US20010026789A1 - Photostabilized sunscreen compositions comprising dibenzoylmethane compounds and benzylidenecamphor-substituted silanes/organosiloxanes - Google Patents
Photostabilized sunscreen compositions comprising dibenzoylmethane compounds and benzylidenecamphor-substituted silanes/organosiloxanes Download PDFInfo
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- US20010026789A1 US20010026789A1 US09/761,827 US76182701A US2001026789A1 US 20010026789 A1 US20010026789 A1 US 20010026789A1 US 76182701 A US76182701 A US 76182701A US 2001026789 A1 US2001026789 A1 US 2001026789A1
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- Prior art keywords
- radical
- formula
- compound
- dibenzoylmethane
- composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 92
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical class C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000000516 sunscreening agent Substances 0.000 title claims abstract description 17
- 230000000475 sunscreen effect Effects 0.000 title claims abstract description 14
- 125000005375 organosiloxane group Chemical group 0.000 title claims abstract description 11
- -1 benzylidenecamphor-substituted silanes Chemical class 0.000 title claims description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- 238000012216 screening Methods 0.000 claims abstract description 25
- OIQXFRANQVWXJF-QBFSEMIESA-N (2z)-2-benzylidene-4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical group CC1(C)C2CCC1(C)C(=O)\C2=C/C1=CC=CC=C1 OIQXFRANQVWXJF-QBFSEMIESA-N 0.000 claims abstract description 17
- 229910000077 silane Inorganic materials 0.000 claims abstract description 17
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002537 cosmetic Substances 0.000 claims abstract description 12
- 210000004209 hair Anatomy 0.000 claims abstract description 7
- 230000003711 photoprotective effect Effects 0.000 claims abstract description 5
- 150000003254 radicals Chemical class 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- XNEFYCZVKIDDMS-UHFFFAOYSA-N avobenzone Chemical compound C1=CC(OC)=CC=C1C(=O)CC(=O)C1=CC=C(C(C)(C)C)C=C1 XNEFYCZVKIDDMS-UHFFFAOYSA-N 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 11
- 239000000499 gel Substances 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- LALVCWMSKLEQMK-UHFFFAOYSA-N 1-phenyl-3-(4-propan-2-ylphenyl)propane-1,3-dione Chemical compound C1=CC(C(C)C)=CC=C1C(=O)CC(=O)C1=CC=CC=C1 LALVCWMSKLEQMK-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000006071 cream Substances 0.000 claims description 5
- 239000006210 lotion Substances 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000002671 adjuvant Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 239000008267 milk Substances 0.000 claims description 3
- 235000013336 milk Nutrition 0.000 claims description 3
- 210000004080 milk Anatomy 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 150000004756 silanes Chemical class 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 239000002562 thickening agent Substances 0.000 claims description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical class NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002535 acidifier Substances 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- 150000001565 benzotriazoles Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 239000003974 emollient agent Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims description 2
- 150000001261 hydroxy acids Chemical class 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical group [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 2
- 239000007764 o/w emulsion Substances 0.000 claims description 2
- 239000002674 ointment Substances 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 239000003380 propellant Substances 0.000 claims description 2
- 239000003352 sequestering agent Substances 0.000 claims description 2
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- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
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- 229930003231 vitamin Natural products 0.000 claims description 2
- 235000013343 vitamin Nutrition 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
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- 239000004922 lacquer Substances 0.000 claims 1
- 239000006072 paste Substances 0.000 claims 1
- 230000002335 preservative effect Effects 0.000 claims 1
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- 239000007762 w/o emulsion Substances 0.000 claims 1
- 230000005855 radiation Effects 0.000 abstract description 19
- 230000000254 damaging effect Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000003921 oil Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 210000003491 skin Anatomy 0.000 description 11
- 0 *C.CC.CCC12CCC(/C(=C\C3=CC=CC=C3)C1=O)C2(C)C Chemical compound *C.CC.CCC12CCC(/C(=C\C3=CC=CC=C3)C1=O)C2(C)C 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000000921 elemental analysis Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000012230 colorless oil Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- HEOCBCNFKCOKBX-RELGSGGGSA-N (1s,2e,4r)-4,7,7-trimethyl-2-[(4-methylphenyl)methylidene]bicyclo[2.2.1]heptan-3-one Chemical compound C1=CC(C)=CC=C1\C=C/1C(=O)[C@]2(C)CC[C@H]\1C2(C)C HEOCBCNFKCOKBX-RELGSGGGSA-N 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 241000723346 Cinnamomum camphora Species 0.000 description 3
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 229960000846 camphor Drugs 0.000 description 3
- 229930008380 camphor Natural products 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 229930195733 hydrocarbon Natural products 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- KPMKEVXVVHNIEY-UHFFFAOYSA-N norcamphor Chemical compound C1CC2C(=O)CC1C2 KPMKEVXVVHNIEY-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- RMFFCSRJWUBPBJ-UHFFFAOYSA-N 15-hydroxypentadecyl benzoate Chemical compound OCCCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1 RMFFCSRJWUBPBJ-UHFFFAOYSA-N 0.000 description 2
- KXTAOXNYQGASTA-UHFFFAOYSA-N 2-benzylidenepropanedioic acid Chemical class OC(=O)C(C(O)=O)=CC1=CC=CC=C1 KXTAOXNYQGASTA-UHFFFAOYSA-N 0.000 description 2
- QXDDDCNYAAJLBT-UHFFFAOYSA-N 3-chloropropyl(trimethyl)silane Chemical compound C[Si](C)(C)CCCCl QXDDDCNYAAJLBT-UHFFFAOYSA-N 0.000 description 2
- HNTPGIFEBNWRJC-UHFFFAOYSA-N 3-methoxy-4-(3-trimethylsilylpropoxy)benzaldehyde Chemical compound COC1=CC(C=O)=CC=C1OCCC[Si](C)(C)C HNTPGIFEBNWRJC-UHFFFAOYSA-N 0.000 description 2
- BGCCAUANSKYICF-UHFFFAOYSA-N 4-(3-trimethylsilylpropoxy)benzaldehyde Chemical compound C[Si](C)(C)CCCOC1=CC=C(C=O)C=C1 BGCCAUANSKYICF-UHFFFAOYSA-N 0.000 description 2
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 2
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- JQZUMFHYRULBEN-UHFFFAOYSA-N diethyl(methyl)silicon Chemical compound CC[Si](C)CC JQZUMFHYRULBEN-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- DLAHAXOYRFRPFQ-UHFFFAOYSA-N dodecyl benzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1 DLAHAXOYRFRPFQ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 210000000720 eyelash Anatomy 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000005338 frosted glass Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229920013818 hydroxypropyl guar gum Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940119170 jojoba wax Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010469 macadamia oil Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- 229940105132 myristate Drugs 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 231100000760 phototoxic Toxicity 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000037307 sensitive skin Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 231100000075 skin burn Toxicity 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- YSIQPJVFCSCUMU-UHFFFAOYSA-N trimethyl-[methyl-[3-(oxiran-2-ylmethoxy)propyl]-trimethylsilyloxysilyl]oxysilane Chemical compound C[Si](C)(C)O[Si](C)(O[Si](C)(C)C)CCCOCC1CO1 YSIQPJVFCSCUMU-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/893—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
- A61K8/585—Organosilicon compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/52—Stabilizers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/57—Compounds covalently linked to a(n inert) carrier molecule, e.g. conjugates, pro-fragrances
Definitions
- the present invention relates to improving the photostability of at least one dibenzoylmethane sunscreen compound with respect to UV radiation, by intimately admixing therewith an effective photostabilizing amount of a silane or organosiloxane compound bearing a benzylidenecamphor substituent.
- UV-A irradiation with wavelengths of from 320 to 400 nm, which tans the skin, is apt to induce an adverse change therein, in particular in the case of sensitive skin or skin which is continually exposed to solar radiation.
- UV-A radiation in particular causes a loss of elasticity of the skin and the appearance of wrinkles, promoting premature aging.
- Such irradiation promotes triggering of the erythemal reaction or enhances this reaction in certain individuals and may even be the source of phototoxic or photoallergic reactions.
- an ever-increasing number of subjects wish to control the effect of UV-A rays on their skin. It is thus desirable to also screen UV-A radiation from the skin.
- one particularly advantageous class of UV-A screening agents currently includes dibenzoylmethane derivatives, and in particular 4-(tert-butyl)-4′-methoxydibenzoylmethane, which have high intrinsic absorption power.
- dibenzoylmethane derivatives which are compounds that are well known per se as screening agents that are active in the UV-A range, are particularly described in FR-A-2,326,405 and FR-A-2,440,933, as well as in EP-A-0,114,607;
- 4-(tert-butyl)-4′-methoxydibenzoylmethane is moreover commercially available under the trademark “PARSOL 1789” from Givaudan.
- dibenzoylmethane derivatives are compounds that are relatively sensitive to ultraviolet radiation (especially UV-A radiation), namely, more specifically, they exhibit an annoying tendency to be degraded more or less rapidly under the influence of such radiation.
- UV-A radiation especially UV-A radiation
- this substantial lack of photochemical stability of dibenzoylmethane derivatives in the face of the ultraviolet radiation to which they are by nature intended to be subjected does not guarantee constant protection during prolonged exposure to the sun, such that, in a restricting manner, repeated applications at regular and close time intervals must be carried out by the user in order to obtain effective protection of the skin against UV radiation.
