (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) O.08 Ingredients (wfw)% anionic amphoteric Surfactants (Lumorol RK) 0.7 butyl glycol S.O 55 isopropanol 2O.O d-limonene 4.OO Example B10: Preparation of a Rouge (powder colorant (D&C Green No. 2) O.OS Compound (ESS-01) (INCI: Tris O.OS Ingredients (wfw)% (tetramethylhydroxypiperidinol) citrate) Merocyanine (MC-01) O.O1 60 Talcum 56 Compound (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) O.O3 Zinc Stearate 15 water, demin. ad. 100 Rice starch 15 Iron Oxide Red 12 Perfume C.S. Preparation: Merocyanine (MC-03) O.O2 65 Compound (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) O.08 The components are dissolved in the indicated sequence until a clear homogeneous mixture is obtained. US 8,454,940 B2 53 54 -continued
Example B11: Preparation of a Foundation cream Example B12: Preparation of an Eveliner Ingredients (wfw)% Ingredients (wfw)% 5 Tinogard TT (INCI Pentaerythrityl Tetra-di-t-butyl O.OS hydroxyhydrocinnamate) Titanium dioxide 12.79 Water to 100 Oleyl alcohol 4.57 Glyceryl Stearate 3.65 Propylene glycol 3.65 10 Stearic acid 1.83 Magnesium aluminium silicate O.91 Example B13: Preparation of an Eyelash Makeup Triethanolamine 99% O.91 Iron Oxide Yellow O.64 Ingredients (wfw)% Iron Oxide Red O.32 15 Paraffin W 1O.OO 88 8X CI Pigment Brown 6 0.37 Starch S.OO Carboxymethyl cellulose O.10 Polyethylene S.OO Merocyanine (MC-03) O.O2S Iron Oxide Black 7.OO Compound (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) 0.075 Carbomer (Carbopol, BFGoodrich) OSO 2O Hydroxyethylcellulose OSO Water ad 100 Panthenol 2.OO Merocyanine (MC-03) O.O1 Compound (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) O.04 Water ad 100
25 Example B12: Preparation of an Eyeliner Ingredients (wfw)% Example B14: Preparation of a Nail Vanish Polysaccharide resin (Kama KM 13, Kama) 8 Iron Oxide Black 6.50 Ingredients (wfw)% Carnauba wax 1.00 30 Triethanolamin, 99% 1.00 Poly(1-trimethylsilylpropylene) O.30 Hydrogenated polyisobutane 1.OO Nitrocellulose 12.OO Hydrogenated poly decene 1.00 Alkyd resin 1O.OO Sorbitan Sesquioleate 1.00 Dibutyl phthalate 4.OO Xanthum gum OSO Camphor 2.OO Carboxymethyl cellulose O40 35 Butyl acetate 49.50 Magnesium aluminium silicate O40 Toluene 2O.OO Methyl paraben O.35 Pigment Red 57.1 1.OO Stearic acid 2.50 Quaternary bentonite 1.OO Lecithin O.20 Merocyanine (MC-03) O.O6 Imidazolidinyl urea O.10 compound (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) O.14 Merocyanine (MC-03) O.O2 40 Tinogard NOA (INCI Tetrabutyl Ethylidinebisphenol) O.10 Compound (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) O.08
Example B15: High Protection Sunscreen High protection Sunscreen (1) A. B C D NCI-Name % Wiw % Wiw % Wiw % Wiw
Synthetic Beeswax O.S O.S O.S O.S Ethylhexyl Methoxycinnamate 9.8 9.8 9.8 9.8 Soamyl p-Methoxycinnamate 2.O 2.0 2.0 2.0 Ethylhexyl Salicylate S.O S.O S.O S.O Butyl Methoxydibenzoylmethane 4.0 4.0 4.0 4.0 4-Methylbenzylidene Camphor 4.0 4.0 4.0 4.0 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2.O 3.0 2.0 1.O Octadecene/MA Copolymer (and) Methyl Acethyl 3.0 Ricinoleate (and) Di-methylhepthyl Adipate C30-38 olefinisopropyl maleate/MA copolymer 2.0 Hydrogenated Dimer Dillinoleyl. Dimethylcarbonate 3.0 Copolymer Dimethicone 4.5 4.5 4.5 4.5 C20-22 Alkyl Phosphate (and) C20-22 Alcohols 3.0 Candelilla Jojoba Rice Bran Polyglyceryl-3 