CN1791379A - 作为多步化妆品涂敷的化妆品体系 - Google Patents
作为多步化妆品涂敷的化妆品体系 Download PDFInfo
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- CN1791379A CN1791379A CNA2004800132594A CN200480013259A CN1791379A CN 1791379 A CN1791379 A CN 1791379A CN A2004800132594 A CNA2004800132594 A CN A2004800132594A CN 200480013259 A CN200480013259 A CN 200480013259A CN 1791379 A CN1791379 A CN 1791379A
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Abstract
适于用作多步皮肤化妆品被涂敷到皮肤上的化妆品体系。该体系包括两种组合物。第一组合物由约5%至约90%的、在一个大气压和25℃下蒸汽压小于10mmHg的低挥发性物质以及约0.05%至约10%的可溶解或分散于低挥发性物质中的乳化剂组成。第二组合物由与第一组合物中低挥发性物质的界面张力为至少零达因/厘米的连续相流体、固体、凝胶或半固体组成。第二组合物在第一组合物之后被局部涂敷到皮肤上。本发明进一步涉及使用化妆品体系向使用者皮肤有效递送令人满意的粉底产品的方法。
Description
发明领域
本发明涉及适于一种用作多步化妆品的化妆品体系。具体地讲,该化妆品体系包括至少两种局部和循序涂敷到皮肤上的组合物。
发明背景
众所周知,在皮肤美容护理领域,可使用化妆品组合物如粉底来提供皮肤有益效果,这些有益效果包括光泽控制、吸油、自然的皮肤外观、皮肤感觉和抗转移性。然而,这些皮肤有益效果无法通过一个粉底体系而同时获得,因为这向能否配制符合消费者多重需要的组合物提出了挑战。例如,具有抗转移性质的粉底典型地不具有良好的皮肤感觉特征。此外,具有较好吸油有益效果的组合物也许不具有良好的抗转移性质。
仍需要有一种可通过一个粉底体系递送较好抗转移性、光泽控制、敷用、皮肤感觉和外观有益效果的化妆品组合物。申请人已发现,使用两步体系来显著改善这些有益效果是可能的,该两步体系能使消费者向皮肤表面涂敷较高含量的关键有益效果活性物质,而不会有将相同含量活性物质掺入到单一制剂中所可能带来的负面敷用、感觉或外观性质。而且,在研发两步化妆品体系过程中,已发现,重要的是设计美容上可接受的用于两步的载体,以使它们能够在改善敷用、感觉和外观性质方面一起协同作用。因此,仍需要有一种可通过两步粉底体系递送较好有益效果的粉底,其中通过施用后可使第二步乳化于第一步中的特殊配制方法,使该体系中第二步的涂抹特性变得优异。
发明概述
本发明涉及适宜作为多步化妆品涂敷到皮肤的化妆品体系。该体系包括至少两种组合物。第一组合物由约5%至约90%的、在一个大气压和25℃下蒸汽压为至少约0mmHg至约10mmHg的低挥发性流体、凝胶或半固体以及0.05%至10%的可溶解或分散于低挥发性物质中的乳化剂组成。第二组合物由至少部分与来自第一组合物中的低挥发性物质不相混合的连续相流体、固体、凝胶或半固体组成。在两种连续相均为流体的情况下,可通过两相之间存在的弯液面和可测量的大于零达因/厘米的界面张力将其量化。第二组合物在第一组合物之后被局部涂敷到皮肤上。
本发明进一步涉及使用化妆品体系以向使用者皮肤有效递送令人满意的粉底产品的方法。
发明详述
本发明涉及适宜作为多步化妆品涂敷的化妆品体系。令人惊奇的是,本发明的发明者已发现,可能通过一个两步粉底体系产生具有较好有益效果的粉底,其中通过施用后可使第二步乳化于第一步中的特殊配制方法,可使该体系中第二步的涂抹特性变得优异。将第二步乳化于第一步中的能力导致在涂敷/涂抹特性以及光滑感和自然外观方面产生意想不到的有益效果。相反,如果第二组合物的连续相实际溶解/混溶于第一组合物的剩余薄膜中,则第二组合物将实际上再溶于第一组合物的残余物中,并产生更加粘稠、更加拖曳的涂敷体验。随着必须随后被第二组合物再溶解/再润湿的成膜聚合物和颗粒的掺入,这个问题被进一步复杂化。
下面描述化妆品体系的基本组分。还包括可用于本发明实施方案中的各种非必需和优选组分的非排除性描述。
本文所用的“安全有效量”是指化合物、组分或组合物(当适用时)的量足以显著引起积极效果(例如,提供显著的美容有益效果),但其量又足够低以避免严重的副作用(例如,不适当的毒性或过敏反应),即在合理的医学判断范围内提供合理的效险比。
本文所用的“化妆品体系”是指任何有色化妆品或护肤产品。“化妆品体系”包括但不限于在面部留下色彩的产品,其包括化妆品、液体粉底、睫毛膏、隐蔽物、眼线、眉彩、眼影、腮红、唇膏、唇香膏、化妆底粉、固体乳液粉底、粉末粉底等等。术语“粉底”是指液体、乳剂、摩丝、粉饼、致密物、隐蔽物或由化妆品公司制造或重新引进的使皮肤的总体色调均匀的类似产品。此外,“化妆品体系”可包括润湿剂、防晒剂产品、自晒黑产品、止汗剂组合物、修面膏和洁肤剂。
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。该术语包括术语“由...组成”和“基本上由...组成”。本发明的产品、组合物和方法/工艺可包括、由或基本上由本文所述的基本成分和限制条件以及本文所述的任何附加或非必需成分、组分、步骤或限制条件组成。
除非另外指明,所有的百分比、份数和比率均以本发明组合物的总重量计。有关所列成分的所有重量均基于活性物质的含量,因此除非另外指明,它们不包括可能包括在市售材料中的溶剂或副产物。本文中,术语“重量百分比”可表示为“wt.%”。
化妆品组合物的优选pH值范围为约3至约10,更优选为约4至约9。
除非另外指明,所有测量均在25℃的温度下进行。
第一组合物
A.
低挥发性物质
本发明化妆品体系包括低挥发性物质。包括在受权利要求书保护的化妆品体系中的适宜低挥发性物质包括但不限于疏水性非极性物质、亲水性极性物质以及它们的混合物。本发明的低挥发性流体、凝胶和半固体定义为在一个大气压和25℃下具有的蒸汽压为至少约0mmHg至约10mmHg,优选至少约0mmHg至约5mmHg,甚至更优选至少约0mmHg至约3mmHg的流体、凝胶和半固体。
本发明的疏水性非极性物质定义为按Hildebrand标度测定,具有的溶解度参数为约11.0或11.0以下的物质。本发明的亲水性极性物质定义为按Hildebrand标度测定,具有的溶解度参数为约12.0或12.0以上的物质。Hildebrand研究出从物质沸点、分子量和比重导出溶解度参数的方法;参见J.H.Hildebrand、J.M.Prausnitz和R.L.Scott的“Regular and Related Solutions”,New York;Van Nostrand Reinholdt(1950),该文献引入本文以供参考。在“Cosmetic Bench Reference”,Carol Stream Ill.,AlluredPublishing(1992年)和A.F.Barton的“Handbook of SolubilityParameters and Other Cohesion Parameters”,第二版,Boca Raton,CRC Press(1992年)中,公布了许多化妆品和药物的Hildebrand溶解度参数。
按所述化妆品体系的重量计,本发明的化妆品体系包含约5.0%至约90.0%,优选约8.0%至约70.0%的低挥发性物质。在优选的实施方案中,化妆品体系中低挥发性物质的含量按所述化妆品体系的重量计为约10.0%至约60.0%。
第一组合物还可包括与低挥发性物质结合的具有更大挥发性的物质,在一个大气压和25℃下,该物质具有的蒸汽压大于约10mmHg。适用于第一组合物的亲水性和疏水性流体的实施例可选自下列物质,只要它们符合本发明的挥发性标准。
1.
