CN1444470A - 用于防止过氧化物引起的皮肤损害的化妆品或皮肤用制剂 - Google Patents

用于防止过氧化物引起的皮肤损害的化妆品或皮肤用制剂 Download PDF

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CN1444470A
CN1444470A CN01813293A CN01813293A CN1444470A CN 1444470 A CN1444470 A CN 1444470A CN 01813293 A CN01813293 A CN 01813293A CN 01813293 A CN01813293 A CN 01813293A CN 1444470 A CN1444470 A CN 1444470A
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A·杰特茨施
H·F·祖托里斯
G·瓦根布拉斯特
S·哈雷泽
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Abstract

本发明涉及用于防止或降低因内源或外源因素形成的过氧化物或氢过氧化物造成的皮肤损害的化妆品或皮肤用制剂。所述制剂包含a)至少一种作为O-或C-自由基清除剂的活性抗氧化剂和b)至少一种有机或无机皮肤耐受性化合物,该皮肤耐受性化合物将过氧化物或氢过氧化物还原成相应的醇而不产生随后的活性自由基阶段。所述化合物以在体温下比皮肤中的含硫化合物明显更快地反应的方式选择。

Description

用于防止过氧化物引起的皮肤损害的化妆品或皮肤用制剂
本发明涉及抗氧化剂和过氧化物分解剂的组合的用途,其中过氧化物分解剂不与过氧化物形成后续自由基阶段而还原过氧化物且与过氧化物或氢过氧化物的反应比皮肤固有的含硫化合物更快,涉及包含该组合的化妆品和皮肤用(dermatological)制剂。
人皮肤会发生一些老化过程,其中一些被认为对皮肤过程是固有的(随时间老化(chronoaging)),而其中一些被认为源于外来因素(环境,例如光老化)。此外,皮肤外观可能产生暂时和永久变化,如粉刺、油脂性或干燥性皮肤、角化病、酒渣鼻、光敏反应、炎性反应、红斑反应、变应性反应或自身免疫反应,如皮肤病、光照性皮肤病等,其准确起因和影响它们的因素通常仅被部分了解。
外源因素尤其包括阳光或具有类似光谱的人造辐射源,以及可能因辐射而产生的化合物,如不确定的反应性光化产物,其也可以是自由基或离子性的。然而,这些因素也包括有害的或反应性化合物如臭氧,自由基,例如羟自由基、单线态氧和其他反应性氧或氮化合物,香烟烟雾,天然和合成毒素,以及干扰皮肤的自然生理学或形态的其他因素。这些因素的作用尤其可能导致对皮肤细胞DNA的直接损害以及对影响皮肤坚牢性的胞外基质的胶原蛋白、弹性蛋白或粘多糖分子的损害。此外,信号转导链可能受到影响,导致激活有害因素,例如基质降解酶。这些酶的重要代表是基质金属蛋白酶(MMP,例如胶原酶、明胶酶、基质溶素),其活性也受TIMP(基质金属蛋白酶的组织抑制剂)调节。
此外,有害作用导致皮肤本身细胞的损害。其结果是例如降低了皮肤的再生能力。
另一结果可能是炎性反应,且尤其释放免疫调节化合物,如白细胞介素、前列腺素和组胺。结果尤其影响免疫活性细胞并加强了炎性反应。
老化的后果是皮肤变薄、表皮和真皮的成网变弱、细胞数目和供血血管减少。老化过程导致形成细线和皱纹,皮肤变得呈革质、泛黄且开始松垂,并出现色素疾病。
具有抗氧化作用的化合物通常用于皮肤或化妆品制剂中来防止衰老。然而,它们还可用于降低发生在人或动物皮肤中的有害或不希望的氧化过程。已知这类过程在皮肤老化中起着重要作用。皮肤暴露于由于过氧化物和氢过氧化物形成引起的永久氧化应力,这些应力中的一些来源于皮肤的外部环境,而另一些则内源性形成。为了对抗该应力,皮肤自身具有大量保护机理。然而,这些保护机理不足以完全防止皮肤中的氧化过程。相反,通常假定这些极具氧化性的过程对皮肤老化具有显著的贡献,而且也对皮肤中的一般或病理变化具有显著的贡献。
具体而言,通常认识到了脂质过氧化对老化的重要性。脂质氢过氧化物及其分解产物的毒性作用也尤其被W.A.Prior(ACS Sysup.Ser.(1985),277,77-96)描述。对于过氧化物、氢过氧化物或过氧化氢的分解,也已经就化妆品提出了各种体系,例如使用金属卟啉(Metallphosphyrinen)(JP 3273082)、植酸锌盐(JP 08104635)、触酶(JP 08175035)和其他酶(JP 67165553)。此外,JP 06345797公开了使用含半胱氨酸的二肽来漂白皮肤、用于防止脂质过氧化和用于分解脂质过氧化物。
因此,为了有助于内源性保护机理,将具有抗氧化作用,即作为O-或C-自由基清除剂有效的组分加入化妆品和皮肤用制剂中(例如DE19739349)。然而,实际所达到的作用迄今为止尚不是期望的那种。尤其是抗氧化剂加入量的增加通常并不能达到相应更高的抗氧化作用。
本发明的目的是提出一种用于化妆品或皮肤用制剂中的活性成分体系,使用它可以显著增加抗氧化效果。
通常而言,过氧化物或氢过氧化物的形成机理符合下列方案:
Figure A0181329300061
尽管常规抗氧化剂主要是O-或C-自由基清除剂,但本发明的目的是通过在另一位点额外介入该方案的机理而由其他措施更有效地防止皮肤损害。为此,考虑根据以下方案的离子和还原性进攻。
Figure A0181329300071
令人惊奇的是现已发现使用作为自由基清除剂的抗氧化剂和具有还原作用的过氧化物分解剂的组合具有优异的协同效应。就此而言,过氧化物分解剂的选择必须使得其在体外比对应有效的皮肤固有的含硫化合物如胱氨酸或半胱氨酸明显更具反应性。
具体地,我们发现该目的通过用于防止或降低由外源或内源因素形成的过氧化物或氢过氧化物所引起的皮肤损害的化妆品或皮肤用制剂达到,所述制剂包含有效量的a)至少一种作为O-或C-自由基清除剂有效的抗氧化剂,和b)至少一种有机或无机皮肤相容性化合物,该化合物将过氧化物或氢过氧化物还原成对应的醇而不形成后续反应性自由基阶段,其中该化合物以在体温下比皮肤固有的含硫化合物明显更快地反应的方式选择。
该化妆品或皮肤用制剂基于最终的制剂通常包含0.001-30重量%,优选0.01-10重量%,尤其是1-5重量%的抗氧化剂(a)和0.001-30重量%,优选0.01-10重量%,尤其是1-5重量%的至少一种过氧化物或氢过氧化物分解剂(b)。
过氧化物或氢过氧化物分解剂(b)可以属于非常宽种类的化合物。就此而言,不用说这些类型化合物中仅有皮肤相容性代表物质或皮肤相容性浓度是合适的。此外,它们必须具有比皮肤固有的化合物如半胱氨酸或胱氨酸显著更大的分解(还原)作用。某些化合物是否适用于本发明例如可以在体外由如下事实看出:在室温下以0.05m/l的摩尔浓度溶于极性或非极性溶剂中时,它们在3分钟内将过氧化物或氢过氧化物浓度降低至少20%,优选50%,尤其是90%。
具体而言,合适类型的化合物是其中硫以低于+6的氧化态存在的含硫化合物、其中磷以低于+5的氧化态存在的含磷化合物以及芳族胺。含硫-或磷-化合物可以是有机或无机化合物,优选有机化合物。
合适的含硫类化合物是硫醇,二烷基、二芳基或芳基烷基硫醚,二烷基二硫化物,二烷基亚砜,亚磺酸及其酯和酰胺,次磺酸酯或酰胺,硫酯,硫代酰胺,硫脲,硫羰基化合物,硫缩醛,酮缩硫醇,包括呈环状形式的那些。可以提到的实例是亚硫酸钠、亚硫酸氢钠、硫代硫酸钠,特别优选5-硫杂棕榈酸、硫代苯甲酰胺和2-巯基咪唑。
合适的含磷化合物是膦或含氧磷化合物,例如原亚磷酸或原亚磷酸的酯。原亚磷酸的酯也称为亚磷酸酯。原亚磷酸也可以呈盐形式(在大多数情况下呈碱金属或铵盐形式)。磷的优选键合配对是元素C、S、O、N和/或H。
还合适的尤其是已知为稳定剂的亚膦酸酯(亚膦酸的酯)。
特别合适的亚磷酸酯(即原亚磷酸的酯)和亚膦酸酯(亚膦酸的酯)包括例如亚磷酸三苯基酯、亚磷酸二苯基·烷基酯、亚磷酸苯基·二烷基酯、亚磷酸三(壬基苯基)酯、亚磷酸三月桂基酯、亚磷酸三(O-生育基)酯、亚磷酸三(十八烷基)酯、二亚磷酸二硬脂基季戊四醇酯、亚磷酸三(2,4-二叔丁基苯基)酯、二亚磷酸二异癸基季戊四醇酯、二亚磷酸双(2,4-二叔丁基苯基)季戊四醇酯、二亚磷酸双(2,6-二叔丁基-4-甲基苯基)季戊四醇酯、二亚磷酸二异癸氧基季戊四醇酯、二亚磷酸双(2,4-二叔丁基-6-甲基苯基)季戊四醇酯、二亚磷酸双(2,4,6-三(叔丁基苯基)季戊四醇酯、三亚磷酸三硬脂基山梨醇酯、二亚磷酸四(2,4-二叔丁基苯基)-4,4’-亚联苯基酯、二亚膦酸四(2,4-二叔丁基苯基)-4,4’-亚联苯基酯、6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并[d,g]-1,3,2-二氧杂磷杂环辛三烯(dioxaphosphocin)、6-氟-2,4,8,10-四叔丁基-12-甲基二苯并[d,g]-1,3,2-二氧杂磷杂环辛三烯、亚磷酸双(2,4-二叔丁基-6-甲基苯基)·甲基酯、亚磷酸双(2,4-二叔丁基-6-甲基苯基)·乙基酯和三苯基膦。
有利的是,这里使用式(I)原亚磷酸的酯(亚磷酸酯)或式(II)亚膦酸的酯(亚膦酸酯):
Figure A0181329300081
其中R、R’、R”可以相同或不同且为有机基团,尤其是C1-C20-烷基,具有2-4个碳原子的羟烷基,卤代烷基,尤其是具有2-4个碳原子的氯代烷基,芳基,尤其是苯基或被C1-C8-烷基取代的芳基(尤其是被C1-C4-烷基取代的苯基)。三个有机基团R、R’和R”中的两个也可以与磷和两个氧原子一起形成杂环(例如5-或6-元杂环)。
可以提及的是亚磷酸三甲酯、亚磷酸三乙酯、亚磷酸三丁酯、亚磷酸三己酯、亚磷酸三辛酯、亚磷酸三苯酯、亚磷酸三对甲苯酯、亚磷酸三-二甲苯酯、亚磷酸三甲苯酯和亚磷酸三-β-氯乙基酯。然而,也合适的是亚磷酸二甲酯、亚磷酸二乙酯、亚磷酸二丁酯、亚磷酸二辛酯、亚磷酸二苯酯、亚磷酸二甲苯酯和亚磷酸二-二甲苯酯。特别合适的产品是以如下商品名已知的那些:Irgafos68(Ciba AG)、IrgafosP-EPQ(Ciba AG)或Ultranox626(GE-Speciality Chemicals GmbH)。
合适的胺主要是例如是具有至少一个芳基的式III仲胺:
Figure A0181329300091
其中RIII是低分子量烷基或芳基且RIV为低分子量烷基或烷氧基。具体而言,式III的化合物可以是二苯基胺衍生物,或其中RIII与苯基一起形成环的杂环化合物。
可以提及的实例是式(IIIa)的吩噻嗪以及2-甲氧基吩噻嗪。
上述过氧化物分解剂可以是亲水性和/或亲油性的且相应地分别溶于油相中或水相中。
特别优选有机含硫-和/或磷化合物。
具体而言,特别优选提及下列化合物:2,2,4-三甲基-6-乙氧基-1,2-二氢喹啉(乙氧基喹),式IV的化合物
