CN103347482A - 含有12-羟基硬脂酸和乙氧基化氢化蓖麻油的留存型非固体皮肤调理组合物 - Google Patents
含有12-羟基硬脂酸和乙氧基化氢化蓖麻油的留存型非固体皮肤调理组合物 Download PDFInfo
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- CN103347482A CN103347482A CN2011800676220A CN201180067622A CN103347482A CN 103347482 A CN103347482 A CN 103347482A CN 2011800676220 A CN2011800676220 A CN 2011800676220A CN 201180067622 A CN201180067622 A CN 201180067622A CN 103347482 A CN103347482 A CN 103347482A
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- acid
- castor oil
- skin
- hydrogenated castor
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- 239000000203 mixture Substances 0.000 title claims abstract description 185
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000007787 solid Substances 0.000 title claims abstract description 15
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- 229940114072 12-hydroxystearic acid Drugs 0.000 title claims abstract description 9
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- 235000019438 castor oil Nutrition 0.000 title claims description 27
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 title claims description 27
- 230000002441 reversible effect Effects 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims description 36
- 150000003839 salts Chemical class 0.000 claims description 17
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- 230000014759 maintenance of location Effects 0.000 claims description 12
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
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Abstract
本发明包含12-羟基硬脂酸(12HSA)的留存型非固体皮肤调理组合物。组合物含有12HSA,还具有相对低的粘度,从而适合涂抹于皮肤上,并为储存稳定的和在温度循环中结构可逆的。
Description
发明背景
12-羟基硬脂酸盐,即皂已被描述于洗掉型身体清洁组合物中(JP 4,266,904;JP 59/227,999、JP 56/074,197)。12-羟基硬脂酸(下文为“12HSA”)被报道具有广泛的有益皮肤美容效果,例如它是一种已知的PPAR-α(过氧物酶体增殖物激活受体α亚型)激活剂、皮肤美白剂、和皮脂分泌抑制剂。参见例如Alaluf等的US 6,423,325、Mayes等的US 6,713,051、WO 2006/056283(Hindustan Lever)、Madison的US 2009/0317341、Minami等的US 6,197,343、Granger等的US 2004/0043044。同样地,非常需要含有12HSA的美容留存型产品。JP 09-048962描述了12HSA或其盐作为凝固抑制剂有效成分的用途,以抑制液体洗涤剂或液体化妆品的凝固;全部实施例含有12HSA 完全中和的盐。不幸地是,12HSA是固体并且不具有水溶解性和具有有限的油溶解性。事实上,12HSA在传统上例如在唇膏和止汗药组合物中用作凝胶剂。还参见EP 0129528、US 6680285、Abbas等的US 6,680,285、Tanner等的US 5,759,524、WO 95/31961(宝洁)、Kawa等的US 2004/0044078(描述了12HSA增加美容组合物粘度的用途)、和JP 2010/138,110。12HSA盐水溶性仅稍好。因此,非常需要含有12HSA的非固体皮肤调理留存型组合物。
发明概述
本发明包括一种留存型非固体皮肤调理组合物,包含:
(a) 占组合物约0.01-约15wt%的12-羟基硬脂酸;
(b) 占组合物约0.1-约30wt%的非离子表面活性剂,包含
(b1) HLB高于10的高HLB乙氧基化氢化蓖麻油,和