疏水性非极性物质:
适宜的疏水性组分的非限制性实施例选自以下那些:
(1)还称为凡士林液体的矿物油是可得自石油的液体烃混合物。参见The Merck Index,第10版,第7048条,第1033页(1983)和International Cosmetic Ingredient Dictionary,第5版,第1卷,第415至417页(1993)。
(2)还称为石油凝胶的凡士林是非直链固体烃和高沸点液体烃的胶态体系,其中大多数液体烃保留在胶束内部。参见The Merck Index,第10版,第7047条,1033页(1983);Schindler,Drug.Cosmet.Ind.,89,36至37页,76,78至80页,82(1961);和International Cosmetic Ingredient Dictionary,第5版,第1卷,第537页(1993)。
(3)具有约7至约40个碳原子的直链和支链烃。这些烃物质的非限制性实施例包括十二烷、异十二烷、角鲨烷、胆固醇、氢化聚异丁烯、二十二烷(即C22烃)、十六烷、异十六烷(一种以Permethyl101A由Prespers市售的烃)。其它有用的是C7至C40异链烷烃、它们是C7至C40的支链烃。
(4)C1至C30羧酸和C2至C30二羧酸的C1至C30醇酯,其中所述羧酸包括直链和支链物质以及芳族衍生物(用于本文,涉及疏水性组分、一元和多元羧酸,包括直链、支链和芳基羧酸)。非限制性实施例包括癸二酸二异丙酯、己二酸二异丙酯、肉豆蔻酸异丙酯、棕榈酸异丙酯、棕榈酸甲酯、丙酸十四烷基酯、棕榈酸2-乙基己基酯、新戊酸异癸酯、马来酸二-2-乙基己基酯、棕榈酸鲸蜡酯、肉豆蔻酸十四烷基酯、硬脂酸十八烷基酯、硬脂酸异丙酯、硬脂酸甲酯、硬脂酸鲸蜡酯、山嵛酸山嵛酯、马来酸二辛酯、癸二酸二辛酯、己二酸二异丙酯、辛酸鲸蜡酯和二亚油酸二异丙酯。
(5)C1至C30羧酸的甘油一酯、甘油二酯和甘油三酯,例如,辛酸/癸酸甘油三酯、PEG-6辛酸/癸酸甘油三酯、PEG-8辛酸/癸酸甘油三酯。
(6)C1至C30羧酸的烷撑二醇酯,例如,C1至C30羧酸的乙二醇单酯和二酯,以及C1至C30羧酸的丙二醇单酯和二酯,如乙二醇二硬脂酸酯。
(7)上述物质的丙氧基化和乙氧基化衍生物。
(8)糖和相关物质的C1至C30的单酯和多酯。这些酯衍生自糖或多元醇部分和一种或多种羧酸部分。根据酸和糖组分,这些酯在室温下可以呈液体或固体的形式。液体酯的实施例包括:葡萄糖四油酸酯、大豆油脂肪酸(不饱和的)的葡萄糖四酯、混合的大豆油脂肪酸的甘露糖四酯、油酸的半乳糖四酯、亚油酸的阿拉伯糖四酯、木糖四亚油酸酯、半乳糖五油酸酯、山梨醇四油酸酯、不饱和大豆油脂肪酸山梨醇六酯、木糖醇五油酸酯、蔗糖四油酸酯、蔗糖五油酸酯、蔗糖六油酸酯、蔗糖七油酸酯、蔗糖八油酸酯以及它们的混合物。固体酯的实施例包括:山梨醇六酯,其中羧酸酯部分是摩尔比为1∶2的棕榈油酸酯和花生酸酯;棉子糖的八酯,其中羧酸酯部分是摩尔比为1∶3的亚油酸酯和山嵛酸酯;麦芽糖的七酯,其中酯化羧酸部分是摩尔比为3∶4的向日葵籽油脂肪酸和二十四烷酸酯;蔗糖的八酯,其中酯化羧酸部分是摩尔比为2∶6的油酸酯和山嵛酸酯;以及蔗糖的八酯,其中酯化羧酸部分是摩尔比为1∶3∶4的月桂酸酯、亚油酸酯和山嵛酸酯。优选的固体材料是酯化度为7至8的蔗糖多酯,且其中脂肪酸部分是C18一元和/或二元不饱和脂肪酸和二十二烷酸,不饱和脂肪酸与二十二烷酸的摩尔比为1∶7至3∶5。尤其优选的固体糖多酯是蔗糖八酯,其中分子中约有7份二十二烷基脂肪酸部分和约1份油酸部分。其它物质包括蔗糖的棉籽油或大豆油脂肪酸酯。酯物质还描述于美国专利2,831,854、美国专利4,005,196、美国专利4,005,195、美国专利5,306,516、美国专利5,306,515、美国专利5,305,514、美国专利4,797,300、美国专利3,963,699、美国专利4,518,772、和美国专利4,517,360中。
(9)有机聚硅氧烷油。适宜硅氧烷的非限制性实施例公开于美国专利5,069,897中。合适的有机硅氧烷油的实施例包括聚烷基硅氧烷、环聚烷基硅氧烷和聚烷基芳基硅氧烷。
用于本文组合物中的聚烷基硅氧烷包括25℃下粘度为约0.5厘沲至约1,000,000厘沲的聚烷基硅氧烷。上述聚烷基硅氧烷可以化学通式R3SiO[R2SiO]xSiR3表示,其中R是具有约1至约30个碳原子的烷基(R优选为甲基或乙基,更优选为甲基;混合烷基也可用于同一分子中),并且x是为约0至约10,000的整数,选择x以达到超过约10,000,000范围的所需分子量。市售的聚烷基硅氧烷包括聚二甲基硅氧烷,其还被称为聚二甲基硅氧烷,其实施例包括由General Electric Company出售的Vicasil系列和由Dow CorningCorporation出售的Dow Corning200系列。适宜聚二甲基硅氧烷的具体实例包括粘度为0.65厘沲且沸点为100℃的Dow Coming200流体、粘度为10厘沲且沸点大于200℃的Dow Corning225流体和粘度分别为50厘沲、350厘沲和12,500厘沲且沸点大于200℃的Dow Corning200流体。适宜的聚二甲基硅氧烷包括以化学式(CH3)3SiO[(CH3)2SiO]x[CH3RSiO]ySi(CH3)3表示的那些,其中R是具有约2至约30个碳原子的直链或支链烷基,并且x和y各为1或更大的整数,选择x、y以达到超过约10,000,000范围的所需分子量。这些烷基取代的聚二甲硅氧烷的实施例包括鲸蜡基聚二甲硅氧烷和月桂基聚二甲硅氧烷。
适用于组合物中的环状聚烷基硅氧烷包括以化学式[SiR2-O]n表示的那些,其中R是烷基(R优选为甲基或乙基,更优选为甲基),并且n是为约3至约8,更优选约3至约7,甚至更优选约4至约6的整数。当R为甲基时,这些物质典型地称为环状聚甲基硅氧烷。市售环状聚甲基硅氧烷包括粘度为2.5厘沲、并且沸点为172℃、主要含有环状聚甲基硅氧烷四聚体(即n=4)的Dow Corning244液体,粘度为2.5厘沲、并且沸点为178、主要含有环状聚甲基硅氧烷五聚体(即n=5)的Dow Corning344液体,粘度为4.2厘沲、沸点为205℃、主要含有环状聚甲基硅氧烷四聚体与五聚体混合物(即n=4和5)的Dow Corning245液体,粘度为4.5厘沲、并且沸点为217℃、主要含有环状聚甲基硅氧烷四聚体、五聚体与六聚体混合物(即n=4、5和6)的Dow Corning345液体。
聚二甲基硅氧烷醇也适用于该组合物。这些化合物可以化学式R3SiO[R2SiO]xSiR2OH和HOR2SiO[R2SiO]xSiR2OH表示,其中R是烷基(R优选为甲基或乙基,更优选为甲基),并且x是0至约500的整数,选择x以达到所需的分子量。市售聚二甲基硅氧烷醇典型地是作为与聚二甲基硅氧烷或环状聚甲基硅氧烷的混合物(例如DowCorning1401,1402,和1403液体)销售的。
聚烷基芳基硅氧烷也适用于组合物。在25℃时粘度为约15厘沲至约65厘沲的聚甲基苯基硅氧烷是特别有用的。
优选用于本文的是选自下列的有机聚硅氧烷:聚烷基硅氧烷、烷基取代的聚二甲基硅氧烷、环状聚甲基硅氧烷、三甲基甲硅烷氧基硅酸酯、聚二甲基硅氧烷醇、聚烷基芳基硅氧烷和它们的混合物。更优选用于本发明的是聚烷基硅氧烷和环状聚甲基硅氧烷。在聚烷基硅氧烷当中,聚二甲基硅氧烷是优选的。
(10)植物油和氢化植物油。植物油和氢化植物油的实施例包括红花油、蓖麻油、椰子油、棉籽油、鲱油、棕榈仁油、棕榈油、花生油、豆油、油菜籽油、亚麻籽油、米糠油、松油、芝麻油、向日葵籽油、氢化红花油、氢化蓖麻油、氢化椰子油、氢化棉子油、氢化鲱油、氢化棕榈仁油、氢化棕榈油、氢化花生油、氢化豆油、氢化油菜籽油、氢化亚麻籽油、氢化米糠油、氢化芝麻油、氢化向日葵籽油以及它们的混合物。
(11)动物脂和油(例如羊毛脂及其衍生物,鳕鱼肝油)
(12)含氟烃流体。实施例包括但不限于,购自3M Corporation的氢氟醚和全氟聚醚(由Montefluos生产的Fomblin系列、由Daikin Industries生产的Demnum系列和由DuPont Corporation生产的Krytox系列)。
(13)还可用的是聚丙二醇的C4至C20烷基醚、聚丙二醇的C1至C20羧酸酯和二C8至C30烷基醚。这些物质的非限制性实施例包括PPG-14丁基醚、PPG-15硬脂基醚、二辛基醚、十二烷基辛基醚以及它们的混合物。
2.
亲水性极性物质
亲水性极性物质的实施例包括但不限于水、乙醇、异丙醇或在一个大气压和25℃下蒸汽压为至少约0mmHg至约10mmHg的任何醇或二元醇。
可用于本发明的亲水性极性物质的实施例包括但不限于下列物质,如尿素、胍、乙醇酸和甘醇酸盐(如铵盐和四烷基铵盐)、乳酸和乳酸盐(如铵盐和四烷基铵盐)、各种形式的芦荟(如芦荟凝胶)、多羟基醇(如山梨醇、甘油、己三醇、丙二醇、丁二醇、己二醇等)、聚乙二醇、糖和淀粉、糖和淀粉衍生物(如烷氧基化葡萄糖)、透明质酸、甲壳质、支化淀粉聚丙烯酸钠,如Sanwet(RTM)IM-1000、IM-1500和IM-2500,(购自Celanese Superabsorbent Materials)、乳酰胺单乙醇胺、乙酰胺单乙醇胺、丙氧基化甘油(如美国专利4,976,953中所描述的)以及它们的混合物。
B.