Figure A0181329300101
硫代硫酸钠以及5-硫杂棕榈酸、硫代苯甲酰胺和2-巯基咪唑。
上述种类化合物的选择基于皮肤相容性或皮肤相容性浓度的条件以及过氧化物或氢过氧化物分解的有效性进行。为此,将可考虑的化合物以0.05m/l的摩尔浓度溶于极性溶剂(例如乙酸)或非极性溶剂(例如甲苯)中,并测量在3分钟内过氧化物或氢过氧化物的分解速率。就此而言,过氧化物或氢过氧化物的浓度应降低至少20%,优选50%,尤其是90%。
抗氧化剂(a)通常为本身已知的化合物。抗氧化剂有利的是选自类胡萝卜素、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(例如二氢硫辛酸),还有(金属)螯合剂,EDTA,EGTA及其衍生物,泛醌和泛醌醇及其衍生物,维生素C及衍生物(例如棕榈酸抗坏血酸酯、磷酸抗坏血酸酯镁、乙酸抗坏血酸酯),生育酚及衍生物(例如维生素E乙酸酯),维生素A及衍生物(维生素A棕榈酸酯),丁羟基甲苯,丁羟基茴香醚,以及化妆品制剂中常用的其他抗氧化剂。
上述抗氧化剂(a)在最终制剂中的量例如为0.001-30重量%,优选0.01-10重量%,尤其是1-5重量%。
本发明的化妆品和皮肤用制剂对如下方面提供有效的保护:-氧化过程,-由辐射或反应性化合物引起的过程。
对于它们的其他成分,本发明化妆品和皮肤用制剂可以具有常规组成且可在化妆品中用于处理、护理和清洁皮肤。组成在这里取决于抑制剂的有效性、活性物质通过角质层(Stratum Corneum)的渗透性能及其在皮肤中形成储库的能力。
令人吃惊的是,本发明活性成分组合的应用允许化妆品上有效的处理,而且还防止了-过早老化的皮肤(例如皱纹、年龄斑、毛细管扩张、色素疾病)和/或过早老化的皮肤附件-辐射诱发的皮肤损害或辐射诱发的皮肤和/或皮肤附件的不利变化-环境诱发(臭氧,自由基,单线态氧,反应性氧或氮化合物,香烟烟雾,毒素)的皮肤损害或环境诱发的皮肤和/或皮肤附件的不利变化-皮肤和/或皮肤附件中的光敏性、炎性、红斑、变应性或自身免疫反应变化(尤其是粉刺、油脂性或干性皮肤、角化病、酒渣鼻、皮肤病,特应性湿疹,脂溢性湿疹,光照性皮肤病,多态性光皮肤病)-皮肤和/或皮肤附件的缺陷、敏感或低活动状态-瘙痒,以及干性皮肤状态和角质层屏障疾病。
为了使用,将本发明的化妆品和皮肤用制剂以常用于化妆品的方式以足够量施用于皮肤(和/或头发)。
例如,将本发明的活性成分用于清洁皮肤的化妆品组合物(如条皂、香皂、粒皂、透明皂、高级香皂、祛臭皂、乳皂(Cremeseifen)、婴儿皂、皮肤保护皂、擦洗皂、合成洗涤剂、液体皂、糊状皂、软皂、洗涤糊),液体洗涤、淋浴和浴用制剂(如洗涤化妆水、淋浴制剂、淋浴凝胶、泡沫浴、膏状泡沫浴、油浴、浴用香精),擦洗制剂,现场产品,刮脸泡沫,刮脸液,刮脸膏中。
此外,它们适于皮肤化妆品制剂,如W/O或O/W护肤和护体霜、日霜和晚霜、光保护组合物、日晒后产品、护手产品、面霜、多相乳状液、面膜(Gelees)、微乳液、脂质体制剂、乙氧基化脂肪醇类脂质体制剂、抗皱霜、面用油、脂凝胶(Lipogele)、户外用凝胶、润肤膏霜、漂白霜、维生素霜、皮肤洗剂、护理液、安瓿剂、刮脸后护肤蜜、刮脸前制剂、保湿洗液、晒黑洗液、脂肪团霜、去色素组合物、按摩制剂、爽身粉、爽面水(Gesichtswasser)、祛臭剂、防汗剂、鼻用条、防粉刺组合物、拒斥剂及其他。
此外,本发明的活性成分可以用于护发化妆品组合物,如固发剂(Haarkuren)、美发乳、护发素、发用乳液、分岔液(Spitzenfluids)、长效卷发剂用中和剂、焗油处理制剂、调理剂、定型液、香波、染发剂、喷发胶、吹卷发水、吹卷定型组合物、光亮喷发胶(Glanzsprays)、发蜡、头发定型产品、爽发水、秃发症护理组合物及其他。
取决于应用领域,化妆品或皮肤用制剂可以呈喷雾剂(泵型喷雾剂或气雾剂)、泡沫、凝胶、凝胶喷雾剂、洗液、霜剂、摩丝、软膏、悬浮液或粉末形式。
也有利的是将活性成分以包封形式给予,例如以纤维素包封形式、以明胶包封、用聚酰胺包封、以乙氧基化脂肪醇类脂质体、蜡基质包封、用环糊精包封或脂质体包封。
本发明的制剂通常包含其他常用于该类制剂中的助剂,例如防腐剂、杀菌剂、香料、消泡剂、染料、颜料、增稠剂、表面活性物质、乳化剂、润肤剂、整理剂、脂肪、油、蜡或化妆品或皮肤用配方的其他常用成分,如醇、多元醇、聚合物、泡沫稳定剂、溶解性促进剂、电解质、有机酸、有机溶剂或聚硅氧烷衍生物。
除了所述添加剂外,本发明制剂可包含其他具有抗氧化、自由基清除、润肤或保湿、抗红斑、抗炎或抗变应作用的化合物,以补充或加强其作用。具体而言,这些化合物可以选自维生素、植物提取物、α-和β-羟基酸,神经酰胺,抗炎、抗菌或UV过滤物质,及其衍生物和混合物。
有利的是,本发明的制剂还可包含在UV-B和/或UV-A区吸收UV辐射的物质。
油相有利的是选自如下物质:矿物油,矿物蜡,支化和/或未支化烃和烃蜡,饱和和/或不饱和、支化和/或未支化C8-C24-链烷羧酸的甘油三酯;它们可以选自合成、半合成或天然油,如橄榄油、棕榈油、杏仁油或混合物;油、脂肪或蜡,饱和和/或不饱和、支化和/或未支化C3-C30-链烷羧酸与饱和和/或不饱和、支化和/或未支化C3-C30-醇的酯,芳族羧酸与饱和和/或不饱和、支化和/或未支化C3-C30-醇的酯,例如肉豆蔻酸异丙酯、硬脂酸异丙酯、硬脂酸十六烷基癸基酯、油酸油基酯,以及此类酯的合成、半合成和天然混合物,如霍霍巴油,苯甲酸烷基酯或硅油,如环状聚二甲基硅氧烷、二甲基聚硅氧烷、二乙基聚硅氧烷、八甲基环四硅氧烷及其混合物或二烷基醚。
本发明制剂的水相任选有利地包含低碳数的醇、二醇或多元醇及其醚,优选乙醇、异丙醇、丙二醇、甘油、乙二醇单乙醚。
合适的乳化剂优选是已知的W/O和O/W乳化剂,如聚甘油酯、脱水山梨醇酯或部分酯化的甘油酯。
合适的溶解性促进剂尤其是乙氧基化脱水山梨醇酯、乙氧基化羊毛脂醇和乙氧基化蓖麻油。
配方中常用的天然和合成增稠剂或凝胶形成剂是交联的聚丙烯酸及其衍生物,多糖,如黄原胶或藻酸盐,羧甲基纤维素或羟基羧甲基纤维素,亲水胶体如阿拉伯胶或蒙脱石矿物,如膨润土或脂肪醇、聚乙烯醇和聚乙烯基吡咯烷酮。
适用于本发明气雾剂的推进剂是常用的推进剂,例如丙烷、丁烷、戊烷及其他。
实施例1(过氧化物分解的测量)
根据下面给出的实验方案研究表1和2所列的待用于本发明的化合物的过氧化物分解作用,并与胱氨酸和半胱氨酸相比。试验描述:
制备下列溶液:
1.过氧化氢叔丁基在CD3COOD中的0.05M溶液
2.潜在氢过氧化物分解剂在CD3COOD中的0.055M溶液
由此通过混合350μl溶液1和350μl各溶液2制备测量溶液;然后将测量溶液引入NMR管中并转移到NMR仪器中。这些溶液的制备以及测量的进行总是在23℃下进行。直到进行测量的时间约为3分钟。所有测量使用Varian的INOVA 500 500MHz NMR光谱仪进行。对各测量溶液,记录1H-NMR光谱和2D-HSQC(1H/13C)光谱。过氧化氢叔丁基和叔丁醇各自具有的CH3质子信号非常接近;将信号分配给tBuOOH或tBuOH通过参考2D-HSQC光谱进行。这两个组分的相对比例通过对对应组分在1H光谱中的信号或在HSQC光谱中的交叉峰(Kreuzpeaks)进行积分而确定(文献:W.Wilker等人,Magn.Reson.Chem.31,287-292(1993))。
另外的测试系列类似于上述试验系列在氘代甲苯(=N)而不是CD3COOD(=S)中进行。
在每种情况下,将350μl 0174(A80)和350μl其他样品混合。所用溶剂为甲苯-d8(=N)或CD3COOD(=S)。
实施例过氧化物或氢过氧化物分解剂(b):溶剂:CD3COOD(=S),甲苯-D8(=N)
对比化合物(非本发明)
  实施例号       物质   溶剂 在22℃下在3分钟内的t-BuOOH降低(%)
    1     L-胱氨酸    S     0%
    2     L-半胱氨酸    S     0%
    3     S-苄基-L-半胱氨酸    S     0%
    4     L-蛋氨酸    S     4%
    5     D(+)-生物素    S     0%
    6     T-α-硫辛酸    S     3%
本发明的P化合物
  实施例号       物质   溶剂 在22℃下在3分钟内的t-BuOOH降低(%)
    7     三苯基膦    N     100%
    8     亚磷酸三乙酯    N     22%
    9     亚磷酸三壬基苯基酯    S     29%
    10     Irgafos PEP-Q*)    N     80%
    11     亚磷酸三(O-生育基)酯    N     22%
本发明的S-化合物
   实施例号         物质  溶剂 在22℃下在3分钟内的t-BuOOH降低(%)
    12     5-硫杂棕榈酸    S     26%
    13     硫代苯甲酰胺    S     59%
    14     2-巯基咪唑    S     21%
    15     亚硫酸钠    S     40%
    16     亚硫酸氢钠    S     33%
根据本发明的芳族胺
 实施例号        物质  溶剂 在22℃下在3分钟内的t-BuOOH降低(%)
    17     吩噻嗪   S     22%
    18     2-甲氧基吩噻嗪   S     25%
    19     乙氧基喹   N     67%
*)Irgafos-P-EPQ=式子IV化合物化妆品制剂实施例:制剂类型                 应用领域                         实施例
                                                      号O/W乳液                  软皮肤洗剂                       1-13W/O乳液                  护手霜                           14-26
                     防晒液(Sun Care Lotion)          27-39多相乳状液               W/O/W乳液                        40-52微乳液                   微乳液                           53-65亲水性凝胶               脂质体凝胶                       66-78亲油性凝胶               钝化(Blunted)油凝胶              79-91
