CN1347307A - 化妆品制剂 - Google Patents
化妆品制剂 Download PDFInfo
- Publication number
- CN1347307A CN1347307A CN00806362A CN00806362A CN1347307A CN 1347307 A CN1347307 A CN 1347307A CN 00806362 A CN00806362 A CN 00806362A CN 00806362 A CN00806362 A CN 00806362A CN 1347307 A CN1347307 A CN 1347307A
- Authority
- CN
- China
- Prior art keywords
- acid
- ester
- glucosan
- alcohol
- purposes
- 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.)
- Granted
Links
- 239000002537 cosmetic Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 21
- 229920001503 Glucan Polymers 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims description 44
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 claims description 40
- 239000002105 nanoparticle Substances 0.000 claims description 15
- 239000000084 colloidal system Substances 0.000 claims description 8
- 238000009472 formulation Methods 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000000516 sunscreening agent Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 241000235070 Saccharomyces Species 0.000 claims description 2
- 241000223259 Trichoderma Species 0.000 claims description 2
- 239000008194 pharmaceutical composition Substances 0.000 claims 1
- 239000011814 protection agent Substances 0.000 claims 1
- 229920002498 Beta-glucan Polymers 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 108010076876 Keratins Proteins 0.000 abstract description 3
- 102000011782 Keratins Human genes 0.000 abstract description 3
- 230000035515 penetration Effects 0.000 abstract 1
- 239000000825 pharmaceutical preparation Substances 0.000 abstract 1
- 210000003491 skin Anatomy 0.000 abstract 1
- 210000000434 stratum corneum Anatomy 0.000 abstract 1
- -1 stick Substances 0.000 description 110
- 150000002148 esters Chemical class 0.000 description 36
- 239000000194 fatty acid Substances 0.000 description 36
- 235000014113 dietary fatty acids Nutrition 0.000 description 34
- 229930195729 fatty acid Natural products 0.000 description 34
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 31
- 229910052799 carbon Inorganic materials 0.000 description 28
- 241001597008 Nomeidae Species 0.000 description 26
- 150000004665 fatty acids Chemical class 0.000 description 25
- 150000001721 carbon Chemical group 0.000 description 23
- 239000003921 oil Substances 0.000 description 23
- 235000019198 oils Nutrition 0.000 description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 239000001993 wax Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000003995 emulsifying agent Substances 0.000 description 13
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 11
- 235000011187 glycerol Nutrition 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 9
- 235000019197 fats Nutrition 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 210000000582 semen Anatomy 0.000 description 9
- 150000005846 sugar alcohols Polymers 0.000 description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000005642 Oleic acid Substances 0.000 description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 8
- 235000021355 Stearic acid Nutrition 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000008117 stearic acid Substances 0.000 description 8
- FYGDTMLNYKFZSV-URKRLVJHSA-N (2s,3r,4s,5s,6r)-2-[(2r,4r,5r,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5r,6s)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1[C@@H](CO)O[C@@H](OC2[C@H](O[C@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-URKRLVJHSA-N 0.000 description 7
