CN1660047A - 含有8-十六碳烯-1,16-二羧酸的贫乳化剂的制剂 - Google Patents
含有8-十六碳烯-1,16-二羧酸的贫乳化剂的制剂 Download PDFInfo
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- CN1660047A CN1660047A CN2004101032843A CN200410103284A CN1660047A CN 1660047 A CN1660047 A CN 1660047A CN 2004101032843 A CN2004101032843 A CN 2004101032843A CN 200410103284 A CN200410103284 A CN 200410103284A CN 1660047 A CN1660047 A CN 1660047A
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Abstract
包含细分散的至少一种亲脂和亲水相的且含有8-十六碳烯-1,16-二羧酸的美容或护肤制剂,其特征在于以制剂计其含有少于3重量%的乳化剂,不含PEG-十六碳烯芳基醚并且所含的亲脂相的量小于10重量%。
Description
本发明涉及将本身已知的活性成分用于美容和局部皮肤的光亮上,或者用于防止皮肤的褐化,特别是由于UV辐射而引起的皮肤褐化,以及用于增亮天然发色。
在一个优选实施方式中,本发明涉及的是美容或护肤剂,其用于预防和治疗美容学或皮肤病学上的皮肤病变,如不希望的色素沉积,诸如局部色素沉着过度和局部色素沉着不足(例如肝痣,雀斑),以及天然色素沉积的抑制,但也可仅用于增亮更大一些的且完全适于个人肤型的有色素沉积的皮肤表面。
皮肤的色素沉积应归咎于黑素细胞,这些细胞能作为——根据皮肤类型的不同——零星的或是或多或少成堆出现的能形成色素的细胞,出现在表皮的最下层中,基底层和基细胞附近。黑素细胞含有作为特征细胞器官的且在其中能形成黑色素的暗色体。此外,当受到UV辐射的激发时黑色素还会增强。该黑色素会经由表皮的活跃层(角朊细胞)而最后被传输到角质层(角质细胞)中,并或多或少地形成颜色鲜明的褐色到棕黑色的肤色。黑色素是在氧化过程的最终阶段形成的,在该过程中酪氨酸会在酪氨酸酶的协同作用下经过多个中间阶段转化为褐色至棕黑色的真黑素(DHICA-黑色素和DHI-黑色素),或者是在含硫化合物的参与下转化为红色的棕黑素。DHICA-黑色素和DHI-黑色素的形成经由了共同的中间阶段多巴醌和多巴色素(phnomelanin)。而后者又会部分地在其他酶的参与下转化成吲哚-5,6-醌羧酸或是吲哚-5,6-醌,从中形成两种所述的真黑素。另外,棕黑素的形成还要经历中间产物多巴醌和半胱酰胺多巴。
类似于皮肤的色素沉积过程,头发的颜色(头发的色素沉积)也要归因于产生黑色素的黑素细胞。头发中黑色素的量和组成决定了天然的由基因确定的发色。
皮肤上色素沉积过度问题有多方面的原因,或者说是多个生物学过程的伴随现象,如UV辐射(如雀斑)、遗传体质、伤口愈合或结疤时皮肤上色素沉着缺失或者皮肤的老化(如老年性雀斑样痣)。
在本文中细分散的、含有至少一种亲脂和亲水相的美容或护肤剂是油包水型(W/O)或是水包油型(O/W)的乳液,或者是如水包油包水型(W/O/W)或是油包水包油型(O/W/O)的多重乳液,是水分散液或是脂分散液,凝胶,固态棒剂或者是气溶胶。
在本文中,8-十六碳烯-1,16-二元羧酸是假丝酵母菌株酵母细胞的代谢产物。其特征在于以下结构:
作为起始物的是纯植物来源的脂肪酸。该物质转化为羟基脂肪酸,然后该羟基脂肪酸又会被氧化成脂肪酸醛,最后再被氧化成二元羧酸。该酵母细胞来自经选择的突变体。商业产品的纯度为95%。其中8-十六碳烯-1,16-二羧酸以顺式和反式异构体混合物的形式存在,并且顺式异构体的量又是占大多数的。产品中还附带含有浓度约为3%的油酸。8-十六碳烯-1,16-二羧酸也可被记作二酸,CAS号20701-68-2;目前的INCI名称为十八碳烯二酸。
本发明范围内的乳化剂是指乳化剂和乳化剂组合物,它们可以选自如下一组物质,即甘油硬脂酸酯的Ceteareth-20、Ceteareth-25和Ceteareth-6结合硬脂醇,十六烷基硬脂醇结合PEG-40-蓖麻油和十六烷基硬脂基硫酸钠,Triceteareth-4磷酸酯,甘油硬脂酸酯,十六烷基硬脂基硫酸钠,卵磷脂Trilaureth-4磷酸酯,Laureth-4磷酸酯,硬脂酸,硬脂酸丙二醇酯SE,PEG-25-氢化蓖麻油,PEG-54-氢化蓖麻油,PEG-6辛酸/癸酸甘油酯,油酸甘油酯结合的丙二醇,PEG-9-硬脂酸酯,PEG-20硬脂酸酯,PEG-30-硬脂酸酯,PEG-40-硬脂酸酯,PEG-100-硬脂酸酯,Ceteth-2,Ceteth-20,聚山梨酸酯-20,聚山梨酸酯-60,聚山梨酸酯-65,聚山梨酸酯-100,甘油硬脂酸酯结合的PEG-100硬脂酸酯,肉豆蔻酸甘油酯,月桂酸甘油酯,PEG-40-脱水上梨糖醇过油酸酯,Laureth-4,Ceteareth-3,异硬脂酰甘油醚,十六烷硬脂酰醇结合的十六烷硬脂酰硫酸钠,Laureth-23,Steareth-2,甘油硬脂酸酯结合的PEG-30硬脂酸酯,PEG-40-硬脂酸酯,二硬脂酸乙二醇酯,PEG-22-十二烷基乙二醇共聚物,聚甘油基-2-PEG-4-硬脂酸酯,Ceteareth-12,Ceteareth-20,Ceteareth-30,甲基-葡萄糖倍半硬脂酸酯,Steareth-10,PEG-20-硬脂酸酯,Steareth-2结合的PEG-8-二硬脂酸酯,Steareth-21,Steareth-20,Isosteareth-20,PEG-45/十二烷基乙二醇共聚物,甲氧基-PEG-22/十二烷基乙二醇共聚物,PEG-40-脱水山梨糖醇过油酸酯,PEG-40-脱水山梨糖醇过异硬脂酸酯,PEG-20-甘油硬脂酸酯,PEG-20-甘油硬脂酸酯,PEG-8-蜂蜡,聚甘油基-2-月桂酸酯,异硬脂酰二甘油基琥珀酸酯,硬脂酰