CN1688277A - 微细煅烧氧化铝的局部使用 - Google Patents
微细煅烧氧化铝的局部使用 Download PDFInfo
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- CN1688277A CN1688277A CNA038238349A CN03823834A CN1688277A CN 1688277 A CN1688277 A CN 1688277A CN A038238349 A CNA038238349 A CN A038238349A CN 03823834 A CN03823834 A CN 03823834A CN 1688277 A CN1688277 A CN 1688277A
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Abstract
一种分散体，其包含悬浮在化妆可接受的载体中的粒径小于约5μ、更窄为1μ或更小，约0.5wt％－约30wt％的分散的微细煅烧氧化铝、不锈钢或黄金颗粒，其能有用地作为用于皮肤和毛发防晒霜，同时使皮肤和毛发更光滑、更均匀、有光泽，具有可见的吸引力和健康的外观。
Description
关于联邦资助研究的声明不适用
发明背景
发明领域.本发明涉及超细煅烧氧化铝，或其它超细的医学级惰性颗粒如不锈钢或黄金的新的有机分散体，所述有机分散体适合用于皮肤和毛发的防晒霜(sunblock)和化妆制品中。
现有技术.已经知道皮肤承受某种形式损害的各种皮肤病和病情可以被太阳辐射暴露恶化，或者直接或间接追溯至太阳辐射暴露，就如对毛发的破坏一样。例如在紫外线引起的皮肤灼伤和由日光引起的皮肤加速老化就是这样的例子。连续的日光照射可以导致前癌和癌，包括黑素瘤(melanoma)在内。因此，在相当多的公共健康和化妆品方面需要着力于促进用于暴露的皮肤表面的遮光剂(sunscreen)和防晒产品。
传统遮光剂一般是通过在化妆可接受的洗液、油、膏或乳剂中悬浮或溶解吸收和/或减少有害紫外线(UV)辐射的有机化合物来制备，所述有机化合物，例如羟甲氧苯酮(2-羟基-4-甲氧基二苯甲酮)、二羟甲氧苯酮(2，2′)-二羟基-4-甲氧基二苯甲酮)、氨基苯甲酸、甲氧桂乙酯(2-乙氧基乙基-对甲氧基肉桂酸酯)、二乙醇胺-对甲氧基肉桂酸酯、二没食子酰三油酸酯、乙基-4-双(羟丙基)氨基苯甲酸酯、2-乙基己基水杨酸酯，甘油基氨基苯甲酸酯、高水杨酯(homosalate)(3，3，5-三甲基环乙基水杨酸酯、三乙醇胺水杨酸酯、2-苯基苯并咪唑-5-磺酸、磺异苯酮(2-羟基-4-甲氧基二苯甲酮-5-磺酸)、帕地马酯A(对二甲基氨基苯甲酸戊酯)、帕地马酯O(二甲基对氨基苯甲酸辛酯)、4-叔丁基-4′-甲氧基二苯甲酰甲烷、2-羟基-1，4-萘醌和二羟丙酮、氨茴酸甲酯的结合物。
相反，防晒霜通常包含反射太阳射线的无机化合物。最著名的防晒霜是氧化锌，它是第一个配制成厚白膏涂在常常晒红的救生员鼻子上而出名，但是较不明显的浅色氧化锌和更适于使用的包含替代的悬浮在化妆可接受的载体中的二氧化钛、菱锌矿和热解硅石已经有所描述。(参见例如Fukui等人的美国专利4801445和Wortzman的美国专利4822600；在此整体引入这些专利和下述引用的专利，作为参考。)
因为在遮光剂中用作活性成分的不同有机化合物能吸收不同波长的辐射，并且以不同的效率吸收辐射，遮光剂对UVA和UVB射线的保护是不同的。另外，较少有遮光剂能挡住可见或红外(IR)辐射，它们比紫外射线穿透更深并且也会造成损伤。所以，对太阳辐射最有效保护是提供防晒霜，因为其能对所有波长的辐射提供保护。然而，许多含分散的无机粉末如氧化锌和二氧化钛的防晒霜不美观，当用于皮肤时它们涂抹糟糕并有讨厌的厚重和拖沓的感觉，因为它们是颜料，它们会留下白色/蓝色残余物，特别是在较高的浓度时。即使被微粉碎，使超细颗粒的尺寸达到0.01μ-0.15μ，二氧化钛聚集成更大颗粒尺寸的团块，这是不适合用于化妆品使用的。已经建议了不同的分散剂和预处理方法来改善包含这些防晒无机物的配方特性，比如用植物油、矿物油、脂肪酸酯或盐、磷脂、硅酮聚合物薄膜，支链有机物等涂覆所述颗粒。(参见例如上面引用的Fukui等人和Wortzman，和Zecchino等人的美国专利5468471，和在这些专利中评论的其它公开内容)。具有表现出期望性质的可供选择的防晒霜将是有益的。
发明概述