乳化剂和两亲分子
本发明的第一组合物包含乳化剂、两亲分子或它们的混合物。在优选的一个实施方案中,按由乳化剂或两亲分子形成的所述组合物的重量计,该组合物包含约0.05%至约10%,更优选约0.1%至约7.5%,甚至更优选约0.5%至约5%的乳化剂。
在该组合物中,可使用已知的或常用的乳化剂,只要所选的乳化剂或两亲分子可混溶、溶解或分散于第一组合物中,且具有下列性能:1)能够有效地降低第一组合物和第二组合物外相之间的界面张力,和/或2)能够使第二组合物的连续相乳化到第一组合物的连续相中。适宜的乳化剂可包括任何公开于前述专利和其它参考文献中的各种非离子、阳离子、阴离子和两性离子乳化剂。参见Allured PublishingCorporation公布的McCutcheon的“Detergents and Emulsifiers”北美版(1986年)、美国专利5,011,681、美国专利4,421,769、和美国专利3,755,560。
适宜的乳化剂类型包括甘油酯、丙二醇酯、聚乙二醇脂肪酸酯、聚丙二醇脂肪酸酯、山梨醇酯、脱水山梨糖醇酯、羧酸共聚物、葡萄糖酯和葡萄糖醚、乙氧基化醚、乙氧基化醇、磷酸烷基酯、聚氧乙烯脂肪醚磷酸酯、脂肪酸酰胺、酰基乳酸盐、皂以及它们的混合物。可用于本文的包含非硅氧烷的乳化剂的非限制性实施例包括:聚乙二醇20脱水山梨糖醇一月桂酸酯(聚山梨酸酯20)、聚乙二醇5大豆甾醇、硬脂基聚氧乙烯醚-20、鲸蜡硬酯基聚氧乙烯醚-20、PPG-2甲基葡萄糖醚二硬脂酸盐、十六烷基聚氧乙烯醚-10、聚山梨酸酯80、鲸蜡基磷酸盐、鲸蜡基磷酸钾、二乙醇胺鲸蜡基磷酸盐、聚山梨酸酯60、硬脂酸甘油酯、PEG-100硬脂酸盐、聚氧化乙烯20脱水山梨糖醇三油酸酯(聚山梨酸酯85)、脱水山梨糖醇一月桂酸酯、聚氧化乙烯-4-月桂基醚硬脂酸钠、聚甘油基-4-异硬脂酸酯、月桂酸己酯、硬脂基聚氧乙烯醚-20、鲸蜡硬酯基聚氧乙烯醚-20、PPG-2甲基葡萄糖醚二硬脂酸盐、十六烷基聚氧乙烯醚-10、二乙醇胺鲸蜡基磷酸盐、硬脂酸甘油酯、PEG-100硬脂酸酯和它们的混合物。
适宜的乳化剂还可包括硅氧烷乳化剂,其典型地为有机改性的有机聚硅氧烷,还被本领域的技术人员称为硅氧烷表面活性剂。有用的硅氧烷乳化剂包括聚二甲基硅氧烷共聚多元醇。这些物质是进行过改性以引入聚醚侧链的聚二甲基硅氧烷,该聚醚侧链,如聚环氧乙烷链、聚环氧丙烷链、这些链的混合物,和含有衍生自环氧乙烷与环氧丙烷部分的聚醚链。其它实施例包括烷基修饰的聚二甲基硅氧烷共聚多元醇,即含有C2至C30侧链的化合物。其它还有用的聚二甲基硅氧烷共聚多元醇还包括具有各种的阳离子、阴离子、两性和两性离子侧链部分的物质。
可用于本发明的聚二甲基硅氧烷共聚多元醇乳化剂可由下列通用结构描述:
其中R是C1至C30直链、支链或环状烷基,且R2选自
--(CH2)n--O--(CH2CHR3O)m--H
和
--(CH2)n--O--(CH2CHR3O)m--(CH2CHR4O)o--H,
其中n是约3至约10的整数;R3和R4选自H和C1至C6直链或支链烷基,以使R3和R4不同时为同一种基团;并且,选定m、o、x和y,使得分子的整体分子量为约200至约10,000,000,而m、o、x和y独立地选自零或更大的整数,以使m和o不能同时为零,且z独立地选自1或更大的整数。应当认识到,可获得这些共聚多元醇的位置异构体。上文描述的包含R3和R4基团的R2部分的化学表示并不旨在进行限制,而只是为了表示方便。
也可用于本发明中但不严格归类的聚二甲基硅氧烷共聚多元醇是在前面段落的结构中描述的硅氧烷表面活性剂,其中R2是:
--(CH2)n--O--R5,
其中R5是阳离子、阴离子、两性的或两性离子部分。
可用作本文乳化剂的聚二甲基硅氧烷共聚多元醇和其它硅氧烷表面活性剂的非限制性实施例包括:具有聚氧化乙烯侧链的聚二甲基硅氧烷聚醚共聚物,具有聚氧化丙烯侧链的聚二甲基硅氧烷聚醚共聚物,具有混合的聚氧化乙烯和聚氧化丙烯侧链的聚二甲基硅氧烷聚醚共聚物,具有混合的聚氧化(乙烯)(丙烯)侧链的聚二甲基硅氧烷聚醚共聚物,具有有机甜菜碱侧链的聚二甲基硅氧烷聚醚共聚物,具有羧酸盐侧链的聚二甲基硅氧烷聚醚共聚物、具有季铵侧链的聚二甲基硅氧烷聚醚共聚物,以及含有C2至C30直链、支链、或环状烷基部分侧链的上述共聚物的进一步改性物。可用于本发明的由DowCorning Corporation销售的市售聚二甲基硅氧烷共聚多元醇的实施例有Dow Corning190、193、Q2-5220、2501蜡、2-5324液体和3225C(后者作为与环状聚甲基硅氧烷的混合物销售)。鲸蜡基聚二甲基硅氧烷共聚多元醇是作为与聚甘油基-4-异硬脂酸酯(和)月桂酸己酯的混合物商购获得,并且以商品名ABILWE-09销售(购自Goldschmidt)。鲸蜡基聚二甲基硅氧烷共聚多元醇还作为与月桂酸己酯(和)聚甘油基-3油酸酯(和)鲸蜡基聚二甲基硅氧烷的混合物市售,并且以商品名ABILWS-08销售(也购自Goldschmidt)。其它非限制性实施例包括购自Crompton/OSi的SILWET系列和SILSOFT系列。聚二甲基硅氧烷共聚多元醇的其它非限制性实施例还包括月桂基聚二甲基硅氧烷共聚多元醇、聚二甲基硅氧烷共聚多元醇乙酸酯、聚二甲基硅氧烷共聚多元醇己二酸酯、聚二甲基硅氧烷共聚多元醇胺、聚二甲基硅氧烷共聚多元醇二十二烷酸酯、聚二甲基硅氧烷共聚多元醇丁基醚、聚二甲基硅氧烷共聚多元醇羟基硬脂酸酯、聚二甲基硅氧烷共聚多元醇异硬脂酸酯、聚二甲基硅氧烷共聚多元醇月桂酸酯、聚二甲基硅氧烷共聚多元醇甲基醚、聚二甲基硅氧烷共聚多元醇磷酸酯和聚二甲基硅氧烷共聚多元醇硬脂酸酯。参见“International Cosmetic Ingredient Dictionary”,第5版,1993年。
第二组合物
化妆品体系的第二组合物包含与第一组合物低挥发性物质的界面张力大于零达因/厘米的连续相流体、固体、凝胶或半固体。第二组合物在第一组合物之后被局部涂敷到皮肤上。
由于在第一组合物连续相的低挥发性物质(不包括任何乳化剂或两亲分子)与第二组合物连续相之间具有大于零达因/厘米的界面张力,根据定义,这两相至少部分不相混溶。这意味着当在一个大气压和25℃下将此两种组合物的连续相流体合并到一个烧杯中时,其显示具有弯液面。如果出现明显的弯液面,则流体至少部分不相混溶,并从而符合本发明的描述。确定组合物之间是否至少部分不相混溶的方法描述于W.M.Jackson和J.S.Drury在“Handbook of Chemistryand Physics”第65版,CRC Press,第C-703页所写的标题为“Miscibility of Organic Solvent Pairs”的文章中。在第一组合物低挥发性物质的折射指数与第二组合物连续相物质的折射指数相匹配的情况下,弯液面即使存在,也可能不明显。为说明这种可能性,可能需要在第一组合物和第二组合物的流体相混合之前,将极性染料溶解在亲水性连续相流体中。通过观察存在于更大极性相中更大含量极性染料分子的最强色的色强差别,可视觉可见存在至少部分不相混溶的情况。此外,可能需要一个张力计来测量两相之间是否存在可测量的界面张力。用于测量界面张力的适宜方法的一个实施例是ASTM方法D971-99a。
包括在受权利要求书保护的化妆品体系中的适宜连续相流体、固体、凝胶或半固体包括但不限于如上文第一组合物中所述的疏水性非极性物质、亲水性极性物质以及它们的混合物。按所述化妆品体系的重量计,本化妆品体系包含约5.0%至约90.0%,优选约8.0%至约70.0%的连续相流体、固体、凝胶或半固体。在优选的实施方案中,连续相流体、固体、凝胶或半固体在化妆品体系中的含量按所述化妆品体系的重量计为约10.0%至约60.0%。
第二组合物不受限于其挥发性或蒸汽压。适用于第二组合物的亲水性和疏水性流体的实施例与第一组合物中所述的那些相同。
非必需成分
A.
