CN108367176A - 基于小颗粒o/w乳剂的防晒组合物 - Google Patents
基于小颗粒o/w乳剂的防晒组合物 Download PDFInfo
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- CN108367176A CN108367176A CN201680073341.9A CN201680073341A CN108367176A CN 108367176 A CN108367176 A CN 108367176A CN 201680073341 A CN201680073341 A CN 201680073341A CN 108367176 A CN108367176 A CN 108367176A
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Abstract
本发明涉及一种用于角蛋白材料例如皮肤的防晒组合物,特别是具有分散在水相中的油相的水包油(O/W)乳剂形式的防晒化妆品组合物,其包含(a)至少一种油,(b)至少一种亲水UV过滤剂;(c)水;和(d)至少一种乳化剂,其中油相液滴的数均直径低于200 nm。根据本发明的组合物能够提供改善的UV防护效果。
Description
技术领域
本发明涉及一种用于角蛋白物质例如皮肤的防晒组合物,特别是水包油(O/W)乳剂形式的防晒化妆品组合物。
背景技术
在化妆品或皮肤病学领域中使用O/W乳剂是已知的实践。这些由分散在水相中的油相构成的乳剂具有外部水相,因此基于O/W乳剂的化妆品/皮肤病学产品由于外部水相能够提供的清爽感觉而令人愉悦地被使用。
由于O/W乳剂的这个益处,它们还能够被在用于皮肤的防晒化妆品产品中使用。对于防晒产品,良好的UV防护效果是关键功效之一。
发明的公开内容
本发明的一个目的是提供一种组合物,优选一种用于角蛋白物质例如皮肤的O/W乳剂形式的化妆品组合物,其能够提供改善的UV防护效果。
本发明的上述目的能够通过具有分散在水相中的油相的O/W乳剂形式的组合物实现,所述组合物包含:
(a)至少一种油;
(b)至少一种亲水UV过滤剂;
(c)水;和
(d)至少一种乳化剂,
其中油相液滴的数均直径为低于200 nm,并且相对于所述组合物的总重量,所述油的量为0.1至15重量%。
所述油相液滴的数均直径可以低于180 nm,优选低于160 nm,更优选低于140 nm。
所述油相液滴的数均直径可以为大于1 nm,更优选大于5 nm,并甚至更优选大于10 nm,并特别是大于20 nm。
所述油可以选自酯油,优选具有低于600 g/mol的分子量,例如肉豆蔻酸异丙酯、棕榈酸异丙酯、棕榈酸乙基己酯;人造甘油三酯,例如癸酸辛酸甘油酯;烃油;和矿物油例如石蜡油,和其混合物。
相对于所述组合物的总重量,所述油的量可以为0.5至10重量%,特别是1至5重量%。
所述亲水UV过滤剂可以选自至少一种亲水UV-A过滤剂和至少一种亲水UV-B过滤剂的组合。
所述亲水UV过滤剂可以选自苯基苯并咪唑磺酸、对苯二亚甲基二樟脑磺酸、和其混合物。
相对于所述组合物的总重量,所述亲水UV过滤剂的量可以为1至40重量%,优选3至30重量%,并更优选5至25重量%。
相对于所述组合物的总重量,该组合物中水的量可以为50至99重量%,优选55至95重量%,更优选60至90重量%。
相对于所述组合物的总重量,该组合物可以包含至少一种疏水UV过滤剂,其量优选为0.1至10重量%,更优选0.2至5重量%。
相对于所述组合物的总重量,该组合物可以进一步包含至少一种胶凝剂,其量优选为0.1至20重量%,优选0.2至15重量%,并更优选1至10重量%。
所述乳化剂可以选自非离子乳化剂,优选选自脂肪酸、脂肪醇、聚乙氧基化脂肪酸、聚甘油化脂肪酸和其混合物。
相对于所述组合物的总重量,所述乳化剂的量可以为0.1至30重量%,优选0.5至20重量%,并更优选1至10重量%。
所述组合物可以为一种化妆品组合物,优选一种用于角蛋白物质的化妆品组合物,并更优选一种皮肤用化妆品组合物。
本发明还涉及一种防护角蛋白物质免受紫外线辐射的方法,其包括施加根据权利要求1-14任一项的组合物至角蛋白物质上。
执行本发明的最佳模式
在潜心研究之后,发明人已经发现将纳米尺寸的油相引入包含亲水UV过滤剂的水相中能够令人意外地提供具有改善的UV防护效果的O/W乳剂形式的组合物。
因此,根据本发明的具有分散在水相中的油相的O/W乳剂形式的组合物,优选用于角蛋白物质优选皮肤的化妆品组合物包含:
(a)至少一种油;
(b)至少一种亲水UV过滤剂;
(c)水;和
(d)至少一种乳化剂;
其中油相液滴的数均直径低于200 nm。
根据本发明的组合物能够展现出改善的UV防护效果。
在后文中,将以详细叙述的方式描述根据本发明的组合物。
[组合物]
根据本发明的组合物为具有分散在水相中的油相的O/W乳剂形式,其中所述油相形成具有低于200 nm的数均直径的纳米尺寸的液滴。所述组合物包含(a)至少一种油、(b)至少一种亲水UV过滤剂、(c)水和(d)至少一种乳化剂。
