CN1305456C - 组合物 - Google Patents
组合物 Download PDFInfo
- Publication number
- CN1305456C CN1305456C CNB961987359A CN96198735A CN1305456C CN 1305456 C CN1305456 C CN 1305456C CN B961987359 A CNB961987359 A CN B961987359A CN 96198735 A CN96198735 A CN 96198735A CN 1305456 C CN1305456 C CN 1305456C
- Authority
- CN
- China
- Prior art keywords
- skin
- weight
- compositions according
- cationic polymer
- compositions
- 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 - Lifetime
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- 239000000203 mixture Substances 0.000 title claims abstract description 135
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 38
- 230000000694 effects Effects 0.000 claims abstract description 26
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 11
- -1 siloxanes Chemical class 0.000 claims description 100
- 239000000344 soap Substances 0.000 claims description 93
- ICUTUKXCWQYESQ-UHFFFAOYSA-N triclocarban Chemical compound C1=CC(Cl)=CC=C1NC(=O)NC1=CC=C(Cl)C(Cl)=C1 ICUTUKXCWQYESQ-UHFFFAOYSA-N 0.000 claims description 31
- 229940099259 vaseline Drugs 0.000 claims description 25
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- 239000007787 solid Substances 0.000 claims description 20
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 claims description 19
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 16
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- 235000013599 spices Nutrition 0.000 claims description 11
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- 238000002360 preparation method Methods 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 8
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 8
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 7
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- 206010040844 Skin exfoliation Diseases 0.000 claims 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 claims 1
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
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- 238000006243 chemical reaction Methods 0.000 description 8
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
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- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 7
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- 239000007788 liquid Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
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- 125000003342 alkenyl group Chemical group 0.000 description 6
- 230000002421 anti-septic effect Effects 0.000 description 6
- 239000000284 extract Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 5
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- 241000196324 Embryophyta Species 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229920002907 Guar gum Polymers 0.000 description 5
- 241001597008 Nomeidae Species 0.000 description 5
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 5
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 5
- 229960003237 betaine Drugs 0.000 description 5
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- 239000012188 paraffin wax Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 4
