CN1050361C - 滤光剂,含该滤光剂的防晒化妆组合物及其用途 - Google Patents
滤光剂,含该滤光剂的防晒化妆组合物及其用途 Download PDFInfo
- Publication number
- CN1050361C CN1050361C CN95120080A CN95120080A CN1050361C CN 1050361 C CN1050361 C CN 1050361C CN 95120080 A CN95120080 A CN 95120080A CN 95120080 A CN95120080 A CN 95120080A CN 1050361 C CN1050361 C CN 1050361C
- Authority
- CN
- China
- Prior art keywords
- formula
- compound
- group
- hydrogen
- following formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002537 cosmetic Substances 0.000 title claims abstract description 32
- 238000001914 filtration Methods 0.000 title claims abstract description 26
- 239000000516 sunscreening agent Substances 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 title claims description 48
- 239000003795 chemical substances by application Substances 0.000 title description 20
- -1 3,3,3-trifluoropropyl Chemical group 0.000 claims abstract description 54
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 71
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000003223 protective agent Substances 0.000 claims description 8
- 239000003581 cosmetic carrier Substances 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 210000004209 hair Anatomy 0.000 abstract description 21
- 125000000217 alkyl group Chemical group 0.000 abstract description 11
- 239000012964 benzotriazole Substances 0.000 abstract description 9
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 abstract description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 7
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract description 7
- 239000012965 benzophenone Substances 0.000 abstract description 7
- 229910000077 silane Inorganic materials 0.000 abstract description 7
- 230000000475 sunscreen effect Effects 0.000 abstract description 7
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 abstract description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- OIQXFRANQVWXJF-QBFSEMIESA-N (2z)-2-benzylidene-4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical compound CC1(C)C2CCC1(C)C(=O)\C2=C/C1=CC=CC=C1 OIQXFRANQVWXJF-QBFSEMIESA-N 0.000 abstract description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 27
- 210000003491 skin Anatomy 0.000 description 18
- 230000003287 optical effect Effects 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical class C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000006459 hydrosilylation reaction Methods 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 241000723346 Cinnamomum camphora Species 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 6
- 229930008380 camphor Natural products 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229960000846 camphor Drugs 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 235000019197 fats Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000006071 cream Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000000565 sulfonamide group Chemical group 0.000 description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 206010015150 Erythema Diseases 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- RCFKEIREOSXLET-UHFFFAOYSA-N disulfamide Chemical compound CC1=CC(Cl)=C(S(N)(=O)=O)C=C1S(N)(=O)=O RCFKEIREOSXLET-UHFFFAOYSA-N 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 231100000321 erythema Toxicity 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 235000013599 spices Nutrition 0.000 description 3
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 239000004166 Lanolin Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 229940039717 lanolin Drugs 0.000 description 2