- 235000021357 Behenic acid Nutrition 0.000 description 7
- 244000056139 Brassica cretica Species 0.000 description 7
- 235000003351 Brassica cretica Nutrition 0.000 description 7
- 235000003343 Brassica rupestris Nutrition 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 229940116226 behenic acid Drugs 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229930182478 glucoside Natural products 0.000 description 7
- 235000010460 mustard Nutrition 0.000 description 7
- 239000012177 spermaceti Substances 0.000 description 7
- 229940084106 spermaceti Drugs 0.000 description 7
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 6
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 6
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 150000005690 diesters Chemical class 0.000 description 6
- 150000008131 glucosides Chemical group 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 6
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N isooctadecyl alcohol Natural products CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 6
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 229920001661 Chitosan Polymers 0.000 description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 5
- 235000021360 Myristic acid Nutrition 0.000 description 5
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 5
- BQODPTQLXVVEJG-UHFFFAOYSA-N [O].C=C Chemical group [O].C=C BQODPTQLXVVEJG-UHFFFAOYSA-N 0.000 description 5
- 239000002280 amphoteric surfactant Substances 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 230000002421 anti-septic effect Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000004359 castor oil Substances 0.000 description 5
- 229940081733 cetearyl alcohol Drugs 0.000 description 5
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- BARWIPMJPCRCTP-CLFAGFIQSA-N oleyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC BARWIPMJPCRCTP-CLFAGFIQSA-N 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 108090000765 processed proteins & peptides Proteins 0.000 description 5
- 235000018102 proteins Nutrition 0.000 description 5
- 102000004169 proteins and genes Human genes 0.000 description 5
- 108090000623 proteins and genes Proteins 0.000 description 5
- CDOSHBSSFJOMGT-SNVBAGLBSA-N (S)-linalool Chemical compound CC(C)=CCC[C@](C)(O)C=C CDOSHBSSFJOMGT-SNVBAGLBSA-N 0.000 description 4
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 4
- 102000008186 Collagen Human genes 0.000 description 4
- 108010035532 Collagen Proteins 0.000 description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 4
- 239000004471 Glycine Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 235000019438 castor oil Nutrition 0.000 description 4
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 4
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- 239000006071 cream Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
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- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 3
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- 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 3
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Abstract
本发明涉及将水溶性β-(1,3)葡聚糖用于制备化妆品和/或药用制剂的用途,其中该水溶性β-(1,3)葡聚糖基本不含β-(1,6)键,并且颗粒制剂为10-300nm。局部应用时,超细分散的颗粒比现有技术的葡聚糖更易快速渗透入皮肤角质层和毛发的角蛋白纤维中。
