TW200301136A - Stabilization of vitamins in water-in-silicone oil (W/O) emulsions - Google Patents
Stabilization of vitamins in water-in-silicone oil (W/O) emulsions Download PDFInfo
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- TW200301136A TW200301136A TW091135838A TW91135838A TW200301136A TW 200301136 A TW200301136 A TW 200301136A TW 091135838 A TW091135838 A TW 091135838A TW 91135838 A TW91135838 A TW 91135838A TW 200301136 A TW200301136 A TW 200301136A
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- Prior art keywords
- emulsion
- silicone
- tocopherol
- vitamin
- patent application
- Prior art date
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- 239000000839 emulsion Substances 0.000 title claims abstract description 28
- 229940088594 vitamin Drugs 0.000 title claims abstract description 13
- 229930003231 vitamin Natural products 0.000 title claims abstract description 13
- 235000013343 vitamin Nutrition 0.000 title claims abstract description 13
- 239000011782 vitamin Substances 0.000 title claims abstract description 13
- 229920002545 silicone oil Polymers 0.000 title description 4
- 230000006641 stabilisation Effects 0.000 title description 3
- 238000011105 stabilization Methods 0.000 title description 3
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 42
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 34
- 239000012071 phase Substances 0.000 claims abstract description 26
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 23
- 229920000570 polyether Polymers 0.000 claims abstract description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004480 active ingredient Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000008346 aqueous phase Substances 0.000 claims abstract description 9
- 150000003722 vitamin derivatives Chemical class 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 45
- -1 Tocopheryl palmitate Chemical compound 0.000 claims description 39
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000011732 tocopherol Substances 0.000 claims description 7
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 claims description 6
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 claims description 6
- 229930003799 tocopherol Natural products 0.000 claims description 6
- 229960001295 tocopherol Drugs 0.000 claims description 6
- 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 claims description 6
- 229930003427 Vitamin E Natural products 0.000 claims description 5
- 235000010384 tocopherol Nutrition 0.000 claims description 5
- 239000011709 vitamin E Substances 0.000 claims description 5
- 235000019165 vitamin E Nutrition 0.000 claims description 5
- 229940046009 vitamin E Drugs 0.000 claims description 5
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 claims description 4
- PGTMTTGPWLZNQO-UHFFFAOYSA-N 2-dodecyl-1,3,5,7,9,11-hexaoxa-2,4,6,8,10,12-hexasilacyclododecane Chemical compound C(CCCCCCCCCCC)[SiH]1O[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH2]O1 PGTMTTGPWLZNQO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 claims description 3