本发明是基于如下发现：微细煅烧氧化铝可分散在局部组合物(topicalcompositions)中，该组合物不仅起到防晒霜的作用，而且还能掩饰皮肤缺陷比如皱纹、伤痕和皮肤上的扩大毛孔和毛干(hair shaft)的圆柱形角蛋白外部上的结构裂纹。尽管不希望受限于任何理论，超细煅烧氧化铝颗粒看来起到如同皮肤或毛发表面上的一块小镜子的作用。它们能反射入射辐射，从而起到防晒霜的作用。同时，陷入皮肤和外部的毛干缺陷中的颗粒使表面平滑，以便反射的入射光更少散射，结果裂纹变得更不易发现。皮肤和毛发保护和化妆品益处得以实现。
因此，本发明的目的在于提供用于皮肤和毛发的可供选择的防晒霜组合物。另一个目的在于提供局部组合物，所述局部组合物增加了它们所施用的皮肤和毛发的平滑度和表面均匀性。本发明进一步的和重要的目的在于以下的方法，该方法通过将局部组合物施用在暴露表皮区域上，防止皮肤免于受到日光照射的有害效果，同时掩饰皱纹、伤痕、凹坑、扩大的毛孔和其它皮肤缺陷。同样相关的目的在于提供用于保护毛发免受辐射引起的损害，并且使单独毛发更光滑、更易梳理和光亮的相应组合物。
本发明提供了悬浮在化妆品载体中的分散微细煅烧氧化铝、不锈钢和/或黄金颗粒的乳剂，由此实现了本发明的这些和其它目，所述颗粒一般具有约25μ或更小的粒径，优选为约10μ或更小的粒径，更优选为约5μ或1μ或更小的粒径。典型的乳剂含有悬浮在化妆品载体中约0.5％-约30％，更窄的约5％-约25％的分散颗粒。如下文所述，在防水和成膜硅酮类载体中含有约3wt％-约10wt％颗粒的配制物表现出局部施用于皮肤的各种所需性质。示例性的毛发组合物配制成冲洗剂(rinse)。
本发明也包括通过局部施用本发明的分散体，使用微细分散的颗粒乳剂来保护哺乳动物皮肤或毛发不受紫外线和红外辐射(尤其前者)，并且使皮肤和毛发更均匀和更光滑的方法。
发明概述
在本发明的实践中，制备在化妆品的可接受载体中的微细煅烧氧化铝、不锈钢或黄金颗粒的分散体，并局部施加到哺乳动物皮肤或毛发上。当这样施加时，分散体起到防晒霜的作用，保护皮肤和毛发免受紫外线和红外辐射。微细颗粒分散体也使皮肤和毛发更均匀和更平滑、更有光泽和具有更健康的外观。
在此使用时，术语“超细”和“微细”同义。制备本发明配制物中使用的优选微细颗粒具有小于约25μ，一般小于约10μ，优选小于约5μ，更优选小于约1μ的粒径。有用颗粒包括微细煅烧氧化铝、不锈钢、黄金或它们的混合物。下文所述的优选实施方案使用具有1μ或更小粒径的煅烧氧化铝。“煅烧氧化铝”是指已经被加热到高温，通常高于1000℃，以除去挥发性杂质如发现于粗金属氧化物样品中的纯碱(soda)的氧化铝即Al2O3，有时也称为“α-刚玉”。“不锈钢”是指铁和含镍、铬或两者的碳的坚韧和弹性合金，其坚硬且不失去光泽。可根据不同用途，购买非常细的专业级的煅烧氧化铝、不锈钢和黄金颗，特别是做为耐高温材料(refractory)。优选为高质量、纯医学级颗粒，牙科级(dental grade)的煅烧氧化铝或黄金也同样优选。实际上，本发明的优势在于煅烧氧化铝、不锈钢和黄金是可铸的耐高温材料，它们已经用于医学和牙科的植入装置中和植入表面上，且表现出极其稳定的、化学惰性的、无毒的、无刺激性的和非敏化的，就如用于牙膏、漱口剂、抛光剂、牙齿外套等牙科等级的煅烧氧化铝。在随后的实施例中使用医学级煅烧氧化铝颗粒。
该微细颗粒分散在化妆可接受的载体中形成局部施用于皮肤或毛发的悬浮液、乳剂或微乳剂。优选为微乳剂。“化妆可接受的载体”是指本身惰性且对其施用的皮肤或毛发不产生任何副作用的载体。载体典型地为常规用于皮肤学以促进局部施用的洗液、霜、膏、皂等，优选的载体会在施用的皮肤或毛发上形成膜或层，以局部化应用，并提供对由于浸入水中或由排汗产生的洗脱的抵抗，同时起到防晒霜的作用。现有技术中已经直到多种制剂，并且这些制剂使用常规方法配制，包括含油和/或醇和润肤剂植物油、烃油和蜡、硅油、动物或海产的脂肪或油、甘油酯衍生物、脂肪酸或脂肪酸酯或醇类或醇醚、卵磷脂、羊毛脂及其衍生物、多羟基醇或酯、蜡酯、甾醇、磷脂等的洗液，通常也包括乳化剂(非离子的、阳离子的或阴离子的)，尽管一些润肤剂本身就具有乳化特性。同样这些普通成分可以通过使用不同比例的成分和/或通过掺入增稠剂如树胶或其它形式的亲水胶体来配制到霜内而非洗液内，或配入到凝胶内。同样，毛发配制剂典型地为香波、漂洗剂和凝胶而非洗液或霜，但包含适合皮肤用的相同普通成分。
以下说明的一些局部施用于皮肤的优选方案使用一种或多种防水的、成膜硅酮类，其在遮光剂和化妆品中显示出为安全的。多种这样的产品可商购，且包括硅酮(silicone)和硅酮共聚物、二甲基硅酮、硅氧烷(siloxane)或具有十六烷基或其它烷基的硅酮、或环己基衍生物例如(但不限于)甲基聚硅氧烷(methicone)、二甲基聚硅氧烷(dimethicone)、十六烷基二甲基聚硅氧烷、十六烷基二甲基聚硅氧烷共聚多元醇、环甲基聚硅氧烷、聚二甲基硅氧烷及其混合物。通过混合和/或研磨载体中的颗粒以及任选地与下述如下述其它成分中的那些，可形成乳剂。到目前为止基于临床研究已经测定的范围，没有遇到不良副作用。