- 235000019388 lanolin Nutrition 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002453 shampoo Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical group NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 229940099259 vaseline Drugs 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical class NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 206010011469 Crying Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- AKQOBHZKBDHWQI-BZEFIUHZSA-N O[C@H]1C[C@@H](CCC1)N1C(C2(C3=C1N=C(N=C3)NC1=CC=C(C=C1)S(=O)(=O)NC([2H])([2H])[2H])CC2)=O Chemical compound O[C@H]1C[C@@H](CCC1)N1C(C2(C3=C1N=C(N=C3)NC1=CC=C(C=C1)S(=O)(=O)NC([2H])([2H])[2H])CC2)=O AKQOBHZKBDHWQI-BZEFIUHZSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 206010053615 Thermal burn Diseases 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000000172 allergic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229940127108 compound 5g Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000490 cosmetic additive Substances 0.000 description 1
- 239000008278 cosmetic cream Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- QXFRSYUSOOWTIF-UHFFFAOYSA-N diphenylmethanone;sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 QXFRSYUSOOWTIF-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- DLAHAXOYRFRPFQ-UHFFFAOYSA-N dodecyl benzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1 DLAHAXOYRFRPFQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 210000000720 eyelash Anatomy 0.000 description 1
- 210000000744 eyelid Anatomy 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003292 glue 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
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 235000019866 hydrogenated palm kernel oil Nutrition 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000002752 melanocyte Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JPQBRSQJGWOTGC-UHFFFAOYSA-N methyl(silyloxysilyloxy)silane Chemical class C[SiH2]O[SiH2]O[SiH3] JPQBRSQJGWOTGC-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940056211 paraffin Drugs 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 231100000075 skin burn Toxicity 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- 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
- A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
- A61K8/899—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing sulfur, e.g. sodium PG-propyldimethicone thiosulfate copolyol
-
- 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
- C07F7/0803—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
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- 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
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Dermatology (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Cosmetics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
本发明提出链状或环状短链二或三有机硅氧烷类新化合物,其中包括含有选自3-亚苄基樟脑衍生物,苯并三唑,二苯甲酮和苯并咪唑的磺酰胺官能团的滤光单元,这些化合物尤其可在旨在保护皮肤和毛发、使其不受紫外光线照射的化妆组合物中用作有机防晒剂或光保护剂。本发明还涉及上述化合物在上述化妆方面的用途以及含有这些化合物的高性能化妆组合物。
Description
本发明涉及新的链状或环状短链二有机(聚)硅氧烷类或三有机硅烷类化合物,这些化合物具有所有包括至少一个特殊和适当选定的并且含磺酰胺官能团的滤光或防晒或防光照单元的化合物的共同特征,这些化合物尤其可在旨在保护皮肤和头发或毛发、使其不受紫外线照射的化妆组合物中用作为有机防晒剂或有机滤光剂或有机防光照剂,或称为光保护剂。本发明还涉及这些化合物在上述化妆领域中的应用或用途以及含有这些化合物的高性能或高品质化妆组合物。
已知受波长为280-400nm的光线照射可使人体皮肤或表皮晒黑,尤其是波长为280-320nm的光线,也称为UV-B的光线可引起红斑并使皮肤灼伤,而这会妨碍天然黑色或黑素的产生或形成,因此应当滤出或滤除UV-B光线。
还已知可使皮肤晒黑的波长为320-400nm的UV-A光线容易诱使皮肤产生不利的变化,尤其是在过敏性皮肤或连续受阳光照射的皮肤情况下就更是如此。更具体地讲,UV-A光线可使皮肤失去弹性并且出现皱纹,从而导致皮肤过早衰老或老化。这类光线在某些个案情况下更有助于引发红斑反应或加剧这种反应,甚至可成为光中毒或光过敏反应的根源。因此,也需要滤出或滤除UV-A光线。
为保护皮肤、使其免受(UV-A和/或UV-B)光照,到目前为止,已提出许多化合物。
大多数这类化合物均为芳族或芳香化合物,可在280-315nm范围内或在315-400nm范围内或在这两个范围内吸收UV光线。这些化合物通常配制成防阳光照射或防晒组合物,其形式为水包油类乳液(即由连续分散水相和不连续分散油相构成的化妆用载体),该组合物因此可含有各种浓度的一或多种常用有机滤光剂,这些滤光剂可选择性吸收有害的UV光线,其中含有亲脂和/或亲水芳族官能团,这些滤光剂(及其用量)可根据所要求的保护因子进行选择(在数学上,保护因子(IP)可表示为在用UV滤光剂的情况下开始产生红斑所需光照时间与不用UV滤光剂的情况下开始产生红斑所需光照时间之比)。