- YFCGDEUVHLPRCZ-UHFFFAOYSA-N [dimethyl(trimethylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C YFCGDEUVHLPRCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229960002685 biotin Drugs 0.000 claims description 3
- 235000020958 biotin Nutrition 0.000 claims description 3
- 239000011616 biotin Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- YDWFEBCFKZDCTM-UHFFFAOYSA-N hexadecyl(silyloxysilyloxysilyloxysilyloxysilyloxysilyloxy)silane Chemical compound C(CCCCCCCCCCCCCCC)[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH3] YDWFEBCFKZDCTM-UHFFFAOYSA-N 0.000 claims description 3
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 3
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 3
- KKADPXVIOXHVKN-UHFFFAOYSA-N 4-hydroxyphenylpyruvic acid Chemical compound OC(=O)C(=O)CC1=CC=C(O)C=C1 KKADPXVIOXHVKN-UHFFFAOYSA-N 0.000 claims description 2
- GHOKWGTUZJEAQD-UHFFFAOYSA-N Chick antidermatitis factor Natural products OCC(C)(C)C(O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-UHFFFAOYSA-N 0.000 claims description 2
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 claims description 2
- IELOKBJPULMYRW-NJQVLOCASA-N D-alpha-Tocopheryl Acid Succinate Chemical compound OC(=O)CCC(=O)OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C IELOKBJPULMYRW-NJQVLOCASA-N 0.000 claims description 2
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 claims description 2
- MSCCTZZBYHQMQJ-AZAGJHQNSA-N Tocopheryl nicotinate Chemical compound C([C@@](OC1=C(C)C=2C)(C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)CC1=C(C)C=2OC(=O)C1=CC=CN=C1 MSCCTZZBYHQMQJ-AZAGJHQNSA-N 0.000 claims description 2
- 229930003471 Vitamin B2 Natural products 0.000 claims description 2
- 125000005376 alkyl siloxane group Chemical group 0.000 claims description 2
- 229940099418 d- alpha-tocopherol succinate Drugs 0.000 claims description 2
- HNDMWPOGQFUHIL-UHFFFAOYSA-N dodecyl(silyloxysilyloxysilyloxysilyloxy)silane Chemical compound CCCCCCCCCCCC[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH3] HNDMWPOGQFUHIL-UHFFFAOYSA-N 0.000 claims description 2
- 229960000304 folic acid Drugs 0.000 claims description 2
- 235000019152 folic acid Nutrition 0.000 claims description 2
- 239000011724 folic acid Substances 0.000 claims description 2
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940055726 pantothenic acid Drugs 0.000 claims description 2
- 235000019161 pantothenic acid Nutrition 0.000 claims description 2
- 239000011713 pantothenic acid Substances 0.000 claims description 2
- 229960002477 riboflavin Drugs 0.000 claims description 2
- 229960000984 tocofersolan Drugs 0.000 claims description 2
- 229950009883 tocopheryl nicotinate Drugs 0.000 claims description 2
- 235000019164 vitamin B2 Nutrition 0.000 claims description 2
- 239000011716 vitamin B2 Substances 0.000 claims description 2
- WGVKWNUPNGFDFJ-DQCZWYHMSA-N β-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C WGVKWNUPNGFDFJ-DQCZWYHMSA-N 0.000 claims 2