本发明的局部分散体可以包括当局部施用时显示出有益于皮肤和/或毛发的其它成分，特别是那些能显示出有益地防止辐射引起的皮肤或毛发损害的成分，和通常在皮肤和/或毛发护理组合物和化妆品中发现的成分，如着色剂、润肤剂、调节剂、乳化剂、增湿剂、防腐剂、抗氧化剂、香料、螯合剂等。那些能增强遮光剂(如，Finsolv TNTM)的SPF的化合物，如C12和C14烷基苯甲酸酯，也可以加入到本发明的防晒霜中。
防腐剂包括，但不限于，C1-C3烷基对羟苯甲酸酯和苯氧乙醇；基于组合物总量，防腐剂的量一般为约0.5wt％-约2.0wt％。润肤剂包括但不限于脂肪酸酯、脂肪醇、矿物油、聚醚硅氧烷共聚物及其混合物；基于组合物总量，润肤剂的量一般为约0.01％-5％。增湿剂包括但不限于多元醇如甘油、聚烷撑二醇(例如丁二醇、丙二醇、二丙二醇、聚丙二醇和聚乙二醇)及其衍生物、烷撑多元醇(alkylene polyol)及其衍生物、山梨糖醇、羟基山梨糖醇、己二醇、1，3-二丁二醇、1，2，6-己三醇、乙氧化甘油、丙氧基化甘油及其混合物；基于组合物总量，增湿剂的量一般为约0.1wt％-约5wt％。乳化剂包括但不限于硬脂酸、十六烷醇、十八烷醇，硬脂醇醚(steareth)2、硬脂醇醚20、丙烯酸酯/丙烯酸C10-30烷基酯交联聚合物及其混合物；基于组合物的重量，乳化剂的量一般为约1％-约10％。螯合剂包括但不限于乙二胺四乙酸(EDTA)和其衍生物和盐、二羟基乙基甘氨酸、酒石酸及其混合物；其量一般为约0.01％-约2wt％。抗氧化剂包括但不限于丁羟甲苯(BHT)；丁羟氢化茴香醚(BHA)；苯基-α-萘胺；对苯二酚；没食子酸丙酯；去甲二氢四酸(nordihydroquiaretic acid)；绿茶提取物；混合的多酚及其混合物；抗氧化剂的量一般为该组合物的约0.02wt％-约0.5wt％。
在多种组合物中使用缓冲剂。缓冲剂的量优选为使得组合物的pH值为约4.5-约8.5，更优选为约5.5-约8.5，最优选为约6.5-约8.0。典型的缓冲剂为在化妆品中化学性质和物理性质稳定的试剂，可以包括也是附加成分的化合物如柠檬酸、苹果酸和羟基乙酸缓冲液。
本发明的优点：当施用于皮肤或毛发时，微细颗粒组合物实质上是透明的。颗粒是如此微细以至于乳剂具有良好感觉并容易施用。作为防晒霜，优选方案显示出的SPF值(日光防晒因子)为至少约15，优选约25-30，有时超过约45。这样就能反射宽谱辐射，从而提供优异的所有波长辐射防护，包括防护UVA和UVB紫外线辐射，以及可见光和红外线。粗糙的皮肤和毛发会散射光，这种方式突出了开口和缺陷，所以施用本发明的微细颗粒乳剂同时能对皮肤和毛发提供更健康的外观和光泽。沉积的颗粒填充扩张的孔、皮肤坑和伤痕，以及抚平皱纹、起皱、伤痕和其它皮肤斑点，从而提供更光滑、更平整的表面反射光，以致于皮肤在视觉上显得更完美和更吸引人。本发明的分散体能用于多种化妆品，包括粉底、眼影、口红、美颜粉末等。类似地，用本发明的分散体处理的毛发变得不仅在物理上更平滑，而且更柔顺、更有光彩和更易梳理。颗粒和载体是惰性的，所以没有观察到不良反应。
实施例
在下列不受限的实施例中使用二批具有1μ或更小的初级粒径的医学级煅烧氧化铝。每份的化学分析得到99.60wt％Al2O3、0.42wt％Na2O，0.01wt％Fe2O3；另一份具有99.50wt％Al2O3、0.44wt％Na2O、0.01wt％Fe2O3。该百分比是基于重量。
实施例1
通过乳化下列成分制备三份防晒霜，含量表示为％w/w：
| 成分 | A | B | C |
| 水 | 足量至100 | 足量至100 | 足量至100 |
| EDTA-Na2 | 0.10 | 0.10 | 0.10 |
| 氯化钠 | 0.80 | 0.80 | 0.80 |
| Aloe-Vera 200∶1 | 0.05 | 0.05 | 0.05 |
| 棕榈酸异丙酯 | 10.00 | 5.00 | 10.00 |
| Finsolve TNTM | 5.00 | 5.00 | 5.00 |
| ABIL We-09 | 6.00 | 6.00 | 6.00 |
| 十六烷基二甲基聚硅氧烷 | 2.00 | 2.00 | 2.00 |