Description
所属领域
本发明属于纳米颗粒领域,并且涉及将特定纳米标量的β-(1,3)葡聚糖用于化妆品的用途。
现有技术
术语葡聚糖是指基于葡萄糖的同多糖。根据立体链接的不同存在β-(1,3)、β-(1,4)和β-(1,6)葡聚糖的区别。β-(1,3)葡聚糖一般具有螺旋结构,其中含(1,4)键的葡聚糖一般具有直链结构。葡聚糖及其衍生物可在不同情况下用于化妆品中。在专利US 5223491中提出将由酵母菌酿酒酵母中提取的羧甲基化β-1,3-葡聚糖用于局部应用。但该葡聚糖不溶于水,从而配制时十分麻烦。根据欧洲专利EP-B10500718(Donzis)中进一步采用水不溶性β-(1,3)葡聚糖用于皮肤活化,其可由已知的酵母细胞壁制得。最后,在WO98/40082(Henkel)中提出采用水溶性β-(1,3)葡聚糖作为皮肤护理用活性成分。但这类优选是裂裥多糖或云芝多糖(即真菌提取物)的葡聚糖在实施时不能表现出足够的功效。
葡聚糖的作用通常与化合物的吸收和再吸收的比例有关。对于该现有技术中业已利用的材料实际上仍可进行改善。本发明的任务是通过利用新的给药剂型经局部施用促进葡聚糖的吸收。
发明概述
本发明的目的是将纳米标量的基本不含β-(1,6)键、且粒径为10-300nm的水溶性β-(1,3)葡聚糖用于制备化妆品和药品制剂的用途。
意外地发现当基本不含β-(1,6)键的β-(1,3)葡聚糖在为纳米颗粒、即平均粒径为10-300nm、优选50-150nm时,皮肤角质层和毛发的角蛋白纤维对其再吸收会显著最高。水溶性β-(1,3)葡聚糖
本发明的β-葡聚糖具有(1,3)结构,即其基本不含不利的(1,6)键。优选适用的该β-(1,3)葡聚糖的侧链仅位于(1,3)键上。该成分具体含有基于酵母属真菌特别是酿酒酵母制得的葡聚糖。这类葡聚糖可根据已知方法以技术量应用。国际专利申请WO95/30022(Biotec-Mackzymal)中例如描述了一种用于生产该物质的方法,其中将含β-(1,3)和β-(1,6)键的葡聚糖均与β-(1,6)葡聚糖酶按所述方式接触,则几乎所有β-(1,6)键均断开了。优选适用于制备这类葡聚糖的是基于木霉harzianum的葡聚糖酶。对于含这类成分的葡聚糖的制备和应用可参见以上引用的公开文献。纳米颗粒的制备
采用超临界溶液快速释放以生产纳米颗粒的方法(超临界溶液快速扩散法RESS)例如可由S.Chihlar,M.Turk和K.Schaber在第三届颗粒技术国际会议(Brighton,1998)论文集中的论文获知。制备纳米颗粒的方法由以下步骤组成:
(a)在超临界或接近临界条件下将水溶性β-(1,3)葡聚糖溶于适宜的溶剂中,
(b)通过真空、气体或液态喷嘴分散液体混合物,并且
(c)同时蒸发溶剂。
为防止纳米颗粒再次聚结,建议在适宜的防护胶体或乳化剂存在下溶解原料,和/或将临界溶液在防护胶体或乳化剂的水和/或醇溶液中分散,或分散于化妆品油中,其中也可含有溶解的乳化剂和/或防护胶体。适用于此的防护胶体例如有:明胶、酪蛋白、阿拉伯树胶、卵清酸、淀粉,以及聚合物,如聚乙烯醇、聚乙烯吡咯烷酮、聚亚烷基二醇和聚丙烯酸酯。因此优选采用纳米标量的葡聚糖是被防护胶体和/或乳化剂包围的。防护胶体或乳化剂的用量一般占葡聚糖的0.1-20%(重量),优选为5-15%(重量)。
其他适用于生产纳米标量颗粒的方法由蒸发技术达到。在该情况下,首先将原料溶于适宜的有机溶剂(例如烷烃、植物油、醚、酯、酮、乙醛等)中。然后将溶液加入水或另一非溶剂中,其中可含有表面活性剂,由此,不相混溶的溶剂经均质后会得到纳米颗粒沉淀,优选蒸发该有机溶剂。除采用含水溶液,还可采用水包油型乳剂、水包油型微晶乳化体。也可采用上述已用作乳化剂和防护胶体的表面活性剂。纳米颗粒的生产还可采用称为“气体法”(气体反溶剂重结晶法)。该方法采用压缩气体或超临界液体(例如二氧化碳)用作被溶解材料结晶的非溶剂。将压缩气相导入原料的初始溶液中并被吸收,从而液体体积增加,溶解度降低,微细颗粒沉淀出来。PCA法也适用(压缩液体反溶剂的制备)。该方法中将初始原料的初始溶液导入超临界液体中,形成微细分布的小液滴,进行扩散步骤。在PGSS法(气体饱和溶液制颗粒)中,将初始原料熔融并加载加压气体(例如二氧化碳或丙烷)。应力和温度接近临界或超临界状态。气相溶于固体中,并降低了熔融温度、粘度和表面张力。通过喷嘴扩散,冷却作用导致颗粒形成。商业实用性
本发明的有关的葡聚糖,特别是基本不合β-(1,6)键的水溶性β-(1,3)葡聚糖是方案中最接近于现有技术的特征,将特定粒度的颗粒局部应用可令其更快透入角质层。纳米标量化合物的所需用量一般占制剂的0.1-5%(重量),优选0.5-3%(重量),特别是1-2%(重量)。化妆品和/或药品制剂
运用本发明可制得各种含纳米标量的β-(1,3)葡聚糖的制剂,例如:洗发剂、发用乳液、泡沫浴液、浴液、膏霜、凝胶、乳液、醇和/或水溶液、乳液、蜡/脂肪物质、棒剂、粉剂或软膏剂,其中还可含有附加辅剂或调节剂,其中包括温和的表面活性剂、油类、乳化剂、高脂肪成分、珠光蜡、稠度剂、增稠剂、聚合物、含硅化合物、脂肪、蜡、稳定剂、生物活性成分、除臭剂、去头屑剂、成膜剂、膨胀剂、防紫外线因子、抗氧剂、无机着色颜料、水溶助剂、防腐剂、驱虫剂、助晒剂、增溶剂、香精油、着色剂等。
适用的温和性(即特别是与皮肤相容的)表面活性剂的实例是脂肪醇聚二醇醚硫酸盐,硫酸单甘酯、单-和/或二烷基磺基琥珀酸酯,脂肪酸羟乙磺酸盐、脂肪酸肌氨酸盐、脂肪酸牛磺酸盐、脂肪酸谷氨酸盐、α-烯烃磺酸盐、醚羧酸、烷基低聚糖苷、脂肪酸葡糖胺、烷基酰氨基甜菜碱和/或蛋白质脂肪酸缩聚物,蛋白质脂肪酸缩聚物中优选值得一提的是其基于小麦蛋白。
适用的油类部分例如有:格尔伯特醇,其基于6-18个碳原子、优选8-10个碳原子的脂肪醇,C6-C22直链脂肪酸与C6-C22直链脂肪醇形成的酯,支链C6-C13羧酸与C6-C22直链脂肪醇形成的酯,例如肉豆蔻酸肉豆蔻醇酯、棕榈酸肉豆蔻醇酯、硬脂酸肉豆蔻醇酯、异硬脂酸肉豆蔻醇酯、油酸肉豆蔻醇酯、二十二烷酸肉豆蔻醇酯、芥酸肉豆蔻醇酯、肉豆蔻酸鲸蜡醇酯、棕榈酸鲸蜡醇酯、硬脂酸鲸蜡醇酯、异硬脂酸鲸蜡醇酯、油酸鲸蜡醇酯、二十二烷酸鲸蜡醇酯、芥酸鲸蜡醇酯、肉豆蔻酸硬脂醇酯、棕榈酸硬脂醇酯、硬脂酸硬脂醇酯、异硬脂酸硬脂醇酯、油酸硬脂醇酯、二十二烷酸硬脂醇酯、芥酸硬脂醇酯、肉豆蔻酸异硬脂醇酯、棕榈酸异硬脂醇酯、硬脂酸异硬脂醇酯、异硬脂酸异硬脂醇酯、油酸异硬脂醇酯、二十二烷酸异硬脂醇酯、油酸异硬脂醇酯、肉豆蔻酸油醇酯、棕榈酸油醇酯、硬脂酸油醇酯、异硬脂酸油醇酯、油酸油醇酯、二十二烷酸油醇酯、芥酸油醇酯、肉豆蔻酸二十二烷醇酯、棕榈酸二十二烷醇酯、硬脂酸二十二烷醇酯、异硬脂酸二十二烷醇酯、油酸二十二烷醇酯、二十二烷酸二十二烷醇酯、芥酸二十二烷醇酯、肉豆蔻酸芥醇酯、棕榈酸芥醇酯、硬脂酸芥醇酯、异硬脂酸芥醇酯、油酸芥醇酯、二十二烷酸芥醇酯、芥酸芥醇酯。此外还有C6-C22直链脂肪酸与支链醇特别是2-乙基己醇形成的酯,羟基羧酸与直链或支链C6-C22脂肪酸形成的酯,特别是马来酸二辛酯,直链和/或支链脂肪酸与多元醇(例如聚丙二醇、二聚二醇或三聚三醇)和/或格尔伯特醇形成的酯,基于C6-C10脂肪酸的三甘酯,基于C6-C18脂肪酸的单-/二-/三甘酯的液体混合物,C6-C22脂肪醇和/或格尔伯特醇与芳族羧酸特别是苯甲酸形成的酯,C2-C12二羧酸与含1-22个碳原子的直链或支链醇或含2-10个碳原子及2-6个羟基的多元醇形成的酯,植物油,支链伯醇,经取代的环己烷,直链或支链C6-C22脂肪醇碳酸酯,格尔伯特醇碳酸酯,苯甲酸与直链和/或支链C6-C22脂肪醇形成的酯(例如FinsolvTN),直链或支链、对称或非对称二烷基醚,其中每个烷基含6-22个碳原子,环氧化脂肪酸多元醇酯的开环产品,硅油和/或脂族或环烷烃,例如角鲨烷或二烷基环己烷也均适用。
例如可用作乳化剂的非离子表面活性剂中,可采用以下成分中的至少一种:
(1)2-30mol氧化乙烯和/或0-5mol氧化丙烯在含8-22个碳原子的直链脂肪醇、在含12-22个碳原子的脂肪酸和在含8-15个碳原子的烷基酚的烷基上的加成产物;
(2)1-30mol氧乙烯和甘油的C12/18脂肪酸单酯和二酯加成产物;
(3)含6-22个碳原子的饱和或不饱和脂肪酸甘油单酯和二酯,以及脱水山梨醇单酯或二酯,及其氧乙烯加成产物;
(4)烷基部分含8-22个碳原子的烷基单糖苷和低聚糖苷,及其乙氧基化类似物;
(5)蓖麻油和/或硬化蓖麻油的15-60mol氧乙烯加成产物;
(6)多元醇特别是聚甘油酯,例如聚蓖麻油酸聚甘油酯、聚-12-羟基硬脂酸聚甘油酯,或二聚异硬脂酸聚甘油酯,以及选自多种这类物质的化合物的混合物;
(7)蓖麻油和/或硬化蓖麻油的2-15mol氧乙烯加成产物;
(8)直链、支链、不饱和或饱和C6/22脂肪酸、蓖麻油酸和12-羟基硬脂酸与甘油、聚甘油、季戊四醇、二聚季戊四醇、糖醇(例如山梨醇)、烷基糖苷(例如甲基糖苷、丁基糖苷、月桂基糖苷)以及聚糖苷(例如纤维素)的偏酯;
(9)单-、二和三烷基磷酸酯,以及单-、二和/或三PEG烷基磷酸酯及其盐;
(10)木蜡醇;
(11)聚硅氧烷/聚烷基/聚醚共聚物或相应的衍生物;
(12)DE 1165574 PS中公开的季戊四醇、脂肪酸、柠檬酸和脂肪醇混合酯,和/或含6-22个碳原子的脂肪酸、甲基葡萄糖和多元醇优选甘油或聚甘油的混合酯,
(13)聚亚烷基二醇,以及
(14)甘油碳酸酯。
脂肪醇、脂肪酸、烷基酚、甘油单酯和二酯、以及脂肪酸脱水山梨醇单酯和二酯、或蓖麻油的氧乙烯和/或氧丙烯加成产物均为可商购的已知产品。其为同系物混合物,其平均烷氧基化度相应于氧化乙烯和/或氧化丙烯成分与进行加成反应的反应物的用量比。由DE2024051 PS中已知C12/18脂肪酸单酯和二酯在甘油上氧乙烯加成产物是用于化妆品制剂的还原脂肪成分。
现有技术已知C8/18烷基单糖苷和低聚糖苷、其制备和应用。其制备具体可由葡萄糖或低聚糖与含8-18个碳原子的伯醇进行反应。单糖苷的糖苷部分中的环糖基是与脂肪醇相连的糖苷键,低聚糖苷的低聚度优选适于约为8。低聚度是基于技术量的常用于这类产品的均聚物的分布的统计平均值。
两性离子表面活性剂也可用作乳化剂。术语两性离子表面活性剂是指其分子中含有至少一个季铵基和至少一个羧酸根和磺酸根的表面活性化合物。特别适用的两性离子表面活性剂被称为甜菜碱,如N-烷基-N,N-二甲基甘氨酸铵,例如椰油基烷基二甲基甘氨酸铵,N-酰基氨基丙基-N,N-二甲基甘氨酸铵,例如椰油基酰基氨基丙基二甲基甘氨酸铵,以及2-烷基-3-羧甲基-羟乙基咪唑啉,其中在各情况下烷基或酰基含8-18个碳原子,以及椰油基酰基氨基乙基羟乙基羧甲基甘氨酸盐。特别优选CTFA命名的椰油酰氨基丙基甜菜碱,其已知是脂肪酰胺衍生物。适用的乳化剂还有两性表面活性剂。两性表面活性剂是分子中除C8/8烷基或酰基之外还含有至少一个游离氨基和至少一个-COOH或-SO3H基从而可形成内盐的表面活性化合物。适用的两性表面活性剂有N-烷基甘氨酸、N-烷基丙酸、N-烷基氨基丁酸、N-烷基亚氨基二丙酸、N-羟乙基-N-烷基酰氨基丙基甘氨酸、N-烷基牛磺酸、N-烷基肌氨酸、2-烷基氨基丙酸和烷基烷基氨基乙酸,其中各烷基中约含8-18个碳原子。特别优选的两性表面活性剂是N-椰油烷基氨基丙酸盐,椰油酰基氨基乙基氨基丙酸盐和C12/18酰基肌氨酸。除两性表面活性剂之外,还可采用季铵乳化剂,特别优选酯季铵的酯盐,其中优选甲基季铵化二聚脂肪酸三乙醇胺酯盐。
可采用高脂肪成分,例如羊毛脂和卵磷脂,以及聚乙氧基化或酰化羊毛脂和卵磷脂衍生物,多元醇脂肪酸酯,单甘酯和脂肪酸烷醇酰胺,其中脂肪醇烷醇酰胺还可用作泡沫稳定剂。
典型的珠光蜡中值得一提的如下:亚烷基二醇酯,特别是二硬脂酸乙二醇酯;脂肪酸烷醇酰胺,特别是椰油脂肪酸二乙醇酰胺;偏甘酯,特别是硬脂酸单甘酯;可由羟基取代羧酸与含6-22个碳原子脂肪醇形成的多价酯,特别是酒石酸长链酯;脂肪成分,例如脂肪醇,脂肪酮,脂肪醛,脂肪醚和脂肪碳酸酯,其中碳原子数至少为24,特别是月桂酮和硬脂基醚;脂肪酸如硬脂酸、羟基硬脂酸或二十二烷酸,含12-22个碳原子烯烃环氧化物与含12-22个碳原子脂肪醇和/或含2-15个碳原子并含有2-10个羟基多元醇的开环产物,以及它们的混合物。
稠度剂优选采用含12-22个碳原子的脂肪醇或羟基脂肪醇,优选含16-18个碳原子,以及其他偏甘酯、脂肪酸或羟基脂肪酸。还可采用这些成分与烷基低聚糖苷和/或具有相同链长的脂肪酸-N-甲基葡糖酰胺和/或聚甘油-聚-12-羟基硬脂酸酯的混合物。
适用的增稠剂例如有:二氧化硅气凝胶(亲水硅酸),多糖,特别是黄原胶,瓜尔胶,琼脂,藻酸盐和纤基乙酸钠,羧甲基纤维素和羟乙基纤维素,以及脂肪酸高分子聚乙二醇单酯和二酯,聚丙烯酸酯(例如购自Goodrich的Carbopol或购自Sigma的Synthalene),聚丙烯酰胺,聚乙烯醇和聚乙烯吡咯烷酮,表面活性剂例如乙氧基化脂肪酸甘油酯,脂肪酸与多元醇如季戊四醇或三羟甲基丙烷形成的酯,脂肪醇乙氧基化物的窄带分布同系物,或烷基低聚葡糖苷,以及电解质如氯化钠或氯化铵。
适用的阳离子聚合物例如有:阳离子纤维素衍生物,例如季铵化羟乙基纤维素,其可以名称聚合物JR400购自Amerchol,阳离子淀粉,二烯丙基铵盐和丙烯酰胺的共聚物,季铵化乙烯基吡咯烷酮/乙烯基咪唑聚合物,例如Luviquat(BASF),聚二醇和胺的缩聚产物,季铵化胶原多肽,例如月桂基二甲基铵羟丙基水解胶原(LamequatL/Grunau),季铵化小麦多肽,聚乙烯亚胺,阳离子聚硅氧烷聚合物,例如酰氨基甲基聚硅氧烷,己二酸和二甲基氨基羟丙基二乙烯三胺的共聚物(Cartaretine/Sandoz),丙烯酸和二甲基二烯丙基氯化铵的共聚物(Merquat550/Chemiviron),聚氨基聚酰胺,例如基于FR 2252840A,及其交联水溶性聚合物,阳离子壳多糖衍生物例如季铵化壳聚糖,其可经微晶分散,二卤代烷基,例如二溴代丁烷,与二烷基胺的缩聚产物,例如双-二甲基氨基-1,3-丙烷,阳离子瓜尔胶,例如购自Celanese的JaguarCBS、JaguarC-17、JaguarC-16,季铵盐聚合物,例如购自Miranol的MirapolA-15、MirapolAD-1、MirapolAZ-1。
可采用以下典型的阴离子、两性离子、两性和非离子聚合物:乙酸乙烯基酯/巴豆酸共聚物,乙烯基吡咯烷酮/乙烯基丙烯酸酯共聚物,乙酸乙烯基酯/马来酸丁酯/丙烯酸异龙脑酯共聚物,甲基乙烯基醚/马来酸酐共聚物及其酯,非交联和与多醇交联的聚丙烯酸,丙烯酰氨基丙基三甲基氯化铵/丙烯酸酯共聚物,辛基丙烯酰胺/甲基丙烯酸甲酯/甲基丙烯酸叔丁氨基乙基酯/甲基丙烯酸2-羟基丙酯共聚物,聚乙烯吡咯烷酮,乙烯基吡咯烷酮/乙酸乙烯基酯共聚物,乙烯基吡咯烷酮/二甲基氨基乙基甲基丙烯酸酯/乙烯基己内酰胺三元共聚物,以及可能衍生的纤维素醚和聚硅氧烷。
适用的含硅化合物例如是二甲基聚硅氧烷,甲基苯基聚硅氧烷,环聚硅氧烷,以及经氨基、脂肪酸、醇、聚醚、环氧、氟、糖苷和/或烷基改性的含硅化合物,其在室温下成液态和树脂态。适用的的还有硅甲基聚硅氧烷,其为链长平均含200-300二甲基硅氧烷单元的聚二甲基硅氧烷与氢化硅酸酯的混合物。对适用的挥发性聚硅氧烷的详细综述可参见Todd等人在《化妆品和盥洗用品》91,27(1976)中所述内容。
所列举的典型脂肪是甘油酯,可采用天然蜡用作蜡成分,例如小烛树蜡、巴西棕榈蜡、野漆树蜡、西班牙草蜡、软木蜡、guaruma蜡、稻米油蜡、甘蔗蜡、小冠巴西棕榈蜡、褐煤蜡、蜂蜡、紫胶蜡、鲸蜡、羊毛蜡、burzel脂肪、纯地蜡、地蜡、矿脂、石蜡、微晶蜡、经化学改性的蜡(硬蜡),例如褐煤酸酯蜡,sasot蜡、氢化西蒙得木蜡,以及合成蜡,例如聚亚烷基蜡和聚乙二醇蜡。
脂肪酸金属盐可用作稳定剂,例如硬脂酸或蓖麻油酸的镁盐、铝盐和/或锌盐。