除了其滤光能力而外,这些具有抗UV活性的化合物还应当具有在含有这些化合物的组合物中显示出优良化妆性能,在常用溶剂,尤其是脂肪物质如油和脂中的优良溶解性以及优良的耐水耐汗性(持久保持)。
在为此提出的所有化合物中,尤其可举出对氨基苯甲酸衍生物,亚苄基(或苯亚甲基)樟脑衍生物,特别是3-亚苄基(或苯亚甲基)樟脑衍生物,肉桂酸衍生物和苯并三唑衍生物。但是,有些这类物质并不具有在防阳光照射或防晒组合物中用作UV滤光剂所要求的全部性能。更具体地讲,这些化合物固有的滤光能力不足,在用于防阳光照射的各种配方中的溶解性(尤其是其脂溶性)也并不总是足够高,另外这些化合物受光照的稳定性(光稳定性)可能不够高并且其耐水和耐汗性也可能差。而且,还要求这些滤光物质不会渗透进入皮肤。
因此,在苯并三唑或3-亚苄基(或苯亚甲基)樟脑类滤光物质的更具体情况下,一直在寻求获得其性能,尤其是其脂溶性和化妆性能得以提高的产品,其中用亚烷基或亚烷氧基类连接链单元通过接枝(氢化硅烷化)将苯并三唑或3-亚苄基(或苯亚甲基)樟脑滤光基团连到(聚)硅氧烷(有机聚硅氧烷)类大分子链上。这项技术已分别记载在专利申请EP-A-0,392,883(苯并三唑)和EP-A-0,335,777(3-亚苄基(或苯亚甲基)樟脑)之中,这两项申请均为本申请人的申请,已证实应用该技术可得到有效的化合物(这些化合物一般称为“滤光性(聚)硅氧烷”或“(聚)硅氧烷类滤光剂”),但是这些化合物的脂溶性仍显不足,而且为了用这类产品获得令人满意的滤光性能,常需应用相当大量的这类聚合物,这也通过含有这些化合物的配方显示出不良或差的化妆性能而反映出来。
本发明旨在克服或解决上述问题,其中提出含有特殊滤光单元的滤光性(聚)硅氧烷类新化合物,这些化合物的性能,尤其是其在脂肪物质中的溶解性和其化妆性能均得到提高。
更具体地讲,本发明已发现通过含有磺酰胺官能团的特殊连接链单元经过接枝过程,尤其是经过氢化硅烷化反应将一或多个选自3-亚苄基(或苯亚甲基)樟脑衍生物,苯并三唑,二苯甲酮和苯并咪唑的特殊滤光单元连接到适当选定的链状或环状(聚)硅氧烷链上或连接到适当选定的硅烷上,就能够获得滤光性(聚)硅氧烷类新化合物,从而消除或克服现有技术中滤光性(聚)硅氧烷类化合物的缺点。更具体地讲,不管是在UV-A范围内还是在UV-B范围内,根据其化学结构,这些化合物均具有很高的滤光性能,而且在常用有机溶剂,尤其是脂肪物质如油中具有极好的溶解性,此外还有优异的化妆性能,这使其特别适宜于在旨在保护皮肤和/或毛发、使其不致于受紫外线照射的化妆组合物中用作为防光照或防晒剂或光保护剂,或者用于制备这种化妆组合物。
A-Si(R′)3 (3)式(1)至(3)中:
R可相同或不同,选自C1-C10烷基,苯基和3,3,3-三氟丙基,其中按数目计至少80%的R是甲基,
B可相同或不同,选自上述基团R和下述基团A,
R’可相同或不同,选自C1-C8烷基或苯基,
r是0-50的整数(含0和50),s是0-20的整数(含0和20),条件是如果s是0,则两个基团B中至少一个是A,
u是1-6的整数(含1和6),t是0-10的整数(含0和10),其中应当使t+u等于或大于3,
并且A是与硅原子直接相连的基团,该基团如下列式(4.1)至(4.4)之一所示:式(4.1)中:
R1是氢或C1-C4烷基或羟烷基,
R2是氢或C1-C6烷基或C1-C6烷氧基,
p是1-10的整数(含1和10),
端部-CH2-直接与硅原子相连;
式(4.1)中应注意的是:
X1,X2和X3之一必须是二价基团-Y-,并且其它两个基团均不能是二价基团-Y-,
如果X1是氢,X2和X3须不同并且都不能是基团Z,
如果X1是二价基团-Y-,X2和X3不能同时是基团Z,
式(4.2)中:
*X4是氢,C1-C8烷基或二价基团-Y-,
*X5是氢或卤原子,C1-C4烷基或烷氧基或二价基团-Y-,
*R3是C1-C8烷基,
式(4.2)中应注意的是:
上式(1)和(3)中,A为选自3-亚苄基(或苯亚甲基)樟脑衍生物(式4.1),苯并三唑(式4.2),苯并咪唑(式4.3)和二苯甲酮(式4.4)的滤光基团,在将其连到初始(聚)硅氧烷短链上或连到初始硅烷上之后可使链状二有机(聚)硅氧烷类化合物(式(1))或环状二有机(聚)硅氧烷类化合物(式(2))或三有机硅烷类化合物(式(3))对波长范围为280-400nm的紫外光线具有吸收性能。如上所述,并且如上列式(4.1)至(4.4)的定义所示,该基团须带有至少一个磺酰胺官能团(式5),该官能团由可保证将滤光单元连接到(聚)硅氧烷链上或连接到硅烷上的链单元提供。本发明化合物,尤其是滤光单元A如式(4.1)或式(4.2)所示的化合物的优点之一在于可根据该滤光单元A所带有的各种取代基的性质和/或位置而获得既可纯粹滤出或滤除UV-A或相反纯粹滤出或滤除UV-B并且具有特别高的消光系数的制剂。
正如上列定义所示,链单元-SO2-N(R1)-(CH2)P-CH(R2)-CH2-(即如式(5)所示带磺酰胺官能团的二价基团-Y-)可根据本发明连接到来自3-亚苄基(或苯亚甲基)樟脑的滤光单元上,该单元因而保证上列单元与(聚)硅氧烷链或硅烷中的硅原子相连,该连接可在由X1,X2和X3占据的位置中任何一个位置上进行,而所说链单元中的-SO2-端部则与来自3-亚苄基(或苯亚甲基)樟脑的单元相连,并且其-CH2-端部则与(聚)硅氧烷链或硅烷中的硅原子相连。而且,在所用滤光单元为3-亚苄基(或苯亚甲基)樟脑衍生物的特殊情况下,还应当注意到的是:该滤光单元可任选具有两个连接链单元(在X1是二价基团-Y-时和在X2或X3同时是带有这一相同二价基团-Y-的基团Z时,这可能是有效的),因而可连到两条不同的(聚)硅氧烷链上或连到两个不同的甲硅烷基化单元上。
在苯并三唑类(式4.2)或苯并咪唑类(式4.3)或二苯甲酮类(式4.4)滤光单元情况下,仅有单一的连接链单元-Y-,在苯并三唑情况下该链单元位于X4和X5所占据的位置之一处,而在后二种情况下则位于明确定义的确定位置上。
在上式(1)至(3)中,烷基可为直链或支链,尤其可选自甲基,乙基正丙基,异丙基,正丁基,异丁基,叔丁基,正戊基,异戊基,新戊基,正己基,正庚基,正辛基,2-乙基己基和叔辛基。本发明中烷基R,R’和B优选是甲基,乙基,丙基,正丁基,正辛基和2-乙基己基。更为优选的是,基团R,R’和B均是甲基。至于卤素则可具体选自氯,氟和溴,优选为氯。烷氧基尤其可选自甲氧基,乙氧基,正丙氧基,异丙氧基,正丁氧基和异丁氧基。
在上式(1)至(3)的化合物中,优选用式(1)或式(2)的化合物,即链状或环状短链二有机硅氧烷。
本发明范围内的链状或环状二有机硅氧烷中,尤其优选至少具有下列定义之一,特别优选具有下列全部定义的无规衍生物或明确定义的嵌段衍生物(只是在滤光单元为3-亚苄基(或苯亚甲基)樟脑衍生物时对于X1,X2和X3,或在滤光单元为苯并三唑时对于X4和X5,上述相互排除情况除外):
R是烷基,优选是甲基,
B是烷基,优选是甲基(在式(1)的链状化合物情况下),
r是0-3(含0和3);s是0-3(含0和3)(在式(1)的链状化合物情况下),
t+u是3-5(在式(2)环状化合物情况下),
R1是H,
R2是H或甲基,
p是1-3(含1和3),
X1是H或-Y-,
X2是H,甲基,甲氧基,-Y-或Z,
X3是H或-Y-,
X4是叔丁基或-Y-,
X5是H或-Y-,
R3是甲基或叔丁基。
本发明范围内式(1)至(3)的优选化合物为滤光单元A选自上列式(4.1)的3-亚苄基(或苯亚甲基)樟脑衍生物的化合物。
为了得到式(1)和(2)的(聚)硅氧烷滤光剂,可按普通程序(途径1)进行加氢甲硅烷基化(或叫氢化硅烷化)反应:其中用例如所有基团A均为氢的相应(聚)硅氧烷开始进行操作。这种起始(聚)硅氧烷以下称为含SiH的衍生物,SiH基可存在于(聚)硅氧烷链之中或端部。这些含SiH的衍生物是(聚)硅氧烷工业上已众所周知的产品并且一般可在市场上买到。这些化合物例如已在美国专利US3,220,972,US3,697,473和US4,340,709中作了说明。
或表示为下式(2bis):式中R,t和u同上式(2)定义。
所以,可在有效催化量铂催化剂存在下用式(1bis)或(2bis)所示含SiH的这种衍生物进行普通的氢化硅烷化反应,其中根据情况(即待接枝的滤光单元的性质)用下列化合物进行反应:
用下式(4.1bis)的有机3-亚苄基(或苯亚甲基)樟脑进行反应:式中X1,X2和X3同上式(4.1)定义,只是这三个基团之一不是上式(5)的饱和二价基团-Y-,而在这种情况下是下式(5bis)的相应不饱和同系一价基团-Y’:式中R1,R2和p同式(5)定义;