胺丙基-PG-二monium氯磷酸盐,甘油硬脂酸酯SE,Ceteth-20,三乙基柠檬酸酯,PEG-20-甲基葡萄糖倍半硬脂酸酯,硬脂酸柠檬酸甘油酯,十六烷基磷酸酯,十六碳烯芳基硫酸酯,脱水山梨糖醇倍半油酸酯,Triceteareth-4-磷酸酯,Trilaureth-4-磷酸酯,聚甘油基-甲基葡萄糖二硬脂酸酯,十六烷基磷酸钾,Isosteareth-10,聚甘油基-2-倍半异硬脂酸酯,Ceteth-10,Oleth-20,Isoceteth-20,甘油硬脂酸酯结合的Ceteareth-20,Ceteareth-12,十六烷基硬脂醇和十六烷基棕榈酸酯,十六烷基硬脂醇结合的PEG-20-硬脂酸酯,PEG-30-硬脂酸酯,PEG-40-硬脂酸酯,PEG-100-硬脂酸酯,脱水山梨糖醇硬脂酸酯,硬脂酸柠檬酸甘油酯,十六烷基磷酸酯,聚甘油基-3二硬脂酸酯,甲基葡萄糖硬脂酸酯。
在本文中,使制剂具有较小粘性触觉的聚合物可以例如,优选选自橡胶类化合物。属于这种橡胶类物质的是在空气下能硬化并形成树脂的植物汁液或树汁,或者是水植物的提取物。在本文中,选自该组的比较理想的物质可以是阿拉伯树胶,角豆粉,黄芪胶,刺梧桐树胶,瓜尔胶,果胶,Gellan胶,鹿角菜,琼脂,褐藻胶,角叉菜,黄原胶。此外,使用衍生胶也是比较理想的,如羟丙基瓜尔胶(JaguarHP 8),其中瓜尔胶-羟丙基三甲基氯化铵的电荷密度可为0.4至1.0meq/g,并且分子量可为100000至1800000。特别有益的是Jaguar系列,特别是来自Rhodia公司提供的Jaguar Excel产品的瓜尔胶-羟丙基三甲基氯化铵。另外,比较理想的还能使用多糖和多糖衍生物,特别是透明质酸,甲壳质和脱乙酰壳聚糖,软骨素硫酸盐,淀粉和淀粉衍生物以及纤维素衍生物如甲基纤维素,羧甲基纤维素,羟乙基纤维素,羟丙基甲基纤维素以及使用聚丙烯酸酯如Noveon公司提供的Carbopol型产品(Carbopol 980,981,1382,5984,2984,ETD 2001,ETD 2020,ETD 2050或Pemulen TR1 & TR2),使用聚丙烯酰胺(Seppigel 305),聚乙烯醇,PVP,PVP/VA共聚物,聚乙二醇。
在本文中,地中海深色肤型或是亚洲肤型也被称作肤型V。该肤型不受阳光作用即具有棕色的皮肤和主要是深棕色至黑色的头发和眼睛。一般而言,中欧人属于肤型I,II和III。南欧人则多数是肤型IV。属于肤型V的有色素强烈沉积的南欧人,北非人,南美人和亚洲人。黑非洲人和美国黑人则列入色素沉积型VI。特别的,所谓“地中海深色肤型或亚洲肤型”应理解为地中海人,中国人,泰国人域日本人的皮肤。
本文中的热带则是指位于南北回归线之间的气候带。从其皮肤湿含量,皮肤类型和其对于皮肤护理产品的要求来看,生活在这个气候带内的人的需求明显不同于欧洲人或是北美人。例如,那些能强烈润湿皮肤的皮肤护理产品对于此地的人们兴趣则不大,因为由于气候条件,他们的皮肤本身已经是具有较高的湿含量了。
已知的产品含有相对较多的油相并且皮肤感觉很强烈。而如上所述,生活在热带的居民则对于护肤霜所带来的润湿度和皮肤感受有着特殊的要求。已知的产品会在皮肤上遗留下油/脂的残余并且皮肤感觉也很不舒适。
现已发现,这些缺点可以通过大量减少油相和乳化剂含量而克服。
文献DE 10150734中公开了含有一定量8-十六碳烯-1,16-二羧酸的制剂,但是并没有公开有关含有极小量乳化剂的制剂的内容。
文献WO 01/66067公开了一种用于治疗皮肤病的方法,其中使用了局部施用的紫苏油(schwarznessell),但是也没有公开有关含有极小量乳化剂的特殊制剂的内容。
WO 01/51013公开了包封有微生物的美容内含物在美容剂中的用途,但是也没有公开有关含有极小量乳化剂的特殊制剂的内容。
US 5807561公开了某种用于光亮皮肤的美容剂,但是并没有哪个含有8-十六碳烯-1,16-二羧酸且不含PEG-十六碳烯芳基醚(PEG-Cetearyl-Ether)。相反,没有公开有关含有极小量乳化剂的制剂和较小脂肪相的内容。
WO 95/00115公开了某些短链的寡肽在皮肤光亮剂中的用途,但也没有公开这种含有8-十六碳烯-1,16-二羧酸的制剂。
EP 1249232中公开了一种经皮释放材料,该材料包括含有活性成分的聚合物颗粒。但是没有公开含有一定量8-十六碳烯-1,16-二羧酸的制剂。
稍远一些的先有技术记载在US 2001/0029253,US 5961990,WO 01/51014中。
对于技术人员来说是不可能预见性地特地使用如下一种美容或护肤剂来消除现有技术的缺陷,即该制剂包含有细分散的至少一种亲脂和亲水相且含有8-十六碳烯-1,16-二羧酸,同时以制剂计其中还含有少于3重量%的乳化剂,不含PEG-十六碳烯芳基醚并且所含的亲脂相的量小于10重量%。
使用这种制剂导致了皮肤变得柔软,保湿或不干燥,同时也不会显得油腻或发亮。在使用时还另外会形成一种清新感,不会使皮肤有粘性触感。此外,该制剂还能使皮肤色泽鲜亮,同时又作用温和,不会导致皮肤刺激,红肿,过敏反应,起丘疹或斑疹。在使用时,本发明的制剂外观较少油腻,粘性或粘稠并且感觉适用于亚洲人的肤型。
现又进一步发现,优选乳化剂量为0.5至2重量%。特别优选还含有能赋予制剂较少粘性触觉的聚合物。
并且进一步优选以制剂的总重计,8-十六碳烯-1,16-二羧酸以0.001-10重量%,优选0.005-8重量%,特别优选0.05-5重量%的总浓度存在。本发明的制剂优选能防治不希望出现的皮肤色素沉积和/或能治疗色素沉积紊乱,防治地中海深色肤型或亚洲肤型皮肤不希望出现的色素沉积以及肪治不希望出现的头发色素沉积和/或用于亮发。特别优选用在热带地区。
单个组分的缺失会对整体组合物的独特性质产生不利影响。因此,为实现本发明,本发明制剂中所有上述组分都是必不可少的。