一般认为生物活性成分例如有:生育酚、乙酸生育酚酯、棕榈酸生育酚酯、抗坏血酸、脱氧核糖核酸、视黄醇、没药醇、尿囊素、植烷三醇、泛醇、果酸、氨基酸、神经酰胺、假性神经酰胺、香精油、植物提取物和维生素复合物。
除臭活性成分例如有抑汗剂,如所述的水合氯化铝。该成分为无色、吸湿性晶体,其易于在环境条件下熔融,其可由氯化铝水溶液蒸发得到。水合氯化铝用于制备抑汗和除臭制剂,并且其可能是通过蛋白质和/或多糖沉淀部分封闭汗腺而起效的[可参见《化妆品化学学会会刊》J.Soc.Cosm.Chem.24,281(1973)]。市售的例如有购自Hoechst AG(Frankfurt/FRG)商标名为Locron的产品,其为水合氯化铝,其相应于式[Al2(OH)5Cl]·2.5H2O所示,并且特别优选采用该成分[参见《药物化学杂志》J.Pharm.Pharmacol.26,531(1975)]。除水合氯化物之外,还可采用羟基乙酸铝,以及酸的铝/锆盐。去臭活性成分还可加入酯酶抑制剂。优选柠檬酸三烷基酯,如柠檬酸三甲酯、柠檬酸三丙酯、柠檬酸三异丙酯、柠檬酸三丁酯,特别是柠檬酸三乙酯(HydagenCAT,Henkel KGaA,Dusseldorf/FRG)。这类成分可抑制酶活性,从而可降低异味的形成。可通过柠檬酸酯分解释放出游离酸,该酸可降低皮肤的pH值,从而抑制酶活性。其他可用作酯酶抑制剂的成分有:硫酸甾醇酯或磷酸甾醇酯,例如硫酸或磷酸的羊毛甾醇、胆甾醇、菜子甾醇、豆甾醇和谷甾醇酯,以及二羧酸及其酯,例如戊二酸、戊二酸单乙酯、戊二酸二乙酯、己二酸、己二酸单乙酯、己二酸二乙酯,丙二酸和丙二酸二乙酯,羟基羧酸及其酯,例如柠檬酸、马来酸、酒石酸或酒石酸二乙酯。抗菌活性成分,其可影响菌丛并可杀灭使汗液产生异味的细菌或抑制其生长,该成分可制成针剂形式。其实例有壳聚糖、苯氧基乙醇和葡糖酸洗必太。5-氯-2-(2,4-二氯苯氧基)-酚也具有特别良好的效果,并且该产品由Ciba-Geigy(Basel/CH)公司以商品名Irgasan销售。
去头屑剂可采用climbazol、羟甲辛吡酮和吡啶硫酮锌。适用的成膜剂例如有:壳聚糖,微晶壳聚糖,季铵化壳聚糖,聚乙烯吡咯烷酮,乙烯基吡咯烷酮/乙酸乙烯基酯共聚物,丙烯酸聚合物,纤维素季铵衍生物,胶原,透明质酸或其盐,以及类似化合物。水相膨胀剂可见采用水相蒙脱石、粘土无机成分、pemulen,以及经烷基改性的Carbopol类(Goodrich)。其他适用的聚合物或膨胀剂可基于R.Lochhead在《化妆品和盥洗用品》Cosm.Toil.108,95(1993)中的综述。
防紫外线因子是室温下呈液态或晶体形式的有机物质(防晒滤光剂),其能吸收紫外线辐射,并能将所吸收的能量以长波形式(例如热的形式)释放出来。UVB滤光剂可溶于油或水中。以下是值得一提的油溶性物质的实例:
·3-亚苄基樟脑,分别是3-亚苄基降樟脑及其衍生物,例如3-(4-甲基亚苄基)樟脑,见于EP-B1 0693471;
·4-氨基苯甲酸衍生物,优选4-(二甲基氨基)苯甲酸2-乙基己酯,4-(二甲基氨基)苯甲酸2-辛酯和4-(二甲基氨基)苯甲酸戊酯;
·肉桂酸酯,优选4-甲氧基肉桂酸2-乙基己酯,4-甲氧基肉桂酸丙酯,4-甲氧基肉桂酸异戊酯,2-氰基-3,3-苯基肉桂酸2-乙基己酯(氰双苯丙烯酸辛酯);
·水杨酸酯,优选水杨酸2-乙基己酯,水杨酸4-异丙基苄基酯,水杨酸高薄荷基酯;
·二苯酮衍生物,优选2-羟基-4-甲氧基二苯酮,2-羟基-4-甲氧基-4′-甲基二苯酮,2,2′-二羟基-4-甲氧基二苯酮;
·亚苄基丙二酸酯,优选4-甲氧基亚苄基丙二酸2-乙基己酯,
·三嗪衍生物,例如2,4,6-三苯氨基-(对羰-2 ′-乙基-1′-己氧基)-1,3,5-三嗪和辛基三嗪酮,可见于EP A1 0818450;
·丙-1,3-二酮,例如1-(4-叔丁基苯基)-3-(4′-甲氧基苯基)-丙-1,3-二酮;
·酮三环(5,2,1,0)-癸烷衍生物,见于EP-B1 06945521。
水溶性成分中值得一提的如下:
·2-苯基苯并咪唑-5-磺酸和碱金属,碱土金属,铵,烷基铵,链烷醇铵和葡糖铵盐;
·二苯酮的磺酸衍生物,优选2-羟基-4-甲氧基二苯酮-5-磺酸及其盐;
·3-亚苄基莰烯的磺酸衍生物,例如4-(2-氧-3-亚龙脑基甲基)-苯磺酸和2-甲基-5-(2-氧-亚龙脑基)磺酸及其盐。
典型的UV-A滤光剂特别是所述的苯甲酰甲烷衍生物,例如1-(4′-叔丁基苯基)-3-(4′-甲氧基苯基)丙-1,3-二酮、4-叔丁基-4′-甲氧基二苯甲酰甲烷(Parsol 1789)或1-苯基-3-(4′-异丙基苯基)丙-1,3-二酮。UV-A和UV-B滤光剂当然可以混合物形式应用。在该情况下,氰双苯丙烯酸辛酯或樟脑衍生物与丁基甲氧基二苯甲酰甲烷的混合物尤其是光敏性的。
除提及的水溶性成分之外,不溶性防晒颜料也适用于此,即细化分散金属氧化物或盐。适用的金属氧化物的实例具体有:氧化锌和二氧化钛,以及铁、锆、硅、锰、铝和铈氧化物,以及它们的混合物。硅酸盐(述及)、硫酸钡或硬脂酸锌也适用。氧化物和盐以颜料形式用于皮肤护理和保护用乳液和彩妆品中。颗粒的平均直径低于100nm,优选为5-50nm,特别是15-30nm。其可为球形,但也可以椭圆形或非球形应用。在防晒剂中优选采用被称为微颜料或纳米颜料的成分。优选采用微粉化氧化锌。其他适用的UV防晒剂成分可见于P.Finkel在SOFW杂志122,543(1996)中的综述。
除基本防晒成分之外,还可含有抗氧剂类二级防晒成分,发现其可中止光化学反应链,该反应是由UV辐射透入皮肤引发的。这类成分的典型实例有:氨基酸(例如甘氨酸、组氨酸、酪氨酸、色氨酸)及其衍生物,咪唑类(咪唑丙烯酸)及其衍生物,肽如D,L-肌肽、D-肌肽、L-肌肽及其衍生物(例如鹅肌肽),类胡萝卜素,胡萝卜素(例如α-胡萝卜素、β-胡萝卜素、菌脂色素)及其衍生物,绿原酸及其衍生物,脂酮酸及其衍生物(例如二氢脂酮酸),金硫葡糖,丙基硫氧嘧啶和其他硫醇(例如thioredoxin、谷胱甘肽、半胱氨酸、胱氨酸、胱胺,以及它们的葡基、正乙酰基、甲基、乙基、丙基、戊基、丁基和月桂基、棕榈酰基、油基、γ-亚油基、胆甾醇基和甘油基酯),以及它们的盐,硫代二丙酸二月桂基酯,硫代二丙酸二硬脂酸酯,硫代二丙酸及其衍生物(酯、醚、肽、脂类、核苷酸、核苷及其盐),以及少量相容剂量(例如pmol-μmol/kg)的磺基肟(sulfoximine)化合物(例如丁硫堇(buthionin)磺基肟、高半胱氨酸磺基肟、丁硫堇(butionin)砜、戊-、己-、庚硫堇磺基肟),还有(金属)螯合剂(例如α-羟基脂肪酸、棕榈酸、肌醇六磷酸、乳铁蛋白),α-羟基酸(例如柠檬酸、乳酸、苹果酸),腐黑酸,没食子酸,没食子提取物,胆红素,bifiverdin,EDTA,EGTA及其衍生物,不饱和脂肪酸及其衍生物(γ-亚油酸、亚麻酸、油酸),叶酸及其衍生物,ubichinon和ubichinol及其衍生物,维生素C及其衍生物(例如棕榈酸抗坏血酸基酯,抗坏血酸基磷酸镁、乙酸抗坏血酸基酯),生育酚及其衍生物(例如乙酸维生素E),维生素A及其衍生物(棕榈酸维生素A),以及安息香树脂的苯甲酸松(koniferyl)脂,芸香亭酸及其衍生物,α-葡基芸香苷,阿魏酸,亚糠基glucitol,肌肤,丁羟基甲苯,丁羟基苯甲醚,去甲二氢愈创木酸,去甲二氢愈创木酸,三羟基丁酰苯,尿酸及其衍生物,甘露糖及其衍生物,超氧化歧化酶,锌及其衍生物(例如氧化锌、硫酸锌),硒(selen)及其衍生物(例如硒-甲硫氨酸),1,2-二苯乙烯及其衍生物(例如氧化二苯乙烯,反式氧化二苯乙烯),以及这些成分适用于本发明的衍生物(盐、酯、醚、糖、核苷酸、核苷、肽和脂类)。
用于改善流动特性的还可采用水溶助剂,例如乙醇、异丙醇或乙醇。此时适用的的多元醇优选含2-15个碳原子和至少2个羟基。多元醇中还可含有功能基特别是氨基,或经N改性。典型的实例有:
·甘油;
·亚烷基二醇,例如乙二醇,二甘醇,丙二醇,丁二醇,己二醇以及平均分子量为100-1000道尔顿的聚乙二醇;