- 208000001840 Dandruff Diseases 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 4
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 4
- 150000002632 lipids Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
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- 239000008107 starch Substances 0.000 description 4
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
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- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 3
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
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Abstract
一种人体用清洗组合物,该组合物包括:(a)有效洁肤量的表面活性剂或表面活性剂混合物,(b)一种有效量的对皮肤具有有益作用的疏水性活性组分,良好的皮肤状况、使皮肤免受刺激的保护作用以及抗菌剂效果都是该皮肤有益作用的组成方面,(c)含有碳氢化合物的组分,及(d)阳离子聚合物;组分c和d的选用量是那些使二者能够同时对组分b的益肤作用产生增强作用的用量,而不是仅使组分c或d单独发挥辅助作用的用量。
Description
发明背景
碱性皮肤清洗活性物在洁肤产品制造业中早已被采用。有效去除皮肤上的尘土是世界性消费群体的一个要求,该需求也正是皮肤清洗产品所面临解决的任务。除碱性清洗产品外,广大消费者还希望有其他洁肤用品。良好的皮肤状况,即光滑度、皮肤质地等,是理想的皮肤特质,而碱性皮肤清洗组合物通过其所含有的润肤剂来达得这种护肤效果。另外,那些对皮肤具有抗菌功效的组分现在也已被认为是皮肤清洗组合物的可接受成分,并且这些抗菌物质符合广大消费者的使用需求。
为了使消费者们能够感知到或不同程度地测定出这些有益效果,具有护肤功效的活性成分要与皮肤相接触。由于沉积的增加通常会使护肤效果增强并减少活性成分用量,也就降低了制剂的成本,因此,理想的是能够在皮肤上沉积出更多的活性成分。
现有技术的内容举例如下,WO 95/02388公开了一种分散相流体调理组合物,含有(1)烷氧基化或未烷氧基化的烷基硫酸盐;(2)N-酰氨基酸阴离子表面活性剂及其盐;(3)非挥发性不溶液体调理剂;(4)用于调理剂的晶体悬浮剂;以及(5)至少约40%(重量)的水,分散液悬浮剂总量不超过组合物的约30%(重量)。
WO95/22311公开的组合物含有(1)表面活性剂;(2)一种有益剂,该有益剂可以通过阻止皮肤或头发中水分的减少而起到软化的有益效果;及(3)一种沉积助剂,该助剂是一种阳离子共聚物,其电荷密度在0.0001-0.05eq/g之间,平均分子量高于2百万道尔顿。
WO 95/26710公开了一种清洗皂条组合物,该组合物能够在皮肤表面沉积出有效量的脂质,其中的固体组合物包括(1)约5-40份的脂质皮肤湿润剂;(2)约10-50份的刚性晶体骨架网络结构的物质,这类物质基本是由某些脂肪酸的皂类或这些皂类与某些脂肪酸的混合物组成的;(3)约1-50份的起沫性合成表面活性剂;及(4)约10-50份的水。
EP 0 366 070公开了一种洗浴组合物,该组合物包括非离子表面活性剂、油性成分和阳离子聚合物。该文献认为组合物中所含有的非离子表面活性剂的份数不能高于油性成分含量。
现已发现一种新的促使疏水性活性组分自皮肤清洗组合物中沉积出来的方法。无论是液体的还是固体的皮肤清洗组合物,该方法都能够使它们在日常洁肤过程中在皮肤上产生更多的活性组分,和/或能够使它们在皮肤上存留时间较长。
发明概述
本发明涉及了一种人体用清洗组合物,该组合物包括:
a.有效洁肤量的表面活性剂或表面活性剂混合物,
b.一种有效量的对皮肤具有有益作用的疏水性活性组分,其中良好的皮肤状况、使皮肤免受刺激的保护作用及抗菌剂效果都是该皮肤有益作用的组成方面。
c.含有碳氢化合物的组分,及
d.阳离子聚合物,组分c和d的选用量是那些使二者能够同时对组分b益肤作用产生增强作用的用量,而不是仅使组分c或d单独发挥辅助作用的用量。
另外,本发明还涉及上述类似组合物在皮肤清洗中的应用方法。
本发明还进一步涉及了一种人体用清洗组合物,该组合物包括:
a.约9-90%(重量)的表面活性剂或表面活性剂混合物,
b.含量约为0.01-10%重量的能具有益肤作用的疏水性活性组分,其中良好的皮肤状况、使皮肤免受刺激的保护作用及抗菌剂效果是该皮肤有益作用的组成方面。
c.含量约为0.5-5%(重量)的含碳氢化合物组分,及
d.含量约为0.01-3%重量的阳离子聚合物。
发明详述
本发明组合物具有良好的皮肤有益功效,这种功效是由那些已知的皮肤有益物质提供的。虽然不受这种理论的约束,但是可以肯定皮肤表面上有益物质沉积的增加产生了上述益肤作用,或者有益物质与皮肤表面接触时发挥出其益肤作用。因此,许多有益物质因其特有的作用而可以被使用。另外,有益物质能够更长时间地保留在皮肤表面上或与皮肤相接触,从而使作用的维持时间更长。上述这两种有益效果可以同时出现或仅出现一种。很清楚地是,至少有两种参数指标可以反映这些有益物质增强了的有益作用。第一种皮肤有益作用是有益物质的活性,例如皮肤调理水平、弱化皮肤刺激性及减少皮肤表面上可测出的细菌存在量。第二种作用是指以时间来衡量的活性作用持续性。对于要从皮肤上清洗掉的组合物产品而言后者尤其重要,该产品可例如是面部和手部的洗涤物、喷胶及其类似物。
为了发挥组合物的清洗活性,组合物中必须要含有有效皮肤清洗量的表面活性剂。组合物中可以包含有皂类物质,即支链或直链的长链烷基或链烯基的羧酸盐,例如钠盐、钾盐、铵盐或取代铵盐。其中的长链烷基或链烯基可例如是那些链长约为8-22个碳原子的基团,优选链长为10-20个碳原子的基团,更优选上述链长的烷基,最优选直链或仅带有极短支链的烷基。尤其当“烷基”来源于天然产物,例如牛油、椰子油及类似物时,烷基主链部分还可能存在少数烯键(碳碳双键)。
本发明组合物还可含有其他表面活性剂。这些表面活性剂可以例如是阴离子、两性、非离子和阳离子表面活性剂。两性阴离子表面活性剂包括但不限于是烷基硫酸盐、阴离子酰基肌氨酸盐、甲基酰基牛磺酸盐、N-酰基谷氨酸盐、酰基羟乙磺酸盐、烷基磺基琥珀酸盐、烷基磷酸酯、乙氧基化烷基磷酸酯、十三烷基硫酸盐、蛋白缩合物、乙氧基化烷基硫酸盐混合物及其类似物。
这些表面活性剂的烷基链长在C8-C22之间,优选是C10-C18,最优选的是C12-C14。
