CN1107085C - 亲油的聚合紫外吸收剂 - Google Patents
亲油的聚合紫外吸收剂 Download PDFInfo
- Publication number
- CN1107085C CN1107085C CN98117499A CN98117499A CN1107085C CN 1107085 C CN1107085 C CN 1107085C CN 98117499 A CN98117499 A CN 98117499A CN 98117499 A CN98117499 A CN 98117499A CN 1107085 C CN1107085 C CN 1107085C
- Authority
- CN
- China
- Prior art keywords
- alkyl
- polymkeric substance
- value
- peg
- ester
- 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
- 239000006096 absorbing agent Substances 0.000 title claims abstract description 14
- 239000000126 substance Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000002537 cosmetic Substances 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- 239000008194 pharmaceutical composition Substances 0.000 claims 2
- 239000004480 active ingredient Substances 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 20
- -1 vinyl lactam Chemical class 0.000 description 20
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- DWANEFRJKWXRSG-UHFFFAOYSA-N 1,2-tetradecanediol Chemical compound CCCCCCCCCCCCC(O)CO DWANEFRJKWXRSG-UHFFFAOYSA-N 0.000 description 11
- 239000004359 castor oil Substances 0.000 description 11
- 235000019438 castor oil Nutrition 0.000 description 11
- 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 11
- 239000004408 titanium dioxide Substances 0.000 description 11
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 description 10
- 235000011187 glycerol Nutrition 0.000 description 10
- 229960001679 octinoxate Drugs 0.000 description 10
- 229940119170 jojoba wax Drugs 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 description 8
- 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 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 7
- 229940043232 butyl acetate Drugs 0.000 description 7
- 229960004697 enzacamene Drugs 0.000 description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 7
- XUGNVMKQXJXZCD-UHFFFAOYSA-N isopropyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(C)C XUGNVMKQXJXZCD-UHFFFAOYSA-N 0.000 description 7
- 235000019359 magnesium stearate Nutrition 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 229940042585 tocopherol acetate Drugs 0.000 description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 5
- 235000013599 spices Nutrition 0.000 description 5