·技术量的低聚甘油混合物,其内缩聚度为1.5-10,例如技术量的二甘油混合物,其中二甘油的含量为40-50%(重量);
·羟甲基混合物,特别是三羟甲基乙烷,三羟甲基丙烷,三羟甲基丁烷,季戊四醇和二季戊四醇;
·低级烷基糖苷,特别是其中烷基部分含1-8个碳原子,例如甲基和丁基糖苷;
·含5-12个碳原子的糖,例如山梨糖醇或甘露糖醇;
·含5-12个碳原子的糖醇,例如葡萄糖或蔗糖;
·氨基糖,例如葡糖胺;
·二醇胺,如二乙醇胺或2-氨基-1,3-丙二醇。
防腐剂是另一类成分,例如有苯氧基乙醇,甲醛溶液,对羟基苯甲酸酯类、戊二醇或山梨酸,以及在附件6中提到的化妆品规则的A和B部分。值得一提的还有驱虫剂N,N-二乙基-间-甲苯甲酰胺,1,2-戊二醇或驱虫剂3535,助晒剂二羟基丙酮也适用。
天然和合成加香成分的香精油混合物值得一提。天然加香成分是花(百合、熏衣草、玫瑰、茉莉、橙花醇、夷兰)、茎和叶(香叶、绿叶刺蕊草、petitgrain)、果实(茴香、芫荽、藏茴香、杜松)、果皮(佛手柑、柠檬、橘子)、根(肉豆蔻、当归、芹菜、豆蔻、木香、鸢尾、菖蒲)、木质(石松、檀木、愈创木、雪松、红木)、全草或草(龙蒿、香峰叶、洋苏草、百里香)、针叶和细枝(云杉、枞树、松树、traipsed)、树脂和香脂(波斯树脂、榄香脂、安息香脂、没药、乳香、愈伤草树脂)的提取物。来自动物的原料也适用,例如灵猫香和海狸香。典型的合成加香化合物是得自酯类、醚类、醛类、酮类、醇类和烃类的产品。得自酯类的加香化合物例如有:乙酸苄酯、异丁酸苯氧基乙酯、乙酸对叔丁基环己酯、乙酸芳樟基酯、乙酸二甲基苄基羰基甲醇酯、乙酸苯乙基酯、苯甲酸芳樟基酯、甲酸苄酯、甘氨酸乙基甲基苯基酯、丙酸烯丙基环己酯、丙酸苏合香烯丙酯和水杨酸苄酯。苄基乙基醚属于醚类化合物的实例,醛类例如有含8-18个碳原子的直链烷基醛,柠檬醛、香茅醛、香茅基羟基乙醛、仙客来醛、羟基香茅醛、百合醛和borugeonal,酮类例如有紫罗兰酮、∝-异甲基紫罗兰酮和甲基柏木酮,醇类有:茴香醇、香茅醇、丁香酚、异丁香酚、香叶醇、芫荽醇、苯乙醇、松油醇;烃类主要有萜烯和香脂类。但优选不同加香成分的混合物,其能共同形成宜人的气味。常用作芳香组分的低挥发性的醚油也适用作香精油,例如洋苏草油、春黄菊油。康乃馨油、蜂花油、薄荷油、肉桂叶油、枸橼花油、杜松子油、岩兰草油、乳香油、波斯树脂油、labolanum油和熏衣草油。优选适用的是佛手柑油、二氢月桂烯醇、百合醛、lyral、香茅醇、苯乙醇、α-己基肉桂醛、香叶醇、苄基丙酮、仙客来醛、芫荽醇、boisambrene forte、豕草烷(ambroxane)、吲哚、hedione、檀香、柠檬油、橘子油、甜橙油、甘醇酸烯丙基戊酯、环三叶草醛、熏衣草油、muskateller洋苏草油、β-大马酮、香叶油香兰素、水杨酸环己酯、vertofix coeur、异-E-super、fixolid NP、evemyl、iraidenin gamma、苯基乙酸、醋酸香叶酯、乙酸苄酯、玫瑰氧化物、romillate、irotyl和floramate,这些成分可单用或共用。
可采用适于和被批准用于化妆品用途的着色剂,例如在公开文献“Farbstoffkommission der Deutschen Forshungsgemeinschaft”中《化妆品染料》中述及的那些成分(Verlag Chemie出版,Weinheim,1984,81-106页)。这些染料的应用浓度一般占混合物总量的0.001-0.1%(重量)。
抑菌成分的典型实例是对革兰氏阳性菌具有特定作用的防腐剂,如2,2,4′-三氯-2 ′-羟基二苯基醚,洗必太(chlorohexidin)(2,6-二-4-氯苯基-二胍基-己烷)或TCC(3,4,4′-三氯碳酰苯胺)。许多加香成分和醚油也具有抗菌特性。其典型实例是存在于康乃馨油、薄荷油和百里香油中的丁香酚、薄荷醇和百里酚活性成分。适用的天然除臭成分是萜烯醇famesol(3,7,11-三甲基-2,6,10-十二碳三烯-1-醇),其存在于枸橼花油中,具有幽谷百合的香气。甘油单月桂酸酯也可用作抑菌剂。其他抑菌剂的含量可约为0.1-2%(重量)(以制剂的固体含量计)。
辅剂和附加成分的总含量可占制剂的1-50%(重量),优选为5-40%(重量)。制剂的制备可采用常规的冷却或加热法;优选采用相转化温度法进行制备。
实施例
在制备纳米标量的葡聚糖(实施例1-3)时,首先从恒压为60巴的容器中导出二氧化碳,并用活性炭和一副分子筛清洁柱。二氧化碳经液化后采用恒定流量为3.5升/下式的膈式泵压缩至所需的超临界压力。其后在预加热容器中将溶剂加热到所需温度T1,加入负载有葡聚糖的提取柱(钢制,400ml)。在T2温度下,所得的超临界液体化合物通过长喷嘴(长830μm、直径45μm)喷入有机玻璃分散室中,该分散室中含有乳化剂或防护胶体的4%(重量)水溶液。蒸发液体介质,并分散得到被防护胶体包埋的纳米颗粒。制备实施例4的纳米颗粒时,在40℃、剧烈搅拌和40毫巴减压条件下将1%(重量)的含水葡聚糖乳液滴加入4%(重量)椰油剂糖苷水溶液中。蒸发溶剂在冷阱中凝结,剩下纳米颗粒分散体。步骤条件和平均粒径(根据3-WEM法经光度法测定)列于表1中。表1-纳米颗粒
下表中包括若干含有葡聚糖纳米颗粒的制剂实施例。
实施例 | 葡聚糖 | 溶剂 | 压力(巴) | T1℃ | T2℃ | 乳化剂/防护胶体 | PGBnm |
1 | β-葡聚糖* | CO2 | 200 | 80 | 175 | 聚乙烯醇 | 50-125 |
2 | β-葡聚糖* | CO2 | 180 | 70 | 160 | 聚乙二醇(M=400) | 70-130 |
3 | β-葡聚糖* | CO2 | 200 | 85 | 175 | 椰油基糖苷 | 50-150 |
4 | β-葡聚糖* | - | - | - | - | 椰油基糖苷 | 65-140 |
表1-化妆品制剂(水、防腐剂加至100%(重量))
组合物(INCI) | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
DehymulsPGPH聚甘油-2二多羟基硬脂酸酯 | 4.0 | 3.0 | - | 5.0 | - | - | - | - | - | - |
LameformTGI聚甘油-3异硬脂酸酯 | 2.0 | 1.0 | - | - | - | - | - | - | - | - |
EmulgadePL 68/50鲸蜡硬脂基糖苷(和)鲸蜡硬脂醇 | - | - | - | - | 4.0 | - | - | - | 3.0 | - |
EumulginB2鲸蜡硬脂基醚-20 | - | - | - | - | - | - | - | 2.0 | - | - |
TegocarePS聚甘油-3-甲基葡糖二硬脂酸酯 | - | - | 3.0 | - | - | - | 4.0 | - | - | - |
EumulginVL 75聚甘油-3-二多羟基硬脂酸酯(和)月桂基糖苷(和)甘油 | - | - | - | - | - | 3.5 | - | - | 2.5 | - |
蜂蜡 | 3.0 | 2.0 | 5.0 | 2.0 | - | - | - | - | - | - |
CutinaGMS鲸蜡硬脂醇 | - | - | - | - | - | 2.0 | 4.0 | - | - | 4.0 |
LanetteO鲸蜡硬脂醇 | - | - | 2.0 | - | 2.0 | 4.0 | 2.0 | 4.0 | 4.0 | 1.0 |
AntaronV216PVP/十六烯共聚物 | - | - | - | - | - | 3.0 | - | - | - | 2.0 |
Myritol818椰油基甘油酯 | 5.0 | - | 10.0 | - | 8.0 | 6.0 | 6.0 | - | 5.0 | 5.0 |