(b2) HLB低于10的低HLB乙氧基化氢化蓖麻油;
其中高HLB乙氧基化氢化蓖麻油与低HLB乙氧基化氢化蓖麻油的重量比为约80:20-约5:95;
(c) 以维持组合物的pH于约5.5-约8.0的量的无机中和剂;
(d) 约0.05%-约10%的增稠聚合物;
其中组合物的粘度为约1 Pas-约500 Pas;和
其中组合物在室温和50℃之间的温度循环中是结构可逆的。
根据本发明,已制备了含12HSA的结构可逆的非固体皮肤调理组合物。含有12HSA的配方的结构可逆性对防止产品在储存期间、或在涂抹于皮肤上时固化使其变得不可用和/或生物无效是至关重要的。本发明还包括制备和使用该组合物的方法。
发明详述
除非在实施例中、或另有明确说明的地方,本说明书中表示物质的量或反应条件、物质的物理性质和/或用途的全部数字被理解为通过单词“约”修正。除非另有说明,全部量都是基于最终组合物的重量。
应当注意的是在指定任何浓度或量的范围时,任何特定的较高浓度可与任何特定的较低浓度或量相联系。
为了避免疑问,单词“包含”意指“包括”但不必须“由……组成(consisting of)”或“由……构成(composed of)”。换句话说,所列步骤或选项不需要是穷举的。
如本文所发现的,本发明公开被认为覆盖了如权利要求书中所发现的如彼此间多重从属的全部实施方案,而不考虑权利要求可能无多重从属或冗余的事实。
如本文所用,“调理”指预防和处理干燥皮肤、粉刺、光受损肌肤、皱纹出现、老年斑、老化皮肤、增加角质层弹性、美白肤色、控制皮脂分泌和一般地提高皮肤质量。该组合物可用以改善皮肤脱屑和表皮分化以及改善皮肤外貌或一般美学。
如本文所用,“留存型”是指应用于皮肤上并在一定时期内不意欲被洗刷掉或漂洗掉的组合物,如与清洁或洗掉型或漂洗掉组合物型相比较。
如本文所用,“非固体”指可测粘度(例如可用布氏粘度计DV-I +(20RPM, RV6, 30秒)测量)在1 Pas-500 Pas,优选2 Pas-100 Pas,更优选3 Pas-50Pas的范围内的组合物。
如本文所用,“稳定的”或“稳定性”指不分离和不为粒状和不凝固和不固化或形成硬凝胶的组合物。
如本文所用,“结构可逆”是指组合物(i)当最初配制时不形成硬凝胶或固体、不分离、和不凝固;和(ii)在于50℃暴露24小时、并随后允许冷却至室温之后维持结构完整性(即,初始外貌和结构)。结构可逆性通过撒布3-5克配方于暗的光滑平整表面(例如黑色实验室台面)上并肉眼观察膜的质地来测量。显示结构可逆性的样品具有光滑的均质外貌,而不显示结构可逆性的样品具有粒状表面外观。
12HSA
本发明的组合物包含12HSA。该组合物典型地含有至少40%的以其酸形式的总12HSA,优选至少50%,更优选至少60%,以最优化生物利用度、和由此的功效。当与其它脂肪酸一起时,12HSA的表观pKa预期为大于8。在该pKa下,脂肪酸将以50%脂肪酸盐和50%酸存在。因此,优选本发明的组合物的pH为小于约8,更优选为5.5-8,最优选为6-8。12HSA以0.01-15%,优选0.1-12%,更优选0.5-10%,和最佳地1-5%的量包括于本发明的组合物中。在本文中12HSA的量既包括酸也包括盐的量。12HSA或其盐的量不意在包括于本文中的表面活性剂的量之中。
乙氧基化氢化蓖麻油表面活性剂
已发现,作为本发明的一部分,非离子表面活性剂的特别定制的混合提供了结构可逆的组合物。具有地,适用于本文的非离子表面活性剂得自环氧烷与油或脂肪酸的缩合反应。优选的非离子表面活性剂为聚乙氧基化蓖麻油型的。最优选的是聚乙氧基化氢化蓖麻油型的。使用了乙氧基化氢化蓖麻油表面活性剂的混合物,该混合物通常具有至少约5的最小HLB(Griffin法),优选约5-15。用表面活性剂的混合物制备表面活性剂组合物以允许多功能性和较高的稳定性。表面活性剂组分通常含有至少一种HLB低于10、优选低于8的低HLB表面活性剂和至少一种HLB大于10、优选大于12的高HLB表面活性剂。高HLB乙氧基化氢化蓖麻油表面活性剂中特别优选的是PEG-60氢化蓖麻油,Cremophor RH60,和低HLB乙氧基化氢化蓖麻油表面活性剂中特别优选的是PEG-7氢化蓖麻油,Cremophor WO7,两者均可商购自BASF。聚乙氧基化氢化蓖麻油表面活性剂的一些其它实例包括:Cremophor RH 40和Cremophor EL。任选地也可使用非衍生自蓖麻油的Cremophors,一个实例是Cremophor GS 32,聚甘油基-3二硬脂酸酯。
根据本发明,所述两种乙氧基化氢化蓖麻油表面活性剂的比例对于在非固体配方中提供主要为酸形式的12HSA、并确保该配方是结构可逆的而言是重要的。高HLB乙氧基化氢化蓖麻油与低HLB乙氧基化氢化蓖麻油的比例为80:20-5:95,更优选70:30-10:90,最优选65:35-25:75。
增稠聚合物
在本发明中与如本文所述的其它成分联合使用了增稠聚合物,以确保本发明的组合物为非固体的并是结构可逆的。12HSA本身在本发明的组合物中不提供增厚功能性。
该增稠聚合物选自生物聚合物、合成聚合物、和其混合物。
生物聚合物可选自,例如,角叉胶、红藻胶、果胶、藻酸盐、琼脂、琼脂糖、结冷胶、葡甘露聚糖(例如,魔芋(Konjac))、半乳甘露聚糖(例如,刺槐豆胶、瓜尔豆)、黄原胶、改性纤维素、葡聚糖(例如,淀粉、可得然胶)、明胶、乳清蛋白质或其混合物。更优选地,使用的生物聚合物为黄原胶或改性纤维素。在最优选实施方案中,使用的生物聚合物为黄原胶。适用于本发明的生物聚合物可商购自供应商Ashland Aqualon。可用于本发明的生物聚合物类型的额外描述可见于Food Gels,第1章,Peter Harris编写,Elsevier,1990和US 6,673,371和US 5,738,897,其公开内容通过参考引入本文。