或用下式(4.2bis)的有机苯并三唑衍生物进行反应:式中X4和X5定义同上式(4.2),只是这两个基团之一不是上式(5)的饱和二价基团-Y-,而在这种情况下是上式(5bis)的相应不饱和同系一价基团-Y’;
或用下式(4.4bis)的有机二苯甲酮衍生物进行反应:式中Y’是上式(5bis)的不饱和一价基团,为式(4.4)中饱和二价基团-Y-的同系物。
在特别适合于本发明范围的上式(4.1bis)化合物中,可具体举出:
a)N-烯丙基-4-(4,7,7-三甲基-3-氧代双环[2.2.1]庚-2-亚基甲基)苯磺酰胺,
b)N-烯丙基-C-[3-(4-甲氧基亚苄基或苯亚甲基)-7,7-二甲基-2-氧代双环[2.2.1]庚-1-基]甲磺酰胺,
c)N-烯丙基-C-(3-亚苄基或苯亚甲基-7,7-二甲基-2-氧化双环[2.2.1]庚-1-基)甲磺酰胺,
d)N-烯丙基-C-(3-苯并[1,3]二氧戊环-5-基亚甲基-7,7-二甲基-2-氧代双环[2.2.1]庚-1-基)甲磺酰胺,以及
e)N-(2-甲基烯丙基)-4-(4,7,7-三甲基-3-氧代双环[2.2.1]庚-2-亚基甲基)苯磺酰胺。
上述式(4.1bis)至(4.4bis)的产品本身也可按常规方式得到(在这方面,就式4.1bis的化合物而言,尤其可参见FR-A-2,529,887),其中将(i)下式相应的不饱和胺:式中R1,R2和p同上式(5)定义,与(ii)要求用其接枝的滤光单元的磺酰氯反应,因此其例子可举出:
选自下式(4.1ter)的有机3-亚苄基(或苯亚甲基)樟脑衍生物的磺酰氯:式中X1,X2和X3同上式(4.1)定义,只是这三个基团之一不是上式(5)的二价基团-Y-,而在这种情况下是一价基团-SO2Cl;
或下式(4.4ter)的二苯甲酮磺酰氯:
所有上述磺酰氯均可按常规方法在溶剂如二甲基甲酰胺(DMF)中将(i)相应的磺酸钠(即式4.1bis,4.2bis,4.3bis和4.4bis中基团-Y-在此情况下是-SO3Na)与(ii)亚硫酰(二)氯反应(这方面尤其可参见上述专利申请FR-A-2,529,887)。
用于进行上式(1bis)或(2bis)的化合物与上式(4.1bis)至(4.4bis)的化合物之间的氢化硅烷化(加氢甲硅烷化)反应的铂催化剂已众所周知并已在文献中作了广泛的说明,其例子尤其可举出美国专利US3,159,601,US3,159,602,US3,220,972及欧洲专利申请EP-A-0,057,459,EP-A-0,188,978和EP-A-0,190,530中所述的铂和有机产品的配合物以及美国专利US3,419,593,US3,377,432和US3,814,730中所述铂和含乙烯基的有机聚硅氧烷的配合物。为了将式(1bis)或(2bis)的化合物与式(4.1bis)至(4.4bis)的化合物进行反应,铂催化剂的用量以金属铂重量计一般为5-600ppm,优选10-200ppm,均以式(1bis)或(2bis)的化合物重量为基准。该氢化硅烷化反应可在本体中进行或在挥发性有机溶剂如甲苯,庚烷,二甲苯,四氢呋喃或四氯乙烯中进行。在反应完成所要求的时间内一般要求将反应混合物加热到60-120℃的温度。式(1bis)或(2bis)的化合物也可滴加到式(4.1bis),(4.2bis),(4.3bis)或(4.4bis)的化合物在含催化剂的有机溶剂中的溶液中。式(1bis)或(2bis)的化合物和式(4.1bis)(或分别为式(4.2bis)至(4.4bis))的化合物还可同时加到催化剂在有机溶剂中的悬浮体中。建议用醇中氢氧化钾测试剩余的SiH来检查反应是否已完全进行,然后去除溶剂,如经减压蒸馏去除溶剂。所得粗油状物例如要经过二氧化硅吸收柱而得以提纯。
至于上式(3)的三有机硅烷滤光剂的制备过程,可按上述进行该工艺过程,仍然是进行氢化硅烷化反应,这次用式(R’)3SiH(式(3bis)中R’同上式(3)定义)的起始硅烷与(根据最终产品所要求的滤光单元)选自上式(4.1)的有机3-亚苄基(或苯亚甲基)樟脑衍生物,上式(4.2bis)的有机苯并三唑衍生物,上式(4.3bis)的有机苯并咪唑衍生物和上式(4.4bis)的有机二苯甲酮衍生物的有机衍生物反应。
适用于制备式(1)和(2)的(聚)硅氧烷滤光剂的另一可行的合成途径(途径2)在于用分别对应于式(1)或(2)中所有基团A均用下式(5quater)代替的衍生物开始进行反应:式中R1,R2和p同式(5)定义。
式(5quater)的基团可存在于(聚)硅氧烷链之中和/或(聚)硅氧烷链端部。这些起始的氨基硅氧烷衍生物也可表示为下式(1ter)(链状氨基硅氧烷衍生物):式中R,r和s同式(1)定义,而基团B”相同或不同,选自基团R和式(5quater)的基团,
上式(1ter)或(2ter)的氨基硅氧烷衍生物在(聚)氧烷工业上是众所周知的产品并且一般可在市场上买得。另外,这些衍生物尤其在专利申请DE-A-3,702,631中作了说明,其中称之为短链(聚)硅氧烷。
然后可将这些氨基硅氧烷衍生物与要求进行接枝的滤光单元的磺酸氯进行反应,即:
与选自上式(4.1ter)的有机3-亚苄基樟脑衍生物的磺酰氯反应;
或与选自上式(4.2ter)的有机苯并三唑衍生物的磺酰氯反应;
或与选自上式(4.3ter)的苯并咪唑的磺酰氯反应;
或与上式(4.4ter)的二苯甲酮的磺酰氯进行反应。
与现有的,尤其是与上述专利申请EP-A-0,392,883和EP-A-0,335,777所述的滤光性(聚)硅氧烷相比,本发明的滤光性(聚)硅氧烷因而具有一或多项基本的结构差异,这是其值得注意的性能的根源,其中尤其可举出:首先,(聚)硅氧烷链更短,该链上已接枝了选定的滤光单元;其次,选定的滤光单元总是带有磺酰胺官能团。
如上所述,上式(1)至(3)的化合物针对紫外光线具有优异的固有滤光能力(根据产品的结构适用于UV-A和/或UV-B)。将不同结构的产品混合在一起,即具体地讲将本发明中纯粹具有UV-A滤光活性的产品与本发明中纯粹具有UV-B滤光活性的产品混合在一起,就可得到在整个UV范围(UV-A+UV-B)内均具有滤光活性的组合物,这是一大优点。此外,由于具有很高的脂溶性,所以上式(1)至(3)的化合物可以高浓度应用,从而使最终组合物达到极高的保护因子,而且这些化合物可均匀分散在含有至少一种脂肪相或化妆用有机溶剂的普通化妆载体中,因此可将其涂抹在皮肤或毛发上而形成有效的保护膜。最后,这些化合物的化妆性能很好,尤其是这些产品与现有的滤光性(聚)硅氧烷比起来不那么粘手并且更为柔和。
本发明主题还包括化妆组合物,其中于优选含至少一种脂肪相或有机溶剂的化妆用载体中含有有效量至少一种上式(1)至(3)的化合物。
式(1)至(3)的化合物用量以组合物总重量计一般为0.1-20wt%(重量百分比,下同),优选0.5-10wt%。
本发明化妆组合物可用作保护人体表皮或皮肤或毛发、使其不受紫外线照射的组合物,用作防阳光照射或防晒组合物或用作化妆产品。
该组合物尤其可制成洗液,增稠洗液,凝胶,乳膏,奶液,粉末或固体棒状形式,并且可任选调成气溶胶以及呈泡沫或喷剂形式。
该组合物还可以含有化妆领域中常用的化妆添加剂如脂肪物质,有机溶剂,(聚)硅氧烷,增稠剂,软化剂,补充防晒剂或光保护剂,防沫剂,润肤剂,香料,防腐剂,表面活性剂,填料,螯合剂,阴离子、阳离子、非离子或两性聚合物或其混合物,推进剂,碱化或酸化剂,染色剂,颜料或纤细颜料,尤其是旨在通过物理方式达到排除紫外线照射的补充光保护效果的添加剂,或任何其它常用于化妆品,特别是用于制造防晒组合物的成分。
有机溶剂中可举出低级醇和多元醇如乙醇,异丙醇,丙二醇,甘油和山梨(糖)醇。
脂肪物质可由油或蜡或其混合物,脂肪酸,脂肪酸酯,脂肪醇,凡士林,石蜡,羊毛脂,氢化羊毛脂或乙酰化羊毛脂构成。油可选自动物,植物,矿物或合成油,尤其是氢化棕榈油,氢化蓖麻油,凡士林油,石蜡油,Purcellin油,挥发性或非挥发性(聚)硅氧烷油和异链烷烃。
更具体地讲,本发明化妆组合物用于保护人体表皮或皮肤、使其不受紫外光照射或用作防晒的组合物时,可将其在溶剂或脂肪物质中制成悬浮体或分散体形式,或制成乳液形式(尤其是H/E(水包油)或E/H(油包水),但优选H/E类形式)如乳膏或雪花膏或奶液,或制成脂囊体或脂质分散体,香脂或软膏,凝胶,固体棒或气溶胶形式。乳液另外还可含有阴离子、非离子、阳离子或两性表面活性剂。
本发明化妆组合物用于保护毛发时,可将其制成洗发膏,洗发液或护发素,定型胶或有待冲洗,或有待在洗发前后,将毛发染色或脱色前后,将毛发卷成或烫成波浪形或拉直之前,之间或之后进行涂抹的组合物形式,或制成制做发式或治疗或处理用洗剂或发胶,梳理或定型用洗剂或发胶,洗发或护发浆,电烫毛发或将毛发拉直所用组合物或将头发染色或脱色所用的组合物形式。