                     油凝胶                           92-104棒制剂                   防晒护唇棒                       105-117水性化妆品               冷却洗体液(Cooling Body Splash)  118-130装饰性化妆品             美容品                           131-143
                     湿粉底                           144-156油                       防晒油                           157-169洁体组合物               擦面清洁剂                       170-182头发后处理漂洗护发素     调理剂                           183-195头发后处理滞留护发素     发蜡                             196-208
                     去头屑爽发水                     209-221气雾剂                   足用祛臭喷雾剂                   222-234
                     喷发胶                           235-247配方1-13:软皮肤洗剂
                                                             %w/w十六/十八醇聚氧乙烯(6)醚和硬脂醇                                 2.50十六/十八醇聚氧乙烯(25)醚                                        2.50氢化椰油酸甘油酯(Hydrogenated Coco-Glycerides)                   1.50PEG-40十二烷基二醇共聚物(PEG-40 Dodecyl Glycol Copolymer)        3.00聚二甲基硅氧烷                                                   3.00苯乙基聚二甲基硅氧烷                                             2.00环状聚二甲基硅氧烷                                               1.00辛酸十六/十八烷基酯                                              5.00鳄梨油                                                           1.00甜杏仁油                                                         2.00小麦胚芽油                                                       0.80泛醇USP                                                          1.00植烷三醇(Phytantriol)                                            0.20生育酚乙酸酯                                                     0.30丙二醇                                                           5.00实施例7-19中的过氧化物分解剂                                     1.00磷酸抗坏血酸酯钠                                                 2.00香料(Parfum)                                                     适量防腐剂                                                           适量水(Aqua)                                                         加至100配方14-26:护手霜
                                                             %w/w十六/十八醇                                                      1.00硬脂酸甘油酯                                                     1.50硬脂醇                                                           1.50棕榈酸十六烷基酯                                                 2.00生育酚乙酸酯                                                     0.50聚二甲基硅氧烷                                                   8.00十六/十八醇聚氧乙烯(6)醚和硬脂醇                                      3.00甲氧基肉桂酸辛酯                                                      5.00丙二醇                                                                8.00泛醇                                                                  1.00月见草油                                                              3.00PEG-7氢化蓖麻油                                                       6.00油酸甘油酯                                                            1.00苯乙基聚二甲基硅氧烷                                                  3.00蜂蜡                                                                  1.50刺槐豆胶                                                              0.80丝粉                                                                  0.80硼砂                                                                  0.10防腐剂                                                                适量香料                                                                  适量实施例7-19中的过氧化物分解剂                                          1.20水                                                                    加至100配方27-39:防晒液
                                                                  %w/wPEG-7氢化蓖麻油                                                       6.00PEG-40氢化蓖麻油                                                      0.50棕榈酸异丙酯                                                          7.00PEG-45/十二烷基二醇共聚物                                             2.00霍霍巴油                                                              3.00硬脂酸镁                                                              0.60甲氧基肉桂酸辛酯                                                      8.00苯甲酸C12-15烷基酯                                                    5.00二氧化钛                                                              4.00丙二醇                                                                5.00EDTA                                                                  0.20防腐剂                                                                适量磷酸抗坏血酸酯钠                                                      1.00生育酚乙酸酯                                                           0.50实施例7-19中的过氧化物分解剂                                           0.05香料                                                                   适量水                                                                     加至100配方40-52:多相乳状液