- EP-A-0,709,080 describes combining dibenzoylmethane derivatives with benzalmalonate derivatives in order to reduce the photoinstability of said dibenzoylmethane derivatives. Nonetheless, the photostabilization of dibenzoylmethane derivatives with respect to UV radiation constitutes, to date, a problem which has not yet been solved completely satisfactorily.
- FR-2,607,996 and WO-94/04131 describe combining dibenzoylmethane derivatives with hydrocarbon-based benzylidenecamphor derivatives such as 3-(4-methylbenzylidene)camphor in order to reduce the photoinstability of said dibenzoylmethane derivatives.
- oils have been typically employed such as esters, and more particularly C 12 -C 15 alkyl benzoates (“Finsolv TN” marketed by Finetex), or triglycerides, and in particular C 8 -C 12 fatty acid triglycerides (“Miglyol 812” marketed by Hüls), but these various products exhibit solubilizing properties with respect to the aforesaid screening agents that remain insufficient.
- oils have been typically employed such as esters, and more particularly C 12 -C 15 alkyl benzoates (“Finsolv TN” marketed by Finetex), or triglycerides, and in particular C 8 -C 12 fatty acid triglycerides (“Miglyol 812” marketed by Hüls), but these various products exhibit solubilizing properties with respect to the aforesaid screening agents that remain insufficient.
- silane or organosiloxane compounds containing a benzylidenecamphor functional group are effective photostabilizing agents, which is also very surprising compared with the known hydrocarbon-based organic screening agents derived from benzylidenecamphor, and constitute a family of solvents which are particularly noteworthy for the screening agents of dibenzoylmethane derivative type such as, for example, 4-(tert-butyl)-4′-methoxydibenzoylmethane; this permits, for an equal amount of solvent, formulating greater amounts of screening agents.
- the present invention features enhancing the stability of at least one dibenzoylmethane compound with respect to UV radiation, by intimately formulating therewith an effective photostabilizing amount of a silane or organosiloxane derivative bearing a benzylidenecamphor substituent.
- compositions according to this invention present the advantage of being particularly photostable, even after prolonged exposure to UV-A and UV-B radiation.
- radiation can be of natural origin (sunlight) or artificial origin (UV lamp).
- the present invention thus, also features formulating a silane or organosiloxane compound containing a benzylidenecamphor functional group into a cosmetic or dermatological composition including at least one dibenzoylmethane sunscreen compound, to enhance the stability of said dibenzoylmethane sunscreen with respect to UV radiation.
- the subject dibenzoylmethane sunscreens are well known per se and are described, in particular, in FR-A-2,326,405, FR-A-2,440,933 and EP-A-0,114,607.
- dibenzoylmethane derivatives suitable for formulation according to the present invention particularly exemplary are:
- Another dibenzoylmethane derivative which is preferred according to the present invention is 4-isopropyldibenzoylmethane.
- This sunscreen agent is marketed under the trademark “Eusolex 8020” by Merck, and has the following structural formula:
- the subject dibenzoylmethane derivative(s) are advantageously present in the compositions stabilized in accordance with the present invention in contents generally ranging from 0.01% to 10% by weight, and preferably in contents ranging from 0.3% to 5% by weight, relative to the total weight of the composition.
- a second compound in the compositions according to the invention comprises a silane or organosiloxane compound substituted by a benzylidenecamphor functional group.
- silane or organosiloxane compound bearing a benzylidenecamphor substituent preferably has the structural formula (I) below:
- radicals R 1 which may be identical or different, are each a hydrogen atom, an OH radical, a saturated or unsaturated, linear or branched, C 1 -C 10 alkyl radical, a linear or branched C 1 -C 10 alkoxy radical or an —OSi(CH 3 ) 3 radical, with the proviso that two adjacent groups R 1 may together form an alkylidenedioxy group in which the alkylidene radical contains 1 or 2 carbon atoms; a is an integer ranging from 1 to 3; A is a hydrogen atom or a radical of formula —L—W such that L is a divalent radical of formula (II a ) or (II b ) below:
- R 2 and R 3 which may be identical or different, are each a hydrogen atom or a linear or branched C 1 -C 5 alkyl radical
- Z is a linear or branched, saturated or unsaturated C 1 -C 6 diyl radical, optionally substituted with a hydroxyl or linear or branched, saturated or unsaturated C 2 -C 8 alkyl radical
- Y is —O—, —NR 4 —, —SO 2 NH—, —(CO)O—, —(CO)NH— or —O(CO)NH—
- R 4 is a hydrogen atom or a C 1 -C 5 alkyl radical
- m is an integer ranging from 0 to 10
- n is 0 or 1
- o is 0 or 1
- p is 0 or 1
- q is 0 or 1
- a 1 is a hydrogen atom or a radical —L 1 —W in which the radical L 1 has the definition of L, with the pro
- radicals R 6 which may be identical or different, are each a linear or branched C 1 -C 30 alkyl, phenyl, 3,3,3-trifluoropropyl or trimethylsilyloxy radical, at least 80%, by number, of the radicals R 6 being methyl radicals;
- radicals B which may be identical or different, are each a radical R 6 or a radical X of the formula below:
- R 1 H, OCH 3 , CH 3 or two adjacent radicals R 1 form a methylenedioxy radical
- R 2 H or CH 3 ,
- R 6 is methyl
- r ranges from 5 to 20, inclusive
- s ranges from 2 to 15, inclusive
- t+u ranges from 3 to 10, inclusive
- R 3 is a hydrogen atom or a methyl radical.
- Another family of novel compounds of formula (I) includes the silane compounds in which W is a radical of formula (3) and n is equal to 0.
- W is a radical of formula (3)
- n is equal to 0.
- the compounds ( 10 ), ( 11 ) and ( 12 ) as described above are exemplary.
- an amount of silane or organosiloxane compound bearing a benzylidenecamphor substituent is intended an amount which is sufficient to provide an appreciable and significant improvement in the photostability of the dibenzoylmethane derivative(s) contained in the composition.
- the minimum amount of stabilizer to be formulated which can vary depending on the nature of the cosmetically acceptable support (vehicle, diluent or carrier) selected for the composition, can be determined without any difficulty via a conventional test for measuring photostability, as described in FR-A-2,607,700.
- the silane or organosiloxane compounds bearing a benzylidenecamphor substituent are generally present in the compositions according to the invention at a content at least equal to 0.5% by weight, relative to the total weight of the composition. Even more preferably, this content ranges from 0.5% to 20% by weight relative to the total weight of the composition.
- the cosmetic and/or dermatological compositions of the present invention can contain one or more complementary hydrophilic or lipophilic sunscreens that are active in the UV-A and/or UV-B range (absorbers).
- These complementary screening agents are advantageously selected from among cinnamic derivatives, salicylic derivatives, benzophenone derivatives, benzotriazole derivatives, benzimidazole derivatives, triazine derivatives, benzalmalonate derivatives, ⁇ ′-diphenylacrylate derivatives, p-aminobenzoic acid derivatives, and the screening polymers and screening silicones described in WO-93/04665.
- organic sunscreens are set forth in EP-A-0,487,404.
- compositions according to the invention can also contain agents for artificially tanning and/or browning the skin (self-tanning agents), such as, for example, dihydroxyacetone (DHA).
- self-tanning agents such as, for example, dihydroxyacetone (DHA).
- the cosmetic and/or dermatological compositions according to the invention can also contain pigments or nanopigments (average size of the primary particles: generally ranging from 5 nm to 100 nm, preferably from 10 to 50 nm) of coated or uncoated metal oxides, such as, for example, nanopigments of titanium dioxide (amorphous or crystallized in rutile and/or anatase form), of iron oxide, of zinc oxide, of zirconium oxide or of cerium oxide, which are all photoprotective agents that are well known per se, which act by physically blocking out (reflecting and/or scattering) the UV radiation.
- Conventional coating agents are, moreover, alumina and/or aluminum stearate.
- Such coated or uncoated metal oxide nanopigments are described, in particular, in EP-A-0,518,772 and EP-A-0,518,773.
- compositions of this invention can also comprise conventional cosmetic additives and adjuvants selected, in particular, from among fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, anti-free radical agents, opacifiers, stabilizers, emollients, silicones, hydroxy acids, antifoaming agents, moisturizers, vitamins, fragrances, preservatives, surfactants, fillers, sequestering agents, polymers, propellants, basifying or acidifying agents, colorants, dyes or any other ingredient usually used in the cosmetics and/or dermatological field, in particular for the manufacture of antisun compositions in the form of emulsions.
- conventional cosmetic additives and adjuvants selected, in particular, from among fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, anti-free radical agents, opacifiers, stabilizers, emollients, silicones, hydroxy acids, antifoaming agents, moisturizer
- any additional ingredient liable to be introduced into the compositions in accordance with the invention must be such that it does not substantially affect or disrupt the photostabilizing effect exerted by the silane or organosiloxane compounds containing a benzylidenecamphor function with respect to the dibenzoylmethane derivatives.
- Fatty substances can include an oil or a wax or mixtures thereof.
- oil is intended a compound which is liquid at room temperature.
- wax is intended a compound which is solid or substantially solid at room temperature and whose melting point is generally greater than 35° C.