本发明的制剂还可以有利地含有油成分。这些成分可以选自由饱和和/或不饱和、支链和/或直链的且链长为3至30个C原子的烷基羧酸与饱和和/或不饱和、支链和/或直链的且链长为3至30个C原子的醇生成的酯类,选自由芳香族羧酸与饱和和/或不饱和、支链和/或直链的且链长为3至30个C原子的醇生成的酯类。这些酯油可以优选选自下组:肉豆蔻酸异丙酯,棕榈酸异丙酯,硬脂酸异丙酯,油酸异丙酯,硬脂酸正丁酯,月桂酸正己酯,油酸正癸酯,硬脂酸异辛酯,硬脂酸异壬酯,异壬酸异壬酯,棕榈酸2-乙基己酯,月桂酸2-乙基己酯,硬脂酸2-己基癸酯,棕榈酸2-辛基十二烷基酯,油基油酸酯,油基芥酸酯,瓢儿菜基油酸酯,瓢儿菜基芥酸酯以及这些酯的合成、半合成和天然的混合物,例如霍霍巴油。
另外,油成分还优选可选自支链和直链的烃和烃蜡、硅油、二烷基醚、二烷基碳酸酯,选自饱和或不饱和、支链或直链的醇以及甘油三脂肪酸酯,即饱和和/或不饱和、支链和/或非支链且链长为8至24、特别是12至18个C原子的烷基羧酸的甘油三酸酯。这些甘油三脂肪酸酯可以优选选自诸如合成、半合成和天然的油,如橄榄油、葵花油、大豆油、花生油、菜籽油、杏仁油、棕榈油、可可油、棕榈果油和其他更多类似物。
根据本发明,使用任意的这种油和蜡成分的混合物也是比较理想的。视情况使用蜡也是有利的,如十六酸鲸蜡酯作为油相仅有的油脂成分。
油成分可以比较有利地选自异硬脂酸2-乙基己酯、辛基十二烷醇、异壬酸异十三烷基酯、异二十烷、可可酸2-乙基己酯、苯甲酸C12-15烷基酯、癸酰基-癸酸-甘油三酸酯、二辛酰醚、二辛酰碳酸酯。
特别有益的是使用苯甲酸C12-15烷基酯和异硬脂酸2-乙基己酯的混合物,苯甲酸C12-15烷基酯和异壬酸异十三烷基酯的混合物以及苯甲酸C12-15烷基酯、异硬脂酸2-乙基己酯和异壬酸异十三烷基酯的混合物。
根据本发明,烃优选使用石蜡油、异十六烷、异三十烷和三十碳六烯。
此外,还优选油成分具有一定量的环状硅油或直链硅油或完全由这种油组成,其中更优选除了硅油外还使用一定量的其他油相成分。
优选将环二甲基硅酮(八甲基环四硅氧烷)用作本发明中待用的硅油。但根据本发明思想也可优选使用其他一些硅油,如六甲基环三硅氧烷、聚二甲基硅氧烷、聚(甲基苯基硅氧烷)。
此外,特别优选的是环二甲基硅酮和异壬酸异十三烷基酯的混合物和环二甲基硅酮和异硬脂酸2-乙基己酯的混合物。
另外,油成分也可优选选自磷脂类物质。这些磷脂是酰基化的甘油的磷酸酯。这些磷脂酰胆碱中最为重要的是诸如可由下面的一般结构表征的卵磷脂,
其中的R’和R”典型地为直链的具有15或17个碳原子和不超过4个顺式双键的脂族基团。
根据本发明,也能比较好地制备出一种其主要目的虽不在于防护阳光但仍然含有一定量UV防护物质的美容或护肤剂。如此,就可以例如将常规的UV-A-或UV-B-过滤物质添加到日霜或化妆产品中。UV防护物质以及抗氧化剂,如果希望还有保存剂,本身也能对制剂起到抗腐败的有效作用。该美容或护肤剂也可较好地做成防晒剂的形式。
根据本发明,与此相应地,该制剂优选含有至少一种UV-A-和/或UV-B-过滤物质。尽管非必要,但该配方中还可以含有一种或多种有机和/或无机的且能存在于水相和/或油相中的色素作为UV过滤剂。
优选的无机色素是金属氧化物和/或其他难溶于水或不溶于水的金属化合物,特别是氧化钛(TiO2)、氧化锌(ZnO)、氧化铁(如Fe2O3)、氧化锆(ZrO2)、氧化硅(SiO2)、氧化锰(如MnO)、氧化铝(Al2O3)、氧化铈(如Ce2O3)、相应金属的混合氧化物以及这些氧化物的混合物,以及硫酸钡(BaSO4)。
二氧化钛色素既可以存在于结晶改性的金红石中也能作为锐钛矿存在,并且根据本发明,其优选是可经过表面处理的(“经涂覆”),从而能形成或保持诸如亲水性、亲水亲油性或疏水性。这种表面处理过程可以是以本身已知的方法将一种稀释的亲水和/或疏水的无机和/或有机涂层施涂到色素上。根据本发明,各种表面涂层也可以含有水。
根据本发明,也可以使用市售含油或含水预分散体形式的所述的经涂层和未经涂层的二氧化钛。可优选向这些预分散体中添加入分散助剂和/或增溶介质。
根据本发明的二氧化钛,其特征在于初级颗粒粒径在10nm至不超过150nm。
商品名 | 涂层 | 预分散体的添加组分 | 制造商 |
MT-100TV | 氢氧化铝硬脂酸 | - | Tayca公司 |
MT-100Z | 氢氧化铝硬脂酸 | - | Tayca公司 |
MT-100F | 硬脂酸氧化铁 | - | Tayca公司 |
MT-500SAS | 氧化铝,氧化硅硅氧烷 | - | Tayca公司 |
MT-100AQ | 氧化硅氢氧化铝 | - | Tayca公司 |
褐藻酸 | |||
Eusolex T-2000 | 氧化铝二甲基硅油 | - | Merck KgaA |
Eosolex TS | 氧化铝,硬脂酸 | - | Merck KgaA |
Titandioxid P25 | 无 | - | Degussa |
Titandioxid T805(Uvinul TiO2) | 辛基三甲基硅烷 | - | Degussa |
UV-Titan X170 | 氧化铝二甲聚硅氧烷 | - | Kemira |
UV-Titan X 161 | 氧化铝,氧化硅硬脂酸 | - | Kemira |
Tioveil AQ 10PG | 氧化铝氧化硅 | 水丙二醇 | SolaveilUniquema |
Mirasun TiW 60 | 氧化铝氧化硅 | 水 | Rhone-Poulenc |
根据本发明,特别优选的二氧化钛是Tayca公司提供的MT-100Z和MT-100TV,Merck公司提供的Eusolex T-2000和Eusolex TS和Degussa公司提供的Titandioxid T805。
根据本发明思想,也可以使用市售的含油或含水预分散体形式的氧化锌。适合本发明的氧化锌颗粒和氧化锌颗粒的预分散体,其特征在于颗粒粒径为<300nm并且可从以下公司购得,商标列于下表:
商品名 | 涂层 | 制造商 |
Z-Cote HP1 | 2%二甲基硅油 | BASF |
Z-Cote | / | BASF |
ZnO NDM | 5%二甲基硅油 | H&R |
MZ 707M | 7%二甲基硅油 | M.Tayca公司 |
Nanox 500 | / | Elementis |
ZnO Neutral | / | H&R |
