CN100343377C - O/w乳化剂、o/w乳液及其用途 - Google Patents
O/w乳化剂、o/w乳液及其用途 Download PDFInfo
- Publication number
- CN100343377C CN100343377C CNB2004800177167A CN200480017716A CN100343377C CN 100343377 C CN100343377 C CN 100343377C CN B2004800177167 A CNB2004800177167 A CN B2004800177167A CN 200480017716 A CN200480017716 A CN 200480017716A CN 100343377 C CN100343377 C CN 100343377C
- Authority
- CN
- China
- Prior art keywords
- emulsifying agent
- acid
- citric acid
- weight
- oleic acid
- 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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- 239000007764 o/w emulsion Substances 0.000 title abstract 2
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Abstract
本发明涉及O/W乳化剂、由该乳化剂制备的O/W乳液及其应用。根据本发明,O/W乳化剂包含(a)70-90重量%的油酸柠檬酸甘油酯和(b)10-30重量%的粘度为1-10,000mPas的粘度调节剂。
Description
本发明涉及O/W乳化剂、由该乳化剂制备的O/W乳液及其用途。
作为人体最大的器官,人的皮肤执行许多重要的功能。成年人皮肤平均表面积大约2m2,皮肤作为防护和感觉器官具有重要的作用。该器官的任务是传递和抵御机械、热、光化学、化学和生物刺激。它还在人体新陈代谢中作为调节器官和靶器官起着重要作用。
化妆品皮肤护理主要涉及加强或修复皮肤的天然功能,如抵御环境影响(例如灰尘、化学药品、微生物)和防止身体物质(如水、天然脂肪、电解质)丧失的屏障以及当它受损时支持其角质层的自然再生能力。如果皮肤的屏障性能被破坏,就会导致有毒或致敏性物质更大程度上的再吸收或导致微生物的侵袭,引起毒性或过敏性皮肤反应。皮肤护理的另一目的是补偿由日常清洗所引起的皮肤中脂肪和水分的丧失。这在自然再生能力不足的情况下尤其重要。皮肤护理产品还应该抵御环境影响、特别是阳光和风的影响,并延缓皮肤老化。
医用局部组合物一般包含一种或多种有效浓度的药物。简便起见,为了清楚地区分化妆品和医疗的用量以及得到相应产品,参考德意志联邦共和国的法律规定(例如,德国化妆品法令、食品法和药品法)。
乳液理解为包含两种液体的非均相体系,所述两种液体不能混溶或相互仅具有有限的混溶性,传统上称之为相。在乳液中,两种液体之一以极细微滴的形式分散在另一种液体中。如果这两种液体是水和油并且油滴微细分散在水中,那么它就是水包油型乳液(O/W乳液,例如奶)。O/W乳液的基本特征由水决定。在油包水型乳液中(W/O乳液,例如奶油),原理相反,基本特征由油决定。本领域技术人员自然知道配制用于化妆品或皮肤病应用的稳定O/W制剂的多种可能,例如以在室温至皮肤温度的范围内可以涂开的乳霜和软膏的形式或者是作为在该温度范围内更易流动的洗液、乳剂。这些体系通常含有乳化剂。
乳化剂是制备和稳定乳液的辅助物质,通常是油状至蜡状形式,还可为粉状物质。为了使得乳液长期稳定,需要乳化剂来抑制或延迟两相例如油和水的分离,直至乳液完成它的使命才达到热力学稳定的最终状态。
乳化剂降低两相之间的界面张力和减少界面活性并且稳定所形成的乳液。乳化剂通过界面膜和通过形成空间或电屏障来防止乳化颗粒流到一起(聚结),从而使所形成的乳液稳定。界面膜的弹性和粘度是乳液稳定中的重要因素,并受乳化剂的强烈影响。稳定已经形成的乳液是乳化剂最重要的性能,并且比促进各相的初级分布更为重要,因为相的初级分布可以采用足够的机械辅助来实现。乳化剂最重要的要求如下:
a)乳化剂必须集中在相间的边界层处。为此,它必须具有界面活性或表面活性,即减少不能混溶相之间的界面张力。
b)乳化剂还必须使颗粒带电,使得它们相互排斥或者在颗粒周围形成稳定的、通常是高粘度的或甚至是固态的保护层。
这些特性本身对许多应用来说是足够的。但是为了制备在特别长时期内稳定的乳液,必须防止已分散颗粒分层或沉降并且还要进一步减少它们的聚结趋势。这通过增加外相的粘度和/或形成保护性粘滞结构例如液晶或凝胶相来实现。在这种情况下,除了乳化剂本身,乳化剂体系还必须含有附加组分,该附加组分已知为辅助乳化剂、稳定剂或者根据活性机理而作为稠度调节剂(consistency modifier)或保护性胶体。
为了使化合物有效地成为乳化剂,它们必须具有独特的分子结构。这种化合物的结构特征是它们的两亲分子结构。这种化合物的分子具有至少一个亲高极性物质的基团(极性基团)和至少一个亲非极性物质的基团(非极性基团)。极性基团是其电子分布赋予分子相当大的偶极矩的官能团。这种基团决定了对极性液体的亲合力,尤其是对水的亲合力,以及化合物的亲水特性。因此,极性官能团也称为亲水基。
另一方面,非极性基团是分子中其电子分布对偶极矩没有显著贡献的那部分。非极性基团决定了对非极性液体的亲合力,尤其是低极性有机溶剂,因此这种官能团也称为亲油基。在分子中亲水基和亲油基的结合存在使得乳化剂能同时与亲水相和亲油相作用。这导致了在界面上的定向,这种定向是该化合物的界面活性的前提。
乳化剂表征的决定性特征是分子中亲水和亲油构成的比率,表示为亲水-亲油平衡(HLB体系),有许多实验和理论数学方法来确定该特征,所有的这些方法均基于确定分子组成中亲水基对亲油基的比率。具有高HLB值的乳化剂产生O/W乳液,具有低HLB值的乳液优选形成W/O乳液。
但是,从现有技术中已知仅有少数O/W乳化剂形成这种低粘度且例如可以喷射的O/W乳液。它们大多含有聚乙二醇。另外,现有技术的低粘度O/W乳液通常具有不稳定、应用限于狭小范围或成分选择严格等缺点。因此,目前在市场上还没有低粘度、可冷处理的O/W乳液,例如充分稳定的高极性油,所述高极性油例如其他常用于商品中的植物油。根据现有技术,配制具有低粘度并表现出如市售产品所需的贮存稳定性的O/W乳液存在巨大的困难。因此这种配方的选择受到极大的限制。但是,该配方会给消费者提供前所未知的化妆好处。
从EP 1 049 452中已知一种低粘度的化妆或皮肤病用O/W乳液,其含有一种或多种部分中和的饱和脂肪酸单酸甘油酯和/或二酸甘油酯与柠檬酸的酯和一种或多种选自包含具有12-40个碳原子的支链和非支链烷基醇的脂肪醇。
US 2003/0012801公开了一种特殊的乳液,其含有一种或多种部分中和的饱和脂肪酸单酸甘油酯和/或二酸甘油酯与柠檬酸的酯、环糊精和类维生素A。
从WO 99/62468中已知一种毛发护理剂,除了特定的季戊四醇酯油外,其还含有第二油组分。其中作为第二油组分的实例,要求保护通式中具有1-30个碳原子的不饱和烷基的柠檬酸酯油。没有列出这类物质的具体化合物。
本发明的目的具体而言是提供克服现有技术缺点的O/W乳化剂。
通过具有权利要求1中所述特征和与其相关的用途的O/W乳化剂来实现该目的。
根据本发明,O/W乳化剂含有
(a)70-90重量%的油酸柠檬酸甘油酯(glyceryl oleate citrate)和
(b)10-30重量%的粘度为1-10,000mPas的粘度调节剂。
根据本发明的O/W乳化剂主要特征如下:
-通过热/热、热/冷和尤其是冷/冷处理,制备O/W乳液的能力;
-甚至在例如小于2%的低浓度下使用时,形成热稳定乳液;
-多方面的适用性,适用于较高粘度的乳霜、中粘度的乳剂和洗液,和适用于低粘度的可喷射洗液;
-与已知的O/W乳化剂相比,在乳液体系中的固体分散性改善;
-与已知的O/W乳化剂相比,所混合固体的分散性更大;
-以此设计的配方中具有基本与pH无关的特性;
-能够用于具有极性和非极性油的配方中;
-与水凝胶前体和水胶体的相容性;
-没有聚乙二醇;
-能够与辅助乳化剂和稠度调节剂组分组合;和
-能够与UV-A和UV-B滤光剂组合以改善防晒产品的水附着性。
用该乳化剂制备的O/W乳液主要特征如下:
-低能耗生产:水相或者甚至是水和油相(具有适当选择的其它组分)均可冷处理,
-良好的粘度稳定性,
-高pH稳定性,
-良好的温度稳定性,
-具有光滑表面的非常微细和均匀的乳液结构,
-直接加入极性和非极性油,其中优选可以经水相或油相加入O/W乳化剂,和
-有关采购和贮存用于洗液和乳霜的单一O/W乳化剂的商业和运销优势。
油酸柠檬酸甘油酯优选是单油酸和/或二油酸甘油酯与柠檬酸的酯,其中具体是可以通过柠檬酸与单油酸甘油酯以0.3∶1-1.5∶1,优选0.7∶1-1.2∶1的摩尔比进行酯化反应得到该酯。具体地,具有上述特性的油酸柠檬酸甘油酯改善O/W乳化剂和基于它的乳液的稳定性。
还优选油酸柠檬酸甘油酯通过中和而具有5-8的pH值,特别是5.8-6.2,尤其是6.0(每种情况下均在10%的1∶1水/甲醇混合物中测量)。尤其优选完全中和的酯。例如氢氧化钠适合用于中和。
根据本发明的O/W乳化剂中的油酸柠檬酸甘油酯优选具有9-15的HLB值,尤其是11-13。
还优选O/W乳化剂中的油酸柠檬酸甘油酯即组分(a)的比例为75-85重量%,尤其是80重量%。
经过上述改进,O/W乳化剂的长期稳定性可明显改善而且可以支持稳定O/W乳液的生产。
还优选粘度调节剂的粘度为1-1000mPas,尤其优选1-100mPas。通过符合特定的范围限制,可以调节O/W乳化剂的流变性,以使其在室温下自由流动。这允许O/W乳液进行冷处理。所述粘度值在每种情况下均对25℃有效并利用配有适用于特定粘度范围的转子(spindle)的布氏粘度计(Brookfield viscometer)(RV型)在合适的测量转速下测得。测定根据本发明的纯粘度调节剂的粘度时,用于测量动态粘度的其它合适的粘度计可用来替代指定的粘度计,这是由于一般来说它们提供的结果仅略微不同。
粘度调节剂优选天然油,尤其是辛酸/癸酸三酸甘油酯(CAS登记号65381-09-1)。后一种粘度调节剂是混合物的形式且包含在三酸甘油酯中的脂肪酸优选具有含量为50-72重量%的辛酸和含量为26-45重量%的癸酸。选择辛酸/癸酸三酸甘油酯本身作为粘度调节剂对O/W乳化剂和由其制备的乳液的稳定性具有令人惊讶的积极影响。辛酸/癸酸三酸甘油酯例如可以从Henkel KGaA,Germany获得,商品名为Myritol或从Symrise GmbH & Co.KG,Germany获得,商品名为Neutral Oil(2/950160)。
乳液形式的化妆和皮肤病用组合物优选含有占整个配方比例为2-5重量%的根据本发明的O/W乳化剂。如果在上述类型的组合物中使用辅助乳化剂,那么在整个配方中它们的含量优选为1-10重量%。任选存在的任意稳定剂在整个配方中的含量优选为0.1-5重量%。
已经发现,乳液中的油酸柠檬酸甘油酯或O/W乳化剂单独或者与其它化妆性辅助物质一起具有下列效果:
提高UV滤光剂的防晒系数(UVA和/或UVB防护);稳定UV滤光剂(改善耐光性);改善固体UV滤光剂的溶解性和/或悬浮性;增加防晒产品的耐水性;支持凝胶网络结构的形成;增加活性物质例如抗氧化剂、防腐剂、亮肤剂和晒黑剂、芳香油、螯合剂的有效性;增加活性成分在皮肤和/或毛发上的牢固性;改善化妆用油(植物油、矿物油、柔润剂)、活性成分、维生素、芳香油和精油在皮肤上的分布;支持相斥的活性成分均匀分布;有助于水相中防腐剂体系的最佳分布;支持皮肤的屏障功能;减少无机UV滤光剂(二氧化钛、氧化锌)和彩色颜料的聚结率;支持止汗剂产品中铝盐的分布;与醇以及乙醇相容;作为主或辅助乳化剂改善乳液的稳定性。
配方实例:护肤霜(O/W)、爽身水、防晒霜(O/W)、防晒乳(O/W)、喷雾防晒乳(O/W)、敏感香液滚珠(sensitive balsam roll-on)和霜(O/W)、喷雾祛臭液、止汗液、护发素(hair treatment rinse)、男士发胶蜡(hair gel wax)、发乳、彩色日霜、睫毛膏、湿拭纸用调湿液。
油酸柠檬酸甘油酯或O/W乳化剂可以与光稳定剂一起调配。合适的光稳定剂为例如有机UV吸收剂,该有机UV吸收剂来自4-氨基苯甲酸及其衍生物、水杨酸衍生物、二苯甲酮衍生物、二苯甲酰甲烷衍生物、二苯基丙烯酸酯、3-咪唑-4-基丙烯酸及其酯、苯并呋喃衍生物、丙二酸亚苄酯衍生物、聚合物UV吸收剂(含有一种或多种有机硅基团)、肉桂酸衍生物、樟脑衍生物、三苯胺基-s-三嗪衍生物、2-羟苯基苯并三唑衍生物、2-苯基苯并咪唑-5-磺酸及其盐、邻氨基苯甲酸基酯、苯并三唑衍生物。
油酸柠檬酸甘油酯或O/W乳化剂还可以混入含有颜料优选微粒颜料的化妆和/或皮肤病用制剂中。它们可以是有机或者无机颜料。优选的有机颜料是2,2’-亚甲基二-[6-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)苯酚](TinosorbM)。基于难溶或不溶于水的金属氧化物和/或其它金属化合物的无机颜料或微细颜料具体是钛的氧化物(TiO2)、锌的氧化物(ZnO)、铁的氧化物(例如Fe2O3)、锆的氧化物(ZrO2)、硅的氧化物(SiO2)、锰的氧化物(例如MnO)、铝的氧化物(Al2O3)、铈的氧化物(例如Ce2O3)、相应金属的混合氧化物(mixed oxide)和这些氧化物的混合物。这些颜料是X-射线无定形的或者是非X-射线无定形的。尤其优选基于TiO2和ZnO的微粒颜料。
油酸柠檬酸甘油酯或O/W乳化剂还可以混入到具有传统组成的化妆和/或皮肤病用制剂中,并用于化妆和/或皮肤病遮光,还用于皮肤和/或毛发的修护、调理和清洁和在彩妆中作为粉底产品。根据它们的结构,这种制剂可因此用作护肤霜、洁肤奶、防晒液、皮肤养料、日或晚霜等。这种制剂因此可以采用诸如乳液、洗液、乳剂、霜、水分散凝胶、香膏、喷雾、泡沫、香波、护发产品、毛发调理剂、滚珠、棒或粉底(make-up)的形式。
任选可以并有利的是,使用这种制剂作为药用配方的基础。具体优选为护肤或粉底产品形式的这种化妆和皮肤病用制剂。
使用时,以化妆品的传统方式,将足够量的作为实例提及的化妆和皮肤病用制剂施用于皮肤和/或毛发。
脂相可有利地选自下列物质:
矿物油、矿物蜡;天然油例如蓖麻油;脂肪、蜡和其它天然和合成的脂肪体,优选低C数醇例如异丙醇、丙二醇或丙三醇的脂肪酸酯,或脂肪醇与低C数烷基酸或脂肪酸的酯;烷基苯甲酸酯;硅油例如二甲基聚硅氧烷、二乙基聚硅氧烷、二苯基聚硅氧烷及其混合形式。
在本公开内容意义内的乳液、油凝胶或水分散体或脂分散体的脂相有利地选自包含具有3-30个C原子链长的饱和和/或不饱和、支链和/或非支链的链烷羧酸和具有3-30个C原子链长的饱和和/或不饱和、支链和/或非支链的醇的酯,选自包含芳族羧酸和具有3-30个C原子链长的饱和和/或不饱和、支链和/或非支链的醇的酯。因而这种酯油可以有利地选自包含异丙基肉豆蔻酸酯、棕榈酸酯、硬脂酸酯、油酸酯、硬脂酸正丁酯、月桂酸正己酯、油酸正癸脂、硬脂酸异辛酯、硬脂酸异壬酯、异壬酸异壬酯、2-乙基己基棕榈酸酯、月桂酸乙基己基酯、2-己基癸基硬脂酸酯、2-辛基十二烷基棕榈酸酯、油酸油醇酯、芥酸油醇酯、瓢儿菜醇油酸酯(erucyl oleate)以及所述酯的合成、半合成和天然的混合物,例如霍霍巴油、2-乙基己酸-2-乙基己酯、2-乙基己酸十六/十八烷酯、己二酸二异丙酯、三异壬酸甘油酯的集合。
脂相还可有利地选自包含支链和非支链烃和烃蜡、硅油、二烷基醚,选自饱和或不饱和、支链或非支链醇,和三脂肪酸甘油酯,尤其是具有8-24个、特别是12-18个C原子链长的饱和和/或不饱和、支链和/或非支链的链烷羧酸的三酸甘油酯的集合。例如,三脂肪酸甘油酯可以有利地选自包含合成、半合成和天然油的油,例如橄榄油、向日葵油、大豆油、花生油、菜籽油、杏仁油、棕榈油、椰子油、棕榈仁油等。
在本发明内容中,还可以有利地使用所述油和蜡成分的任意混合物。
在本发明内容中,有利的是使用环甲基硅氧烷(八甲基环四硅氧烷)作为所用的硅油。但是,也可以类似有利地使用其它硅油,例如六甲基环三硅氧烷、聚二甲基硅氧烷、聚(甲基苯基硅氧烷)。
环甲基硅氧烷和异壬酸异十三烷酯的混合物、环甲基硅氧烷和2-乙基己基异硬脂酸酯的混合物也特别有利。
有利的是本发明内容中的制剂的水相任选地含有水溶性植物提取物、醇、二醇或多元醇(低烷基)及其醚,优选乙醇、异丙醇、丙二醇、甘油、乙二醇单乙基或单丁基醚、丙二醇单甲基、单乙基或单丁基醚、二乙二醇单甲基或单乙基醚和类似产品、以及醇(低烷基)例如乙醇、1,2-丙二醇、甘油和尤其是一种或多种增稠剂,所述增稠剂可有利地选自二氧化硅、硅酸铝、多糖或其衍生物例如透明质酸、黄原胶、羟丙甲基纤维素的集合,特别有利地选自聚丙烯酸酯,优选选自所谓卡波姆(carbopol)例如卡波姆980、981、1382、2984、5984的聚丙烯酸酯,单独或者组合使用。
本发明内容中的化妆和皮肤病用制剂可以含有化妆用辅助物质,如传统上用于所述制剂的物质,例如防腐剂、抗氧化剂、维生素、杀菌剂、香料、防止起泡的物质、染料、具有着色效果的颜料、增稠剂、表面活性剂、柔润剂、乳化剂、湿润和/或保湿物质、增湿剂、脂肪、油、蜡、植物提取物或化妆和皮肤病用配方中的其它常规成分例如醇、低烷基醇、多醇、低烷基多醇、聚合物、泡沫稳定剂、配位剂、电解质、有机溶剂、推进剂气体、硅氧烷或硅氧烷衍生物。
根据具体产品的特性,本领域技术人员可容易地确定在每种情况下要使用的化妆或皮肤病用辅助物质和载体以及香料的量。
通常优选额外含量的抗氧化剂。所有适合或通常可用于化妆和/或皮肤病应用的抗氧化剂均可用作有利的抗氧化剂。
相对于制剂的总重量,制剂中抗氧化剂(一种或多种化合物)的量优选为0.001-30重量%,特别优选0.05-20重量%,尤其是1-10重量%。
抗氧化剂有利地选自:氨基酸(例如甘氨酸、组氨酸、3,4-二羟苯丙氨酸、酪氨酸、色氨酸)及其衍生物、咪唑(例如咪唑丙烯酸)及其衍生物、肽(例如D,L-肌肽、D-肌肽、L-肌肽、鹅肌肽)及其衍生物、类胡萝卜素、胡萝卜素(例如α-胡萝卜素、β-胡萝卜素、番茄红素)及其衍生物、绿原酸及其衍生物、硫辛酸及其衍生物、金硫葡糖、丙硫尿嘧啶和其它硫醇(例如硫氧环蛋白(thioredoxine)、谷胱甘肽、半胱氨酸、胱氨酸、胱胺及其糖基和N-酰基衍生物或其烷基酯)及其盐、硫代二丙酸二月桂酯、硫代二丙酸双十八烷酯、硫代二丙酸及其衍生物和酚苄胺的酚酸酰胺(例如高香草酸、3,4-二羟基苯乙酸、阿魏酸、芥子酸、咖啡酸、二氢阿魏酸、二氢咖啡酸、香草扁桃酸(vanillomandelic acid)、或者3,4-二羟基苄基、2,3,4-三羟基苄基或3,4,5-三羟基苄胺的3,4-二羟基扁桃酸酰胺)、邻苯二酚肟或邻苯二酚肟醚(例如3,4-二羟基苯甲醛肟或3,4-二羟基苯甲醛-O-乙基肟)、2-肼基-1,3-噻唑和衍生物、以及(金属)螯合剂(例如2-羟基脂肪酸、植酸、乳铁蛋白)、腐殖酸、胆汁酸、胆汁提取物、胆红素、胆绿素、叶酸及其衍生物、泛醌和泛醌醇及其衍生物、维生素C及其衍生物(例如棕榈酸抗坏血酸酯、磷酸抗坏血酸酯盐镁、乙酸抗坏血酸酯)、生育酚和衍生物(例如维生素E乙酸酯)、维生素A和衍生物(维生素A棕榈酸酯)、芸香亭酸及其衍生物、类黄酮(例如栎精、α-糖基芸香苷)及其衍生物、酚酸(例如没食子酸、阿魏酸)及其衍生物(例如没食子酸丙酯、乙酯、辛酯)、亚糠基葡萄糖醇、二丁基羟基甲苯、丁基羟基苯甲醚、尿酸及其衍生物、甘露糖及其衍生物、锌及其衍生物(例如ZnO、ZnSO4)、硒及其衍生物(例如硒代蛋氨酸)、茋及其衍生物(例如氧化茋、白藜芦醇)。
同样有利的抗氧化剂描述于EP-A 900781、EP-A 1 029 849、EP-A 1 066 821、WO-A 01/43712、WO-A 01/70176、WO-A 01/98235中或于WO-A 01/98258中。
如果维生素E和/或其衍生物用作抗氧化剂,则相对于配方的总重量,它们的浓度有利地选自0.001-10重量%的范围。
如果维生素A或维生素A衍生物或者胡萝卜素或其衍生物用作抗氧化剂,相对于配方的总重量,它们的浓度有利地选自0.001-10重量%的范围。
下面通过实施例提供十个配方,其中根据本发明的O/W乳化剂被称为DracorinGOC。Dracorin GOC含有70-90重量%的油酸柠檬酸甘油酯和10-30重量%的三辛酸/癸酸甘油酯。相对于在三辛酸/癸酸甘油酯中含有的脂肪酸,辛酸的含量为50-65重量%,癸酸的含量为35-45重量%。该三辛酸/癸酸甘油酯具有大约30mPas的粘度。
在10%的1∶1水/甲醇混合物中测量时,该O/W乳化剂具有大约6的pH值和大约12的HLB值。
实施例(1):可冷处理的爽身水(O/W),实施例(2)和(4):防晒乳(O/W),实施例(3),防晒面霜(O/W);
名称 | INCI名称 | (1) | (2) | (3) | (4) | |
A | Abil 100 | 聚二甲基硅氧烷 | 0.3 | |||
Cetiol OE | 二辛酰基醚 | 5.0 | 1.5 | |||
Copherol 1250 | 生育酚乙酸酯 | 0.5 | 0.5 | 0.5 | ||
Corapan TQ | 2,6-萘二甲酸二乙基己酯 | 5.0 | 5.0 | 2.5 | ||
Cutina FS 45 | 棕榈酸(和)硬脂酸 | 2.0 | ||||
Cutina MD | 硬脂酸甘油酯 | 1.0 | 2.0 | |||
DC 345 | 环甲基硅氧烷 | 2.0 | ||||
Dracorin GOC2/008580 | 油酸柠檬酸甘油酯(和)三辛酸/癸酸甘油酯 | 2.0 | 4.0 | 5.0 | 4.0 | |
Dragoxat EH 2/044115 | 2-乙基己酸-2-乙基己酯 | 1.5 | ||||
Edeta BD | 乙二胺四乙酸二钠 | 0.1 | ||||
Hoatacerin DGMS | 硬脂酸聚甘油(2)酯 | 4.0 | ||||
棕榈酸异丙酯 | 棕榈酸异丙酯 | 7.0 | ||||
Keltrol T | 黄原酸胶 | 0.4 | ||||
Lanette 16 | 十六醇 | 1.5 | ||||
Lanette O | 十六/十八醇 | 1.0 | ||||
Miglyol 812 | 三辛酸/癸酸甘油酯 | 5.0 |
Neo Heliopan 357 | 丁基甲氧基二苯甲酰甲烷 | 0.8 | 2.0 | 1.5 | ||
Neo Heliopan HMS | 水杨酸高酯 | 5.0 | 8.0 | |||
Neo Heliopan MBC | 4-甲基亚苄基樟脑 | 3.0 | ||||
Neo Heliopan OS | 水杨酸乙基己酯 | 5.0 | ||||
PCL液100 2/066240 | 2-乙基己酸十六/十八烷酯 | 8.0 | 5.0 | |||
Prisorine 3505 | 异硬脂酸 | 0.5 | ||||
SF 1214 | 环戊硅氧烷(和)聚二甲基硅氧烷 | 1.0 | ||||
Solbrol P | 对羟基苯甲酸丙酯 | 0.1 | 0.1 | 0.1 | ||
Tegosoft TN | C12-15烷基苯甲酸酯 | 4.0 | ||||
Triton BD | EDTA | 0.1 | ||||
氧化锌中性H&R | 氧化锌 | 7.0 | ||||
B | 1,3-丁二醇 | 丁二醇 | 3.0 | |||
Carbopol 1382 | 卡波姆(carbomer) | 0.2 | ||||
Carbopol ETD 2050 | 卡波姆 | 0.2 | 0.3 | |||
99%甘油 | 甘油 | 3.0 | 4.0 | |||
Karion F | 山梨醇 | 5.0 | ||||
Keltrol T | 黄原酸胶 | 0.2 | 0.5 | |||
Lanette E | 十六/十八烷基硫酸钠 | 0.75 | ||||
氢氧化钠溶液,10%水溶液 | 氢氧化钠 | 0.2 | 2.5 | |||
Dragocid液2/060140 | 苯氧基乙醇,甲基-、乙基-、丁基-、丙基-、异丁基对羟基苯甲酸酯 | 0.8 |
Neo HeliopanAP | 苯基二苯并咪唑四磺酸二钠 | 2.2 | ||||
Neo HeliopanAP,NaOH中和的10%溶液 | 苯基二苯并咪唑四磺酸二钠 | 22.0 | 25.0 | |||
苯氧基乙醇 | 苯氧基乙醇 | 0.7 | 0.7 | 0.7 | ||
Solbrol M | 对羟基苯甲酸甲酯 | 0.2 | 0.2 | 0.2 | ||
蒸馏水 | 水(液态) | 74.5 | 43.5 | 36.9 | 50.55 | |
C | 氢氧化钠溶液,10%水溶液 | 氢氧化钠 | 2.4 | 3.5 | ||
芳香油 | 香料(parfum) | 0.5 | ||||
D | 芳香油 | 香料(parfum) | 0.3 | 0.3 | 0.3 | |
天然α-没药醇 | 没药醇 | 0.1 | 0.1 | |||
(所有值%) | 总量 | 100 | 100 | 100 | 100 |
实施例(1)-制备方法(所有步骤均在环境温度下进行):分别称出A/C和B部分的重量。利用Ultra Turrax在Carbopol中混合,然后中和。利用Ultra Turrax将B部分加入到A/C部分中,然后乳化。
实施例(2)、(3)-制备方法:
加热A部分至大约85℃。对B部分,称出没有Carbopol和Keltrol的原料的重量。利用Ultra Turrax在Carbopol和Keltrol中混合。加热至大约85℃。将B部分加入到A部分中。立即将C部分加入到A/B中,然后在高温下均匀化(Ultra Turrax)。使其冷却,同时搅拌,加入D部分并搅拌。
实施例(4)-制备方法:
加热A部分至大约85℃(没有Keltrol和氧化锌)。用Ultra Turrax将Keltrol和氧化锌混合到热脂相中。加热B部分至大约85℃。将B部分加入到A部分中。冷却至60℃同时搅拌并均匀化(Ultra Turrax)。然后使其冷却至室温同时搅拌。加入C部分并均匀化。
实施例(5):男士用发胶蜡DGHST 0086/01;实施例(6):发乳(O/W)DCHST0087/00;实施例(7):含有Dragoderm的护发素(O/W)DLHCR 0088/00;实施例(8):敏感香液滚珠(O/W)DRDEO 0089/00;实施例(9):湿拭纸用调湿液(O/W)DDTSS0091/00;实施例(10):皮肤调理霜(O/W)DCSKN 0092/00
原料 | INCI名称 | (5) | (6) | (7) | (8) | (9) | (10) | |
A | Abil 350 | 聚二甲基硅氧烷 | 1.5 | |||||
Abil B 8852 | 含聚氧乙烯或聚氧丙烯侧链的聚二甲基硅氧烷 | 1.0 | ||||||
Cetiol HE | PEG-7椰油酸甘油酯 | 1.0 | ||||||
Cutina HR Plv. | 氢化蓖麻油 | 0.5 | ||||||
Dracorin GMS2/008474 | 硬脂酸甘油酯 | 3.0 | 2.0 | 1.0 | ||||
Drago-Oat-Active2/060900 | 水(液态)、丁二醇、燕麦仁提取物 | 1.0 | ||||||
Dragoxat EH2/044115 | 乙基己酸乙基己酯 | 7.0 | ||||||
Dracorin GOC2/008580 | 油酸柠檬酸甘油酯(和)三辛酸/癸酸甘油酯 | 5.0 | 3.0 | 3.0 | 4.0 | |||
Eumulgin B2 | 十六/十八醇聚氧乙烯(20)醚 | 2.0 | ||||||
Farnesol2/027040 | 法呢醇 | 0.1 | ||||||
Fitoderm | 植物squamane | 3.0 | ||||||
Lanette 16 | 十六醇 | 2.5 | 4.0 | |||||
Lanette O | 十六/十八醇 | 4.0 | 1.5 | |||||
助溶液2/014170 | PEG-40氢化蓖麻油、十三烷基聚氧乙烯(9)醚、水(液态) | 15.0 | ||||||
Neo-Dragocid液2/060110 | 三甘醇、咪唑烷基脲、对羟基苯甲酸甲酯、对羟基苯甲酸丙酯、脱氢乙酸 | 0.4 |
中性油2/950161 | 三辛酸/癸酸甘油酯 | 10.0 | ||||||
PCL液100 2/066240 | 乙基己酸十六/十八烷酯 | 5.0 | 2.0 | 0.5 | 1 | |||
Pemulen TR-2 | 丙烯酸酯/C10-30烷基丙烯酸酯交联共聚物 | 0.2 | ||||||
Rewoderm LI520-70 | PEG-200氢化棕榈酸甘油酯 | 1.5 | ||||||
Varisoft BT 85 | 二十二烷基三甲基氯化铵 | 1.0 | ||||||
Varisoft TA100 | 二硬脂基二甲基氯化铵 | 2.0 | ||||||
水 | 水(液态) | 76.6 | ||||||
B | -(-α-)没药醇,天然2/012685 | 没药醇 | 0.1 | |||||
Aloe Vera GelConc.10/12/912800 | 水(液态)、巴巴多芦荟凝胶 | 1.0 | ||||||
丁二醇 | 丁二醇 | 1.0 | ||||||
柠檬酸10%水溶液 | 柠檬酸 | 0.3 | ||||||
Dragocid液2/060140 | 苯氧基乙醇,甲基-、乙基-、丁基-、丙基-、异丁基对羟基苯甲酸酯 | 0.8 | 0.8 | 0.8 | ||||
Dragoxat EH2/044115 | 乙基己酸乙基己酯 | 8.0 | ||||||
Dracorin GOC | 油酸柠檬酸甘油酯(和)三辛酸/癸酸甘油酯 | 2.0 | 0.8 | |||||
Glycerin 99.5P | 甘油 | 6.0 | 3.0 | |||||
Glydant Plus液 | 二甲基二羟甲基乙内酰脲,碘丙炔基丁基氨基甲酸酯 | 0.2 | ||||||
Keltrol F | 黄原酸胶 | 0.25 | ||||||
石蜡油5Gr.E | 液体石蜡 | 8.3 | ||||||
PCL液100 2/066240 | 乙基己酸十六/十八烷酯 | 3.9 | ||||||
水 | 水(液态) | 60.8 | 82.7 | 84.7 | 85.7 | 75.15 |
C | Deolite2/027095 | 戊二醇、二甲基苯丙醇 | 1.0 | |||||
Dragocid液2/060140 | 苯氧基乙醇、对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丁酯、对羟基苯甲酸丙酯、对羟基苯甲酸异丁酯 | 0.8 | ||||||
Dragoderm2/012550 | 甘油、小麦胚芽麸质、水(液态) | 3.5 | ||||||
10%氢氧化钠溶液 | 氢氧化钠 | 0.4 | ||||||
芳香油 | 香料 | 0.2 | 0.4 | 0.5 | 1.0 | |||
D | 芳香油 | 香料 | 0.3 | 0.3 | ||||
(全部%) | 总量 | 100 | 100 | 100 | 100 | 100 | 100 |
实施例(5)-制备方法:
分别加热A和B相至大约75℃。结合适度搅拌直到凝胶蜡均匀。然后使其冷却,在大约40℃加入C相并搅拌直至均匀。pH:约5.2。
实施例(6)-制备方法:
混合所有来自A相的原料,加热至80℃并利用Ultra Turrax均匀化。利用桨式搅拌器冷搅拌,随着温度下降而减小搅拌速率。在大约35℃加入C相。pH:约5.9。
实施例(7)和(8)-制备方法:
分别加热A和B相至大约80℃。将B相加入A相(Ultra Turrax)并乳化。利用桨式搅拌器冷搅拌,随着温度下降而减小搅拌速率。在大约30℃加入C相。pH:(7)约4.2、(8)约5.2。
实施例(9)和(10)-制备方法:
在水中用Ultra Turrax使Pemulen TR-2或Keltrol F溶胀。分别加热A和B相至大约80℃。将B相加入A相(Ultra Turrax)并乳化。加入C相并再次均匀化。利用桨式搅拌器冷搅拌,随着温度下降而减小搅拌速度。在大约35℃加入D相。pH:(9)约5.5、(10)约5.2。
Claims (20)
1.一种O/W乳化剂,该乳化剂含有
70-90重量%的油酸柠檬酸甘油酯和
10-30重量%的天然油作为粘度调节剂,其粘度为1-10,000mPas。
2.根据权利要求1的O/W乳化剂,其特征在于所述油酸柠檬酸甘油酯是单油酸和/或二油酸甘油酯与柠檬酸的酯。
3.根据权利要求2的O/W乳化剂,其特征在于所述油酸柠檬酸甘油酯通过摩尔比为0.3∶1-1.5∶1的柠檬酸与单油酸甘油酯的酯化反应获得。
4.根据权利要求3的O/W乳化剂,其特征在于所述摩尔比为0.7∶1-1.2∶1。
5.根据权利要求1的O/W乳化剂,其特征在于所述油酸柠檬酸甘油酯被完全中和。
6.根据权利要求1的O/W乳化剂,其特征在于所述油酸柠檬酸甘油酯的pH值为5-8。
7.根据权利要求6的O/W乳化剂,其特征在于所述pH值为5.8-6.2。
8.根据权利要求7的O/W乳化剂,其特征在于所述pH值为6.0。
9.根据权利要求1的O/W乳化剂,其特征在于所述油酸柠檬酸甘油酯的HLB值为9-15。
10.根据权利要求9的O/W乳化剂,其特征在于所述HLB值为11-13。
11.根据权利要求1的O/W乳化剂,其特征在于所述油酸柠檬酸甘油酯在所述O/W乳化剂中的比例为75-85重量%。
12.根据权利要求11的O/W乳化剂,其特征在于所述油酸柠檬酸甘油酯在所述O/W乳化剂中的比例为80重量%。
13.根据权利要求1的O/W乳化剂,其特征在于所述粘度调节剂的粘度为1-1000mPas。
14.根据权利要求13的O/W乳化剂,其特征在于所述粘度调节剂的粘度为1-100mPas。
15.根据权利要求1的O/W乳化剂,其特征在于所述粘度调节剂是辛酸/癸酸三酸甘油酯。
16.根据权利要求15的O/W乳化剂,其特征在于,相对于所述三酸甘油酯中所含的脂肪酸,辛酸含量为50-72重量%,癸酸含量为26-45重量%。
17.根据权利要求1-16中任一项的O/W乳化剂的用途,用于化妆或皮肤病用组合物中。
18.根据权利要求17的用途,用于络合亲油体系中的痕量金属,用作抗氧化剂的增效剂和溶液助剂,或用于皮肤护理或粉底产品中。
19.根据权利要求17的用途,其特征在于所述化妆或皮肤病用组合物是乳液,并且在整个配方中O/W乳化剂的含量为2-5重量%。
20.含有根据权利要求1-16中任一项的O/W乳化剂的O/W乳液。
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DE10328686 | 2003-06-26 | ||
DE10331760.0 | 2003-07-14 |
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CN1813051A CN1813051A (zh) | 2006-08-02 |
CN100343377C true CN100343377C (zh) | 2007-10-17 |
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ES2553132T3 (es) | 2008-04-22 | 2015-12-04 | Azelis Deutschland Kosmetik Gmbh | Utilización de ésteres de ácido cítrico como emulsionantes W/O |
DE102013225549A1 (de) * | 2013-12-11 | 2015-06-11 | Henkel Ag & Co. Kgaa | Herstellung von Emulsionen enthaltend Wachse im Kaltverfahren |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999037282A2 (de) * | 1998-01-22 | 1999-07-29 | Beiersdorf Ag | Lipidreduzierte, fliessfähige kosmetische oder dermatologische zubereitungen |
WO1999062468A1 (en) * | 1998-06-04 | 1999-12-09 | The Procter & Gamble Company | Hair conditioning composition comprising primary oil and secondary oil |
US20030012801A1 (en) * | 1999-09-13 | 2003-01-16 | Beiersdorf Ag | Active ingredient combinations of surface-active citric esters and inclusion compounds of cyclodextrins and retinoids, and cosmetic and dermatological preparations containing such mixtures |
-
2003
- 2003-07-14 DE DE10331760A patent/DE10331760A1/de not_active Ceased
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2004
- 2004-05-28 CN CNB2004800177167A patent/CN100343377C/zh not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999037282A2 (de) * | 1998-01-22 | 1999-07-29 | Beiersdorf Ag | Lipidreduzierte, fliessfähige kosmetische oder dermatologische zubereitungen |
WO1999062468A1 (en) * | 1998-06-04 | 1999-12-09 | The Procter & Gamble Company | Hair conditioning composition comprising primary oil and secondary oil |
US20030012801A1 (en) * | 1999-09-13 | 2003-01-16 | Beiersdorf Ag | Active ingredient combinations of surface-active citric esters and inclusion compounds of cyclodextrins and retinoids, and cosmetic and dermatological preparations containing such mixtures |
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CN1813051A (zh) | 2006-08-02 |
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