- Exemplary oils include the mineral oils (petroleum jelly); plant oils (sweet almond oil, macadamia oil, blackcurrant pip oil, jojoba oil); and synthetic oils such as perhydrosqualene, fatty alcohols, fatty acids or fatty esters (such as C 12 -C 15 alkyl benzoate marketed under the trademark “Finsolv TN” by Finetex, octyl palmitate, isopropyl lanolate, triglycerides, including capric/caprylic acid triglycerides), oxyethylenated or oxypropylenated fatty esters and ethers; silicone oils (cyclomethicone, polydimethylsiloxanes or PDMS) or fluoro oils, and polyalkylenes.
- mineral oils mineral oils
- plant oils sweet almond oil, macadamia oil, blackcurrant pip oil, jojoba oil
- synthetic oils such as perhydrosqualene, fatty alcohols, fatty
- Exemplary waxy compounds include paraffin, carnauba wax, beeswax and hydrogenated castor oil.
- exemplary organic solvents include the lower alcohols and polyols.
- the thickeners are advantageously selected, in particular, from among crosslinked polyacrylic acids, and modified or unmodified guar gums and cellulose gums, such as hydroxypropyl guar gum, methylhydroxyethylcellulose and hydroxpropylmethyl cellulose.
- compositions according to the invention are easily formulated according to techniques which are well known to this art, in particular those intended for the preparation of emulsions of oil-in-water or water-in-oil type.
- compositions can be, in particular, in the form of a simple or complex (O/W, W/O, O/W/O or W/O/W) emulsion, such as a cream or a milk, or in the form of a gel or a cream-gel, a powder or a solid tube and can optionally be packaged as an aerosol and can be in the form of a mousse or a spray.
- a simple or complex (O/W, W/O, O/W/O or W/O/W) emulsion such as a cream or a milk, or in the form of a gel or a cream-gel, a powder or a solid tube and can optionally be packaged as an aerosol and can be in the form of a mousse or a spray.
- compositions according to the invention are preferably formulated as oil-in-water emulsions.
- the aqueous phase thereof can comprise a nonionic vesicle dispersion prepared according to known techniques (Bangham, Standish and Watkins, J. Mol. Biol., 13, 238 (1965), FR-2,315,991 and FR 2,416,008).
- compositions of the invention are useful for protecting the human epidermis or the hair against ultraviolet radiation, as an antisun composition or as a makeup product.
- the cosmetic compositions according to the invention are for protecting the human epidermis against UV rays, or as an antisun (sunscreen) composition
- these can be formulated as suspensions or dispersions in solvents or fatty substances, in the form of a nonionic vesicle dispersion or in the form of an emulsion, preferably of oil-in-water type, such as a cream or a milk, in the form of an ointment, a gel, a cream-gel, a solid tube, a stick, a lotion, an aerosol mousse or a spray.
- the cosmetic compositions according to the invention when used for protecting the hair, same can be in the form of a shampoo, a lotion, a gel, an emulsion or a nonionic vesicle dispersion, and can constitute, for example, a rinse-out composition, to be applied before or after shampooing, before or after dyeing or bleaching, before, during or after permanent-waving or straightening the hair, a styling or treating lotion or gel, a blow-drying or hairsetting lotion or gel, or a permanent-waving, straightening, dyeing or bleaching composition for the hair.
- a rinse-out composition to be applied before or after shampooing, before or after dyeing or bleaching, before, during or after permanent-waving or straightening the hair
- a styling or treating lotion or gel a blow-drying or hairsetting lotion or gel, or a permanent-waving, straightening, dyeing or bleaching composition for the hair.
- the eyebrows or the skin such as an epidermal treatment cream, a foundation, a lipstick, an eyeshadow, a face powder, a mascara or an eyeliner
- anhydrous or aqueous form such as oil-in-water or water-in-oil emulsions, nonionic vesicle dispersions or alternatively suspensions.
- the aqueous phase in particular comprising the hydrophilic screening agents
- the oily phase in particular comprising the lipophilic screening agents
- the (co)emulsifier(s) generally represent(s) from 0.5% to 20% by weight, preferably from 2% to 10% by weight, relative to the entire formulation.
- 3-chloropropyltrimethylsilane (33.14 g, 0.22 mol) was added dropwise over 20 minutes to a mixture of vanillin (30.4 g, 0.2 mol) and potassium carbonate (30.4 g, 0.22 mol) in 150 ml of dry DMF heated to 80° C. under nitrogen. The mixture was maintained for 4 hours at 95°-110° C. The reaction mixture was cooled and poured into ice-cold water. The aqueous phase was extracted three times with dichloromethane. The organic phases were dried over sodium sulfate and concentrated under vacuum.
- compositions described below were formulated (the amounts are expressed as a % by weight relative to the total weight of the composition):
- Composition A (comparative) Ingredients Composition A Isopropyl myristate 30 Parsol 1789 1.5 Ethanol q.s. 100
- Composition A′ (comparative) Ingredients Composition A′ Isopropyl myristate 30 3-(4-methylbenzylidene- 5 camphor (Eusolex 6300) Parsol 1789 1.5 Ethanol q.s. 100
- compositions B to E also comprised 5% by weight of a silicone benzylidenecamphor compound of this invention.
- Composition Composition Composition Composition Composition Composition Ingredients B C D E Isopropyl 30 30 30 30 30 myristate Parsol 1789 1.5 1.5 1.5 1.5 Silicone Example 5
- Example 6 Example 7
- Example 2 benzyl-idene- camphor according to the invention Ethanol qs 100 qs 100 qs 100 qs 100 qs 100 qs 100 qs 100
- the samples were then assayed in the following manner: the screening agents were extracted by immersing each plate in 50 g of ethanol in order to dissolve the screening agents. The plates and the solvent containing the screening agents were then treated with ultrasound for 15 minutes in order to ensure efficient extraction. The solutions obtained were analyzed by spectrophotometry at the ⁇ max of each of the screening agents.
- the level of residual 4-tert-butyl-4′-methoxydibenzoylmethane after irradiation was given by the ratio of its concentration in the irradiated sample to its concentrated in the non-irradiated sample.
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- General Health & Medical Sciences (AREA)
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- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Emergency Medicine (AREA)
- Dermatology (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Improvedly photostable, topically applicable cosmetic/dermatological sunscreen compositions well suited for enhanced photoprotection of human skin and/or hair against the damaging effects of UV-A and UV-B irradiation, particularly solar radiation, comprise (i) a photoprotecting effective amount of at least one dibenzoylmethane UV-screening compound, and (ii) an amount of at least one silane or organosiloxane substituted by a benzylidenecamphor functional group effective to photostabilize said at least one dibenzoylmethane UV-screening compound (i).
Description
- This application is a divisional of application Ser. No. 09/350,910, filed Jul. 12, 1999, now allowed, incorporated by reference herein in its entirety and relied upon, which claims priority under 35 U.S.C. §119 of FR-98/08937, filed Jul. 10, 1998, assigned to the assignee hereof and hereby expressly incorporated by reference.
- 1. Technical Field of the Invention
- The present invention relates to improving the photostability of at least one dibenzoylmethane sunscreen compound with respect to UV radiation, by intimately admixing therewith an effective photostabilizing amount of a silane or organosiloxane compound bearing a benzylidenecamphor substituent.
- 2. Description of the Prior Art
- It is known to this art that light radiation with wavelengths of from 280 nm to 400 nm promotes tanning of the human epidermis, and that irradiation with wavelengths more particularly ranging from 280 to 320 nm, i.e., UV-B irradiation, causes erythema and skin burns which can be harmful to the development of a natural tan. For these reasons, as well as for aesthetic reasons, a constant demand exists for controlling this natural tanning and, also, the coloration of the skin; such UV-B radiation should thus be screened from the skin.
- It is also known to this art that UV-A irradiation, with wavelengths of from 320 to 400 nm, which tans the skin, is apt to induce an adverse change therein, in particular in the case of sensitive skin or skin which is continually exposed to solar radiation. UV-A radiation in particular causes a loss of elasticity of the skin and the appearance of wrinkles, promoting premature aging. Such irradiation promotes triggering of the erythemal reaction or enhances this reaction in certain individuals and may even be the source of phototoxic or photoallergic reactions. Thus, for aesthetic and cosmetic reasons such as conserving the skins' natural elasticity, for example, an ever-increasing number of subjects wish to control the effect of UV-A rays on their skin. It is thus desirable to also screen UV-A radiation from the skin.
- In this regard, one particularly advantageous class of UV-A screening agents currently includes dibenzoylmethane derivatives, and in particular 4-(tert-butyl)-4′-methoxydibenzoylmethane, which have high intrinsic absorption power. These dibenzoylmethane derivatives, which are compounds that are well known per se as screening agents that are active in the UV-A range, are particularly described in FR-A-2,326,405 and FR-A-2,440,933, as well as in EP-A-0,114,607; 4-(tert-butyl)-4′-methoxydibenzoylmethane is moreover commercially available under the trademark “PARSOL 1789” from Givaudan.