也可适用的说明性合成增稠剂(或聚合增粘剂)包括烷基化聚乙烯吡咯烷酮,如在名称Ganex? 类(line)下由ISP Corporation销售的丁基化聚乙烯吡咯烷酮;对苯二甲酸酯聚酯,如聚对苯二甲酸丙二酯和丙烯酰二甲基牛磺酸铵/VP共聚物,两者均在Aristoflex? 类下由Clariant A.G.销售;和聚(甲基乙烯基/醚马来酸)钠盐的单烷基酯,如包括在可购自ISP Corporation的EZ Sperse?类中的,以及(3-二甲基氨基丙基)-甲基丙烯酰胺/3-甲基丙烯酰氨基丙基)-十二烷基-二甲基-氯化铵,如包括在可购自ISP Corporation的Styleze?类中的。其它适用的增稠剂包括通常分类为丙烯酸/丙烯酸乙酯共聚合物和羧基乙烯基聚合物(可在Carbopol名称下购自B.F. Goodrich Company)的那些。这类增稠剂基本上由用交联剂(如聚烯丙基蔗糖或聚烯丙基季戊四醇)交联的丙烯酸的胶状水溶性多烯基聚醚交联聚合物组成。这些增稠剂包括,例如,Carbopol 934、940、950、951、980和981。
用于本文的适合的合成增稠剂的其它实例包括在名称Carbopol Ultrez 10、Carbopol Ultrez 21、Carbopol ETD2020、Carbopol 1342、Carbopol 1382、和Pemulen TR-1(CTFA名称:丙烯酸酯/10-30烷基丙烯酸酯交联聚合物)下销售的那些。适合的增稠剂的其它实例包括可在名称Sepigel 305和Sepiplus下购自Seppic的那些。进一步的其它实例可包括来自BASF的聚氨酯烷氧基化聚合物,又被称作聚氨酯-39,在商标Luvigel STAR下销售。如果需要,也可使用合成增稠剂的组合。
优选地,增稠聚合物选自生物聚合物或合成增稠剂,更优选生物聚合物和合成聚合物的混合,最佳地黄原胶和牛磺酸盐聚合物的混合物(例如Aristoflex AVC)。
增稠聚合物以0.05%-10%,优选0.1-8%,更优选0.1-5%,最佳地0.2-2%的量包括于本发明的组合物中。
无机中和剂
本发明的组合物包含无机中和剂,以实现结构可逆性;还已发现当加入了无机中和剂时,本发明的组合物可以以降低的非离子表面活性剂总水平来制备。该无机中和剂选自氢氧化钾、氢氧化钠、氯化镁、硫酸镁、氯化钙、碳酸钙、氧化钙、氧化镁、氢氧化钙、氢氧化镁、氯化锌、氧化锌、氯化铝、氢氧化铝、氧化铝、和其混合物。优选的无机中和剂选自氢氧化钠、氢氧化钾和氧化锌。已发现,作为本发明的一部分,有机中和剂不提供所需的结构可逆性。
如上所解释的,本发明的组合物含有大量的,优选主导量的酸形式的12HSA。因此,无机中和剂必须以维持如上所讨论的优选pH范围的量使用。
水
本发明的组合物优选是水性的并通常包括40-99%的水,优选50-98%,最优选60-97%,最佳地65-95%的水。
组合物形态
本发明的组合物是非固体。本质上,组合物的“非固体性”指组合物的粘度,例如使用Brookfield DV-I +粘度计(20RPM,RV6,30秒)测量的。粘度通常在1 Pas-500 Pas,优选1 Pas-200 Pas,更优选2 Pas-100 Pas,最优选3 Pas-50 Pas的范围内。
本发明的组合物为留存型组合物。本发明的组合物意在应用以保留在皮肤上。这些留存型组合物与应用于皮肤并随后在应用该产品之后或期间通过洗刷、冲洗、擦拭等移除的组合物相区别。典型地用于漂洗掉型组合物的表面活性剂具有给予它们在使用中产生泡沫/皂泡并易于漂洗能力的物理化学性质;它们可由阴离子、阳离子、两性离子、和非离子的混合物组成。但是用于留存型组合物的表面活性剂不需要具有该性质。相反,因为留存型组合物不意欲被漂洗掉,所以它们需要是无刺激性的并因此需要最小化留存型组合物中表面活性剂的总水平、和特别是阴离子表面活性剂的总水平。因此,对于表面活性剂来说,本发明的组合物主要含有非离子表面活性剂。阴离子表面活性剂以最多5%,优选0.01-4%,更优选0.01-3%,最优选0.01-2%的量存在,并最佳地为基本上不存在(小于1%,优选小于0.1%,或甚至小于0.01%)。12HSA的盐在本文中不被认为是阴离子表面活性剂。本发明的组合物中表面活性剂的总水平优选不大于10%,更优选低于8%,最优选最多5%。
本发明的组合物典型地为乳液形式,其可为水包油、或油包水;优选的组合物为水包油乳液。其它优选的形式为乳膏,进一步更优选地为具有雪花膏基质的乳膏。雪花膏基质为包含5-40%脂肪酸和0.1-20%皂的乳膏。在该乳膏中,该脂肪酸优选主要为硬脂酸和棕榈酸的混合物并且该皂优选为该脂肪酸混合物的钾盐,虽然也可使用其它抗衡离子和其混合物。往往使用hystric酸制备雪花膏基质中的脂肪酸,所述hystric酸主要(通常约90-95%)是硬脂酸和棕榈酸的混合物。典型的hystric酸包含占总的棕榈-硬脂酸混合物的约52-55%的棕榈酸和45-48%的硬脂酸。因此,包含hystric酸和其皂以制备雪花膏基质处于本发明范围之内。特别优选的是组合物包含高于7%,优选高于10%,更优选高于12%的脂肪酸。
本发明的组合物为储存时稳定的。该组合物于45℃下保持稳定至少1周,更优选1个月,最优选3个月,和最佳地至少6个月。
此外,本发明的非固体留存型组合物还在室温和50℃之间的温度循环中是结构可逆的。发明人发现递送更佳的含有12HSA的留存型配方具有主要呈在干燥膜中的非纤维结晶形式的12HSA。
可选成分
额外的表面活性剂