根据本发明,特别优选的氧化锌是BASF公司的Z-Cote HP1和Haarmann &Reimer公司的氧化锌NDM。
在制成的美容剂中一种或多种无机色素的总量优选在0.1重量%至25重量%的范围,更优选在0.5重量%至18重量%。
根据本发明,优选的有机色素是2,2’-亚甲基-二-(6-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)-酚)[INCI:二辛基三唑],其可由以下化学结构式表征,并可从CIBA-Chemikalien GmbH购得,商标为TinosorbM。
根据本发明,优选的UV-A-过滤物质是联苯甲酰甲烷衍生物,特别是4-(叔丁基)-4’-甲氧基联苯甲酰甲烷(CAS号70356-09-1),其能从Givaudan公司购得,商标为Marke Parsol1789以及从Merck公司购得,商标为Eusolex9020。
此外优选的UV-A过滤物质还有亚苯基-1,4-二-(2-苯并咪唑基)-3,3’-5,5’-四磺酸
及其盐,特别是相应的钠盐、钾盐或三乙醇胺盐,特别优选亚苯基-1,4-二-(2-苯并咪唑基)-3,3’-5,5’-四磺酸-二-钠盐
其INCI名为二咪唑盐,并可以,例如,从Haarmann & Reimer公司购得,商标为Neo Heliopan AP。
另外优选的还有1,4-二(2-氧代-10-硫代-3-亚冰片基甲基)-苯及其盐(特别是相应的10-硫酸根化合物,更尤其是相应的钠盐、钾盐或三乙醇胺盐),其也能称为苯-1,4-二(2-氧代-3-亚冰片基甲基-10-磺酸)并且可用以下结构式来表征:
其他优选的UV-A过滤物质是能由下面的结构式表征的羟基二苯甲酮:
其中
·R1和R2各自独立地为氢、C1-C20烷基、C3-C10-环烷基或C3-C10-环烯基,并且取代基R1和R2共同连结着氮原子,它们可以形成一个5元或6元环,和
·R3表示C1-C20-烷基。
在本发明范畴内,特别优选的羟基二苯甲酮是2-(4’-二乙基氨-2’-羟基苯甲酰)-苯甲酸己酯(也是:氨基二苯甲酮),其可以通过以下结构表征:
并且能从BASF公司购得,商品名为Uvinul A Plus。
根据本发明,优选的UV-过滤物质还是所谓的宽带过滤剂,即能吸收UV-A-和UV-B-辐射的过滤剂。
较好的宽带过滤剂或UV-B-过滤物质为,例如,具有以下结构的二间苯二酚基-三嗪衍生物:
其中R1,R2和R3各自独立地选自支链或直链且具有1至10个碳原子的烷基或是氢原子。特别优选的是2,4-二-{[4-(2-乙基己氧基)-2-羟基]-苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪(INCI:异三嗪),其能从CIBA-Chemikalien GmbH购得,商标为TinosorbS。
在本发明范畴内,特别有益的且特征在于能具有很高或极高UV-A防护作用的制剂优选含有多种UV-A-和/或宽带过滤剂,特别是二苯甲酰甲烷衍生物[例如4-(叔丁基)-4’-甲氧基二苯甲酰甲烷],苯并三唑衍生物[例如2,2’-亚甲基-二-(6-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)-酚)],亚苯基-1,4-二-(2-苯并咪唑基)-3,3’-5,5’-四磺酸和/或其盐,1,4-二(2-氧代-10-硫代-3-亚冰片基甲基)-苯和/或其盐和/或2,4-二-{[4-(2-乙基己氧基)-2-羟基]-苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪,各自单独或以相互任意组合的方式使用。
根据本发明,具有如下结构主题的其他UV-过滤物质也是较好的,
例如那些记载在欧洲专利公开文献EP 570838 A1中的s-三嗪衍生物,其化学结构可以由以下通式表示
其中
R代表支链或直链的C1-C18-烷基,C5-C12-环烷基,适当时它们还能被一个或多个C1-C4-烷基取代,
X代表氧原子或NH基团,
R1代表支链或直链的C1-C18的烷基,C5-C12环烷基,适当时它们还能被一个或多个C1-C4的烷基取代,或者是表示氢原子,碱金属原子,氨基基团或具有如下通式的基团
其中
A代表支链或直链的C1-C18-烷基,C5-C12-环烷基或芳基,适当时它们还能被一个或多个C1-C4-烷基取代,
R3代表氢原子或甲基基团,
n代表1至10之间的数,
R2当X为NH基时,为支链或直链的C1-C18烷基,C5-C12环烷基,适当时它们还能被一个或多个C1-C4烷基取代;并且
当X为氧原子时,为支链或直链的C1-C18烷基,C5-C12环烷基,适当时它们还能被一个或多个C1-C4烷基取代,或者是氢原子,碱金属原子,氨基基团或具有如下通式的基团
其中
A代表支链或直链的C1-C18-烷基,C5-C12-环烷基,适当时它们还能被一个或多个C1-C4-烷基取代,
R3代表氢原子或甲基基团,
n代表1至10之间的数。
根据本发明,特别优选的UV-过滤物质还能是不对称取代的s-三嗪,其化学结构可以通过如下结构式表示,
其在下文也被记作二辛基丁基氨基三嗪酮(INCI:二辛基丁氨基三嗪酮)并且可以从Sigma 3V公司购得,商标为UVASORB HEB。
根据本发明,也优选对称取代的s-三嗪,4,4’,4”-(1,3,5-三嗪-2,4,6-三基三亚氨基)-三-苯甲酸-三(2-乙基己酯),也就是:2,4,6-反-[苯胺基-(对羰-2’-乙基-1’-己氧基)]-1,3,5-三嗪(INCI:辛基三嗪酮),其能从BASF股份公司购得,其商品名为UVINULT150。
优选使用的还有记载在欧洲专利公开文献775698中的二间苯二酚基三嗪衍生物,其化学结构可通过如下通式表示
其中的R1,R2和A1代表不同的有机基团。