- Unfortunately, it has been determined that dibenzoylmethane derivatives are compounds that are relatively sensitive to ultraviolet radiation (especially UV-A radiation), namely, more specifically, they exhibit an annoying tendency to be degraded more or less rapidly under the influence of such radiation. Thus, this substantial lack of photochemical stability of dibenzoylmethane derivatives in the face of the ultraviolet radiation to which they are by nature intended to be subjected, does not guarantee constant protection during prolonged exposure to the sun, such that, in a restricting manner, repeated applications at regular and close time intervals must be carried out by the user in order to obtain effective protection of the skin against UV radiation.
- Thus, EP-A-0,709,080 describes combining dibenzoylmethane derivatives with benzalmalonate derivatives in order to reduce the photoinstability of said dibenzoylmethane derivatives. Nonetheless, the photostabilization of dibenzoylmethane derivatives with respect to UV radiation constitutes, to date, a problem which has not yet been solved completely satisfactorily.
- FR-2,607,996 and WO-94/04131 describe combining dibenzoylmethane derivatives with hydrocarbon-based benzylidenecamphor derivatives such as 3-(4-methylbenzylidene)camphor in order to reduce the photoinstability of said dibenzoylmethane derivatives.
- Another difficulty, independent of the one indicated above, encountered with dibenzoylmethane derivatives is that these are lipophilic sunscreen agents with the particular feature, and also present the disadvantage of being solid at room temperature. Accordingly, formulating same into antisun cosmetic compositions entails certain constraints as regards their processing, in particular for determining solvents for properly dissolving same, whether alone or in combination with other screening agents. In this regard, oils have been typically employed such as esters, and more particularly C12-C15 alkyl benzoates (“Finsolv TN” marketed by Finetex), or triglycerides, and in particular C8-C12 fatty acid triglycerides (“Miglyol 812” marketed by Hüls), but these various products exhibit solubilizing properties with respect to the aforesaid screening agents that remain insufficient.
- Sunscreen formulations based on dibenzoylmethane derivatives and on 3-(4-methylbenzylidene) camphor as described in FR-2,607,996 and WO-94/04131 do not obviate this problem of solubility of said dibenzoylmethane derivatives completely satisfactorily.
- It has now unexpectedly and surprisingly been found that formulating the dibenzoylmethane derivatives indicated above with an effective amount of a silane or organosiloxane compound containing a benzylidenecamphor substituent, substantially and markedly improves the photochemical stability (or photostability) of these same dibenzoylmethane derivatives.
- It has also been determined that the silane or organosiloxane compounds containing a benzylidenecamphor functional group according to the present invention are effective photostabilizing agents, which is also very surprising compared with the known hydrocarbon-based organic screening agents derived from benzylidenecamphor, and constitute a family of solvents which are particularly noteworthy for the screening agents of dibenzoylmethane derivative type such as, for example, 4-(tert-butyl)-4′-methoxydibenzoylmethane; this permits, for an equal amount of solvent, formulating greater amounts of screening agents.
- Thus, the present invention features enhancing the stability of at least one dibenzoylmethane compound with respect to UV radiation, by intimately formulating therewith an effective photostabilizing amount of a silane or organosiloxane derivative bearing a benzylidenecamphor substituent.
- The cosmetic and/or dermatological compositions according to this invention present the advantage of being particularly photostable, even after prolonged exposure to UV-A and UV-B radiation. Such radiation can be of natural origin (sunlight) or artificial origin (UV lamp).
- The present invention, thus, also features formulating a silane or organosiloxane compound containing a benzylidenecamphor functional group into a cosmetic or dermatological composition including at least one dibenzoylmethane sunscreen compound, to enhance the stability of said dibenzoylmethane sunscreen with respect to UV radiation.
- More particularly according to the present invention, the subject dibenzoylmethane sunscreens are well known per se and are described, in particular, in FR-A-2,326,405, FR-A-2,440,933 and EP-A-0,114,607.
- Consistent herewith, it is intended, of course, to formulate one or more of said dibenzoylmethane compounds into the compositions of the invention.
- Among the dibenzoylmethane derivatives suitable for formulation according to the present invention, particularly exemplary are:
- 2-methyldibenzoylmethane;
- 4-methyldibenzoylmethane;
- 4-isopropyldibenzoylmethane;
- 4-tert-butyldibenzoylmethane;
- 2,4-dimethyldibenzoylmethane;
- 2,5-dimethyldibenzoylmethane;
- 4,4′-diisopropyldibenzoylmethane;
- 4,4′-dimethoxydibenzoylmethane;
- 4-tert-butyl-4′-methoxydibenzoylmethane;
- 2-methyl-5-isopropyl-4′-methoxydibenzoylmethane;
- 2-methyl-5-tert-butyl-4′-methoxydibenzoylmethane,;
- 2,4-dimethyl-4′-methoxydibenzoylmethane;
- 2,6-dimethyl-4-tert-butyl-4′-methoxydibenzoylmethane; and
- 4,4′-dimethoxydibenzoylmethane.
-
-
- The subject dibenzoylmethane derivative(s) are advantageously present in the compositions stabilized in accordance with the present invention in contents generally ranging from 0.01% to 10% by weight, and preferably in contents ranging from 0.3% to 5% by weight, relative to the total weight of the composition.
- A second compound in the compositions according to the invention comprises a silane or organosiloxane compound substituted by a benzylidenecamphor functional group. These compounds are known to this art and are described, as well as processes for the synthesis thereof, in EP-A-0,325,881, EP-A-0,335,777 and EP-A-0,712,855.
-
- in which the radicals R1, which may be identical or different, are each a hydrogen atom, an OH radical, a saturated or unsaturated, linear or branched, C1-C10 alkyl radical, a linear or branched C1-C10 alkoxy radical or an —OSi(CH3)3 radical, with the proviso that two adjacent groups R1 may together form an alkylidenedioxy group in which the alkylidene radical contains 1 or 2 carbon atoms; a is an integer ranging from 1 to 3; A is a hydrogen atom or a radical of formula —L—W such that L is a divalent radical of formula (IIa) or (IIb) below:
- —CH2—CHR2—[C(R3)2]m—(CO)n—(O)o—(Z)p—(Y)q— (IIa)
- —CH=CR2—[C(R3)2]m—(CO)n—(O)o—(Z)p—(Y)q— (IIb)
-
-
- in which R1, L, L1 and a are as defined above; r is an integer ranging from 0 to 200, inclusive, and s is an integer ranging from 0 to 50, inclusive, and, if s=0, at least one of the two symbols B is X; u is an integer ranging from 1 to 10, inclusive, and t is an integer ranging from 0 to 10, inclusive, with the proviso that t+u is greater than or equal to 3.
- Among the above compounds, particularly preferred is the family of compounds which has at least one, preferably all, of the following characteristics:
- R1=H, OCH3, CH3 or two adjacent radicals R1 form a methylenedioxy radical,
- R2=H or CH3,
- n=0,
- q=1.
- Among such compounds, preferred are those which have at least one, preferably all, of the following characteristics:
- R6 is methyl,
- B is methyl,
- r ranges from 5 to 20, inclusive,
- s ranges from 2 to 15, inclusive,
- t+u ranges from 3 to 10, inclusive,
- m=1, and
- R3 is a hydrogen atom or a methyl radical.
- These compounds and the process for preparing same are described, for example, in EP-A-0,335,777.
- A second family of preferred compounds comprises the compounds of formula (I) in which s=0.
-
- Among the compounds of formula (I) , certain of these are novel and constitute another aspect of the present invention.
- This is the case for the compounds of formula (I) as defined above in which p is 1 and the radical Z is a linear or branched, saturated or unsaturated C1-C6 diyl radical substituted by a hydroxyl or linear or branched, saturated or unsaturated C2-C8 alkyl radical. Exemplary of these specific compounds is the compound (7) as described above.
- Another family of novel compounds of formula (I) includes the silane compounds in which W is a radical of formula (3) and n is equal to 0. Among such compounds, the compounds (10), (11) and (12) as described above are exemplary.
- According to the invention, by the expression “effective amount of silane or organosiloxane compound bearing a benzylidenecamphor substituent” is intended an amount which is sufficient to provide an appreciable and significant improvement in the photostability of the dibenzoylmethane derivative(s) contained in the composition. The minimum amount of stabilizer to be formulated, which can vary depending on the nature of the cosmetically acceptable support (vehicle, diluent or carrier) selected for the composition, can be determined without any difficulty via a conventional test for measuring photostability, as described in FR-A-2,607,700.
- The silane or organosiloxane compounds bearing a benzylidenecamphor substituent are generally present in the compositions according to the invention at a content at least equal to 0.5% by weight, relative to the total weight of the composition. Even more preferably, this content ranges from 0.5% to 20% by weight relative to the total weight of the composition.
- Nonetheless, the cosmetic and/or dermatological compositions of the present invention can contain one or more complementary hydrophilic or lipophilic sunscreens that are active in the UV-A and/or UV-B range (absorbers). These complementary screening agents are advantageously selected from among cinnamic derivatives, salicylic derivatives, benzophenone derivatives, benzotriazole derivatives, benzimidazole derivatives, triazine derivatives, benzalmalonate derivatives, ββ′-diphenylacrylate derivatives, p-aminobenzoic acid derivatives, and the screening polymers and screening silicones described in WO-93/04665. Other examples of organic sunscreens are set forth in EP-A-0,487,404.
- The compositions according to the invention can also contain agents for artificially tanning and/or browning the skin (self-tanning agents), such as, for example, dihydroxyacetone (DHA).