| 十六烷基二甲基聚硅氧烷共聚多元醇 | 1.75 | 1.75 | 1.75 |
| 蜂蜡 | 1.20 | 1.20 | 1.20 |
| 乙酸酯维生素E | 0.10 | 0.10 | 0.10 |
| Permethyl 99A | - | - | 0.50 |
| Germaben IIETM | 0.50 | 0.50 | 0.50 |
| 煅烧氧化铝 | 10.00 | 4.00 | 3.00 |
全部的三个配方都显示出良好的粘性和流动特性，并且容易施用于皮肤上且令人愉快。用户的反应一致良好。
实施例2
通过乳化下述成分制备施用时给予皮肤更光滑、更均匀外观粉底霜：
| 成分 | ％w/w |
| 纯化水 | 足量至100.00 |
| Quatemium-15 | 0.20 |
| DHA-Na | 0.10 |
| 透明质酸钠 | 2.00 |
| 煅烧氧化铝 | 3.00 |
| HDI/三羟甲基己内酯 | 15.00 |
| 聚二甲基硅氧烷 | 4.50 |
| 滑石/二甲基聚硅氧烷 | 1.90 |
该配制剂具有软霜的均匀性，并可舒适地施用于皮肤上，致使它看起来更平坦和更完美，这样在化妆上更具吸引力。
上述描述的目的在于教导本领域的普通技术人员如何实践本发明，并不打算详述所有那些显而易见的修改和变化，而这些修改和变化对本领域技术人员来说在阅读该描述后是显而易见的。然而，所有这些显而易见的修改和变化是包括在本发明范围内，该范围由所附权利要求来限定。该权利要求意在覆盖能有效满足所需目标的、所要求的组分和步骤，以任何次序，除非上下文明确地表示相反的意思。
Claims (30)
1.在化妆可接受的载体中的粒径小于约25μ的煅烧氧化铝、不锈钢或黄金颗粒的分散体。
2.权利要求1所述的分散体，其粒径为约10μ或更小。
3.权利要求2所述的分散体，其粒径为约5μ或更小。
4.权利要求3所述的分散体，其粒径为约1μ或更小。
5.权利要求1所述的分散体，其包含煅烧氧化铝颗粒。
6.权利要求1所述的分散体，其包含不锈钢颗粒。
7.权利要求1所述的分散体，其包含黄金颗粒。
8.权利要求1所述的分散体，其中载体包括成膜硅酮。
9.权利要求8所述的分散体，其中载体包括甲基聚硅氧烷。
10.权利要求1所述的分散体，其包括约0.5％-约30wt％的颗粒。
11.权利要求10所述的分散体，其包括约5％-约25wt％的颗粒。
12.权利要求1所述的分散体，其为防晒霜。
13.权利要求12所述的分散体，其具有至少约15的SPF值。
14.权利要求13所述的分散体，其具有至少约25的SPF值。
15.权利要求1所述的分散体，其为化妆品组合物，当施用到皮肤上时能使它更均匀和更光滑。
16.权利要求1所述的分散体，其为毛发处理组合物。
17.权利要求1所述的分散体，其包含悬浮在含硅酮的化妆可接受的载体中的约5％-约25wt％的煅烧氧化铝颗粒，所述颗粒的粒径为约1μ或更小。
18.一种保护哺乳动物皮肤或毛发避免辐射引起的皮肤损害的方法，其包括将在化妆可接受的载体中包含微细煅烧氧化铝、不锈钢或黄金颗粒的分散体以有效的量施用到暴露的皮肤或毛发上。
19.权利要求18所述的方法，其中所述颗粒的粒径小于约10μ。
20.权利要求18所述的方法，其中所述颗粒是煅烧氧化铝。
21.权利要求18所述的方法，其中所述颗粒是不锈钢。
22.权利要求18所述的方法，其中所述颗粒是黄金。
23.权利要求18所述的方法，其中所述分散体包括约0.5％-约30wt％的颗粒。
24.一种用于处理哺乳动物皮肤或毛发以使其更均匀和更光滑的方法，其包括将在化妆可接受的载体中包含煅烧氧化铝、不锈钢或黄金颗粒的分散体以有效量施用到皮肤或毛发上。
25.权利要求24所述的方法，其中所述颗粒的粒径小于约10μ。
26.权利要求24所述的方法，其中所述分散体包括约0.5％-约30wt％的颗粒。
27.权利要求24所述的方法，其中所述颗粒是煅烧氧化铝。
28.权利要求24所述的方法，其中所述颗粒是不锈钢。
29.权利要求24所述的方法，其中所述颗粒是黄金。
30.权利要求24所述的方法，其包括将包含粒径小于1μ的、约0.5wt％-约25wt％的煅烧氧化铝颗粒的分散体施加到皮肤上，所述分散体悬浮在含成膜硅酮的化妆可接受的载体中。
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| US10/269,581 | 2002-10-11 | ||
| US10/269,581 US7037512B2 (en) | 2002-10-11 | 2002-10-11 | Topical use of microfine calcined alumina |