esters 4.0 (and) glyceryl Stearate (and) Cetearyl alcohol (and) Sodium stearoyl lactylate Glyceryl oleate citrate (and) Caprylic/Capric 6.O Triglycerides Cetearyl Alcohol (and) Dicetyl Phosphate (and) 4.5 Ceteth-10 Phosphate Cetyl Ricinoleate 3.0 3.0 3.0 3.0 US 8,454,940 B2 55 56 -continued Example B15: High Protection Sunscreen Pentaerythrityl Distearate 1.5 Glyceryl Dibelhenate (and) Tribehenin (and) Glyceryl 2.0 Behenate Hydroxypropyl Dimethicone Behenate 2.2 1.O 2.2 Decyl Cocoate 1.O 1.O 1.O 1.O Aqua to 100 Qs to 100 Qs to 100 Qs to 100 Propylene Glycol 3.0 3.0 3.0 3.0 Methylene Bis-Benzotriazolyl Tetramethylbutylphenol S.O 4.0 8.0 (and) Aqua (and) Decyl Glucoside (and) Propylene Glycol (and) Xanthan Gum Decyl Glucoside Acrylates/Vinyl Neodecanoate Crosspolymer Ammonium Acryloyldimethyltaurate? VP Copolymer Phenylbenzimidazole Sulfonic Acid 2.O 2.0 Disteareth-75 IPDI 3.0 Disteareth-100 IPDI O.3 Acrylates/C10-30 Alkyl Acrylate Crosspolymer Disodium EDTA Tromethamine Cyclohexasiloxane (and) Cyclopentasiloxane Phenoxyethanol (and) Methylparaben (and) Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Tocopheryl Acetate 0.4 O4 0.4 0.4 CAS-Regno. 88122-99-0, Ethylhexyl triazone (Octyl 2.O 1.5 2.0 triazone; Uvinul T 150) CAS-Regno. 6197-30-4, Octocrylene 3.0 4.0 CAS-Regno. 180898-37-7, Disodium 3.0 4.0 3.0 phenyldibenzimidazoletetrasulfonate Neo Heliopan AP or Neo-Heliopan APC CAS-Regno. 3.02776-68-7, Uvinul A Plus 4.0 CAS-Regno. 444811-29-4, Propanedioic acid. (4- 3.0 hydroxy-3,5-dimethoxyphenyl)methylene-, bis(2- ethylhexyl) ester (Oxynex ST) CAS-Regno. 477844-93-2, Octofluorene 3.0 1.O 2-phenylethylbenzoate 1.O 1.O CAS-Regno. 68890-66-4, Octopirox 2.O 3.0 Tinogard TT (INCI Tetradibutyl Pentaerithrityl 1.O 1.O 1.O Hydroxy-hydrocinnamate) Tinogard HS (INCI Sodium Benzotriazolyl 2.O 3.0 Butylphenol Sulfonate) compound (BT-01) (INCI Benzotriazolyl Dodecyl p 2.O 1.O 1.O Cresol) Merocyanine (MC-03) 1.O O.3 O.3 Cibafast H Liquid (INCI Sodium Benzotriazolyl 1.O Butylphenol Sulfonate, Buteth-3, Tributyl Citrate) Tinogard AS (INCI Bumetrizole) 2.O 1.O Tris(tetramethylhydroxypiperidinol) citrate of the 1.O 1.O Compound (ESS-01) 220410-74-24-Piperidinol, 1-hydroxy-2.2,6,6- 1.O tetramethyl-, 2-hydroxy-1,2,3-propanetricarboxylate (3:1) (salt) CAS-Regno. 1750-49-8, N-(2-Hydroxypropyl)urea CAS-Regno. 2078-71-9, N-(2-Hydroxyethyl)urea mixture of n-butylphthalimide and isopropylphthalimide
High protection Sunscreen (1) E G I NCI-Name % Wiw % Wiw
Synthetic Beeswax O.S O.S O.S O.S O.S Ethylhexyl Methoxycinnamate 9.8 9.8 9.8 9.8 9.8 Soamyl p-Methoxycinnamate 2.0 2.O 2.0 2.O 2.0 Ethylhexyl Salicylate S.O S.O S.O S.O S.O Butyl Methoxydibenzoylmethane 4.0 4.0 3.0 4.0 3.0 4-Methylbenzylidene Camphor 4.0 4.0 4.0 4.0 4.0 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 1.O 1.O 1.O 1.O 1.O Cyclopentasiloxane (and) Acrylates/Polytrimethyl 7.0 siloxymethacrylate Copolymer sododecane (and) Acrylates/Polytrimethylsiloxy 8.0 methacrylate Copolymer Poly(Glycol Adipate)/Bis-Hydroxyethyoxypropyl Dimethicone Copolymer Dimethicone 4.5 4.5 4.5 4.5 4.5 C20-22 Alkyl Phosphate (and) C20-22 Alcohols 3.0 Candelilla Jojoba Rice Bran Polyglyceryl-3 esters 4.0 (and) glyceryl Stearate (and) Cetearyl alcohol (and) Sodium stearoyl lactylate US 8,454,940 B2 57 -continued Example B15: High Protection Sunscreen Glyceryl oleate citrate (and) Caprylic/Capric 6.0 