- LADGBHLMCUINGV-UHFFFAOYSA-N tricaprin Chemical compound CCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCC)COC(=O)CCCCCCCCC LADGBHLMCUINGV-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- FWQNGGDYDNOXFB-UHFFFAOYSA-N C(C)(=O)OC=C.CN(C)C1=C(C(=O)O)C=CC=C1 Chemical compound C(C)(=O)OC=C.CN(C)C1=C(C(=O)O)C=CC=C1 FWQNGGDYDNOXFB-UHFFFAOYSA-N 0.000 description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- ZRWACTCEUKFNFM-UHFFFAOYSA-N ethenyl acetate nonanoic acid Chemical compound C(C)(=O)OC=C.C(CCCCCCCC)(=O)O ZRWACTCEUKFNFM-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- ZCTXEAQXZGPWFG-UHFFFAOYSA-N imidurea Chemical compound O=C1NC(=O)N(CO)C1NC(=O)NCNC(=O)NC1C(=O)NC(=O)N1CO ZCTXEAQXZGPWFG-UHFFFAOYSA-N 0.000 description 4
- 229940113174 imidurea Drugs 0.000 description 4
- 229940095102 methyl benzoate Drugs 0.000 description 4
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 description 4
- 239000004405 propyl p-hydroxybenzoate Substances 0.000 description 4
- 229960003415 propylparaben Drugs 0.000 description 4
- 230000000475 sunscreen effect Effects 0.000 description 4
- 239000000516 sunscreening agent Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 description 3
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 2
- RJWUMFHQJJBBOD-UHFFFAOYSA-N 2-methylheptadecane Chemical compound CCCCCCCCCCCCCCCC(C)C RJWUMFHQJJBBOD-UHFFFAOYSA-N 0.000 description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- UBNYRXMKIIGMKK-RMKNXTFCSA-N amiloxate Chemical compound COC1=CC=C(\C=C\C(=O)OCCC(C)C)C=C1 UBNYRXMKIIGMKK-RMKNXTFCSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 235000013871 bee wax Nutrition 0.000 description 2
- 239000012166 beeswax Substances 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 229940049294 glyceryl stearate se Drugs 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 2
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 2
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- 235000019808 microcrystalline wax Nutrition 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229960005323 phenoxyethanol Drugs 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- WXSLOYPZKHFWII-UHFFFAOYSA-N propyl 4-hydroxybenzoate;sodium Chemical compound [Na].CCCOC(=O)C1=CC=C(O)C=C1 WXSLOYPZKHFWII-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229960001295 tocopherol Drugs 0.000 description 2
- 229930003799 tocopherol Natural products 0.000 description 2
- 235000010384 tocopherol Nutrition 0.000 description 2
- 239000011732 tocopherol Substances 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 description 1
- KNUPSOXBESCJLY-UHFFFAOYSA-N 2-methoxy-1-phenylhexan-1-one Chemical compound CCCCC(OC)C(=O)C1=CC=CC=C1 KNUPSOXBESCJLY-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- AHSWWYHKKHJZIC-UHFFFAOYSA-N C=C.CN(C)C1=C(C(=O)O)C=CC=C1 Chemical compound C=C.CN(C)C1=C(C(=O)O)C=CC=C1 AHSWWYHKKHJZIC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 235000009392 Vitis Nutrition 0.000 description 1