着色剂
化妆品体系的组合物可进一步包含着色剂。适宜的着色剂包括但不限于,D&C黄7号、D&C红36号、FD&C红4号、D&C橙4号、D&C红6号、D&C红34号、FD&C黄6号、D&C红33号、FD&C黄5号、D&C棕1号、D&C红17号、FD&C绿3号、D&C蓝4号、D&C黄8号、D&C橙5号、D&C红22号、D&C红21号、D&C红28号、D&C橙11号、D&C黄10号、D&C紫2号、Ex t.D&C紫2号、D&C绿6号、D&C绿5号、D&C红30号、D&C绿8号、D&C红7号、FD&C蓝1号、D&C黄7号、D&C红27号、D&C橙10号、D&C红31号、FD&C红40号、D&C黄11号、胭脂树提取物、β胡萝卜素、鸟嘌呤、胭脂红、铝粉、群青颜料、氯氧化铋、氧化铬绿、氢氧化铬绿、氧化铁、亚铁氰化铁、锰紫、二氧化钛、钛酸盐云母(即,涂敷二氧化钛的云母)、氧化铁钛酸云母、氧化锌、焦糖染色、云母、氰亚铁酸铵铁、二羟基丙酮、愈创烯、叶蜡石、青铜粉、铜粉、硬脂酸铝、硬脂酸钙、核黄素、硬脂酸镁、硬脂酸锌、辣椒红/辣椒玉红素、膨润土、硫酸钡、碳酸钙、硫酸钙、碳黑、碳酸镁、硅酸镁、有色二氧化硅、二氧化硅(包括球形二氧化硅、水合二氧化硅和二氧化硅小球)、CI 10020、CI 11680、CI 15630、CI 15865、CI 16185、CI 16255、CI 16255、CI 45430、CI 69825、CI 73000、CI 73015、CI 74160、CI 75100、CI 77002、CI 77346、CI 77480、尼龙粉末、聚乙烯粉末、乙烯丙烯酸酯共聚物粉末、甲基丙烯酸酯粉末、聚苯乙烯粉末、丝绸粉末、结晶纤维素、淀粉、氯氧化铋、鸟嘌呤、高岭土、白垩、硅藻土、微海绵、氮化硼等。另外,也可使用这些着色剂的色淀或组合物。可用于本发明的附加着色剂、颜料和粉末描述于美国专利5,505,937中。
B.
成膜剂
化妆品体系的组合物可进一步包含成膜剂。按所述组合物的重量计,该组合物包含优选为约0%至约20%,更优选约0.05%至约10%,甚至更优选约0.1%至约5%的成膜剂。
适用于本套盒组合物的成膜剂的实施例包括:
a)硫聚酯树脂,例如AQ硫聚酯树脂,如AQ29D、AQ35S、AQ38D、AQ38S、AQ48S和AQ55S(购自Eastman Chemicals);
b)聚乙酸乙烯酯/聚乙烯醇聚合物,如购自Air Products的Vinex树脂,包括Vinex 2034、Vinex 2144和Vinex 2019;
c)丙烯酸树脂,包括购自National Starch的商品名为“Dermacryl”的水可分散丙烯酸树脂,包括Dermacryl LT;
d)聚乙烯吡咯烷酮(PVP),包括Luviskol K17、K30和K90(购自BASF)、水溶性PVP共聚物,包括PVP/VA S-630和W-735、和PVP/二甲氨基甲基丙烯酸乙酯共聚物,如购自ISP的共聚物845和共聚物937,以及其它PVP聚合物,其由E.S.Barabas公开于“Encyclopedia of Polymer Science and Engineering”第2版第17卷第198至257页中;
e)高分子量聚硅氧烷,如聚二甲基硅氧烷和有机取代的聚二甲基硅氧烷,尤其是粘度大于约50,000mPas的那些聚硅氧烷;
f)粘度大于约50,000mPas的高分子量烃聚合物;
g)硅氧烷-丙烯酸酯共聚物,包括VS-70(3M)、SA-70(3M)、KP-545(Shin-Etsu);
h)有机硅氧烷,包括有机硅氧烷树脂、流体二有机聚硅氧烷聚合物和硅氧烷酯蜡;
i)聚氨酯,包括购自Alzo,Corp.的Polyderm系列聚合物;和
j)疏水性丙烯酸酯共聚物,包括丙烯酸酯/甲基丙烯酸烷基酯共聚物Lipacryl(Rohm & Haas)或其乳化、水可分散形式Allianz OPT(ISP)。
这些聚合物和包含它们的化妆品组合物的实施例可存在于PCT公布WO96/33689、WO97/17058和美国专利5,505,937中。适用于本文的其它成膜聚合物包括含水乳液中的水不溶性聚合材料和水溶性成膜聚合物,其描述于PCT公布WO98/18431中。粘度大于约50,000mPas的高分子量烃聚合物的实施例包括聚丁烯、聚对苯二甲酸丁二酯、聚癸烯、聚环戊二烯和类似的直链和支链高分子量烃。
适宜的成膜聚合物还包括有机硅氧烷树脂,其包含R3SiO1/2“M”单元、R2SiO“D”单元、RSiO3/2“T”单元、SiO2“Q”单元的组合,这些单元互相成一定比例,以满足RnSiO(4-n)/2的关系,其中n值为1.0至1.50,且R为甲基。注意由于加工的原因在树脂结构中存在少量的高达5%的硅烷醇或烷氧基官能度。有机硅氧烷树脂必须在约25℃下为固体,且具有约1,000克/摩尔至约10,000克/摩尔的分子量。树脂可溶解于有机溶剂,如甲苯、二甲苯、异链烷烃和环硅氧烷或挥发性载体,这意味着树脂不是完全交联,这样会使树脂不溶于挥发性载体。尤其优选的树脂包含重复单官能团或R3SiO1/2“M”单元和四官能团或SiO2“Q”单元,该树脂还被称为“MQ”树脂,其公开于美国专利5,330,747中。在本发明中,“M”和“Q”官能单元的比率优选为约0.7,且n值为1.2。诸如这些的有机硅氧烷树脂是市售的,如购自Wacker Silicones Corporation的Wacker 803和804及购自G.E.General Electric Company的G.E.1170-002。
其它用于增强耐磨性或耐转移性的物质包括三甲基化二氧化硅。此类适宜的二氧化硅和包含它们的化妆品组合物描述于美国专利5,800,816中。
C.
吸收剂
本发明组合物可包含一种或多种吸收性材料。这些吸收剂可用于实现通常存在于皮肤上的各种流体的吸收,如汗液、油和/或皮脂。适合的吸收剂包括,但不限于,二氧化硅、硅酸盐、聚丙烯酸酯、交联硅氧烷、交联烃、活性炭、淀粉基物质(例如玉米淀粉(局部用淀粉)、滑石、米淀粉、燕麦淀粉、木薯淀粉、马铃薯淀粉、豆淀粉、大豆淀粉、芜菁淀粉)、微晶纤维素(如Avicel)、辛烯基琥珀酸铝淀粉(由National Starch & Chemical Co.以Dry FloPure、Dry FloXT、Dry FloPC、和/或Dry FloAF(无铝级)出售)、高岭土、硅酸钙、非晶形二氧化硅、碳酸钙、碳酸镁、或碳酸锌以及它们的混合物。可用于本发明的硅酸盐和碳酸盐的某些具体实施例更充分地说明于Van Nostrand Reinhold的“Encyclopedia of Chemistry”,第四版(1984年),第155、169、556和849页中。
D.
抗痤疮活性物质
可用于本发明的抗痤疮活性物质的实施例包括但不限于,角质层分离物,如水杨酸(邻羟基苯甲酸)、水杨酸衍生物如5-辛酰基水杨酸以及间苯二酚;类视色素,如视黄酸及其衍生物(如顺式和反式);含硫的D和L氨基酸及其衍生物和盐,尤其是它们的N-乙酰基衍生物,其优选的实施例为N-乙酰基-L-半胱氨酸;硫辛酸;抗生素和抗微生物剂,如过氧化苯甲酰、羟甲辛吡酮、四环素、2,4,4′-三氯-2′-羟基二苯醚、3,4,4′-三氯二苯基脲、壬二酸及其衍生物、苯氧基乙醇、苯氧基丙醇、苯氧基异丙醇、乙酸乙酯、克林霉素和甲氯环素;皮脂盐,如类黄酮;以及胆汁盐,如鲨胆甾醇硫酸盐及其衍生物、脱氧胆酸盐和胆酸盐。
E.
止汗剂活性物质
止汗剂活性物质也可包含在本发明的组合物中。适宜的止汗剂活性物质包括收敛剂金属盐,尤其是铝、锆和锌的无机盐和有机盐以及它们的混合物。尤其优选的是含铝和/或含锆物质或盐,如卤化铝、水合氯化铝、羟基卤化铝、卤氧化锆、羟基卤氧化锆以及它们的混合物。F.
抗皱与抗皮肤萎缩活性物质
可用于本发明的抗皱和抗皮肤萎缩活性物质的实施例包括,但不限于,视黄酸及其衍生物(例如,顺式和反式);视黄醇;视黄酯;烟酰胺及其衍生物;含硫的D和L氨基酸及其衍生物和盐,尤其是N-乙酰基衍生物,其优选的实施例是N-乙酰基-L-半胱氨酸;硫醇(例如乙硫醇);萜烯醇(例如,金合欢醇);羟基酸、植酸、硫辛酸;溶血磷脂酸,α-羟基酸(例如,乳酸和乙醇酸),β-羟基酸(例如水杨酸)和蜕皮剂(例如,苯酚等)。
G.
仿晒黑活性物质和促进剂
可用于本发明组合物的仿晒黑活性物质和促进剂的实施例包括,但不限于,二羟基丙酮、酪氨酸、酪氨酸酯如酪氨酸乙酯、磷酸基-DOPA以及它们的混合物。
H.
收敛剂
本发明的组合物可包含收敛剂。收敛剂用于收缩皮肤的毛孔。适合的收敛剂包括,但不限于,丁香油、药用拟层孔菌提取物、绣线菊提取物、薄荷醇、樟脑、桉树油、丁子香酚、乳酸薄荷酯、金缕梅馏出液、铝盐、丹宁酸、乙醇以及它们的组合。
I.