适合的额外的非离子清洁剂活性化合物可被广泛地描述为通过环氧烷基(其本质上为亲水的)与有机疏水化合物(其本质上可为脂肪族的或烷基芳香族的)的缩合制备的化合物。可容易地调节亲水或聚氧化烯基(其与任意特定的疏水基缩合)的长度以生成具有所需亲水和疏水成分平衡度的水溶性化合物。
具体实例包括具有8-22个碳原子的、直链或支链结构的脂肪族醇与环氧乙烷的缩合产物,如具有每摩尔椰子醇2-15摩尔环氧乙烷的椰子油环氧乙烷缩合物;烷基苯酚(其烷基含有6-12个碳原子)与每摩尔烷基苯酚5-25摩尔环氧乙烷的缩合物;乙二胺和环氧丙烷的反应产物与环氧乙烷的缩合物,该缩合物含有40-80重量%的聚氧化乙烯基并具有5,000-11,000的分子量;结构R3NO的叔胺氧化物,其中一个基团R为8-18个碳原子的烷基且其它两个各自为甲基、乙基或羟基乙基,例如二甲基十二烷基胺氧化物;结构R3PO的叔膦氧化物,其中一个基团R为10-18个碳原子的烷基,且其它两个各自为1-3个碳原子的烷基或羟基烷基,例如二甲基十二烷基膦氧化物;和结构R2SO的二烷基亚砜,其中R2为烷基,其可为10-18个碳支化的,例如甲基十四烷基亚砜;其它实例为脂肪酸与胺的缩合产物以形成RCONR1CH2X,其中R为C8-C22(可被支化或乙氧基化的)、R1为氢或甲基、乙基、CH2CH2OH;X为CH2OH、CH2OR4(R4=乙氧基化的即CH2CH2OH、CH2CH2OCH2CH2OH)。
额外的非离子表面活性剂的进一步实例:
烷基多糖苷
烷基多糖苷由脂肪醇和糖制备。优选地,形成烷基多糖苷的脂肪单元的C8-C22或C14-C22脂肪醇包括分别含有8-22或14-22个碳原子的饱和或不饱和的支化或线性烷基链。这包括在该脂肪醇为线性脂肪醇的任何子范围中的C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20、C21、和C22。优选地,烷基多糖苷的脂肪单元包括癸基、鲸蜡基(cetyl)、山嵛基、二十烷基、硬脂基、棕榈基、十四烷基、十二烷基、辛基或十六烷基(hexadecanyl)单元和它们的混合物(如鲸蜡硬脂基(C16-C18混合物))中的任一种。
优选的烷基多糖苷,例如癸基糖苷和十二烷基糖苷,例如由Henkel公司在各自的名称Plantaren 2000和Plantaren 1200下销售的,鲸蜡硬脂基糖苷,例如在名称Tegocare CG90下由Goldschmidt公司销售的和在名称Emulgade KE3302下由Henkel公司销售的。任选地这类表面活性剂,例如鲸蜡硬脂基糖苷,可作为与鲸蜡硬脂醇的混合物(例如在名称Montanov 68下由Seppic公司)销售,和二十烷基糖苷,例如以二十烷基和山嵛基醇与二十烷基糖苷的混合物形式在名称Montanov 202下由Seppic公司销售。
多羟基脂肪酰胺
适用于本文的多羟基脂肪酰胺为具有结构式R2CONR1Z的那些,其中:R1为H、C1-C4、乙酰基、2-羟基乙基、2-羟基丙基、乙氧基、丙氧基、或其混合物,优选C1-C4烷基,更优选C1或C2烷基,最优选C1烷基(即,甲基);R2为C5-C31,优选直链C5-C19烷基或烯基,含杂原子(氧、氮)、支化(烷基或OH);更优选直链C9-C17烷基或烯基,最优选直链C11-C17烷基或烯基,或其混合物;Z为具有带至少2个直接与链连接的羟基的线性烃链的多羟基,或其烷氧基化衍生物(优选乙氧基化或丙氧基化)。Z优选衍生自糖类;更优选Z为糖基。
优选满足以下条件的非离子多羟基脂肪酰胺表面活性剂:R2为C7-C16、R1为C1-C4烷基,更优选C1-C2烷基,最优选C1烷基即甲基;Z为具有带至少2个与链连接的羟基的直链烃基链的多羟基。最优选的烷基多糖苷选自十六烷基多糖苷、十八烷基多糖苷、癸基多糖苷、十二烷基多糖苷、和其混合物。
糖脂肪酸酯
脂肪酸和糖的酯包括线性或支化和饱和或不饱和C12-C22脂肪酸和蔗糖、麦芽糖、葡萄糖、果糖、甘露糖、半乳糖、阿拉伯糖、木糖、乳糖、海藻糖或甲基葡萄糖的酯或酯的混合物。这些酯优选选自单-、二-、三-和四酯、聚酯和它们的混合物。该C12-C22脂肪酸包括在任何子范围或组合中的C12、C13、C14、C15、C16、C17、C18、C19、C20、C21、和C22。这些酯优选选自硬脂酸酯、山嵛酸酯、椰油酸酯、花生四烯酸酯、棕榈酸酯、肉豆蔻酸酯、月桂酸酯、辛酸酯(carprates)、油酸酯、月桂酸酯和它们的混合物。这些化合物可特别地作为乳化表面活性剂使用。这些衍生物的混合物是可能的。
优选使用蔗糖酯。优选的蔗糖酯包括蔗糖椰油酸酯、蔗糖单辛酸酯、蔗糖单癸酸酯、蔗糖单-或二月桂酸酯、蔗糖单肉豆蔻酸酯、蔗糖单-或二棕榈酸酯、蔗糖单-和二硬脂酸酯、蔗糖单-、二-或三油酸酯、蔗糖单-或二亚油酸酯,蔗糖聚酯,如蔗糖五油酸酯、六油酸酯、七油酸酯或八油酸酯,和混合酯,如蔗糖棕榈酸酯/硬脂酸酯。混合物是可能的。
优选的脂肪酸和蔗糖的酯或酯的混合物包括由Crodesta公司在名称F160、F140、F110、F90、F70或SL40(分别表示由73%单酯和27%二-和三酯、61%单酯和39%二-、三-和四酯、52%单酯和48%二-、三-和四酯、45%单酯和55%二-、三-和四酯、39%单酯和61%二-、三-和四酯所构成的蔗糖棕榈酸酯/硬脂酸酯,或蔗糖单月桂酸酯)下销售的那些。也可使用由Mitsubishi公司在名称Ryoto Sugar ester下,例如在查询号B370(相应于由20%单酯和80%二-、三-和聚酯构成的蔗糖山嵛酸酯)下销售的那些。也可提及由Goldschmidt公司在名称“Tegosoft PSE”下销售的蔗糖单-和二棕榈酸酯/硬脂酸酯。也可使用这些各种产品的混合物。
糖酯也可以以与其它不是衍生自糖的化合物的混合物存在;并且优选的实例包括山梨聚糖硬脂酸酯和蔗糖椰油酸酯的混合物,在名称“Arlatone 2121”下由ICI公司销售。