- 229930003451 Vitamin B1 Natural products 0.000 claims 1
- 229940087168 alpha tocopherol Drugs 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 229940066595 beta tocopherol Drugs 0.000 claims 1
- 238000010586 diagram Methods 0.000 claims 1
- 230000004151 fermentation Effects 0.000 claims 1
- 238000000855 fermentation Methods 0.000 claims 1
- 235000010382 gamma-tocopherol Nutrition 0.000 claims 1
- 229960003495 thiamine Drugs 0.000 claims 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 claims 1
- 235000010374 vitamin B1 Nutrition 0.000 claims 1
- 239000011691 vitamin B1 Substances 0.000 claims 1
- 235000004835 α-tocopherol Nutrition 0.000 claims 1
- 239000002076 α-tocopherol Substances 0.000 claims 1
- 239000011590 β-tocopherol Substances 0.000 claims 1
- 235000007680 β-tocopherol Nutrition 0.000 claims 1
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 claims 1
- 239000002478 γ-tocopherol Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000007762 w/o emulsion Substances 0.000 abstract description 2
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- 238000000034 method Methods 0.000 description 18
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- 238000009835 boiling Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 125000005702 oxyalkylene group Chemical group 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
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- 239000003431 cross linking reagent Substances 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- 229960001484 edetic acid Drugs 0.000 description 5
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 5
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- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 4
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- 239000003054 catalyst Substances 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- 229940045997 vitamin a Drugs 0.000 description 1
- 229940011671 vitamin b6 Drugs 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 1
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- 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
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
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- A61K8/06—Emulsions
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
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- 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
- A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
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- A61K8/00—Cosmetics or similar toiletry preparations
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- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/67—Vitamins
- A61K8/678—Tocopherol, i.e. vitamin E
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- 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
- A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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Description