亲水性调理剂
本发明还可包含一种或多种亲水性调理剂。亲水性调理剂的非限制性实施例包括选自下列的那些物质:多元醇、聚丙二醇、聚乙二醇、尿素、吡咯烷酮羧酸、乙氧基化的和/或丙氧基化的C3至C6二醇和三醇、α-羟基C2至C6羧酸、乙氧基化的和/或丙氧基化的糖、聚丙烯酸共聚物、具有多达约12个碳原子的糖、具有多达约12个碳原子的糖醇以及它们的混合物。有用的亲水性调理剂的具体实施例包括以下物质,例如尿素,胍,乙醇酸和乙醇酸盐(例如,铵盐和四烷基铵盐),乳酸和乳酸盐(例如,铵盐和四烷基铵盐),蔗糖、果糖、葡萄糖、赤藓糖、赤藓醇、山梨醇、甘露糖醇、甘油、己三醇、丙二醇、丁二醇、己二醇等,聚乙二醇如PEG-2、PEG-3、PEG-30、PEG-50,聚丙二醇如PPG-9、PPG-12、PPG-15、PPG-17、PPG-20、PPG-26、PPG-30、PPG-34,烷氧基化葡萄糖,透明质酸,阳离子皮肤调理聚合物(例如,季铵聚合物如聚季铵聚合物)以及它们的混合物。具体地讲,在本发明中,甘油是优选的亲水性调理剂。还可用的物质如各种形式的芦荟(例如,芦荟凝胶)、脱乙酰壳多糖和脱乙酰壳多糖衍生物(如乳酸脱乙酰壳多糖乳酸酯、乳酰胺单乙醇胺)、乙酰胺单乙醇胺以及它们的混合物。还有用的是丙氧基化的甘油,参见美国专利4,976,953。
J.
疏水性调理剂
该组合物可包含一种或多种疏水性调理剂。优选的疏水性调理剂选自矿物油、凡士林、卵磷脂、氢化卵磷脂、羊毛脂、羊毛脂衍生物、C7至C40支链烃、C1至C30羧酸的C1至C30醇酯、C2至C30二羧酸的C1至C30醇酯、C1至C30羧酸的甘油单酯、C1至C30羧酸的甘油二酯、C1至C30羧酸的甘油三酯、C1至C30羧酸的乙二醇单酯、C1至C30羧酸的乙二醇二酯、C1至C30羧酸的丙二醇单酯、C1至C30羧酸的丙二醇二酯、糖的C1至C30羧酸单酯和多酯、聚二烷基硅氧烷、聚二芳基硅氧烷、聚烷基芳基硅氧烷、具有3至9个硅原子的环二甲基硅氧烷、植物油、氢化植物油、聚丙二醇C4至C20烷基醚、二C8至C30烷基醚以及它们的组合。
K.
散光剂
该组合物可包含散光剂。散光剂可用于通过减少纹理如孔和细纹的出现来改善皮肤外观。包含在本发明体系组合物中的适宜散光剂包括,但不限于,二氧化硅、尼龙、聚乙烯、聚甲基丙烯酸甲酯、聚苯乙烯、甲基硅氧烷共聚物、聚四氟乙烯共聚物、氮化硼、硅氧烷树脂粉末、硅氧烷橡胶粉末、乙烯丙烯酸酯共聚物、云母、二氧化钛、氧化铁、氧化锌以及它们的组合。
L.
油溶性的聚合胶凝剂
本发明的组合物可以非必需地包括一种或多种聚合材料,该聚合材料是油溶性的,并且与包含在组合物中的疏水性物质(例如,油)形成凝胶。这种聚合物有益于构建这些材料,以得到具有改善的稳定性和抗剪切的柔韧性凝胶。
尤其适合的是软化点小于160℃的至少部分交联的油溶性聚合材料。适宜的材料来自于下列物质的化学基团:PE(聚乙烯)、PVA(聚乙烯醇)及衍生物、PVP(聚乙烯吡咯烷酮)及衍生物、PVP/烯烃共聚物、PVP/VA共聚物、PVM/MA(甲基乙烯基醚/马来酸酐)共聚物和它们的酯和醚,尤其是(烷基乙烯醚)-(马来酸酐)共聚物、乙烯/VA共聚物、丙烯酸酯/烷基甲基丙烯酸酯共聚物、苯乙烯/异戊二烯、苯乙烯/乙烯/丁烯、苯乙烯/乙烯/丙烯、苯乙烯/乙烯/丁烯/苯乙烯、苯乙烯/丁二烯共聚物、膨润土粘土,锂蒙脱石粘土、有机蜡和硅氧烷蜡。适宜的材料可购自,例如,Dupont(ELVAX型)、BASF(LUVISKOL型)、Shell(KRATON聚合物)、ISP(PVP、GANTREZ、GANEX和ALLIANZOPT型)和Rohm & Haas(LIPACRYL)。
M.
亲水性胶凝剂
本发明组合物可非必需地包含亲水性胶凝剂。胶凝剂所具有的粘度(1%水溶液,20℃,Brookfield RVT)优选至少约4000mPas,更优选至少约10,000mPas,甚至更优选至少50,000mPas。
适宜的亲水性胶凝剂通常可描述为水溶性或胶状水溶性聚合物,并且包括纤维素醚(如羟乙基纤维素、甲基纤维素、羟丙基甲基纤维素)、膨润土粘土、锂蒙脱石粘土、聚乙烯吡咯烷酮、聚乙烯醇、聚季胺盐-10、瓜尔胶、羟丙基瓜尔胶和黄原胶。
其中适合的亲水性凝胶剂是丙烯酸/丙烯酸乙酯共聚物和由B.F.Goodrich Company以商标Carbopol树脂出售的羧基乙烯基聚合物。这些树脂基本上由胶态水溶性聚烯基聚醚交联聚合物组成,所述聚合物是由丙烯酸与约0.75%至约2.00%的交联剂如聚烯丙基蔗糖或聚烯丙基季戊四醇交联而得到的。其实施例包括Carbopol 934、Carbopol 940、Carbopol 950、Carbopol 980、Carbopol 951和Carbopol 981。Carbopol 934是丙烯酸与约1%的蔗糖聚烯丙基醚交联形成的水溶性聚合物,其中每个蔗糖分子平均具有约5.8个烯丙基。还适用于本文的是具有两性分子特性的丙烯酸的疏水改性的交联聚合物,其以商品名Carbopol 1382、Carbopol 1342和Pemulen TR-1(CTFA名称:丙烯酸酯/10至30烷基丙烯酸酯交联聚合物)市售。聚烯基聚醚交联的丙烯酸聚合物和疏水改性交联的丙烯酸聚合物的组合物也适用于本文。其它适用于本发明的适合的胶凝剂是油凝胶,例如三羟基硬脂精和羟基硬脂酸铝镁。本文的胶凝剂在常温和高温下对于提供极好的稳定性来说是尤其有价值的。
适用于中和包含本文亲水胶凝剂的酸性基团的中和剂包括氢氧化钠、氢氧化钾、氢氧化铵、单乙醇胺、二乙醇胺和三乙醇胺。
N.
交联硅氧烷聚合物
本发明的组合物可非必需地包含性质上为非直链的聚合物。包含在受权利要求书保护的组合物中适合的聚合物包括,但不限于为交联有机聚硅氧烷聚合物凝胶网络的聚硅氧烷。例如,尤其适合的交联有机聚硅氧烷聚合物凝胶网络是由环氧官能化的有机聚硅氧烷在酸催化剂的存在下通过聚合反应形成的。有机聚硅氧烷聚合物为选自非乳化聚合物凝胶网络、乳化聚合物凝胶网络以及它们的组合的交联有机聚硅氧烷聚合物凝胶网络。该物质的具体实施例描述于美国专利6,531,540 B1、美国专利6,538,061 B2、美国专利6,444,745 B1、美国专利6,346,583 B1、美国专利5,654,362、美国专利5,811,487、美国专利5,880,210、美国专利5,889,108、美国专利5,929,164、美国专利5,948,855、美国专利5,969,035、美国专利5,977,280、美国专利6,080,394、美国专利6,168,782、美国专利6,177,071、美国专利6,200,581、美国专利6,207,717、美国专利6,221,927、美国专利6,221,979、美国专利6,238,657和美国专利4,987,169中。
适合的有机聚硅氧烷聚合物网络粉末包括乙烯基聚二甲基硅氧烷/聚甲基硅氧烷倍半硅氧烷交联聚合物如Shin-Etsu的KSP-100、KSP-101、KSP-102、KSP-103、KSP-104、KSP-105,包含氟代烷基基团的混合硅氧烷粉末如Shin-Etsu的KSP-200,以及包含苯基基团的混合硅氧烷粉末例如Shin-Etsu的KSP-300;和Dow Corning的DC 9506。
优选的有机聚硅氧烷组合物为聚二甲基硅氧烷/乙烯基聚二甲基硅氧烷交联聚合物。上述聚二甲基硅氧烷/乙烯基聚二甲基硅氧烷交联聚合物由许多供货商提供,包括Dow Corning(DC 9040和DC 9041)、General Electric(Velvesil 125)、General Electric(SFE 839)、Shin Etsu(KSG-15、16、18[聚二甲基硅氧烷/苯基乙烯基聚二甲基硅氧烷交联聚合物]和KSG-21[聚二甲基硅氧烷共聚多元醇交联聚合物])、Grant Industries(GransilTM系列物质)、由Shin Etsu提供的月桂基聚二甲基硅氧烷/乙烯基聚二甲基硅氧烷交联聚合物(如,KSG-41、KSG-42、KSG-43和KSG-44)、也由Shin-Etsu提供的月桂基聚二甲基硅氧烷/聚二甲基硅氧烷共聚多元醇交联聚合物(如,KSG-31、KSG-32、KSG-33和KSG-34)、和Wacker(Belsil RG-100)。适用于本发明的其它来自于Shin-Etsu的聚合物包括KSG-210、-310、-320、-330和-340。可用于本发明的交联有机聚硅氧烷聚合物凝胶网络和制备它们的方法进一步描述于美国专利4,970,252、美国专利5,760,116、美国专利5,654,362和日本专利申请JP61-18708中。
O.
