CN1140254C - 包含硅氧烷弹性体的化妆品组合物 - Google Patents

包含硅氧烷弹性体的化妆品组合物 Download PDF

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CN1140254C
CN1140254C CNB971958211A CN97195821A CN1140254C CN 1140254 C CN1140254 C CN 1140254C CN B971958211 A CNB971958211 A CN B971958211A CN 97195821 A CN97195821 A CN 97195821A CN 1140254 C CN1140254 C CN 1140254C
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B��J���Ų��Ʒ�˹��
B·J·杜布科夫斯基
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A·P·兹奈登
M·C·切尼
W·罗瑟
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/894Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241Containing particulates characterized by their shape and/or structure
    • AHUMAN NECESSITIES
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/345Alcohols containing more than one hydroxy group
    • AHUMAN NECESSITIES
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    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36Carboxylic acids; Salts or anhydrides thereof
    • A61K8/365Hydroxycarboxylic acids; Ketocarboxylic acids
    • AHUMAN NECESSITIES
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    • A61K8/58Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
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    • AHUMAN NECESSITIES
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    • A61K8/89Polysiloxanes
    • AHUMAN NECESSITIES
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    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/895Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/30Characterized by the absence of a particular group of ingredients
    • A61K2800/31Anhydrous
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60Particulates further characterized by their structure or composition
    • A61K2800/65Characterized by the composition of the particulate/core
    • A61K2800/654The particulate/core comprising macromolecular material

Abstract

提供一种包括交联非乳化硅氧烷弹性体、皮肤调理剂、挥发性硅氧烷和不超过5%的水的皮肤处理组合物。烃如凡士林和多元醇如丙三醇是优选的皮肤调理剂。包含所述弹性体给皮肤提供了非-传统的匀和/柔滑的感觉,擦用时没有呆滞之感。

Description

包含硅氧烷弹性体的化妆品组合物
本发明背景
本发明领域
本发明涉及用于局部施用到皮肤上、其性能通过并入某些弹性体硅氧烷而得到增强的无水化妆品组合物。
相关技术
包括有机酯和烃、特别是凡士林的柔润剂很早以前在医学上已作为皮肤调理剂来使用。作为滋润成分,这些物质是仅次于水的第二个选择。它们主要起闭合阻挡层的作用。在干燥皮肤的症状中,人类皮肤角质层外层的水含量是一个控制因素。当角质层含有10-20%的适量水时,皮肤就会保持柔韧性。然而当水的含量低于10%时,角质层通常会变脆及粗糙,可表现出脱皮和裂纹的现象。
通过渗滤或使表皮直接与水接触,角质层从表皮的深层处得到了其水分。渗滤过程受皮肤水分的含量及浓度梯度的控制。在相当干燥的环境中,水在皮肤外层中的损失可以相当显著,并通常超过由于渗滤所补偿的速度。将闭合或半闭合阻挡层的物质置于皮肤表面上将起着减少水分损失到环境中的作用。它同时也使皮肤表面通过渗滤机理得到再次水化。
虽然现在有许多有效和经济的皮肤调理剂,但它们仍具有一些缺点。
通常柔润剂类型是以油包水乳状液的形式提供的。很难获得使油相和水相之间的临界配方平衡达到足以确保长期贮存稳定性的程度。该临界平衡的一个内容是内相的体积。必须获得使产生和稳定体系的物化作用达到最大的临界体积。如果该临界体积得不到适当的平衡,则产物将发生粘度变化,最终导致相分离。通常最佳体积是很大的,它限制了外相体积的大小,并赋予体系一个呆滞、不适宜缓慢的破裂属性。这个临界内相体积限制可以减少官能度,并增加不适感的特性。
无水体系避免了乳状液稳定性的问题。但是很不幸的是,由于无水的体系而产生了其他美学上的问题。不是所有油相的材料在高浓度时都可相容。此外,闭合剂如凡士林都是较为油腻的。它们具有粘到衣服上的缺点,并且不容易将其从皮肤上洗去。它们也不能适量地渗透进表皮中。
美国专利5,387,417(Rentsch)报道,通过凡士林基与交联的有机聚硅氧烷-聚氧化烯乳化剂的乳化作用,可获得在化妆上可接受的半透明润湿洗剂。根据该公开,不但得到了相容性,而且该硅氧烷还使连续相和非连续相的折射指数相匹配。
美国专利5,280,019(Klimisch)报道可增强水分在皮肤上的吸附和保留的组合物。通过使用有机硅化合物(它是羧基官能化的聚硅氧烷或其金属羧酸盐)可获得这些结果。
EP 0295 886(Harashima等人)公开了并入有机聚硅氧烷弹性体颗粒的洗面剂。这些体系使用水而不是挥发性的硅氧烷作为主要载体。JP 07 267 820(Takahashi等人,由Chemical Abstract(卷124(4)、第37399期)所登载)公开了含有有机聚硅氧烷弹性体颗粒和疏水性处理过的粉末的两层油质化妆品。在该公开中未描述改进皮肤润湿情况所需的亲水性官能成分如丙三醇。
从上述先有技术中很显然某些类型的并入亲水性官能度的聚硅氧烷,如聚氧化烯或羧酸酯单元可以有助于油相的乳化作用。实际上这些公开提出在硅氧烷上要求有亲水性官能度。很不幸的是,用于乳化作用的亲水性基团的并入使硅氧烷提供一种柔软光滑的用后感(afterfeel)的能力受损。这些先有技术的亲水性硅氧烷也不能完全解决油相和水相相容的问题。需要能携带较高浓度水基润湿成分(如丙三醇)的新体系。同时还需要当将乳化液擦进皮肤时可获得较匀和的破乳效果以使正面感官/感觉的属性达到最大的硅氧烷。带有亲水性的硅氧烷对闭合剂的无水体系也没有任何好处,因它们通常会导致相分离。
因此,本发明的一个目的是提供一种无水但又能提供改进的肤感性能的皮肤处理组合物。
本发明的另一个目的是提供一种甚至在冷冻/解冻循环的条件下仍具有防止相分离的稳定性的皮肤处理组合物。
本发明的再一个目的是提供一种在初始施用到皮肤上能获得平滑不呆滞的擦进的皮肤处理组合物。
从以下的概要和详述中,本发明的这些和其他目的将变得更加显而易见。
本发明概要
我们提供一种皮肤处理组合物,它包括:
(i)0.1-30%的交联非乳化硅氧烷弹性体;
(ii)1-50%的皮肤调理剂;
(iii)10-80%的挥发性硅氧烷;和
(iv)0-5%的水。
在本发明中特别优选的调理剂是烃如凡士林和增湿多元醇如丙三醇。环甲基硅酮是优选的挥发性硅氧烷。本发明的弹性体优选通过二乙烯基化合物、特别是具有至少两个游离乙烯基的硅氧烷聚合物与聚硅氧烷主链上的Si-H键反应来形成。最优选的弹性体是通过位于分子球形MQ树脂上的Si-H交联的二甲基聚硅氧烷。
本发明的组合物基于以下概念:使用交联的非乳化硅氧烷弹性体与具有胶粘性质的皮肤调理剂混合。虽然我们不希望受缚于理论,但我们相信这些调理剂(当亲水性时)提供给弹性体和挥发性硅氧烷混合物的内相。所述挥发性硅氧烷起着外相的作用,同时还分散否则不溶的交联硅氧烷弹性体粉末。当这个体系施用到皮肤上时,所述挥发性硅氧烷进行蒸发,留下与皮肤流体更能相容的官能材料而被角质层上层所截留。与这些身体流体不相容的硅氧烷弹性体则停留在皮肤表面。由于该弹性体完全分散于挥发性硅氧烷中,因此它以相当均匀的一层沉积于皮肤上。稠密的三维交联的硅氧烷弹性体膜在不溶的水/皮肤的脂质和外部环境之间起着中间层的作用。这种机制遮掩了高浓度亲水性官能成分如甘油的负面感觉特征。
本发明详述
我们现已发现,交联的非乳化硅氧烷弹性体与皮肤调理剂和挥发性硅氧烷混合,得到一种高度稳定的体系,并且给皮肤提供一种独特的柔软光滑的用后感。
交联的非乳化硅氧烷弹性体是本发明的第一个基本成分。通常它们的数均分子量超过2,000、优选超过1,000,000。它们一般为10,000-20,000,000。术语“非乳化”定义为不存在聚氧化烯单元的硅氧烷。最好弹性体由二乙烯基化合物、特别是具有至少两个游离乙烯基的聚合物与聚硅氧烷主链如分子球形MQ树脂的Si-H键反应来形成。适宜的弹性体组合物可从General Electric Company购得,产品名称为General Electric Silicone 1229、推荐的CTFA名为环甲基硅酮和乙烯基二甲基硅酮(Vinyl Dimethicone)/Methicone交联聚合物,所提供的是环甲基硅酮载体中的20-35%弹性体。CTFA名为交联硬脂酰基甲基二甲基硅氧烷共聚物的相关弹性体组合物可从Grant Industries,Inc.,Elmwood Park,New Jersey以Gransil SR-CYC(环甲基硅酮载体中的25-35%弹性体)的商品名获得。优选将来自General Electric和GrantIndustries的商业产品进一步处理,使其在声谱显示仪(Soholator)中循环10-60个行程进行高压(约5,000psi)(其中,1psi=6.8947×104达因/厘米2)处理。超声(Sonolation)得到了平均粒度为0.2-10微米、优选为0.5-5微米的弹性体的所得流体。当在25℃下通过Brookfield LV粘度计测量时(大小4巴,60转/分,15秒)粘度为300-20,000cps(0.3-20帕·秒)为最佳。
弹性体的量可为组合物重量的0.1-30%、最适为1-15%、最优选为3-10%。
本发明第二个基本成分是皮肤调理剂。优选这些调理剂选自保湿剂、剥离剂、柔润剂及其混合物。
保湿剂通常是用于润湿、减少脱皮并促进累积的鳞片从皮肤上去除的多元醇。常见的多元醇包括聚(亚烷基)二醇、更优选为烯化多醇及其衍生物。解说性的例子为丙二醇、二聚丙二醇、聚丙二醇、聚乙二醇、山梨醇、羟丙基山梨醇、己二醇、1,3-丁二醇、1,2,6-己三醇、乙氧基丙三醇、丙氧基丙三醇及其混合物。最优选的保湿剂是丙三醇。乙氧基丙三醇、丙氧基丙三醇及其混合物。最优选的保湿剂是丙三醇。保湿剂的量可为1-50%(重量)、优选为10-40%(重量)、最适为25-35%(重量)。
根据本发明的剥离剂优选选自α-羟基羧酸、β-羟基羧酸及这些酸的盐。羧酸优选为C2-C30羧酸。最优选的是羟基乙酸、乳酸和水杨酸及其铵盐。剥离剂的量优选为1-15%(重量)、更优选为2-10%(重量)。
可以使用许多各种各样的C2-C30α-羟基羧酸。其适宜的例子包括:
-羟基乙酸
-羟基丙酸
-羟基己酸
-羟基辛酸
-羟基癸酸
-羟基十二酸
-羟基十四酸
-羟基十六酸
-羟基十八酸
-羟基二十酸
-羟基二十二酸
-羟基二十六酸,和
-羟基二十八酸
当调理剂是柔润剂时优选选自烃、脂肪酸、脂肪醇和酯。凡士林是最优选的烃型柔润调理剂。其他可以使用的烃包括矿物油、聚烯烃如聚癸烯以及链烷烃(parafins)如异十六烷(例如Permethyl 99和Permethyl 101)。
脂肪酸和脂肪醇优选具有10-30个碳原子。这类化合物的解说性例子是壬酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、异硬脂酸、羟基硬脂酸、油酸、亚油酸、蓖麻油酸、花生酸、山嵛酸、芥酸和醇。
油酯柔润剂优选为选自以下种类的一种或多种:
1.甘油三酯如植物脂肪和油及动物脂肪和油。其例子包括蓖麻油、可可油、红花油、棉子油、玉米油、橄榄油、鳕鱼肝油、杏仁油、鳄梨油、棕榈油、芝麻油、角鲨烯、Kikui油和豆油。
2.乙酰甘油酯,如乙酰化的单酸甘油酯。
3.乙氧基化的甘油酯,如乙氧基化的一硬脂酸甘油酯。
4.具有10-20个碳原子的脂肪酸的烷基酯。脂肪酸的甲基酯、异丙基酯和丁基酯在此处都是有用的。其例子包括月桂酸己酯、月桂酸异己酯、棕榈酸异己酯、棕榈酸异丙酯、油酸癸酯、油酸异癸酯、硬脂酸十六酯、硬脂酸癸酯、异硬脂酸异丙酯、己二酸二异丙酯、己二酸二异己酯、已二酸二己基癸酯、癸二酸二异丙酯、乳酸月桂酯、乳酸肉豆蔻酯和乳酸鲸腊酯。
5.具有10-20个碳原子的脂肪酸的链烯酯。其例子包括肉豆蔻酸油酯、硬脂酸油酯和油酸油酯。
6.醚-酯如乙氧基化的脂肪族醇的脂肪酸酯。
7.多元醇酯。乙二醇一-和二-脂肪酸酯、二乙二醇一-和二-脂肪酸酯、聚乙二醇(200-6000)一-和二-脂肪酸酯、丙二醇一-和二-脂肪酸酯、一油酸聚丙二醇2000酯、一硬脂酸聚丙二醇2000酯、一硬脂酸乙氧基化的丙二醇酯、一-和二-脂肪酸甘油酯、聚脂肪酸聚甘油酯、一硬脂酸乙氧基化的甘油酯、一硬脂酸1,2-丁二醇酯、二硬脂酸1,2-丁二醇酯、脂肪酸聚氧乙烯多元醇酯、脂肪酸山梨醇酯和脂肪酸聚氧乙烯山梨醇酯是令人满意的多元醇酯。
8.蜡酯如蜂蜡、鲸蜡、肉豆蔻酸肉豆蔻酯、硬脂酸硬脂酰酯。
皮肤调理剂的量可为1-50%(重量)、优选为3-25%(重量)、最适为5-20%(重量)。
本发明第三个基本成分是挥发性硅氧烷。术语“挥发性”指在环境条件下那些具有可测量压力的那些物质。此处有用的挥发性聚有机硅氧烷可以是环状的、也可以是直链的。优选的环状硅氧烷包括含有约3-约9个硅原子、优选含有约4-约5个硅原子的聚二甲基硅氧烷(通常称为环甲基硅酮)。优选的直链硅油包括含有约3-约9个硅原子的聚二甲基硅氧烷。25℃时直链挥发性硅氧烷通常的粘度小于约5厘沲,而环状硅油的粘度小于约10厘沲、优选为0.1-8厘沲。在本发明中有用的硅油的例子包括:Dow Corning 244、Dow Corning 245和DowCorning 344、Dow Corning 345和Dow Corning 200(由Dow Corning公司制造);Silicone 7207和Silicone 7158(由Union Carbide公司制造);SF1202(由General Electric制造)。
挥发性硅氧烷的量可为10-80%(重量)、优选为20-70%(重量)、最适为30-65%(重量)。
本发明的化妆品组合物基本上是无水的。可将水的量限制在0-5%(重量)、优选不超过4%(重量)、更优选不超过3%(重量)、最优选不超过2%(重量)、最适不超过0.5%(重量)。
除了所述基本成分外,根据所需化妆品组合物的具体类型可以包括其它材料。例如可将各种表面活性剂配制进所述组合物中。这些表面活性剂可以选自非离子、阴离子、阳离子或两性乳化剂。其量可为约0.1-约20%(重量)。解说性的非离子表面活性剂为基于C10-C22脂肪醇和酸的烷氧基化合物和脱水山梨糖醇。这些材料可从例如ShellChemical Company(以Neodol为商标)购得。由BASF Corporation(以Pluronic为商标)销售的聚氧丙烯-聚氧乙烯共聚物有时也是有用的。从Henkel Corporation购得的烷基聚苷也可以用于本发明的这个目的。
阴离子型表面活性剂包括脂肪酸皂、十二烷基硫酸钠、月桂基醚硫酸钠、烷基苯磺酸酯、一-和二-烷基酸磷酸酯和脂酰羟乙磺酸钠。
两性表面活性剂包括如氧化二烷基胺和各种类型的甜菜碱(如可可酰氨基丙基甜菜碱)的那些材料。
少量添加剂成分也可包括如香料、遮光剂和着色剂,它们每一种都为其各自的有效量以完成各自的作用。
以下实施例将更加详细地解说本发明的实施方案。除非另有说明,否则此处以及所附的权利要求书中提及的所有份数、百分数和比例均以重量计。
实施例1
本发明说明无水皮肤处理组合物。将在下表中列举的各种组分在60℃下一起加入到容器中,并用均化搅拌器混合。然后将其在800-1,000psi下进行超声5-10分钟。所得产物为一种具有相当柔滑用后感的不油腻半固体。
              表I
    组分     重量%
    凡士林     18.5
    Gransil SR-CYC     30
    DC 344 Fluid 7     51.5
实施例2
本实施例说明根据本发明的另一种无水皮肤处理组合物。采用在下表中所列举的各种组分以和实施例1基本上相似的方式进行配制。所得产物具有匀和柔滑的用后感。
              表II
    组分     重量%
    凡士林     22
    Gransil SR-CYC     43
    DC 344 Fluid 7     35
实施例3
进行了一系列的实验以评估水对本发明各种组合物的影响。配方和性能特征列举于下表III。
                                                             表III
    组分     CTFA名称                                  配方(重量%)
   A B C     D
    GE SE1229(在D4/D5挥发性硅氧烷中的25%弹性体)   乙烯基二甲基硅酮/硅酮交联共聚物    31 31 31     31
    Dow 345硅氧烷流体   环甲基硅酮    31 38 35     26
    Dow 344硅氧烷流体   环甲基硅酮    8.5 8.5 8.5     8.5
    凡士林   凡士林    11 11 11     11
    丙三醇(DRY)   丙三醇    8 8 8     8
    Abil EM 90   鲸蜡基二甲基硅酮共聚醇    0.5 0.5 0.5     0.5
    DI水   软化水    0 3 6     15
    性能
    施用到皮肤上的初始感觉    最好 良好 不良     不良
   非传统的柔和/光滑“粉状”的感觉,擦用时不呆滞 非传统的柔和/光滑“粉状”的感觉,擦用时稍有呆滞感 更传统的失去“粉状”的转变,擦用时有呆滞感     传统的擦用转变,相当呆滞
    相稳定性(冷冻/解冻)    通过 通过 不通过     不通过
表III中的实验结果表明,含有6%水的配方没有通过冷冻/解冻循环稳定性的评估。此外产物初次施用的肤感显示,6%水时擦用时有呆滞的感觉。相反,0%水时观察到匀和的擦用。3%水时仅有轻微的呆滞感。

Claims (8)

1.一种皮肤处理组合物,它包含:
(i)0.1-30%的交联非乳化硅氧烷弹性体;
(ii)1-50%的皮肤调理剂;
(iii)10-80%的挥发性硅氧烷;和
(iv)0-5%的水。
2.根据权利要求1的组合物,其中所述皮肤调理剂选自保湿剂、剥离剂、柔润剂及其混合物。
3.根据权利要求2的组合物,其中所述柔润剂是烃。
4.根据权利要求3的组合物,其中所述烃是凡士林。
5.根据权利要求2-4中任一项的组合物,其中所述保湿剂是选自丙三醇、丙二醇、聚乙二醇及其混合物的多元醇。
6.根据权利要求2的组合物,其中所述剥离剂选自α-羟基羧酸、β-羟基羧酸及其盐。
7.根据权利要求1的组合物,其中存在的水为0-3%重量。
8.根据权利要求1的组合物,其中所述交联的非乳化硅氧烷弹性体是通过联乙烯基化合物与聚硅氧烷的Si-H键反应来形成的。
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