                                                                   %w/w矿物油                                                                 7.50辛酸十六/十八烷基酯                                                    2.50硬脂酸铝                                                               0.25硬脂酸镁                                                               0.25微晶蜡H                                                                0.50十六/十八醇                                                            1.00羊毛脂醇                                                               1.50矿物醇和羊毛脂醇                                                       1.50PEG-7氢化蓖麻油                                                        0.75PEG-45/十二烷基二醇共聚物                                              2.00生育酚乙酸酯                                                           3.50十六/十八醇聚氧乙烯(6)醚和硬脂醇                                       2.00十六/十八醇聚氧乙烯(25)醚                                              2.00三[月桂基聚氧乙烯(4)醚]磷酸酯                                          1.00羟乙基纤维素                                                           0.20丙二醇                                                                 7.50硫酸镁                                                                 0.25实施例7-19的过氧化物分解剂                                             2.00水                                                                     加至100配方53-65:微乳液
                                                                   %w/w十六/十八醇聚氧乙烯(25)醚                                              13.00聚氧乙烯(7)甘油醚椰油酸酯                                              20.00辛基十二烷醇                                                           5.00磷酸抗坏血酸酯钠                                                      0.50实施例7-19中的过氧化物分解剂                                          0.80防腐剂                                                                适量水                                                                    加至100配方66-78:脂质体凝胶
                                                                  %w/wPEG-40氢化蓖麻油                                                      1.00外消旋没药醇                                                          0.10丙二醇                                                                8.00泛醇                                                                  0.50水、生育酚乙酸酯、聚山梨酸酯80、辛酸/癸酸甘油三酯和卵磷脂                                                            3.00防腐剂                                                                适量香料                                                                  适量Carbomer                                                              0.50实施例7-19中的过氧化物分解剂                                          0.80三乙醇胺                                                              0.70水                                                                    加至100配方79-91:钝化油凝胶
                                                                  %w/w二氧化硅                                                              5.00聚二甲基硅氧烷                                                        10.00辛酸十六/十八烷基酯                                                   40.00辛酸/癸酸甘油三酯                                                     8.00苯乙基聚二甲基硅氧烷                                                  2.00矿物油                                                                26.00甜杏仁油                                                              5.00生育酚乙酸酯                                                          1.00植烷三醇                                                              0.30实施例7-19中的过氧化物分解剂                                          1.50生育酚                                                                0.50香料                                                                  0.70配方92-104:油凝胶
                                                                  %w/w二氧化硅                                                              5.00聚二甲基硅氧烷                                                        10.00辛酸十六/十八烷基酯                                                   30.00肉豆蔻酸异丙酯                                                        5.00辛酸/癸酸甘油三酯                                                     10.00苯乙基聚二甲基硅氧烷                                                  5.00矿物油                                                                25.70霍霍巴油                                                              5.00生育酚乙酸酯                                                          1.00植烷三醇                                                              0.30实施例7-19中的过氧化物分解剂                                          1.50生育酚                                                                0.50香料                                                                  1.00配方105-117:防晒护唇膏