Triglycerides Cetearyl Alcohol (and) Dicetyl Phosphate (and) 4.5 4.5 Ceteth-10 Phosphate Cetyl Ricinoleate 3.0 3.0 3.0 3.0 3.0 Pentaerythrityl Distearate 3.0 S.O Glyceryl Dibelhenate (and) Tribehenin (and) Glyceryl 4.0 Behenate Hydroxypropyl Dimethicone Behenate 2.2 O.S 2.2 Decyl Cocoate 1.O 1.O 1.O 1.O 1.O Aqua Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Propylene Glycol 3.0 3.0 3.0 3.0 3.0 Methylene Bis-Benzotriazolyl Tetramethylbutyl- S.O 1O.O 1O.O S.O 1O.O phenol (and) Aqua (and) Decyl Glucoside (and) Propylene Glycol (and) Xanthan Gum Decyl Glucoside O.S O.S O.S O.S O.S Acrylates/Vinyl Neodecanoate Crosspolymer Ammonium Acryloyldimethyltaurate? VP Copolymer O.3 O.3 O.3 O.3 O.3 PVP, dimethylconylacrylate/polycarbamyl/polyglycol 1O.O ester Polyester-5 3.0 Phenylbenzimidazole Sulfonic Acid 2.0 2.O 2.0 2.O 2.0 Disteareth-75 IPDI Disteareth-100 IPDI 3.0 Acrylates/Vinyl Neodecanoate Crosspolymer 1.5 S.O 8.0 Acrylates/C10-30 Alkyl Acrylate Crosspolymer O.2 Disodium EDTA O.2 O.2 O.2 O.2 O.2 Tromethamine O.8 O.8 O.8 O.8 O.8 Cyclohexasiloxane (and) Cyclopentasiloxane O.8 O.8 O.8 O.8 O.8 Phenoxyethanol (and) Methylparaben (and) Ethyl- O.8 O.8 O.8 O.8 O.8 paraben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Tocopheryl Acetate 0.4 0.4 0.4 0.4 0.4 CAS-Regno. 88122-99-0, Ethylhexyl triazone 1.O 3.0 (Octyl triazone; Uvinul T 150) CAS-Regno. 6197-30-4, Octocrylene 1.O S.O CAS-Regno. 180898-37-7, Disodium 2.0 phenyldibenzimidazoletetrasulfonate Neo Heliopan AP or Neo-Heliopan APC CAS-Regno. 68890-66-4, Octopirox 1.O Tinogard TT (INCI Tetradibutyl Pentaerithrityl 3.0 1.O Hydroxy-hydrocinnamate) Tinogard HS (INCI Sodium Benzotriazolyl 3.0 Butylphenol Sulfonate) compound (BT-01) (INCI Benzotriazolyl Dodecyl p- O.9 1.O 3.0 O.S 1.O Cresol) Merocyanine (MC-03) O.3 1.O 1.O O.S O.3 Cibafast H Liquid (INCI Sodium Benzotriazolyl Butylphenol Sulfonate, Buteth-3, Tributyl Citrate) Tinogard AS (INCI Bumetrizole) 1.O 1.O Tris(tetramethylhydroxypiperidinol) citrate of the 1.O 1.O Compound (ESS-01) 220410-74-24-Piperidinol, 1-hydroxy-2.2,6,6- 1.O tetramethyl-, 2-hydroxy-1,2,3-propanetricarboxylate (3:1) (salt) CAS-Regno. 1750-49-8, N-(2-Hydroxypropyl)urea 1O.O CAS-Regno. 2078-71-9, N-(2-Hydroxyethyl)urea 1O.O mixture of n-butylphthalimide and 3.0 isopropylphthalimide
Example B16: High Protection Sunscreen High protection Sunscreen (2) A. B C D INCI-Name % ww % Wiw % Wiw % Wiw
Synthetic Beeswax O.S O.S O.S O.S Ethylhexyl Methoxycinnamate (stabilized by 9.8 9.8 9.8 9.8 incorporating into a polymer) Isoamyl p-Methoxycinnamate 2.O 2.0 2.0 2.0 Ethylhexyl Salicylate S.O S.O S.O S.O Butyl Methoxydibenzoylmethane (stabilized by 4.0 4.0 S.O 4.0 incorporating into a polymer) 4-Methylbenzylidene Camphor 4.0 4.0 4.0 4.0 US 8,454,940 B2 59 60 -continued Example B16: High Protection Sunscreen Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2.O 3.0 2.0 1.O Octadecene/MA Copolymer (and) Methyl Acethyl 3.0 Ricinoleate (and) Di-methylhepthyl Adipate C30-38 olefinisopropyl maleate/MA copolymer 2.0 Hydrogenated Dimer Dillinoleyl. Dimethylcarbonate 3.0 Copolymer Dimethicone 4.5 4.5 4.5 4.5 C20-22 Alkyl Phosphate (and) C20-22 Alcohols 3.0 Candelilla Jojoba Rice Bran Polyglyceryl-3 esters 4.0 (and) glyceryl Stearate (and) Cetearyl alcohol (and) Sodium stearoyl lactylate Glyceryl oleate citrate (and) Caprylic/Capric 6.O Triglycerides Cetearyl Alcohol (and) Dicetyl Phosphate (and) 4.5 Ceteth-10 Phosphate Cetyl Ricinoleate 3.0 3.0 3.0 3.0 Pentaerythrityl Distearate 1.5 Glyceryl Dibelhenate (and) Tribehenin (and) Glyceryl 2.0 Behenate Hydroxypropyl Dimethicone Behenate 2.2 1.O 2.2 Decyl Cocoate 1.O 1.O 1.O 1.O Aqua Qs to 100 Qs to 100 Qs to 100 Qs to 100 Propylene Glycol 3.0 3.0 3.0 3.0 Decyl Glucoside O.S O.S Acrylates/Vinyl Neodecanoate Crosspolymer Ammonium Acryloyldimethyltaurate? VP Copolymer O.3 O.3 O.3 O.3 PVP, dimethylconylacrylate/polycarbamyl/polyglycol ester Polyester-5 Phenylbenzimidazole Sulfonic Acid 2.O 2.0 2.0 2.0 Disteareth-75 IPDI O.3 3.0 Disteareth-100 IPDI O.3 Acrylates/C10-30 Alkyl Acrylate Crosspolymer Disodium EDTA Methylene Bis-Benzotriazolyl Tetramethylbutylphenol Tromethamine Cyclohexasiloxane (and) Cyclopentasiloxane Phenoxyethanol (and) Methylparaben (and) Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Tocopheryl Acetate 0.4 0.4 0.4 0.4 CAS-Regno. 88122-99-0, Ethylhexyl triazone (Octyl 2.O 1.5 2.0 triazone: Uvinul T 150) CAS-Regno. 6197-30-4, Octocrylene 3.0 4.0 CAS-Regno. 180898-37-7, Disodium 3.0 4.0 3.0 phenyldibenzimidazoletetrasulfonate Neo Heliopan AP or Neo-Heliopan APC CAS-Regno. 3.02776-68-7, Uvinul A Plus 4.0 CAS-Regno. 444811-29-4, Propanedioic acid, (4- 3.0 hydroxy-3,5-dimethoxyphenyl)methylene-, bis(2- ethylhexyl) ester (Oxynex ST) CAS-Regno. 477844-93-2, Octofluorene 3.0 2-phenylethylbenzoate 1.O CAS-Regno. 68890-66-4, Octopirox 2.O 3.0 Tinogard TT (INCI Tetradibutyl Pentaerithrityl 1.O 1.O Hydroxy-hydrocinnamate) Tinogard HS (INCI Sodium Benzotriazolyl 2.0 Butylphenol Sulfonate) compound (BT-01) (INCI Benzotriazolyl Dodecyl p 2.O 1.O 1.O Cresol) Merocyanine (MC-03) 2.O 2.0 1.O Cibafast H Liquid (INCI Sodium Benzotriazolyl 1.O Butylphenol Sulfonate, Buteth-3, Tributyl Citrate) Tinogard AS (INCI Bumetrizole) 2.O Tris(tetramethylhydroxypiperidinol) citrate 1.O Compound (ESS-01) 220410-74-24-Piperidinol, 1-hydroxy-2.2,6,6- tetramethyl-, 2-hydroxy-1,2,3-propanetricarboxylate (3:1) (salt) CAS-Regno. 1750-49-8, N-(2-Hydroxypropyl)urea CAS-Regno. 2078-71-9, N-(2-Hydroxyethyl)urea mixture of n-butylphthalimide and isopropylphthalimide US 8,454,940 B2 61 -continued Example B16: High Protection Sunscreen High protection Sunscreen (2) E F G H I INCI-Name % Wiw % Wiw % Wiw % Wiw % Wiw
Synthetic Beeswax O.S O.S O.S O.S O.S Ethylhexyl Methoxycinnamate (stabilized by 9.8 9.8 9.8 9.8 9.8 incorporating into a polymer) Isoamyl p-Methoxycinnamate 2.0 2.0 2.0 2.0 2.0 Ethylhexyl Salicylate S.O S.O S.O S.O S.O Butyl Methoxydibenzoylmethane (stabilized 4.0 4.0 3.0 S.O 3.0 by incorporating into a polymer) 4-Methylbenzylidene Camphor 4.0 4.0 4.0 4.0 4.0 Bis-Ethylhexyloxyphenol Methoxyphenyl 1.O 1.O 1.O 1.O 1.O Triazine Cyclopentasiloxane (and) 7.0 Acrylates/Polytrimethylsiloxymethacrylate Copolymer Isododecane (and) 8.0 Acrylates/Polytrimethylsiloxymethacrylate Copolymer Poly(Glycol Adipate)/Bis- S.O Hydroxyethyoxypropyl Dimethicone Copolymer Dimethicone 4.5 4.5 4.5 4.5 4.5 C20-22 Alkyl Phosphate (and) C20-22 3.0 Alcohols Candelilla Jojoba Rice Bran Polyglyceryl-3 4.0 esters (and) glyceryl Stearate (and) Cetearyl alcohol (and) Sodium stearoyl lactylate Glyceryl oleate citrate (and) Caprylic/Capric 6.O Triglycerides Cetearyl Alcohol (and) Dicetyl Phosphate 4.5 4.5 (and) Ceteth-10 Phosphate Cetyl Ricinoleate 3.0 3.0 3.0 3.0 3.0 Pentaerythrityl Distearate 3.0 