- 241000219095 Vitis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 230000002075 anti-alcohol Effects 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 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
- 239000012530 fluid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008786 sensory perception of smell Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- A61K8/90—Block copolymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F216/18—Acyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/14—Esters of polycarboxylic acids
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Dermatology (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Cosmetics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
基于如下式I所示的单元的聚合的紫外吸收剂，其中单元的顺序是任意的，a+b+c+d的总数＝100，且a是5至95的值，b是0至70的值，c是5至95的值，d是0至70的值且基团R具有的在说明书中解释的意思已得到了说明。
Description
本发明涉及基于苯甲酸衍生物发色团的，亲油的聚合紫外吸收剂，和用于保护皮肤和头发免于紫外线照射的，具有与聚合物连接的苯甲酸发色团的化妆品组合物。
涂敷于皮肤的防晒化妆品组合物经常需要具有良好的防水性。如果皮肤非常频繁地与水或水性流体例如汗水接触，这个特性就是特别需要的。为了实现所需的防水性，经常将聚合物加入到这样的组合物中。
另一个可能性在于将紫外吸收基共价地连接于聚合物上。
WO 89/4824公开了吸收紫外的苯乙烯和马来酐、乙烯基吡咯烷酮或丙烯酸酯的共聚物。这些共聚物具有高的水溶性和低的皮肤渗透性。
JP 60/88066公开了通过氨基甲酸乙酯间隔基连接到(甲基)丙烯酸酯上的吸收紫外的二苯酮衍生物。这些聚合物适合作目镜透镜组和柔性焦距透镜组的原料。
EP 123368公开了由下述单体合成的聚合防晒组合物：
(a)烯属对-氨基苯甲酸酯，
(b)N-乙烯基吡咯烷酮和
(c)乙烯基内酰胺，丙烯酸酯或甲基丙烯酸酯，且也可以是其混合物。
JP 03220213公开了由下述物质组成的聚合的紫外吸收剂；
(a)N，N-二甲基氨基苯甲酸乙烯酯，
(b)甲基丙烯酸甲酯，
(c)苯乙烯，
(d)羟基丁基乙烯基醚
(e)甲基丙烯酸和
(f)二乙烯基苯。
除了好的防水性，该化妆品组合物还应满足于许多其它性质，例如为避免由于毒物和嗅觉原因产生的问题而应具有的低皮肤渗透性，低残留单体含量，以及与其它化妆品组合物的成分的良好的可加工性、可混合性和稳定性。
另外，该聚合的紫外吸收剂在紫外线范围内应具有高的吸光性和良好的油溶性。
我们发现亲油聚合的紫外吸收剂具有如下式I所示的单元其中该单元的顺序是任意的，a+b+c+d的总数＝100，且a是5至95的值，b是0至70的值，c是5至95的值，d是0至70的值R1、R2彼此独立地是H、C1-C8烷基R3是X1、X2彼此独立地是H、C1-C8烷基X3是H、C1-C8烷基X4是H、C1-C8烷基X5、X6彼此独立地是H、C1-C8烷基
X7是C1至C8烷基；
R4是-(CO)n-R5，
R5是C1至C28烷基，
n是0或1，
R6是C1至C22烷基，
R7、R8彼此独立地是H或CH3。
优选聚合物的单体单元a至d具有下述值：
a 15-50
b 5-70
c 3-80
d 0-20
构成单元的优选单体是那些其中R1和R2彼此独立地是H，CH3，C2H5，特别优选R1和R2是CH3的单体
构成单元b的优选单体如下式所示，
用于单元b的单体的制备是公知的或是本领域技术人员由类似的反应很容易进行。
式II的单体的制备公开于US 661005和FR 691020。
式IV的单体的制备披露于G.Ciolfi等人，Vitis(1995)，34(3)，195-196其中R3是
或
(X1＝X2＝H)对于R3＝
X3＝CH3
其制备披露于M.Majeric等人的，Tetrahedron：Asymmetry(1996)，7(3)，815-824。
对于R3＝
X4＝CH3
其制备披露于T.G.Biryukova等人的Vysokomol.Soedin.，Ser.B(1978)，20(8)，565-568。
对于R3＝
其制备披露于US 5155253和US 921013。
一般来说，通过相应的含羧基的吸收紫外光的发色团与乙酸乙烯酯的酯基转移而制得含发色团的乙烯基酯。(参见G.Heublein，B.Heublein，B.Heyroth，E.Brendel，Z.Chem.19(1979)104)。