在本发明范畴内较为优选的还有2,4-二-{[4-(3-Sulfonato)-2-羟基-丙氧基]-2-羟基-苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪钠盐,2,4-二-{[4-(3-(2-丙氧基)-2-羟基-丙氧基)-2-羟基]-苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪,2,4-二-{[4-(2-乙基-己氧基)-2-羟基]-苯基}-6-[4-(2-甲氧基乙基-羧基)-苯氨基]-1,3,5-三嗪,2,4-二-{[4-(3-(2-丙氧基)-2-羟基-丙氧基)-2-羟基]-苯基}-6-[4-(2-乙基-羧基)-苯氨基]-1,3,5-三嗪,2,4-二-{[4-(2-乙基己氧基)-2-羟基]-苯基}-6-(1-甲基-吡咯-2-基)-1,3,5-三嗪,2,4-二-{[4-三(三甲基甲硅烷氧基-甲硅烷基丙氧基)-2-羟基]-苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪,2,4-二-{[4-(2”-甲基丙烯基氧基)-2-羟基]-苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪和2,4-二-{[4-(1’,1’,1’,3’,5’,5’,5’-七甲基甲硅烷氧基-2”-甲基-丙氧基)-2-羟基]-苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪。
根据本发明,优选的宽带过滤剂是2,2’-亚甲基-二-(6-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)-酚),其可通过以下的化学结构式表示,并可从CIBA-chemikalien GmbH购得,商品牌号为TinosorbM。
在本发明范畴内优选的宽带过滤剂还有2-(2H-苯并三唑-2-基)-4-甲基-6-[2-甲基-3-[1,3,3,3-四甲基-1-[(三甲基甲硅烷基)氧代]二硅氧烷基]丙基]-酚(CAS号:155633-54-8),其INCI名为苯并三唑基甲基苯酚三硅氧烷(Drometrizole Trisiloxane)且可以由以下化学结构式表示。
UV-B过滤剂和/或宽带过滤剂可以是油溶性的或是水溶性的。优选的油溶性的UV-B过滤剂和/或宽带过滤剂是,例如:
·3-亚苄基樟脑-衍生物,优选为3-(4-甲基亚苄基)樟脑,3-亚苄基樟脑;
·4-氨基苯甲酸-衍生物,优选为4-(二甲基氨基)-苯甲酸(2-乙基己基)酯,4-(二甲基氨基)苯甲酸戊酯;
·2,4,6-三苯胺基-(对羰-2’-乙基-1’-己氧基)-1,3,5-三嗪;
·亚苄基丙二酸酯,优选为4-甲氧基亚苄基丙二酸二(2-乙基己基)酯;
·肉桂酸酯,优选为4-甲氧基肉桂酸(2-乙基己基)酯,4-甲氧基肉桂酸异戊酯;
·苯甲酮的衍生物,优选为2-羟基-4-甲氧基二苯甲酮,2-羟基-4-甲氧基-4’-甲氧基-4’-甲基二苯甲酮,2,2’-二羟基-4-甲氧基二苯甲酮
·以及连结在聚合物上的UV-过滤剂。
优选的水溶性UV-B-过滤剂和/或宽带过滤物质是,例如:
·2-苯基苯并咪唑-5-磺酸的盐,如它的钠盐、钾盐或它的三乙醇铵盐,以及该磺酸本身;
·3-亚苄基樟脑的磺酸衍生物,如4-(2-氧代-3-亚冰片基甲基)苯磺酸,2-甲基-5-(2-氧代-3-亚冰片基甲基)磺酸及其盐。
在本发明范畴内特别优选于室温下呈液态的UV过滤剂是高薄荷基水杨酸酯(INCI:Homosalate)、2-乙基己基-2-羟基苯甲酸酯(2-乙基己基水杨酸酯,水杨酸辛酯,INCI:水杨酸辛酯)、4-异丙基苄基水杨酸盐和肉桂酸的酯,优选为4-甲氧基肉桂酸(2-乙基己基)酯(2-乙基己基-4-甲氧基肉桂酸酯,INCI:甲氧基肉桂酸辛酯)和4-甲氧基肉桂酸异戊酯(异戊基-4-甲氧基肉桂酸酯,INCI:异戊基对甲氧基肉桂酸酯),3-(4-(2,2-二乙氧基羰基乙烯基)-苯氧基)丙烯基)-甲氧基硅氧烷/二甲基硅氧烷共聚物(INCI:Dimethicodiethylbenzalmalonat),其可以例如从Hoffmann La Roche公司购得,商品名为ParsolSLX。
另一符合本发明且较为优选的可供使用的防晒滤光物质为乙基己基-2-氰基-3,3-联苯丙烯酸酯(Octocrylen),其可从BASF公司购得,商品名为UvinulN 539并且可由以下结构表征:
在本发明的制剂中使用聚合连接或聚合的UV-过滤剂也是极具优点的,特别是记载在WO-A-92/20690中的那些。
很明显,可用在本发明中的UV过滤物质不仅仅局限于上述所列的那些。
为了提供能护发或皮肤不受全区域紫外线辐射侵害的美容剂,本发明的制剂优选含有能吸收在UV-A和/或UV-B区域内的UV辐射的物质,其总量为例如0.1重量%至30重量%,优选0.5至20重量%,特别优选1.0至15.0重量%,各以制剂的总重计。它们也能被用作头发或皮肤的防晒剂。
根据本发明,也可以较好地使用在食品技术中允许的且具有如下E号的保存剂。
E200 | 山梨糖酸 | E227 | 亚硫酸氢钙 |
E201 | 山梨酸钠 | E228 | 亚硫酸氢钾 |
E202 | 山梨酸钾 | E230 | 联二苯(联苯) |
E203 | 山梨酸钙 | E231 | 邻苯基苯酚 |
E210 | 苯甲酸 | E232 | 邻苯基苯酚钠 |
E211 | 苯甲酸钠 | E233 | 噻苯哒唑 |
E212 | 苯甲酸钾 | E235 | 游霉素 |
E213 | 苯甲酸钙 | E236 | 蚁酸 |
E214 | 对羟基苯甲酸乙酯 | E237 | 甲酸钠 |
E215 | 对羟基苯甲酸乙酯-钠盐 | E238 | 甲酸钙 |
E216 | 对羟基苯甲酸正丙酯 | E239 | 六亚甲基四胺 |
E217 | 对羟基苯甲酸正丙酯-钠盐 | E249 | 亚硝酸钾 |
E218 | 对羟基苯甲酸甲酯 | E250 | 亚硝酸钠 |
E219 | 对羟基苯甲酸甲酯-钠盐 | E251 | 硝酸钠 |
E220 | 二氧化硫 | E252 | 硝酸钾 |
E221 | 亚硫酸钠 | E280 | 丙酸 |
E222 | 亚硫酸氢钠 | E281 | 丙酸钠 |