本发明化妆组合物用作睫毛,眉毛,皮肤或毛发的化妆品如处理皮肤的乳液或雪花膏,染色或化妆底霜,唇膏,眼睑或眼影膏,面部化妆品,俗称“eye-liner”的眼线膏,mascara或染色凝胶时,可将其制成固体或浆糊状无水或含水形式如水包油或油包水乳液,悬浮液或胶料。
本发明主题还包括保护皮肤和毛发、使其不受紫外线照射,尤其是不受阳光照射的方法,其中在皮肤或毛发上涂抹有效量的上述化妆组合物或上式(1),(2)或(3)的化合物。
以下实施例说明本发明,但并不限制本发明。
实施例1
该实施例说明N-3-[1,3,3,3-四甲基-1-[(三甲基甲硅烷基)氧基]二硅氧烷基]丙基-4-(4,7,7-三甲基)-3-氧代双环[2.2.1]庚-2-亚基甲基)苯磺酰胺,即本发明下式化合物(按途径1)的制备方法:式中A是:(该产品对应于式(1)中R=B=CH3;r=0,s=1;X1=X3=H;R1=R2=H;p=1的化合物)。
a)第一步:
将34.2g4-(4,7,7-三甲基-3-氧代双环[2.2.1]庚-2-亚基甲基)苯磺酸钠盐和200ml二甲基甲酰胺(DMF)引入500ml反应器中。然后滴加入13g亚硫酰(二)氯。反应混合物于室温下搅拌2小时。再滴加入烯丙基胺(6.3g)后滴加三乙胺(11.1g)并维持搅拌3小时。反应混合物倒入300ml水中。所得固体脱水后干燥,再提纯而得21.4gN-烯丙基-4-(4,7,7-三甲基-3-氧代双环[2.2.1]庚-2-亚基甲基)苯磺酰胺,其特征如下:
白粉状
Pf(熔点):131℃
元素分析:理论值:C 67.09 H 7.04 N 3.66 S 8.88实测值:C 66.82 H 7.01 N 3.90 S 8.92
b)第二步
将17.97g上述产物和50ml甲苯引入反应器中。混合物于氮气中升温到80℃。加入氢化硅烷化催化剂(环状乙烯基甲基硅氧烷中含3-3.5%Pt的配合物,得自Huls Petrarch PC085,100μl),然后加入11.24g七甲基三硅氧烷。
氮气中80℃下4小时后将反应介质浓缩并用二氧化硅在压力下进行色层分离(洗脱液:庚烷/EtOAc 97/3)而得到21.8g要求的最终产物,其特征如下:
白粉状
Pf:73℃
元素分析:理论值:C 55.72 H 8.14 N 2.41 S 5.51 Si 14.48实测值:C 55.88 H 8.09 N 2.62 S 5.49 Si 14.28
该产品的UV吸收特性(乙醇中测定)如下:
λmax:295nm εmax:28,900
该产品可极其有效地用作在UV-B范围内具有活性的防晒剂或光保护剂。
实施例2
所得上列化合物A,B,C和D可极其有效地用作分别在UV-A,UV-B,UV-A和UV-B范围内具有活性的防晒剂或光保护剂。
实施例3
该例说明双-N-{3-[1,3,3,3-四甲基-1-[(三甲基甲硅烷基)氧基]二硅氧烷基]丙基}-3,3’-对苯二亚甲基-10,10’-二樟脑磺酰胺,即本发明下式化合物(按途径2)的制备方法:(该产品对应于式(1)中R=B=CH3;r=0,s=1;X1=-Y-且R1=R2=H和p=1;X2=Z;X3=H的化合物)。
将4g3,3’-对苯二亚甲基-10,10’-二樟脑磺酸二钠盐和16ml DMF引入反应器中。然后向其中滴加入1.1ml亚硫酰(二)氯并搅拌半小时。该多相混合物分批加入三乙胺(3.04g)和1-氨基-1-[1,3,3,3-四甲基-3-[(三甲基甲硅烷基)氧基]二硅氧烷基]丙烷(4.2g)的混合物中。该反应混合物室温下保持3小时后倒入100ml冰水中,再用二氯甲烷萃取。有机相用硫酸钠干燥并浓缩。用二氧化硅进行色层分离(洗脱液:CH2Cl2)后得到3g要求的最终产物,其特征如下:
白粉状
Pf:176-177℃
元素分析:理论值:C 52.23 H 8.00 N 2.65 S 6.06 Si 15.93实测值:C 52.92 H 8.12 N 2.43 S 5.94 Si 15.37
该产品的UV吸收特性(CHCl3中测定)如下:
λmax:344nm εmax:47,100
该产品可极其有效地用作在UV-A范围内具有活性的防晒剂。
实施例4
该例说明2-苯基-1H-苯并咪唑-5-{N-3-[1,3,3,3-四甲基-1-[(三甲基甲硅烷基)氧基]二硅氧烷基]丙基}磺酰胺,即本发明中如下式化合物的制备方法:式中A如下式:(该产品对应于式(1)中R=B=CH3;r=0,s=1;R1=R2=H和p=1的化合物)。
将100ml无水二氯甲烷,60ml三乙胺和67g七甲基氨基丙基三硅氧烷(该产品对应于式(1ter)中R=B”=CH3;r=0,s=1;R1=R2=H,p=1的化合物)引入反应器中。室温下半小时内向该混合物中分批加入23.4g 2-苯基-1H-苯并咪唑-5磺酰氯。所得多相混合物再于60℃下加热3小时。冷却后将反应混合物倒入300ml水中。用二氯甲烷萃取后用二氧化硅进行色层分离(洗脱液:庚烷/CH2Cl2 50/50)提纯而得到8g要求的最终产物,其特征如下:
白粉状
Pf:169-170℃
该产品的UV吸收特性(乙醇中测定)如下:
λmax:305nm εmax:29,500
λmax:317nm εmax:19,675
该产品可极其有效地用作在UV-B范围内具有活性的防晒剂或光保护剂。
实施例5
该产品的UV吸收特性(乙醇中测定)如下:
λmax:294nm εmax:12,100
λmax:325nm εmax:7,300
该产品可极其有效地用作在UV-B和UV-A范围内具有活性的防晒剂或光保护剂。
实施例6
以下列出本发明防晒化妆组合物或光保护性化妆组合物,即防晒霜的具体配方:
实施例1的化合物 5g
鲸蜡基硬脂醇和用33mol EO
氧乙烯化或环氧乙烷化的鲸蜡基硬脂醇
(HENKEL的“SINOVAX AO”)的混合物 7g
非自乳化的甘油一和二硬酸酯的
混合物 2g
鲸蜡醇 1.5g
苯甲酸C12-C15醇酯(WITCO的“FINSOLV TN”) 20g
聚二甲基硅氧烷 1.5g
甘油 17.5g
香料,防腐剂 qs(适量)
水 qsp(适量至) 100g
可按制备乳液的普通工艺得到该防晒霜,其中将滤光剂溶于含有乳化剂的脂肪相中,将该脂肪相加热到约70-80℃后充分搅拌条件下加入已加热到同一温度的水。持续搅拌10-15分钟后温和搅拌条件下放冷,达到40℃后再加入香料和防腐剂。
Claims (13)
1.式(1)的化合物:式(1)中:
R是甲基,
B是甲基,
R’可相同或不同,选自C1-C8烷基或苯基,
r是0-3(含0和3),
s是0<s≤3,
X1是氢或下式(5)的二价基团-Y-:式(5)中:
R1是氢,
R2是氢或甲基,
p是1-3(含1和3),
X3是氢或与X2共同形成所述的亚烷二氧基;条件是:
X4是上述二价基团-Y-,
X5是氢,
Y具有如上所述的定义。
2.权利要求1的化合物,其特征在于A对应于式(4.1)。
3.权利要求2的化合物,其特征在于X2是氢,甲基,甲氧基或-Y-。
4.权利要求2或3的化合物,其特征在于X3是氢。
5.权利要求1的化合物,其特征在于A对应于式(4.2)。
6.权利要求1的化合物,其特征在于A对应于式(4.3)。
7.滤除紫外光的化妆组合物,其特征在于其中于化妆用载体中包括有效量的至少一种权利要求1-6中任何一项所定义的化合物。
8.权利要求7的化妆组合物,其特征在于所说化妆用载体含有至少一种脂肪相或有机溶剂。
9.权利要求8的化妆组合物,其特征在于所说化妆用载体呈水包油或油包水类乳液形式。
10.权利要求9的化妆组合物,其特征在于所说化妆用载体呈水包油类乳液形式。
11.权利要求7-10中任何一项的化妆组合物,其特征在于滤光化合物含量按组合物总重量计为0.1-20wt%。
12.权利要求11的化妆组合物,其特征在于所说含量为0.5-10wt%。
13.权利要求1-6中任何一项所定义的化合物作为在UV-A和/或UV-B范围内具有活性的防晒剂或光保护剂的用途。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9413771A FR2727115B1 (fr) | 1994-11-17 | 1994-11-17 | Nouveaux filtres solaires, compositions cosmetiques photoprotectrices les contenant et utilisations |