防晒活性物质
还可用于本发明的是防晒活性物质。各种各样的防晒活性物质描述于美国专利5,087,445、美国专利5,073,372、美国专利5,073,371和Sagarin等人所写的“Cosmetics Science andTechnology”第VIII章第189页以下各页中。用于本发明组合物的防晒剂的非限制性实施例选自对甲氧基肉桂酸-2-乙基己基酯、N,N-二甲基对氨基苯甲酸-2-乙基己基酯、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、水杨酸高薄荷酯、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、二氧化硅、氧化铁以及它们的混合物。其它可用的防晒剂还有那些公开于1990年6月26日公布的授予Sabatelli的美国专利4,937,370、和1991年3月12日公布的授予Sabatelli等人的美国专利4,999,186中的物质。这些防晒剂的尤其优选的实施例包括选自以下物质的那些:2,4-二羟基二苯甲酮的4-N,N-(2-乙基己基)甲氨基苯甲酸酯、含4-羟基二苯甲酰基甲烷的4-N,N-(2-乙基己基)甲氨基苯甲酸酯、2-羟基-4-(2-羟基乙氧基)二苯酮的4-N,N-(2-乙基己基)甲氨基苯甲酸酯、4-(2-羟基乙氧基)二苯甲酰甲烷的4-N,N-(2-乙基己基)甲氨基苯甲酸酯、以及它们的混合物。可使用的防晒剂的准确用量应取决于所选的防晒剂和要达到的所需防晒因子(SPF)。SPF是防晒剂的抗红斑光保护作用的常用量度。
P.
附加非必需成分
本发明组合物还可包括如下成分,其分类为脱皮剂、亮肤剂、皮肤抚慰和皮肤愈合活性物质、维生素化合物及前体、螯合剂、酶、类黄酮(完全公开于美国专利5,686,082和5,686,367中)以及甾醇化合物。
相关方法
申请者已经发现本发明组合物可用于多种涉及增强哺乳动物皮肤的应用。本文公开的和要求保护的组合物的使用方法包括但不限于:1)增加化妆品对于皮肤亲和性的方法;2)使皮肤保湿的方法;3)改善皮肤天然外观的方法;4)向皮肤涂敷有色化妆品的方法;5)防止、延缓和/或处理皱纹的方法;6)向皮肤提供紫外线防护的方法;7)防止、延缓和/或控制泛油外观的方法;8)调节皮肤感觉和纹理的方法;9)提供均匀皮肤色调的方法;10)防止、延缓和/或处理辐射状血管和静脉曲张的外观的方法;11)掩盖皮肤上毫毛的外观的方法;12)隐藏人皮肤上缺陷和/或瑕疵,包括粉刺、老年斑、雀斑、痣、疤痕、眼袋、胎记、炎症后的色素过渡沉着的方法;13)增强或调节皮肤色彩,如颜色变亮、颜色变深、显得更粉红、显得更黄、显得不那么暗淡、显得不那么苍白、显得不那么橙色、显得更容光焕发的方法;14)仿真晒成褐色皮肤的方法;15)隐藏白癜风的方法;16)隐藏皮肤由于创伤的结果遭受损害的方法,例如,整容手术、烧伤、皮肤的拉伸等等;和17)隐藏皱纹、细纹、毛孔、皮肤表面粗糙等的方法。本文论述的每一个方法包括向皮肤局部应用受权利要求书保护的组合物。
实施例
下列是本发明组合物的非限制性实施例。实施例的给出仅是为了举例说明之目的,不应被解释为是对本发明的限制,因为在不背离本发明的精神和范围的情况下,其许多改变是可能的,这将被本领域的普通技术人员所认识到。在这些实施例中,除非另外指明,所有浓度以重量百分比列出,并排除了微量物质,如稀释剂、填充剂等。因此,所列制剂包括所列组分和任何与该组分相关的微量组分。对本领域普通的技术人员来说显而易见的是,这些微量组分的选定将根据选定的具体成分的物理和化学特性而不同,以制造本文所述的发明。
实施例1至5
硅氧烷包水和油包水型第一组合物实施例:
成分 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | |
A1 | 十二甲基环六硅氧烷 | 12.450 | 12.000 | 11.550 | 12.000 | ---- |
A2 | 二氧化硅1 | 2.000 | 2.000 | 2.000 | 2.000 | 2.000 |
A3 | 新戊酸十三烷基酯 | 5.000 | 6.000 | 5.000 | 6.000 | 10.000 |
A4 | 聚乙二醇20脱水山梨糖醇单月桂酸酯 | ---- | ---- | ---- | ---- | 2.000 |
A5 | 异十二烷 | ---- | ---- | ---- | ---- | 18.000 |
A6 | 异硬脂酸异硬脂醇酯 | ---- | ---- | 3.000 | ---- | 12.000 |
A7 | 聚二甲基硅氧烷(500厘沲) | ---- | ---- | ---- | 30.00 | |
A8 | 环戊硅氧烷(和)聚二甲基硅氧烷共聚多元醇 | 8.000 | 8.900 | ---- | 8.900 | ---- |
A9 | 环戊硅氧烷(和)C30至45烷基鲸腊硬脂基聚二甲基硅氧烷交联聚合物(87.5%)2 | 22.000 | 30.000 | 24.000 | ---- | |
A10 | 环戊硅氧烷(和)C30至45烷基鲸腊硬脂基聚二甲基硅氧烷交联聚合物(70.0%)2 | 9.500 | ---- | ---- | ---- | ---- |
A11 | 环戊硅氧烷(和)C30至 | ---- | ---- | 12.000 | ---- | ---- |
45烷基鲸腊硬脂基聚二甲基硅氧烷交联聚合物(和)PEG/PPG 20/15聚二甲基硅氧烷3 | ||||||
B1 | 氧化锌 | 3.000 | 3.00 | 3.000 | 3.00 | 3.000 |
C1 | 对羟基苯甲酸丙酯 | 0.200 | 0.200 | 0.200 | 0.200 | 0.200 |
C2 | 甲氧基肉桂酸辛酯 | 6.000 | 6.000 | 6.000 | 6.000 | 6.000 |
D1 | SD醇 | 8.500 | 8.500 | 10.000 | 8.500 | ---- |
D2 | 去离子水 | 16.050 | 16.500 | 15.950 | 16.500 | 40.5 |
D3 | 氯化钠 | 1.000 | 1.000 | ---- | 1.000 | ---- |
D4 | 对羟基苯甲酸甲酯 | 0.200 | 0.200 | 0.200 | 0.200 | 0.200 |
D5 | 甘油 | 4.000 | 4.000 | 5.000 | 4.000 | 4.000 |
D6 | 乙二胺四乙酸三钠盐 | 0.100 | 0.100 | 0.100 | 0.100 | 0.100 |
D7 | 苯氧基乙醇 | 0.400 | ---- | 0.400 | ---- | 0.400 |
E1 | 丙烯酸酯/C12至22甲基丙烯酸烷基酯4 | 1.600 | 1.600 | 1.600 | 1.600 | 1.600 |
1.Kobo产品-Silica Shells
2.General Electric Silicones-Velvesil 125
3.General Electric Silicones-1120-21-381
4.Rohm and Haas-Allianz OPT
步骤:
1.将成分D1和D5混合至不锈钢大烧杯中。提供最大的螺旋搅拌器搅拌而无空气带入。
2.将A和B相成分加入到不锈钢容器中。高剪切搅拌15分钟或直至达到均匀。
3.将C相成分加入到另一个烧杯中。手动搅拌直至对羟基苯甲酸酯溶解。
4.将C相加入到配料中。持续高剪切直至均匀。
5.一旦ABC相被均匀地置入匀化器中,则加入D相并持续均化直至达到均匀。
6.加入E相,并且用螺旋搅拌器搅拌直至外观和稠度均匀。
实施例6至10
水包硅氧烷和水包油型第二组合物实施例:
成分 | 实施例6 | 实施例7 | 实施例8 | 实施例9 | 实施例10 | |
A1 | 十甲基环戊硅氧烷 | 9.000 | 9.145 | 9.145 | ---- | ---- |
A2 | 十二甲基环己硅氧烷 | 2.000 | 2.065 | 5.065 | ---- | ---- |
A3 | 新戊酸十三烷基酯 | 8.000 | 8.000 | 10.000 | 12.000 | 12.00 |
A4 | PCA聚二甲基硅氧烷 | 2.000 | 2.000 | 2.000 | ---- | ---- |
A5 | 异十二烷 | ---- | ----- | ---- | 20.000 | 20.000 |
A6 | 对羟基苯甲酸丙酯 | 0.200 | 0.150 | 0.150 | .150 | .150 |
A7 | 二十二烷酸二十烷基酯 | --- | 0.300 | 0.300 | 0.300 | 0.300 |
A8 | 硬脂醇 | 0.625 | 0.750 | 0.750 | 0.7500 | 0.7500 |
A9 | 二十二醇 | 0.625 | --- | --- | --- | --- |
A10 | 甲基葡萄糖倍半硬脂酸酯 | 1.200 | --- | --- | --- | --- |
B1 | 二氧化钛(和)聚甘油基-4异硬脂酸酯(和)鲸蜡基聚二甲硅氧烷共聚多元醇(和)月桂酸己酯(和)异丙基三异硬脂酸钛1 | 9.075 | 9.075 | ---- | 9.075 | ---- |
B2 | 氧化铁(CI 77492)(和)聚甘油基-4异硬脂酸酯(和)鲸蜡基聚二甲硅氧烷共聚多元醇(和)月桂酸己酯(和)异丙基三异硬脂酸钛1 | 0.811 | 0.811 | ----- | 0.811 | ----- |
B3 | 氧化铁(CI 77491)(和)聚甘油基-4异硬脂酸酯(和)鲸蜡基聚二甲硅氧烷共聚多元醇(和)月桂酸己酯(和)异丙基三异硬脂酸钛1 | 0.262 | 0.262 | ----- | 0.262 | ----- |
B4 | 氧化铁(CI 77499)(和)聚甘油基-4异硬脂酸酯(和)鲸蜡基聚二甲硅氧烷共聚多元醇(和)月桂酸己酯(和)异丙基三异硬脂酸钛1 | 0.143 | 0.143 | ----- | 0.143 | ----- |
B5 | 二氧化硅2 | --- | 2.00 | --- | 2.000 | 2.000 |