可例举的非皂类阴离子表面活性剂是有机硫酸碱金属盐,其分子结构是含有约为8-22个碳原子的烷基与磺酸或硫酸生成的酯基团(所谓烷基还包括带有高级酰基基团的烷基)。优选烷基硫酸的钠盐、铵盐、钾盐或三乙醇胺盐,特别优选那些高级醇(C8-C18碳原子)的硫酸化产物,例如椰油脂肪酸单甘油酯硫酸钠和磺酸钠;硫酸酯的钠盐或钾盐,该硫酸酯是1摩尔高级脂肪醇(例如牛油醇或椰油醇)与1-12摩尔环氧乙烷的反应产物;烷基苯酚环氧乙烷醚硫酸钠盐或钾盐,其中各分子中含有1-10个单位的环氧乙烷,并且烷基基团中含有8-12个碳原子,如烷基甘油基醚硫酸钠;含有10-22个碳原子的脂肪酸与羟乙磺酸发生酯化反应,并经氢氧化钠中和所得到的反应产物;脂肪酸与肌氨酸的缩合产物的水溶性盐;以及其他本领域已知的物质。
可大量例举出的两性离子表面活性剂是脂族季铵盐、磷盐、和锍化物的衍生物,该脂族基团可以是直链的或支链的基团,其中的一个脂族取代基含有约8-18个碳原子同时另一个脂族取代基含有水溶性阴离子基团,例如羧基、磺酸盐、硫酸盐、磷酸盐、或膦酸盐。这些化合物的通式是:
其中R2含有大约8-18个碳原子的烷基、链烯基、或羟烷基基团,0-10个环氧乙烷部分和0-1个甘油部分;Y选自由氮、磷和硫组成的原子;R3是带有1-3个碳原子的烷基或一元羟基烷基;当Y是硫原子时X为1,Y是氮或磷原子时X为2,R4是含有约0-4个碳原子的链烯基或羟基链烯基,Z选自一组由羧酸盐、磺酸盐、硫酸盐、膦酸盐和磷酸盐组成的基团。
具体实例包括:4-[N,N-二(2-羟乙基)-N-十八烷基铵基]-丁烷-1-羧酸盐、5-[S-3-羟丙基-S-十六烷基锍基]-3-羟戊烷-1-硫酸盐、3-[P,P,P-二乙基-P3,6,9三氧代十四烷基-磷基]-2-羟基丙烷-1-磷酸盐、3-[N,N-二丙基-N-3十二烷氧基-2-羟丙基铵基]-丙烷-1-膦酸盐、3-(N,N-二-甲基-N-十六烷基铵基)-丙烷-1-磺酸盐、3-(N,N-二-甲基-N-十六烷基铵基)-2-羟丙烷-1-磺酸盐、4-[N,N-二(2-羟乙基)-N-(2-羟基十二烷基)铵基]-丁烷-1-羧酸盐、3-[S-乙基-S-(3-十二烷氧基-2-羟丙基)-锍基]-丙烷-1-磷酸盐、3-(P,P-二甲基-P-十二烷基膦基)-丙烷-1-膦酸酯和5-[N,N-二(3-羟丙基)-N-十六烷基铵基]-2-羟基-戊烷-1-硫酸盐。
可以大量例举的用于本发明组合物的两性表面活性剂是脂族仲胺和叔胺的衍生物,该脂族基团可以是直链的或支链的基团,其中的一个脂族取代基含有约8-18个碳原子同时另一个脂族取代基含有水溶性阴离子基团,例如羧基、磺酸盐、硫酸盐、磷酸盐、或膦酸盐。该定义范围内的化合物实例是:3-十二烷基氨基丙酸钠、3-十二烷基氨基丙烷磺酸钠、N-烷基牛磺酸,例如可根据U.S.专利2,658,072所述方法将十二烷基胺与羟乙磺酸钠反应得到的产物;N-高级烷基天冬氨酸,例如按照U.S.专利2,438,091所述方法生产的产物,和以商品名为“Miranol”上市并根据U.S.专利2,528,378所述方法制备的产品。本发明组合物还可使用其他两性物质,如甜菜碱类物质。
可在本发明中采用的甜菜碱类化合物实例包括了:高级烷基甜菜碱、例如,椰基二甲基羧甲基甜菜碱、十二烷基二甲基羧甲基甜菜碱、十二烷基二甲基α-羧乙基甜菜碱、十六烷基二甲基羧甲基甜菜碱、十二烷基-二-(2-羟乙基)羧甲基甜菜碱、硬脂基-二-(2-羟丙基)-羧甲基甜菜碱、油基二甲基γ-羧丙基甜菜碱、十二烷基-二-(2-羟丙基)-α-羧乙基甜菜碱等。组合物中还可以含有磺基甜菜碱,如椰基二甲基磺丙基甜菜碱、硬脂基二甲基磺丙基甜菜碱、酰氨基甜菜碱、酰氨基磺基甜菜碱以及类似化合物。
许多阳离子表面活性剂是现有技术中熟知的物质。为了举例列出下列化合物:
-硬脂基二甲基苄基氯化铵;
-十二烷基三甲基氯化铵;
-壬基苄基乙基二甲基硝酸铵;
-十四烷基溴化吡啶;
-十二烷基氯化吡啶;
-十六烷基氯化吡啶;
-十二烷基氯化吡啶;
-十二烷基溴化异喹啉
-二牛油基(己氢化)二甲基氯化铵;
-二-十二烷基二甲基氯化铵;和
-硬脂基烷基氯化物(stearalkonium chloide)
其他阳离子表面活性剂在美国专利4,303,543的第4栏第58行和第5栏第1-42行中有描述,在此作为参考。还可以参见CTFA化妆用成分字典(Cosmetic Ingredient Dictionary),第4版,1991,第509-514页中描述的长链烷基阳离子表面活性剂;该文献在此作为参考。
非离子表面活性剂可以广义地定义为亚烷基氧化物基团(亲水性)与疏水性有机化合物缩合后得到的化合物,其中疏水性化合物可以是脂族或烷基芳香族类物质。非离子表面活性剂中,优选类型中的具体实例是:
1.聚环氧乙烷的烷基苯酚缩合物,例如烷基苯酚与环氧乙烷的缩合物,其中的烷基是指含有6-12个碳原子的直链或支链构型的基团,基于每摩尔烷基苯酚,环氧乙烷的含量是10-60摩尔。在此类化合物中的烷基取代基可以例如是聚合的丙烯、二异丁烯、辛烷、或壬烷的衍生物。
2.环氧乙烷与由环氧丙烷和乙二胺反应得到的产物进行缩合而得到的衍生物,其中各物质在组合物中的含量可以根据所需疏水性和亲水性组成单元的平衡来改变。例如,化合物中可以含有40-80%(重量)的聚氧乙烯且其分子量约是5,000-11,000,该聚氧乙烯是环氧乙烷与分子量为2,500-3,000的疏水性碱的反应产物,其中的疏水性碱由乙二胺和过量环氧丙烷的反应产物组成,产物令人满意。
3.含有8-18个碳原子的直链或支链构型的脂肪醇与环氧乙烷的缩合产物,例如椰醇环氧乙烷缩合物,其中每摩尔椰醇对应有10-30摩尔的环氧乙烷,椰醇部分含有10-14个碳原子。其他环氧乙烷的缩合产物是乙氧基化的脂肪酸多元醇酯(例如,Tween 20-聚氧乙烯(20)山梨醇单月桂酸酯)。
4.具有下面通式的长链叔胺氧化物:
R1R2R3N→O
其中,R1包含有约8-18个碳原子的烷基、链烯基或单羟基烷基基团,约0-10个环氧乙烷部分,和0-1个甘油部分;R2和R3含有1-3个碳原子和0-1个羟基,例如甲基、乙基、丙基、羟乙基、或羟丙基基团。通式中的箭头通常代表一个半极性键。适用于本发明的胺氧化物实例包括:二甲基十二烷基胺氧化物、油基-二-(2-羟乙基)胺氧化物、二甲基辛基胺氧化物、二甲基癸基胺氧化物、二甲基十四烷基胺氧化物、3,6,9-三氧杂十七烷基二乙基胺氧化物、二(2-羟乙基)十四烷基胺氧化物、2-十二烷氧基乙基二甲基胺氧化物、3-十二烷氧基-2-羟丙基二(3-羟丙基)胺氧化物、二甲基十六烷基胺氧化物。
5.下面通式表示的长链叔膦氧化物:
RR’R”P→O
其中,R包含有链长约为8-20个碳原子的烷基、链烯基或单羟基烷基基团,约0-10个环氧乙烷部分,和0-1个甘油部分;及,R’和R”各是含有1-3个碳原子的烷基或单羟基烷基基团。通式中的箭头通常代表了一个半极性键。膦氧化物的合适例子有:十二烷基二甲基膦氧化物、十四烷基甲基乙基膦氧化物、3,6,9-三氧杂十八烷基二甲基膦氧化物、十六烷基二甲基膦氧化物、3-十二烷基氧-2-羟丙基二(2-羟乙基)膦氧化物、硬脂基二甲基膦氧化物、十六烷基乙基丙基膦氧化物、油基二乙基膦氧化物、十二烷基二乙基膦氧化物、十四烷基二乙基膦氧化物、十二烷基二丙基膦氧化物、十二烷基二(羟甲基)膦氧化物、十二烷基二(2-羟乙基)膦氧化物、十四烷基甲基-2-羟丙基膦氧化物、油基二甲基膦氧化物、2-羟基十二烷基二甲基膦氧化物。