FinsolvTNC12/15烷基苯甲酸酯 | - | 6.0 | - | 2.0 | - | - | 3.0 | - | - | 2.0 |
CetiolJ600芥酸油醇酯 | 7.0 | 4.0 | 3.0 | 5.0 | 4.0 | 3.0 | 3.0 | - | 5.0 | 4.0 |
CetiolOE二辛基醚 | 3.0 | - | 6.0 | 8.0 | 6.0 | 1.0 | 4.0 | 3.0 | 4.0 | 6.0 |
矿物油 | - | 4.0 | - | 4.0 | - | 2.0 | - | 1.0 | - | - |
CetiolPGL十六醇(和)月桂酸十六醇酯 | - | 7.0 | 3.0 | 7.0 | 4.0 | - | - | - | 1.0 | - |
泛醇/没药醇 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 |
实施例1的β-葡聚糖纳米颗粒 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
CopherolF 1300生育酚/乙酸生育酚 | 0.5 | 1.0 | 1.0 | 2.0 | 1.0 | 1.0 | 1.0 | 2.0 | 0.5 | 2.0 |
Neo HeliopanHydro苯基苯并咪唑磺酸钠 | 3.0 | - | - | 3.0 | - | - | 2.0 | - | 2.0 | - |
Neo Heliopan303氰双苯丙烯酸辛酯 | - | 5.0 | - | - | - | 4.0 | 5.0 | - | - | 10.0 |
Neo HeliopanBB二苯酮-3 | 1.5 | - | - | 2.0 | 1.5 | - | - | - | 2.0 | - |
Neo HeliopanE 1000对甲氧基肉桂酸异戊酯 | 5.0 | - | 4.0 | - | 2.0 | 2.0 | 4.0 | 10.0 | - | - |
Neo HeliopanAV甲氧基内桂酸辛酯 | 4.0 | - | 4.0 | 3.0 | 2.0 | 3.0 | 4.0 | - | 10.0 | 2.0 |
UvinulT 150辛基三嗪酮 | 2.0 | 4.0 | 3.0 | 1.0 | 1.0 | 1.0 | 4.0 | 3.0 | 3.0 | 3.0 |
氧化锌 | - | - | - | - | 4.0 | - | - | - | - | 5.0 |
二氧化钛 | - | 2.0 | 2.0 | - | - | - | - | 5.0 | - | - |
甘油(86%(重量)) | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
(1)油包水型防晒霜、(2-4)油包水型防晒乳液、(5,8,10)水包油型防晒乳液、(6,7,9)水包油型防晒霜表1-化妆品制剂(水、防腐剂加至100%(重量))-(续表)
组合物(INCI) | 21 | 22 | 23 | 24 | 25 | 26 | 27 | 28 | 29 | 30 |
TexaponNSO月桂基醚硫酸钠 | - | 30.0 | 30.0 | - | 25.0 | - | - | - | - | - |
Plantacare818椰油基葡糖苷 | - | 10.0 | - | - | 20.0 | - | - | - | - | - |
PlantacarePS 10月桂基醚硫酸钠(和)椰油基葡糖苷 | 22.0 | - | 5.0 | 22.0 | - | - | - | - | - | - |
DehytonPK 45椰油酰氨基丙基甜菜碱 | 15.0 | 10.0 | 15.0 | 15.0 | 20.0 | - | - | - | - | - |
EulgadeSE硬脂酸甘油酯(和)鲸蜡硬脂基醚12/20(和)鲸蜡硬脂醇(和)棕榈酸鲸蜡醇酯 | - | - | - | - | - | 5.0 | 5.0 | 4.0 | - | - |
EumulginB1鲸蜡硬脂基醚-12 | - | - | - | - | - | - | - | 1.0 | - | - |
Lame formTGI聚甘油-3异硬脂酸酯 | - | - | - | - | - | - | - | - | 4.0 | - |
DehymulsPGPH聚甘油-2二多羟基硬脂酸酯 | - | - | - | - | - | - | - | - | - | 4.0 |
Monomuls90-O 18油酸甘油酯 | - | - | - | - | - | - | - | - | 2.0 | - |
CetiolHEPEG-7椰油酸甘油酯 | 2.0 | - | - | 2.0 | 5.0 | - | - | - | - | 2.0 |
CetiolOE辛酰基醚 | - | - | - | - | - | - | - | - | 5.0 | 6.0 |
CetiolPGL十六醇(和)月桂酸十六醇酯 | - | - | - | - | - | - | - | 3.0 | 10.0 | 9.0 |
CetiolSN异壬酸鲸蜡硬脂醇酯 | - | - | - | - | - | 3.0 | 3.0 | - | - | - |
CetiolV油酸癸酯 | - | - | - | - | - | 3.0 | 3.0 | - | - | - |
Myritol318椰油基辛/癸酸酯 | - | - | - | - | - | - | - | 3.0 | 5.0 | 5.0 |
蜂蜡 | - | - | - | - | - | - | - | - | 7.0 | 5.0 |
NutrilanKeratin E20水解弹性蛋白 | - | - | - | - | - | 2.0 | - | - | - | - |
NutrilanI-50水解胶原 | - | - | - | - | 2.0 | - | 2.0 | - | - | - |
GluadinAGP水解麦谷蛋白 | 0.5 | 0.5 | 0.5 | - | - | - | - | 0.5 | - | - |
GluadinWK椰油基水解小麦蛋白钠盐 | 2.0 | 2.0 | 2.0 | 2.0 | 5.0 | - | - | - | 0.5 | 0.5 |
EuperlanPK 3000AM二硬脂酸甘油酯(和)月桂基醚-4(和)椰油酰氨基丙基甜菜碱 | 5.0 | - | - | 5.0 | - | - | - | - | - | - |
ArylponF月桂基醚-2 | - | - | - | - | - | - | - | - | - | - |
HighcareenGSβ-葡聚糖 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
七水合硫酸镁 | - | - | - | - | - | - | - | - | 1.0 | 1.0 |
甘油(86%(重量)) | - | - | - | - | - | 3.0 | 3.0 | 5.0 | 5.0 | 3.0 |
(11-15)泡沫浴液、(16)软化膏霜、(17,18)滋润乳液、(19,20)晚霜
Claims (9)
1.纳米标量的水溶性β-(1,3)葡聚糖用于制备化妆品和/或药用制剂的用途,其中该水溶性β-(1,3)葡聚糖基本不含β-(1,6)键,并且颗粒制剂为10-300nm。
2.权利要求1的用途,其特征在于其中含有基于酵母属真菌制得的葡聚糖。
3.权利要求1和/或2的用途,其特征在于其中所含的葡聚糖是通过将含β-(1,3)和β-(1,6)键的葡聚糖均与β-(1,6)葡聚糖酶接触使几乎所有β-(1,6)键均断开得到的。
4.权利要求3的用途,其特征在于所用的葡聚糖预先经基于木霉harzianum的葡聚糖酶处理。
5.权利要求1-4中至少一个权利要求所述的用途,其特征在于其中采用的纳米颗粒经防护胶体包埋。