- The cosmetic and/or dermatological compositions according to the invention can also contain pigments or nanopigments (average size of the primary particles: generally ranging from 5 nm to 100 nm, preferably from 10 to 50 nm) of coated or uncoated metal oxides, such as, for example, nanopigments of titanium dioxide (amorphous or crystallized in rutile and/or anatase form), of iron oxide, of zinc oxide, of zirconium oxide or of cerium oxide, which are all photoprotective agents that are well known per se, which act by physically blocking out (reflecting and/or scattering) the UV radiation. Conventional coating agents are, moreover, alumina and/or aluminum stearate. Such coated or uncoated metal oxide nanopigments are described, in particular, in EP-A-0,518,772 and EP-A-0,518,773.
- The compositions of this invention can also comprise conventional cosmetic additives and adjuvants selected, in particular, from among fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, anti-free radical agents, opacifiers, stabilizers, emollients, silicones, hydroxy acids, antifoaming agents, moisturizers, vitamins, fragrances, preservatives, surfactants, fillers, sequestering agents, polymers, propellants, basifying or acidifying agents, colorants, dyes or any other ingredient usually used in the cosmetics and/or dermatological field, in particular for the manufacture of antisun compositions in the form of emulsions. Too, any additional ingredient liable to be introduced into the compositions in accordance with the invention must be such that it does not substantially affect or disrupt the photostabilizing effect exerted by the silane or organosiloxane compounds containing a benzylidenecamphor function with respect to the dibenzoylmethane derivatives.
- Fatty substances can include an oil or a wax or mixtures thereof. By the term “oil” is intended a compound which is liquid at room temperature. By the term “wax” is intended a compound which is solid or substantially solid at room temperature and whose melting point is generally greater than 35° C.
- Exemplary oils include the mineral oils (petroleum jelly); plant oils (sweet almond oil, macadamia oil, blackcurrant pip oil, jojoba oil); and synthetic oils such as perhydrosqualene, fatty alcohols, fatty acids or fatty esters (such as C12-C15 alkyl benzoate marketed under the trademark “Finsolv TN” by Finetex, octyl palmitate, isopropyl lanolate, triglycerides, including capric/caprylic acid triglycerides), oxyethylenated or oxypropylenated fatty esters and ethers; silicone oils (cyclomethicone, polydimethylsiloxanes or PDMS) or fluoro oils, and polyalkylenes.
- Exemplary waxy compounds include paraffin, carnauba wax, beeswax and hydrogenated castor oil.
- And exemplary organic solvents include the lower alcohols and polyols.
- The thickeners are advantageously selected, in particular, from among crosslinked polyacrylic acids, and modified or unmodified guar gums and cellulose gums, such as hydroxypropyl guar gum, methylhydroxyethylcellulose and hydroxpropylmethyl cellulose.
- The compositions according to the invention are easily formulated according to techniques which are well known to this art, in particular those intended for the preparation of emulsions of oil-in-water or water-in-oil type.
- This compositions can be, in particular, in the form of a simple or complex (O/W, W/O, O/W/O or W/O/W) emulsion, such as a cream or a milk, or in the form of a gel or a cream-gel, a powder or a solid tube and can optionally be packaged as an aerosol and can be in the form of a mousse or a spray.
- The compositions according to the invention are preferably formulated as oil-in-water emulsions.
- When it is an emulsion, the aqueous phase thereof can comprise a nonionic vesicle dispersion prepared according to known techniques (Bangham, Standish and Watkins,J. Mol. Biol., 13, 238 (1965), FR-2,315,991 and FR 2,416,008).
- The cosmetic and/or dermatological compositions of the invention are useful for protecting the human epidermis or the hair against ultraviolet radiation, as an antisun composition or as a makeup product.
- When the cosmetic compositions according to the invention are for protecting the human epidermis against UV rays, or as an antisun (sunscreen) composition, these can be formulated as suspensions or dispersions in solvents or fatty substances, in the form of a nonionic vesicle dispersion or in the form of an emulsion, preferably of oil-in-water type, such as a cream or a milk, in the form of an ointment, a gel, a cream-gel, a solid tube, a stick, a lotion, an aerosol mousse or a spray.
- When the cosmetic compositions according to the invention are used for protecting the hair, same can be in the form of a shampoo, a lotion, a gel, an emulsion or a nonionic vesicle dispersion, and can constitute, for example, a rinse-out composition, to be applied before or after shampooing, before or after dyeing or bleaching, before, during or after permanent-waving or straightening the hair, a styling or treating lotion or gel, a blow-drying or hairsetting lotion or gel, or a permanent-waving, straightening, dyeing or bleaching composition for the hair.
- When the subject compositions are used as makeup product for the eyelashes, the eyebrows or the skin, such as an epidermal treatment cream, a foundation, a lipstick, an eyeshadow, a face powder, a mascara or an eyeliner, same can be in solid or pasty, anhydrous or aqueous form, such as oil-in-water or water-in-oil emulsions, nonionic vesicle dispersions or alternatively suspensions.
- For illustrative purposes, for the antisun formulations in accordance with the invention which contain a support of oil-in-water emulsion type, the aqueous phase (in particular comprising the hydrophilic screening agents) generally constituting from 50% to 95% by weight, preferably from 70% to 90% by weight, relative to the total weight of the overall formulation, the oily phase (in particular comprising the lipophilic screening agents) generally constitutes from 5% to 50% by weight, preferably from 10% to 30% by weight, relative to the entire formulation, and the (co)emulsifier(s) generally represent(s) from 0.5% to 20% by weight, preferably from 2% to 10% by weight, relative to the entire formulation.
- In order to further illustrate the present invention and the advantages thereof, the following specific examples are given, it being understood that same are intended only as illustrative and in nowise limitative.
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- 37.53 g (0.169 mol) of heptamethyltrisiloxane were added dropwise over 30 minutes to a solution of 3-(4-allyloxy-benzylidene)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one, prepared in accordance with Example 8 of FR-A-2,430,938 (50 g, 0.169 mol), and of catalyst (complex containing 3%-3.5% by weight of Pt in cyclovinylmethylsiloxane marketed by Hüls Petrarch PC085: 200 μl) in 140 ml of dry toluene heated to 80° C. The mixture was maintained at this temperature for 6 hours. The reaction mixture was concentrated. The residue was taken up in dichloromethane and this solution was passed through a bed of Celite. The pale yellow oil obtained was crystallized from heptane. 31 g (yield: 41%) of the target compound of this Example 1 were thus obtained in the form of a white powder:
- m.p.: 47°-48° C.
- UV (95% ethanol) λmax=318 nm, εmax=27,000
- Elemental analysis for C27H46O4Si3:
- Theory: C62.50 H8.94 Si16.24
- Found: C62.43 H9.00 Si16.26
-
- 12.2 g (0.055 mol) of heptamethyltrisiloxane were added dropwise over 30 minutes to a solution of 1,7,7-trimethyl-3-[4-(2-methylallyloxy)benzylidene] bicyclo[2.2.1]heptan-2-one (15.5 g, 0.05 mol) and catalyst (complex containing 3%-3.5% by weight of Pt in cyclovinylmethylsiloxane marketed by Hüls Petrarch PC085:100 μl) in 35 ml of dry toluene heated to 80° C. The mixture was maintained at this temperature for 3 hours. The reaction mixture was concentrated and, after chromatography on silica (eluent: 50/50 heptane/dichloromethane), 23 g (yield: 86%) of a colorless oil of the target compound of this Example 2 were obtained:
- UV (ethanol) λmax=320 nm, εmax=26,200
- Elemental analysis for C28H48O4Si3:
- Theory: C63.10 H9.08 Si15.81
- Found: C63.02 H9.00 Si15.64
-
- 50 g (0.117 mol) of α,ω-dodecamethyl-hexasiloxane were added dropwise over 1 hour, 30 minutes, to a solution of 1,7,7-trimethyl-3-[4-(2-methylallyl-oxy)benzylidene]bicyclo[2.2.1] heptan-2-one (69.8 g, 0.235 mol) and of catalyst (complex containing 3%-3.5% by weight of Pt in cyclovinylmethylsiloxane marketed by Hüls Petrarch PC085: 100 μl) in 110 ml of dry toluene heated to 80° C. The mixture was maintained at this temperature for 1 hour, 30 minutes. The reaction mixture was concentrated and, after chromatography on silica (eluent: 98/2 heptane/ethyl acetate followed by gradient up to 50/50 heptane/ethyl acetate), 47.5 g (yield: 40%) of a viscous, pale yellow oil of the target compound of this Example 3 was obtained:
- UV (ethanol) λmax=320 nm, εmax=26,200
- Elemental analysis for C52H86O9Si6:
Theory: C61.01 H8.47 Si16.46 Found: C61.04 H8.52 Si16.10 -
- A mixture of 3-(4-hydroxybenzylidene)1,7,7-trimethyl-N-bicyclo [2.2.1] heptan-2-one (10 g, 0.039 mol) and 3-glycidyloxypropyl-bis-(trimethylsiloxy) methylsilane (14.8 g, 0.044 mol) in the presence of tetrabutylammonium bromide (0.6 g) was maintained at 110° C. for 6 hours, while bubbling nitrogen there-through. The crude oil obtained was chromatographed on silica (eluent: 20/80 ethyl acetate/heptane) to give, in medium fractions, 10 g (yield: 43%) of the target compound of this Example 4 in the form of a colorless oil:
- UV (ethanol) λmax=318 nm, εmax=26,900
- Elemental analysis for C30H52O6Si3:
Theory: C60.76 H8.84 Si14.21 Found: C60.54 H8.87 Si13.96 -
- 5.37 g (0.0525 mol) of diethylmethylsilane were added dropwise over 20 minutes to a solution of 1,7,7-trimethyl-3-[4-(2-methylallyloxy)benzylidene] bicyclo[2.2.1] heptan-2-one (15.5 g, 0.05 mol) and of catalyst (complex containing 3%-3.5% by weight of Pt in cyclovinylmethylsiloxane marketed by Hüls Petrarch PC085: 200 μl) in 10 ml of dry toluene heated to 70° C. The mixture was maintained at this temperature for 48 hours. The reaction mixture was concentrated and, after chromatography on silica (eluent: heptane/ dichloromethane), 11.8 g (yield: 57%) of a viscous colorless oil of the target compound of this Example 5, which crystallized, were obtained:
- m.p.: 39°-40° C.