其它优选的糖酯包括,例如,葡萄糖三油酸酯、半乳糖二-、三-、四-或五油酸酯、阿拉伯糖二-、三-或四亚油酸酯或木糖二-、三-或四亚油酸酯。混合物是可能的。
其它优选的脂肪酸和甲基葡萄糖的酯或酯的混合物包括甲基葡萄糖和多甘油-3的二硬脂酸酯,由Goldschmidt公司在名称Tegocare 450下销售。也可提及葡萄糖或麦芽糖单酯,如甲基O-十六烷基-6-D-葡糖苷和(lacuna)O-十六烷基-6-D-麦芽糖。
其它可用于本发明的组合物的糖脂肪酸酯衍生物包括糖脂肪酯,其任选地是氧烷基化(氧乙基化和/或氧丙基化)或多甘油化的。优选的脂肪酸和糖的氧乙基化酯包括氧乙基化(20 EO)甲基葡萄糖倍半硬脂酸酯,例如在名称“Glucamate SSE20”下由Amerchol公司销售的产品。
醛糖二糖酰胺(Aldobionamides)
醛糖二糖酰胺定义为醛糖二糖酸的酰胺(或醛糖二糖内酯)并且醛糖二糖酸是一种其中醛基(通常出现在糖的C1位)已被羧酸替代的糖物质(例如,任何包含至少2个糖类单元的环状糖),其在干燥时环化成醛糖二糖内酯。
醛糖二糖酰胺可基于包含2个糖类单元的化合物(例如,来自该醛糖二糖酰胺键的乳糖酰胺或麦芽糖酰胺),或者它们可基于包含多于2个糖类单元的化合物,只要该多糖的末端糖具有醛基即可。按照定义,醛糖二糖酰胺必须具有至少2个糖类单元并且不能为线性的。二糖化合物,如乳糖酰胺或麦芽糖酰胺,为优选的化合物。可用的醛糖二糖酰胺(二糖)的其它实例包括纤维二糖酰胺、蜜二糖酰胺(melibionamides)和龙胆二糖酰胺(gentiobionamides)。
可用于本发明目的的醛糖二糖酰胺的一个具体实例为二糖乳糖酰胺。
适合的/优选的额外的非离子表面活性剂包括乙氧基化山梨聚糖脂肪酸酯(又被称作吐温系列,来自Croda/Uniquema)、乙氧基化脂肪酸(又被称作Brij系列,来自Croda/Uniquema),或者也可任选加入其它脂肪酸。
额外的脂肪酸
在优选实施方案中,除了12HSA之外,本发明的组合物可进一步包含酸,如脂肪酸。可使用的脂肪酸的说明性非限制性实例包括分别含有8-22或14-22个碳原子的饱和或不饱和的支化或线性烷基链。这包括C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C18:1、C18:2、C18:3、C19、C20、C21、和C22。
阴离子表面活性剂
阴离子表面活性剂的实例包括肌氨酸盐、硫酸盐、羟乙基磺酸盐、氨基乙酸盐、牛磺酸盐、磷酸盐、乳酸盐、谷氨酸盐和其混合物。羟乙基磺酸盐中优选烷氧基羟乙基磺酸盐,如椰油基羟乙基磺酸钠、月桂酰羟乙基磺酸钠和混合物。适合的阴离子清洁剂活性化合物为分子结构中具有含8-22个碳原子的烷基、和选自磺酸或硫酸酯基的基团、和其混合物的有机硫反应产物的水溶性盐。适合的阴离子清洁剂的实例为醇硫酸钠和钾盐,特别是通过硫酸化高级醇获得的那些,所述高级醇是通过还原牛脂或椰子油的甘油酯制备的;烷基苯磺酸钠和钾盐,如其中烷基含有9-15个碳原子的那些;烷基甘油醚硫酸钠,特别是衍生自牛脂和椰子油的高级醇的那些醚;椰子油脂肪酸单甘油酯硫酸钠;1摩尔高级脂肪醇和1-6摩尔环氧乙烷的反应产物的硫酸酯钠和钾盐;带有1-8个环氧乙烷分子单元且其中烷基含有4-14个碳原子的烷基苯酚环氧乙烷醚硫酸钠和钾盐;用羟乙基磺酸酯化并用氢氧化钠中和的脂肪酸的反应产物,其中,例如,该脂肪酸衍生自椰子油和其混合物。
优选的水溶合成阴离子清洁剂活性化合物为高级烷基苯磺酸酯的碱金属(例如钠和钾)和碱土金属(例如钙和镁)盐,和与烯烃磺酸酯和高级烷基硫酸酯的混合物、和高级脂肪酸单甘油酯硫酸盐。
可用于本文的其它阴离子物质为通常具有约8-约24个碳原子,优选约10-约20个碳原子的脂肪酸的皂(即,碱金属盐,例如,钠或钾盐或铵或三乙醇胺盐)。用于制备所述皂的脂肪酸可自天然来源获得,例如,植物或动物来源的甘油酯(例如,棕榈油、椰子油、豆油、蓖麻油、牛脂、猪油等)。该脂肪酸也可以是合成制备的。脂肪酸盐更详尽地描述于US 4,557,853中。
流变改性剂
可包含流变改性剂,其选自二氧化硅,如气相二氧化硅或亲水性二氧化硅,和粘土,如硅酸镁铝、膨润土、锂蒙脱石、锂藻土,和其混合物。流变改性剂以0.01-2%,优选0.05-1%的量使用。
润肤剂
润肤剂物质可充当化妆品可接受的载体。这些可为硅油、酯和烃的形式。润肤剂的量可为组合物的约0.1-约95重量%,优选约1-约50重量%,和最优选1-20重量%。
硅油可分为挥发性和不挥发性种类的。如本文所用,术语“挥发性”指在室温下具有可测气压的那些物质。挥发性硅油优选选自含有3-9个,优选4-6个硅原子的环(环聚二甲基硅氧烷)或线性聚二甲基硅氧烷。
可用作润肤剂物质的不挥发性硅油包括聚烷基硅氧烷、聚烷基芳基硅氧烷和聚醚硅氧烷共聚物。本文所用的基本上不挥发的聚烷基硅氧烷包括,例如,在25℃下粘度为约5 x 10-6-0.1 m2/s的聚二甲基硅氧烷。可用于本发明的组合物的优选的不挥发性润肤剂是在25℃下粘度为约1 x 10-5-约4 x 10-4 m2/s的聚二甲基硅氧烷。
其它类不挥发性硅氧烷为乳化和非乳化硅氧烷弹性体。该类代表为可作为Dow Corning 9040、General Electric SFE 839、和Shin-Etsu KSG-18商购获得的二聚二甲基硅氧烷/乙烯基二聚二甲基硅氧烷交联聚合物(Dimethicone/Vinyl Dimethicone Crosspolymer)。也可用硅氧烷蜡,如Silwax WS-L(Dimethicone Copolyol Laurate)。
酯润肤剂为:
1)具有10-24个碳原子的饱和脂肪酸烷基酯。其实例包括新戊酸山嵛醇酯(behenyl neopentanoate)、硬脂酸异丙酯、油酸异丙酯、异壬基isonanonoate、肉豆蔻酸异丙酯和硬脂酸辛酯及其混合物。
2)多元醇酯。乙二醇单和二-脂肪酸酯、二乙二醇单-和二-脂肪酸酯、聚乙二醇(200-6000)二-脂肪酸酯、丙二醇单-和二-脂肪酸酯、聚丙二醇2000单硬脂酸酯、乙氧基化丙二醇单硬脂酸酯、甘油基二-脂肪酸酯、多甘油聚脂肪酯、乙氧基化甘油基单-硬脂酸酯、1,3-丁二醇单硬脂酸酯、1,3-丁二醇二硬脂酸酯、聚氧乙烯多醇脂肪酸酯是令人满意的多元醇酯。特别有用的是季戊四醇、三羟甲基丙烷和C1-C30醇的新戊二醇酯。
3)蜡酯,如蜂蜡、鲸蜡和三山嵛精蜡。
适合的化妆品可接受的载体烃包括矿脂、矿物油、C11-C13异链烷烃,尤其是可作为Permethyl 101A商购自Presperse Inc的异十六烷。
优选可用以改善感官特性(特别是用于意欲施加于面部的产品)并选自不与12-HSA形成硬凝胶的油的润肤剂;这些包括聚丙二醇-14丁基醚(又被称作Tegosoft PBE)、或PPG15硬脂醚(如Tegosoft E)、其它油,例如酯,特别是,肉豆蔻酸异丙酯、棕榈酸异丙酯,其它油可包括蓖麻油和其衍生物。
多元醇类湿润剂可用作化妆品可接受的载体。典型的多元醇包括甘油、聚亚烷基二醇和更优选地亚烷基多醇和它们的衍生物,包括丙二醇、二丙二醇、聚丙二醇、聚乙二醇和其衍生物、山梨醇、羟丙基山梨醇、己二醇、1,3-丁二醇、异戊二醇、1,2,6-己三醇、乙氧基化甘油、丙氧基化甘油和其混合物。湿润剂的量可为组合物的0.5-50重量%,优选1-15重量%。
可包含皮肤保湿剂,例如透明质酸和/或其前体N-乙酰基葡糖胺。N-乙酰基葡糖胺可见于鲨鱼软骨或香菇并可商购自Maypro Industries, Inc(New York)。其它优选的保湿剂包括羟丙基三(C1-C3烷基)铵盐。这些盐可以各种合成过程获得,最特别地通过氯羟丙基三(C1-C3烷基)铵盐水解获得。最优选的种类为1,2-二羟丙基三甲基氯化铵,其中C1-C3烷基为甲基。盐的量可为主题组合物的约0.2-约30重量%,并优选为约0.5-约20重量%,最佳地为约1%-约12重量%,包括其中的所有子范围。
通常,季铵基上的C1-C3烷基成分将为甲基、乙基、正丙基、异丙基或羟基乙基和其混合物。特别优选的是通过INCI命名法称作“三甲基铵(trimonium)”基的三甲基铵基。任意阴离子可用于季盐。该阴离子可为有机的或无机的,条件是该物质是化妆品可接受的。典型的无机阴离子为卤离子、硫酸根、磷酸根、硝酸根和硼酸根。最优选的是卤离子,特别是氯离子。有机阴离子抗衡离子包括甲基硫酸根、甲苯酰硫酸根、乙酸根、柠檬酸根、酒石酸根、乳酸根、葡糖酸根、和苯磺酸根。
可使用,特别是可与前述铵盐联合使用的进一步的其它的优选保湿剂包括取代的脲,如羟甲基脲、羟乙基脲、羟丙基脲;双(羟甲基)脲;双(羟乙基)脲;双(羟丙基)脲;N,N’-二羟甲基脲;N,N’-二羟乙基脲;N,N’-二羟丙基脲;N,N,N’-三羟乙基脲;四(羟甲基)脲;四(羟乙基)脲;四(羟丙基脲;N-甲基,N’-羟乙基脲;N-乙基-N’-羟乙基脲;N-羟丙基-N’-羟乙基脲和N,N’二甲基-N-羟乙基脲。出现术语羟丙基处,该含义通用于3-羟基正丙基、2-羟基正丙基、3-羟基-异丙基或2-羟基-异丙基。最优选的是羟乙基脲。后者可作为50%的水性液体在商标Hydrovance下购自National Starch & Chemical Division of ICI。
可用于本发明主题组合物的取代的脲的量为基于组合物的总重量的约0.01-约20%,和优选地,约0.5-约15%,和最优选地,约2-约10%,并包括其中的全部子范围。
当使用铵盐和取代的脲时,在最特别优选的实施方案中,使用基于主题组合物的总重量的至少约0.01-约25%,和优选地,约0.2-约20%,和最优选地,约1-约15%的湿润剂,如甘油并包括其中的全部子范围。
皮肤有益成分
发明组合物优选包含额外的皮肤美白化合物,以用最适宜的成本获得最适宜的皮肤美白性能。示例性物质为胎盘提取物、乳酸、烟酰胺、熊果苷、曲酸、阿魏酸、对苯二酚、间苯二酚和衍生物(包括4-取代间苯二酚)和其组合。更优选地,该额外的皮肤美白化合物为酪氨酸酶抑制剂,以补充取代单胺的黑素生成抑制活性,最优选选自曲酸、对苯二酚和4-取代间苯二酚的化合物。同样,还有通式HOOC-(CxHy)-COOH表示的二羧酸,其中x=4-20和y=6-40,如壬二酸、癸二酸、乙二酸、丁二酸、反丁烯二酸、十八碳烯二酸或它们的盐或其混合物,最优选反丁烯二酸或其盐,尤其是二钠盐。已发现12HSA与反丁烯二酸或其盐的组合是特别优选的,尤其是对于皮肤美白配方。这些试剂的量可为组合物的约0.1-约10重量%,优选约0.5-约2重量%。优选根据本发明的皮肤美白辅助活性物(coactive)为维生素B3或其衍生物并选自烟酰胺、烟酸酯、烟酸的非血管舒张酯、烟基氨基酸、羧酸的烟基醇酯、烟酸N-氧化物、烟酰胺N-氧化物和其混合物。
遮光剂是发明组合物的另一种优选成分。特别优选的是如乙基己基p-甲氧基肉桂酸酯(可作为Parsol MCX?获得)、Avobenzene(可作为Parsol 1789?获得)、水杨酸辛酯(可作为Dermablock OS?获得)、对苯二亚甲基二樟脑磺酸(可作为Mexoryl SX?获得)、苯甲酮-4和苯甲酮-3(Oxybenzone)的物质。可使用无机遮光剂活性物,如超细二氧化钛、氧化锌、聚乙烯和各种其它聚合物。术语“超细”指平均粒径为约10-约200 nm,优选约20-约100 nm。当存在时,遮光剂的量可通常为组合物的0.1-30重量%,优选2-20重量%,最佳地4-10重量%。
更优选的本发明的组合物同时包含额外的皮肤美白化合物,尤其是酪氨酸酶抑制剂,和遮光剂化合物。
本发明的组合物的另一种优选成分为维甲酸(retinoid)。如本文所用,“维甲酸”包括维生素A或视黄醇类化合物的全部天然和/或合成类似物(其在皮肤中拥有维生素A的生物活性)以及这些化合物的几何异构体和立体异构体。维甲酸优选地为视黄醇、视黄醇酯(例如,视黄醇的C2-C22烷基酯,包括棕榈酸视黄醇酯、乙酸视黄醇酯、丙酸视黄醇酯)、视网膜酸、和/或视黄酸(包括全反式视黄酸和/或13-顺-视黄酸),更优选除视黄酸之外的维甲酸。这些化合物是本领域所熟知的并可商购自多种来源,例如,Sigma Chemical Company(St. Louis, Mo.)、和Boerhinger Mannheim(Indianapolis, Ind.)。可用于本文的其它维甲酸描述于U.S.专利号4,677,120(Parish等,公布于1987年6月30日);U.S.专利号4,885,311(Parish等,公布于1989年12月5日);U.S.专利号5,049,584(Purcell等,公布于1991年9月17日);U.S.专利号5,124,356(Purcell等,公布于1992年6月23日);和U.S.再公布专利号34,075(Purcell等,公布于1992年9月22日)。其它适合的维甲酸为生育酚视黄酸酯[视黄酸的生育酚酯(反式或顺式)、阿达帕林{6-[3-(1-金刚烷基)-4-甲氧基苯基]-2-萘酸}、和他扎罗汀(6-[2-(4,4-二甲基硫色满-6-基)-乙炔基]烟酸乙酯)。优选的维甲酸为视黄醇、棕榈酸视黄醇酯、乙酸视黄醇酯、丙酸视黄醇酯、视网膜和其组合。维甲酸优选大体上纯的,更优选基本上纯的。本发明的组合物可含有安全和有效量的维甲酸,使得所得组合物能够安全且有效地调节胶质组织状况,优选调节皮肤中的可视和/或触觉不连续,更优选调节皮肤老化信号,甚至更优选调节与皮肤老化有关的皮肤质地上的可视和/或触觉不连续。组合物优选含有约0.005%或约0.005%-约2%或约2%,更优选0.01%-约2%或约2%的维甲酸。视黄醇优选以约0.01%或约0.01%-约0.15%或约0.15%的量使用;视黄醇酯优选以约0.01%或约0.01%-约2%或约2%(例如,约1%)的量使用;视黄酸优选以约0.01%或约0.01%-约0.25%或约0.25%的量使用;生育酚视黄酸酯、阿达帕林、和他扎罗汀优选以约0.01%或约0.01%-约2%或约2%的量使用。
防腐剂可合意地并入本发明的美容组合物中以防止潜在有害的微生物的生长。适用于本发明的组合物的传统防腐剂为对羟基苯甲酸的烷基酯。其它最近已投入使用的防腐剂包括乙内酰脲衍生物、丙酸盐、和各种各样的季铵化合物。美容药剂师熟悉适合的防腐剂并常规选择它们以满足防腐挑战测试和提供产品稳定性。特别优选的防腐剂为苯氧基乙醇、尼泊金甲酯、尼泊金丙酯、咪唑烷基脲、脱氢乙酸钠和苄醇。防腐剂应根据组合物用途和防腐剂与乳液中的其它成分之间可能的不相容性而选择。优选以组合物0.01%-2重量%的量使用防腐剂。
本发明的组合物可包含维生素。示例性维生素为维生素A(视黄醇)、维生素B2、维生素B3(烟酰胺)、维生素B6、维生素B12、维生素C、维生素D、维生素E、维生素K和生物素。也可使用维生素的衍生物。例如,维生素C衍生物包括抗坏血酸四异棕榈酸酯、抗坏血酸磷酸镁和抗坏血酸苷。维生素E的衍生物包括维生素E乙酸酯、维生素E棕榈酸酯和维生素E亚油酸酯。也可使用DL-泛酰醇和衍生物。特别适合的维生素B6衍生物为维生素B6棕榈酸酯。也可使用类黄酮,特别是葡糖基橙皮苷、芸香苷、和大豆异黄酮(包括染料木黄酮、大豆甙元、雌马酚、和它们的葡糖基衍生物)和其混合物。当存在时,维生素或类黄酮的总量可为组合物的0.0001-10重量%,优选0.01%-1重量%,最佳地0.1-0.5重量%。
其它类型的可用物质可为酶类,如氧化酶、蛋白酶、脂肪酶和组合。特别优选的是超氧化物岐化酶,可作为Biocell SOD商购自Brooks Company, USA。
可存在脱屑促进剂。示例为单羧酸。单羧酸可被长度最大为16的碳链取代或未取代。特别优选的羧酸为α-羟基羧酸、β-羟基羧酸或多羟基羧酸。术语“酸”意在不仅包括游离酸还包括其盐和C1-C30烷基或芳基酯和由水的去除(以形成环状或线性内酯结构)产生的内酯。代表性酸为乙醇酸、乳酸苹果酸和酒石酸。特别优选的代表性盐是乳酸铵。水杨酸是β-羟基羧酸的代表。当存在时,这些物质的量可为组合物的约0.01-约15重量%。其它酚酸包括阿魏酸、水杨酸、曲酸和它们的盐。
多种药草提取物可任选地包含于本发明的组合物中。示例是石榴、白桦(Betula Alba)、绿茶、甘菊、甘草和其提取物组合。该提取物可为水溶性或水不溶性的,分别携带于亲水或疏水溶剂中。水和乙醇是优选的萃取溶剂。
也可包含此类物质,如白藜芦醇、α-硫辛酸、鞣花酸、激动素、视黄氧基三甲基硅烷(可在商标Silcare 1M-75下购自Clariant Corp.)、脱氢表雄酮(DHEA)和其组合。神经酰胺(包括神经酰胺1、神经酰胺3、神经酰胺3B、神经酰胺6和神经酰胺7)以及伪神经酰胺也可用于多种本发明的组合物但也可排除在外。这些物质的量可为组合物的约0.000001-约10重量%,优选约0.0001-约1重量%。
着色剂、乳浊剂和研磨剂也可包含于本发明的组合物中。这些物质中的每一种可为组合物的约0.05-约5重量%,优选0.1-3重量%。
本发明的组合物可含有安全和有效量的选自五肽、五肽衍生物、和其混合物的肽活性物。如本文所用,“五肽”指天然存在的五肽和合成五肽。本文也可用含有五肽的天然存在的和可商购的组合物。优选的可商购的含五肽衍生物的组合物为Matrixyl?,其可商购自Sederma,法国。优选以组合物的约0.000001重量%-约10重量%,更优选约0.000001重量%-约0.1重量%,进一步更优选约0.00001重量%-约0.01重量%的量包含五肽和/或五肽衍生物。在其中使用含五肽的组合物——Matrixyl?的实施方案中,所得组合物优选含有占所得组合物的约0.01重量%-约50重量%,更优选约0.05重量%-约20重量%,和甚至更优选约0.1重量%-约10重量%的MatrixylTM。
额外的肽,包括但不限于二-、三-、和四肽和其衍生物、和分子量为200-20000的多氨基酸序列。氨基酸可为天然存在的或合成的、右旋的或左旋的、直链的或环状的,并可以以安全和有效的量包含于本发明的组合物中。如本文所用,“肽”指天然存在的肽和合成肽。可用于本文还有天然存在的和可商购的含肽的组合物。
适用于本文的二肽包括肌肽。优选的三肽和其衍生物可作为Biopeptide CLTM和作为lamin市售的铜衍生物从Sigma(St.Louis, Mo.)购买。
可用于本文折皮肤护理组合物的进一步成分可选自以下任意和全部:皮肤调理剂、肤感温和剂、悬浮剂、辅助增稠剂、粘度调节剂、分散剂、溶解剂/澄清剂、稳定剂、乳浊剂/珠光剂、螯合剂/多价螯合剂、助水溶物、杀菌剂/杀真菌剂、抗氧化剂、pH调节剂、缓冲剂、着色剂和香精/香料、水、其它可选成分(辅助剂)等。
也可将本发明的组合物任选地并入水可溶性基质中,用于例如以处理擦(treated wipe)的形式应用至皮肤。
制备组合物的方法
以如下方式制备本发明范围内的组合物。混合全部的水溶性成分(包括防腐剂、增稠聚合物、任选的甘油、和水)并加热至70-90℃的温度。在分离的容器中混合全部油溶性成分(包括糖表面活性剂和12HSA)至70-90℃的温度。在70-90℃的温度于搅拌下将油相添加至水相。任选地,在40℃下加入香料和苯氧乙醇。在混合下冷却混合物至室温。
使用组合物的方法
根据本发明的组合物意欲主要作为用于局部施加至人类皮肤的产品,特别是作为调理和抚平皮肤、和防止或减少皱缩或老化皮肤、或老年斑的出现、或美白皮肤的产品。
在使用中,将少量的组合物,例如1-5ml,由适合的容器或施用器应用至皮肤的暴露区域并且,如果需要,随后使用手或手指或适合的装置摸开和/或擦入皮肤。
虽然以上概述了本发明,但对于本领域技术人员来说,显而易见的是可作出修正、变种和改变而不偏离如本文所描述并要求保护的本发明范围和精神。现将在以下非限制性实施例中进一步阐述本发明。
实施例
使用Brookfield DV-I +粘度计(20 rpm,RV6,30秒)进行粘度测量。实施例中使用的乙氧基化蓖麻油表面活性剂的HLB值如下:
Peg-60 氢化蓖麻油 (Cremophor RH 60) HLB=15-17
Peg-7 氢化蓖麻油 (Cremophor WO 7) HLB= 4-6。
实施例1
本发明范围之内的组合物(1-7)和本发明范围之外的对比组合物(A-C)通过在80℃于搅拌下向水相中加入油相制备。将含有聚合物的油相和水相单独加热至80℃并随后在该温度下混合。在40℃下加入香料和苯氧乙醇。然后将混合物在混合下冷却至室温。对比组合物A缺少中和剂。对比组合物B缺少增稠聚合物,对比组合物C缺少乙氧基化蓖麻油表面活性剂。
由表1的结果可看出本发明范围之内的组合物是结构可逆的,而对比组合物A-C不是。
实施例2
如实施例1所述制备进一步的组合物。组合物8处于本发明范围之内,对比组合物D-H处于本发明范围之外。
组合物D含有有机中和剂,而不是权利要求所要求的无机中和剂。组合物E含有高HLB乙氧基化蓖麻油表面活性剂,但不含低HLB乙氧基化蓖麻油表面活性剂。组合物F含有低HLB乙氧基化蓖麻油表面活性剂,而不含高HLB乙氧基化蓖麻油表面活性剂。组合物G和H具有处于所要求范围之外的两表面活性剂之比。
由表2的结果可看出本发明范围之内的组合物(组合物8)是结构可逆的,而对比组合物D-H不是。
虽然根据目前优选的实施方案进行了描述,但应理解该公开不解释为限制。对于本领域技术人员而言,毫无疑问将在已阅读以上公开之后想到各种变形和替代。相应地,所附权利要求书意欲解释为覆盖落入本发明真正精神和范围之内的所有所述变形和替代。
Claims (7)
1.一种留存型非固体皮肤调理组合物,其包含:
(a) 占所述组合物0.01-15wt%的12-羟基硬脂酸;
(b) 占所述组合物0.1-30wt%的非离子表面活性剂,包含
(b1) HLB高于10的高HLB乙氧基化氢化蓖麻油,和
(b2) HLB低于10的低HLB乙氧基化氢化蓖麻油,
其中所述高HLB乙氧基化氢化蓖麻油与所述低HLB乙氧基化氢化蓖麻油的重量比为80:20-5:95;
(c) 以维持所述组合物的pH于5.5-8.0的量的无机中和剂;
(d) 0.05%-10%的增稠聚合物;
其中所述组合物的粘度在1 Pas-500 Pas的范围内;和
其中所述组合物在室温和50?C之间的温度循环中是结构可逆的。
2.权利要求1的组合物,其中至少40%的12-羟基硬脂酸呈酸的形式。
3.权利要求1或2的组合物,其中所述组合物于45?C下保持稳定至少1周。
4.根据前述权利要求任一项的组合物,其进一步包含阴离子表面活性剂。
5.根据前述权利要求任一项的组合物,其中所述无机中和剂选自氢氧化钾、氢氧化钠、氯化镁、硫酸镁、氯化钙、碳酸钙、氧化钙、氧化镁、氢氧化钙、氢氧化镁、氯化锌、氧化锌、氯化铝、氢氧化铝、氧化铝、和其混合物。
6.根据前述权利要求任一项的组合物,其进一步包含反丁烯二酸或其盐。
7.调理皮肤的方法,所述方法包括将前述权利要求任一项的组合物施用于皮肤。
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