FR9413771 | 1994-11-17 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1133292A CN1133292A (zh) | 1996-10-16 |
CN1050361C true CN1050361C (zh) | 2000-03-15 |
Family
ID=9468886
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN95120080A Expired - Fee Related CN1050361C (zh) | 1994-11-17 | 1995-11-16 | 滤光剂,含该滤光剂的防晒化妆组合物及其用途 |
Country Status (17)
Country | Link |
---|---|
EP (1) | EP0712855B1 (zh) |
JP (1) | JP2821405B2 (zh) |
KR (1) | KR100217968B1 (zh) |
CN (1) | CN1050361C (zh) |
AR (1) | AR000136A1 (zh) |
AT (1) | ATE158294T1 (zh) |
AU (1) | AU678911B2 (zh) |
BR (1) | BR9504923A (zh) |
CA (1) | CA2163073C (zh) |
DE (1) | DE69500729T2 (zh) |
ES (1) | ES2112617T3 (zh) |
FR (1) | FR2727115B1 (zh) |
HU (1) | HUT74046A (zh) |
MX (1) | MX9504683A (zh) |
PL (1) | PL182416B1 (zh) |
RU (1) | RU2123006C1 (zh) |
ZA (1) | ZA959069B (zh) |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2726562B1 (fr) * | 1994-11-08 | 1996-12-27 | Oreal | Nouveaux filtres solaires, compositions cosmetiques photoprotectrices les contenant et utilisations |
FR2727114B1 (fr) * | 1994-11-17 | 1996-12-27 | Oreal | Nouveaux filtres solaires, compositions cosmetiques photoprotectrices les contenant et utilisations |
FR2772030B1 (fr) * | 1997-12-04 | 2000-01-28 | Oreal | Nouveaux derives silicies de benz-x-azoles filtres, compositions cosmetiques photoprotectrices les contenant et utilisations |
FR2780975B1 (fr) * | 1998-07-10 | 2002-02-15 | Oreal | Procede de photostabilisation de filtres solaires derives du dibenzoylmethane, compositions cosmetiques filtrantes photostabilisees ainsi obtenues et leurs utilisations |
FR2833164B1 (fr) | 2001-12-07 | 2004-07-16 | Oreal | Compositions cosmetiques antisolaires a base d'un melange synergique de filtres et utilisations |
ATE460152T1 (de) | 2002-04-12 | 2010-03-15 | Dsm Ip Assets Bv | Organosilikon-derivate von amino- hydroxybenzophenonen und ihre verwendung als uv-a-filter in kosmetischen zubereitungen |
FR2862641B1 (fr) * | 2003-11-25 | 2006-03-03 | Oreal | Composes diorganopolysiloxaniques a fonction 4,4-diarylbutadiene compositions photoprotectrices les contenant; utilisations |
US7229610B2 (en) | 2003-11-25 | 2007-06-12 | L'oreal | Diarylbutadiene-substituted diorganopolysiloxanes and photoprotective compositions comprised thereof |
JP2008545843A (ja) * | 2005-05-31 | 2008-12-18 | ディーエスエム アイピー アセッツ ビー.ブイ. | 新規なポリシロキサン日焼け止め剤 |
US20150157539A1 (en) | 2012-07-13 | 2015-06-11 | L'oreal | Cosmetic composition comprising composite particles |
JP6100896B2 (ja) | 2012-07-13 | 2017-03-22 | ロレアル | 複合顔料及びその調製方法 |
WO2014010101A1 (en) | 2012-07-13 | 2014-01-16 | L'oreal | Composite pigment and method for preparing the same |
FR2993176B1 (fr) | 2012-07-13 | 2014-06-27 | Oreal | Composition cosmetique contenant des particules composites filtrantes de taille moyenne superieure a 0,1 micron et des particules de filtre inorganique et une phase aqueuse |
JP6096898B2 (ja) | 2012-07-13 | 2017-03-15 | ロレアル | 化粧料組成物 |
WO2014111566A2 (en) | 2013-01-21 | 2014-07-24 | L'oreal | Cosmetic or dermatological composition comprising a merocyanine and an insoluble organic uv-screening agent and/or an insoluble inorganic uv- screening agent |
WO2014152686A2 (en) | 2013-03-14 | 2014-09-25 | Momentive Performance Material Inc. | High refractive index siloxanes |
WO2016030839A1 (fr) | 2014-08-28 | 2016-03-03 | L'oreal | Composition gel/gel comprenant un filtre uv |
EP3223777A1 (fr) | 2014-11-24 | 2017-10-04 | L'Oréal | Composition cosmetique comprenant un phyllosilicate synthetique et un polyol et/ou un filtre uv |
FR3037243B1 (fr) | 2015-06-11 | 2018-11-16 | L'oreal | Composition comprenant un filtre uv, un polymere hydrophile reticule anionique, un tensioactif ayant une hlb inferieure ou egale a 5 et un copolymere silicone |