- UV (ethanol) λmax=320 nm, εmax=28,230
- Elemental analysis for C26H40O2Si:
Theory: C75.67 H9.77 Si6.81 Found: C75.42 H9.77 Si7.10 -
- (a) First step: Preparation of 3-methoxy-4-(3- trimethylsilanylpropyloxy) benzaldehyde
- 3-chloropropyltrimethylsilane (33.14 g, 0.22 mol) was added dropwise over 20 minutes to a mixture of vanillin (30.4 g, 0.2 mol) and potassium carbonate (30.4 g, 0.22 mol) in 150 ml of dry DMF heated to 80° C. under nitrogen. The mixture was maintained for 4 hours at 95°-110° C. The reaction mixture was cooled and poured into ice-cold water. The aqueous phase was extracted three times with dichloromethane. The organic phases were dried over sodium sulfate and concentrated under vacuum. After distillation under vacuum (0.04 mm Hg), 47.5 g (yield: 89%) of 3-methoxy-4-(3-trimethylsilanylpropyloxy) benzaldehyde were obtained in the form of a slightly pinkish oil distilling at 112°-114° C. and employed without further purification in the following step.
- (b) Second step: Preparation of the target compound of this Example 6
- A mixture of camphor (8.36 g, 0.055 mol) and NaH at 50% in oil (2.64 g, 0.055 mol; rinsed with dry heptane and then with dry dimethoxyethane) in 40 ml of dry dimethoxyethane was heated at 80° C. for 30 minutes. The step (a) derivative (13.32 g, 0.05 mol) dissolved in 30 ml of dimethoxyethane was added dropwise thereto over 20 minutes at 80° C. The mixture was maintained under stirring at 80° C. for 3 hours. After cooling, the mixture was poured into ice-cold water. The precipitate obtained was washed with water and then recrystallized from ethanol to give 12.4 g (yield: 62%) of the target compound of this Example 6 in the form of a white powder:
- m.p.: 79°-80° C.
- UV (ethanol) λmax=331 nm, εmax=21,300
- Elemental analysis for C24H36O3Si:
Theory: C71.95 H9.06 Si7.01 Found: C71.80 H9.05 Si6.80 -
- (a) First step: preparation of 4-(3-trimethylsilanylpropyloxy)benzaldehyde
- 3-chloropropyltrimethylsilane (33.14 g, 0.22 mol) was added dropwise over 10 minutes to a mixture of 4-hydroxybenzaldehyde (24.4 g, 0.2 mol) and potassium carbonate (30.4 g, 0.22 mol) in 150 ml of dry DMF maintained at 120° C. under nitrogen. The mixture was maintained for 2 hours, 30 minutes, at 120°-130° C. The reaction mixture was cooled and poured into ice-cold water. The aqueous phase was extracted 3 times with dichloromethane. The organic phases were dried over sodium sulfate and concentrated under vacuum. After distillation under vacuum (0.2 mmHg), 40.5 g (yield: 86%) of 4-(3-trimethylsilanylpropyloxy) benzaldehyde were obtained in the form of a colorless oil distilling at 110-114° C. and employed without further purification in the following step.
- (b) Second step: preparation of the target compound of this Example 7
- A mixture of camphor (15.2 g, 0.1 mol) and NaH at 50% in oil (4.8 g, 0.1 mol); rinsed with dry heptane and then with dry dimethoxyethane) in 50 ml of dry dimethoxyethane were heated at 80° C. for 30 minutes. The above step (a) derivative (21.3 g, 0.09 mol) dissolved in 30 ml of diethoxyethane was added dropwise thereto over 20 minutes at 80° C. The mixture was maintained under stirring at 80° C. for 2 hours. After cooling, the mixture was poured into ice-cold water. The precipitate obtained was washed with water and then recrystallized from ethanol to give 20.6 g (yield: 60%) of the target compound of this Example 7 in the form of a white powder:
- m.p.: 100°-101° C.
- UV (ethanol) λmax=320 nm, εmax=26,530
- Elemental analysis for C23H34O2Si:
Theory: C74.54 H9.25 Si7.58 Found: C74.62 H9.17 Si7.80 - The compositions described below were formulated (the amounts are expressed as a % by weight relative to the total weight of the composition):
- Composition A (comparative)
Ingredients Composition A Isopropyl myristate 30 Parsol 1789 1.5 Ethanol q.s. 100 - Composition A′ (comparative)
Ingredients Composition A′ Isopropyl myristate 30 3-(4-methylbenzylidene- 5 camphor (Eusolex 6300) Parsol 1789 1.5 Ethanol q.s. 100 - The following compositions B to E (according to the present invention) also comprised 5% by weight of a silicone benzylidenecamphor compound of this invention.
Composition Composition Composition Composition Ingredients B C D E Isopropyl 30 30 30 30 myristate Parsol 1789 1.5 1.5 1.5 1.5 Silicone Example 5 Example 6 Example 7 Example 2 benzyl-idene- camphor according to the invention Ethanol qs 100 qs 100 qs 100 qs 100 - For each of these compositions, the percentage of residual Parsol 1789 (4-tert-butyl-4′-methoxydibenzoylmethane) after irradiation with UV according to the following procedure was determined: for each formula, three control samples and three test samples were prepared. 2 μl/cm2 of formula were spread by hand onto frosted glass plates. The plates were then exposed in a chamber, the temperature of which was adjusted to about 35°-40° C. (Heraeus Suntest CPS), for the time required to obtain an exposure, expressed relative to the UVA flux, of 30 J/cm2, in order to simulate natural UV irradiation by storing the control plates in darkness during the period of irradiation of the other plates.
- The samples were then assayed in the following manner: the screening agents were extracted by immersing each plate in 50 g of ethanol in order to dissolve the screening agents. The plates and the solvent containing the screening agents were then treated with ultrasound for 15 minutes in order to ensure efficient extraction. The solutions obtained were analyzed by spectrophotometry at the λmax of each of the screening agents.
- For each test formula, the level of residual 4-tert-butyl-4′-methoxydibenzoylmethane after irradiation was given by the ratio of its concentration in the irradiated sample to its concentrated in the non-irradiated sample.
- The results, as a percentage of 4-tert-butyl-4′-methoxydibenzoylmethane remaining, are reported in the Table below:
TABLE OD % of residual Composition Parsol 1789 Composition A (comparative) 5 ± 1 Composition A′ (comparative) 58.8 Composition B (invention) 76 ± 6 Composition C (invention) 81 ± 6 Composition D (invention) 79 ± 7 Composition E (invention) 69 ± 3 - These results clearly evidenced that the presence of a silane or organosilxane compound containing a benzylidenecamphor group improved the photostability of 4-tert-butyl-4′-methoxydibenzoylmethane.
- These results also evidenced that the photostability of 4-tert-butyl-4′-methoxydibenzoyl-methane obtained in the presence of a hydrocarbon-based benzylidenecamphor compound was further improved by formulating therewith, in place of the latter compound, silane or organosiloxane compounds containing a benzylidenecamphor group.
- While the invention has been described in terms of various preferred embodiments, the skilled artisan will appreciate that various modifications, substitutions, omissions, and changes may be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the present invention be limited solely by the scope of the following claims, including equivalents thereof.
Claims (34)
1. A method for photostabilizing a topically applicable cosmetic/dermatological sunscreen composition suited for the uv-photoprotection of human skin and/or hair comprising a photoprotecting effective amount of at least one dibenzoylmethane UV-screening compound, said method comprising admixing into said composition an amount of at least one silane or organosiloxane substituted by a benzylidenecamphor functional group effective to photostabilize said at least one dibenzoylmethane UV-screening compound.
