CN1291468A - 稠合苯衍生物作为抗氧化剂或自由基清除剂在化妆品制剂中的用途 - Google Patents
稠合苯衍生物作为抗氧化剂或自由基清除剂在化妆品制剂中的用途 Download PDFInfo
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- CN1291468A CN1291468A CN00126881A CN00126881A CN1291468A CN 1291468 A CN1291468 A CN 1291468A CN 00126881 A CN00126881 A CN 00126881A CN 00126881 A CN00126881 A CN 00126881A CN 1291468 A CN1291468 A CN 1291468A
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- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/52—Stabilizers
- A61K2800/522—Antioxidants; Radical scavengers
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- A—HUMAN NECESSITIES
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- A—HUMAN NECESSITIES
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Abstract
式Ⅰ的稠合苯衍生物作为抗氧化剂和/或自由基清除剂在化妆品或皮肤科制剂中的用途,其中取代基分别独立地是如下定义的:R1是氢,C1-C12-酰基;R2是氢,C1-C12-烷基;R3和R4是C1-C12-烷基;R5和R6是氢,C1-C12-烷基;X是-CH2-,-(CH2)2-。
Description
本发明申请涉及稠合苯衍生物作为抗氧化剂或自由基清除剂在化妆品制剂中的用途。本发明进一步涉及具有有效含量的熔化的苯衍生物的化妆品和皮肤科制剂。更具体地说,本发明涉及不但能有效防止皮肤中的有害的氧化作用而且能保护化妆品制剂本身或保护化妆品制剂的组成免于有害的氧化过程的化妆品制剂。
在一优选的实施方案中,本发明涉及预防和治疗美容或皮肤病皮肤的改变的化妆品和皮肤科制剂,例如皮肤老化,特别是由氧化作用造成的皮肤老化。
而且,本发明涉及含有至少一种稠合苯衍生物,来进行美容和皮肤病治疗或预防红斑、发炎、过敏或自体免疫反应症状,特别是皮肤病的制剂。
本发明还涉及用于预防和治疗光敏皮肤,特别是光照性皮肤病的活性成分的组合物和制剂。
太阳辐射的紫外线部分对皮肤的有害影响是公知的。波长小于290nm(UV-C区域)的射线被大气中的臭氧层吸收,290nm-320nm间的射线(UV-B区域)造成红斑、简单的太阳灼烧或甚至不同程度的晒伤。
对红斑的最大太阳光活性在相对窄的范围,308nm左右。
防止UV-B辐射的许多化合物是已知的。它们特别是3-亚苄基樟脑的衍生物、4-氨基苯甲酸的衍生物、肉桂酸的衍生物、水杨酸的衍生物、二苯甲酮的衍生物,还有2-苯基苯并咪唑的衍生物。
对在约320nm-约400nm的范围(UV-A区域)来说,具有可得到的过滤器物质也是重要的,因为该区域的射线也能造成在光敏皮肤中反应。已经证实UV-A辐射导致结缔组织的弹性和胶原纤维破坏,造成皮肤过早的老化,它被认为是许多光毒性反应和光敏反应的原因。UV-B辐射的有害作用也被UV-A辐射所强化。
因此,为了防治UV-A区域的射线,特别使用二苯甲酰基甲烷的衍生物,其光稳定性是不充分的(Int.J.Cosm.Science 10,53(1988))。
但是,UV射线也能导致光化学反应,在此情况下,光化学反应产物参与皮肤的新陈代谢。
该光化学反应产物主要是自由基化合物,例如羟基。在皮肤本身中形成的不确定的自由基光产物也能引发不受控制的继发的反应,这是因为它们的高反应性。但是,单线态氧,氧分子的非自由激发态,在UV照射过程中和短寿命的环氧化物和许多其它物质一样也能出现。例如,单线态氧由于其增加的反应性,不同于正常的三线态氧(自由基基态)。但是,也存在着氧分子的活化的反应的(自由基)三线态状态。
并且,UV辐射是一种电离辐射的形式。因此有在UV照射过程中离子物质也将形成的危险,离子物质部分能够氧化参与进生化作用中。
为了防止这些反应,可以往化妆品或皮肤科制剂中添加附加的抗氧化剂和/或自由基清除剂。
已经提出在防晒配方中添加维生素E(具有已知的抗氧化作用的物质),尽管在此其所达到的作用不及所希望达到的作用。
因此,本发明的目的是提供用于预防和治疗光敏皮肤,特别是光照性皮肤病,优选PLD的化妆品和皮肤科制剂和防晒配方。
多种形式的光皮肤病的其它术语是PLD、PLE、Mallorca痤疮和许多其它术语在文献中给出(例如,A.Voelckel等人,ZentralblattHaut-und Geschlechtskrankheiten(1989),156,P.2)。
红斑皮肤症状也会伴随某些皮肤紊乱或不规则的症状产生。例如,典型的痤疮的皮疹症状一般是较重或较轻的红。