200301136 ⑴ 玖、發明說明 (發明說明應敛明:發明所屬之技術領域、先前技術、内容、實施方式及圖式簡單說明) 技術領域 本發明係關於組合物及將維生素(例如,維生素E)加入 石夕油包水乳化液(w/〇)中並使其安定化之方法。更詳細 地說’本發明係關於使用通常為線型矽酮聚醚作為該矽 酮乳化劑’合併有機乳化劑使維生素於該W/〇乳化液内 安定化之用途。 先前技藝 已知維生素A及維生素C可加入矽油包水(w/〇)組合物 内供皮膚保養應用,且其在市場上大受歡迎。 ,、、:而、’隹生素E之活性型式(亦即,生育紛)在此種w /〇 系統内通常顯示降解現象。因此,在個人保養領域内有 需要安定化維生素,特別為含安定化維生素£之矽油包 水乳化液(W/0)。 雖然國際專利公告w〇 00/728 1 7 Al(2000年,12月7日) 描述某些含維生素之W/0乳化液,但是用以製備w/〇乳 化液之該碎酮彈性體組份是一種可藉由使用交聯劑(其係 為含矽原子之不飽和化合物’㈣’乙埽基末端性矽酮) 得到之組合物。 然而根據本發明,已意外發現可藉由佬 田使用X聯劑(其 係為不含矽原子之不飽和化合物,亦即, ^ Μ,03、二烯交聯 性碎酮彈性體)得到之矽酮彈性組合物取 丨入丄述矽酮彈性 體組合物以製成新穎且改良之W/〇乳化液。 發明說明續頁 200301136 (2) 發明内容 本發明係關於組合物,例如,具有非連績水性相分散 在連續油相内之油包水(W/0)乳化液。該W/0乳化液之連 績油相包含線型矽酮聚醚,α,ω -二烯交聯性碎酮彈性體 ,及非離子性有機乳化劑。該W/0乳化液不含使用含矽 原子之不飽和化合物製成之梦酮彈性體。 該W / Ο乳化液之非連續水性相或該W / 0乳化液之連續 油相較佳分別含水(溶性活性成份或油溶性活性成份)。 該W / 0乳化液之連續油相可包含一或多種溶劑,例如 ,八甲基環四矽氧烷,十甲基環五矽氧烷,十二甲基環 六矽氧烷,六甲基二矽氧烷,八甲基三矽氧烷,十甲基 二矽氧燒,八甲基三矽氧燒,十甲基四矽氧燒,十二甲 基五矽氧烷,十四甲基六矽氧烷,十六甲基七矽氧烷。 自詳細說明文之考慮事項可瞭解本發明這些及其它特 徵。 實施方法 線型(亦即,非交聯)矽酮聚醚 使用以製備根據本發明之組合物之該線型(亦即,非交 聯)碎酮I聚醚通常可分散在該油相中。其可具有耙型結構 ’其中該聚氧乙締或聚氧乙烯-聚氧丙埽共聚單位可接枝 在孩碎氧烷主鏈上,或該SPE可具有ΑΒΑ嵌段共聚結構 其中Α表示該ΑΒΑ結構之聚酸部份,而該Β表示該碎氧 烷部份。 文中適用之非交聯矽酮聚醚具該通式 200301136 (3) 發明說明續頁: ’最佳為該通式MDo^oD’i.soM,其中Μ表示單官能基單 位R3Si01/2,D表示二官能基單位!,而D,表示二 官能基單位RR’Si〇2/2。在這些通式中,r是含1-6個碳原 子之烷基,或芳基,且R,是含氧伸烷基部份。該R,基可 以只含環氧乙燒(EO)單位;環氧乙烷(E〇)及環氧丙烷(p〇) 單位之組合;或環氧乙烷(E〇)單位,環氧丙烷(p〇)單位 ’及環氧丁燒(BO)單位之組合。R,基較佳包括呈e〇31〇〇 POhco大約比率(最佳呈Ε〇3·3()Ρ〇ι·3()之比率)之氧伸烷基 單位。 R1部份通常包括可以連接該R,之氧伸烷基部份與該矽 氧燒主鏈之一價基團,例如,-CmH2m-,其中m為2-8。此 種部份亦含該R1之氧伸烷基部份之端基,例如,氫,羥 基,或烷基,芳基,烷氧基,或醋酸基。 文中使用之非交聯矽酮聚醚亦可以是一種具有該通式 最佳為該通式%丨〇丨㈠之種 類,其中NT表示單官能基單位R2R,Si〇i/2 , 〇表示二官能 基單位RsSi02/2,且D,表示二官能基單位RR,si〇^。在 這些通式中,R可以是含丨_6個碳原子之烷基,或芳基, 而且R表示含氧伸燒基部份。如前述,R,基通常只含環 氧乙燒(EO)單位或環氧乙烷(E〇)及環氧丙烷(p〇)單位之 組合。此種R,基團包括呈e〇3 i〇〇p〇〇 i〇〇(最佳e〇3 3〇ρ〇ΐ 3。) 比之這些氧伸烷基單位。 亦如上述,R’部份通常包括用以連接&,之氧伸烷基部 份與該碎氧燒主鏈之二價基團-CmH2m_,其中111為。此 200301136 發明說明續頁 (4) 外,該R’部份包括Rf氧伸烷基部份之端基,例如,氫, 藉基,垸基,芳基,燒氧基,或酷酸基。 此外,文中使用之非交聯矽酮聚醚可具有該通式 D’MooDYmM,其中D”表示二官能基單位RR”Si02/2, 且11”為含1-40個碳原子之烷基。M,D,D’,及R如同上 文定義。 表1表示與這些通式相符之部份代表性線型(亦即,非 交聯)矽酮聚醚,其可以使用以製備根據本發明之乳化液。 表1
線型矽酮聚醚 線型(亦即,非交聯)矽酮聚醚之公稱結 構 A MD86D’36M 其中 R為-CH3 且 R’為 -(CH2)3(EO)12OH B MD108Df10M 其中 R為-CH3 且 Rf 為 -(CH2)3(EO)10(PO)4OH C μτγ75μ’其中 r^-ch3jlr’為 -(CH2)3(EO)18(PO)18OAc D M’D’5〇Mf 其中 R為-CH3JLRf 為 -(CH2)3(EO)18(PO)18OH E ΜΤΓ13Μ’其中 R^-CH3 且 R’為 -(CH2)3(EO)12OH F MD22D’2M 其中 R^-CH3 且 R’為 .(CH2)3(EO)12(PO)12OH G MD396D’4M其中R為-CH3且尺為 -(CH2)3(EO)18(PO)18OH 揮發性矽酮,亦即該溶劑 文中使用之溶劑為揮發性矽酮,通常為低分子量矽酮 20〇301I36 (5) 頁 油’且最佳為該通式(R’f’2SiO)d環狀烷基矽氧烷或該通式 R…3Si〇(Rm2si0)eSiR’’Y·型烷基矽氧烷,其中r,m為含 1-6個碳原子之烷基,d為3-6,且e為〇_5。然而,最佳為 該通式{(CH3)2SiO}d揮發性環狀甲基矽氧烷及該通式 (CH3)3SiO{(CH3)2SiO}eSi(CH3)3,且其中 d為 3-6 而 e為 0-5 。該揮發性甲基矽氧烷之沸點較佳小於2 5 0 °C,黏度為 0.65-5.0厘斯(毫米2/秒)。 線型揮發性甲基矽氧烷之部份實例為通式 Me3SiOSiMe3六甲基二矽氧烷(MM),其沸點為l〇〇°C,黏 度為0.65毫米2/秒;通式Me3SiOMe2SiOSiMe3八曱基三矽 氧烷(MDM).,其沸點為152 °C,黏度為1.04毫米2/秒;通 式為Me3SiO(Me2SiO)2SiMe3十甲基四矽氧烷(MD2M),其 沸點為194 °C , 黏度為1·53毫米2/秒;通式 Me3SiO(Me2SiO)3SiMe3十二甲基五矽氧烷(MD3M),其沸 點為229 °C , 黏度為2.06毫米2/秒,及通式 Me3SiO(Me2SiO)4SiMe3十四甲基六矽氧烷(MD4M),其沸 點為245 °C , 黏度為2.63毫米2/秒,及通式 Me3SiO(Me2SiO)5SiMe3十六甲基七矽氧烷(MD5M),其沸 點為270 °C ,黏度為3.24毫米2/秒。在這些及以下通式中 之Me表示該甲基CH3。 環狀揮發性甲基矽氧烷之部份實例為通式(1^^23丨0)3六 甲基環三矽氧烷(D3),其於室溫下為固體,且沸點為134 °C ;通式(Me2SiO)4八甲基環四矽氧烷(D4),其沸點為176°C, 黏度為2·3毫米2/秒;通式(Me2SiO)5十甲基環五矽氧烷(D5) -10- 200301136 發明說_明續頁 (6) ,其沸點為210°C,黏度為3·87毫米2/秒;及通式(Me2SiO)6 十二甲基環六矽氧烷(D6),其沸點為245 °C,黏度為6.62 毫米2/秒。 矽酮樹膠