S.O Glyceryl Dibelhenate (and) Tribehenin (and) 4.0 Glyceryl Behenate Hydroxypropyl Dimethicone Behenate 2.2 O.S 2.2 Decyl Cocoate 1.O 1.O 1.O 1.O 1.O Aqua Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Propylene Glycol 3.0 3.0 3.0 3.0 3.0 Decyl Glucoside O.S O.S O.S O.S O.S Acrylates/Vinyl Neodecanoate Crosspolymer Ammonium Acryloyldimethyltaurate/VP O.3 O.3 O.3 O.3 O.3 Copolymer PVP dimethylconylacrylate/polycarbamyl/polyglycol 1O.O ester Polyester-5 3.0 Phenylbenzimidazole Sulfonic Acid 2.0 2.0 2.0 2.0 2.0 Disteareth-75 IPDI Disteareth-100 IPDI 3.0 Acrylates/Vinyl Neodecanoate 1.5 S.O 8.0 Crosspolymer Acrylates/C10-30 Alkyl Acrylate O.2 Crosspolymer Disodium EDTA O.2 O.2 O.2 O.2 O.2 Methylene Bis-Benzotriazolyl S.O S.O S.O S.O S.O Tetramethylbutylphenol Tromethamine O.8 O.8 O.8 O.8 O.8 Cyclohexasiloxane (and) O.8 O.8 O.8 O.8 O.8 Cyclopentasiloxane Phenoxyethanol (and) Methylparaben (and) O.8 O.8 O.8 O.8 O.8 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Tocopheryl Acetate 0.4 0.4 0.4 0.4 0.4 CAS-Regno. 88122-99-0, Ethylhexyl 1.O 3.0 triazone (Octyl triazone: Uvinul T 150) CAS-Regno. 6197-30-4, Octocrylene 1.O S.O CAS-Regno. 180898-37-7, Disodium 2.0 phenyldibenzimidazoletetrasulfonate Neo Heliopan AP or Neo-Heliopan APC CAS-Regno. 68890-66-4, Octopirox 1.O Tinogard TT (INCI Tetradibutyl 3.0 1.O Pentaerithrityl Hydroxy-hydrocinnamate) Tinogard HS (INCI Sodium Benzotriazolyl 3.0 Butylphenol Sulfonate) compound (BT-01) (INCI Benzotriazolyl O.S 1.O 3.0 O.9 1.O Dodecyl p-Cresol) US 8,454,940 B2 63 64 -continued Example B16: High Protection Sunscreen Merocyanine (MC-03) Tinogard AS (INCI Bumetrizole) Tris(tetramethylhydroxypiperidinol) citrate Compound (ESS-01) 220410-74-24-Piperidinol, 1-hydroxy 2.2,6,6-tetramethyl-, 2-hydroxy-1,2,3- propanetricarboxylate (3:1) (salt) CAS-Regno. 1750-49-8, N-(2- Hydroxypropyl)urea CAS-Regno. 2078-71-9, N-(2- Hydroxyethyl)urea mixture of n-butylphthalimide and 3.0 isopropylphthalimide
Example B17: High Protection Sunscreen High protection Sunscreen (3) A. B C D NCI-Name % Wiw % Wiw % Wiw % Wiw Synthetic Beeswax O.S O.S O.S O.S Ethylhexyl Methoxycinnamate 9.8 9.8 9.8 9.8 Soamyl p-Methoxycinnamate 2.0 2.0 2.0 2.0 Ethylhexyl Salicylate S.O S.O S.O S.O Butyl Methoxydibenzoylmethane 4.0 4.0 4.0 4.0 4-Methylbenzylidene Camphor 4.0 4.0 4.0 4.0 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2.0 3.0 2.0 1.O Octadecene/MA Copolymer (and) Methyl Acethyl 3.0 Ricinoleate (and) Di-methylhepthyl Adipate C30-38 olefinisopropyl maleate/MA copolymer 2.0 Hydrogenated Dimer Dilinoley/Dimethylcarbonate 3.0 Copolymer Dimethicone 4.5 4.5 4.5 4.5 C20-22 Alkyl Phosphate (and) C20-22 Alcohols 3.0 Candelilla Jojoba Rice Bran Polyglyceryl-3 esters 4.0 (and) glyceryl Stearate (and) Cetearyl alcohol (and) Sodium stearoyl lactylate Glyceryl oleate citrate (and) Caprylic/Capric 6.O Triglycerides Cetearyl Alcohol (and) Dicetyl Phosphate (and) 4.5 Ceteth-10 Phosphate Cetyl Ricinoleate 3.0 3.0 3.0 3.0 Pentaerythrityl Distearate 1.5 Glyceryl Dibelhenate (and) Tribehenin (and) 2.0 Glyceryl Behenate Hydroxypropyl Dimethicone Behenate 2.2 1.O 2.2 Decyl Cocoate 1.O 1.O 1.O 1.O Aqua Qs to 100 Qs to 100 Qs to 100 Qs to 100 Propylene Glycol 3.0 3.0 3.0 3.0 Methylene Bis-Benzotriazolyl Tetramethyl S.O 4.0 6.O 8.0 butylphenol (and) Aqua (and) Decyl Glucoside (and) Propylene Glycol (and) Xanthan Gum Decyl Glucoside O.S