E223 | 二亚硫酸钠 | E282 | 丙酸钙 |
E224 | 二亚硫酸钾 | E283 | 丙酸钾 |
E226 | 亚硫酸钙 | E290 | 二氧化碳 |
此外,根据本发明还适合用于化妆品中的保存剂或保存助剂是二溴二氰基丁烷(2-溴-2-溴甲基戊二腈),3-碘-2-丙炔基丁基氨基甲酸酯,2-溴-2-硝基-丙基-1,3-二醇,咪唑烷基脲,5-氯-2-甲基-4-异噻唑啉-3-酮,2-氯乙酰胺,氯化二苄基·二甲基·烷基胺,苄醇,DMDM乙内酰脲,IPBC(甲醛裂解物)。
另外,苯基羟烷基醚,特别是公知的名称为苯氧基乙醇的化合物,由于其能对一定数量的微生物起到杀菌和杀真菌作用,因此适宜作为保存剂。
其他一些抑菌剂同样也是适合于添加入本发明制剂中的。优选的物质是,例如,2,4,4’-三氯-2’-羟基二苯基醚(Irgasan),1,6-二-(4-氯苯基双胍)-己烷(洗必泰),3,4,4’-三氯对称二苯脲,季铵化合物,丁子香油,薄荷油,百里香油,柠檬酸三乙酯,金合欢醇(3,7,11-三甲基-2,6,10-十二-三烯-1-醇)以及记载在专利公开文献DE-3740186,DE-3938140,DE-4204321,DE-4229707,DE-4309372,DE-4411664,DE-19541967,DE-19543695,DE-19543696,DE-19547160,DE-19602108,DE-19602110,DE-19602111,DE-19631003,DE-19631004和DE-19634019中和专利文献DE-4229737,DE-4237081,DE-4324219,DE-4429467,DE-4423410和DE-19516705中的活性成分或活性成分组合物。使用碳酸氢钠也是比较有益的。
此外,本发明的制剂中还优选含有,例如,能改善配方使用感觉和美容特性的填料,色素、保湿剂、调节剂、水、醇、香料、颜料、抗微生物物质、返油剂、络合剂和螯合剂、珍珠光亮剂、植物提取物、维生素、活性成分、杀菌剂、防护剂。
在各种使用情况中,可能会很轻易超过或是未超过上述的浓度范围,但是仍然可以得到本发明的制剂。由于技术人员不可能不预见到这类制剂的各个适合的成分的种类功能繁多,因此他们知道,当这种过量或未过量的情况出现时,不会脱离本发明的实质。
以下实施例将用来阐释而不是限制本发明。实施例中的数值表示重量百分比,且以各种制剂的总重量计。
实施例
O/W乳液
1 | 2 | 3 | 4 | 5 | |
硬脂酸柠檬酸甘油酯 | 1.0 | 1.5 | 1.5 | 0.5 | 0.25 |
十六烷基十八烷醇 | 2.5 | 5 | 0.5 | 2.0 | 1.5 |
乙基己基甲氧基肉桂酸酯 | 5.0 | 3.0 | 2.0 | 2.0 | 5.0 |
乙基己基甘油 | 1 | - | 0.5 | 1 | - |
水合氯化铝 | - | 1 | 0.02 | 1 | - |
乙醇 | - | - | 3.0 | 1 | - |
丙烯酰二甲基塔日(tairat)铵/VP共聚物 | 0.5 | 0.75 | 0.5 | 2.0 | 0.25 |
蓝色水溶性颜料(1号兰) | 0.5 | 1.0 | 0.4 | 3.0 | 0.25 |
Carbomer | - | - | 0.2 | - | 0.1 |
磷酸盐化的淀粉 | 1.0 | - | 4.0 | - | 0.5 |
8-十六碳烯-1,16-二羟酸 | 0.5 | 0.75 | 1.0 | 1.5 | 2.5 |
辛基十二烷醇 | 0.5 | - | 1.0 | - | 2.0 |
辛酸/癸酸三甘油酯 | - | - | 1.0 | - | 0.5 |
肉豆蔻酸肉豆蔻酯 | - | 1.5 | 1.0 | 2.5 | - |
香料 | 适量 | 适量 | 适量 | 适量 | 适量 |
对羟基苯甲酸甲酯 | 0.4 | 0.1 | 0.2 | 0.3 | 0.4 |
对羟基苯甲酸丙酯 | 0.3 | 0.4 | 0.05 | 0.15 | - |
碘代丙炔基丁基氨基甲酸酯 | - | - | 0.18 | - | 0.1 |
苯氧基乙醇 | 0.5 | - | 0.25 | - | 1.0 |
海盐 | - | - | 0.01 | 0.5 | - |
甘油 | 5 | 10 | 7.5 | 15 | 7.5 |
生育酚乙酸酯 | 0.5 | 0.25 | 0.5 | 0.1 | - |
亚氨基二琥珀酸酯,四钠盐 | 0.1 | 0.25 | 0.04 | - | 0.2 |
二氧化钛 | - | 2.5 | 1.2 | 0.15 | - |
水 | 补足100 | 补足100 | 补足100 | 补足100 | 补足100 |
O/W乳液
6 | 7 | 8 | 9 | 10 | |
聚乙二醇(21)硬脂醚 | 1 | - | 0.5 | 2 | 1.5 |
聚乙二醇(2)硬脂醚 | 1 | - | 1.5 | 3 | 0.5 |
十六碳烯芳基葡糖苷 | - | 2.0 | - | - | - |
环二甲基硅酮 | 12.5 | 15 | 8.0 | 5.0 | 1.5 |
聚二甲基硅氧烷 | 5.0 | 3.0 | 1.0 | 2.0 | 1.0 |
山俞醇 | 3 | 2 | - | 1 | - |
硬脂醇 | 3 | 2 | - | 2 | - |
十六烷基硬脂醇 | 3 | 4 | - | - | 2 |
氢化聚异丁烯 | 0.5 | 0.75 | 1.0 | 2.0 | 0.25 |
8-十六碳烯-1,16-二羧酸 | 0.5 | 0.75 | 1.0 | 1.5 | 2.5 |
辛基十二烷醇 | 0.5 | 1.0 | 0.75 | 3.0 | 0.25 |
甘油 | 5 | 10 | 15 | 3 | 7.5 |
泛醇 | 0.5 | 1.0 | 0.75 | 0.25 | 0.1 |
香料 | 适量 | 适量 | 适量 | 适量 | 适量 |
对羟基苯甲酸甲酯 | 0.4 | 0.1 | 0.05 | 0.3 | 0.4 |
对羟基苯甲酸丙酯 | 0.3 | 0.4 | 0.25 | 0.15 | - |