6.长链二烷基亚砜,其中含有一条链长约为1-3个碳原子的短链烷基或羟基烷基基团(通常为甲基),和一条疏水性长链,该疏水性长链中含有链长约为8-20个碳原子的烷基、链烯基、羟烷基、或氧代烷基基团、0至约10个环氧乙烷部分和0-1个甘油部分。化合物实例包括:十八烷基甲基亚砜、2-氧代十三烷基甲基亚砜、3,6,9-三氧杂-十八烷基-2-羟乙基亚砜、十二烷基甲基亚砜、油基3-羟丙基亚砜、十四烷基甲基亚砜、3-甲氧基十三烷基甲基亚砜、3-羟基十三烷基甲基亚砜、3-羟基-4-十二烷氧基丁基甲基亚砜。
本发明组合物中可以采用任意量的具有皮肤清洗作用的表面活性剂或表面活性剂混合物。通常,组合物中至少含有1%(重量)份的表面活性剂(a)。组合物中表面活性剂的最低优选量是至少3,5,7,10,20和30%。表面活性剂的最高含量要根据所用组合物的物理混合物及其中的组分b,c,d的用量而定。通常,表面活性剂的含量约不超过95-97%(重量),特别约不超过90%(重量)。将表面活性剂的最大含量选定为20、30、40、50、60、70、80或85%(重量),这样的选择很便利。
组分b是提供皮肤有益效果的疏水性物质。本说明书中的“疏水性”是指物质具有较高的脂溶性及较低的水溶性,脂溶性的含义是不溶于水。优选的物质是那些在水中溶解度很低并且其特性基本是非离子性而不是离子性的物质。这类物质的实例包括但不限于润肤剂、抗微生物剂、防晒剂、香料、驱虫剂、抗霉菌剂和抗炎剂。
用于说明本发明范围内润肤剂的实例包括:长链饱和或不饱和脂肪酸,例如月桂酸、油酸、肉豆蔻酸、棕榈酸、硬脂酸,它们可以是支链的也可是直链的;硅氧烷,例如二甲基硅氧烷、甲基苯基硅氧烷、甲基高级烷基硅氧烷,即第二烷基最多含有25个碳原子的丙氧基化硅氧烷,所有这些硅氧烷具有约15,000厘沲的最低粘度值,优选的粘度约是40,000厘沲,硅氧烷的最大粘度要是保证硅氧烷呈流体状态,并且不是树胶、羊毛脂、酯类,如含有支链的脂类,具体例如棕榈酸乙基己基酯、硬脂酸异丙酯、肉豆蔻酸异丙酯,己二酸、乳酸、油酸、硬脂酸、异硬脂酸、肉豆蔻酸、或亚油酸的十六烷基异癸酯或异丙酯;饱和及不饱和的脂肪醇,如角鲨烯和角鲨烷,山嵛醇、十六烷醇;长链酯类,如硬脂酸硬脂基酯、棕榈酸癸酯、花生酸十二烷基酯及类似物。本发明组合物不包括硅氧烷树胶。
适用的抗菌剂实例有二-N-碳酰苯胺类物质,例如三氯卡班,即也可称为三氯N-碳酰苯胺,CAS(美国化学文摘)登记号为101-20-2;三氯生,卤代的二苯基醚,其CAS登记号是3380-34-5,通常是指Ciba-Geigy生产的DP-300;六氯代苯,即3,4,5-三溴代水杨酰苯胺,及2-吡啶乙硫醇-1-氧化物的盐。
本发明组合物还可包括那些能够调节皮肤所承受的紫外线辐射量的有机防晒剂。用来说明这类物质的实例包括:二苯酮、对氨基苯甲酸、和辛基二甲基对氨基苯甲酸酯,但不局限于此。
组合物的释放体系是由含碳氢化合物的组分c和阳离子聚合物d结合成的体系,其中该体系能够提高组合物中的疏水性活性护肤组分b的沉积。
组分c可以是常规的碳氢化合物,例如蜡、矿脂、矿物油、蜂蜡,“全甲基物”为由长链支化烃组成,可购自PermethylCorporation。全甲基化合物的通式是:
其中,n在约4-超过200变化。当n=4,16,38,214时,相应各产物的商品名分别是Permethyl102A,104A,106A,和1082A。
适用于本发明的矿脂可以是任何级别的本领域所熟知的并且是人体可接受的白色或黄色矿脂。优选的矿脂是那些熔点在大约35-50℃范围内的矿脂。本发明组合物中的矿脂允许包括碳氢化合物混合物,与矿物油配制和/或与不同熔点的石蜡结合;但矿物油或石蜡与矿脂相比含量都很低。优选不含有额外物质的矿脂。蜡质实例有微晶蜡,其通常称为石蜡、蜂蜡和由植物中提炼出的天然蜡的蜡类,在固体组合物中特别优选采用。
阳离子聚合物是那些通常在清洁、漂洗过程中和使用后都对皮肤产生良好感觉的一类物质。
阳离子聚合物包括下列种类的物质,但不局限于此:
(I)阳离子多糖;
(II)糖类和合成的阳离子单体的阳离子共聚物;
(III)选自由下列物质组成的各组合成聚合物:
(A)阳离子聚亚烷基亚胺
(B)阳离子乙氧基聚亚烷基亚胺
(C)阳离子聚[N-[3-(二甲基铵)丙基]-N’[3-(亚乙氧基亚乙基二甲基铵)丙基]二氯化脲]
(D)含有季氨盐或取代铵离子的常规聚合物
阳离子多糖类物质包括那些以5碳糖或6碳糖为基础并在其多糖主链上因结合有阳离子部分而呈阳离子性的衍生物。它们由一种或多种类型的糖组成,即上述衍生物和阳离子物质的共聚物。聚合单体既可在直链也可在支链上进行几何排列。阳离子多糖聚合物包括:阳离子纤维素和羟乙基纤维素;阳离子淀粉和羟基烷基淀粉;阿拉伯糖为单体的阳离子聚合物,例如那些由阿拉伯糖植物胶中提取的物质;由木糖聚合物组成的阳离子聚合物,这种阳离子聚合物可来源于木头、草、棉籽壳和玉米芯;由岩藻糖聚合物衍生出的阳离子聚合物,该类聚合物是海藻细胞壁的组成之一;由果糖聚合物衍生的阳离子聚合物,例如在某些植物中发现的菊粉;基于含酸糖的阳离子聚合物,例如半乳糖醛酸和葡糖醛酸的阳离子聚合物;基于胺糖如半乳糖胺和葡糖胺的阳离子聚合物;以5元和6元环的多元醇为基础的阳离子聚合物;以半乳糖为单体的阳离子聚合物,这种物质存在于植物胶和粘质中;以甘露糖为单体的阳离子聚合物,例如在植物、酵母和赤藻中发现的聚合物;半乳甘露聚糖共聚物为基础的阳离子聚合物,已知的有来源于瓜耳豆胚乳的瓜耳胶。
阳离子多糖类物质的组成物的特例包括:Union CarbideCorporation生产的阳离子羟乙基纤维素JR 400;Staley,Inc.生产的阳离子淀粉Stalok100、200、300和400;以瓜耳胶为基础的阳离子半乳甘露聚糖,该阳离子物质是由Henkel公司提供的Galactasol800系列和Celanese Corporation提供的Jaguar系列产品。
本发明采用由糖类及合成阳离子单体组成的阳离子共聚物,其中包括含有下列糖类的物质:葡萄糖、半乳糖、甘露糖、阿拉伯糖、木糖、岩藻糖、果糖、葡糖胺、半乳糖胺、配体醛酸、半乳糖醛酸、及5元或6元环的多元醇。该共聚物还包括上述糖类的羟甲基、羟乙基和羟丙基衍生物。当共聚物中的糖类物质彼此键合时,它们可以是几种排列顺序中的任何一种,例如1,4-a、1,4-β、1,3-a、1,3-β和1,6连接。这类共聚物所采用的合成阳离子单体可包括:二甲基二烯丙基氯化铵、二甲基氨基乙基甲基丙烯酸酯、二乙基二烯丙基氯化铵、N,N-二烯丙基,N-N-二烷基卤化铵及类似物。优选的阳离子聚合物是由二甲基二烷基氯化铵和丙烯酰胺单体共同制成的Polyquaternium 7。
由糖类与合成的阳离子单体组成的共聚物类实例包括那些由纤维素衍生物(例如羟乙基纤维素)与N,N-二烯丙基,N-N-二烷基氯化铵构成的物质,由National Starch Corporation生产并以Celquat为商品名出售。