O.S O.S O.S Acrylates/Vinyl Neodecanoate Crosspolymer Ammonium Acryloyldimethyltaurate? VP Copolymer O.3 O.3 O.3 O.3 Phenylbenzimidazole Sulfonic Acid 2.0 2.0 2.0 2.0 Disteareth-75 IPDI O.3 3.0 Disteareth-100 IPDI O.3 Acrylates/C10-30 Alkyl Acrylate Crosspolymer O.2 Disodium EDTA O.2 O.2 O.2 O.2 Tromethamine O.8 O.8 O.8 O.8 Cyclohexasiloxane (and) Cyclopentasiloxane O.8 O.8 O.8 O.8 Phenoxyethanol (and) Methylparaben (and) O.8 O.8 O.8 O.8 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Tocopheryl Acetate 0.4 0.4 0.4 0.4 CAS-Regno. 88122-99-0, Ethylhexyl triazone 2.0 1.5 2.0 (Octyl triazone: Uvinul T 150) CAS-Regno. 6197-30-4, Octocrylene 3.0 4.0 S.O CAS-Regno. 180898-37-7, Disodium 3.0 4.0 S.O 3.0 phenyldibenzimidazoletetrasulfonate Neo Heliopan AP or Neo-Heliopan APC CAS-Regno. 3.02776-68-7, Uvinul A Plus 4.0 S.O CAS-Regno. 444811-29-4, Propanedioic acid, (4- 3.0 1.O US 8,454,940 B2 65 66 -continued Example B17: High Protection Sunscreen High protection Sunscreen (3) A. B C D INCI-Name % Wiw % Wiw % Wiw % Wiw hydroxy-3,5-dimethoxyphenyl)methylene-, bis(2- ethylhexyl) ester (Oxynex ST) CAS-Regno. 477844-93-2, Octofluorene 3.0 1.O 2-phenylethylbenzoate 1.O 1.O CAS-Regno. 68890-66-4, Octopirox 2.O 3.0 Tinogard TT (INCI Tetradibutyl Pentaerithrityl 1.O 1.O 1.O Hydroxy-hydrocinnamate) Tinogard HS (INCI Sodium Benzotriazolyl 2.0 3.0 Butylphenol Sulfonate) compound (BT-01) (INCI Benzotriazolyl Dodecyl p 2.O 1.O 1.O Cresol) Merocyanine (MC-03) 1.O O.3 O.3 Cibafast H Liquid (INCI Sodium Benzotriazolyl 1.O Butylphenol Sulfonate, Buteth-3, Tributyl Citrate) Tinogard AS (INCI Bumetrizole) 2.O 1.O CAS-Regn. 30538-92-2 (Compound ESS-06) O.OS O.O1 220410-74-24-Piperidinol, 1-hydroxy-2.2,6,6- 1.O tetramethyl-, 2-hydroxy-1,2,3-propanetricarboxylate (3:1) (salt) CAS-Regno. 1750-49-8, N-(2-Hydroxypropyl)urea CAS-Regno. 2078-71-9, N-(2-Hydroxyethyl)urea 1O.O mixture of n-butylphthalimide and S.O isopropylphthalimide
The invention claimed is:
1. A stabilizing composition for the protection of body care (4a) and household products against the deleterious effects of 30 light, heat and oxygen comprising (a) an effective stabilizing amount of a merocyanine derivative
35 R is hydrogen; C-C alkyl, C-Calkoxy; halogen; or hydroxy, -Cl O 'N-1 Ra and Rs each independently of the other are hydrogen; or N 2 C-C alkyl, 40 Š m is 1 or 2: n is 0 or 1; if m=1, R is hydrogen; unsubstituted or phenyl-substituted having an absorption maximum of 350 to 400 nm, and 45 C-C2alkyl, or Co-Coaryl; (b) at least one UV filter comprising a benzotriazole; and if m=2, optionally R2 is the direct bond; or -(CH2) ; and (c) at least one excited State quencher, and optionally p is 1 to 3. (d) at least one salicylate. 50 3. A composition according to claim 1, wherein component 2. A composition according to claim 1, wherein component (b) is at least one benzotriazole of formula (5) (b) is at least one benzotriazole of formula (4) (5) 55 HO R (4) N e N N N / N 60 R2 wherein wherein R is C-Coalkyl, C-Csalkoxy; C-Csalkoxycarbonyl: 65 R is a random statistical mixture of at least three isomeric Cs-C,cycloalkyl; Co-Caryl; aralkyl, -SOM; or a branched secondary alkyl groups each having 8 to 30 radical of formula (4a): carbon atoms of the radical US 8,454,940 B2 67 68 an ester, ether, hydroxy, OXO, cyanohydrine, amide, amino, carboxy or urethane group; X is an inorganic or organic