C1 | 去离子水 | 53.655 | 52.000 | 59.291 | 40.579 | 51.500 |
C2 | 对羟基苯甲酸甲酯 | 0.250 | 0.200 | 0.200 | 0.200 | 0.200 |
C3 | 2-苯氧基乙醇 | --- | 0.500 | 0.500 | 0.500 | 0.500 |
C4 | 羟丙基淀粉磷酸盐 | --- | 2.000 | 2.000 | 2.000 | 2.000 |
C5 | 甘油 | 2.250 | 2.250 | 2.250 | 2.250 | 2.250 |
C6 | 丁二醇 | 2.250 | 2.250 | 2.250 | 2.250 | 2.250 |
C7 | 聚乙烯吡咯烷酮 | --- | 1.000 | 1.000 | 1.000 | 1.000 |
C8 | 乙二胺四乙酸三钠盐 | 0.100 | 0.100 | 0.100 | 0.100 | 0.100 |
C9 | 棕榈酸蔗糖酯(和)硬脂酸甘油酯(和)硬脂酸柠檬酸甘油酯(和)蔗糖(和)甘露聚糖(和)黄原胶3 | --- | 2.000 | 2.000 | 2.000 | 2.000 |
C10 | 辛烯基琥珀酸铝淀粉4 | 1.004 | 3.00 | 3.000 | 3.000 | 3.000 |
C11 | POE 20甲基葡萄糖倍半硬脂酸酯 | 1.800 | ||||
D1 | 2-苯氧基乙醇 | 0.750 | ||||
D2 | 丙烯酸羟乙酯/丙烯酰二甲基牛磺酸钠共聚物和角鲨烷以及聚山梨酸酯605 | 4.000 |
1.Kobo产品-ITT Coated Pigments
2.Kobo产品-Silica Shells
3.Uniquima-Arlatone V-175
4.National Starch-Dry Flo Elite BN
5.Seppic-Simulgel NS
实施例6的步骤:
1.合并C相成分,并用螺旋混合器混合10分钟。将C相加热至75℃。
2.在单独的不锈钢容器中,合并A相和B相成分,并用高剪切搅拌20至30分钟,以分散颗粒(6000rpm)。在混合相期间,加热至75℃。
3.在使用高剪切(6000rpm)的同时,将AB相导入到C相中。匀化20至30分钟。
4.将产品冷却至60℃以下并加入D1。剪切10分钟。
5.加入D2并用螺旋混合器混合10分钟或直至均匀。
实施例7至10的步骤:
1.用最大螺旋搅拌器混合成分C1和C9。
2.加入C相成分2、3、5、6、7、8和10。提供最大的螺旋搅拌器搅拌而无空气带入。
3.将C相加热至70℃至80℃。一旦批料达到70℃至80℃,加入50%的C4。
4.将A相成分1-5加入至独立的容器中并开始匀化配料。
5.将A相加热至70℃至80℃。
6.将B相加入A相中,在高档剪切约20至30分钟。
7.一旦AB相达到70℃至80℃,并加入A相成分6-8。
8.将AB相转移至C相中,同时螺旋搅拌。搅拌直至外观均匀。
9.用高剪切匀化配料。加入剩余50%的C4。保持直至达到均匀。
实施例11至15
水包油和水包硅氧烷型第一组合物实施例:
成分 | 实施例 11 | 实施例 12 | 实施例 13 | 实施例 14 | 实施例 15 | |
A1 | 十甲基环-戊硅氧烷 | 9.135 | 9.135 | 9.135 | 9.135 | 9.135 |
A2 | 十二甲基环己硅氧烷 | 2.065 | 2.065 | 2.065 | 2.065 | 2.065 |
A3 | 新戊酸十三烷基酯 | 5.000 | 5.000 | 5.000 | 5.000 | 5.000 |
A4 | PCA聚二甲基硅氧烷 | 2.000 | 2.000 | 2.000 | 2.000 | 2.000 |
A5 | 对羟基苯甲酸丙酯 | 0.150 | 0.150 | 0.150 | 0.150 | 0.150 |
A6 | 二十二烷酸二十烷基酯 | 0.300 | 0.300 | 0.300 | 0.300 | 0.300 |
A7 | 硬脂醇 | 0.750 | 0.750 | 0.750 | 0.750 | 0.750 |
B1 | 二氧化硅1 | 2.000 | 2.000 | 2.000 | 2.000 | 2.000 |
B2 | 二氧化钛 | ---- | 0.500 | 0.500 | 0.500 | 0.500 |
B3 | 聚甲基倍半硅氧烷2 | ---- | 2.000 | 2.000 | 2.000 | ---- |
B4 | 辛烯基琥珀酸铝淀粉(和)氮化硼3 | 1.300 | 1.300 | 1.300 | 1.300 | 1.300 |
C1 | 去离子水 | 57.000 | 49.000 | 49.000 | 54.000 | 41.000 |
C2 | 对羟基苯甲酸甲酯 | 0.200 | 0.200 | 0.200 | 0.200 | 0.200 |
C3 | 苯氧基乙醇 | 0.500 | 0.500 | 0.500 | 0.500 | 0.500 |
C4 | 羟丙基淀粉磷酸酯4 | 2.000 | 2.000 | 2.000 | 2.000 | 2.000 |
C5 | 甘油 | 2.250 | 4.000 | 10.000 | 10.000 | 10.000 |
C6 | 丁二醇 | 2.250 | 10.000 | 5.000 | 5.000 | 5.000 |
C7 | 丙二醇 | 10.00 | 6.000 | 5.000 | ---- | 15.000 |
C8 | 聚乙烯吡咯烷酮 | 1.000 | 1.000 | 1.000 | 1.000 | 1.000 |
C9 | 乙二胺四乙酸三钠盐 | 0.100 | 0.100 | 0.100 | 0.100 | 0.100 |
C10 | 棕榈酸蔗糖酯(和)硬脂酸甘油酯(和)硬脂酸柠檬酸甘油酯(和)蔗糖(和)甘露聚糖(和)黄原胶5 | 2.000 | 2.000 | 2.000 | 2.000 | 2.000 |
1.Kobo产品-Silica Shells
2.General Electric-Tospearl 145
3.National Starch-Dry Flow Elite BN
4.National Starch-Structure Zea
5.Uniquima-Arlatone V-175步骤:
1.用最大螺旋搅拌器混合成分C1和C10。
2.加入C相成分2、3、5、6、7、8和9。提供最大的螺旋搅拌器搅拌而无空气带入。
3.将C相加热至70℃至80℃。一旦批料达到70℃至80℃,加入C4。
4.将A相成分1-5加入至独立的容器中并开始匀化配料。
5.将A相加热至70℃至80℃。
6.将B相加入到A相中,在高档剪切约20至30分钟。
7.一旦AB相达到70℃至80℃,加入A相成分6-7。
8.将AB相转移至C相中,同时螺旋搅拌。搅拌直至外观均匀。
9.用高剪切匀化配料。保持高剪切,直至达到均匀。
实施例16至21
硅氧烷包水和油包水型第二组合物实施例:
成分 | 实施例 16 | 实施例 17 | 实施例 18 | 实施例 19 | 实施例 20 | 实施例 21 | |
A1 | 环戊硅氧烷(和)聚二甲基硅氧烷共聚多元醇 | 8.000 | 8.000 | ---- | ---- | 8.000 | 8.000 |
A2 | 聚乙二醇20脱水山梨糖醇单月桂酸酯 | ---- | ---- | 2.000 | 2.000 | ---- | ---- |
A3 | 异硬脂酸异硬脂醇酯 | 16.000 | 16.000 | ||||
A4 | 新戊酸十三烷基酯 | 6.000 | 6.000 | 6.000 | 6.000 | 6.000 | 6.000 |
A5 | 鲸蜡基聚二甲基硅氧烷共聚醇1 | 2.000 | 2.000 | 2.000 | 2.000 | 2.000 | 2.000 |
A6 | 环己硅氧烷 | --- | --- | ---- | ---- | ||
A7 | 环戊硅氧烷 | 31.700 | 25.700 | 15.700 | 15.700 | 10.700 | 4.700 |
B1 | 乙氧基化C10至16醇2 | 0.500 | 0.500 | 0.500 | 0.500 | 0.500 | 0.500 |
B2 | 对羟基苯甲酸丙酯 | 0.150 | 0.150 | 0.150 | 0.150 | 0.150 | 0.150 |
C2 | 辛烯基琥珀酸铝淀粉(和)氮化硼3 | 3.500 | 3.500 | 3.500 | 3.500 | 3.500 | 3.500 |
C3 | 聚甲基倍半硅氧烷4 | 1.500 | 1.500 | 1.500 | 1.500 | 1.500 | 1.500 |
C4 | 1,6-己二异氰酸酯/聚丙烯/聚已内酯交联聚合物(和)二氧化硅5 | 1.500 | 1.500 | 1.500 | 1.500 | 1.500 | 1.500 |
C5 | 聚二甲基硅氧烷/乙烯基聚二甲基硅氧烷交联聚合物6 | 1.500 | 1.500 | 1.500 | 1.500 | 1.500 | 1.500 |
C6 | 环戊硅氧烷(和)C30至45烷基鲸腊硬脂基聚二甲基硅氧烷交联聚合物7 | --- | --- | --- | --- | 20.000 | 20.000 |
C7 | 红色氧化铁 | --- | 0.800 | 0.800 | ---- | --- | 0.800 |
C8 | 黄色氧化铁 | --- | 1.000 | 1.000 | ---- | --- | 1.000 |
C9 | 黑色氧化铁 | --- | 0.200 | 0.200 | ---- | --- | 0.200 |
C10 | 二氧化钛 | --- | 8.000 | 8.000 | ---- | --- | 8.000 |
D1 | 去离子水 | 48.000 | 43.000 | 43.000 | 54.000 | 48.000 | 44.000 |