本发明所用的其他合成阳离子聚合物是阳离子聚亚烷基亚胺、乙氧基聚亚烷基亚胺、和聚{N-[3-(二甲基铵基)-丙基]-N’-[3-(亚乙氧基亚乙基二甲基铵基)丙基]二氯化脲},后者是由MiranolChemical Company,Inc.生产并以商标为Miranol A-15出售,该物质的CAS登记号是68555-336-2。优选在本发明中作为皮肤调理剂的阳离子聚合物是那些阳离子瓜耳胶类的阳离子多糖,这些阳离子聚合物的分子量在1,000-3,000,000之间。更优选聚合物分子量在2,500-350,000之间。这些聚合物中含有由半乳甘露聚糖单元组成的多糖主链,聚合物还有一定的阳离子取代范围,该范围是每单位葡糖酐带有大约0.04-0.80单位的阳离子取代基团,取代基团是2,3-环氧丙基-三甲基氯化铵与天然多糖主链的加合物。例如Celanese Corporation出售的JAGUAR C-14-S、C-15和C-17,这些产品的说明书中标明它们具有125cps至大约3500±500cps(厘泊)的1%粘度。
其他阳离子聚合物的实例还包括:聚合物,例如某些季铵盐的聚合物;不同物质的共聚物,例如羟乙基纤维素和二烷基二甲基氯化铵,丙烯酰胺和β甲基丙烯酰氧基乙基三甲基N-甲硫酸铵的共聚物;甲基和硬脂基的二甲基氨乙基甲基丙烯酸酯经二甲基硫酸酯季铵化得到的季铵盐;由二乙基硫酸酯反应得到的季铵聚合物;乙烯吡咯烷酮和二甲基氨乙基甲基丙烯酸酯的共聚物;季铵化的瓜耳胶和瓜耳树胶及其类似物。可以形成本发明配合物的阳离子聚合物的实例有:如CTFA国际妆用成分字典(International Cosmetic Ingredient Dictionary)(第4版,1991,第461-464)中公开的物质;Polyquaternium-1,-2,-4(羟乙基纤维素和二烯丙基二甲基氯化铵的共聚物)、-5(丙烯酰胺和β甲基丙烯酰氧基乙基三甲基N-甲硫酸铵的共聚物)、-6(二甲基二烯丙基氯化铵的聚合物)、-7(丙烯酰胺和二甲基二烯丙基氯化铵单体的聚合季铵盐)、-8(甲基和硬脂基的二甲基氨乙基甲基丙烯酸酯经二甲基硫酸酯季铵化得到的聚合季铵盐)、-9(由聚二甲基氨基乙基甲基丙烯酸酯经溴甲烷季铵化得到的聚合季铵盐)、-10(羟乙基纤维素与被三甲基铵取代的环氧化物反应得到的聚合季铵盐)、-11(由二乙基硫酸酯与乙烯吡咯烷酮和二甲基氨基乙基甲基丙烯酸酯的共聚物反应得到的季铵聚合物)、-12(甲基丙烯酸乙酯/甲基丙烯酸松基酯/二乙基氨基乙基甲基丙烯酸酯的共聚物与二甲基硫酸酯反应得到的聚合季铵盐)、-13(甲基丙烯酸乙酯/甲基丙烯酸油基酯/二乙基氨基乙基甲基丙烯酸酯共聚物与二甲基硫酸酯反应得到的聚合季铵盐)、-14,-15(丙烯酰胺和β甲基丙烯酰氧基乙基三甲基氯化铵的共聚物)、-16(甲基乙烯基咪唑基氯化物与乙烯吡咯烷酮形成的聚合季铵盐)、-17,-18,-19(由聚乙烯醇与2,3-环氧-丙胺反应制得的聚合季铵盐)、-20(由聚乙烯十八烷基醚与2,3-环氧丙胺反应制得的聚合季铵盐)、-22,-24(羟乙基纤维素与十二烷基二甲基铵取代的环氧化物反应得到的聚合季铵盐)、-27(由Polyquaternium-2(参阅文献)与Polyquaternium-17(参阅文献)反应制得的嵌段共聚物)、-28,-29(是由Chitosan(参阅文献)与环氧丙烷反应并且经表氯醇季铵化反应制得)、及-30。
优选的表面活性剂是阴离子表面活性剂,例如皂类;烷基羟乙磺酸酯,例如羟乙磺酸钠椰油基酯;磺酸酯;硫酸酯(可以被乙氧基化)及类似物。
对于本发明组合物,其中的阴离子表面活性剂含量可优选是那些不同于早已被探讨过的表面活性剂常规含量范围的约1-96%(重量),特别优选在5-85%范围内。相对本发明液体组合物而言,尤其是含水组合物,阴离子表面活性剂约占组合物的2-20%(重量),更优选约占组合物的5-15%(重量)。对于固体组合物,阴离子表面活性剂约占5-90%(重量),优选约10-50%(重量);“syndet”皂条中优选的表面活性剂含量约为10-50%(重量);“combar”皂条中表面活性剂约占55-80%(重量);并且在仅含有一种阴离子表面活性剂的固体组合物中,例如皂类,阴离子表面活性剂约占组合物70-90%(重量),优选约为75-85%(重量)。
作为疏水剂的组分b的含量须根据其在组合物中所要达到的效果来进行具体选择。组分b的含量约为组合物的0.01-10%(重量),只要可以对皮肤产生有益作用。通常,对于在极低含量就可以显现功效的物质而言,例如抗菌剂,它们在组合物中的含量范围很小。例如,当三氯生和三氯N-碳酰苯胺的含量约是组合物的0.01-1.5%重量时就产生抗菌效果,尤其是在固体组合物中。这些物质的优选含量约是0.05-1.4%重量,更优选约是0.1-1.0%重量。那些组合在一起的物质通常是具有更高端值的重量百分含量范围,这些物质的含量通常约是1.0-10%重量,例如游离脂肪酸和酯类,尤其是在固体组合物中。优选范围约是2-8%(重量)。所用疏水剂的含量范围很宽,这类物质可例如是硅氧烷,优选最低粘度约是15,000厘泊的二甲基硅氧烷,优选40,000厘泊的二甲基硅氧烷。在固体组合物中优选采用硅氧烷,而硅氧烷不仅能够产生良好的皮肤感觉,还通过使皮肤水分储存起来而达到显著真切的护肤作用。硅氧烷的含量约占组合物重量的0.5-10%,优选约是0.75-4%重量,并且更优选约占组合物的1.0-3.0%重量。
组合物中的组分c是含有碳氢化合物并与实际为阳离子聚合物的组分d共存的物质,组分c能够加强组分b物质的益肤作用。这种增强了的益肤作用被认为是由于组分c在皮肤上沉积量的增加。在本发明中各种成分都可作为组分c。例如,这类物质包括矿脂、微晶蜡、石蜡和如上所述的全甲基物。微晶蜡是在许多文献中都有描述的已知物质。矿脂是本发明组合物中的优选成分,尤其是在固体组合物中更优选使用它。这些碳氢化物的混合物具有不同的软化点或范围。组分c的含量约占组合物的0.1-10%重量。通常,优选约是0.25-4%重量。
组分d是阳离子聚合物。最优选的阳离子聚合物种类是无纤维物、无糖的阳离子聚合物,例如在CTFA International CosmeticIngredient Dictionary,第4版,1991,中被描述为Polyquat 6和Polyquat 7的聚合物,它们分别是聚合的二甲基二烯丙基氯化铵和丙烯酰胺与二甲基二烯丙基氯化铵的聚合季铵盐。阳离子聚合物的含量是指能够与组分c物质共同增强益肤作用的有效量。通常,该阳离子聚合物的含量约是组合物的0.01-3.0%(重量),优选约是0.02-0.9%重量,最优选约是0.05-0.75%重量。通常,优选组分c和组分d共同产生更高益肤效果的含量值,而不是仅有组分c和组分d二者之一能够产生作用的含量。
对组合物的物理特性没有严格的要求,组合物可以是固体、液体或凝胶。若是固体组合物,优选组分b是硅氧烷。固体中的水分含量可以约是6-22%(重量)。组合物通常是采用标准皮肤清洗组合物制备技术来制得的。然而,为了使本发明组合物达到最大有益效果,优选的是:当组分b,c,d还没有与本发明组合物的其他成分,尤其是组分a接触时,先将这些组分混合起来。最优选的是先将组分b和c混合,再将组分d加入到b和c的混合物中。进一步地说,当制备例如皂条的固体组合物时,优选首先将组分b,c和d制成预制混合物,然后将组合物中一种或多种其他材料物在搅拌机内加入到上述预制混合物中,尤其是当组分b是硅氧烷或抗菌剂时采用此方法。对于组分加入时的相应温度,优选搅拌步骤的加料温度约是20-30℃,特别优选在室温条件下完成;但是,当在调和锅中制备时就可以在较高温度条件下进行,例如80-85℃,尤其当组分c是硅氧烷时应采用高温。
下面是制备本发明固体组合物的标准方法。
固体组合物
%(重量)
皂片 94.82%
(85/15,牛油/椰油皂10%水分)
TCC 0.7%