該矽酮樹膠最佳為高分子量矽烷醇官能性聚合物,但 是亦包括聚二甲基矽氧烷樹膠。此種樹膠為本技藝所知 ,且很容易購自賣方,例如,The Dow Corning Corporation, Midland, Michigan。此種材質之結構通常如下式: R2 R2 —Si—ο--S,·— ·〇 R2 *Si—R1 R2 R2 R2 其中n為5,000至50,000整數 表示-OH ;具有1-6個碳原子 ,或丙基;芳基,例如,苯 ,甲苯基或二甲苯基;或芳 基,或2-苯基丙基。R2表示 如,曱基,乙基,或丙基; ;烷芳基,例如,曱苯基或 ,爷基,苯基乙基,或2 -苯 烯基(例如,乙晞基)之矽酮 為-OH而R2為甲基之矽酮樹 之矽酮樹膠。 ,較佳為 10,000-50,000。R1 之烷基,例如,曱基,乙基 基或聯苯基;燒芳基,例如 烷基,例如,芊基,苯基乙 具有1 - 6個碳原子之烷基,例 芳基,例如,苯基或聯苯基 二甲苯基;或芳烷基,例如 基丙基。亦可使用其中R1為 樹膠。然而,最佳為其中R1 膠;及其中R1及R2皆為曱基 -11 - 200301136 (7) 發明說明績頁 α,ω-二晞交聯矽酮彈性體 如文中使用,該名辭α,ω-二烯交聯矽酮彈性體意指其 結構内不含氧伸烷基單位之α,ω-二烯交聯矽酮彈性體。 其通常在本技藝中被稱為非乳化性矽酮彈性體,其意指 不含聚氧伸烷基。另一方面,根據本發明適用之該α,ω_ 二烯交聯矽酮彈性體為美國專利第5,6 54,362號( 1 997年8 月5日)所述之組合物。 如該美國專利第5,654,362號所詳述,該α,ω-二烯交聯 矽 酮彈性體之製 法為使 (Α) 該通式 R3SiO(R、SiO)a(R’’HSiO)bSiR3 含 sSi-H之聚矽氧烷或視需 要選用之通式 HR2SiO(R’2SiO)eSiR2H 或通式 HR2SiO(R’2SiO)a(R”HSiO)bSiR2H含 sSi-H之聚矽氧烷(其 中R,R’,Rn為具1-6個碳原子之烷基,a為0-250,b為1-250,c 為 0-250)與(B)通式 CH2 = CH(CH2)XCH = CH2(其中 X 為1-20)ω-二烯進行反應。該反應係於鉑觸媒及(C)低分 子量矽酮油或其它溶劑存在下進行。與過去使用以製備 矽酮橡膠粉末比較,該反應系統具非水性。 矽酮橡膠粉末 如文中使用,該名辭矽酮橡膠粉末意指通常根據美國 專利第4,742,142號(1988年5月3日)所述之方法製成之組 合物。 矽酮橡膠粉末(有時候稱為Ε-粉末)是具平均顆粒大小 分佈約0 · 1 - 2 0 0微米之硫化矽酮橡膠,亦即,交聯聚二甲 基矽氧烷(PDMS)。使用水性乳化方法以製備該矽酮橡膠 200301136 杳鸮說明績頁] (8) 粉末,因為此種方法可產生球形之該顆粒,並得到該所 要顆粒大小分佈。本質上,該乳化法由以下步騾組成: 在水中使用一或多種表面活化劑乳化可固化,液態矽酮 彈性體組合物,繼而進行固化步驟,最後移除水。該乳 化法之特性為可以產生球形之該顆粒及在某範圍内可以 相當良好地控制顆粒大小分佈。 通常採用兩種交聯矽氧烷聚合物之固化之反應,其中 一種為於鉑觸媒存在下添加氫化矽〇SiH)至乙烯基官能 性矽氧烷内,亦即氫甲矽烷化反應,而另一種方法為使 用反應性矽使矽烷醇官能性矽氧烷進行縮合反應。根據 該交聯步驟使用那一種方法(縮合反應或氫甲矽烷化反應) ,用以製造矽酮橡膠粉末之聚合物為OH或乙烯基官能性 聚合物。這些聚合物通常具適當低分子量(MW),因為其 同時具備的低黏度可以使其容易經由習用方法乳化。就 製備矽酮橡膠粉末而言,較佳為黏度低於約1 000 cP(厘 泊)之聚合物。 交聯劑實際上可以是可溶於該聚合物内之任何多官能 性反應性矽氧烷或矽烷。較佳交聯劑為氫化矽( = SiH)官 能性矽氧烷,因為其具高反應性及不會產生副產物。這 些矽氧烷可以是線型聚甲基氫矽氧烷,或聚二甲基矽氧 烷與聚甲基氫矽氧烷之共聚物。該氫甲矽烷化反應(添加 = SiH至乙烯基官能性矽氧烷内)之優點為不會形成副產物 。反之,該縮合反應( = SiH與=SiOH之反應)會釋放大量H2。 可使用標準乳化高剪切設備(例如,均質器或膠體磨機) 200301136 發明說明續頁 (9) 進行該乳化程序。所使用表面活化劑可以具離子性或非 離子性,或兩者之組合,但是較佳為非離子表面活化劑 。較佳非離子表面活化劑為乙氧化烷酯。表面活化劑之 含量佔該矽酮聚合物重量之約0.5 - 5 %。應該瞭解一旦移 除水時,該表面活化劑仍然留在該矽酮橡膠粉末内。
必需已形成該顆粒後,才進行矽酮橡膠粉末内之交聯 作用。然而,一旦合併這三種基本成份(亦即’(i)該官能 性聚合物,(ii)該交聯劑,及(iii)該觸媒)時,即可進行 交聯反應。因此,必需使用某些方法以確保該重要的交 聯反應開始之前,形成顆粒。可以使用觸媒抑制劑或乳 化後添加該觸媒以完成上述步驟。在某些情況下,必需 使該乳化液經加熱以增加該交聯反應之速率。一旦完成 交聯反應時,可藉由移除水以採集該顆粒。可藉由使用 例如,真空蒸餾法或噴霧乾燥法完成該水移除步騾。在 真空蒸餾法中,必需於真空下使用混合機,提供熱及攪 拌。然而較佳方法為噴霧乾燥法,因為其具高效率,且 可以連續操作。 部份交聯矽酮聚醚 使用在本申請案之各該實例中之以二級矽為主之乳化 劑為如通常在美國專利第4,853,474號(1989年8月1日)及 第5,136,068號(1992年,8月4日,所述之矽酮組合物, 這兩種專利其各教示製造此種部份交聯組合物之方法。 這些組合物亦很容易以商業基礎購自賣方,例如,the Dow Corning Corporation, Midland, Michigan。 -14- 200301136 發明說明續頁 (ίο) 有機乳化劑(群) 如文中使用,該各辭有機乳化劑有意排除含矽原子之 乳化劑。另一方面,該有機乳化劑為非離子表面活性劑 。一些適合的非離子表面活化劑種類為羧基化醇乙氧化 物,羧基化烷基酚乙氧化物,乙氧化醇,乙氧化脂肪酸 ,乙氧化脂肪酸,乙氧化脂肪油,甘油酯,聚甘油脂肪 酉旨,乙氧化甘油醋,山梨糖醇纤衍生物,蔑糖i旨及衍生 物,葡萄糖酯及衍生物。最能代表本發明之有機乳化劑 實例為乙氧化脂肪酸,例如,EMULSYNT 1 05 5,及山梨 糖醇酐衍生物,例如,TWEEN 20。更詳細地說,EMULSYNT 1 0 5 5為聚甘油脂肪酯(亦即,聚甘油-4油酸酯)及乙氧化 脂肪酯(亦即,PEG-8丙二醇可可酯)之混合物。另一方面 ,TWEEN 20為聚氧乙烯(20)山梨糖醇酐單月桂酸酯。 活性成份 可以加入根據本發明組合物内之一些活性成份實例為 水溶性維生素及水溶性藥物,其包括維生素B i,維生素 B2,維生素B6,維生素Bi2,於驗酸,葉酸,生物素,及 泛酸。 此外,該組合物亦可含有油溶性活性成份,例如,維 生物及藥物,其包括維生素E,生育酚,維生素E酯,α-生育齡,β -生育紛,γ -生育齡,△-生育紛,Tocophersolan ,生育酚醋酸酯,生育酚棕櫚酸酯,生育酚亞油酸酯, 生育酚菸鹼酸酯,生育酚琥珀酸酯,及其混合物。 鹽組份 -15- 200301136 發明說明續頁 (11) 如文中使用,該名辭”鹽”意指無機鹽或有機鹽,其包 括通稱為電解質之化合物。