一般地，通过含OH吸收紫外光的发色团与乙炔反应可以制得含发色团的乙烯基酯。(参见Organikum Deutscher Verlag der Wissenschaften，Berlin，1979.P.338)。
在构成单元C的单体中间，其中R4＝-CO-R9是优选的，R9是具有6至12个碳原子的支链烷烃，特别是且R10和R11共包括6至7个C原子。更优选的是R4是
R10，R11是烷基，具有的附加条件是R10+R11包括6至7个碳原子。
在构成单元d的单体中间，其中R6是C4至C18的烷基，特别地，叔丁基，2-乙基己基或月桂基是优选的。
根据本发明的聚合物是通过在通常条件下使构成相应的单元a-d的单体进行自由基聚合反应而制得的。
适合的溶剂是常用的有机溶剂，特别是醇例如乙醇、异丙醇、丁醇、酯例如乙酸乙酯和乙酸丁酯，酮例如丙酮、甲基乙基酮、环己酮，醚例如四氢呋喃和甲基叔丁基醚和烷烃例如己烷，庚烷、环己烷和辛烷。在化妆品油例如石蜡油，苯甲酸和长链脂肪醇的酯，甘油和长链脂肪酸的酯，2-辛基十二烷醇，异十八烷醇或2-乙基己酸和长链脂防醇的酯中的聚合反应也是优选的。这里苯甲酸和C12-C16醇的酯是特别优选的，在水中的聚合反应也是可以的，通过乳化水中的单体和使用水溶引发剂聚合而进行的。
合适的引发剂是偶氮引发剂例如，例如偶氮异丁腈和过氧化物，例如过氧化二苯酰，2-乙基过己酸叔丁酯或过氧化硫酸氢盐。反应温度是30至160℃，优选80至120℃。
通常，根据本发明的聚合物具有2000至50000优选4000至20000g/mol的分子量。
得到的聚合物根据用途，接着与通常化妆品中的助剂和添加剂配合。用于防晒组合物的合适的助剂和添加剂披露于W.Umbach，Kosmetik Georg-Thieme-VerlayStuttgart，1988。
除了与聚合物连接的紫外吸收剂，该化妆品组合物也含有其它可溶紫外吸收剂。
优选，混合的其它紫外吸收剂补充了与聚合物连接的紫外吸收剂的吸收范围。这样使得在尽可能宽的紫外线范围实现有效的保护。
特别是，通过与聚合物连接的紫外B吸收剂一起，添加可溶的紫外A吸收剂，
根据本发明的化妆品组合物由于其高度的防水性，良好的皮肤容忍性和低的皮肤渗透性，而显示出优异性。它们也具好良好的对水解的稳定性，优异的油溶性和高吸光性。
本发明通过下述实施例进行进一步说明。
实施例1
亲油的吸收紫外光的聚合物的制备
在氮气环境中，先加入20g乙酸丁酯，且加热至100℃。在2小时时间内，将来自各自容器的溶于32g新壬酸乙烯酯的8g二甲基氨基苯甲酸乙烯酯的溶液和溶于10g乙酸丁酯的0.4g过氧化-2-乙基己酸叔丁酯溶液计量加入。在完全加入两种溶液之后，该混合物在100℃下搅拌4小时。冷却之后，该溶液被注入800ml乙醇中，且沉淀聚合物通过过滤排出。
产出：21g
软化点：115至118℃
GPC：Mn＝14000g/mol，多分散性＝2.30
UV：310nm，E1 1＝346
实施例2
亲油的吸收紫外光的聚合物的制备
在氮气环境中，先加入20g乙酸丁酯，并加热至100℃。在2小时时间内，将来自各自容器的溶于28g新壬酸乙烯酯的12g二甲基氨基苯甲酸乙烯酯的溶液和溶于10g乙酸丁酯的0.4g过氧化-2-乙基己酸叔丁酯溶液计量加入。在完全加入两种溶液之后，该混合物在100℃下搅拌4小时。冷却之后，该溶液被注入1000ml甲醇中，且沉淀的聚合物通过过滤排出。
产出：19.1g
软化点：98至102℃
GPC：Mn＝8900g/mol，多分散性＝2.27
UV：308nm， E1 1＝503
实施例3
亲油的吸收紫外光的聚合物的制备
在氮气环境中，先加入20g乙酸丁酯，并加热至100℃。在2小时时间内，将来自各自容器的溶于24g新壬酸乙烯酯的16g二甲基氨基苯甲酸乙烯内，将来自各自容器的溶于24g新壬酸乙烯酯的16g二甲基氨基苯甲酸乙烯酯的溶液和溶于10g乙酸丁酯的0.4g过氧化-2-乙基己酸叔丁酯溶液计量加入。在完全加入两种溶液之后，该混合物在100℃下搅拌4小时。冷却之后，该溶液被注入1000ml乙醇中，且沉淀的聚合物通过过滤排出。
产出：10.9g
软化点：107至110℃
GPC：Mn＝9400g/mol，多分散性＝1.94
UV：308nm，E1 1＝606用于化妆品目的的乳液的制备的一般制备工艺
在搅拌容器中所有油溶成份被加热至85℃。当所有的成份已经熔化或作为液相存在时，水相在均质条件下加入。搅拌下，该乳液冷却至约40℃，发香，均质，且在连续搅拌下，被冷却至25℃。
制剂
实施例4
唇膏组合物
至100 Eucerinum anhydricum
10.00 甘油
10.00 二氧化钛
0.5-10 实施例1的聚合物
8.00 甲氧基肉桂酸辛酯
5.00 氧化锌
4.00 蓖麻油
4.00 季戊四醇基硬脂酸酯/癸酸酯/辛酸酯/己二酸酯
3.00 硬酯酸甘油酯SE
2.00 蜂蜡
2.00 微晶蜡
2.00 quatemium-18膨润土
1.50 PEG-45/十二烷基甘醇共聚物
实施例5
唇膏组合物
至100 Eucerinum anhydricum
10.00 甘油
10.00 二氧化钛
0.5-10 实施例1聚合物
5.00 丁基甲氧基二苯甲酰基甲烷
5.00 氧化锌
4.00 蓖麻油
4.00 季戊四醇基硬脂酸酯/癸酸酯/辛酸酯/己二酸酯
3.00 硬酯酸甘油酯SE
2.00 蜂蜡
2.00 微晶蜡
2.00 quatemium-18膨润土
1.50 PEG-45/十二烷基甘醇共聚物
实施例6
具有微细颜料的防晒组合物
至100 水
5.00 丁基甲氧基二苯甲酰基甲烷
6.00 PEG-7氢化蓖麻油
6.00 二氧化钛
0.5-10 实施例3的聚合物
5.00 矿物油
5.00 对甲氧基肉桂酸异戊酯
5.00 丙二醇
3.00 霍霍巴油
3.00 4-甲基亚苄基樟脑
2.00 PEG-45/十二烷基甘醇共聚物
1.00 聚二甲基硅氧烷
0.50 PEG-40氢化蓖麻油
0.50 乙酸生育酚酯
0.50 苯氧基乙醇
0.20 EDTA
实施例7
具有微细颜料的防晒组合物
至100 水