                                                                  %w/w蜂蜡                                                                  12.00氢化椰油酸甘油酯                                                      5.00蓖麻油                                                                40.00棕榈酸异丙酯                                                          10.00矿物油                                                                7.50小烛树蜡                                                              8.00苯乙基聚二甲基硅氧烷                                                  5.00生育酚乙酸酯                                                          1.00实施例7-19中的过氧化物分解剂                                          1.50矿脂                                                                  5.00二苯甲酮-3                                                            5.00配方118-130:冷却洗体液
                                                              %w/wPEG-40氢化蓖麻油                                                  2.00乳酸薄荷酯                                                        0.20醇                                                                5.00聚氧乙烯(7)甘油醚椰油酸酯                                         2.00金缕梅                                                            5.00尿囊素                                                            0.10外消旋没药醇                                                      0.20丙二醇                                                            5.00生育酚乙酸酯                                                      1.00磷酸抗坏血酸酯钠                                                  0.20泛醇USP                                                           0.50乳酸(80%)                                                        0.20实施例7-19中的过氧化物分解剂                                      2.50香料                                                              适量水                                                                加至100配方131-143:美容品
                                                              %w/w十六/十八醇聚氧乙烯(6)醚和硬脂醇                                  9.00聚二甲基硅氧烷                                                    5.00辛酸十六/十八烷基酯                                               8.00澳洲坚果油                                                        5.00丙二醇                                                            5.00水                                                                53.00Sicovit White E 171                                               8.00Sicomet Brown 70 13E 2717                                         2.00生育酚乙酸酯                                                      0.20实施例7-19中的过氧化物分解剂                                      0.50香料                                                                 适量二苯甲酮-3                                                           4.30配方144-156:湿粉底
                                                                 %w/w十六/十八醇聚氧乙烯(6)醚和硬脂醇                                     7.00十六/十八醇聚氧乙烯(25)醚                                            5.00聚二甲基硅氧烷                                                       5.00辛酸十六/十八烷基酯                                                  8.00澳洲坚果油                                                           5.00丙二醇                                                               5.00水                                                                   53.00Sicovit White E 171                                                  8.00Sicomet Brown 70 13E 3717                                            1.00生育酚乙酸酯                                                         0.20实施例7-19中的过氧化物分解剂                                         0.50香料                                                                 适量二苯甲酮-3                                                           4.30配方157-169:防晒油
                                                                 %w/w辛酸十六/十八烷基酯                                                  38.00辛酸/癸酸甘油三酯                                                    28.20月见草油                                                             3.00澳洲坚果油                                                           5.00棕榈酸异丙酯                                                         5.00聚二甲基硅氧烷                                                       3.00甲氧基肉桂酸辛酯                                                     8.002-氰基-3,3-二苯基丙烯酸2-乙基己酯                                   5.00二苯甲酮-3                                                           2.00生育酚乙酸酯                                                         2.00植烷三醇                                                             0.10实施例7-19中的过氧化物分解剂                                         0.50生育酚乙酸酯                                                         0.20香料                                                                 适量配方170-182:擦面清洁剂