一些適合的無機鹽實例包括氯化#5,硫酸鎂,氯化鎂 ,硫酸#3,硫代硫酸#3,氯化鋼,磷酸銷,氯化铵,碳 酸銨,硫酸鐵,硫酸鋁,氯化鋁,鋁氯水合物,鋁倍半 氯水合物,鋁二氯水合物,鋁錘四氯水合甘胺酸,鋁锆 三氯水合物,鋁結四氯水合物,鋁锆五氯水合物,及鋁 锆八氯水合物。
一些適合的有機鹽實例包括乳酸铭納,酷酸納,去氫 酷酸鋼,丁氧基乙氧基酷酸制,辛酸鋼,檸檬酸納,乳 酸鈉,二羥基甘胺酸鈉,葡萄糖酸鈉,麩胺酸鈉,羥基 甲基磺酸鈉,草酸鈉,苯酚鈉,丙酸鈉,糖精鈉,柳酸 鈉,肌胺酸納,甲苯續酸鋼,天冬胺酸鎂,丙酸#5,糖 精鈣,d -羥基蔗糖鈣,銥基醋酸鈣,辛酸鋁,擰檬酸鎂 ,二醋酸鋁,甘胺酸鋁,乳酸鋁,曱二磺酸鋁,苯酚磺 酸鋁,天冬胺酸鉀,雙酞酸鉀,雙酒石酸鉀,糖硫酸鉀 ,山梨酸鉀,黢基醋酸鉀,甲苯磺酸鉀,及乳酸鎂。 選用組份 由於乳化液很容易被微生物污染所以需要使用防腐劑 作為本發明該組合物之選用組份,且可以使用之一些化 合物實例包括曱醛,柳酸,苯氧基乙醇,DMDM乙内醯 脲(1,3 -二羥甲基-5,5 -二甲基乙内醯脲),5 -溴-5 -硝基-1,3 -二哼烷,對羥基苯甲酸甲酯,對羥基苯甲酸丙酯,山梨 酸,咪唑烷基(其係以品名GERMALL® II購自Sutton -16- 200301136 (12) 發明說巧績頁
Laboratories,Chatham, New Jersey),苯甲酸鋼,5 -氯- 2-甲基-4-異噻唑啉-3-酮(以品名KATHON CG講自Rohm & Haas Company,Philadelphia,Pennsylvania,丁基胺基甲 fei 礎丙块酉旨(以品名 GLYCACIL® L講自 Lonza Incorporated, Fair Lawn,New Jersey 0 該組合物可包含凍結/解凍安定劑作為選用組份,其包 括下述化合物,例如,乙二醇,1,2 -丙二醇,甘油,1,3 -丙二醇。 该乳化液可包含之另一種選用組份為腐姓抑制劑,例 如燒醇胺;無機磷酸鹽,例如,二硫磷酸鋅;無機膦酸 鹽;無機亞硝酸鹽,例如,亞硝酸鈉;矽酸鹽;烴基矽 酸鹽,基磷酸胺;號珀酸纤,例如,十二晞基號珀酸 酐’琥珀酸胺;或鹼土磺酸鹽,例如,磺酸鈉或磺酸鈣。 亦可包含螯合劑,例如,乙二胺四醋酸(EDTA)及氮三 醋酸(NTA)。 可藉由合併該油相A及水相B中各該下述代表量(其係 以重量%表示)之組份,形成根據本發明之組合物。 (1)以10 0 %孩乳化劑為基準計(不包括任何溶劑),〇. 2· 3 · 0 %該矽酮乳化劑(群); (ii) 20-80%該揮發性矽_ ; (iii) 以100%琢樹勝為基準計(不包括任何溶劑),〇·8% 該矽酮樹膠; (iv) 以100%該彈性體為基準計(不包括任何溶劑),〇 2_ 10%該矽酮彈性體; 36
(13) 發明1¾明續買 (V)〇-5%非根據本發明之组合物之該矽酮橡膠粉末; (v〇CM-4%該有機乳化劑(群),其包括該油相及水 用之乳化劑; (vii)15-75% 水; (viii)〇.l-3%該電解質,亦即,氯化執; (iX)0.1-3%該螯合劑’亦即,EDTA,或其它選用组份 ;及 (X) 0 · 1 - 8 %該活性成份(群),亦即,維生素。 可以使用機械方法製備根據本發明之組合物,且該方 法簡單地包括將該油相及水相混合在一起,然後使用實 驗室均質械或其它可應用激烈攪拌之裝置使該相混合物 均質化。 實例
陳述以下實例以更詳細說明本發明 實例I-III 如表2所示,製成了種維生素E W/0組合物。使用以製 備該組合物之各該成份含量係以重量%表示。比較實例I 及II顯示在約2天内發生幾乎立即的分離現象,或顯示顏 色變化;然而’如實例III之W/0組合物(其係為根據本發 明之組合物)於5 0 °C下經過一些時間(約7週)仍呈安定狀 態,且於室溫下貯存時,其安定性可維持5個月之久。 -18· 200301136 (14) 表2 相A 說明-油相 I-比較實例 II-比較實例 III-本發明 第一級矽酮 乳化劑 10%線型(亦即,非交聯) 矽酮聚醚及90% D5 8.5 10.0 8.5 揮發性矽酮 十甲基環五矽氧烷(D5) 16.25 20.0 18.0 矽酮樹膠及 揮發性矽酮 15% OH末端嵌段聚矽氧 烷及85%DS 1.0 1.0 2.0 矽酮彈性體 12% α,ω-二晞交聯矽酮彈 性體及88% D5 3.0 5.0 3.0 矽酮粉末 矽酮橡膠粉末 2.5 0.5 無 第一級有機 乳化劑 非離子表面活性劑 Emulsynt 1055,聚甘油-4 油酸酯及PEG-8丙二醇可 可酸酯 無 無 2.0 第二級矽酮 乳化劑 部份交聯矽酮聚醚 無 1.0 無 相B 說明-水相 I-比較實例 II-比較實例 III-本發明 H20 水 66.5 60.7 64.7 第二級有機 乳化劑 聚氧乙晞(20)山梨糖醇酐 單月桂酸酯-TWEEN 20 0.5 0.5 0.5
-19- 200301136 發明說明續頁 (15) 電解質 氯化鈉 1.0 1.0 1.0 螯合劑 乙二胺四醋酸,EDTA 0.1 0.1 0.1 維生素E 生育酚 0.7 0.7 0.7
在比較實例I中,已發現當添加生育酚時,該黏性會降 低,且會產生幾乎立即的分離現象。在比較實例II中, 可發現黏性只稍為降低。需注意,比較實例II所使用之 該矽酮橡膠粉末係以後添加方式進行。然而,比較實例II 中之該W/0組合物之安定性僅能維持數天。在實例III(其 係為根據本發明該組合物)中,於製備該組合物之整個過 程從頭至尾,該W/0組合物之黏性仍可維持安定。於室 溫下在塑膠容器内該W/0組合物之貯存安定性可維持5個 月。 使用100克份量以製備表2所示這3種W/0組合物。這些 W/0組合物之製法為合併使用以形成部份該組合物之油 相A之該矽酮乳化劑,該揮發性矽酮,該矽酮樹膠,該 矽酮彈性體;及/或該矽酮橡膠粉末,該第一級有機乳化 劑。使用以形成水性相B之各該組份分散在各別的容器 内。緩慢添加水性相B至油相B中,並於紊流條件下混合 。B相添加至油相内需費時約1 5-20分鐘。然後再使已合 併之A相及B相一起混合15-20分鐘,形成該最終W/0組合 物0 -20- 200301136 發明說明續頁 (16) 應該注意的是比較實例I及II各表示W/0乳化液,其中 該矽酮組份(亦即,該矽酮橡膠粉末)是一種藉由使用交 聯劑(其係為含矽原子之不飽和化合物,亦即,乙晞基端 基矽酮)得到之組合物。反之,實例111(其係為根據本發 明該實例)可不含該矽酮橡膠粉末,且可以使用α,ω二烯 交聯矽酮彈性體取代。 根據本發明製成之組合物可用於各種在店面裡買賣 (OTC)的個人保護產品内。因此,其可使用在下述產品 中:抑汗劑,除臭劑,皮膚乳膏,皮膚保養水,保濕劑 ,臉部處理劑(例如,粉刺或皺紋去除劑),個人及臉部 清潔劑,沐浴油,香水,古龍水,香粉,防曬劑,刮鬍 前及刮鬍後之洗劑,液態皂,刮鬍皂,刮鬍泡末,洗髮 精,護髮劑,噴髮劑,泡泳乳膠,持久劑,脫毛劑,角 質層護膜劑,化粧品,色粧品,粉底,胳紅,口紅,唇 膏,眼線筆,睫毛膏,除油劑,色粧去除劑,散劑。該 組合物亦可作為藥劑,殺生物劑,除草劑之載劑,該載 劑可以將各種水溶性物質及油溶性物質加入親水性及疏 水性系統内。 只要不達背本發明之基本特徵,文中所述之化合物, 組合物,及方法可以有各種變異。明確地說。文中所說 明之各該具體實例僅為例證用,並無意限制該附加申請 專利範圍以外之本發明範圍。 •21 -