10.00 甲氧基肉桂酸辛酯
6.00 PEG-7氢化蓖麻油
6.00 二氧化钛
0.5-10 实施例2的聚合物
5.00 矿物油
5.00 对甲氧基肉桂酸异戊酯
5.00 丙二醇
3.00 霍霍巴油
3.00 4-甲基亚苄基樟脑
2.00 PEG-45/十二烷基甘醇共聚物
1.00 聚二甲基硅氧烷
0.50 PEG-40氢化蓖麻油
0.50 乙酸生育酚酯
0.50 苯氧基乙醇
0.20 EDTA
实施例8
无脂凝胶
至100 水
8.00 甲氧基肉桂酸辛酯
7.00 二氧化钛
0.5-10 实施例2的聚合物
5.00 甘油
5.00 PEG-25PABA
1.00 4-甲基亚苄基樟脑
0.40 丙烯酸酯C10-C30烷基丙烯交叉共聚物
0.30 咪唑烷基脲
0.25 羟乙基纤维素
0.25 对羧基苯甲酸甲酯钠盐
0.20 乙二胺四乙酸二钠
0.15 香料
0.15 对羟基苯甲酸丙酯钠盐
0.10 氢氧化钠
实施例9
无脂凝胶
至100 水
8.00 甲氧基肉桂酸辛酯
7.00 二氧化钛
0.5-10 实施例1的聚合物
5.00 甘油
5.00 PEG-25PABA
1.00 丁基甲氧基二苯甲酰基甲烷
0.40 丙烯酸酯C10-C30烷基丙烯酯交叉共聚物
0.30 咪唑烷基脲
0.25 羟乙基纤维素
0.25 对羧基苯甲酸甲酯钠盐
0.20 乙二胺四乙酸二钠
0.15 香料
0.15 对羟基苯甲酸丙酯钠盐
0.10 氢氧化钠
实施例10
晒黑霜
至100水
8.00 甲氧基肉桂酸辛酯
8.00 二氧化钛
6.00 PEG-7氢化蓖麻油
0.5-10 实施例3的聚合物
6.00 矿物油
5.00 氧化锌
5.00 棕榈酸异丙酯
5.00 咪唑烷基脲
3.00 霍霍巴油
2.00 PEG-45/十二烷基甘醇共聚物
1.00 4-甲基亚苄基樟脑
0.60 硬脂酸镁
0.50 乙酸生育酚酯
0.25 对羧基苯甲酸甲酯
0.20 乙二胺四乙酸二钠
0.15 对羟基苯甲酸丙酯
实施例11
晒黑霜
至100水
8.00 甲氧基肉桂酸辛酯
8.00 二氧化钛
6.00 PEG-7氢化蓖麻油
0.5-10 实施例2的聚合物
6.00 矿物油
5.00 氧化锌
5.00 棕榈酸异丙酯
5.00 咪唑烷基脲
3.00 霍霍巴油
2.00 PEG-45/十二烷基甘醇共聚物
1.00 4-甲基亚苄基樟脑
0.60 硬脂酸镁
0.50 乙酸生育酚酯
0.25 对羧基苯甲酸甲酯
0.20 乙二胺四乙酸二钠
0.15 对羟基苯甲酸丙酯
实施例12
防水晒黑霜
至100水
4.0 丁基甲氧基二苯甲酰基甲烷
8.00 甲氧基肉桂酸辛酯
5.00 PEG-7氢化蓖麻油
5.00 丙二醇
4.00 棕榈酸异丙酯
4.00 辛酸/癸酸甘油三酯
0.5-10 实施例1的聚合物
4.00 甘油
3.00 霍霍巴油
2.00 4-甲基亚苄基樟脑
2.00 二氧化钛
1.50 PEG-45/十二烷基甘醇共聚物
1.50 聚二甲基硅烷
0.70 硫酸镁
0.50 硬脂酸镁
0.15 香料
实施例13
防水晒黑膏
至100
8.00 甲氧基肉桂酸辛酯
5.00 PEG-7氢化蓖麻油
5.00 丙二醇
4.00 棕榈酸异丙酯
4.00 辛酸/癸酸甘油三酯
0.5-10 实施例2聚合物
4.00 甘油
3.00 霍霍巴油
2.00 4-甲基亚苄基樟脑
2.00 二氧化钛
1.50 PEG-4 5/十二烷基甘醇共聚物
1.50 聚二甲基硅烷
0.70 硫酸镁
0.50 硬脂酸镁
0.15 香料
实施例14
晒黑乳液
至100 水
10.00 矿物油
6.00 PEG-7氢化蓖麻油
5.00 棕榈酸异丙酯
3.50 丁基甲氧基二苯甲酰基甲烷
0.5-10 实施例2的聚合物
3.00 辛酸/癸酸甘油三酯
3.00 霍霍巴油
2.00 PEG-45/十二烷基甘醇共聚物
0.70 硫酸镁
0.60 硬脂酸镁
0.50 乙酸生育酚酯
0.30 甘油
0.25 对羟基苯甲酸甲酯
0.15 对羟基苯甲酸丙酯
0.05 生育酚
实施例15
晒黑乳液
至100 水
10.00 矿物油
6.00 PEG-7氢化蓖麻油
5.00 棕榈酸异丙酯
3.50 甲氧基肉桂酸辛酯
0.5-10 实施例1的聚合物
3.00 辛酸/癸酸甘油三酯
3.00 霍霍巴油
2.00 PEG-45/十二烷基甘醇共聚物
0.70 硫酸镁
0.60 硬脂酸镁
0.50 乙酸生育酚酯
0.30 甘油
0.25 对羟基苯甲酸甲酯
0.15 对羟基苯甲酸丙酯
0.05 生育酚
实施例16
防水晒黑霜
至100水
8.00 甲氧基肉桂酸辛酯
5.00 PEG-7氢化蓖麻油
5.00 丙二醇
4.00 棕榈酸异丙酯
4.00 辛酸/癸酸甘油三酯
0.5-10 实施例1的聚合物
0.5-10 实施例3的聚合物
4.00 甘油
3.00 霍霍巴油
2.00 丁基甲氧基苯甲酰基甲烷
2.00 二氧化钛
1.50 PEG-45/十二烷基甘醇共聚物
1.50 聚二甲基硅烷
0.70 硫酸镁
0.50 硬脂酸镁
0.15 香料
Claims (7)
1、一种聚合的紫外吸收剂，基于如下式I所示的单元其中单元的顺序是任意的，a+b+c+d的总数＝100，且
a是5至95的值，
b是0至70的值，
c是5至95的值，
d是0至70的值
R1、R2彼此独立地是H、C1-C8烷基
R3是
X1、X2彼此独立地是H，C1-C8烷基
X3是H、C1-C8烷基
X4是H、C1-C8烷基X5、X6彼此独立地是H、C1-C8烷基
X7是H，C1至C8烷基；
R4是-(CO)n-R5，
R5是C1-C28-烷基，
n是0或1，
R6是C1-C22-烷基，
R7、R8彼此独立地是H或CH3。
2、如权利要求1的聚合物，其中
R4是-CO-R9，
R9是具有6至12个碳原子的支链烷基。
3、根据权利要求2的聚合物，其中R4是
R10，R11是烷基，具有的附加条件是R10+R11包括6至7个碳原子。
4、根据权利要求1至3任一项的聚合物，其中
a是15至50的值，
b是0至70的值，