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| JP (1) | JP2006504730A (zh) |
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| US7037512B2 (en) * | 2002-10-11 | 2006-05-02 | Perricone Nicholas V | Topical use of microfine calcined alumina |
| US7476395B2 (en) * | 2006-04-11 | 2009-01-13 | Conopco, Inc. | Cosmetic composition with soft focus properties |
| US20070280895A1 (en) * | 2006-06-02 | 2007-12-06 | Weimer Alan W | Coated particles and sunscreen and cosmetic products containing same |
| US9295621B2 (en) * | 2007-07-31 | 2016-03-29 | Elc Management Llc | Emulsion cosmetic compositions containing resveratrol derivatives and silicone surfactant |
| US8080583B2 (en) | 2007-07-31 | 2011-12-20 | Elc Management Llc | Emulsion cosmetic compositions containing resveratrol derivatives and linear or branched silicone |
| US20090035236A1 (en) * | 2007-07-31 | 2009-02-05 | Maes Daniel H | Emulsion Cosmetic Compositions Containing Resveratrol Derivatives And An Oil Phase Structuring Agent |
| CN101854903B (zh) * | 2007-09-08 | 2012-07-04 | Elc管理有限责任公司 | 阿魏酸白藜芦醇酯化合物、包含该化合物的组合物及其使用方法 |
| US20110262560A1 (en) * | 2008-04-24 | 2011-10-27 | Dabe Michelle L | Pigmented Emulsion Makeup Compositions With Gemstones |
| JP2013511515A (ja) * | 2009-11-20 | 2013-04-04 | 株式会社アモーレパシフィック | 無機粉末を含有する化粧料組成物 |
| US8414869B2 (en) | 2010-11-30 | 2013-04-09 | N.V. Perricone Llc | Melanin promoting topical composition |
| US8574032B2 (en) * | 2011-03-22 | 2013-11-05 | Pcw Holdings, Llc | UV protective coating composition and method |
| KR102460163B1 (ko) * | 2020-10-14 | 2022-10-31 | 그린코스 주식회사 | 무기분체를 이용한 피지 조절용 메이크업용 화장료 조성물 |
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| AU521549B2 (en) * | 1976-12-27 | 1982-04-08 | Colgate-Palmolive Company, The | Reduction of abrasiveness in dentifrices |
| FR2554715B1 (fr) * | 1983-11-10 | 1987-07-24 | Roullier Anne | Gamme de produits cosmetiques contenant des particules de poudre d'or |