Claims (1)
- 200301136 拾、申請專利範圍 1· 一種含油包水(W/0)乳化液之組合物,該乳化液具有 非連續水性相分散在連續油相中,該W/0乳化液之連 續油相含線型矽酮聚醚,α,ω -二烯交聯矽酮彈性體, 及非離子有機乳化劑,使用含碎原子之不飽和化合物 所製成之該W/0乳化液不含矽酮彈性體。 2. 根據申請專利範圍第1項之組合物,其中該W/0乳化液 之非連續水性相或該W/0乳化液之連續油相之一分別 含水溶性活性成份或油溶性活性成份。 3. 根據申請專利範圍第2項之組合物,其中該活性成份 係選自以下所組成之群組:維生素Β 1,維生素Β2,維 生素β6,維生素β12,於驗酸,葉酸,生物素,泛酸, 維生素Ε,生育酚,α-生育酚,β-生育酚,γ-生育酚, △-生育紛,To cop hers 〇 lan,生育齡酷酸酯,生育紛棕 櫚酸酯,生育酚亞油酸酯,生育酚菸鹼酸酯,生育酚 琥珀酸酯,及其混合物。 4. 根據申請專利範圍第1項之組合物,該W/0乳化液之連 續油相含0 · 2 - 3 · 0重量%該線型矽酮聚醚,0 · 2 -1 0重量% 該cc,co-二晞交聯矽酮彈性體,及0.1-4.0重量%該非離 子有機乳化劑,該W/0乳化液之其餘成份包含溶劑及 水。 5. 根據申請專利範圍第4項之組合物,其中該溶劑為通 式(R f ’ f 2 S i Ο ) d揮發性環狀烷基矽氧烷,或通式 (R"f3SiO(Rf"2SiO)eSiR…3揮發性線型烷基矽氧烷,其 200301136 申請專利範圍績頁 中R…為含1-6個碳原子之烷基,d為3-6,而e為0-5。 6.根據申請專利範圍第5項之組合物,其中該溶劑係選 自以下所組成之群組:六甲基環三矽氧烷,八甲基環 四矽氧烷,十甲基環五矽氧烷,十二甲基環六矽氧烷 ,六甲基二矽氧烷,八甲基三矽氧烷,十甲基四矽氧 烷,十二甲基五矽氧烷,十四甲基六矽氧烷,及十六 甲基七矽氧烷。200301136 陸、(一)、本案指定代表圖為:第_圖 (二)、本代表圖之元件代表符號簡單說明: 柒、本案若有化學式時,請揭示最能顯示發明特徵的化學式:
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| US10/024,983 US6861061B2 (en) | 2001-12-19 | 2001-12-19 | Stabilization of vitamins in water-in silicone oil (W/O) emulsions |
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| JP (1) | JP2005514391A (zh) |
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| WO2005102248A2 (en) * | 2004-04-20 | 2005-11-03 | Dow Corning Corporation | Silicone vesicles containing actives |
| EP1745087B1 (en) | 2004-04-20 | 2009-06-24 | Dow Corning Corporation | Aqueous dispersions of silicone polyether block copolymers |
| KR101188643B1 (ko) * | 2004-04-20 | 2012-10-09 | 다우 코닝 코포레이션 | 고분자량 실리콘 폴리에테르의 소낭 |
| EP1951193A2 (en) * | 2005-11-01 | 2008-08-06 | Dow Corning Corporation | Silicone vesicles containing actives |
| KR20080103974A (ko) * | 2006-02-28 | 2008-11-28 | 다우 코닝 코포레이션 | 활성제를 함유하는 실리콘 소포체 |
| US20070207107A1 (en) * | 2006-03-03 | 2007-09-06 | Gareth Winckle | Silicone based emulsions for topical drug delivery |
| US7790701B2 (en) * | 2006-04-19 | 2010-09-07 | Gelest Technologies, Inc. | Silicon-based tocopherol derivatives |
| US20080059313A1 (en) * | 2006-08-30 | 2008-03-06 | Oblong John E | Hair care compositions, methods, and articles of commerce that can increase the appearance of thicker and fuller hair |
| WO2008144084A2 (en) * | 2007-02-09 | 2008-11-27 | Mcneil-Ppc, Inc. | Lotion composition for personal use |
| US8425923B2 (en) * | 2007-02-09 | 2013-04-23 | Dow Corning Corporation and McNeil-PPC, Inc. | Lotion composition for personal use |
| CA2716612C (en) * | 2008-02-29 | 2014-02-18 | The Procter & Gamble Company | Hair care compositions and methods for increasing hair diameter |
| CN101297680B (zh) * | 2008-04-25 | 2010-11-03 | 天津生机集团股份有限公司 | 一种复合维生素乳液及其制备方法 |