碘代丙炔基丁基氨基甲酸酯 | - | - | 0.05 | - | 0.1 |
改性淀粉 | 0.5 | - | - | 0.15 | - |
水 | 补足100 | 补足100 | 补足100 | 补足100 | 补足100 |
O/W乳液
11 | 12 | 13 | 14 | 15 | |
硬脂酸柠檬酸甘油酯 | 1.0 | 0.5 | 1.25 | 0.5 | 0.3 |
聚乙二醇(20)十六碳烯芳基醚 | 1.0 | 1.0 | 0.5 | - | - |
三甘油甲基葡萄糖二硬脂酸酯 | - | - | - | - | 2.5 |
8-十六碳烯-1,16-二羧酸 | 0.5 | 0.75 | 1.0 | 1.5 | 2.5 |
环二甲基硅酮 | - | - | - | 1 | - |
聚二甲基硅氧烷 | 0.5 | 3.0 | 0.75 | 1.5 | 0.2 |
山俞醇 | 1 | - | 2 | 1 | 0.2 |
二辛酰碳酸酯 | 3 | 5 | 10 | 15 | 5 |
硬脂醇 | - | - | - | 1 | 0.2 |
十六烷基硬脂醇 | - | - | 1 | 1 | 0.2 |
维生素E | 0.5 | 0.5 | 0.75 | 0.25 | 0.1 |
辛基十二烷醇 | 0.5 | - | 0.75 | 3.0 | 0.25 |
泛醇 | 0.5 | - | 0.75 | 0.25 | 0.1 |
Carbomer | 0.05 | 0.35 | 0.15 | 0.1 | - |
香料 | 适量 | 适量 | 适量 | 适量 | 适量 |
对羟基苯甲酸甲酯 | 0.4 | 0.3 | 0.05 | 0.3 | 0.4 |
对羟基苯甲酸丙酯 | 0.3 | - | 0.25 | 0.15 | - |
碘代丙炔基丁基氨基甲酸酯 | - | - | 0.05 | - | 0.1 |
苯氧基乙醇 | - | 0.5 | - | 0.15 | - |
山梨糖醇 | 10 | - | - | 5 | - |
丁二醇 | - | - | - | 5 | 10 |
丙二醇 | - | - | 10 | 5 | - |
甘油 | - | 7.5 | - | - | - |
水 | 补足100 | 补足100 | 补足100 | 补足100 | 补足100 |
O/W乳液
16 | 17 | 18 | 19 | 20 | |
硬脂酸 | 1.5 | 2.5 | 0.1 | 0.25 | 0.3 |
硬脂酸钠 | 0.5 | 0.75 | 0.1 | 0.25 | 0.5 |
甘油单硬脂酸酯 | 0.5 | 1.2 | 2 | 1.0 | - |
8-十六碳烯-1,16-二羧酸 | 0.1 | 0.1 | 1.0 | 1.5 | 2.5 |
氢化可可甘油酯 | - | 1.0 | 0.5 | 1 | 1.3 |
聚二甲基硅氧烷 | 2.0 | 0.75 | 0.75 | - | - |
十六烷醇 | 1.5 | 1.5 | - | 1 | 0.2 |
硬脂醇 | - | 1.5 | - | 1 | 0.2 |
十六烷基棕榈酸酯 | 1.0 | - | - | 1.8 | 0.5 |
苯氧基乙醇 | 0.3 | - | - | 0.5 | - |
矿物油 | 1.5 | 3.0 | 1.0 | 2.0 | 0.25 |
Carbomer | 0.05 | 0.1 | 0.15 | 0.1 | - |
凡士林 | - | 2.0 | - | - | 1.0 |
丙烯酸酯/C10-30烷基丙烯酸交联聚合物 | - | 0.1 | - | 0.25 | 0.75 |
香料 | 适量 | 适量 | 适量 | 适量 | 适量 |
生育酚乙酸酯 | 0.1 | 0.1 | 0.75 | 0.25 | 0.1 |
丁基甲氧基二苯甲酰基甲烷 | 0.3 | 0.3 | 2.0 | 0.5 | 0.75 |
乙基己基甲氧基肉桂酸酯 | 1.8 | 1.8 | 2.0 | 0.5 | 3.5 |
氧化硅 | 0.2 | - | - | - | - |
十六碳烯芳基乙基己酸酯 | 1.5 | - | - | - | 2.5 |
对羟基苯甲酸丙酯 | 0.5 | 0.05 | 0.05 | 0.3 | 0.4 |
对羟基苯甲酸甲酯 | 0.15 | 0.15 | 0.05 | 0.3 | 0.4 |
丁二醇 | - | 3.0 | 2.5 | - | - |
钠-EDTA | 0.2 | 0.2 | 0.05 | - | 0.1 |
镁/铝硅酸盐 | 0.2 | - | - | 0.15 | - |
甘油 | 1.0 | 3.5 | 8 | 12 | 10 |
水 | 补足100 | 补足100 | 补足100 | 补足100 | 补足100 |
Claims (8)
1.包含细分散的至少一种亲脂和亲水相的且含有8-十六碳烯-1,16-二羧酸的美容或护肤制剂,其特征在于以制剂计其含有少于3重量%的乳化剂,不含PEG-十六碳烯芳基醚并且所含的亲脂相的量小于10重量%。
2.如权利要求1的制剂,其特征在于乳化剂的量为0.5至2重量%。
3.如上述权利要求之一的制剂,其特征在于还另含有能赋予制剂更小的粘性触觉的聚合物。
4.如上述权利要求之一的制剂,其特征在于8-十六碳烯-1,16-二羧酸以0.001-10重量%,优选0.005-8重量%,特别优选0.05-5重量%的总浓度存在,以制剂的总重计。
5.如权利要求1至5至少一项的制剂的用途,用于防治皮肤上不希望出现的色素沉积和/或用于治疗色素沉积紊乱。
6.如权利要求5的用途,用于防治地中海深色肤型或亚洲肤型皮肤的不希望出现的色素沉积。
7.如权利要求1至4至少一项的制剂的用途,用于防治不希望出现的头发色素沉积和/或用于亮发。
8.如上述权利要求之一的用途,其特征在于用于热带地区。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10348631.3 | 2003-10-15 | ||