                                                                 %w/w椰油酰胺基丙基甜菜碱                                                 5.00椰油酰基水解动物蛋白钾盐                                             7.00PEG-40氢化蓖麻油                                                     2.00Polyquaternium-44                                                    7.70生育酚乙酸酯                                                         1.00外消旋没药醇                                                         0.20泛醇                                                                 1.00香料                                                                 0.50羟乙基纤维素                                                         2.00实施例7-19中的过氧化物分解剂                                         1.00丙二醇                                                               5.00霍霍巴蜡                                                             3.00水                                                                   加至100配方183-195:调理剂
                                                                 %w/w十六/十八醇聚氧乙烯(6)醚和硬脂醇                                     2.00十六/十八醇聚氧乙烯(25)醚                                            1.00辛酸十六/十八烷基酯                                                  6.00十六/十八醇聚氧乙烯(3)醚                                             2.00十六/十八醇                                                          6.00植烷三醇                                                             1.00丙二醇                                                               4.00Polyquaternium-11                                                    5.00生育酚乙酸酯                                                         1.00泛醇                                                                 1.00视黄醇醋酸酯                                                        0.50香料                                                                适量实施例7-19中的过氧化物分解剂                                        1.20防腐剂                                                              适量水                                                                  加至100配方196-208:发蜡
                                                                %w/w聚乙二醇-6                                                          30.00聚乙二醇-75                                                         45.00液体石蜡                                                            0.50PEG-40氢化蓖麻油                                                    1.00甘油                                                                14.00二苯甲酮-3                                                          2.00生育酚乙酸酯                                                        1.00植烷三醇                                                            0.10实施例7-19中的过氧化物分解剂                                        1.00香料                                                                适量水                                                                  加至100配方209-221:去头屑爽发水
                                                                %w/w醇                                                                  45.00芦荟(10-倍浓度)                                                     1.00泛醇                                                                1.00生育酚乙酸酯                                                        0.50PEG-40氢化蓖麻油                                                    0.50尿囊素                                                              0.10水解动物蛋白                                                        1.501-(4-氯苯氧基)-1-(1H-咪唑基)-3,3-二甲基-2-丁酮                     0.30香料                                                                0.10实施例7-19中的过氧化物分解剂                                        1.00水                                                                 加至100配方222-234:足用祛臭喷雾剂
                                                               %w/wPEG-40氢化蓖麻油                                                   0.80醇                                                                 20.00法呢醇                                                             0.08乳酸薄荷醇酯                                                       0.061,2-丙二醇                                                        3.20二苯甲酮-4                                                         1.20聚氧乙烯(7)甘油醚椰油酸酯                                          0.80生育酚乙酸酯                                                       0.05实施例7-19中的过氧化物分解剂                                       0.01香料                                                               适量水                                                                 13.80丁烷                                                               60.00配方235-247:喷发胶