FR3073408B1 (fr) | 2017-11-15 | 2019-10-11 | L'oreal | Compositions comprenant au moins un polymere acrylique et au moins un filtre organique insoluble |
WO2019112205A1 (ko) * | 2017-12-06 | 2019-06-13 | 토모캐미칼 주식회사 | 유무기 복합체, 이의 제조방법 및 이를 이용한 자외선 차단제 |
KR101997870B1 (ko) * | 2017-12-06 | 2019-07-09 | 주식회사 세라수 | 유무기 복합체, 이의 제조방법 및 이를 이용한 자외선 차단제 |
FR3083093A1 (fr) | 2018-06-28 | 2020-01-03 | L'oreal | Composition photoprotectrice comprenant des particules de silice colloidale |
FR3090329B1 (fr) | 2018-12-21 | 2020-12-04 | Oreal | Composition comprenant un filtre UV, un polymère hydrophile réticulé anionique, un tensioactif ayant une HLB inférieure ou égale à 5 et un alcane non volatil |
FR3103705B1 (fr) | 2019-11-29 | 2021-12-17 | Oreal | Composition comprenant un filtre UV, un polymère séquencé à groupe acide phosphonique et une huile hydrocarbonée |
FR3103704B1 (fr) | 2019-11-29 | 2022-07-08 | Oreal | Composition comprenant un filtre UV, un polymère éthylénique à groupe acide phosphonique et une huile hydrocarbonée |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993004666A1 (fr) * | 1991-08-29 | 1993-03-18 | L'oreal | Composition cosmetique filtrante comprenant un nanopigment d'oxyde metallique et un polymere filtre liposoluble |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3159602A (en) | 1962-06-07 | 1964-12-01 | Olin Mathieson | Preparation of polymeric phosphates |
US3220972A (en) | 1962-07-02 | 1965-11-30 | Gen Electric | Organosilicon process using a chloroplatinic acid reaction product as the catalyst |
US3159601A (en) | 1962-07-02 | 1964-12-01 | Gen Electric | Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes |
NL133821C (zh) | 1964-07-31 | |||
NL131800C (zh) | 1965-05-17 | |||
US3814730A (en) | 1970-08-06 | 1974-06-04 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
US3697473A (en) | 1971-01-04 | 1972-10-10 | Dow Corning | Composition curable through si-h and si-ch equals ch2 with improved properties |
US4340709A (en) | 1980-07-16 | 1982-07-20 | General Electric Company | Addition curing silicone compositions |
US4394317A (en) | 1981-02-02 | 1983-07-19 | Sws Silicones Corporation | Platinum-styrene complexes which promote hydrosilation reactions |
LU84264A1 (fr) | 1982-07-08 | 1984-03-22 | Oreal | Nouveaux sulfonamides derives du 3-benzylidene camphre et leur application en tant que filtres u.v.,notamment dans des compositions cosmetiques |
LU85304A1 (fr) * | 1984-04-13 | 1985-11-27 | Oreal | Composition solaire filtrante contenant du polyisobutylene et son utilisation pour la protection de l'epiderme humain contre les radiations ultraviolettes |
FR2575085B1 (fr) | 1984-12-20 | 1987-02-20 | Rhone Poulenc Spec Chim | Complexe platine-triene comme catalyseur de reaction d'hydrosilylation et son procede de preparation |
FR2575086B1 (fr) | 1984-12-20 | 1987-02-20 | Rhone Poulenc Spec Chim | Complexe platine-alcenylcyclohexene comme catalyseur de reaction d'hydrosilylation et son procede de preparation |
GB8602226D0 (en) | 1986-01-30 | 1986-03-05 | Dow Corning Ltd | Preparation of primary aminosiloxanes |
LU87180A1 (fr) * | 1988-03-28 | 1989-10-26 | Oreal | Utilisation en cosmetique de diorganopolysiloxanes a fonction benzylidene-3 camphre et nouvelles compositions cosmetiques contenant ces composes,destinees a la protection de la peau et des cheveux |
FR2642968B1 (fr) * | 1989-02-15 | 1991-06-07 | Oreal | Utilisation en cosmetique de diorganopolysiloxanes a fonction benzotriazole et nouvelles compositions cosmetiques contenant ces composes, destinees a la protection de la peau et des cheveux |