DE10348631A DE10348631A1 (de) | 2003-10-15 | 2003-10-15 | Emulgatorarme Zubereitungen mit 8-Hexadecen-1, 16-dicarbonsäure |
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CN1660047A true CN1660047A (zh) | 2005-08-31 |
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CN2004101032843A Pending CN1660047A (zh) | 2003-10-15 | 2004-10-14 | 含有8-十六碳烯-1,16-二羧酸的贫乳化剂的制剂 |
Country Status (3)
Country | Link |
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KR (1) | KR20050036774A (zh) |
CN (1) | CN1660047A (zh) |
DE (1) | DE10348631A1 (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2889808B1 (fr) * | 2005-08-17 | 2011-07-22 | Oreal | Utilisation de l'acide 8-hexadecene-1,16-dicarboxylique comme agent de soin destine a favoriser la cohesion de la couche cornee |
DE102008047362A1 (de) * | 2008-09-15 | 2010-04-15 | Henkel Ag & Co. Kgaa | Zusammensetzung zur Hautaufhellung |
FR3024037B1 (fr) | 2014-07-25 | 2018-03-02 | Sederma | Ingredient actif cosmetique ou dermatologique comprenant un melange d'acides dicarboxyliques gras insatures, compositions le comprenant et utilisations cosmetiques ou dermatologiques |
Family Cites Families (7)
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DE10150732A1 (de) * | 2001-10-13 | 2003-04-17 | Beiersdorf Ag | Wirkstoffkombination zur Verhinderung unerwünschter Hautpigmentierung |
DE10163786A1 (de) * | 2001-12-22 | 2003-07-03 | Beiersdorf Ag | Kosmetische und/oder dermatologische Wirkstoffkombination |
DE10150742A1 (de) * | 2001-10-13 | 2003-04-24 | Beiersdorf Ag | Wirkstoffkombination zur Verhinderung unerwünschter Hautpigmentierung |
DE10150735A1 (de) * | 2001-10-13 | 2003-04-17 | Beiersdorf Ag | Wirkstoffkombination zur Verhinderung unerwünschter Hautpigmentierung |
DE10150734A1 (de) * | 2001-10-13 | 2003-04-17 | Beiersdorf Ag | Kosmetische und/oder dermatologische Zubereitung |
DE10150731A1 (de) * | 2001-10-13 | 2003-04-17 | Beiersdorf Ag | Wirkstoffkombination zur Verhinderung unerwünschter Hautpigmentierung |
EP1448157A1 (de) * | 2001-11-09 | 2004-08-25 | Beiersdorf AG | Kosmetische und/ oder dermatologische zubereitung enthaltend octadecendicarbons aeure und uv-filtersubstanzen |
-
2003
- 2003-10-15 DE DE10348631A patent/DE10348631A1/de not_active Withdrawn
-
2004
- 2004-10-14 KR KR1020040082083A patent/KR20050036774A/ko not_active Application Discontinuation
- 2004-10-14 CN CN2004101032843A patent/CN1660047A/zh active Pending
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KR20050036774A (ko) | 2005-04-20 |
DE10348631A1 (de) | 2005-05-12 |
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