anion selected from phosphate, El phosphonate, carbonate, bicarbonate, nitrate, chloride, bromide, bisulfite, sulfite, bisulfate, sulfate, borate, for E is a straight-chain C-C alkyl, mate, acetate, benzoate, citrate, oxalate, tartrate, acry E is a straight-chain Ca-Calkyl; wherein the total num late, polyacrylate, fumarate, maleate, itaconate, glyco ber of carbon atoms in E plus E is from 7 to 29; and late, gluconate, malate, mandelate, tiglate, ascorbate, R is C-C alkyl. polymethacrylate, a carboxylate of nitrilotriacetic acid, 4. A composition according to claim 1, wherein component 10 (b) is 2-(2H-benzotriazol-2-yl)-6-dodecycl-4-methyl-phe hydroxyethylethylenediaminetriacetic acid, ethylenedi nol, (BT-01) aminetetraacetic acid or of diethylenetriaminepentaace tic acid, a diethylenetriaminepentameth ylenephosphonate, al alkylsulfonate or an (BT-01) 15 arylsulfonate; and HO C12H25. where the total charge of cations h is equal to the total N charge of anions j. e N N 6. A composition according to claim 5, wherein component N / (c) corresponds to a compound of formula (ESS-01) N CH3 (ESS-01) OH 5. A composition according to claim 1, comprising com ponent (c) which is at least one quencher selected from (c) hindered nitroxyl compounds of formula (6a); 25
(6a)
30 citrate
7. A composition according to claim 1, comprising com ponent (d), which is at least one salicylate selected from 35 salicylic acid, homosalate, 2-ethylhexyl salicylate, benzyl salicylate, ethyl salicylate, methyl salicylate, isoamyl salicy (c) hindered hydroxylamine compounds of formula (6b) late, acetylsalicylic acid and isobutyl salicylate. 8. A composition according to claim 1, wherein component (b) corresponds to a compound of formula (6b) 40 (BT-01)
(BT-01) HO-N HO C12H25
45 N / N and (c) hindered hydroxylamine salt compounds of formula CH3 (6c) 50 and component (c) corresponds to a compound of formula (6c) (ESS-01)
(ESS-01) OH
/ M wherein HO H G and G2 independently from each other are C-C alkyl alkyl; or are together pentamethylene, 65 citrate Z and Z are each methyl; or Z and Z together form a linking moiety which may additionally be substituted by US 8,454,940 B2 69 70 9. A method of protection body care and household prod if m=2, ucts against the deleterious effects of light, heat and oxygen comprising adding to said composition the stabilizing com R2 is the direct bond; or -(CH2) ; and position according to claim 1. p is 1 to 3. 10. Abody-care or a household product comprising a sta 15. The method according to claim 9, wherein component bilizing composition according to claim 1, wherein the stabi (b) is at least one benzotriazole of formula (5) lizing composition is present in the body-care or household product in a concentration of about 5 to about 50000 ppm. (5) 11. A stabilizing composition according to claim 1, HO R wherein the weight ratio of component (a) to component (b) 10 N is from 20:1 to 1:20. e N 12. A stabilizing composition according to claim 1, N S. M wherein the weight ratio of component (a) to component (c) is N from 1:1 to 1000:1. 