| DE3425152A1 (de) * | 1984-07-07 | 1986-01-16 | Henkel KGaA, 4000 Düsseldorf | Zahnpasta |
| US4801445A (en) * | 1985-07-29 | 1989-01-31 | Shiseido Company Ltd. | Cosmetic compositions containing modified powder or particulate material |
| US4822600A (en) * | 1987-05-27 | 1989-04-18 | Neutrogena Corporation | Infrared blocker |
| US4828833A (en) * | 1987-12-08 | 1989-05-09 | Colgate-Palmolive Company | Dentifrice having decreased abrasivity |
| DE4104310A1 (de) * | 1991-02-13 | 1992-08-20 | Merck Patent Gmbh | Plaettchenfoermiges pigment |
| ES2201075T3 (es) * | 1993-02-26 | 2004-03-16 | Estee Lauder Inc. | Dispersiones de dioxido de titanio, composiciones cosmeticas y metodos de utilizacion. |
| US6235270B1 (en) * | 1997-04-18 | 2001-05-22 | Showa Denko K.K. | Cosmetics, silica-coated metal oxide powder and production method therefor |
| US6261713B1 (en) * | 1999-03-29 | 2001-07-17 | Finetex, Inc. | Delivery system for inorganic sunscreens |
| BR0213943A (pt) * | 2001-11-06 | 2004-08-31 | Phild Co Ltd | Loção de pele compreendendo dispersão aquosa de partìculas de metal nobre ultrafinas |
| US7037512B2 (en) * | 2002-10-11 | 2006-05-02 | Perricone Nicholas V | Topical use of microfine calcined alumina |
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| BR0314117A (pt) | 2005-07-12 |
| CA2495641C (en) | 2009-02-10 |
| AU2003279083A1 (en) | 2004-05-04 |
| WO2004032835A2 (en) | 2004-04-22 |
| US20050271607A1 (en) | 2005-12-08 |
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| US7226608B2 (en) | 2007-06-05 |
| EP1549279A2 (en) | 2005-07-06 |
| AU2003279083B2 (en) | 2006-07-13 |
| ZA200502786B (en) | 2006-03-29 |
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| IL166679A0 (en) | 2006-01-15 |
| US20040071639A1 (en) | 2004-04-15 |
| US7037512B2 (en) | 2006-05-02 |
| MXPA05003811A (es) | 2005-06-08 |
| CA2495641A1 (en) | 2004-04-22 |
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