2. The method as defined by , wherein said at least one silane or organosiloxane substituted by a benzylidenecamphor functional group has the structural formula (I):
claim 1
in which the radicals R1, which may be identical or different, are each a hydrogen atom, an OH radical, a saturated or unsaturated, linear or branched, C1-C10 alkyl radical, a linear or branched C1CO10 alkoxy radical or an —OSi(CH3)3 radical, with the proviso that two adjacent groups R1 may together form an alkylidenedioxy group in which the alkylidene radical contains 1 or 2 carbon atoms; a is an integer ranging from 1 to 3; A is a hydrogen atom or a radical of the formula —L—W wherein L is a divalent radical of formula (IIa) or (lIb) below:
—CH2—CHR2—[C(R3)2]m—(CO)n—(O)o—(Z)p—(Y)q— (IIa) —CH=CR2—[C(R3)2]m—(CO)n—(O)o—(Z)p—(Y)q— (IIb)
in which the radicals R2 and R3, which may be identical or different, are each a hydrogen atom or a linear or branched C1-C5 alkyl radical, Z is a linear or branched, saturated or unsaturated C1-C6 diyl radical, optionally substituted with a hydroxyl or linear or branched, saturated or unsaturated C2-C8 alkyl radical, Y is —O—, —NR4—, —SO2NH—, —(CO)O—, —(CO)NH— or —O(CO)NH—, wherein R4 is a hydrogen atom or a C1-C5 alkyl radical; m is an integer ranging from 0 to 10; n is 0 or 1; o is 0 or 1; p is 0 or 1; q is 0 or 1; A1 is a hydrogen atom or a radical —L1—W in which the radical L1 has the definition of L, with the proviso that, when q=1, then Y is —SO2NH—, with the further proviso that only one of the two radicals A and A1 is a hydrogen atom; W is a radical of formula (1), (2) or (3) below:
in which the radicals R6, which may be identical or different, are each a linear or branched C1-C30 alkyl, phenyl, 3,3,3-trifluoropropyl or trimethylsilyloxy radical, at least 80%, by number, of the radicals R6 being methyl radicals; the radicals B, which may be identical or different, are each a radical R6 or a radical X of the formula below:
in which R1, L, L1 and a are as defined above; r is an integer ranging from 0 to 200, inclusive, and s is an integer ranging from 0 to 50, inclusive, and, if s=0, at least one of the two symbols B is X; u is an integer ranging from 1 to 10, inclusive, and t is an integer ranging from 0 to 10, inclusive, with the proviso that t+u is greater than or equal to 3.
3. The method as defined in , wherein in formula (I), at least one of the following conditions is satisfied:
claim 2
R1=H, OCH3, CH3 or two adjacent radicals R1 together form a methylenedioxy group;
R2=H or CH3,
n=0,
q=1.
4. The method as defined by , wherein in formula (I), at least one of the following conditions is satisfied:
claim 2
R6 is methyl;
B is methyl;
r ranges from 5 to 20, inclusive;
s ranges from 2 to 15, inclusive;
t+u ranges from 3 to 10, inclusive;
m=1;
R3 is a hydrogen atom or a methyl radical.
5. The method as defined by , wherein in formula (I), s=0.
claim 2
7. The method as defined by , wherein in formula (I), p is equal to 1 and the radical Z is a linear or branched, saturated or unsaturated C1-C6 diyl radical substituted by a hydroxyl or linear or branched, saturated or unsaturated C2-C8 alkyl radical.
claim 2
9. The method as defined by , wherein in formula (I), W is a radical of formula (3) and n=0.
claim 2
11. The method as defined by , wherein said at least one dibenzoylmethane UV-screening compound comprises
claim 2
2-methyldibenzoylmethane,
4-methyldibenzoylmethane,
4-isopropyldibenzoylmethane,
4-tert-butyldibenzoylmethane,
2,4-dimethyldibenzoylmethane,
2,5-dimethyldibenzoylmethane,
4,4′- diisopropyldibenzoylmethane,
4,4′-dimethoxydibenzoylmethane,
4-tert-butyl-4′-methoxydibenzoylmethane,
2-methyl-5-isopropyl-4′-methoxydibenzoylmethane,
2-methyl-5-tert-butyl-4′-methoxydibenzoylmethane,
2,4-dimethyl-4′-methoxydibenzoylmethane, and/or
2,6-dimethyl-4-tert-butyl-4′-methoxydibenzoylmethane.
12. The method as defined by , wherein said at least one dibenzoylmethane UV-screening compound comprises 4-(tert-butyl)-4′-methoxydibenzoylmethane.
claim 11
13. The method as defined by , wherein said at least one dibenzoylmethane UV-screening compound comprises 4-isopropyldibenzoylmethane.
claim 11
14. The method as defined by , wherein said composition is formulated into a topically applicable, cosmetically/dermatologically acceptable vehicle, diluent or carrier therefor.
claim 1
15. The method as defined by , wherein said composition comprises from 0.01%to 10% by weight of said at least one dibenzoylmethane UV-screening compound.
claim 1
16. The method as defined by , wherein said composition comprises from 0.01% to 6% by weight of said at least one dibenzoylmethane UV-screening compound.
claim 1
17. The method as defined by , wherein said composition comprises at least 0.5% by weight of said at least one substituted silane or organosiloxane.
claim 15
18. The method as defined by , wherein said composition comprises from 0.5% to 20% by weight of said at least one substituted silane or organosiloxane.
claim 15
22. The method as defined by , wherein said composition comprises an oil-in-water emulsion.
claim 1
23. The method as defined by , wherein said composition comprises a water-in-oil emulsion.
claim 1
24. The method as defined by , wherein said composition further comprises at least one additional hydrophilic or lipophilic organic UV-A and/or UV-B sunscreen.
claim 1
25. The method as defined by , wherein said composition further comprises at least one cinnamic derivative, salicylic derivative, triazine derivative, benzotriazole derivative, benzimidazole derivative, benzophenone derivative, β,β-diphenylacrylate derivative, p-aminobenzoic acid derivative, sunscreen polymer, or sunscreen silicone.
claim 24
26. The method as defined by , wherein said composition further comprises a photoprotecting effective amount of particulates of at least one inorganic pigment or nanopigment.
claim 1
27. The method as defined by , wherein said at least one pigment or nanopigment comprises titanium dioxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide, or mixture thereof.
claim 26
28. The method as defined by , wherein said composition further comprises at least one active agent for the artificial tanning and/or browning of human skin.
claim 1
29. The method as defined by , wherein said composition further comprises at least one cosmetically acceptable adjuvant or additive.
claim 1
30. The method as defined by , wherein said at least one adjuvant or additive comprises a fat, organic solvent, ionic or nonionic thickening agent, softener, antioxidant, anti-free-radical antioxidant, opacifying agent, stabilizing agent, emollient, silicone, hydroxy acid, anti-foaming agent, hydrating agent, vitamin, fragrance, preservative, surfactant, filler, sequestering agent, polymer, propellant, basifying of acidifying agent, dye colorant, or mixture thereof.
claim 29
31. The method as defined by , wherein said composition comprises a nonionic vesicle dispersion, emulsion, cream, milk, gel, cream gel, ointment, suspension, dispersion, powder, solid stick, foam or spray.
claim 1
32. The method as defined by , wherein said composition comprises a makeup.
claim 1
33. The method as defined by , wherein said composition comprises an anhydrous or aqueous solid or paste, emulsion, suspension, or dispersion.
claim 32
34. The method as defined by , wherein said composition comprises a shampoo, lotion, gel, emulsion, non-ionic vesicle dispersion, hair lacquer, or rinse.