13. A product according to claim 10, 15 R2 wherein the body-care product is selected from skin-care products, bath or shower additives, preparations con wherein taining fragrances or odoriferous Substances, hair-care products, dentifrices, deodorizing or antiperspirant R is a random statistical mixture of at least three isomeric preparations, decorative preparations, light protection branched secondary alkyl groups each having 8 to 30 formulations and preparations containing active ingre carbon atoms of the radical dients and wherein the household product is selected from washing, *-CH-E: rinsing or dishwashing agents, shoe polishes, polishing 25 waxes, floor detergents or polishes, all purpose cleaners, El 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 E is a straight-chain C-C alkyl, removing rust, color or stains, stain remover salts, 30 E is a straight-chain Ca-Cisalkyl, wherein the total num bleaches, furniture or multipurpose polishes, surface ber of carbon atoms in E plus E is from 7 to 29; and protecting formulations, film forming formulations, air R is C-Csalkyl. care formulations and candles. 14. The method according to claim 9, wherein component 16. The method according to claim 9, wherein component (b) is at least one benzotriazole of formula (4) 35 (b) is 2-(2H-benzotriazol-2-yl)-6-dodecycl-4-methyl-phe nol, (BT-01)
(4) 40 (BT-01) HO C12H25.
45 N / wherein N R is C-Coalkyl, C-Calkoxy; C-Calkoxycarbonyl: Cs-C,cycloalkyl; Co-Caryl; aralkyl, -SOM; or a CH3 radical of formula (4a): 50
(4a) 17. The method according to claim 9, wherein component (c) which is at least one quencher is selected from 55 (c) hindered nitroxyl compounds of formula (6a);
(6a) R is hydrogen; C-C alkyl, C-Calkoxy; halogen; or G1 G2 hydroxy, 60 Rand Rs each independently of the other are hydrogen; or y-Z, C-C alkyl, O-N m is 1 or 2; n is 0 or 1; X-7. G1 G2 if m=1, 65 R is hydrogen; unsubstituted or phenyl-substituted C-C2alkyl, or Co-Coaryl; US 8,454,940 B2 71 72 (c) hindered hydroxylamine compounds of formula (6b) bromide, bisulfite, sulfite, bisulfate, sulfate, borate, for mate, acetate, benzoate, citrate, oxalate, tartrate, acry late, polyacrylate, fumarate, maleate, itaconate, glyco late, gluconate, malate, mandelate, tiglate, ascorbate, polymethacrylate, a carboxylate of nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenedi y-Z, aminetetraacetic acid or of diethylenetriaminepentaace HO-N tic acid, a diethylenetriaminepentameth ylenephosphonate, al alkylsulfonate or an X-7. arylsulfonate; and 10 where the total charge of cations h is equal to the total charge of anions j. and 18. The method according to claim 9, wherein component (c) hindered hydroxylamine salt compounds of formula (c) corresponds to a compound of formula (ESS-01) (6c) 15 (ESS-01) OH (6c)
25 citrate wherein 19. The method according to claim 9, wherein component G and G independently from each other are C-C alkyl (d), is at least one Salicylate selected from Salicylic acid, homosalate, 2-ethylhexyl salicylate, benzyl salicylate, ethyl alkyl; or are together pentamethylene, 30 Z and Z are each methyl; or Z and Z together form a salicylate, methyl salicylate, isoamyl salicylate, acetylsali linking moiety which may additionally be substituted by cylic acid and isobutyl salicylate. an ester, ether, hydroxy, OXO, cyanohydrine, amide, 20. The method according to claim 9, wherein the stabiliz amino, carboxy or urethane group; ing composition is present in the body-care or household X is an inorganic or organic anion selected from phosphate, product in a concentration of about 5 to about 50000 ppm. phosphonate, carbonate, bicarbonate, nitrate, chloride, k k k k k