c是30至80的值，
d是0至70的值
R6是C4至C18的烷基
5、根据权利要求1-4的聚合的紫外吸收剂用于化妆品组合物或药物组合物的用途。
6、一种化妆品或药物组合物包括，除常用助剂以外，还有作为活性成份的如权利要求1至4所述的聚合的紫外吸收剂。
7、一种制备权利要求1至4所述的聚合物的方法，是通过在化妆品油或长链脂肪醇的酯中的聚合反应而进行的。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19734445.3 | 1997-08-08 | ||
| DE19734445A DE19734445A1 (de) | 1997-08-08 | 1997-08-08 | Lipophile polymere UV-Absorber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1216769A CN1216769A (zh) | 1999-05-19 |
| CN1107085C true CN1107085C (zh) | 2003-04-30 |
Family
ID=7838439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98117499A Expired - Fee Related CN1107085C (zh) | 1997-08-08 | 1998-08-08 | 亲油的聚合紫外吸收剂 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US6143850A (zh) |
| EP (1) | EP0896006B1 (zh) |
| JP (1) | JP4093510B2 (zh) |
| CN (1) | CN1107085C (zh) |
| DE (2) | DE19734445A1 (zh) |
| ES (1) | ES2231923T3 (zh) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06306477A (ja) * | 1993-04-26 | 1994-11-01 | Fuji Denshi Kogyo Kk | 長尺状ワークの高周波移動焼入方法 |
| DE19750030A1 (de) * | 1997-11-12 | 1999-05-20 | Merck Patent Gmbh | Lichtstabile kosmetische Formulierung enthaltend Butylmethoxydibenzoylmethan |
| JP3816697B2 (ja) * | 1999-07-07 | 2006-08-30 | 大日精化工業株式会社 | 重合体が結合した機能剤、その製造方法、それらの使用方法及びそれらを使用した物品 |
| WO2003023395A1 (en) * | 2001-09-12 | 2003-03-20 | Microbar Systems, Inc. | Enhanced detection of metal plating additives |
| DE10240322B4 (de) * | 2002-08-31 | 2004-08-26 | Schwan-Stabilo Cosmetics Gmbh & Co. Kg | Lipidhaltige Zubereitung, und deren Verwendung |
| US6899866B2 (en) * | 2002-09-06 | 2005-05-31 | Cph Innovations Corporation | Photostabilization of a sunscreen composition with a combination of an α-cyano-β, β-diphenylacrylate compound and a dialkyl naphithalate |
| US6919473B2 (en) * | 2002-09-17 | 2005-07-19 | Cph Innovations Corporation | Photostabilizers, UV absorbers, and methods of photostabilizing a sunscreen composition |
| US7544350B2 (en) * | 2002-11-22 | 2009-06-09 | Hallstar Innovations Corp. | Method of decreasing the UV light degradation of polymers |
| US7534420B2 (en) * | 2004-02-25 | 2009-05-19 | Hallstar Innovations Corp. | Compounds derived from polyanhydride resins with film-forming, UV-absorbing, and photostablizing properties, compositions containing same, and methods of using the same |
| KR101158942B1 (ko) * | 2004-03-25 | 2012-06-21 | 디에스엠 아이피 어셋츠 비.브이. | 과도하게 분지된 중합체에 공유 결합된 자외선 흡수 발색단 |
| US7235587B2 (en) * | 2004-07-01 | 2007-06-26 | Cph Innovations Corporation | Diesters containing two crylene or fluorene moieties, sunscreen compositions containing the same, and methods of photostabilizing a sunscreen compositions containing the same |