优选的是根据本发明的组合物为化妆品组合物,特别是用于角蛋白物质例如皮肤的化妆品防晒组合物,即皮肤用化妆品组合物。
根据本发明的组合物能够展现出改善的UV防护效果。此外,由于小尺寸的油相,根据本发明的组合物能够具有透明或半透明外观,这对于在用于角蛋白物质例如皮肤的化妆品局部组合物中使用是优选的。
<油相>
根据本发明的O/W乳剂的油相包含至少一种(a)油。相对于该组合物的总重量,所述油相的量可以为0.1至80重量%,优选0.2至60重量%,更优选0.5至30重量%。
所述油相为纳米尺寸的液滴形式。所述油相,即油滴的数均直径为低于200 nm,优选低于180 nm,更优选低于160 nm,特别是低于140 nm。一般而言,所述油相液滴的数均直径优选为大于1 nm,更优选大于5 nm,甚至更优选大于10 nm,特别是大于20 nm。可以通过例如粒度分析仪(Vasco, Cordouan Technologies)测量油滴的尺寸。
能够提供改善的UV防护效果的本发明的一个可想到的假设是纳米尺寸的液滴具有将该组合物均匀地铺放至角蛋白物质表面上的趋势,其能够提供包含在所述组合物中的UV过滤剂在角蛋白物质表面上的均匀且浓厚的沉积。
(油)
根据本发明的组合物包含(a)至少一种油。两种或更多种(a)油可以组合使用。因此,可以使用单一类型的油或不同类型的油的组合。
本文中使用的表达“油”是指在室温(25℃)下在大气压力(760 mmHg)下为液体或浆糊(非固体)形式的脂质化合物或物质。这些油可以为挥发性或非挥发性的,优选非挥发性的。
所述(a)油可以为非极性油,例如烃油、硅油等;极性油例如植物或动物油和酯油或醚油;或其混合物。
优选的是所述(a)油选自植物或动物来源的油、合成油、硅油和烃油,和其混合物。
作为植物油的实例,可以提及例如亚麻籽油、山茶油、澳洲坚果油、玉米油、貂油、橄榄油、鳄梨油、山茶花油、蓖麻油、红花油、荷荷巴油、葵花油、杏仁油、菜籽油、芝麻油、大豆油、花生油和其混合物。
作为动物油的实例,可以提及例如角鲨烯和角鲨烷。
作为合成油的实例,可以提及烷烃油,例如异十二烷和异十六烷、酯油、醚油、和人造甘油三酯。
所述酯油优选为饱和或不饱和、直链或支链的C1-C26脂肪族一元酸或多元酸与饱和或不饱和、直链或支链的C1-C26脂肪族一元醇或多元醇的液体酯,该酯的碳原子的总数优选大于或等于10,并优选小于或等于30。
优选地,对于一元醇的酯,产生本发明的酯的醇和酸的至少一个为支链的。
在一元酸和一元醇的单酯中,可以提及棕榈酸乙酯、棕榈酸乙基己酯、棕榈酸异丙酯、碳酸二辛酯、肉豆蔻酸烷基酯例如肉豆蔻酸异丙酯或肉豆蔻酸乙酯、硬脂酸异鲸蜡酯、异壬酸2-乙基己酯、异壬酸异壬酯、新戊酸异癸酯和新戊酸异硬脂酯。
还可以使用C4-C22二元羧酸或三元羧酸与C1-C22醇的酯和一元羧酸、二元羧酸或三元羧酸与非糖C4-C26二羟基、三羟基、四羟基、或五羟基醇的酯。
特别可以提及:癸二酸二乙酯;月桂酰肌氨酸异丙酯;癸二酸二异丙酯;癸二酸双(2-乙基己酯);己二酸二异丙酯;己二酸二正丙酯;己二酸二辛酯;己二酸双(2-乙基己酯);己二酸二异硬脂酯;马来酸双(2-乙基己酯);柠檬酸三异丙酯;柠檬酸三异鲸蜡酯;柠檬酸三异硬脂酯;三乳酸甘油酯;三辛酸甘油酯;柠檬酸三辛基十二烷基酯;柠檬酸三油醇酯;二庚酸新戊二醇酯;二异壬酸二乙二醇酯。
作为酯油,技术人员可以使用糖酯和C6-C30并优选C12-C22脂肪酸的二酯。术语“糖”是指包含数个醇官能团的含或不含醛或酮官能团并包含至少4个碳原子的含氧的烃基化合物。这些糖可以为单糖、寡糖或多糖。
可以提及的合适的糖的实例包括蔗糖(或甘蔗糖)、葡萄糖、半乳糖、核糖、海藻糖、麦芽糖、果糖、甘露糖、树胶醛糖、木糖和乳糖,和其衍生物,特别是烷基衍生物,例如甲基衍生物,例如甲基葡萄糖。
脂肪酸的糖酯可以特别是选自上文描述的糖和为直链或支链的、饱和或不饱和的C6-C30和优选C12-C22脂肪酸的酯或酯混合物。如果它们不饱和的话,这些化合物可以具有一至三个共轭或非共轭的碳碳双键。
根据这个变体的酯还可以选自单酯、二酯、三酯、四酯和多酯,和其混合物。
这些酯可以例如为油酸酯、月桂酸酯、棕榈酸酯、肉豆蔻酸酯、山嵛酸酯、椰油酸酯、硬脂酸酯、亚油酸酯、亚麻酸酯、癸酸酯和花生四烯酸酯、或其混合物,例如特别是油棕榈酸酯、油硬脂酸酯和棕榈硬脂酸酯混合酯,以及四乙基己酸季戊四醇酯(pentaerythrityl tetraethyl hexanoate)。
更具体地,可以使用单酯和二酯,特别是蔗糖、葡萄糖或甲基葡萄糖单油酸酯或二油酸酯、硬脂酸酯、山嵛酸酯、油棕榈酸酯、亚油酸酯、亚麻酸酯和油硬脂酸酯。
可以提及的实例为由Amerchol公司以名称Glucate® DO出售的产品,其为甲基葡萄糖二油酸酯。
作为优选的酯油的实例,可以提及例如己二酸二异丙酯、己二酸二辛酯、己酸2-乙基己酯、月桂酸乙酯、辛酸鲸蜡酯、辛酸辛基十二烷基酯、新戊酸异癸酯、丙酸肉豆蔻酯、2-乙基己酸2-乙基己酯、辛酸2-乙基己酯、辛酸/癸酸2-乙基己酯、棕榈酸甲酯、棕榈酸乙酯、棕榈酸异丙酯、碳酸二辛酯、月桂酰肌氨酸异丙酯、异壬酸异壬酯、棕榈酸乙基己酯、月桂酸异己酯、月桂酸己酯、硬脂酸异鲸蜡酯、异硬脂酸异丙酯、肉豆蔻酸异丙酯、油酸异癸酯、甘油三(2-乙基己酸酯)、四(2-乙基己酸)季戊四醇酯、琥珀酸2-乙基己酯、癸二酸二乙酯和其混合物。
作为人造甘油三酯的实例,可以提及例如癸酸辛酸甘油酯、三肉豆蔻酸甘油酯、三棕榈酸甘油酯、三亚麻酸甘油酯、三月桂酸甘油酯、三癸酸甘油酯、三辛酸甘油酯、三(癸酸/辛酸)甘油酯和三(癸酸/辛酸/亚麻酸)甘油酯。
作为硅油的实例,可以提及例如线性有机基聚硅氧烷例如二甲基聚硅氧烷、甲基苯基聚硅氧烷、甲基氢聚硅氧烷等;环状有机基聚硅氧烷例如八甲基环四硅氧烷、十甲基环五硅氧烷、十二甲基环六硅氧烷等;和其混合物。
优选地,硅油选自液体聚二烷基硅氧烷,特别是液体聚二甲基硅氧烷(PDMS),和包含至少一个芳基的液体聚有机基硅氧烷。
这些硅油还可以为有机基改性的。根据本发明可以使用的有机基改性的硅油为上文定义的并在它们的结构中包含一个或多个通过烃基连接的有机基官能团的硅油。
在Walter Noll的Chemistry and Technology of Silicones (1968), AcademicPress中更详细地定义了有机基聚硅氧烷。它们可以为挥发性或非挥发性的。
当它们为挥发性的时,硅油更特别选自具有60℃至260℃的沸点的那些,并且甚至更特别选自:
(i) 包含3至7个并优选4至5个硅原子的环状聚二烷基硅氧烷。这些为例如特别是由Union Carbide以名称Volatile Silicone® 7207或由Rhodia以Silbione® 70045 V2出售的八甲基环四硅氧烷,由Union Carbide以名称Volatile Silicone® 7158和由Rhodia以Silbione® 70045 V5出售的十甲基环五硅氧烷、和由Momentive PerformanceMaterials以名称Silsoft 1217出售的十二甲基环五硅氧烷和其混合物。还可以提及例如二甲基硅氧烷/甲基烷基硅氧烷的环状共聚物类型,例如由Union Carbide公司出售的Silicone Volatile® FZ 3109,其具有下式:
其中。
还可以提及环状聚二烷基硅氧烷与有机硅化合物的混合物,例如八甲基环四硅氧烷和四三甲基甲硅烷基季戊四醇的(50/50)混合物和八甲基环四硅氧烷和氧基-1,1’-双(2,2,2’,2’,3,3’-六三甲基甲硅烷基氧基)新戊烷的混合物;
(ii) 包含2至9个硅原子并在25℃下具有小于或等于5×10-6 m2/s的粘度的线性挥发性聚二烷基硅氧烷。实例为特别是由Toray Silicone公司以名称SH 200出售的十甲基四硅氧烷。属于这个类型的硅油还记载于在Cosmetics and Toiletries, Vol. 91, Jan. 76,第27-32页, Todd & Byers, Volatile Silicone Fluids for Cosmetics中公开的文章中。硅油的粘度在25℃下根据ASTM标准445 Appendix C测量。
还可以使用非挥发性聚二烷基硅氧烷。这些非挥发性硅油更特别选自聚二烷基硅氧烷,其中主要可以提及含三甲基甲硅烷基端基的聚二甲基硅氧烷。
在这些聚二烷基硅氧烷中,以非限制的方式可以提及以下商品:
- 47和70 047系列的Silbione®油或由Rhodia 出售的Mirasil®油,例如油70 047 V500 000;
- 由Rhodia 公司出售的Mirasil®系列油;
- 由Dow Corning公司出售的200系列油,例如具有60 000 mm2/s的粘度的DC200;
- 来自General Electric的Viscasil®油和来自General Electric的SF系列的某些油(SF 96, SF 18)。
还可以提及以名称聚二甲基硅氧烷醇(CTFA)已知的包含二甲基硅醇端基的聚二甲基硅氧烷,例如来自Rhodia公司的48系列油。
含芳基的硅油包括聚二芳基硅氧烷,特别是聚二苯基硅氧烷和聚烷基芳基硅氧烷。可以提及的实例包括以以下名称出售的产品:
- 来自Rhodia 的70 641系列的Silbione®油;
- 来自Rhodia 的Rhodorsil® 70 633和763系列油;
- 来自Dow Corning 的Dow Corning 556 Cosmetic Grade Fluid油;
- 来自Bayer 的PK系列的硅油,例如产品PK20;
- 来自General Electric的SF系列的某些油,例如SF 1023、SF 1154、SF 1250和SF1265。
所述有机基改性的液体硅油都可以特别包含聚亚乙基氧基和/或聚亚丙基氧基。因此可以提及由Shin-Etsu提出的硅油KF-6017和来自Union Carbide公司的Silwet®L722和L77油。
烃油可以选自:
- 直链或支链的,任选环状的C6-C16低级烷。可以提及的实例包括己烷、十一烷、十二烷、十三烷和异链烷烃,例如异十六烷、异十二烷和异癸烷;和
- 包含多于16个碳原子的直链或支链烃,例如液体链烷烃、液体矿脂、聚癸烯和氢化聚异丁烯例如Parleam®和角鲨烷。
作为烃油的优选实例,可以提及例如直链或支链烃例如异十六烷、异十二烷、角鲨烷、矿物油(例如液体石蜡)、链烷烃、凡士林或矿脂、萘类等;氢化聚异丁烯、异二十烷和癸烯/丁烯共聚物;和其混合物。
可能优选的是选自在室温下为液体形式的烃油的(a)油。
还可能优选的是选自具有低于600 g/mol的分子量的油的(a)油。
优选地,所述(a)油具有低分子量,例如低于600 g/mol,更优选低于500 g/mol,特别是低于400 g/mol,选自具有一个或多个短烃链的酯或醚油(C1-C18,例如肉豆蔻酸异丙酯、棕榈酸异丙酯、异壬酸异壬酯、碳酸二辛酯、棕榈酸乙基己酯、二辛醚和月桂酰肌氨酸异丙酯)、具有一个或多个短烷基链的烃油(C1-C18,例如异十二烷、异十六烷和角鲨烷)和短醇类型的油例如辛基十二烷醇。
还优选的是所述(a)油选自烃油、C4-C22二元羧酸或三元羧酸和C1-C22醇的酯、和C4-C22一元羧酸、二元羧酸或三元羧酸与非糖C4-C26二羟基、C4-C15三羟基、四羟基或五羟基醇的酯和其混合物。
优选地,所述(a)油选自具有低于600 g/mol的分子量的酯油,例如肉豆蔻酸异丙酯、棕榈酸异丙酯、棕榈酸乙基己酯;人造甘油三酯例如癸酸辛酸甘油酯;烃油;和矿物油例如石蜡油,和其混合物。
相对于所述组合物的总重量,(a)油在根据本发明的组合物中的量为0.1至15重量%,优选0.5至10重量%,特别是1至5 重量%。
<水相>
根据本发明的O/W乳剂的水相包括至少一种(b)亲水UV过滤剂、(c)水和至少一种(d)乳化剂。相对于所述组合物的总重量,所述水相的量可以为1至99重量%,优选10至90重量%,并更优选20至80重量%,甚至更优选30至70重量%。
(亲水UV过滤剂)
根据本发明的组合物包含(b)至少一种亲水UV过滤剂。可以使用两种或更多种(b)亲水UV过滤剂的组合。因此,可以使用单一类型的亲水UV过滤剂或不同类型的亲水UV过滤剂的组合。
本文中的术语“UV”是指紫外线辐射并包括UV-B区域(波长260-320 nm)和UV-A区域(波长320-400)。因此,UV过滤剂是指具有UV-A和/或UV-B区域波长的紫外线辐射的滤光效果的任何材料。
术语“亲水UV过滤剂”理解为是指筛出UV辐射并能够以分子状态完全溶解在乳剂的水相中或能够以胶体形式(例如以胶束形式)分散在O/W乳剂的水相中的任何试剂。
用于本发明的一种或多种亲水UV过滤剂可以单独地或组合地形式在UV-A和/或UV-B区域,优选在UV-A和UV-B区域二者中有活性。因此,可以根据本发明使用的一种或多种亲水UV过滤剂包括能够吸收320至400 nm的UV辐射的亲水UV-A过滤剂、能够吸收280至320nm的UV辐射的亲水UV-B过滤剂和能够吸收280至400 nm的UV辐射的亲水UV-A和UV-B过滤剂。
所述亲水UV-A过滤剂包括,但不限于:
对苯二亚甲基二樟脑磺酸和其盐,例如由Chimex以名称“Mexoryl SX”制造的,
双苯并噁唑基衍生物,例如在专利EP 669 323和US 2,463,264中记载的,更特别是化合物苯基二苯并咪唑四磺酸二钠和其盐,由Haarmann and Reimer以商品名“Neo HeliopanAP”出售的。
亲水UV-B过滤剂包括,但不限于:
对氨基苯甲酸(PABA)衍生物,例如PABA、Glyceryl PABA和PEG-25 PABA和其盐,例如由BASF以名称“Uvinul P25”出售的,
苯基苯并咪唑磺酸和其盐,例如特别是由Merck以商品名“Eusolex 232”出售的,
阿魏酸和其盐,
水杨酸和其盐,
DEA甲氧基肉桂酸酯和其盐,
苄叉基樟脑磺酸和其盐,例如由Chimex以名称“Mexoryl SL”制造的,
樟脑苯甲烃铵甲基硫酸酯和其盐,例如由Chimex以名称“Mexoryl SO”制造的。
亲水UV-A和UV-B过滤剂包括但不限于:
二苯甲酮-4和其盐,例如由BASF以商品名“Uvinul MS40”出售的,
二苯甲酮-5和其盐,和
二苯甲酮-9和其盐。
可以使用的化合物的盐特别是选自碱金属盐,例如钠盐或钾盐;碱土金属盐,例如钙盐、镁盐或锶盐;金属盐,例如锌盐、铝盐、锰盐或铜盐;式NH4+的铵盐;季铵盐;有机胺盐,例如甲胺、二甲胺、三甲胺、三乙胺、乙胺、2-羟基乙胺、双(2-羟基乙基)胺或三(2-羟基乙基)胺的盐;赖氨酸或精氨酸盐。优选使用选自钠、钾、镁、锶、铜、锰或锌盐的盐。优先使用钠盐。
优选地,本发明的(b)亲水UV过滤剂选自至少一种亲水UV-A过滤剂和至少一种亲水UV-B过滤剂的组合。特别地,所述(b)亲水UV过滤剂为苯基苯并咪唑磺酸和对苯二亚甲基二樟脑磺酸的组合。
相对于所述组合物的总重量,该组合物中(b)一种或多种亲水UV过滤剂的量可以为1至40重量%,优选3至30重量%,更优选5至25重量%。
在所述(b)亲水UV过滤剂包含至少一种亲水UV-A过滤剂和至少一种亲水UV-B过滤剂的情况下,相对于该组合物的总重量,所述亲水UV-A过滤剂的量可以为0.5至15重量%,优选1至10重量%,更优选2至10重量%,亲水UV-B过滤剂的量可以为0.5至30重量%,优选1至25重量%,更优选5至20重量%。
(水)
根据本发明的组合物包含(c)水。
(c)水的量不受限,并且相对于该组合物的总重量,可以为50至99重量%,优选55至95重量%,更优选60至90重量%。
(乳化剂)
根据本发明的组合物包含至少一种选自两性、阴离子、阳离子或非离子乳化剂的乳化剂,其单独地或作为混合物使用。
能够在本发明组合物中使用的阴离子乳化剂的实例包括烷基硫酸盐、烷基醚硫酸盐、烷基磺酸盐、烷基醚磺酸盐、烷基苯氧基聚氧基亚乙基乙醇的硫酸盐、α-烯烃磺酸盐、β-烷氧基烯烃磺酸盐、烷基芳基磺酸盐、烷基碳酸盐、琥珀酰胺酸盐、磺基琥珀酸盐、肌氨酸盐、辛基酚聚醚或壬基酚聚醚磷酸盐、牛磺酸盐、脂肪牛磺酸盐(fatty tauride)、硫酸化单甘油酯、脂肪酸氨基聚氧基亚乙基硫酸盐、羟乙基磺酸盐、烷基苯磺酸、聚氧基亚乙基烷基醚硫酸、聚氧基亚乙基烷基醚羧酸和聚氧基亚乙基烷基酰胺醚羧酸和其盐。
在本发明组合物中可使用的非离子乳化剂的实例包括聚乙氧基化脂肪醇或聚甘油化脂肪醇,例如环氧乙烷与月桂醇的加合物,特别是包含9至50个氧基亚乙基单元的那些(月桂醇聚醚-9至月桂醇聚醚-50作为INCI名称),特别是月桂醇聚醚-9,例如由NikkoChemicals Co.以名称“NIKKOL BL-9EX”出售的产品;多元醇和包含例如8至24个碳原子的具有饱和或不饱和链的脂肪酸的酯和它们的氧基亚烷基化衍生物,即包含氧基亚乙基和/或氧基亚丙基单元,例如甘油和C8-C24脂肪酸的酯,和它们的氧基亚烷基化衍生物,特别是聚氧基亚乙基化甘油硬脂酸酯(单-、二-和/或三硬脂酸酯),例如PEG-20甘油基三异硬脂酸酯;糖和C8-C24脂肪酸的酯和它们的氧基亚烷基化衍生物,例如聚乙氧基化的C8-C24脂肪酸山梨醇酯,特别是Polysorbate 80,例如由Croda以名称“TWEEN 80”出售的产品;糖和C8-C24脂肪醇的醚,例如辛基/癸基葡糖苷,例如由SEPPIC以名称“ORAMIX CG 110”出售的产品;聚氧基亚乙基烷基醚;聚氧基亚乙基氧基亚丙基烷基醚;脂肪酸烷醇酰胺;烷基胺氧化物;烷基多糖苷,和其盐。
在本发明组合物中可使用的两性乳化剂的实例包括烷酰基酰胺丙基- N,N-二甲基甘氨酸甜菜碱、烷酰基酰胺丙基- N,N-二甲基-2-羟丙基磺基甜菜碱、烷基-N,N-二甲基甘氨酸甜菜碱、烷酰基酰胺丙基-N,N-二甲基丙基磺基甜菜碱、月桂基-N,N-二甲基-2-羟丙基磺基甜菜碱和其盐。
在本发明组合物中可使用的阳离子乳化剂的实例包括C8-C24长链二烷基二甲基铵盐、长链单烷基单苄基二甲基铵盐和长链单烷基三甲基铵盐,它们全部可以在其中具有酰胺或酯键,并且反荷离子优选为卤素原子例如氯和溴原子、硫酸根和含烷基的硫酸根残基,例如甲基-和乙基-磺酸,和其盐。胺型的阳离子表面活性剂包括具有长链C8-C24烷基的长链二烷基单甲基胺盐,其中可能具有酰胺或酯键,优选为盐酸盐、硫酸盐或磷酸盐形式,和其盐。
上述盐优选包括碱金属或碱土金属盐,例如钾、钠和镁盐,以及烷醇胺盐。
所述(d)乳化剂优选包含阴离子乳化剂,优选选自聚氧基亚乙基烷基醚羧酸,例如以INCI名称命名的月桂醇聚醚-3至月桂醇聚醚-17羧酸油醇聚醚-3至油醇聚醚-10羧酸,特别是月桂醇聚醚-5羧酸,例如由Kao Chemical Co以名称“Akypo RLM 45 CA”出售的产品。乳化剂还优选包含非离子乳化剂,优选选自糖和C8-C24脂肪醇的醚,例如辛基/癸基葡糖苷例如由SEPPIC以名称“ORAMIX CG 110”出售的产品。
相对于所述组合物的总重量,该组合物中的(d)一种或多种乳化剂的量可以为0.1至30重量%,优选0.5至20重量%,更优选1至10重量%。
(其他成分)
根据本发明的组合物还可以包含至少一种另外的成分。
根据本发明的组合物除了(b)亲水UV过滤剂之外可以还包含至少一种疏水UV过滤剂。
在本发明中可使用的疏水UV-A过滤剂可以包括氨基二苯甲酮化合物,例如2-(4-二乙基氨基-2-羟基苯甲酰基)苯甲酸正己酯;二苯甲酰基甲烷化合物,例如4-异丙基二苯甲酰基甲烷,由Merck以名称“Eusolex 8020”出售,和丁基甲氧基二苯甲酰基甲烷,由Merck以商品名“Eusolex 9020”出售;邻氨基苯甲酸化合物,例如由Symrise以名称“NEO HELIPANMA”出售的邻氨基苯甲酸薄荷酯;和4,4-二芳基丁二烯化合物,例如1,1 –二羧基(2,2'-二甲基丙基)-4,4-二苯基丁二烯和二苯基丁二烯丙二酸酯和丙二腈。
本发明中可使用的疏水UV-B过滤剂可以包括三嗪化合物,例如乙基己基三嗪酮,由BASF以名称“UVINUL T-150”出售;对氨基苯甲酸化合物,例如PABA (对氨基苯甲酸)乙酯;水杨酸化合物,例如胡莫柳酯,由Rona/EM Industries以名称“Eusolex HMS”出售;肉桂酸酯化合物,例如甲氧基肉桂酸乙基己酯,由BASF以名称“UVINUL MC 80”出售;β,β-二苯基丙烯酸酯化合物,例如奥克立林,由BASF以名称“UVINUL N539”出售;苄叉基樟脑化合物,例如3-苄叉基樟脑,由CHIMEX以名称“MEXORYL SD”出售;苯基苯并咪唑化合物,例如苯基苯并咪唑磺酸,由Merck以名称“Eusolex 232”出售;咪唑啉化合物,例如二甲氧基苄叉基二氧代咪唑啉丙酸乙基己酯,苄叉基丙二酸酯化合物例如含有苄叉基丙二酸酯基团的聚有机基硅氧烷,例如聚硅氧烷-15,由DSM NUTRITIONAL PRODUCTS以名称“Parsol SLX”出售;和部花青化合物。
本发明中可使用的疏水UV-A和UV-B过滤剂可以包括二苯甲酮化合物,例如由BASF以名称“UVINUL 400”出售的二苯甲酮-1;苯并三唑化合物,例如由BASF以名称“MexorylXL”出售的甲酚曲唑三硅氧烷;双-间苯二酚三嗪,例如由CIBA-GEIGY以名称“TINOSORB S”出售的双-乙基己基氧基苯基甲氧基苯基三嗪;和苯并噁唑化合物,例如由Sigma 3V以名称“Uvasorb K2A”出售的2,4-双[5-(1-二甲基丙基) 苯并噁唑-2-基(4-苯基)亚氨基]-6-(2-乙基己基)亚氨基-1,3,5-三嗪。
相对于所述组合物的总重量,该组合物中的一种或多种疏水UV过滤剂的量可以为0.01至20重量%,优选0.1至10重量%,更优选0.2至5重量%。
根据本发明的组合物可以包含至少一种化妆品可接受的亲水有机溶剂。根据本发明的组合物中可使用的亲水溶剂可以包括例如基本上直链或支链的具有1至8个碳原子的低级一元醇,例如乙醇、丙醇、丁醇、异丙醇和异丁醇;芳族醇,例如苄醇和苯基乙醇;多元醇或多元醇醚,例如丙二醇、二丙二醇、异戊二醇、丁二醇、甘油、山梨醇、乙二醇单甲醚、单乙醚和单丁醚、丙二醇醚,例如丙二醇单甲醚、二乙二醇烷基醚,例如二乙二醇单乙醚或单丁醚;聚乙二醇和它们的衍生物。
相对于所述组合物的总重量,该组合物中一种或多种亲水有机溶剂的量可以为0.1至40重量%,优选1至30重量%,更优选2至25重量%。
根据本发明的组合物可以包含至少一种胶凝剂。根据本发明的组合物中可使用的胶凝剂可以包括水溶性聚合物,例如高分子量交联的丙烯酸均聚物,和丙烯酸酯/C10-30烷基丙烯酸酯交联聚合物,例如Carbopol®和Pemulen®;阴离子丙烯酸酯聚合物,例如Salcare® AST,和阳离子丙烯酸酯聚合物例如Salcare® SC96;丙烯酰胺基丙基三甲基氯化铵/丙烯酰胺;羟乙基甲基丙烯酸酯聚合物,硬脂醇聚醚-10烯丙醚/丙烯酸酯共聚物;丙烯酸酯/ 山嵛醇聚醚-25甲基丙烯酸酯共聚物,已知为Aculyn® 28;甘油基聚甲基丙烯酸酯、丙烯酸酯/ 硬脂醇聚醚-20甲基丙烯酸酯共聚物;膨润土;树胶例如海藻酸盐、鹿角菜胶、金合欢胶、阿拉伯树胶、印度树胶、刺梧桐胶、黄蓍胶、瓜尔豆胶;瓜尔羟丙基三甲基氯化铵、黄原胶或吉兰糖胶;纤维素衍生物例如羧甲基纤维素钠、羟乙基纤维素、羟甲基羧乙基纤维素、羟甲基羧丙基纤维素、乙基纤维素、硫酸化纤维素、羟丙基纤维素、甲基纤维素、羟丙基甲基纤维素、微晶纤维素;琼脂;果胶;明胶;淀粉和其衍生物;壳聚糖和其衍生物,例如羟乙基壳聚糖;聚乙烯醇,PVM/MA共聚物、PVM/MA癸二烯交联聚合物、基于聚(环氧乙烷)的胶凝剂、卡波姆钠和其混合物。
相对于所述组合物的总重量,所述组合物中的一种或多种胶凝剂的量可以为0.1至20重量%,优选0.2至15重量%,更优选1至10重量%。
根据本发明的组合物可以包含化妆品中通常使用的其他添加剂。所述添加剂可以选自阴离子、阳离子、非离子或两性聚合物;阴离子、阳离子或两性表面活性剂;肽和其衍生物;蛋白水解产物;膨胀剂和渗透剂;用于(a)油的天然或合成增稠剂;中和剂,例如三乙醇胺;碱化剂,例如乙醇胺;酸化剂;无机或有机填料;抗氧化剂;防腐剂;杀菌剂;悬浮剂;螯合剂;遮光剂;染料;无机UV过滤剂;不可溶的UV过滤剂;维生素或维生素原;润湿剂;美黑化合物;抗皱纹活性成分;芳香剂;防腐剂;稳定剂;和其混合物。
相对于根据本发明的组合物的总重量,一种或多种其他成分的量不受限,但可以为0.1至30重量%。
本发明的组合物为具有纳米尺寸的油滴作为油相的O/W乳剂形式。所述组合物可以为化妆品组合物,优选用于角蛋白物质的化妆品组合物,更优选皮肤用化妆品组合物。所述组合物可以为洗液、乳状洗液、霜、膏、清液或泡沫,优选透明或半透明组合物的形式。
所述组合物优选展现出适合皮肤的pH并且其一般为3至8并优选4.5至7。
根据本发明的组合物的粘度不特别受限。所述粘度可以在25℃下采用粘度计或流变计(优选具有圆锥-平板或平板-平板几何形状)测量。优选地,所述组合物的粘度在25℃和21s-1下可以例如为3至5000 Pa.s。另外,所述组合物具有牛顿性质。
根据本发明的组合物优选为透明或半透明的。所述组合物的透明度可以通过采用例如浊度计(2100Q便携式, Hach Company)测量浊度确定。优选地,所述组合物具有大于0,优选大于10并低于200,优选低于150的浊度。
根据本发明的组合物可以通过例如在室温(25℃)下一起混合组分(a)至(d)和其他成分制备。一旦制成稠密的预混组合物,其为各相同性溶液,至少包含油、水和乳化剂,然后能够将其稀释以制备所述组合物。在这种情况下,稀释因子可以在5至40变化。
[美容用途]
根据本发明的组合物可以优选用作化妆品组合物,优选用作防晒化妆品组合物。具体地,根据本发明的组合物可以意欲施加至角蛋白物质例如皮肤、头皮和/或嘴唇优选皮肤上。因此,根据本发明的组合物可以用于对皮肤的美容方法。根据本发明的组合物可以进一步构成意欲吸收紫外光,和/或防护角蛋白物质(特别是人类的角蛋白物质)以防紫外线辐射的组合物。在本领域中熟知防护角蛋白物质以防紫外线辐射会导致抗衰老、抗皱纹并保湿。因此,本发明的组合物可以进一步构成意欲抗衰老、抗皱纹和/或保湿的组合物。
根据本发明的用于角蛋白物质例如皮肤的美容方法或美容用途至少包括施加根据本发明的组合物至角蛋白物质上的步骤。本发明还可以涉及一种防护角蛋白物质以防紫外线辐射的方法,包括施加根据本发明的组合物至角蛋白物质,以及一种吸收紫外光的方法,包括施加根据本发明的组合物并对角蛋白物质施以紫外光。这些方法可以定义为非治疗方法。
根据本发明的组合物可以用于局部防晒组合物,其为洗液、乳状洗液、霜、凝胶、膏、清液、泡沫或喷雾的形式,优选为凝胶或喷雾形式,更优选为透明或半透明的凝胶。
实施例
本发明将通过实施例以更详细的方式描述。然而,这些实施例不应该理解为限制本发明的范围。
[实施例1-2和对比例1-2]
(根据实施例1和2的组合物的制备)
通过在室温下采用顶部搅拌器温和混合各成分制备预混组合物1和2。所述成分和其组合物如下所示。各成分的量的数值全部基于“重量%”作为活性原料。
成分 预混组合物1 预混组合物2
月桂醇聚醚-5羧酸 20 20
辛基/癸基葡糖苷 10 10
甲氧基肉桂酸乙基己酯 10 -
棕榈酸乙基己酯 20 20
水 40 50。
通过在室温下温和混合上文分别获得的预混组合物1和2和含苯基苯并咪唑磺酸和对苯二亚甲基二樟脑磺酸作为亲水UV过滤剂和三乙醇胺作为中和剂的水制备根据实施例1和2的组合物。所获得的组合物总结在下表1中。在表1中示出的各成分的量的数值全部基于“重量%”作为活性原料。
(根据对比例1的组合物的制备)
以与上文实施例1和2相同的方式制备根据对比例1的组合物,除了使用以下预混组合物3。这个组合物不包括油,并因此只由水相构成。
成分 预混组合物3
月桂醇聚醚-5羧酸 20
辛基/癸基葡糖苷 10
甲氧基肉桂酸乙基己酯 -
棕榈酸乙基己酯 -
水 60。
(根据对比例2的组合物的制备)
通过在25℃下采用磁力搅拌器以2700 rpm剧烈混合各成分10 min制备表1中示出的根据对比例2的组合物。
表1
实施例1 | 实施例2 | 对比例1 | 对比例2 | |
月桂醇聚醚-5羧酸 | 2.0 | 2.0 | 2.0 | 2.0 |
辛基/癸基葡糖苷 | 1.0 | 1.0 | 1.0 | 1.0 |
甲氧基肉桂酸乙基己酯 | - | 1.0 | - | 1.0 |
棕榈酸乙基己酯 | 2.0 | 2.0 | - | 2.0 |
水 | 74.2 | 73.2 | 76.2 | 73.2 |
苯基苯并咪唑磺酸 | 3.5 | 3.5 | 3.5 | 3.5 |
对苯二亚甲基二樟脑磺酸 | 13.3 | 13.3 | 13.3 | 13.3 |
三乙醇胺 | 4 | 4 | 4 | 4 |
[评价]
如下评价根据实施例1-2和对比例1-2的组合物。
(液滴尺寸)
粒度分析仪(Vasco, Cordouan Technologies)用于测定根据实施例1-2和对比例2的O/W乳剂组合物的油相的液滴尺寸。连续水相的折射率和粘度在25℃下为1.33和0.89 cp。
(浊度)
在室温下通过使用浊度计(2100Q便携式, Hach Company)测量根据实施例1-2和对比例1-2的组合物的浊度。如下定义浊度值(NTU)的含义:
NTU
1-50: 透明
50-150: 半透明
>200: 浑浊或不透明。
根据对比例2的组合物由于其浊度过高而浊度不可测量(>1000 NTU)。
(SPF)
通过将根据实施例1-2和对比例1-2的组合物各20 mg以点状放置在板(Helio plateHD 6, PMMA, 50 mm x 50 mm)上,然后用手指在板上铺展它们3次制备SPF值测量的样品。由UV吸光度数据计算体外SPF值,所述UV吸光度采用紫外分光光度计(UV-2000S,Labsphere Inc)测试样品在250至450 nm波长下的漫透射率获得。
在表2中示出这些评价的结果。
表2
实施例1 | 实施例2 | 对比例1 | 对比例2 | |
油滴尺寸(nm) | 100 | 100 | - | 10000 |
浊度(NTU) | 90 | 110 | 1 | N.A. |
SPF值 | 10 | 11 | 7 | 8 |
N.A. = 不可用。
根据实施例1和2的组合物能够提供更好的UV防护效果。此外,这些组合物的外观为具有低浊度的半透明,它们在用于皮肤用化妆品组合物中是优选的。
另一方面,根据对比例1的组合物,其为由水相构成并且不含油相的均匀组合物,示出差的UV防护效果,即使其包括与根据实施例1和2的组合物同样量的亲水UV过滤剂。另外,根据对比例2的组合物,其包含具有10000 nm的数均直径的油相液滴,还示出差的UV防护效果。此外,根据对比例2的组合物具有这么高的浊度使得其不能采用浊度计测试。
因此,很明显只有根据本发明的组合物作为O/W乳剂能够产生改善的UV防护效果。
Claims (15)
1.一种具有分散在水相中的油相的O/W乳剂形式的组合物,其包含:
(a) 至少一种油;
(b) 至少一种亲水UV过滤剂;
(c) 水;和
(d) 至少一种乳化剂;
其中油相液滴的数均直径低于200 nm,并且相对于所述组合物的总重量,所述油的量为0.1至15重量%。
2.根据权利要求1所述的组合物,其中所述油相液滴的数均直径低于180 nm,优选低于160 nm,更优选低于140 nm。
3.根据权利要求1或2所述的组合物,其中所述油相液滴的数均直径大于1 nm,更优选大于5 nm,甚至更优选大于10 nm,特别是大于20 nm。
4.根据权利要求1至3任一项所述的组合物,其中所述油选自酯油,优选具有低于600g/mol的分子量,例如肉豆蔻酸异丙酯、棕榈酸异丙酯、棕榈酸乙基己酯;人造甘油三酯例如癸酸辛酸甘油酯;烃油;和矿物油例如石蜡油,和其混合物。
5.根据权利要求1至4任一项所述的组合物,其中相对于所述组合物的总重量,所述油的量为0.5至10重量%,特别是1至5重量%。
6.根据权利要求1至5任一项所述的组合物,其中所述亲水UV过滤剂选自至少一种亲水UV-A过滤剂和至少一种亲水UV-B过滤剂的组合。
7.根据权利要求1至6任一项所述的组合物,其中所述亲水UV过滤剂选自苯基苯并咪唑磺酸、对苯二亚甲基二樟脑磺酸和其混合物。
8.根据权利要求1至7任一项所述的组合物,其中相对于所述组合物的总重量,所述亲水UV过滤剂的量为1至40重量%,优选3至30重量%,更优选5至25重量%。
9.根据权利要求1至8任一项所述的组合物,其中相对于所述组合物的总重量,该组合物中水的量为50至99重量%,优选55至95重量%,更优选60至90重量%。
10.根据权利要求1至9任一项所述的组合物,其中所述组合物包含至少一种疏水UV过滤剂,相对于所述组合物的总重量,该疏水UV过滤剂的优选的量为0.1至10重量%,更优选0.2至5重量%。
11.根据权利要求1至10任一项所述的组合物,其中所述组合物进一步包含至少一种胶凝剂,相对于所述组合物的总重量,该胶凝剂的量优选为0.1至20重量%,优选0.2至15重量%,更优选1至10重量%。
12.根据权利要求1至11任一项所述的组合物,其中所述乳化剂选自非离子乳化剂,优选选自脂肪酸、脂肪醇、聚乙氧基化脂肪酸、聚甘油化脂肪酸和其混合物。
13.根据权利要求1至12任一项所述的组合物,其中相对于所述组合物的总重量,所述乳化剂的量为0.1至30重量%,优选0.5至20重量%,更优选1至10重量%。
14.根据权利要求1至13任一项所述的组合物,其中所述组合物为化妆品组合物,优选用于角蛋白物质的化妆品组合物,更优选皮肤用化妆品组合物。
15.一种防护角蛋白物质免受紫外线辐射的方法,其包括施加根据权利要求1至14任一项的组合物至角蛋白物质上。
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EP (1) | EP3393600B1 (zh) |
JP (1) | JP7009046B2 (zh) |
CN (2) | CN108367176A (zh) |
WO (1) | WO2017110153A1 (zh) |
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CN115697291A (zh) * | 2020-06-02 | 2023-02-03 | 联合利华知识产权控股有限公司 | 高spf皮肤清洁组合物 |
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Also Published As
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EP3393600C0 (en) | 2024-02-21 |
EP3393600B1 (en) | 2024-02-21 |
JP7009046B2 (ja) | 2022-01-25 |
EP3393600A1 (en) | 2018-10-31 |
WO2017110153A1 (en) | 2017-06-29 |
CN116889525A (zh) | 2023-10-17 |
JP2017114798A (ja) | 2017-06-29 |
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