claim 1
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/761,827 US6312673B2 (en) | 1998-07-10 | 2001-01-18 | Photostabilized sunscreen compositions comprising dibenzoylmethane compounds and benzylidenecamphor-substituted silanes/organosiloxanes |
US09/960,388 US6429326B1 (en) | 1998-07-10 | 2001-09-24 | Benzylidenecamphor-substituted silanes/organosiloxanes for use in photostabilizing sunscreen compositions comprising dibenzoylmethane compounds |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9808937 | 1998-07-10 | ||
FR9808937A FR2780975B1 (en) | 1998-07-10 | 1998-07-10 | METHOD FOR PHOTOSTABILIZING SUN FILTERS DERIVED FROM DIBENZOYLMETHANE, PHOTOSTABILIZED FILTERING COSMETIC COMPOSITIONS OBTAINED THUS AND THEIR USES |
FR98-08937 | 1998-07-10 | ||
US09/350,910 US6200552B1 (en) | 1998-07-10 | 1999-07-12 | Photostabilized sunscreen compositions comprising dibenzoylmethane compounds |
US09/761,827 US6312673B2 (en) | 1998-07-10 | 2001-01-18 | Photostabilized sunscreen compositions comprising dibenzoylmethane compounds and benzylidenecamphor-substituted silanes/organosiloxanes |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/350,917 Division US6214518B1 (en) | 1998-07-10 | 1999-07-12 | Negative type image recording material and method of plate-making using the same |
US09/350,910 Division US6200552B1 (en) | 1998-07-10 | 1999-07-12 | Photostabilized sunscreen compositions comprising dibenzoylmethane compounds |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US09/960,388 Division US6429326B1 (en) | 1998-07-10 | 2001-09-24 | Benzylidenecamphor-substituted silanes/organosiloxanes for use in photostabilizing sunscreen compositions comprising dibenzoylmethane compounds |
Publications (2)
Publication Number | Publication Date |
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US20010026789A1 true US20010026789A1 (en) | 2001-10-04 |
US6312673B2 US6312673B2 (en) | 2001-11-06 |
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Application Number | Title | Priority Date | Filing Date |
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US09/350,910 Expired - Fee Related US6200552B1 (en) | 1998-07-10 | 1999-07-12 | Photostabilized sunscreen compositions comprising dibenzoylmethane compounds |
US09/761,827 Expired - Fee Related US6312673B2 (en) | 1998-07-10 | 2001-01-18 | Photostabilized sunscreen compositions comprising dibenzoylmethane compounds and benzylidenecamphor-substituted silanes/organosiloxanes |
US09/960,388 Expired - Fee Related US6429326B1 (en) | 1998-07-10 | 2001-09-24 | Benzylidenecamphor-substituted silanes/organosiloxanes for use in photostabilizing sunscreen compositions comprising dibenzoylmethane compounds |
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US09/350,910 Expired - Fee Related US6200552B1 (en) | 1998-07-10 | 1999-07-12 | Photostabilized sunscreen compositions comprising dibenzoylmethane compounds |
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US09/960,388 Expired - Fee Related US6429326B1 (en) | 1998-07-10 | 2001-09-24 | Benzylidenecamphor-substituted silanes/organosiloxanes for use in photostabilizing sunscreen compositions comprising dibenzoylmethane compounds |
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US (3) | US6200552B1 (en) |
EP (1) | EP0970961B1 (en) |
JP (2) | JP3516614B2 (en) |
CA (1) | CA2277691A1 (en) |
DE (1) | DE69900089T2 (en) |
FR (1) | FR2780975B1 (en) |
Cited By (5)
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DE10233963A1 (en) * | 2002-07-25 | 2004-02-12 | Itn-Nanovation Gmbh | Use of silanes in cosmetic products and methods for hair treatment |
US7108860B2 (en) | 2002-06-06 | 2006-09-19 | Playtex Products, Inc. | Sunscreen compositions |
US8540976B2 (en) | 2009-04-01 | 2013-09-24 | University Of Florida Research Foundation, Inc. | Poly (non-conjugated diene) based sunscreens |
CN104706545A (en) * | 2015-01-29 | 2015-06-17 | 国家电网公司 | Sun screening agent hydrogel composition, and preparation method and application thereof |
EP2970593A4 (en) * | 2013-03-14 | 2016-08-17 | Momentive Performance Mat Inc | High refractive index siloxanes |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2780975B1 (en) | 1998-07-10 | 2002-02-15 | Oreal | METHOD FOR PHOTOSTABILIZING SUN FILTERS DERIVED FROM DIBENZOYLMETHANE, PHOTOSTABILIZED FILTERING COSMETIC COMPOSITIONS OBTAINED THUS AND THEIR USES |
USPP13485P2 (en) | 1999-06-01 | 2003-01-21 | Florfis Ag | Geranium plant named ‘Fisrosimo’ |
BR0207731A (en) * | 2001-03-02 | 2004-03-23 | Merck Patent Gmbh | Cosmetic formulation comprising flavonoid derivatives |
FR2886144B1 (en) * | 2005-05-27 | 2007-06-29 | Oreal | METHOD FOR PHOTOSTABILIZING A DIBENZOYLMETHANE DERIVATIVE WITH A MEROCYANINE SULFONE DERIVATIVE; PHOTOPROTECTIVE COSMETIC COMPOSITIONS CONTAINING THE SAME. |
FR2908987B1 (en) * | 2006-11-28 | 2009-01-23 | Oreal | PHOTOPROTECTIVE COMPOSITION CONTAINING A PHOTOSENSITIVE 1,3,5-TRIAZINE DERIVATIVE, A DIBENZOYLMETHANE DERIVATIVE, AND S-TRIAZINE SILICATED AND SUBSTITUTED BY TWO AMINOBENZATIC OR AMINOBENZAMIDE GROUPS |
US8128913B1 (en) | 2007-12-06 | 2012-03-06 | Skinvisible Pharmaceuticals, Inc. | Sunscreen composition with enhanced UV-A absorber stability and methods |
JP4299878B1 (en) | 2008-10-06 | 2009-07-22 | 株式会社パラエルモサ | Cosmetics |
KR101997870B1 (en) * | 2017-12-06 | 2019-07-09 | 주식회사 세라수 | Organic-inorganic complex, Manufacturing method thereof and UV blocking agents using the same |
Family Cites Families (10)
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LU87180A1 (en) * | 1988-03-28 | 1989-10-26 | Oreal | COSMETIC USE OF DIORGANOPOLYSILOXANES WITH A BENZYLIDENE-3 CAMPHER FUNCTION AND NOVEL COSMETIC COMPOSITIONS CONTAINING THESE COMPOUNDS FOR PROTECTION OF THE SKIN AND HAIR |
FR2684551B1 (en) | 1991-12-05 | 1995-04-21 | Oreal | COSMETIC FILTERING OIL CONTAINING A FILTERED SILICONE AND A MIXTURE OF A VOLATILE SILICONE AND A SILICONE OIL OR A SILICONE GUM AND COSMETIC FILTERING EMULSION CONTAINING SUCH AN OIL. |
WO1994004131A1 (en) * | 1992-08-13 | 1994-03-03 | The Procter & Gamble Company | Photostable sunscreen compositions |
EP0709080B1 (en) | 1994-10-14 | 2002-01-30 | F. Hoffmann-La Roche Ag | Photostable cosmetic light screening compositions |
US6004540A (en) * | 1994-11-17 | 1999-12-21 | Societe L'oreal S.A. | Photoprotective/cosmetic compositions comprising sulfonamido-functional polyorganosiloxanes/polyorganosilanes |
FR2727115B1 (en) * | 1994-11-17 | 1996-12-27 | Oreal | NOVEL SOLAR FILTERS, PHOTOPROTECTIVE COSMETIC COMPOSITIONS CONTAINING THEM AND USES THEREOF |
US5605600A (en) | 1995-03-13 | 1997-02-25 | International Business Machines Corporation | Etch profile shaping through wafer temperature control |
FR2760464B1 (en) | 1997-03-07 | 2005-07-01 | Oreal | PROCESS FOR IMPROVING THE PHOTOSTABILITY OF A DIBENZOYLMETHANE DERIVATIVE BY SILANE, BENZALMALONATE, PROCESS FOR THE PREPARATION OF BENZALMALONATE SILANES |
US5921968A (en) * | 1997-11-25 | 1999-07-13 | Merit Medical Systems, Inc. | Valve apparatus with adjustable quick-release mechanism |
FR2780975B1 (en) | 1998-07-10 | 2002-02-15 | Oreal | METHOD FOR PHOTOSTABILIZING SUN FILTERS DERIVED FROM DIBENZOYLMETHANE, PHOTOSTABILIZED FILTERING COSMETIC COMPOSITIONS OBTAINED THUS AND THEIR USES |
-
1998
- 1998-07-10 FR FR9808937A patent/FR2780975B1/en not_active Expired - Fee Related
-
1999
- 1999-06-04 DE DE69900089T patent/DE69900089T2/en not_active Expired - Fee Related
- 1999-06-04 EP EP99401354A patent/EP0970961B1/en not_active Expired - Lifetime
- 1999-07-09 CA CA002277691A patent/CA2277691A1/en not_active Abandoned
- 1999-07-12 JP JP19762099A patent/JP3516614B2/en not_active Expired - Fee Related
- 1999-07-12 US US09/350,910 patent/US6200552B1/en not_active Expired - Fee Related
-
2001
- 2001-01-18 US US09/761,827 patent/US6312673B2/en not_active Expired - Fee Related
- 2001-09-24 US US09/960,388 patent/US6429326B1/en not_active Expired - Fee Related
-
2003
- 2003-09-24 JP JP2003332136A patent/JP2004107349A/en active Pending
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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US7108860B2 (en) | 2002-06-06 | 2006-09-19 | Playtex Products, Inc. | Sunscreen compositions |
DE10233963A1 (en) * | 2002-07-25 | 2004-02-12 | Itn-Nanovation Gmbh | Use of silanes in cosmetic products and methods for hair treatment |
US20060110351A1 (en) * | 2002-07-25 | 2006-05-25 | Sabine Koehler | Use of silanes on cosmetic agents and methods for treating hair |
US8540976B2 (en) | 2009-04-01 | 2013-09-24 | University Of Florida Research Foundation, Inc. | Poly (non-conjugated diene) based sunscreens |
EP2970593A4 (en) * | 2013-03-14 | 2016-08-17 | Momentive Performance Mat Inc | High refractive index siloxanes |
US9963469B2 (en) | 2013-03-14 | 2018-05-08 | Momentive Performance Materials Inc. | High refractive index siloxanes |
US10570162B2 (en) | 2013-03-14 | 2020-02-25 | Momentive Performace Materials Inc. | High refractive index siloxanes |
CN104706545A (en) * | 2015-01-29 | 2015-06-17 | 国家电网公司 | Sun screening agent hydrogel composition, and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
DE69900089T2 (en) | 2001-09-13 |
EP0970961B1 (en) | 2001-04-25 |
FR2780975B1 (en) | 2002-02-15 |
FR2780975A1 (en) | 2000-01-14 |
CA2277691A1 (en) | 2000-01-10 |
DE69900089D1 (en) | 2001-05-31 |
US6312673B2 (en) | 2001-11-06 |
JP2001039846A (en) | 2001-02-13 |
US6429326B1 (en) | 2002-08-06 |
US6200552B1 (en) | 2001-03-13 |
JP3516614B2 (en) | 2004-04-05 |
JP2004107349A (en) | 2004-04-08 |
EP0970961A1 (en) | 2000-01-12 |
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