| US8158678B2 (en) * | 2005-04-07 | 2012-04-17 | Cph Innovations Corp. | Photoabsorbing, highly conjugated compounds of cyanoacrylic esters, sunscreen compositions and methods of use |
| US7989572B2 (en) * | 2008-01-17 | 2011-08-02 | Eastman Chemical Company | Polyvinyl ultraviolet light absorbers for personal care |
| CN101781385B (zh) * | 2009-01-16 | 2012-03-21 | 中国中化股份有限公司 | 苯并三唑类水溶性高分子紫外吸收剂及其制备方法与应用 |
| WO2011069931A1 (de) | 2009-12-09 | 2011-06-16 | Basf Se | Formulierung von lichtempfindlichen pestiziden und uv-absorber haltigen kammpolymeren |
| US20140227212A1 (en) * | 2011-09-09 | 2014-08-14 | University Of Florida Research Foundation, Inc. | Polymerized sunscreen absorbers |
| US9255180B2 (en) | 2012-06-28 | 2016-02-09 | Johnson & Johnson Consumer Inc. | Ultraviolet radiation absorbing polyethers |
| US20140004057A1 (en) | 2012-06-28 | 2014-01-02 | Johnson & Johnson Consumer Companies, Inc. | Sunscreen compositions containing an ultraviolet radiation-absorbing polyester |
| US9469725B2 (en) | 2012-06-28 | 2016-10-18 | Johnson & Johnson Consumer Inc. | Ultraviolet radiation absorbing polymers |
| BR112014032798B8 (pt) | 2012-06-28 | 2022-08-16 | Chenango Two Llc | Composição |
| US10874603B2 (en) | 2014-05-12 | 2020-12-29 | Johnson & Johnson Consumer Inc. | Sunscreen compositions containing a UV-absorbing polyglycerol and a non-UV-absorbing polyglycerol |
| US10596087B2 (en) | 2016-10-05 | 2020-03-24 | Johnson & Johnson Consumer Inc. | Ultraviolet radiation absorbing polymer composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5371148A (en) * | 1993-06-23 | 1994-12-06 | Union Carbide Chemicals & Plastics Technology Corporation | Reactive polymers having pendant flexible side chains prepared from ethylenically unsaturated carbodiimides |
| WO1995023609A1 (en) * | 1994-03-04 | 1995-09-08 | Eli Lilly And Company | Antithrombotic agents |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU65622A1 (zh) * | 1972-06-29 | 1974-01-04 | ||
| GB1460649A (en) * | 1974-11-08 | 1977-01-06 | Gillette Co | Sunscreen compositions |
| US4524061A (en) * | 1983-04-22 | 1985-06-18 | Gaf Corporation | Polymeric sunscreens |
| JPH03220213A (ja) * | 1988-08-30 | 1991-09-27 | Dainippon Ink & Chem Inc | 紫外線吸収剤共重合型非造膜性樹脂エマルジョンの製法ならびに該樹脂を含有する化粧料 |
| JP3238064B2 (ja) * | 1996-02-05 | 2001-12-10 | ティーディーケイ株式会社 | 低誘電性高分子材料の使用方法ならびにそれを用いたフィルム、基板および電子部品の使用方法 |
| DE19634401A1 (de) * | 1996-08-26 | 1998-03-05 | Basf Ag | Kosmetisches Mittel mit polymergebundenen Benzophenonchromophoren |