| WO2013096639A1 (en) | 2011-12-20 | 2013-06-27 | The Procter & Gamble Company | Human skin sample methods and models for assessing tone-specific benefits of agents |
| WO2014186243A1 (en) | 2013-05-16 | 2014-11-20 | The Procter & Gamble Company | Hair thickening compositions and methods of use |
| US9437170B1 (en) * | 2013-08-12 | 2016-09-06 | Roberto Quevedo Montesdeoca | Systems and methods for augmented reality display |
| CN108474239A (zh) | 2016-01-13 | 2018-08-31 | 斯伦贝谢技术有限公司 | 成角度的凿子插入件 |
| CN106243364B (zh) * | 2016-08-03 | 2018-05-01 | 广东工业大学 | 一种聚醚改性有机硅乳液及其制备方法 |
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| US4150048A (en) * | 1978-03-28 | 1979-04-17 | Union Carbide Corporation | Nonhydrolyzable siloxane block copolymers of organosiloxanes and organic ethers |
| JPS62243621A (ja) | 1986-04-17 | 1987-10-24 | Toray Silicone Co Ltd | シリコ−ンゴム粒状物の製造方法 |
| US4853474A (en) | 1987-07-08 | 1989-08-01 | Dow Corning Corporation | Cross-linked organopolysiloxanes and emulsions based thereon |
| US5266321A (en) | 1988-03-31 | 1993-11-30 | Kobayashi Kose Co., Ltd. | Oily make-up cosmetic comprising oil base and silicone gel composition |
| JPH0753646B2 (ja) | 1989-01-31 | 1995-06-07 | 東レ・ダウコーニング・シリコーン株式会社 | 化粧料 |
| US5136068A (en) | 1989-04-26 | 1992-08-04 | Dow Corning Corporation | Cross-linked organopolysiloxanes and emulsions based thereon |
| US5599533A (en) | 1994-12-15 | 1997-02-04 | Estee Lauder, Inc. | Stable water-in-oil emulsion system |
| US5654362A (en) | 1996-03-20 | 1997-08-05 | Dow Corning Corporation | Silicone oils and solvents thickened by silicone elastomers |
| US5750123A (en) | 1996-06-28 | 1998-05-12 | Chesebrough-Pond's Co., Division Of Conopco, Inc. | Vitamin C delivery system |
| US5880210A (en) | 1997-04-01 | 1999-03-09 | Dow Corning Corporation | Silicone fluids and solvents thickened with silicone elastomers |
| US5889108A (en) * | 1997-06-02 | 1999-03-30 | Dow Corning Corporation | Thickening solvents with elastomeric silicone polyethers |
| US5948855A (en) | 1999-01-12 | 1999-09-07 | Dow Corning Corporation | Water-in-oil-in water emulsion |
| US6207717B1 (en) | 1999-01-12 | 2001-03-27 | Dow Corning Corporation | Entrapment of vitamins with an elastomeric silicone polyether |
| US6168782B1 (en) | 1999-05-24 | 2001-01-02 | Dow Corning Corporation | Elastomeric silicone containing an active ingredient |
| AU5146100A (en) | 1999-05-28 | 2000-12-18 | Neutrogena Corporation | Water-in-oil emulsion comprising a silicone gel containing vitamin |
| JP2001002555A (ja) | 1999-06-24 | 2001-01-09 | Shin Etsu Chem Co Ltd | 皮膚化粧料 |
| US6221979B1 (en) | 1999-11-08 | 2001-04-24 | Dow Corning Corporation | Mixtures of silicone elastomers |
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| EP1455735A1 (en) | 2004-09-15 |
| AU2002353003A1 (en) | 2003-07-09 |
| US6861061B2 (en) | 2005-03-01 |
| US20030119779A1 (en) | 2003-06-26 |
| CN1620278A (zh) | 2005-05-25 |
| JP2005514391A (ja) | 2005-05-19 |
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