6.权利要求5的用途,其特征在于其中采用聚乙烯醇或聚乙二醇作为防护胶体。
7.权利要求1-6中至少一个权利要求所述的用途,其特征在于葡聚糖的用量占制剂的0.1-5%(重量)。
8.权利要求1-7中至少一个权利要求所述的用途,其特征在于其中葡聚糖可用于制备护发制剂。
9.权利要求1-7中至少一个权利要求所述的用途,其特征在于其中葡聚糖用于制备护肤和防晒制剂。
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DE19911058A DE19911058B4 (de) | 1999-03-12 | 1999-03-12 | Verwendung von nanoskaligen wasserlöslichen β-(1,3)-Glucanen |
DE19911058.1 | 1999-03-12 |
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US (1) | US6858214B1 (zh) |
EP (1) | EP1165037B1 (zh) |
JP (1) | JP2002539147A (zh) |
KR (1) | KR20010108349A (zh) |
CN (1) | CN1182834C (zh) |
AT (1) | ATE286713T1 (zh) |
AU (1) | AU775786B2 (zh) |
CA (1) | CA2367875A1 (zh) |
DE (2) | DE19911058B4 (zh) |
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DE19911057C2 (de) * | 1999-03-12 | 2001-01-25 | Cognis Deutschland Gmbh | Haarkosmetische Zubereitungen |
US6649154B1 (en) * | 1999-06-03 | 2003-11-18 | Shiseido Co., Ltd. | Hairdressing cosmetic preparation and hairdressing method using the same |
KR20090057480A (ko) * | 2001-04-27 | 2009-06-05 | 아지노모토 가부시키가이샤 | 면역강화제 |
JP4752233B2 (ja) * | 2001-04-27 | 2011-08-17 | 味の素株式会社 | 免疫賦活剤 |
WO2003094865A1 (fr) * | 2002-05-09 | 2003-11-20 | Shiseido Company, Ltd. | Preparations externes pour la peau |
JP2004051561A (ja) * | 2002-07-22 | 2004-02-19 | Shiyuu Uemura Keshohin:Kk | 皮膚化粧料組成物 |
US7018986B2 (en) * | 2002-09-20 | 2006-03-28 | Immudyne | Use of beta glucans for the treatment of osteoporosis and other diseases of bone resorption |
WO2006121803A1 (en) * | 2005-05-05 | 2006-11-16 | Sensient Flavors Inc. | Production of beta-glucans and mannans |
CN1877239A (zh) * | 2005-06-08 | 2006-12-13 | 鸿富锦精密工业(深圳)有限公司 | 热管工作流体及其制备方法 |
CN1948421B (zh) * | 2005-10-13 | 2010-05-26 | 鸿富锦精密工业(深圳)有限公司 | 工作流体 |
US20090226549A1 (en) * | 2008-03-06 | 2009-09-10 | Kenneth John Hughes | Herbal extracts and flavor systems for oral products and methods of making the same |
US8394421B2 (en) * | 2008-07-30 | 2013-03-12 | The Board Of Trustees Of The University Of Illinois | Synthesis of nanoparticles by fungi |
US20100267661A1 (en) * | 2009-03-17 | 2010-10-21 | Immudyne, Inc. | Beta glucans and methods of use thereof |
TW201827040A (zh) * | 2016-09-30 | 2018-08-01 | 日商雷碧爾製藥有限責任公司 | 粒子及其製造方法 |
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JPS56135416A (en) * | 1980-03-27 | 1981-10-22 | Mitsubishi Chem Ind Ltd | Pharmaceutical preparation for skin |
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AUPN166195A0 (en) * | 1995-03-13 | 1995-04-06 | Norvet Research Pty Limited | Process for glucan extraction |
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CN103301040A (zh) * | 2013-06-29 | 2013-09-18 | 上海艳紫化工科技有限公司 | 小麦蛋白护发素 |
CN103301040B (zh) * | 2013-06-29 | 2015-01-21 | 安徽省林锦记食品工业有限公司 | 小麦蛋白护发素 |
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CA2367875A1 (en) | 2000-09-21 |
WO2000054741A1 (de) | 2000-09-21 |
JP2002539147A (ja) | 2002-11-19 |
DE19911058A1 (de) | 2000-09-21 |
ATE286713T1 (de) | 2005-01-15 |
EP1165037A1 (de) | 2002-01-02 |
EP1165037B1 (de) | 2005-01-12 |
US6858214B1 (en) | 2005-02-22 |
KR20010108349A (ko) | 2001-12-07 |
AU775786B2 (en) | 2004-08-12 |
DE50009222D1 (de) | 2005-02-17 |
DE19911058B4 (de) | 2004-09-30 |
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CN1182834C (zh) | 2005-01-05 |
ES2231176T3 (es) | 2005-05-16 |
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