                                                               %w/w氨甲基丙醇                                                         0.40含聚氧乙烯或聚氧丙烯侧链的聚二甲基硅氧烷                           0.03醇                                                                 43.67戊烷                                                               13.20丙烯酸酯/丙烯酰胺共聚物                                            3.40生育酚乙酸酯                                                       1.00实施例7-19中的过氧化物分解剂                                       0.01香料                                                               适量丁烷                                                               2.40异丁烷                                                             35.90

Claims (13)

1.一种用于防止或降低因内源或外源因素形成的过氧化物或氢过氧化物造成的皮肤损害的化妆品或皮肤用制剂,包含a)至少一种作为O-或C-自由基清除剂有效的抗氧化剂,和b)至少一种有机或无机皮肤相容性化合物,该化合物将过氧化物或氢过氧化物还原成对应的醇而不形成后续反应性自由基阶段,其中该化合物以在体温下比皮肤固有的含硫化合物明显更快地反应的方式选择。
2.如权利要求1所要求的化妆品或皮肤用制剂,其基于最终的制剂包含0.001-30重量%抗氧化剂(a)和0.001-30重量%的至少一种过氧化物或氢过氧化物分解剂(b)。
3.如权利要求1所要求的化妆品或皮肤用制剂,其包含作为过氧化物或氢过氧化物分解剂(b)的含硫和/或磷有机化合物。
4.如权利要求1所要求的化妆品或皮肤用制剂,其包含芳族胺作为过氧化物或氢过氧化物分解剂(b)。
5.如权利要求1所要求的化妆品或皮肤用制剂,其包含作为过氧化物或氢过氧化物分解剂(b)的如下化合物:在室温下在体外以0.05m/l的摩尔浓度溶于极性或非极性溶剂时该化合物在10分钟内将过氧化物或氢过氧化物浓度降低至少20%。
6.如权利要求1所要求的化妆品或皮肤用制剂,其包含作为过氧化物或氢过氧化物分解剂(b)的选自硫氧化态低于+6的有机硫化合物和磷氧化态低于+5的有机磷化合物的化合物。
7.如下成分的组合作为用于防止因内源或外源因素形成的过氧化物或氢过氧化物造成的皮肤损害的化妆品或皮肤用制剂的添加剂的用途:a)至少一种作为O-或C-自由基清除剂有效的抗氧化剂,和b)至少一种有机或无机皮肤相容性化合物,该化合物将过氧化物或氢过氧化物还原成对应的醇而不形成后续反应性自由基阶段,其中该化合物以在体温下比皮肤固有的含硫化合物明显更快地反应的方式选择。
8.如权利要求7所要求的如下成分的组合作为用于防止或降低因内源或外源因素形成的过氧化物或氢过氧化物造成的皮肤损害的化妆品或皮肤用制剂的添加剂的用途:a)至少一种作为O-或C-自由基清除剂有效的抗氧化剂,和b)至少一种有机或无机皮肤相容性化合物,该化合物将过氧化物或氢过氧化物还原成对应的醇而不形成后续反应性自由基阶段,其中该化合物以在体温下比皮肤固有的含硫化合物明显更快地反应的方式选择,所述制剂基于最终制剂包含0.001-30重量%的抗氧化剂(a)和0.001-30重量%的至少一种过氧化物或氢过氧化物分解剂(b)。
9.如权利要求7所要求的如下成分的组合作为用于防止因内源或外源因素形成的过氧化物或氢过氧化物造成的皮肤损害的化妆品或皮肤用制剂的添加剂的用途:a)至少一种作为O-或C-自由基清除剂有效的抗氧化剂,和b)至少一种有机或无机皮肤相容性化合物,该化合物将过氧化物或氢过氧化物还原成对应的醇而不形成后续反应性自由基阶段,其中该化合物以在体温下比皮肤固有的含硫化合物明显更快地反应的方式选择,其中含硫-和/或磷化合物用作过氧化物或氢过氧化物分解剂(b)。
10.如权利要求7所要求的如下成分的组合作为用于防止因内源或外源因素形成的过氧化物或氢过氧化物造成的皮肤损害的化妆品或皮肤用制剂的添加剂的用途:a)至少一种作为O-或C-自由基清除剂有效的抗氧化剂,和b)至少一种有机或无机皮肤相容性化合物,该化合物将过氧化物或氢过氧化物还原成对应的醇而不形成后续反应性自由基阶段,其中该化合物以在体温下比皮肤固有的含硫化合物明显更快地反应的方式选择,所述制剂包含芳族胺作为过氧化物或氢过氧化物分解剂(b)。
11.如权利要求7所要求的如下成分的组合作为用于防止因内源或外源因素形成的过氧化物或氢过氧化物造成的皮肤损害的化妆品或皮肤用制剂的添加剂的用途:a)至少一种作为O-或C-自由基清除剂有效的抗氧化剂,和b)至少一种有机或无机皮肤相容性化合物,该化合物将过氧化物或氢过氧化物还原成对应的醇而不形成后续反应性自由基阶段,其中该化合物以在体温下比皮肤固有的含硫化合物明显更快地反应的方式选择,其中在室温下在体外以0.05m/l的摩尔浓度溶于极性或非极性溶剂时化合物(b)在10分钟内将过氧化物或氢过氧化物浓度降低至少20%。
12.如权利要求7所要求的如下成分的组合作为用于防止因内源或外源因素形成的过氧化物或氢过氧化物造成的皮肤损害的化妆品或皮肤用制剂的添加剂的用途:a)至少一种作为O-或C-自由基清除剂有效的抗氧化剂,和b)至少一种有机或无机皮肤相容性化合物,该化合物将过氧化物或氢过氧化物还原成对应的醇而不形成后续反应性自由基阶段,其中该化合物以在体温下比皮肤固有的含硫化合物明显更快地反应的方式选择,其中所用过氧化物或氢过氧化物分解剂(b)是选自硫氧化态低于+6的有机硫化合物和磷氧化态低于+5的有机磷化合物的化合物。
13.如权利要求7所要求的组合在用于补充除去和/或缓解过氧化物或氢过氧化物引起的皮肤损害的化妆品或皮肤用制剂中的用途。
CNB018132936A 2000-07-26 2001-07-19 用于防止过氧化物引起的皮肤损害的化妆品或皮肤用制剂 Expired - Fee Related CN1259032C (zh)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102405215A (zh) * 2008-05-12 2012-04-04 圣保罗研究支持基金会-Fapesp 吩噻嗪化合物阳离子基团的稳定方法、用于预防皮肤疾病和紊乱的药妆制剂和方法
CN101095650B (zh) * 2006-06-20 2012-09-19 莱雅公司 香豆素、丁基化的羟基茴香醚和乙氧喹治疗灰发症的用途
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Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7156859B2 (en) 2001-07-23 2007-01-02 Fos Holding S.A. Device for separating the epithelium layer from the surface of the cornea of an eye
US20060188557A1 (en) * 2003-05-23 2006-08-24 Hisamitsu Pharmaceutical Co., Inc. Prepartaion for external percutaneous administration containing non-steroidal anti-inflammatory drug and interleukin-1 alpha production inhibitor
KR101372783B1 (ko) 2004-01-22 2014-03-11 유니버시티 오브 마이애미 국소용 코-엔자임 큐10 제형 및 그의 사용 방법
US8211449B2 (en) * 2004-06-24 2012-07-03 Dpt Laboratories, Ltd. Pharmaceutically elegant, topical anhydrous aerosol foam
DE102005022292A1 (de) * 2005-05-13 2006-11-16 Basf Ag Verwendung von Peroxidzersetzern in kosmetischen und pharmazeutischen Mitteln zur Behandlung der Haut
BRPI0618951A2 (pt) * 2005-11-24 2016-09-13 Basf Se proteína, uso das proteínas efetoras que se ligam à queratina, dermocosmético, molécula de ácido nucleico, cassete de expressão de dna, vetor, e, célula transgênica
CN101370481A (zh) 2006-01-20 2009-02-18 巴斯夫欧洲公司 两性自组装蛋白质在配制低水溶性的有效物质中的用途
FR2908652B1 (fr) * 2007-01-22 2012-09-28 Oreal Utilisation d'ethoxuquine pour le traitement de la canitie
EP2136787B1 (en) 2007-03-22 2019-08-21 Berg LLC Topical formulations having enhanced bioavailability
MX2010011032A (es) 2008-04-11 2011-03-01 Cytotech Labs Llc Star Metodos y uso de induccion de apoptosis en celulas cancerigenas.