-
1997
- 1997-08-08 DE DE19734445A patent/DE19734445A1/de not_active Withdrawn
-
1998
- 1998-08-07 DE DE59812202T patent/DE59812202D1/de not_active Expired - Lifetime
- 1998-08-07 EP EP98114881A patent/EP0896006B1/de not_active Expired - Lifetime
- 1998-08-07 US US09/131,391 patent/US6143850A/en not_active Expired - Lifetime
- 1998-08-07 JP JP22461198A patent/JP4093510B2/ja not_active Expired - Lifetime
- 1998-08-07 ES ES98114881T patent/ES2231923T3/es not_active Expired - Lifetime
- 1998-08-08 CN CN98117499A patent/CN1107085C/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5371148A (en) * | 1993-06-23 | 1994-12-06 | Union Carbide Chemicals & Plastics Technology Corporation | Reactive polymers having pendant flexible side chains prepared from ethylenically unsaturated carbodiimides |
| WO1995023609A1 (en) * | 1994-03-04 | 1995-09-08 | Eli Lilly And Company | Antithrombotic agents |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11124564A (ja) | 1999-05-11 |
| EP0896006A3 (de) | 2000-09-13 |
| CN1216769A (zh) | 1999-05-19 |
| DE19734445A1 (de) | 1999-02-11 |
| DE59812202D1 (de) | 2005-01-20 |
| ES2231923T3 (es) | 2005-05-16 |
| JP4093510B2 (ja) | 2008-06-04 |
| EP0896006B1 (de) | 2004-11-03 |
| EP0896006A2 (de) | 1999-02-10 |
| US6143850A (en) | 2000-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1107085C (zh) | 亲油的聚合紫外吸收剂 | |
| CN100341902C (zh) | 有机介质中聚合物的分散体及其组合物 | |
| CN1082992C (zh) | 可光致交联的液晶 | |
| CN1279112C (zh) | 接枝共聚物颜料分散剂组合物 | |
| CN1099042A (zh) | 由不饱和的聚氧乙烯单体制取的聚合物眼科接触镜 | |
| CN1145661C (zh) | 可生物降解的和热敏的聚磷腈和它们的制备方法 | |
| CN1909877A (zh) | 含类视色素的制剂 | |
| CN1504488A (zh) | 嵌段聚合物和包含该聚合物的化妆品 | |
| CN1046937C (zh) | 木酚素系化合物的制备方法 | |
| CN1428141A (zh) | 两亲型共聚物的应用，其稳定的分散体和化妆品组合物 | |
| CN86106777A (zh) | 改善低温性能的中间馏分组合物 | |
| CN1122036C (zh) | 用于制备奥氮平的中间体和方法 | |
| CN1168722C (zh) | 二间苯二酚基-烷氧基-和-芳氧基-均三嗪 | |
| CN1026589C (zh) | 制备3r，4r-乙基-[(1-甲基-1h-咪唑-5-基)甲基]-2-吡咯烷酮的n-取代的衍生物的方法 | |
| CN1102041A (zh) | 新型憎醇-憎油含氟表面活性剂，其中间体，制备方法及应用 | |
| CN1223331C (zh) | 美甲产品 | |
| CN1957001A (zh) | 含有一个自由基聚合基团的烷氧基胺 | |
| CN1103577A (zh) | 含有有机氟烃化合物的无水固体分散体及其化妆品用途 | |
| CN1015463B (zh) | 热稳定的烯类聚合物的制备方法 | |
| CN1152662C (zh) | 口红用组合物 | |
| CN1017964B (zh) | 用作化妆品基质的皮肤外用剂 | |
| CN1021450C (zh) | 高环氧当量聚环氧化物的立构稳定化非水相分散体的制法 | |
| CN1102090A (zh) | 以月见草油为原料制取的化妆品 | |
| CN1957907A (zh) | 一种粉底液 | |
| CN1522374A (zh) | 塑料透镜材料、塑料透镜组合物、通过固化该组合物所获得的塑料透镜和生产该塑料透镜的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| 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 |