D2 | 聚乙烯吡咯烷酮 | --- | 1.000 | 1.000 | --- | 1.000 | 1.000 |
D3 | 二氧化硅8 | 1.000 | 1.000 | 1.000 | 1.000 | 1.000 | 1.000 |
D4 | 苯氧基乙醇 | 0.250 | 0.250 | 0.250 | 0.250 | 0.250 | 0.250 |
D5 | 乙二胺四乙酸三钠盐 | 0.100 | 0.100 | 0.100 | 0.100 | 0.100 | 0.100 |
D6 | 氯化钠 | 2.000 | 2.000 | 2.000 | 2.000 | 2.000 | 2.000 |
D7 | 脱氢乙酸钠一水合物 | 0.300 | 0.300 | 0.300 | 0.300 | 0.300 | 0.300 |
1.DeGussa Goldsmith-Abil WE-09
2.Rhodia-Rhodasurf L-7/90
3.National Starch-Dry Flo Elite BN
4.GE-Tospearl 145A
5.Kobo-BPD-500T
6.Dow Corning-9506 Powder
7.GE-Velvesil 125
8.Kobo-Silica Shells
步骤:
1.将D相成分的去离子水和二氧化硅包壳混合,然后用螺旋或分散搅拌机搅拌直至达到均匀。
2.加入剩余的D相成分,然后继续用螺旋或分散搅拌机搅拌。
3.在夹套容器中混合A相成分,然后开始用转子定子磨搅拌。使冷水通过夹套容器再循环。
4.将B相成分一起搅拌十分钟。将混合好的B相加入A相成分中。
5.将C相成分加入AB相中。剪切ABC相直至它完全解附聚,而且颜料被减小至它们的主要粒径。
6.在中等剪切下将D相乳化到ABC相中。用扫壁搅拌混合ABCD相直至均匀。
实施例22
适于用作第二组合物的粉末粉底。
A相 | |
滑石 | 23.90 |
云母 | 17.66 |
云母(绢云母) | 29.04 |
二氧化钛 | 11.60 |
尼龙-12 | 1.76 |
二氧化硅 | 2.64 |
对羟基苯甲酸丙酯,NF | 0.10 |
对羟基苯甲酸甲酯,NF | 0.30 |
脱氢乙酸钠,NF | 0.10 |
红色氧化铁 | 0.43 |
黑色氧化铁 | 0.29 |
黄色氧化铁 | 0.50 |
B相 | |
聚二甲基硅氧烷(和)三甲基甲硅烷氧基硅酸酯 | 6.43 |
琥珀酸二辛酯 | 0.80 |
羟基硬酯酸辛酯 | 0.70 |
羟基硬脂酸胆甾醇酯 | 1.05 |
生育酚 | 0.01 |
甲氧基肉桂酸辛酯 | 2.69 |
100 |
用整体混合将A相成分混合(如螺条搅拌器,双锥鼓混合器或用手),然后用高剪切混合(如锤磨机、粉磨机或切碎刀片)以分解任何颗粒附聚物。用螺旋混合器混合B相成分,然后加热至75℃。将B相成分加入到A相中,然后组合使用整体和高剪切混合进行分散。
尽管已用具体实施方案来说明和描述了本发明,但对于本领域的技术人员显而易见的是,在不背离本发明的精神和保护范围的情况下可作出许多其它的变化和修改。因此,有意识地在附加的权利要求书中包括本发明范围内的所有这些变化和修改。
所有发明背景、发明概述和发明详述中引用的文献的相关部分均引入本文以供参考;任何文献的引用并不可解释为是对其作为本发明
现有技术的认可。
Claims (8)
1.一种适宜作为多步皮肤化妆品涂敷的化妆品体系,所述体系包括:
a.第一组合物,所述组合物包含:
i.5%至90%重量,优选8%至70%重量,更优选10%至60%重量的低挥发性物质,所述低挥发性物质在一个大气压和25℃下具有的蒸汽压为至少0Pa至1333Pa(0mmHg至10mmHg);和
ii.0.05%至10%重量,优选0.1%至7.5%重量,更优选0.5%至5%重量的乳化剂或两亲分子,所述乳化剂或两亲分子可溶解或分散到所述低挥发性物质中;和
b.第二组合物,所述组合物包含与所述第一组合物中所述低挥发性物质的界面张力大于零达因/厘米的连续相流体、固体、凝胶或半固体,
其中所述第二组合物适于在所述第一组合物之后被局部涂敷到皮肤上。
2.如权利要求1所述的化妆品体系,其中所述第一组合物、所述第二组合物或所述第一组合物和所述第二组合物两者还包含着色剂。
3.如权利要求1或2所述的化妆品体系,其中所述第一组合物、所述第二组合物或所述第一组合物和所述第二组合物两者还包含成膜剂。
4.如前述任一项权利要求所述的化妆品体系,其中所述第一组合物、所述第二组合物或所述第一组合物和所述第二组合物两者还包含交联硅氧烷聚合物。
5.如权利要求4所述的化妆品体系,其中所述交联硅氧烷聚合物存在于所述第一组合物中。
6.如前述任一项权利要求所述的化妆品体系,其中所述第一组合物、所述第二组合物或所述第一组合物和所述第二组合物两者还包含吸收性材料。
7.如前述任一项权利要求所述的化妆品体系,其中所述化妆品为粉底。
8.一种向皮肤提供多步化妆品的方法,所述方法包括以下步骤:
a.向所述皮肤涂敷第一组合物,所述第一组合物包含:
i.5%至90%重量的低挥发性物质,所述低挥发性物质在一个大气压和25℃下具有的蒸汽压为至少0Pa至1333Pa(0mmHg至10mmHg);和
ii.0.05%至10%重量的乳化剂,所述乳化剂可溶解或分散到所述低挥发性物质中;和
b.向所述皮肤涂敷第二组合物,所述第二组合物包含与所述第一组合物中所述低挥发性物质的界面张力大于零达因/厘米的连续相流体、固体、凝胶或半固体。
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US (1) | US20040228819A1 (zh) |
EP (1) | EP1626700A2 (zh) |
JP (1) | JP2006526018A (zh) |
KR (1) | KR20060005399A (zh) |
CN (1) | CN1791379A (zh) |
AU (1) | AU2004241096A1 (zh) |
CA (1) | CA2524658A1 (zh) |
MX (1) | MXPA05012321A (zh) |
WO (1) | WO2004103302A2 (zh) |
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- 2004-05-13 AU AU2004241096A patent/AU2004241096A1/en not_active Abandoned
- 2004-05-13 JP JP2006514876A patent/JP2006526018A/ja active Pending
- 2004-05-13 EP EP04752351A patent/EP1626700A2/en not_active Withdrawn
- 2004-05-13 WO PCT/US2004/015321 patent/WO2004103302A2/en not_active Application Discontinuation
- 2004-05-13 MX MXPA05012321A patent/MXPA05012321A/es unknown
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CN105899187A (zh) * | 2014-01-14 | 2016-08-24 | 宝洁公司 | 用于改善人体皮肤外观和感觉的多步方案 |
CN105916481A (zh) * | 2014-01-14 | 2016-08-31 | 宝洁公司 | 用于改善人体皮肤外观和感觉的多步产品 |
CN105899185A (zh) * | 2014-01-14 | 2016-08-24 | 宝洁公司 | 用于改善人体皮肤外观和感觉的多步产品 |
CN105899187B (zh) * | 2014-01-14 | 2020-02-07 | 宝洁公司 | 用于改善人体皮肤外观和感觉的多步方案 |
CN105916480B (zh) * | 2014-01-14 | 2021-08-17 | 宝洁公司 | 用于改善人体皮肤外观和感觉的多步产品 |
CN105916481B (zh) * | 2014-01-14 | 2021-09-10 | 宝洁公司 | 用于改善人体皮肤外观和感觉的多步产品 |
CN105899185B (zh) * | 2014-01-14 | 2021-10-12 | 宝洁公司 | 用于改善人体皮肤外观和感觉的多步产品 |
CN107635543A (zh) * | 2015-05-28 | 2018-01-26 | 宝洁公司 | 用于改善人体皮肤的外观或感觉的多组分产品和多步骤方案 |
CN110072508A (zh) * | 2016-12-14 | 2019-07-30 | 高露洁-棕榄公司 | 无铝止汗剂/除臭剂组合物 |
US11147755B2 (en) | 2016-12-14 | 2021-10-19 | Colgate-Palmolive Company | Aluminum-free antiperspirant / deodorant compositions |
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JP2006526018A (ja) | 2006-11-16 |
US20040228819A1 (en) | 2004-11-18 |
EP1626700A2 (en) | 2006-02-22 |
KR20060005399A (ko) | 2006-01-17 |
WO2004103302A3 (en) | 2005-01-13 |
CA2524658A1 (en) | 2004-12-02 |
WO2004103302A2 (en) | 2004-12-02 |
AU2004241096A1 (en) | 2004-12-02 |
MXPA05012321A (es) | 2006-01-30 |
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