FR2644696B1 (fr) * | 1989-03-22 | 1994-04-15 | Oreal | Utilisation en cosmetique de diorganopolysiloxanes a fonction hydroxy-2 benzophenone et compositions cosmetiques contenant ces composes, destinees a la protection de la peau et des cheveux |
US5164462A (en) * | 1991-04-25 | 1992-11-17 | Allergan, Inc. | Ultraviolet light absorbing compounds and silicone compositions |
FR2727114B1 (fr) * | 1994-11-17 | 1996-12-27 | Oreal | Nouveaux filtres solaires, compositions cosmetiques photoprotectrices les contenant et utilisations |
-
1994
- 1994-11-17 FR FR9413771A patent/FR2727115B1/fr not_active Expired - Fee Related
-
1995
- 1995-10-16 AT AT95402307T patent/ATE158294T1/de active
- 1995-10-16 DE DE69500729T patent/DE69500729T2/de not_active Expired - Fee Related
- 1995-10-16 ES ES95402307T patent/ES2112617T3/es not_active Expired - Lifetime
- 1995-10-16 EP EP95402307A patent/EP0712855B1/fr not_active Expired - Lifetime
- 1995-10-20 AU AU34380/95A patent/AU678911B2/en not_active Ceased
- 1995-10-26 ZA ZA959069A patent/ZA959069B/xx unknown
- 1995-11-07 BR BR9504923A patent/BR9504923A/pt not_active IP Right Cessation
- 1995-11-08 MX MX9504683A patent/MX9504683A/es not_active Application Discontinuation
- 1995-11-15 AR AR33424195A patent/AR000136A1/es unknown
- 1995-11-16 RU RU95120241A patent/RU2123006C1/ru not_active IP Right Cessation
- 1995-11-16 CA CA002163073A patent/CA2163073C/fr not_active Expired - Fee Related
- 1995-11-16 CN CN95120080A patent/CN1050361C/zh not_active Expired - Fee Related
- 1995-11-16 KR KR1019950041701A patent/KR100217968B1/ko not_active IP Right Cessation
- 1995-11-16 PL PL95311397A patent/PL182416B1/pl unknown
- 1995-11-16 HU HU9503279A patent/HUT74046A/hu unknown
- 1995-11-16 JP JP7298739A patent/JP2821405B2/ja not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993004666A1 (fr) * | 1991-08-29 | 1993-03-18 | L'oreal | Composition cosmetique filtrante comprenant un nanopigment d'oxyde metallique et un polymere filtre liposoluble |
Also Published As
Publication number | Publication date |
---|---|
MX9504683A (es) | 1997-04-30 |
AR000136A1 (es) | 1997-05-21 |
AU678911B2 (en) | 1997-06-12 |
HUT74046A (en) | 1996-10-28 |
CA2163073C (fr) | 2000-06-06 |
JPH08225582A (ja) | 1996-09-03 |
EP0712855B1 (fr) | 1997-09-17 |
ES2112617T3 (es) | 1998-04-01 |
FR2727115B1 (fr) | 1996-12-27 |
KR100217968B1 (ko) | 1999-10-01 |
FR2727115A1 (fr) | 1996-05-24 |
DE69500729T2 (de) | 1998-01-08 |
BR9504923A (pt) | 1997-09-02 |
CN1133292A (zh) | 1996-10-16 |
JP2821405B2 (ja) | 1998-11-05 |
ATE158294T1 (de) | 1997-10-15 |
DE69500729D1 (de) | 1997-10-23 |
AU3438095A (en) | 1996-05-23 |
HU9503279D0 (en) | 1996-01-29 |
EP0712855A1 (fr) | 1996-05-22 |
ZA959069B (en) | 1996-05-17 |
CA2163073A1 (fr) | 1996-05-18 |
RU2123006C1 (ru) | 1998-12-10 |
PL311397A1 (en) | 1996-05-27 |
PL182416B1 (pl) | 2001-12-31 |
KR960016878A (ko) | 1996-06-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1050361C (zh) | 滤光剂,含该滤光剂的防晒化妆组合物及其用途 | |
CN1050363C (zh) | 滤光剂,含该滤光剂的防晒化妆组合物及其用途 | |
CN1047779C (zh) | 防晒剂,含有这种防晒剂的光保护性化妆组合物及其应用 | |
EP0841341B1 (fr) | Nouveaux filtres solaires, compositions cosmétiques photoprotectrices les contenant et utilisations | |
US20010053856A1 (en) | PHOTOPROTECTIVE/COSMETIC COMPOSITIONS COMPRISING A LIPOSOLUBLE, PHOTOSTABLE AND UV-PHOTOPROTECTING BENZ-x-AZOLE-SUBSTITUTED SILANE OR SILOXANE | |
CN1052007C (zh) | 防晒剂、含有这些防晒剂的光保护化妆组合物及应用 | |
US5254542A (en) | Organic silicon compounds and cosmetic compositions | |
CN1126725A (zh) | 新的防晒剂,含该防晒剂的光保护化妆组合物及应用 | |
FR2775479A1 (fr) | Utilisation d'un organosiloxane et/ou d'un organosilane antioxydant pour la photoprotection de la couleur des fibres keratiniques colorees naturellement ou artificiellement |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |