CN1224378C - 护肤组合物 - Google Patents
护肤组合物 Download PDFInfo
- Publication number
- CN1224378C CN1224378C CN01823219.1A CN01823219A CN1224378C CN 1224378 C CN1224378 C CN 1224378C CN 01823219 A CN01823219 A CN 01823219A CN 1224378 C CN1224378 C CN 1224378C
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- CN
- China
- Prior art keywords
- compositions
- acid
- water
- skin
- alkyl
- 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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Abstract
本发明公开了护肤组合物,所述组合物包括按重量计:(1)约0.01%至约5%的羧酸/羧酸酯共聚物;(2)约0.1%至约2%的表面活性剂体系,所述表面活性剂体系包括两种或多种非离子表面活性剂,所述非离子表面活性剂选自具有C12-C18烷基取代基的聚氧化烯烷基醚、聚氧化烯氢化蓖麻油和直链或支链的一烷基或三烷基甘油酯;(3)约0.05%至约5%的硅氧烷组分;(4)约0.01%至约5%的润肤油;(5)约0.1%至约10%的皮脂吸收剂;(6)约1%至约20%的水溶性湿润剂;和(7)含水载体;其中表面活性剂体系和润肤油的重量比为约2∶1至约1∶1;其中基本由上述组分(1)至(4),(6)和(7)组成的基础组合物的吸光度在波长340nm处不大于约2。
Description
技术领域
本发明涉及透明的或半透明的护肤组合物,该组合物具有改善的剪切稀释性质和皮脂控制性能。本发明还涉及制备稳定透明的护肤组合物的方法。
发明背景
消费者目前可获得的许多个人处理品主要涉及改善皮肤的健康和/或物理外观。在这些护肤产品中,许多产品涉及延迟、最大程度地减少或甚至消除皮肤皱纹和其它组织学变化,所述组织学变化典型与皮肤老化或环境对人类皮肤的伤害有关。
为了维持或使皮肤恢复健康和/或年轻的状态,典型地用保湿剂处理皮肤。已知的保湿剂包括例如水溶性湿润剂,例如甘油。增加涂敷到皮肤上的保湿剂的含量可典型地改善皮肤的湿润性。也已知增加油组分是有利的,因为它们可提供柔软性、光滑性以及补充细胞间的类脂。
为了给皮肤提供湿润性和柔软性,掺入透明形式的水溶性湿润剂和油类的洗液和乳液在本领域是已知的,例如在PCT出版物WO99/49841、WO00/37029、WO00/61098和WO00/61083中公开的物质。透明外观可吸引消费者,这是由于人们认为涂敷这种组合物将使他们的皮肤变得透明并看起来年轻。如果这种产品能实际上为皮肤提供好象是在涂敷水的感觉,那么它将对消费者更有吸引力。水已知具有非常低的粘度。当将洗液或乳液涂敷到皮肤时,消费者典型在皮肤或手掌上摩擦该产品。因此,为了在涂敷时给皮肤提供这种似水的感觉,需要具有剪切稀释性质的组合物。
另一方面,需要进一步改善这种组合物以提供皮脂控制性能。还在另一方面,需要进一步改善组合物以使皮肤发粘感和油腻感减少,尤其是当具有发粘感的皮肤处理剂如泛醇和烟酰胺掺入所述组合物时。
基于上述原因,需要具有改善的剪切稀释性质和皮脂控制性能的透明或半透明护肤组合物。还需要这种组合物具有改善的性质,以使皮肤的发粘感和油腻感减少,甚至当包括皮肤处理剂时也是如此。还需要制备稳定透明的护肤剂的方法。
现有技术都未能提供本发明的全部优点和益处。
发明概述
本发明涉及护肤组合物,该组合物包括按重量计:
(1)约0.01%至约5%的羧酸/羧酸酯共聚物;
(2)约0.1%至约2%的表面活性剂体系,该体系包括两种或多种非离子表面活性剂,所述非离子表面活性剂选自具有C12-C18烷基取代基的聚氧化烯烷基醚、聚氧化烯氢化蓖麻油和直链或支链的、一烷基或三烷基甘油酯;
(3)约0.05%至约5%的硅氧烷组分;
(4)约0.01%至约5%的润肤油;
(5)约0.1%至约10%的皮脂吸收剂;
(6)约1%至约20%的水溶性湿润剂;和
(7)含水载体;
其中表面活性剂体系与润肤油的重量比为约2∶1至约1∶1;其中基本由上述组分(1)至(4)、(6)和(7)组成的基础组合物的吸光度在波长340nm处不大于约2。
本发明还涉及制备组合物的方法,该方法包括以下步骤:
(a)制备第一混合物,其包括下列步骤:
(a1)在温度为约70-80℃时,将润肤油与表面活性剂体系和水混合,所述水的量为润肤油和表面活性剂体系总重量的约0.5至约5倍;
(a2)将(a1)的产物冷却至约50℃;
(a3)将(a2)的产物加入水中,所述水的温度足够低以便立即将所得混合物冷却至不高于40℃的温度;
(b)制备第二混合物,其包括下列步骤:
(b1)在温度为约70-80℃时,将羧酸/羧酸酯共聚物分散到水中,混合直到均匀;
(b2)将硅氧烷组分加入到步骤(b1)的产物中;和
(c)混合第一混合物和第二混合物;
其中表面活性剂体系包括两种或多种非离子表面活性剂,所述非离子表面活性剂选自具有C12-C18烷基取代基的聚氧化烯烷基醚、聚氧化烯氢化蓖麻油,和直链或支链的一烷基或三烷基甘油酯。
本发明还涉及控制皮脂的方法,所述方法包括将上述护肤组合物涂敷到皮肤上的步骤。
对于本领域技术人员来说,通过阅读本说明书的公开内容,本发明的这些和其它特征、方面和优点将变得显而易见。
发明详述
虽然本说明书通过特别指出并清楚地要求保护本发明的权利要求作出结论,但应该相信由下列说明可更好地理解本发明。
所有引用的参考文献均全文引入本文以供参考。任何文献的引用并不是对其作为要求保护的本发明的现有技术的可获得性的认可。
在本文中,“包括”是指可加入不影响最终结果的其它步骤和其它成分。该术语包括“由……组成”和“基本上由……组成”。
除非另外指明,所有的百分比、份数和比率均以本发明的组合物的总重量计。所有涉及所列出成分的重量均是以其活性物质含量计,因此不包括可能包含在市售产品中的载体或副产物。
组合物
本发明的组合物适于局部涂敷到人体皮肤,尤其适用于面部皮肤。该组合物具有透明或半透明外观,因而尤其适用于透明洗液产品。
本组合物可提供良好的保湿效果、良好的铺展性、改善的剪切稀释性质以及皮脂控制性能。将本组合物在皮肤上涂敷至少约4周后,可提供显著的皮脂控制效果。典型地,所述涂敷以约每天一次的次数在这些延长期内使用,其涂敷率可最高为约每天三次或更多。本组合物在常规贮藏条件下是稳定的。
本组合物实际上包含微乳形式的水不溶性的组分,尤其是油。本组合物的“基础组合物”具有高透明性。“基础组合物”是指本发明组合物仅包含基本组分而缺乏皮脂吸收剂,即基本由羧酸/羧酸酯共聚物、表面活性剂体系、硅氧烷组分、润肤油、水溶性湿润剂和含水载体组成的组合物。基础组合物的吸光度在波长340nm时小于约2,在相同波长处优选为约1至约1.5。在本文中,吸光度可以用TECANCo.Ltd.的微板读数计测量。本文中,“微乳”是指包含作为连续相的水的乳液,水不溶性组分作为小滴分散在其中以使其外观为透明乳液,所述水不溶性组分在其它情况下呈不透明外观。优选地,存在于微乳中的小滴的平均粒径小于约100nm、更优选小于约80nm。小滴的尺寸可用Horiba(日本)的激光散射粒径分布分析仪(LaserScattering Particle Size Distribut ion Analyzer)LA-910测量。在混合30秒后,温度为25℃+/-1℃时用乳液测量小滴的尺寸。本领域的技术人员可以理解,某些硅氧烷组分可能看起来是透明的,甚至当它们以较大的小滴尺寸分散时也是如此。在本发明中,润肤油和硅氧烷组分的小滴尺寸对基础组合物的透明外观非常关键,当小滴尺寸较大时,它们将不再透明。不受理论的约束,据信表面活性剂体系种类和数量的选择为分散润肤油并同时也为分散硅氧烷组分提供了适合的微乳。表面活性剂体系与润肤油的重量比为约2∶1至约1∶1。
组合物可能变得不太透明和稍微不透明,这取决于包括在本组合物中的皮脂吸收剂的种类和数量。优选地,选择皮脂吸试剂的种类和数量以使组合物保持半透明,即非乳状或混浊。
羧酸/羧酸酯共聚物
本发明组合物包括约0.01%至约5%,优选约0.04%至约1%的羧酸/羧酸酯共聚物。不受理论的约束,据信羧酸/羧酸酯共聚物为本组合物提供了剪切稀释性质。剪切稀释性质是指存在于典型的可由手涂敷到皮肤上的剪切压力内的屈服点,超过屈服点的组合物粘度显著减小至可被消费者注意到的程度。在优选实施方案中,在涂敷剪切之前,本发明的组合物具有适合的粘度,优选约100mPa·s至约6000mPa·s、更优选约500mPa·s至约4500mPa·s、还优选约700mPa·s至约4000mPa·s。在25℃时,通过Brookfield LV 以20转/分的转速,用轴#4、5、6或7(这取决于组合物的粘度和特性)可适当地测量本文的粘度。在高度优选的实施方案中,超过屈服点的粘度类似于水中的粘度。在使用后,剪切稀释性质可直接提供低粘度组合物,由此提供类似将水涂敷到皮肤上的感觉。
此外,羧酸/羧酸酯共聚物在含水环境中能分散和稳定润肤油和硅氧烷组分,以使这些组分不会分离出来。羧酸/羧酸酯共聚物也能使组合物保持相对透明以及具有适当的粘度,而不会在使用后使组合物变得发粘或油腻。
本发明的羧酸/羧酸酯共聚物是经过疏水改性的羧酸和羧酸烷基酯的交联共聚物,并具有两亲性质。这些羧酸/羧酸酯共聚物可通过下列物质共聚获得:1)羧酸单体,例如丙烯酸、甲基丙烯酸、马来酸、马来酸酐、衣康酸、富马酸、巴豆酸或氯代丙烯酸;2)具有约1至约30个碳原子的烷基链的羧酸酯;和优选的3)具有下式的交联剂:
其中R52为氢或具有约1至约30个碳原子的烷基;Y1独立地为氧、CH2O、COO、OCO、
其中R53为氢或具有约1至约30个碳原子的烷基;Y2选自(CH2)m″、(CH2CH2O)m″或(CH2CH2CH2O)m″,其中m″为1至约30的整数。据信,由于烷基包含在聚合物中,所以羧酸/羧酸酯共聚物不会使组合物产生不希望的发粘感。
本发明的适宜羧酸/羧酸酯共聚物是具有下式的丙烯酸/丙烯酸烷基酯共聚物:
其中R51独立地为氢或具有1至30个碳原子的烷基,其中至少一个R51为氢,R52如上定义,n、n′、m和m′为整数,其中n+n′+m+m′为约40至约100,n″为1至约30的整数,λ被限定为使共聚物的分子量为约500,000至约3,000,000。
用于本发明的市售羧酸/羧酸酯共聚物包括:CTFA名称为丙烯酸酯/C10-C30烷基丙烯酸酯交联共聚物,其商品名为Pemulene TR-1,Pemulene TR-2,Carbopol 1342,Carbopol 1382和Carbopol ETD2020,这些物质均可购自B.F.Goodrich Company。
组合物可包含中和剂,以中和本发明的羧酸/羧酸酯共聚物。这些中和剂的非限制性实施例包括氢氧化钠、氢氧化钾、氢氧化铵、一乙醇胺、二乙醇胺、三乙醇胺、二异丙醇胺、氨基甲基丙醇、氨基丁三醇(tromethamine)、四羟基丙基乙二胺,及其混合物。
表面活性剂体系
本发明组合物包括约0.1%至约2%,优选约0.05%至约1%的表面活性剂体系,所述表面活性剂体系包含两种或多种非离子表面活性剂,所述非离子表面活性剂选自具有C12-C18烷基取代基的聚氧化烯烷基醚、聚氧化烯氢化蓖麻油,和直链或支链的一烷基或三烷基甘油酯。表面活性剂体系与润肤油的重量比为约2∶1至约1∶1。
表面活性剂体系的亲水-亲脂平衡(HLB)由技术人员根据硅氧烷组分和润肤油的数量和种类来选择。优选地,表面活性剂体系的HLB作为整体大于约10。优选地,在用于表面活性剂体系的表面活性剂中,至少一种表面活性剂的HLB大于10,且至少一种表面活性剂的HLB小于10。更优选地,较高HLB表面活性剂的数量大于较低HLB表面活性剂的数量。不受理论的约束,通过使用较高HLB的表面活性剂和较低HLB的表面活性剂,可以制得含有较低含量的表面活性剂的稳定乳液。在尤其优选的实施方案中,至少使用了3种表面活性剂,这些表面活性剂分别具有不同的HLB。
在制备本发明组合物的优选方法中,表面活性剂体系首先与润肤油混合,然后将该混合物加入到水中。在这一步骤中,所用水的量优选是润肤油和表面活性剂的总重量的约0.5至约5倍,更优选约1至约2.5倍。不受理论的约束,通过以这种方式掺入表面活性剂体系,可制得具有最可能低的含量的表面活性剂的稳定乳液。
适用于本发明的聚氧化烯烷基醚为氧化烯与脂肪酸和脂肪醇的缩合产物(例如,其中聚亚烷基氧化物部分的一端用脂肪酸酯化和在另一端用脂肪醇醚化(例如,通过醚键连接))。这些物质具有式R1CO(X1)zOR2,其中R1和R2独立地为具有约12至约18个碳原子的烷基;X1为-OCH2CH2(其衍生自,例如乙二醇)或-OCH2CHCH3-(衍生自丙二醇或氧化物);z为约6至约50的整数。
衍生自非离子表面活性剂的这种氧化烯的非限制性实施例包括鲸蜡聚氧乙烯醚-6、鲸蜡聚氧乙烯醚-10、鲸蜡聚氧乙烯醚-12、鲸蜡硬脂基聚氧乙烯醚-6、鲸蜡硬脂基聚氧乙烯醚-10、鲸蜡硬脂基聚氧乙烯醚-12、鲸蜡硬脂基聚氧乙烯醚-20、鲸蜡硬脂基聚氧乙烯醚-30、硬脂基聚氧乙烯醚-6、硬脂基聚氧乙烯醚-10、硬脂基聚氧乙烯醚-12、硬脂基聚氧乙烯醚-20、PEG-100硬脂基聚氧乙烯醚、PEG-6硬脂酸酯、PEG-10硬脂酸酯、PEG-12硬脂酸酯、PEG-100硬脂酸酯、PEG-10硬脂酸甘油酯,PEG-20硬脂酸甘油酯、PEG-30椰油酸甘油酯、PEG-80椰油酸甘油酯、PEG-80牛油酸甘油酯、PEG-200牛油酸甘油酯、PEG-8二月桂酸酯、PEG-10二硬脂酸酯,及其混合物;优选鲸蜡硬脂基聚氧乙烯醚-12、鲸蜡硬脂基聚氧乙烯醚-20,和鲸蜡硬脂基聚氧乙烯醚-30。市售的表面活性剂包括商品名为Eumulgin B1的鲸蜡硬脂基聚氧乙烯醚-12、商品名为Eumulgin B2的鲸蜡硬脂基聚氧乙烯醚-20,和商品名为Eumulgin B3的鲸蜡硬脂基聚氧乙烯醚-30,这些物质都可从Henkel公司购得。
适用于本发明的聚氧化烯氢化蓖麻油的实施例包括聚乙烯氢化蓖麻油,优选聚乙烯(20)氢化蓖麻油。
适用于本发明的一烷基或三烷基甘油酯的实施例包括一硬脂酸甘油酯、油酸甘油酯和二异硬脂酸三甘油酯,优选二异硬脂酸三甘油酯。
硅氧烷组分
本发明组合物包括约0.05%至约5%、优选约0.5%至约3%的硅氧烷组分。适用于本发明的硅氧烷组分包括适用于皮肤的挥发性的或非挥发性的不溶性硅氧烷。不溶性是指硅氧烷形成与载体分离的不连续相,例如乳液或悬浮液形式的硅氧烷小滴。本文中硅氧烷组分可通过本领域已知的任何适合的方法制备,包括乳液聚合作用。硅氧烷组分还可以乳液的形式掺入本组合物,其中乳液通过机械混合制得,或通过合成过程经由乳液聚合作用制得,该制备过程可在表面活性剂的辅助下或没有其辅助的情况下进行,所述表面活性剂选自阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂,及其混合物。高分子量的硅氧烷组分可由乳液聚合作用制备。
适用于本发明的硅氧烷组分包括聚烷基聚芳基硅氧烷、硅氧烷树脂、氨基取代的硅氧烷,及其混合物。硅氧烷组分优选选自聚烷基聚芳基硅氧烷、硅氧烷树脂及其混合物,更优选选自一种或多种聚烷基聚芳基硅氧烷。
适用于本发明的聚烷基聚芳基硅氧烷包括具有下列结构(I)的那些物质:
式中R为烷基或芳基,且x为约7至约8,000的整数。“A”代表封闭硅氧烷链末端的基团。只要所得硅氧烷在室温下保持流动性,可分散,在涂敷到皮肤上时无刺激,无毒也没有其它有害作用,与组合物其它组分相容,在常规使用和储存条件下化学稳定以及能够沉积在皮肤上和调节皮肤,那么在硅氧烷链(R)上或在硅氧烷链(A)的末端取代的烷基或芳基可以具有任意结构。适合的A基团包括羟基、甲基、甲氧基、乙氧基、丙氧基以及芳氧基。在硅原子上的两个R基团可以代表相同或不同的基团。优选地,两个R基团代表相同的基团。适合的R基团包括甲基、乙基、丙基、苯基、甲基苯基和苯基甲基。优选的硅氧烷化合物为聚二甲基硅氧烷、聚二乙基硅氧烷和聚甲基苯基硅氧烷。聚二甲基硅氧烷,也称为二甲硅油,是尤其优选的。可使用的聚烷基硅氧烷包括例如聚二甲基硅氧烷。这些硅氧烷化合物可以例如以商品名为Viscasil和SF 96系列购自通用电气公司,和以商品名为Dow Corning 200系列购自道-康宁公司。例如,来自通用电气公司商品名为SF 1075甲基苯基流体或者来自道-康宁公司商品名为556化妆品级流体的聚甲基苯基硅氧烷均适用于本发明。
特别适用的另一种聚烷基聚芳基硅氧烷是硅氧烷树胶。在本文中,术语“硅氧烷树胶”是指在25℃时粘度大于或等于1,000,000厘沲的聚有机硅氧烷材料。应当认识到,本文所述的硅氧烷树胶也可以与上述硅氧烷化合物有一些重复。该重复不是对任何这些物质的限制。Petrarch以及其它文献,包括在1979年5月1日出版的Spitzer等人的美国专利4,152,416,以及Noll,Walter,Chemistryand Technology of Silicones,New York:Academic Press 1968。General Electric Silicone Rubber Pro duct Data Sheets SE 30、SE 33、SE 54和SE 76也描述了硅氧烷树胶。所有这些文献均全文引入本文以供参考。“硅氧烷树胶”的重均分子量典型地在大约200,000以上,通常在约200,000至约1,000,000之间。其具体实施例包括聚二甲基硅氧烷、聚(二甲基硅氧烷甲基乙烯基硅氧烷)共聚物、聚(二甲基硅氧烷二苯基硅氧烷甲基乙烯基硅氧烷)共聚物及其混合物。
还可以使用高度交联的硅氧烷系统的硅氧烷树脂。所述交联是通过在硅氧烷树脂制备期间将三官能和四官能硅烷与单官能或双官能硅烷,或与二者一起掺入而引入的。正如本领域公知的,为得到硅氧烷树脂所需的交联程度将根据掺入硅氧烷树脂中的特定硅烷单元而变化。一般情况下,如果硅氧烷材料具有足够含量的三官能和四官能硅烷单体单元,并因此具有足够水平的交联,从而使得它们在变干时可形成坚硬或坚固的膜,那么这些硅氧烷材料可视为硅氧烷树脂。氧原子与硅原子的比例是具体硅氧烷物质交联水平的指征。每一硅原子具有至少约1.1个氧原子的硅氧烷材料通常是本发明的硅氧烷树脂。优选地,氧原子∶硅原子的比率为至少约1.2∶1.0。可用于制备硅氧烷树脂的硅烷包括一甲基、二甲基、三甲基、一苯基、二苯基、甲基苯基、一乙烯基和甲基乙烯基氯硅烷,以及四氯硅烷,其中甲基取代的硅烷是最常用的。优选的树脂是由通用电气公司供应的GE SS4230和SS4267。市售硅氧烷树脂通常是以在低粘度的挥发性或非挥发性硅氧烷流体中的溶解形式提供。适用于本发明的硅氧烷树脂应当以这样的溶解形式提供和掺入到本发明组合物中,这对于本领域技术人员来说是显而易见的。不受理论的约束,据信硅氧烷树脂能增加其它硅氧烷组分在皮肤上的沉积。
制备这些硅氧烷组分的方法参见“Encyclopedia of PolymerScience and Engineering”,第15卷,第二版,第204-308页,John Wiley & Sons,Inc.,1989。
在一个优选的实施方案中,硅氧烷组分是高粘度硅氧烷化合物和硅氧烷基载体的混合物。
本文中高粘度硅氧烷化合物包括分子量为约200,000至约540,000的选自上述物质的那些化合物,优选选自聚二甲基硅氧烷醇、氟硅氧烷聚二甲基硅氧烷,及其混合物,更优选基本上为聚二甲基硅氧烷醇。尤其优选的聚二甲基硅氧烷醇是具有二甲基硅氧烷重复单元并且以羟基封端的那些物质,其中二甲基硅氧烷部分由约2700至约4500个重复单元构成。
硅氧烷基载体包括粘度为约0.65mPa·s至约100mPa·s,选自具有较低重复单元的环甲基硅氧烷和聚二甲基硅氧烷的那些物质。
适用于本发明的市售的硅氧烷组分包括商品名为DC345购自道-康宁公司的聚二甲基硅氧烷、商品名为SE 30、SE 33、SE 54和SE 76的购自通用电气公司的聚二甲基硅氧烷树脂溶液、商品名为DCQ2-1403和DCQ2-1401的购自道-康宁公司的聚二甲基硅氧烷醇,和购自Toshiba Silicone公司的描述于英国专利申请2,303,857中的乳液聚合的聚二甲基硅氧烷醇。
润肤油
本发明组合物包括约0.5%至约5%,优选约1%至约3%的润肤油。适用于本发明的润肤油是熔点不超过约25℃,且为皮肤提供润肤有益效果的那些物质。用于本发明的润肤油可以是挥发性的或非挥发性的,并包括酯和烃。高度优选低粘度、低分子量或支链结构的润肤油。已经惊奇地发现,通过使用这些油可以减轻对皮肤的发粘感和油腻感。
适用于本发明的润肤油为酯,尤其是具有支链烷基和链烯基的酯,例如,鲸蜡基2-乙基己基、异壬酸十三烷基酯、异硬脂酸异硬脂醇酯、异硬脂酸异鲸蜡酯、异硬脂酸异丙酯、异壬酸异癸基、辛酸鲸蜡酯、异壬酸异壬酯、肉豆蔻酸二异丙酯、肉豆蔻酸异鲸蜡酯、肉豆蔻酸异十三烷基酯、肉豆蔻酸异丙酯、肉豆蔻酸十四烷基酯、棕榈酸异硬脂醇酯、棕榈酸异鲸蜡酯、棕榈酸异癸基酯、棕榈酸异丙酯、肉豆蔻酸异硬脂基酯、棕榈酸辛基酯、辛酸/癸酸甘油三酯、甘油基三-2-乙基己酸盐、新戊基二醇二(2-乙基己酸盐)、新戊基二醇二癸酸盐、二异丙基二聚体盐、三辛甘油酯、三异棕榈酸甘油酯、肉豆蔻酸异丙酯、辛基十二烷基乳酸盐,及其混合物。也可使用甘油三酯如辛酸/癸酸甘油三酯、PEG-6辛酸/癸酸甘油三酯和PEG-8辛酸/癸酸甘油三酯。也可使用CTFA名为池花籽油(Meadowfoam seed oil)的这些甘油三酯的粗混合物。市售油类包括,例如,商品名为Salacos 99购自Nisshin Oil Mills或商品名Lanol 99,购自Seppic的异壬酸异壬酯;以商品名为Crodamol TN购自Croda,以商品名为Hexalan购自Nisshin Seiyu的异壬酸十三烷基酯,和以商品名Cropure MDF购自Croda的池花籽油。
还适用于本发明的润肤油是各种等级和种类的烃。矿物油为衍生自石油的烃的液体混合物。适合的烃的具体实施例包括石蜡油(包括被称为轻石蜡或异链烷烃的那些物质)、矿物油、异三十烷、十二烷、异十二烷、十六烷、异十六烷、二十碳烯、异二十碳烯、十三烷、十四烷、氢化聚异丁烯、二十二烷,及其混合物。适用于本发明的市售烃包括商品名为PERMETHYL 99A、PERMETHYL 101A和PERMETHYL 1082购自Presperse(South Plainfield New Jersey,美国)的异十二烷、异十六烷和异二十碳烯;商品名为BENOL购自Witco的矿物油;商品名为 ISOPAR购自Exxon ChemicalCo.(Hous ton Texas,美国)、商品名为Isoparaffin 2028购自Idemitsu和商品名为Amsco Mineral Spirits购自Ashland的异链烷烃。
皮脂吸收剂
本发明组合物包括约0.1%至约10%、优选约1%至约5%的皮脂吸收剂。适用于本发明的皮脂吸收剂包括可实际上吸收从毛孔分泌出的皮脂,并且与本发明的含水组合物相容的的那些物质。水溶性、水膨胀性或具有较高乳化能力的组分不适于本发明,因为当将其配制在本组合物中时,它们不再具有皮脂吸收能力。
本发明优选的皮脂吸收剂包括多孔球形纤维素粉末、固体硅氧烷弹性体粉末、表面改性多孔二氧化硅粉末、多孔尼龙粉末、多孔丙烯酸酯共聚物,及其混合物。皮脂吸收剂的类型和数量根据产品所需性质来选择。
优选的是公开于JP 61-100514 A和JP 61-189210 A出版物中的多孔球形纤维素粉末。优选这些物质是因为它们在本组合物中具有良好的可分散性,并且在使用后能提供令人满意的皮肤感觉。本发明优选的多孔球形纤维素粉末的平均粒径为约3μm至约50μm,并且不包括粒径大于约100μm的颗粒。任何具有所需皮脂吸收能力和粒径的纤维素粉末均可使用。尤其有用的多孔球形纤维素粉末是根据下列方法制备的那些物质:
(1)将纤维素的氢氧化铜(II)铵溶液分散到有机溶剂如苯中,形成球体,用酸处理,得到纤维素。
(2)提供纤维素酯的有机溶剂溶液,从该溶液中得到纤维素酯细丝,将细丝切成碎片,加热熔化碎片形成球形颗粒,皂化颗粒。
(3)将(2)中提及的溶液分散到几乎不溶或微溶的有机溶剂中,加热该分散体以除去有机溶剂,获得球形颗粒,皂化该颗粒。
可用于上述方法(2)和(3)的纤维素酯包括:纤维素与乙酸、丙酸、丁酸、硝酸和其它酸的部分酯、完全酯和混合酯。在这些酯中,优选纤维素三醋酸酯。
高度适用于本发明的市售多孔球形纤维素粉末包括商品名为Celluflow系列的物质,如Celluflow C025,购自Chisso Corp.。
优选固体硅氧烷弹性体粉末,这些粉末是硅氧烷橡胶的细颗粒,所述颗粒具有公开于EP 661,334 A出版物中的复合结构。优选这些物质是因为它们可提供使用后的光滑感。这些具有复合结构的硅氧烷橡胶细颗粒由熟化的硅氧烷橡胶的球形或球状颗粒组成,所述硅氧烷橡胶的平均颗粒直径为0.1μm至50μm,并具有聚有机倍半硅氧烷(polyorganosilsesquioxane)树脂涂层,聚有机倍半硅氧烷树脂的涂层量按涂层前的硅氧烷橡胶颗粒的重量计为1至500份/100份。
上述定义的硅氧烷树脂涂层的硅氧烷橡胶颗粒可通过下述方法制备,其包括下列步骤:将熟化了的硅氧烷橡胶颗粒的含水分散体与碱性化合物和三烷氧基硅烷化合物混合,所述橡胶平均颗粒直径为0.1至50μm,所述三烷氧基硅烷化合物具有通式R2Si(OR1)3,其中R2为具有1至20个碳原子的未取代的或取代的一价烃基,R1为具有1至6个碳原子的烷基,搅拌温度不超过60℃。
这些细颗粒的特征在于由熟化了的硅氧烷橡胶颗粒组成的颗粒的复合结构,所述硅氧烷橡胶颗粒具有特定的平均颗粒直径,其上的涂层由以特定涂层量的聚有机倍半硅氧烷树脂形成,并且涂层的硅氧烷橡胶颗粒可通过三烷氧基硅烷化合物的就地水解和缩合反应制备,所述反应在含水分散体中存在熟化了的硅氧烷橡胶颗粒时进行,以便在硅氧烷橡胶颗粒的表面上形成聚有机倍半硅氧烷树脂涂层。
形成细核颗粒的硅氧烷橡胶为具有线性二有机硅氧烷片断的熟化的二有机硅氧烷,在所述细核颗粒上形成聚有机倍半硅氧烷树脂涂层,所述线性二有机硅氧烷片断具有下式,其中各个R为相互独立的具有1至20个碳原子的未取代的或取代的一价烃基,其包括例如烷基如甲基、乙基、丙基、丁基;和芳基如苯基和甲苯基;链烯基如乙烯基和烯丙基;和芳烷基如2-苯乙基和2-苯丙基以及那些取代的烃基,所述烃基通过用取代基取代上述指定烃基中的部分或全部氢原子获得,所述取代基包括卤素原子、环氧基、氨基、巯基、(甲)丙烯酰基等如氨甲基和3,3,3-三氟丙基,至少90%摩尔比的基团R优选为甲基,下标a为5至5000的正整数(尽管并不特别限制),优选10至1000。选择这些下标值,以使硅氧烷橡胶颗粒在用硅氧烷树脂涂层后可赋予复合的基质物质以适当的内应力和改善的表面润滑性,并且在制备硅氧烷橡胶颗粒时不会遇到困难。任选的是,形成细颗粒的硅氧烷橡胶与硅氧烷油、有机硅烷化合物、无机的和有机的粉末等混合。
用硅氧烷树脂涂层涂布的硅氧烷橡胶颗粒是尤其有用的,所述硅氧烷树脂的平均颗粒直径为0.1μm至50μm,或优选1μm至20μm。硅氧烷橡胶颗粒的这种平均颗粒直径有利于提供适合的颗粒流动性,而不会增加附聚,同时也不影响组合物的成形制品的表面光滑性或物理特性,所述组合物与硅氧烷树脂涂层的硅氧烷橡胶颗粒混合。
高度适用于本发明的市售的固体硅氧烷弹性体粉末包括乙烯基聚二甲基硅氧烷/甲基硅氧烷倍半硅氧烷交联聚合物,商品名为KSP系列,购自ShinEtsu Chemical Co.,Ltd.,日本东京。
其它市售的皮脂吸收剂包括多孔丙烯酸酯共聚物,商品名为Polytrap,购自道-康宁公司。
水溶性湿润剂
本发明组合物包括约1%至约20%,优选约5%至约15%的水溶性湿润剂。适用于本发明的水溶性湿润剂包括多元醇如甘油、山梨醇、丙二醇、丁二醇、己二醇、乙氧基化葡萄糖、1,2-己二醇、1,2-戊二醇、己三醇、二丙二醇、赤藓醇、海藻糖、二甘油、木糖醇、麦芽糖醇、麦芽糖、葡萄糖、果糖、软骨素硫酸钠、透明质酸钠、腺苷磷酸钠、乳酸钠、吡咯烷酮碳酸盐、葡萄糖胺、环糊精,及其混合物。
适用于本发明的水溶性湿润剂包括水溶性烷氧基化非离子聚合物如分子量最大约1000的聚乙二醇和聚丙二醇,如具有CTFA名称为PEG-200、PEG-400、PEG-600、PEG-1000的那些物质,及其混合物。
适用于本发明的市售的湿润剂包括:甘油,商品名为STAR和SUPEROL,购自宝洁公司;CRODEROL GA7000,购自Croda UniversalLtd.;PRECERIN系列,购自Unichema;与该化学名称相同的商品名,购自NOF;丙二醇,以商品名LEXOL PG-865/855,购自Inolex;1,2-丙二醇USP,购自BASF;山梨醇,商品名为LIPONIC系列,购自Lipo,SORBO;商品名为ALEX,A-625和A-641,购自ICI;以及商品名为UNISWEET 70、UNISWEET CONC,购自UPI;二丙二醇,以相同商品名购自BASF;双甘油,以商品名双甘油购自Solvay GmbH;木糖醇,以相同商品名购自Kyowa和Eizai;麦芽糖醇,以商品名MALBIT购自Hayashibara;软骨素硫酸钠,以相同商品名购自Freeman和Bioiberica,和以商品名ATOMERGIC SODIUM CHONDROITIN SULFATE购自Atomergic Chemetals;透明质酸钠,购自Chisso Corp,也可以商品名ACTIMOIST购自Active Organics;以商品名“AVIAN透明质酸钠”系列购自Intergen;以商品名“透明质酸钠”(HYALURONICACID Na)购自Ichimaru Pharcos;腺苷磷酸钠,以相同商品名购自Asahikasei、Kyowa和Daiichi Seiyaku;乳酸钠,以相同商品名购自Merck、Wako和Showa Kako;环糊精,以商品名CAVITRON购自American Maize;以商品名RHODOCAP系列,购自Rhone-Poulenc,以及以商品名DEXPEARL购自Tomen;聚乙二醇,以商品名CARBOWAX系列购自联合碳化物公司;以及甘油基聚甲基丙烯酸酯、丙二醇和PVM/MA共聚物的混合物,以商品名Lubrajel Oil购自GuardianLab。
含水载体
本发明的组合物包括含水载体。根据与其它组分的相容性和产品所需的其它特性选择载体的含量和种类。
用于本发明的载体包括水和低级烷基醇的水溶液。适用于本发明的低级烷基醇是具有1至6个碳原子的一元醇,更优选乙醇和异丙醇。
优选地,该含水载体基本上是水。优选使用去离子水。根据产品所需的特性,也可使用含无机阳离子的天然来源的水。
本组合物的pH优选为约4至约8、更优选约5至约7。在该pH范围内,适合的粘性皮肤处理剂尤其有效。为获得所需的pH,可以包括缓冲剂和其它pH调节剂。
附加的水溶性聚合物
本发明组合物还可以包括附加的水溶性聚合物,优选其含量为约0.01%至约5%,更优选约0.04%至约1%。本文中附加的水溶性聚合物是水溶性的或可与水混溶的聚合物,与羧酸/羧酸酯共聚物相容。不受理论的约束,据信组合物中受控量的附加的水溶性聚合物为皮肤提供了改善的增湿性和光滑性,但不会产生不希望的发粘感或粘感。
在一个优选的实施方案中,选择附加的水溶性聚合物以便本发明组合物具有优选为约100mPa·s至约6000mPa·s的合适粘度,如上所述。
适用于本发明的其它水溶性聚合物包括阴离子聚合物和非离子聚合物。适用于本发明的有乙烯基聚合物,如交联的丙烯酸聚合物,CTFA名为卡波姆;纤维素衍生物和改性纤维素聚合物,如甲基纤维素、乙基纤维素、羟乙基纤维素、羟乙基乙基纤维素、羟丙基甲基纤维素、硝基纤维素、纤维素硫酸钠、羧甲基纤维素钠、结晶纤维素、纤维素粉末;普鲁兰多糖、甘露聚糖、小核菌葡聚糖、聚乙烯吡咯烷酮、聚乙烯醇、瓜耳胶、羟丙基瓜耳胶、黄原胶、金合欢胶、阿拉伯胶、黄蓍胶、半乳聚糖、长豆角胶、刺梧桐树胶、刺槐豆胶、角叉菜胶、果胶、支链淀粉、琼脂、温柏树籽(榅桲子)、淀粉(水稻、玉米、马铃薯、小麦)、海藻胶(海藻提取物)、微生物聚合物如葡聚糖、琥珀酰葡聚糖;淀粉基聚合物如羧甲基淀粉、甲基羟丙基淀粉;褐藻酸基聚合物如褐藻酸钠、褐藻酸丙二醇酯;丙烯酸酯聚合物如聚丙烯酸酯钠、聚乙基丙烯酸酯、聚丙烯酰胺、聚乙烯亚胺;和无机水溶性物质如斑脱土、硅酸铝镁、硅酸镁铝(laponite)、锂蒙脱石(hectonite)和无水硅酸。
分子量高于约1000的聚亚烷基二醇可用于本发明。可使用具有下式的物质:
式中R95选自H、甲基及其混合物。当R95为H时,这些物质为环氧乙烷的聚合物,它们也被称为聚环氧乙烷、聚氧化乙烯和聚乙二醇。当R95为甲基时,这些物质为环氧丙烷的聚合物,它们也被称为聚环氧丙烷、聚氧化丙烯和聚丙二醇。当R95为甲基时,也可理解可以存在所得聚合物的各种位置的异构体。在上述结构中,x3的平均值为约1500至约25,000、优选约2500至约20,000、更优选约3500至约15,000。其它有用的聚合物包括聚丙二醇和混合的聚乙二醇-聚丙二醇,或聚氧乙烯-聚氧丙烯共聚物聚合物。适用于本发明的聚乙二醇聚合物是PEG-2M,其中R95为H,且x3的平均值为约2,000(PEG-2M也称为Polyox WSRN-10,购自联合碳化物公司,也称为PEG-2,000);PEG-5M,其中R95为H,且x3的平均值为约5,000(PEG-5M也称为Polyox WSRN-35和Polyox WSRN-80,二者均购自联合碳化物公司,也称为PEG-5,000和聚乙二醇300,000);PEG-7M,其中R95为H,且x3的平均值为约7,000(PEG-7M也称为Polyox WSRN-750,购自联合碳化物公司);PEG-9M,其中R95为H,且x3的平均值为约9,000(PEG 9-M也称为Polyox WSRN-3333,购自联合碳化物公司),和PEG-14 M,其中R95为H,且x3的平均值为约14,000(PEG-14M也称为Polyox WSRN-3000,购自联合碳化物公司)。
高度适用于本发明的市售的附加水溶性聚合物包括黄原胶,商品名为Keltrol系列,购自Kelco;卡波姆,商品名为Carbopol934、Carbopol 940、Carbopol 950、Carbopol 980和Carbopol 981,均购自B.F.Goodrich Company;丙烯酸酯/硬脂基聚氧乙烯醚-20异丁烯酸酯共聚物,商品名为ACRYSOL 22,购自Rohm和Hass;壬氧基羟乙基纤维素,商品名为AMERCELL POLYMER HM-1500,购自Amerchol;甲基纤维素,商品名为BENECEL、羟乙基纤维素,商品名为NATROSOL、羟丙基纤维素,商品名为KLUCEL、鲸蜡基羟乙基纤维素,商品名为POLYSURF 67,均由Herculus提供;小核菌葡聚糖,商品名为Clearogel SC11,购自Michel Mercier Products Inc.(NJ,USA));环氧乙烷和/或氧化丙烯基聚合物,商品名为CARBOWAXPEGs、POLYOX WASRs和UCON FLUIDS,均由Amerchol提供。
适用于本发明的其它水溶性聚合物包括两性聚合物。适用于本发明的两性聚合物为包括至少一个阳离子单体和至少一个阴离子单体的那些物质;阳离子单体为季铵离子,优选二烷基二烯丙基氯化铵或酰胺烷基三烷基氯化铵;阴离子单体为羧酸。本发明的两性调理聚合物可包括非离子性单体,如丙烯酰胺、甲基丙烯酸酯或乙基丙烯酸酯。
适用于本发明的有CTFA名为聚季铵22、聚季铵39和聚季铵47的聚合物。这些聚合物包括例如由二甲基二烯丙基氯化铵和丙烯酸组成的共聚物、由二甲基二烯丙基氯化铵和丙烯酰胺组成的三元共聚物和由丙烯酸甲基丙烯酸氨基丙基氯化三甲铵和甲基丙烯酸酯组成的三元共聚物,如具有下式的那些物质,其中n6∶n7∶n8的比率是45∶45∶10:
本文中高度优选的市售两性聚合物包括聚季铵22,商品名为MERQUAT 280、MERQUAT 295;聚季铵39,商品名为MERQUAT PLUS3330、MERQUAT PLUS 3331;和聚季铵47,商品名为MERQUAT 2001、MERQUAT 2001N,均购自Calgon Corporation。
适用于本发明的其它聚合物包括由带有至少一个羧基(如丙烯酸、甲基丙烯酸、马来酸、衣康酸、富马酸、巴豆酸、或α氯丙烯酸)的乙烯基单体与碱性单体共聚而得到的聚合物,所述碱性单体为含有至少一个碱性氮原子的取代的乙烯基化合物,例如二烷基氨基烷基的甲基丙烯酸酯和丙烯酸酯,以及二烷基氨基烷基的甲基丙烯酰胺和丙烯酰胺。
适用于本发明的其它聚合物还有包含由下列物质衍生的单元的聚合物:
i)至少一种选自丙烯酰胺或甲基丙烯酰胺的单体,其中氮原子被烷基取代;
ii)至少一种包含一个或多个反应性羧基的酸共聚单体;和
iii)至少一种碱性共聚单体,例如具有伯、仲和叔胺取代基以及季铵取代基的丙烯酸和甲基丙烯酸的酯,以及二甲基氨基乙基甲基丙烯酸酯与硫酸二甲酯或硫酸二乙酯进行季铵化反应而得到的产品。
最特别优选的N-取代的丙烯酰胺或甲基丙烯酰胺是其中烷基包含2至12个碳原子的那些物质,特别是N-乙基丙烯酰胺、N-叔丁基丙烯酰胺、N-叔辛基丙烯酰胺、N-辛基丙烯酰胺、N-癸基丙烯酰胺和N-十二烷基丙烯酰胺以及相应的甲基丙烯酰胺。上述酸共聚单体尤其选自丙烯酸、甲基丙烯酸、巴豆酸、衣康酸、马来酸和富马酸,以及马来酸或富马酸的烷基单酯,其中烷基具有1至4个碳原子。
优选的碱性共聚单体有氨乙基、丁基氨基乙基、N,N′-二甲基氨基乙基和N-叔丁基氨基乙基甲基丙烯酸酯。
本文中市售的两性调理聚合物包括辛基丙烯酰胺/丙烯酸酯/丁基氨基乙基异丁烯酸酯共聚物,其商品名为AMPHOMER、AMPHOMERSH701、AMPHOMER 28-4910、AMPHOMER LV71,和AMPHOMER LV47,由National Starch & Chemical提供。
粘性皮肤处理剂
本发明组合物还包括约0.5%至约10%,优选约1%至约5%的粘性皮肤处理剂。适用于本发明的皮肤处理剂有助于修复和补充表皮天然水分屏障功能,因此它们能为皮肤提供有益效果如肌理改善。通常已知的是,当长期使用这些试剂时,这些试剂为皮肤提供有用的有益效果,但是当它们单独涂敷时,却易于提供较差的皮肤感觉。
适用于本发明的粘性皮肤处理剂有烟酰胺、烟酸及其酯、烟醇、泛醇、烟基(panthenyl)乙基醚、正乙酰基半胱氨酸、正乙酰基-L-丝氨酸、磷酸二酯酶抑制剂、三甲基甘氨酸、尿素、明胶、可溶胶原、蜂王浆、生育酚烟酸酯、和维生素D3和类似物或衍生物,及其混合物。尤其优选烟酰胺,因为当它以药学有效量使用时,能够减少或减轻慢性斑的强度。烟酰胺适合于通过首先溶解在水中来掺入组合物中。泛醇也是尤其优选的,因为当它以至少约1%的量使用时,它能提供肌理改善的有益效果。烟酰铵和泛醇可从例如Roche商购获得。
皮脂抑制植物提取剂
本发明组合物还包括约0.001%至约5%,更优选约0.05%至约1%的皮脂抑制植物提取剂。适用于本发明的植物提取剂具有减少毛孔尺寸的收敛剂类型效果,或具有5-还原酶的阻聚作用,以及与含水形式的本组合物相容,优选不会改变本组合物的透明或半透明的外观。优选水溶性植物提取剂。适用于本发明的植物提取剂包括丁香(choji)提取物、薏苡(yokuinin)提取物、金缕梅(hamamerisu)提取物,以及它们的混合物。这些植物提取物可购自Iwase。
紫外保护剂
本发明组合物还包含约1%至约10%,更优选约3%至约9.5%的紫外保护剂。紫外保护剂通常防止由于紫外线照射而引起的角质层的过度剥落和肌理变化,并可被加入到本发明的乳液中。适合的紫外保护剂可以为有机物或无机物。可以使用受控量的疏水性的和水不溶性的紫外保护剂。
大量传统的紫外保护剂适用于本发明。参见公布于1992年2月11日的Haffey等人的美国专利5,087,445;公布于1991年12月17日的Turner等人的美国专利5,073,372;公布于1991年12月17日的Turner等人的美国专利5,073,371;和Segarin等人的《Cosmetics Science and Technology》(1972)的第八章,第189页以及下列等等,其中公开了许多适合的紫外保护剂。可用于乳液中的这些紫外保护剂优选选自2-乙基己基-对甲氧基肉桂酸酯(以商品名PARSOL MCX市售)、丁基甲氧基联苯甲酰-甲烷、2-羟基-4-甲氧基二苯酮、2-苯基苯并咪唑-5-磺酸、辛基二甲基-对氨基苯甲酸、氰双苯丙烯酸辛酯、2-乙基己基N,N-二甲基对氨基苯甲酸盐、对氨基苯甲酸、2-苯基苯并咪唑-5-磺酸、氰双苯丙烯酸辛酯、羟甲氧二苯酮、高薄荷基水杨酸盐、水杨酸辛酯、4,4′-甲氧基-叔丁基二苯甲酰基甲烷、4-异丙基二苯甲酰基甲烷、3-亚苄基樟脑、3-(4-甲基亚苄基)樟脑、二氧化钛如MT-100,购自Tayca、氧化锌、二氧化硅、氧化铁、EusolexTM 6300、氰双苯丙烯酸辛酯、Parsol 1789,及其混合物。
尤其适用于本发明的是如公布于1990年6月26目的Sabatelli的美国专利4,937,370和公布于1991年3月12日的Sabatelli的美国专利4,999,186中的那些紫外保护剂。本发明公开的紫外保护剂在单一分子中具有两个截然不同的发色团部分,所述不同发色团部分显示不同的紫外线辐射吸收光谱。其中一个发色团部分主要在UVB辐射范围内有吸收,另一个发色团在UVA辐射范围内有强烈吸收。相对于常规紫外保护剂而言,这些紫外保护剂可提供更高的功效、更宽的紫外吸收范围、更低的皮肤穿透性和更长久的功效。
准确用量将取决于所选的防晒剂以及所需的防晒因子(SPF)。SPF是防晒剂抗红斑的光保护作用的常用量度。参见Federal Register,第43卷,第166期,第38206-38269页,1978年8月25日。
增白剂
本发明的组合物还包括约0.001%至约10%,更优选约0.1%至约5%的增白剂。适用于本发明的增白剂与含水形式的本组合物相容。优选水溶性增白剂。适用于本发明的增白剂是指与处理前相比不仅改变皮肤外观而且还改善色素过度沉着症的活性成分。
适用于本发明的有用的增白剂包括抗坏血酸化合物、壬二酸、丁基羟基苯甲醚、没食子酸及其衍生物、甘草酸、对苯二酚、曲酸、熊果苷、桑树提取物,及其混合物。据信使用增白剂组合物是有利的,因为它们可以通过不同机理提供增白有益效果。
抗坏血酸化合物是有用的增白剂,其具有下式(I):
其中V和W独立地为-OH,R1为-CH(OH)-CH2OH;及其盐。
优选地,适用于本发明的抗坏血酸化合物是抗坏血酸盐或其衍生物,如本领域技术人员通常已知的无毒碱金属盐、碱土金属盐和铵盐,其包括但不局限于由本领域众所周知的方法制备的钠盐、钾盐、锂盐、钙盐、镁盐、钡盐、铵盐和鱼精蛋白盐。
更优选地,适用于本发明的抗坏血酸盐是具有下式(II)的抗坏血酸金属盐:
其中R2和R3独立地选自氢和具有1至约8个碳原子的直链或支链的烷基;M1为金属;x为1至约3的整数。更优选地,R2和R3独立地选自氢和具有1至约3个碳原子的直链或支链的烷基;M1为钠、钾、镁或钙。
其它优选的具有式(II)的抗坏血酸盐的实施例包括抗坏血酸的一价金属盐(例如,抗坏血酸钠、抗坏血酸钾)、二价金属盐(例如,抗坏血酸镁、抗坏血钙)和三价金属盐(例如,抗坏血酸铝)。
优选地,适用于本发明的抗坏血酸盐是具有下式(III)的水溶性抗坏血酸酯:
其中A为硫酸根或磷酸根;R4和R5独立地选自氢和具有1至约8个碳原子的直链或支链的烷基;M2为金属;且y为1至约3的整数。更优选地,R4和R5独立地选自氢和具有1至约3个碳原子的直链或支链的烷基;M2为钠、钾、镁或钙。
其它尤其优选的抗坏血酸化合物有2-o-α-D-葡萄糖吡喃糖-L-抗坏血酸,通常称为L-抗坏血酸2-葡糖苷或抗坏血酸基葡糖苷,及其金属盐。所述化合物购自Hayashibara。
示例的水溶性盐衍生物包括但不限于L-抗坏血酸2-葡糖苷、L-抗坏血酸基磷酸酯盐如L-抗坏血酸基磷酸钠、L-抗坏血酸基磷酸钾,L-抗坏血酸基磷酸钾、L-抗坏血酸基磷酸镁、L-抗坏血酸基磷酸钙、L-抗坏血酸基磷酸铝。也可使用L-抗坏血酸基硫酸酯盐。实施例包括L-抗坏血酸基硫酸钠、L-抗坏血酸基硫酸钾、L-抗坏血酸基硫酸镁、L-抗坏血酸基硫酸钙和L-抗坏血酸基硫酸铝。
附加组分
本发明组合物还可包含其它附加组分,由技术人员根据最终产品的所需特性选择,并且所述附加组分用于使组合物在美容学或审美学上更容易接受,或者为其提供附加用途的有益效果。适用于本发明的组分通过确定的有益效果或其假定作用形式而进行简便分类,然而,给定的分类对其用途没有限制。还应该理解的是一种组分可以提供多重有益效果。
(i)抗氧化剂和自由基捕获剂
抗氧化剂和自由基捕获剂对于提供抗紫外线辐射保护和抵抗其它引起皮肤损害的环境试剂特别有用,所述紫外线辐射可导致角质层中剥落的增加或肌理的改变。
也可以使用抗氧化剂和自由基捕获剂如生育酚(维生素E)、生育酚山梨酸酯、生育酚乙酸酯、生育酚的其它酯、没食子酸丙基酯、尿酸的烷基酯、胺(即,N,N-二乙基羟基胺、氨基胍)、巯基化合物(即,谷胱甘肽)、氧哺氨酸甜菜硷、精氨酸pilolate、生物类黄酮、赖氨酸、甲硫氨酸、脯氨酸、过氧化物歧化酶、水飞蓟素、茶叶提取物、葡萄皮/籽提取物、黑素和迷迭香提取物。优选的抗氧化剂/自由基捕获剂选自生育酚山梨酸酯和其它生育酚酯,更优选生育酚山梨酸酯。例如,可应用于本发明的在局部乳液中使用的生育酚山梨酸酯记载于在1989年7月11日公布的Bissett等人的美国专利4,847,071中。
(ii)抗炎剂
通过例如有助于均匀性和可接受的肤色和/或颜色,抗炎剂可增强皮肤外观的有益效果。
优选地,抗炎剂包括甾族抗炎剂和非甾族抗炎剂。适用的优选甾族抗炎剂是氢化可的松。
属于非甾类抗炎剂的多种化合物是本领域技术人员众所周知的。关于非甾族抗炎剂的化学结构、合成、副作用等的详细公开内容,可参考标准文本,包括《Anti-inflammatory and Anti-RheumaticDrugs》,K.D.Rainsford,第I-III卷,CRC Press,Boca Raton,(1985),和《Anti-inflammatory Agents,Chemistry andPharmacology》,1,R.A.Scherrer等人,Academic Press,纽约(1974),以上文件均引入本文以供参考。
也可使用所谓的“天然”抗炎剂。所述试剂适合于作为提取物通过适当的物理和/或化学分离方法从天然来源(即,植物、真菌、微生物的副产物)中获得。例如,可以使用α红没药醇、芦荟、Manjistha(从茜草属植物,尤其是茜草中提取)、和Guggal(从没药属植物,尤其是印度没药中提取)、可乐果提取物、春黄菊和柳珊瑚提取物。
(iii)抗微生物剂
所用的“抗微生物剂”是指能破坏微生物、防止微生物生长或防止微生物的致病作用的化合物。例如,抗微生物剂可用于控制粉刺。适用于本发明的有用抗微生物剂优选过氧化苯甲酰、红霉素、四环素、克林霉素、壬二酸、硫间苯二酚、苯氧基乙醇和IrgasanTM DP300(Ciba Geigy Corp.,美国)。可在本发明乳液中加入安全有效量的抗微生物剂、优选约0.001%至约10%、更优选约0.01%至约5%、还更优选约0.05%至约2%。
(iv)螯合剂
本发明所使用的“螯合剂”是指通过反应形成配合物从体系中除去金属离子以便金属离子不易参与或催化化学反应的化合物。包含螯合剂对于提供抵抗紫外线辐射和抵抗其它能引起皮肤损害的环境试剂的保护特别有用,所述紫外线辐射会导致过度剥落或皮肤肌理改变。
适用于本发明的示例的螯合剂公开于1996年1月30日公布的Bissett等人的美国专利5,487,884;出版于1995年10月31日的Bush等人的PCT出版物91/16035和91/16034中。优选的螯合剂有糠偶酰二肟及其衍生物。
(v)其它组分
除上述组分之外,本发明组合物还可以包括防腐剂和防腐剂增强剂,如水溶性或可增溶的防腐剂,包括Germall 115、羟基苯甲酸的甲基酯、乙基酯、丙基酯和丁基酯、苄醇、咪唑烷基脲、乙二胺四乙酸及其盐、溴代硝基丙二醇(2-溴代-2-硝基丙烷-1,3-二醇)和苯氧基丙醇;消泡剂;粘合剂;生物添加剂;增量剂;着色剂;香料,精油,及其增溶剂;其它天然提取物;刺激胶原生产的化合物;酵母发酵滤液,及其它物质。
制备方法
本发明还涉及制备稳定透明的水基组合物的方法,所述水基组合物包含硅氧烷组分和润肤油。本方法适用于制造通常称为微乳的物质,如上述“组合物”部分中所解释的那些物质。通过本方法制造的基础组合物如此透明以至于组合物的吸光度在波长340nm处小于约2,优选在相同波长处为约1至约1.5。当本组合物包括皮脂吸收剂时,组合物将变得不太透明。
本方法包括下列步骤:
(a)制备第一混合物,其包括下列步骤:
(a1)在温度为约70-80℃时,将润肤油与表面活性剂体系和水进行混合,所述水的量是润肤油和表面活性剂总重量的约0.5至约5倍;
(a2)冷却(a1)的产物至约50℃;
(a3)将(a2)的产物加入水中,所述水的温度足够低以将所得混合物立即冷却至不高于40℃的温度;
(b)制备第二混合物,其包括下列步骤;
(b1)在温度为约70-80℃时,将羧酸/羧酸酯共聚物分散在水中,并且混合直至均匀;
(b2)将硅氧烷组分加入步骤(b1)的产物中;和
(c)混合第一混合物和第二混合物;
其中表面活性剂体系包括两种或多种非离子表面活性剂,所述非离子表面活性剂选自具有C12-C18烷基取代基的聚氧化烯烷基醚、聚氧化烯氢化蓖麻油和直链或支链的一烷基或三烷基甘油酯。
由本方法制备的组合物包括至少羧酸/羧酸酯共聚物、表面活性剂体系、硅氧烷组分、润肤油和含水载体。虽然对本方法来说水溶性湿润剂不是必需组分,但典型将其加入到组合物中。本方法所用组分与上述的那些组分相同。
第一混合物用特定的表面活性剂体系、润肤油和水制备。在步骤(a1)中,温度为约70℃-80℃时,将润肤油、表面活性剂体系和水在锚定混合器中混合在一起,形成乳液。优选地,表面活性剂体系首先与润肤油混合,然后将该混合物加入水中。步骤(a1)中所用水的量为润肤油和表面活性剂体系总重量的约0.5至约5倍,优选约1至约2.5倍。在步骤(a2)中,将步骤(a1)的产品冷却至50℃,优选在约20分钟内完成该过程。已经发现该冷却过程可以使混合物变得透明。在步骤(a3)中,通过与冷水混合进一步冷却步骤(a2)的产品。将要与步骤(a2)的产品混合的冷水的温度为足够低,以便将所得的混合物立即冷却至不高于40℃,优选约30℃。不受理论的约束,据信第二步冷却过程提供了稳定透明混合物,所述混合物具有尽可能少量的表面活性剂。水溶性湿润剂和防腐剂可以在步骤(a3)之前加入到冷水中。
单独地,第二混合物由羧酸/羧酸酯共聚物、硅氧烷组分和水制备。在步骤(b1)中,羧酸/羧酸酯共聚物和附加的水溶性聚合物(如果存在)在温度为约70℃-80℃时分散到水中直至均匀。步骤(b1)中所用的水量由技术人员选择。可使用高速搅拌器。旋转速度控制为等于约5000转数/分以避免破坏聚合物结构。当需要皮脂吸收剂和/或中和剂时,还包括在步骤(b2)之前将其加入到步骤(b1)的产物中。在步骤(b2)中,将步骤(b1)的产物进一步与硅氧烷组分混合。剩余组分(如果存在)如水溶性湿润剂、粘性皮肤处理剂、皮脂抑制植物提取物、紫外吸收剂以及增白剂,可加入步骤(b2)的产品中。
最后,混合第一混合物和第二混合物直至均匀(步骤c)。这一步骤中的混合优选由锚定混合器以相对低的旋转速度进行,优选约50转数/分至约100转数/分。这个步可在室温下进行。
实施例
下列实施例进一步描述和举例说明了本发明范围内的实施方案。这些实施例仅仅是说明性的,而不是限制本发明的范围,因为在不背离本发明精神和范围的条件下可以进行多种改变。除非下面另有说明,各成分均以化学名或CTFA名称给出。
组合物
相 | 实施1 | 实施2 | 实施3 | 实施4 | 实施5 | 实施6 | |
01 | 鲸蜡硬脂基聚氧乙烯醚-12 *1 | 0.015 | 2.1 | 0.1 | 0.1 | 0.1 | 0.1 |
01 | 鲸蜡硬脂基聚氧乙烯醚-20 *2 | 0.05 | 0.1 | 0.1 | 0.2 | 0.2 | 0.2 |
01 | 鲸蜡硬脂基聚氧乙烯醚-30 *3 | 0.09 | 0.2 | 0.2 | 0.2 | 0.2 | 0.25 |
01 | 聚甘油基-3-二异硬脂酸酯 | 0.1 | 0.2 | 0.2 | 0.1 | 0.1 | |
01 | PEG-20氢化蓖麻油 | 0.04 | 0.05 | 0.05 | 0.1 | 0.1 | 0.2 |
01 | 辛酸鲸蜡基酯 | 0.1 | 0.1 | ||||
01 | 池花籽油 *4 | 0.1 | 0.05 | 0.1 | |||
01 | 异十六烷 *5 | 0.1 | 0.1 | 0.1 | |||
01 | 异十二烷 *6 | 0.1 | |||||
01 | 异壬酸异壬基酯 *7 | 0.1 | |||||
02 | 去离子水 | 2.0 | 5.0 | 4.0 | 4.0 | 4.0 | 4.0 |
03 | 去离子水 | 30.0 | 30.0 | 30.0 | 30.0 | 30.0 | 30.0 |
03 | 1,3-丁二醇 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
03 | 对羟基苯甲酸甲酯 | 0.07 | 0.07 | 0.07 | 0.07 | 0.07 | 0.07 |
03 | 苯甲酸钠 | 0.07 | 0.07 | 0.07 | 0.07 | 0.07 | 0.07 |
04 | 丙烯酸烷基丙烯酸酯共聚物1 *8 | 0.24 | 0.2 | ||||
04 | 丙烯酸烷基丙烯酸酯共聚物2 *9 | 0.25 | 0.24 | 0.24 | 0.3 | ||
04 | 黄原胶 *10 | 0.04 | 0.04 | 0.04 | 0.04 | ||
04 | 卡波姆 *11 | 0.2 | |||||
04 | 透明质酸钠 *12 | 0.05 | 0.02 | 0.02 | |||
04 | 去离子水 | 余量至100% | |||||
05 | 氢氧化钠 | 0.07 | 0.1 | 0.1 | 0.2 | ||
05 | 氨甲基丙醇 | 0.12 | 0.15 | 0.1 | |||
06 | 泛醇 *13 | 1.0 | 1.0 | 1.0 | 1.0 | 2.0 | 1.0 |
06 | 烟酰胺 *14 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
06 | 甘油 | 2.5 | 2.5 | 2.5 | 2.5 | 3.0 | 4.0 |
06 | 1,3-丁二醇 | 5.5 | 4.0 | 2.0 | 7.0 | 4.0 | 4.0 |
06 | 甘油基聚甲基丙烯酸酯和丙二醇和PVM/MA共聚物 *15 | 1.5 | 1.5 | 2.0 | |||
06 | 金缕梅提取物 *6 | 0.1 | |||||
06 | 丁香提取物 *17 | 0.1 | |||||
07 | 抗坏血酸磷酸镁 | 3.0 | |||||
07 | 二苯酮-1 | 2.0 | |||||
07 | 二氧化钛 *18 | 1.0 | |||||
08 | 聚二甲基硅氧烷/聚二甲基硅氧烷醇 *19 | 1.5 | 2.0 | 1.0 | |||
08 | 环聚甲基硅氧烷/聚二甲基硅氧烷醇 *20 | 1.5 | 1.5 | 1.0 | |||
09 | 纤维素粉末 *21 | 1.0 | 3.0 | 3.0 | |||
09 | 乙烯基聚二甲基硅氧烷/甲基硅氧烷倍半硅氧烷交联聚合物 *22 | 3.0 | 5.0 | 5.0 |
10 | 对羟基苯甲酸甲酯 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
10 | 苄醇 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
10 | 苯甲酸钠 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
10 | EDTA-2Na | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
组分的定义
*1鲸蜡硬脂基聚氧乙烯醚-12(POE(12)鲸蜡硬脂基醚):商品名为Eumulgin B1,购自Henkel
*2鲸蜡硬脂基聚氧乙烯醚-20(POE(20)鲸蜡硬脂基醚):商品名为Eumulgin B2,购自Henkel
*3鲸蜡硬脂基聚氧乙烯醚-30(POE(30)鲸蜡硬脂基醚):商品名为Eumulgin B3,购自Henkel
*4池花籽油:商品名为Cropure MDF,购自Croda
*5异十六烷:商品名为Permethyl 101A,购自Presperse
*6异十二烷:商品名为Permethyl 99A,购自Presperse
*7异壬酸异壬酯:商品名为Salacos 99,购自Nisshin OilMills
*8丙烯酸/丙烯酸烷基酯共聚物1:商品名为PEMULEN TR-1购自B.F.Goodrich
*9丙烯酸/丙烯酸烷基酯共聚物2:商品名为PEMULEN TR-2购自B.F.Goodrich
*10黄原胶:商品名为Keltrol T,购自Kelco
*11卡波姆:商品名为Carbopol 981,购自B.F.Goodrich
*12透明质酸钠:购自Chisso corp.
*13泛醇:购自Roche
*14烟酰胺:购自Roche
*15聚甲基丙烯酸甘油酯和丙二醇和PVM/MA共聚物:商品名为Lubrajel Oil,购自Guardian Lab
*16金缕梅提取物:商品名为Hamamerisu Liquid,购自Iwase
*17丁香提取物:商品名为Choji Extract BG,购自Iwase
*18二氧化钛:商品名为二氧化钛MT-100,购自Tayca
*19聚二甲基硅氧烷/聚二甲基硅氧烷醇:商品名为DCQ2-1403,购自道-康宁公司
*20环甲基硅氧烷/聚二甲基硅氧烷醇:商品名为DCQ2-1401购自道-康宁公司
*21纤维素粉末:商品名为Celluflow C-25购自Chisso corp.
*22乙烯基聚二甲基硅氧烷/甲基硅氧烷倍半硅氧烷交联聚合物:商品名为KSP-100,购自Shinetsu Chemical
制备方法
a1)加热相01至约80℃。加热相02至约78℃。通过将相01加入相02并混合来进行乳化。
a2)在约10至约20分钟内冷却a2)的产物至约50℃。
a3)将a2)的产品加入相03,相03为室温。
b1)使用相04的组分,在约80℃的水中加入2%的丙烯酸/丙烯酸烷基酯共聚物溶液、2%的黄原胶(如果存在)溶液和0.4%透明质酸钠溶液,并且用高速搅拌器以等于5000转数/分的转速混合这些溶液直至均匀。在混合条件下加入相09。在混合条件下加入相05进行中和。
b2)在高速搅拌下将相08和相05、06和07(如果存在)加入bl)的产物中。加入相10。
c)混合步骤a3)的产物和步骤b2)的产物,并冷却至低于40℃。前述实施例所公开和代表的实施方案具有许多优点。例如,实施例1至6尤其适用于提供适用于面部皮肤的透明洗液。当用于面部皮肤时,实施例1至6的组合物为皮肤提供保湿的有益效果,而不会给皮肤留下发粘感和/或油腻感。当以每天用于面部皮肤的方式使用超过至少四周时,实施例1至6提供了控制过剩皮脂的显著改善效果。实施例5还提供了长期增白有益效果。实施例6还为皮肤提供了紫外保护有益效果。
通过使用分别如实施例1、2和4所述的但其中没有纤维素粉末的相同组合物,制备实施例7至9。通过使用分别如实施例3、5和6所述的但其中没有乙烯基聚二甲基硅氧烷/甲基硅氧烷倍半硅氧烷的相同组合物,制备实施例10至12。实施例7至12具有透明外观,且吸光度在340nm处等于约2。
Claims (10)
1.护肤组合物,所述组合物包括按重量计:
(1)0.01%至5%的羧酸/羧酸酯共聚物;
(2)0.1%至2%的表面活性剂体系,所述体系包括两种或多种非离子表面活性剂,所述非离子表面活性剂选自具有C12-C18烷基取代基的聚氧化烯烷基醚、聚氧化烯氢化蓖麻油、和直链或支链的一烷基或三烷基甘油酯;
(3)0.05%至5%的硅氧烷组分;
(4)0.01%至5%的润肤油;
(5)0.1%至10%的皮脂吸收剂;
(6)1%至20%的水溶性湿润剂;和
(7)含水载体;
其中所述皮脂吸收剂选自多孔球形纤维素粉末、固体硅氧烷弹性体粉末、表面改性的多孔二氧化硅粉末、多孔尼龙粉末、多孔丙烯酸酯共聚物、及其混合物;且其中所述表面活性剂体系与所述润肤油的重量比为2∶1至1∶1;和其中基本由上述组分(1)至(4)、(6)和(7)组成的基础组合物的吸光度在波长340nm处不大于2。
2.如权利要求1所述的护肤组合物,其中所述皮脂吸收剂为多孔球形纤维素粉末。
3.如权利要求1所述的护肤组合物,所述组合物还包括附加的水溶性聚合物。
4.如权利要求1所述的护肤组合物,所述组合物还包括选自烟酰胺、烟酸及其酯、烟醇、泛醇、烟基乙基醚、正乙酰基半胱氨酸、正乙酰基-L-丝氨酸、磷酸二酯酶抑制剂、三甲基甘氨酸、尿酸、明胶、可溶胶原、蜂王浆、生育酚烟酸酯、维生素D3、及其混合物的粘性皮肤处理剂。
5.如权利要求1所述的护肤组合物,所述组合物还包括选自丁香提取物、薏苡提取物、金缕梅提取物、及其混合物的皮脂抑制植物提取物。
6.如权利要求1所述的护肤组合物,所述组合物还包括紫外保护剂。
7.如权利要求1所述的护肤组合物,所述组合物还包括增白剂。
8.用于制备组合物的方法,所述方法包括下列步骤:
(a)制备第一混合物,其包括下列步骤:
(a1)在温度为70℃-80℃时,将润肤油与表面活性剂体系和水混合;所述水的量为所述润肤油和表面活性剂体系总重量的0.5至5倍;
(a2)冷却(a1)的产物至50℃;
(a3)将(a2)的产物加入水中,所述水的温度足够低以将所得混合物立即冷却至不高于40℃的温度;
(b)制备第二混合物,其包括下列步骤:
(b1)在温度为70℃-80℃时,将羧酸/羧酸酯共聚物分散到水中,并混合直至均匀;
(b2)将硅氧烷组分加入到步骤(b1)的产物中;和
(c)混合所述第一混合物和所述第二混合物;
其中所述表面活性剂体系包括两种或多种非离子表面活性剂,所述非离子表面活性剂选自具有C12-C18烷基取代基的聚氧化烯烷基醚、聚氧化烯氢化蓖麻油和直链或支链的一烷基或三烷基甘油酯。
9.如权利要求8所述的制备方法,其中所述组合物还包括皮脂吸收剂,在步骤(b2)之前将皮脂吸收剂加入到步骤(b1)的产物中,所述皮肤吸收剂选自多孔球形纤维素粉末、固体硅氧烷弹性体粉末、表面改性的多孔二氧化硅粉末、多孔尼龙粉末、多孔丙烯酸酯共聚物、及其混合物。
10.控制过剩皮脂的美容方法,所述方法包括将如权利要求1至7中任一项所述的组合物涂敷到所述皮肤上的步骤。
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PCT/US2001/015045 WO2002092046A1 (en) | 2001-05-10 | 2001-05-10 | Skin care composition |
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CN1507341A CN1507341A (zh) | 2004-06-23 |
CN1224378C true CN1224378C (zh) | 2005-10-26 |
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US (1) | US20040096414A1 (zh) |
EP (1) | EP1385471A1 (zh) |
JP (1) | JP2004529173A (zh) |
CN (1) | CN1224378C (zh) |
MX (1) | MXPA03010217A (zh) |
WO (1) | WO2002092046A1 (zh) |
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TWI220386B (en) | 2002-01-21 | 2004-08-21 | Matsushita Electric Works Ltd | Ultrasonic transdermal permeation device |
WO2004037305A1 (en) | 2002-10-21 | 2004-05-06 | Allegiance Corporation | Coating composition for skin-contacting surface of elastomeric articles and articles containing the same |
JP2006508952A (ja) * | 2002-11-12 | 2006-03-16 | ロレアル | 皮膚をマット(つや消し)にするセルロースマイクロビーズの使用 |
CN100435779C (zh) * | 2003-09-10 | 2008-11-26 | 宝洁公司 | 护肤组合物 |
MXPA06002701A (es) * | 2003-09-10 | 2006-06-06 | Procter & Gamble | Composicion para el cuidado de la piel. |
AU2005202290B2 (en) * | 2004-05-28 | 2010-07-01 | Kao Corporation | Cosmetic preparation |
US8173143B2 (en) * | 2005-06-02 | 2012-05-08 | Tecco Michelle A | Personal skin care compositions containing anti-flammatory and anti-microbial agents |
US7615231B2 (en) * | 2005-10-24 | 2009-11-10 | Fan Tech, Ltd. | Methods for enhancing the morphology, tone, texture and/or appearance of skin or hair using a meadowlactone |
US20070098870A1 (en) * | 2005-10-27 | 2007-05-03 | Trudsoe Jens E | Composition containing alkylene oxide derivative of pectin |
DE102005056497A1 (de) * | 2005-11-28 | 2007-05-31 | Beiersdorf Ag | Transparente oder transluzente Gele |
DE102005056498A1 (de) * | 2005-11-28 | 2007-05-31 | Beiersdorf Ag | Kosmetische Hydrodispersionen |
US20080020023A1 (en) * | 2006-07-20 | 2008-01-24 | Shiping Wang | Nonaqueous coating composition for elastomeric articles and articles containing the same |
US8222192B2 (en) * | 2009-06-19 | 2012-07-17 | R&W Medical LLC | Alcohol-based skin cleanser |
US20120177747A1 (en) * | 2011-01-09 | 2012-07-12 | Noble Ion, Llc | Compositions and Methods for Treating Lameness in Hoofed Domesticated Animals Due to Hairy Foot Warts and Foot Rot |
JP2013047206A (ja) * | 2011-07-25 | 2013-03-07 | Nikko Chemical Co Ltd | 紫外線吸収剤を含有する微細エマルション組成物並びに化粧料 |
FR2992210B1 (fr) * | 2012-06-21 | 2014-11-28 | Oreal | Composition a effet matifiant comprenant des particules d'aerogels hydrophobes et des particules d'elastomeres de silicone |
FR2992188B1 (fr) * | 2012-06-21 | 2014-11-28 | Oreal | Composition a effet matifiant comprenant des particules d'aerogels hydrophobes et un tensioactif non ionique oxyethylene |
FR2992182B1 (fr) * | 2012-06-21 | 2014-06-20 | Oreal | Composition a effet matifiant comprenant des particules d'aerogels hydrophobes et des particules de perlite |
FR2992185B1 (fr) * | 2012-06-21 | 2015-03-27 | Oreal | Composition a effet matifiant comprenant des particules d'aerogels hydrophobes et des particules de silice |
JP2016534154A (ja) * | 2013-10-22 | 2016-11-04 | ユニリーバー・ナームローゼ・ベンノートシヤープ | 組成物 |
JP6567262B2 (ja) * | 2014-09-30 | 2019-08-28 | 小林製薬株式会社 | 外用組成物 |
JP6979874B2 (ja) * | 2015-10-30 | 2021-12-15 | 株式会社 資生堂 | 組成物 |
JP6881908B2 (ja) | 2016-07-26 | 2021-06-02 | ロレアル | マット効果及び優れた質感を有するエマルション |
CN112618456B (zh) * | 2020-12-31 | 2023-06-06 | 彭氏(惠州)实业发展有限公司 | 一种控油收敛套装及其使用方法 |
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JPS61100514A (ja) * | 1984-10-19 | 1986-05-19 | Shiseido Co Ltd | 粉末化粧料 |
US5380528A (en) * | 1990-11-30 | 1995-01-10 | Richardson-Vicks Inc. | Silicone containing skin care compositions having improved oil control |
US5858340A (en) * | 1992-05-22 | 1999-01-12 | The Procter & Gamble Company | Cosmetic compositions |
US5750122A (en) * | 1996-01-16 | 1998-05-12 | The Procter & Gamble Company | Compositions for treating hair or skin |
WO2000061083A1 (en) * | 1999-04-14 | 2000-10-19 | The Procter & Gamble Company | Transparent micro emulsion |
-
2001
- 2001-05-10 EP EP01939010A patent/EP1385471A1/en not_active Withdrawn
- 2001-05-10 CN CN01823219.1A patent/CN1224378C/zh not_active Expired - Lifetime
- 2001-05-10 JP JP2002588965A patent/JP2004529173A/ja active Pending
- 2001-05-10 WO PCT/US2001/015045 patent/WO2002092046A1/en active Application Filing
- 2001-05-10 MX MXPA03010217A patent/MXPA03010217A/es not_active Application Discontinuation
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US20040096414A1 (en) | 2004-05-20 |
WO2002092046A1 (en) | 2002-11-21 |
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JP2004529173A (ja) | 2004-09-24 |
MXPA03010217A (es) | 2004-03-10 |
EP1385471A1 (en) | 2004-02-04 |
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