矿脂 1.4%
Polyquat 7(8%活性物) 1.4%
柠檬酸(50%溶液) 0.15%
二氧化钛 0.5%
防腐剂和香料 1.03%
将TCC分散在矿脂中,然后加入Polyquat 7。在25-28℃条件下,将该混合物加入到在搅拌机内的皂片中,随后加入二氧化钛、防腐剂和香料。将皂片碾磨三次、模压并压制成皂条形状。
下面是制备液体组合物的标准方法。
液体组合物
第1部分
SLES-2(25.6%) 9.0%
防腐剂 0.1%
异丙基苯磺酸钠盐(43%) 7.0%
第2部分
去(头)皮屑剂 0.5%
椰油酰氨基丙基甜菜碱(30%) 9.0%
Polyquat 6(40%) 1.0%
Polyquat 7(8%) 1.0%
第3部分
Isosteareth-2 0.8%
C-20-40醇 4.0%
二硬脂基二甲基氯化铵 0.5%
Permethyl(全甲基物)-106A 2.0%
DP-300 1.0%
第4部分
磷酸二钠盐 0.2%
Dimethicone 60,000 cSt 4.0%
防腐剂 1.0%
香料 0.5%
水分 Q.S
方法:
将第1部分中的所有组分在20-25℃条件下混合。将该混合物加热至85-90℃,然后在此温度条件下分次将第2部分的各成分加入混合物中。另外,将第3部分的组分单独混合,该第3部分的混合物须加热至90-92℃直至溶液依次为澄清/雾状混浊。此混合物加入到第1和第2部分的结合混合物中。随后,在75℃条件下加入磷酸二钠盐和二甲基硅氧烷(dimethicone),在35℃温度下向第1、2和3部分的混合物中加入防腐剂和香料。
下面是本发明的实施例。还包括了本发明的对比例和对照实验例。这些实施例用于说明本发明的范围,但不作为本发明保护范围的限定。
在下面的实施例中,使用了下列缩写:
TCC-三氯卡班,CAS登记号101-20-2
N-(4-氯代苯基)-N’-(3,4-二氯苯基)脲
DP300-三氯生,CAS登记号3380-34-5
5-氯-2-(2,4-二氯苯氧基)苯酚
Permethyl 104a-聚异丁烯,其结构式如前所述,其中的n是16
Polyquat 6-二甲基二烯丙基氯化铵聚合物,在组合物中作为溶于水并占40%(重量)的活性物质
Polyquat 7-丙烯酰胺和二甲基二烯丙基氯化铵单体的共聚物,在组合物中作为溶于水并占8%(重量)的活性物质
雪白矿脂,CAS登记号8009-03-8
皂-来源于牛油和/或植物油的脂肪酸按一定重量百分比形成的钠盐
硅氧烷-粘度约为60,000厘沲的二甲基聚硅氧烷
下面是实施例所用测试体系的工艺方法:
在猪皮表面的沉积
材料和方法
皮肤样品
由年龄为3-6月的成熟Yucatan公猪身上取下包含皮肤各层的整皮。受试动物是在被控制的环境条件中饲养并喂给特殊饲料以保持猪角质层脂质组合物相对稳定。采用兽医学中的方法,将无痛苦处死动物身体上的皮肤小心地取下,并且立即在液氮中冷冻起来。
冷冻的皮肤样品首先在室温下解冻,然后用锋利的曲解刀谨慎地将皮下脂肪除去。余下的皮肤组织用“微孔”水,即超纯水漂洗,然后切割成近1.5平方英寸的块。这种皮肤样品用塑料包装卷起来并冷冻直至需要使用。
样品皂的制备:
用实验室用三辊碾预碾皂片。然后在皂片中加入添加物并混合均匀。皂片在3辊碾中碾磨3次以保证得到均匀的产物。皂液(5%)是由经碾制皂片和硬度为100ppm的水[Ca,Mg]制成的。
样品台架
使用一种特别设计的金属样品台架来处理皮肤样品,该样品台架基本与Hilliard(Clairol)在美国专利4,836,014中描述和绘制的样品台架相似。这种样品台架可以同时处理12个样品,各样品在被处理时都暴露出均匀的皮肤面(约5.72cm2)。样品台架的底板由12个圆凹槽组成,与它们相应的是顶板上也带有12个圆凹槽。样品台架用翼状螺丝固定在一起。
试验方法:
将皮肤样品从冷冻器中取出并在室温下除霜0.5小时。一旦除霜完毕,用几毫升的超纯水漂洗皮肤样品。将皮肤样品码放在样品台架上(的圆凹槽中)并使上下皮肤的角质层相对,然后将样品台架紧紧地固定直至复位。
硅氧烷、TCC和DP-300的沉积情况采用下列方法测定:
用吸量管取2ml的5%(重量)皂液放置在各皮肤样品上。整个样品台架用铝箔包起来以防止处理过程中液体蒸发。样品台架放在一个控温振动器(lab-Line仪器)中并平衡在所需的温度条件下(93%(重量)的皂类和7%(重量)的游离脂肪酸的组合物采用50℃的温度条件,其中60%的皂类来源于牛油且40%的皂类来源于椰油,该组合物缩写为60/40/7;缩写为85/15的皂类采用60℃的温度条件,该皂类是由85%(重量)的牛油和15%(重量)的椰油组成,但不含有额外的游离脂肪酸)。转速定为50rpm,将样品持续处理1小时。然后,将皂液从皮肤样品上吸除掉,各皮肤样品用每份1.5ml的超纯水漂洗3次。
皮肤样品上沉积的硅氧烷沉积物常用下列方法测定:将1.5ml等量的煤油加入到各样品上,然后在温度为25℃的温控振动器中处理5分钟,并且放在转速为75rpm的振动器中振动5分钟。随后,将各样品上的液体吸除并放入瓶中。再进行两次硅氧烷萃取并将萃取液合并成一份试样。其中的硅氧烷浓度用ICP(诱导性偶联氩等离子体)分析法测定。
从皮肤样品中提取的TCC和DP-300采用与硅氧烷相似的方法测定,但测定方法须进行下列改动:用1∶1∶2的己烷∶氯仿∶异丙醇(体积比)来代替煤油以将样品中的抗菌活性物质萃取出来。为了减少溶剂体系的蒸发,处理的时间由5分钟减至3分钟。各样品用4份萃取液萃取而不是3份硅氧烷。提取液中的TCC和DP-300浓度采用紫外吸收光谱法来测定,TCC的测定结果是e265nm=0.14289ppm-1cm-1,DP-300的测定结果是e280nm=0.01553ppm-1cm-1。
另外,还进行了确定硅氧烷、TCC和DP-300可以被皮肤样品回收的试验,该试验中各物质的浓度是参比于沉积时的浓度。回收试验的方法如下:将0.5ml的0.25%皂液吸至各皮肤样品上。样品在1小时的处理过程中不用铝箔覆盖。处理完毕后立刻采用上述方法提取硅氧烷、TCC和DP-300,但不用水漂洗样品。
羊毛底物上TCC或DP-300沉积量的测定方法
为了防止TCC分解,将皂液(5-5.9%)在低温加热条件下制备。通常,皂液温度50℃且加热时间不超过30分钟。用皂液浸渍羊毛样品(48cm2)。皂液放置在烘箱内,在40-45℃条件下保持2小时,或在20-25℃下保持15分钟。处理完毕后,将溶液缸中的液体倾析出去,样品用100ml等份的超纯水漂洗。再漂洗两次并同时搅拌5分钟。用镊子将样品从缸中取出,干燥过夜。
TCC或DP-300的萃取是:将50g2∶1∶1的异丙醇∶己烷∶氯仿(体积比)加入到干燥样品中并同时搅拌15分钟。取出样品,然后采用上述紫外吸收光谱法测定TCC或DP-300的浓度。
实施例1,4和5的产品组合物
组分 重量%
皂片(85/15牛油/椰油) 96.5
10%湿润度
TCC 0.7
释放体系 2.8
实施例6中的皂片组合物
皂片-1
组分 wt.%
皂类(60/40,牛油/椰油) 83
游离脂肪酸 7
水分 10
100
皂片-2
组分 wt.%
皂类(85/15,牛油/椰油) 90
H2O 10
100
实施例1
经5.9%(重量)产品溶液处理2小时接触时间(40-45℃)后,TCC在羊毛样品上的沉积
释放体系 mg TCC/sq.cm.
羊毛样品
Polyquat 6(2.8wt.%) 1.77
Polyquat 7(2.8wt.%) 5.7
Permethyl No.104A(2.8wt.%) 6.4
Permthyl No.104A(1.4wt.%)/Polyquat 6(1.4wt.%) 4.7
Permethyl No.104A(1.4wt.%)/Polyquat 7(1.4wt.%) 9.1
实施例2
经5%(重量)皂液、0.7%(重量)DP-300和2.8%(重量)释放体系的混合物在20-25℃下处理15分钟接触时间后,羊毛样品上DP-300的沉积量
释放体系 DP-3O0沉积量(mg)/平方厘米
羊毛样品
Permethyl No.104A(2.8wt.%) 89.87
(聚异丁烯)
Polyquat 6(2.8wt.%) 44
Polyquat 7(2.8wt.%) 251
Permethyl No.104A(1.4 557
wt.%)/Polyquat 6(1.4wt.%)
实施例3
用5wt.%皂液、0.7wt.%TCC和2.8wt.%释放体系组成的混合物在20-25℃下处理15分钟接触时间后羊毛样品上的TCC沉积量
释放体系 TCC(mg)/cm2
羊毛样品
Permethyl No.104A(2.8wt.%) 116
Polyquat 6(2.8wt.%) 111
Permethyl No.104A(1.4wt.%)和 416
Polyquat 6(1.4wt.%)
实施例4
猪皮试验中的TCC沉积结果
5.0%(重量)产品溶液中的TCC沉积量(60℃)
释放体系 TCC沉积量
(mg TCC/cm2猪皮)
矿脂(2.8wt.%) 12.7±2.3
Polyquat 7(2.8wt.%) 29.2±3.1
矿脂(1.4wt.%)/ 40.0±2.6
Polyquat 7(1.4wt.%)
实施例5
羊毛样品试验中TCC的沉积结果
5.0%(重量)产品溶液中TCC(45℃)沉积量
释放体系 TCC沉积量
(mg TCC/cm2羊毛样品)
Permethyl No.104A(2.8wt.%) 1.7±0.2
Polyquat 6(2.8wt.%) 1.8±0.4
Polyquat 7(2.8wt.%) 4.2±1.3
Permethyl No.104A(1.4wt.%)/ 4.6±1.2
Polyquat 6(1.4wt.%)
Permethyl No.104A(1.4wt.%)/ 9.1±0.5
Polyquat 7(1.4wt.%)
矿脂(1.4wt.%)/ 13.1±3.9
Polyquat 7(1.4wt.%)
实施例6
猪皮样品试验中的硅氧烷沉积结果
样品 | 样品编号 | 二甲基硅氧烷(μg)/猪皮样品 | 二甲基硅氧烷(μg/cm2)皮肤 |
皂片1(95wt.%)+5wt.%二甲基硅氧烷 | 3 | 17.1±2.1a | 3.0 |
皂片1(92wt.%)+5wt.%二甲基硅氧烷+1.5wt.%Polyquat 7和+1.5wt.%Permethyl 104A | 3 | 52.0±18.3b | 9.1 |
a,b表示显著差异
样品 | 样品编号 | 二甲基硅氧烷(μg)/猪皮样品 | 二甲基硅氧烷(μg/cm2)皮肤 |
皂片2(95wt.%)+5wt.%二甲基硅氧烷 | 4 | 35.4±15.1a | 6.2 |
皂片2(92wt.%)+5wt.%二甲基硅氧烷+1.5wt.%Polyquat 7和+1.5wt.%Permethyl 104A | 4 | 94.0±29.4b | 16.4 |
皂片2(93wt.%)+2.5wt.%二甲基硅氧烷+1.5wt.%Polyquat 7和+1.5wt.%Permethyl 104A | 4 | 43.8±11.9a | 7.7 |
a,b表示显著差异
样品 | 样品编号 | 二甲基硅氧烷(μg)/猪皮样品 | 二甲基硅氧烷(μg/cm2)皮肤 |
皂片2(94.5wt.%)+2.5wt.%二甲基硅氧烷+1.5wt.%Polyquat 7和+1.5wt.%Permethyl 104A | 3 | 62.5±12.4a | 10.9 |
皂片2(93wt.%)+2.5wt.%二甲基硅氧烷+3.0wt.%Polyquat 7和+1.5wt.%Permethyl 104A | 3 | 109.5±16.5b | 19.2 |
a,b表示显著差异
表中的二甲基硅氧烷是粘度为60,000厘沲的二甲基硅氧烷
进一步对含有皂类和10%(重量)水分的组合物进行测定,其中该皂类是由85%(重量)牛油来源的羧酸和15%(重量)椰油来源的羧酸组成。组合物中还含有有限量的防腐剂、香料和类似物质。
待测组合物的制备是根据各自所需的重量百分比分别加入下列各物质,其中的重量百分比是相对于皂条终产物重量而言,这些加入到组合物中的物质是:富脂剂,例如柠檬酸或膦酸;疏水剂,例如二甲基硅氧烷;含碳氢化合物的物质,例如矿脂;及阳离子聚合物,例如Polyquat 6。当所用二甲基硅氧烷(二甲基聚硅氧烷)的粘度是60,000厘沲时,对于矿脂、柠檬酸或膦酸和Polyquat 6,各物质的优选用量分别是1%(重量)、3.5%(重量)、1%(重量)的合成富脂剂和0.6%重量的Polyquat 6(40%活性物质)。
将最终优选的组合物与一系列香料共同制备成皂条。对照用皂条也含有同样的香料,但不含有二甲基聚硅氧烷、矿脂和Polyquat组分,同时可含有或不含有1%(重量)的合成富脂剂。根据皂条的活体试验结果,与对照皂条相比时,本发明皂条表现出令人吃惊的抗香料失效高强度。另外,与对照皂条相比,本发明产物具有良好的特性和雾化作用。所谓特性是指减轻了动物来源皂类的异味,因此使香料味不失真并能够维持一定浓度的芳香气味。良好的雾化作用是指香料的“头香”和“尾香”能够连续散发。
还要就各组分(二甲基聚硅氧烷、矿脂和Polyquat 6)对皮肤感觉产生的包被保护作用进行离体的和活体的试验,以确定它们的有效特性,并且将具有肤感包被保护作用的皂条与没有包护作用且不含1%富脂剂的对照皂条相对比。例如,在离体样品试验中,一种仅含有二甲基聚硅氧烷(60,000厘沲)、矿脂和Polyquate 6且各成分重量比分别是1∶2∶0.6的纯净混合物可以防止因气候变化引起的皮肤干燥及抑制天然润湿因子(NMF)的损失。
测定气候变化性皮肤干燥的方法如下所述:
将未经处理的猪皮作为参照物。将猪皮在10℃/17%的相对湿度条件下保持1小时。样品用SKICON仪进行基线电导测量。在室温条件下将纯的活性物涂覆在猪皮表面(2mg/平方厘米)。样品在室温条件下保持1小时。经24小时后同样在10℃/17%条件下,用SKICON电导仪来测定皮肤样品电导值。
观察到电导值显著增大表明,明显抑制了气候变化引起的皮肤干燥。
采用下列方法测定NMF(氨基酸、脲、吡咯烷酮羧酸钠、无机离子)散失抑制作用:
将无杂质的活性物混合物涂覆在猪皮上,涂布量是2mg/cm2。1小时后,用2ml的1%85/15皂液在45℃和振摇条件下将该皮肤样品处理15分钟。以同样的方法用皂液清洗未处理猪皮(未涂布纯净活性混合物)。然后将皂液除去并且采用荧光分析法来检测其中的氨基酸和脲含量,所用荧光分析法与M.Kawai和G.Imokawa,美容化学会志(J.Soc.Cosmetic Chem.),35,147-156(1984)中描述的方法相类似。分析结果表明:与未用二甲基硅氧烷、矿脂和Polyquat涂覆的猪皮样品相比,经处理的猪皮样品损失极少量的NMF。
与对照皂条相比,当使用本发明皂条时,由于疏水性物质发生沉积从而使染料的吸附受到抑制,这是通过采用下列试验步骤的另一个体外试验来证明的:
用本发明的皂条将猪皮样品清洗4次(搓30秒,起沫30秒,漂洗15秒)。将直径1cm的滤纸片放置在1%的D&C Red#28染料溶液中。立即用该滤纸片涂抹猪皮样品,然后将猪皮样品漂洗15秒。皮肤上残余的染料用kimwipe牌纸巾擦去。用Minolta Chromameter记录下皮肤表面的颜色。再用对照皂条以相同的步骤来处理新鲜猪皮样品。经本发明皂条处理过的皮肤样品的染料吸附量远远低于经对照皂条处理的皮肤样品。
可以采用下列方法测定本发明皂条(1%富脂剂、1%的粘度为60,000厘沲的二甲基硅氧烷、3.5%矿脂、0.6%Polyquat 6)对皮肤隔离层的完整性作用:
用5%的含水产品溶液处理猪皮样品。将皮肤样品暴露在该溶液中并持续24小时。然后,用氚代水处理皮肤样品并测定进入到皮肤样品中的氚代水量。水的渗透系数(Kp)可反映皮肤隔离层的完整性。用5%的对照皂液以相同的方法处理新取下的猪皮样品。结果表明:与对照皂条相比,本发明皂条使隔离层受损伤作用减轻。
本发明皂条的上述有益作用还可通过其皂类皮肤通透作用来评价,采用下列试验步骤:
在本发明5%的皂条溶液中掺入C14-月桂酸和氚代水,通过测定示踪月桂酸(月桂酸酯)和氚代水来确定猪皮样品的通透作用。皮肤内残留皂类的检测是通过分析活体取样的猪皮样品来完成的。同样,用对照皂液以相同的试验步骤来处理新鲜猪皮样品。结果表明:与对照皂液相比,本发明皂条显著抑制了月桂酸的经由皮的通透,减少了皮肤中的月桂酸蓄留量,但同时对皮肤中的水分储存量并无显著影响。另外,水分Kp值试验结果表明降低了皮肤的受损程度。
本发明组合物对各种皮肤因子的包护作用可以通过体内试验来测定。例如,通过皮肤电导试验测定皮肤水合度,所用仪器是SKICON。通过水分沉积试验来检测皮肤的储水性能。通过荧光法来测定NMF自皮肤中的析出性,同样还可测定皮肤对水分排斥性。最后,可测定皮肤对染料的吸附性。在上述各试验中,二甲基硅氧烷、矿脂和Polyqute6(1∶3.5∶0.6)的纯净混合物对皮肤表现出了有益效果。例如,能够水合、吸收和蓄留水分,保持皮肤湿润性,并且对皮肤具有包护作用。
使用了含活性混合物的皂条的体内试验可测出染料吸附性并与对照皂条对比。当用本发明皂条清洗皮肤样品时,染料的吸附量明显低于用对照皂液清洗的皮肤样品。
另外,还可采用体内试验对本发明皂条的柔和性进行测定并与对照皂液对比。通过观测临床可见红斑以及测定试验后期的由外作用力引起的皮肤变红发现:反复使用本发明皂条可以显著减小皮肤刺激性。通过检测试验后期的经皮水分损失度可以发现:使用本发明皂条能够减轻隔离层的受损。还有,在柔和性试验中,受试评估者更喜欢本发明皂条而不是对照皂条。
总之,本发明固体组合物含有疏水性组分(二甲基硅氧烷)、含碳氢化合物组分(矿脂)和阳离子聚合物(Polyquat 6),其中表面活性剂为皂类(约70-90%(重量))的本发明组合物具有确定而显著的皮肤屏护作用、低刺激性及极低的皮肤损伤性,不含有这些试剂的固体皂条就不具有这种有益作用。本发明皂条中含有1%(重量)的富脂剂。但对照皂条不含有富脂剂。
Claims (15)
1.一种固体清洗组合物,该组合物包括:
(a)70-90重量%皂类;
(b)一种含量在0.01-5%重量之间的选自聚烷基硅氧烷和三氯卡班或三氯生抗菌剂的疏水性活性组分,该含量的组分能够对皮肤表面产生有益作用;
(c)0.5-5%重量的矿脂;和
(d)0.02-0.9%重量的阳离子聚合物。
2.根据权利要求1所述的组合物,其中的硅氧烷是二甲基聚硅氧烷。
3.根据权利要求1所述的组合物,其中的硅氧烷的含量是组合物重量的0.75-4%。
4.根据权利要求2所述的组合物,其中含有0.01-1.5重量%三氯卡班或三氯生抗菌剂。
5.根据权利要求1所述的组合物,其中的矿脂含量为组合物重量的0.5-4%。
6.根据权利要求1所述的组合物,其中的阳离子聚合物含量为组合物重量的0.05-0.75%。
7.根据权利要求6所述的组合物,其中的阳离子聚合物是不含有纤维素不含有糖类的阳离子聚合物。
8.根据权利要求7所述的组合物,其中的阳离子聚合物是聚合的二甲基二烯丙基氯化铵或丙烯酰胺和二甲基二烯丙基氯化铵的聚合季铵盐。
9.根据权利要求8所述的组合物,其中的阳离子聚合物是聚合的二甲基二烯丙基氯化铵。
10.根据权利要求8所述的组合物,其中的阳离子聚合物是丙烯酰胺和二甲基二烯丙基氯化铵的聚合季铵盐。
11.根据权利要求1所述的组合物,其中组合物中有6-22重量%水份。
12.根据权利要求1所述的组合物,其中所述固体组合物是条状。
13.根据权利要求12所述的组合物,其中所述条状固体是压制的条状。
14.根据权利要求1所述的组合物,其中组合物中还含有香料。
15.权利要求1的组合物用于制备起抑制水份从皮肤中损失和皮肤屏护作用的制剂的应用。
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BR (1) | BR9610849A (zh) |
CZ (1) | CZ134598A3 (zh) |
DE (1) | DE69631338T2 (zh) |
ES (1) | ES2214553T3 (zh) |
HU (1) | HUP9900054A3 (zh) |
IL (1) | IL124217A (zh) |
MX (1) | MX9803492A (zh) |
NO (1) | NO312576B1 (zh) |
NZ (1) | NZ321863A (zh) |
PL (1) | PL187599B1 (zh) |
TR (1) | TR199800776T2 (zh) |
WO (1) | WO1997016168A1 (zh) |
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HUP9900054A2 (hu) | 1999-05-28 |
NO981975L (no) | 1998-07-01 |
CZ134598A3 (cs) | 1998-08-12 |
NO981975D0 (no) | 1998-04-30 |
AU7529596A (en) | 1997-05-22 |
AU704805B2 (en) | 1999-05-06 |
PL187599B1 (pl) | 2004-08-31 |
NO312576B1 (no) | 2002-06-03 |
TR199800776T2 (xx) | 1998-08-21 |
ES2214553T3 (es) | 2004-09-16 |
DE69631338T2 (de) | 2004-11-04 |
US6156713A (en) | 2000-12-05 |
CN1203526A (zh) | 1998-12-30 |
BG102469A (en) | 1999-06-30 |
US6008173A (en) | 1999-12-28 |
BR9610849A (pt) | 1999-07-13 |
PL326557A1 (en) | 1998-09-28 |
DE69631338D1 (de) | 2004-02-19 |
HUP9900054A3 (en) | 2001-11-28 |
NZ321863A (en) | 1998-11-25 |
US6365560B1 (en) | 2002-04-02 |
BG63101B1 (bg) | 2001-04-30 |
IL124217A (en) | 2004-07-25 |
EP0858321B1 (en) | 2004-01-14 |
MX9803492A (es) | 1998-09-30 |
ATE257692T1 (de) | 2004-01-15 |
EP0858321A1 (en) | 1998-08-19 |
WO1997016168A1 (en) | 1997-05-09 |
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