CN102176905A (zh) 2008-08-08 2011-09-07 巴斯夫欧洲公司 具有受控释放的活性成分的含活性成分的纤维层状结构,其用途及其生产方法
EP2684562A1 (de) 2008-08-08 2014-01-15 Basf Se Wirkstoffhaltige Fasernflächengebilde auf Basis von Biopolymeren, ihre Anwendungen und Verfahren zu ihrer Herstellung
MX2011011947A (es) 2009-05-11 2012-01-30 Berg Biosystems Llc Metodos para el diagnostico de trastornos metabolicos usando intercambiadores epimetabolicos, moleculas intracelulares multidimensionales, o influyentes ambientales.
KR102008658B1 (ko) * 2010-03-12 2019-08-08 베르그 엘엘씨 코엔자임 Q10(CoQ10)의 정맥내 제형 및 이의 사용 방법
WO2012020070A2 (en) * 2010-08-10 2012-02-16 Behrooz Kasraee Enhancement of the skin depigmentation
WO2012138765A1 (en) 2011-04-04 2012-10-11 Berg Pharma Llc Methods of treating central nervous system tumors
AU2012271274B2 (en) 2011-06-17 2017-07-27 Berg Llc Inhalable pharmaceutical compositions
KR102279451B1 (ko) 2013-04-08 2021-07-19 버그 엘엘씨 코엔자임 q10 병용 요법을 이용한 암 치료
HUE050060T2 (hu) 2013-09-04 2020-11-30 Berg Llc Eljárások rák kezelésére koenzim Q10 folyamatos infúziójával
EP3882317A1 (de) 2020-03-17 2021-09-22 Covestro Deutschland AG Polyurethandispersionen

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3535249A (en) * 1966-10-24 1970-10-20 Goodyear Tire & Rubber Antioxidant compositions,their use in polymers and products made therefrom
US6090414A (en) * 1970-05-20 2000-07-18 Life Science Labs, Inc. Method and composition to reduce cancer incidence
US3934004A (en) * 1973-03-09 1976-01-20 Orren Leonard J Stain resistant anti-perspirant composition
SU812290A1 (ru) * 1978-06-30 1981-03-15 Научно-Исследовательский Институт Побиологическим Испытаниям Химическихсоединений Способ стабилизации эфиров ненасыщенныхжиРНыХ КиСлОТ
US4847267A (en) * 1986-03-17 1989-07-11 Charles Of The Ritz Group Ltd. Skin treatment composition and method
JPH0296512A (ja) * 1988-09-29 1990-04-09 Seiwa Kasei:Kk パーマネントウェーブ用第一剤
GB8909417D0 (en) * 1989-04-25 1989-06-14 Unilever Plc Shampoo composition
GR1002207B (en) * 1992-08-06 1996-03-27 Johnson & Johnson Consumer Skin care compositions containing imidazoles.
FR2695034B1 (fr) * 1992-09-01 1994-10-07 Oreal Composition cosmétique ou pharmaceutique comprenant en association une peroxydase et un agent anti-oxygène singulet.
US5356439A (en) * 1992-09-14 1994-10-18 Shiseido Co., Ltd. Non-oxidative permanent dye formulation for hair and synthetic fibers
DE4326974A1 (de) * 1993-08-11 1994-05-05 Henkel Kgaa Dauerwellmittel
US5520909A (en) * 1994-12-06 1996-05-28 Conair Corporation Method of permanently restructuring curled or frizzy hair
DE19501053A1 (de) * 1995-01-16 1996-07-18 Basf Ag Stabilisatorgemisch aus Chromanderivaten und inerten organischen Lösungsmitteln sowie dieses Stabilisatorgemisch enthaltende Mikrokapseln
US6497860B1 (en) * 1996-11-04 2002-12-24 Children's Hospital Medical Center Skin lightening compositions
JP3517068B2 (ja) * 1996-11-15 2004-04-05 カネボウ株式会社 皮膚化粧料
EP1272059B1 (de) * 2000-03-17 2005-12-07 Basf Aktiengesellschaft Verfahren zur herstellung öliger suspensionen wasserlöslicher vitamine
FR2809000B1 (fr) * 2000-05-18 2002-08-09 Oreal Utilisation d'ergothioneine et/ou de ses derives comme agent anti-pollution
FR2809007B1 (fr) * 2000-05-18 2003-01-31 Oreal Utilisation de composes contenant une fonction thio-ether, sulfoxyde ou sulfone comme agent cosmetique anti-pollution

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CN110099722A (zh) * 2016-12-22 2019-08-06 荷兰联合利华有限公司 化妆品组合物的臭味减少
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CN108743427A (zh) * 2018-06-29 2018-11-06 华南师范大学 一种新型二氧化钛防晒剂及其制备方法和应用
CN114159321A (zh) * 2021-06-10 2022-03-11 广东嘉丹婷日用品有限公司 一种除氯组合物及其制备方法

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US20030185865A1 (en) 2003-10-02
JP2004504337A (ja) 2004-02-12
CN1259032C (zh) 2006-06-14
WO2002007698A3 (de) 2002-07-18
DE10036655A1 (de) 2002-02-07
BR0112761A (pt) 2003-06-24

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