抗氧化剂主要用作防治含有它们的制剂变质的物质。然而,已知在人和动物的皮肤中同样会产生不希望的氧化作用。该作用在皮肤老化过程中起重要的作用。
在“Oxidative Stress in Dermatology”中的短文“Skin DiseasesAssociated with Oxidative Injury”p.323 ff(Marcel Decker Inc.,New York,Basle,Hong Kong,Editors:Jürgen Fuchs,Frankfurt,and Lester Packer,Berkeley/California)讨论了皮肤氧化损坏和其特别的原因。
如果目的是永久性地染头发,仅头发氧化染色方法在实践中适用。在氧化染色头发时,由于前体(苯酚、氨基酚和难得使用的二胺)以及碱(在大多数情况下是对苯二胺)和氧化剂(大多数情况下是过氧化氢)反应的结果,形成染料发色团。通常使用的过氧化氢的浓度是6%左右。
通常认为,除了染色作用,也发生过氧化氢的漂白作用。在氧化染色的人的头发中,如漂白的头发的情况下,可以在黑色素存在的地方发现细微的洞。
事实上是氧化剂过氧化氢不仅和染料前体反应,还和头发物质发生反应,在一些情况下可造成头发损坏。
抗氧化剂是防止氧化作用或防止含不饱和化合物的脂肪的自氧化的物质。例如,也可用在化妆品和药物领域中的抗氧化剂是α-生育酚,特别是α-生育酚乙酸乙酯的形式,芝麻油、胆汁酸衍生物、丁羟基茴香醚和丁基化的羟基甲苯。
为了防止这类反应,可以在化妆品配方中另外添加抗氧化剂和/或自由基清除剂。
一些抗氧化剂和自由基清除剂是已知的。例如,美国专利US4144325和4248861和许多其他文献已经提出在防晒配方中使用维生素E。
本发明的目的是克服现有技术的缺点。具体地说,目标是提供制剂,其用途如果不能完全防止但至少能够降低由于氧化作用的结果而对皮肤和/或头发的损害。
本发明进一步的目的是制造在用头发染色制剂甚至用那些含强氧化剂如过氧化氢的头发染色制剂处理头发之前或之后,抵销由头发染色制剂的氧化作用造成的损害的可用的化妆品制剂。
我们已经发现这些目的可以通过使用式Ⅰ的稠合苯衍生物作为化妆品或皮肤科制剂中的抗氧化剂和/或自由基清除剂来达到,
其中取代基相互独立地是如下定义的:
R1是氢,C1-C12-酰基;
R2是氢,C1-C12-烷基;
R3和R4是C1-C12-烷基;
R5和R6是氢,C1-C12-烷基;
X是-CH2-,-(CH2)2-。
对于R1的酰基是支链或非支链的,饱和的或不饱和的,选择性地是多不饱和的C1-C12酰基链。
其实例是甲酸、乙酸、丙酸、正丁酸、异丁酸、山梨酸、正戊酸、异戊酸、己酸、辛酸、癸酸、十一酸和月桂酸的酰基。
R1优选的基团是氢和乙酰基,特别优选的是氢。
R2-R6的烷基是支链的或非支链的C1-C12-烷基链,例如甲基、乙基、正丙基、1-甲基乙基、正丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、正己基、1,1-二甲基丙基,1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基、1-乙基-2-甲基丙基、正庚基、正辛基、2-乙基己基、正壬基、正癸基、正十一烷基和正月桂基。
上述所列可提及的优选的R2和R6的烷基是支链或非支链的C3-C6烷基链,例如正丙基、1-甲基乙基、正丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基和正己基。特别优选的R2和R6的基团是叔丁基。
上述所列可提及的优选的R3和R4的烷基是支链或非支链的C3-C8烷基链,例如正丙基、1-甲基乙基、正丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、正己基、正庚基、正辛基或2-乙基己基。特别优选的R3和R4的基团是正戊基、正己基和正辛基。
特别地,目标是提供含有式Ⅰ的该活性成分的制剂,来进行美容和皮肤病治疗和/或预防红斑、炎性症状、过敏或自体免疫反应症状,特别是皮肤病,也是“刺激”症状。
WO94/08930描述了稠合苯衍生物的合成以及其抗氧化特性,特别是其作为试剂抗动脉硬化的用途。Noguchi等人(Archives ofBiochemistry and Biophysics,Vol.342,No.2(1997),236-243和Vol.347,No.1(1997),141-147)描述了2,3-二氢化-5-羟基-2,2-二戊基-4,6-二叔丁基苯并呋喃防止脂质过氧化的抗氧化特性。
因此,令本领域技术人员惊奇和不能预见的是,式Ⅰ的稠合苯衍生物作为抗氧化剂和/或作为自由基清除剂在化妆品或皮肤科制剂中的用途克服了现有技术的缺点。
这些文献不含有可以导向本发明的任何信息。
因此,本领域技术人员不能预见到用于本发明的式Ⅰ的稠合苯衍生物或含有相同的该衍生物的化妆品或皮肤科制剂比现有技术的活性成分、活性成分组合物和制剂能
-更有效抗皮肤老化
-更好地保护皮肤免于光反应
-更好地防止皮肤炎性反应。
此外,不能预见到式Ⅰ的稠合苯衍生物在化妆品或皮肤科制剂中具有比类似的活性成分如维生素C高的稳定性。
因此本发明涉及式Ⅰ的稠合苯衍生物作为抗氧化剂的用途和其控制和/或预防由氧化压力造成的皮肤老化和炎性反应的用途。
本发明的化妆品或皮肤科制剂可具有通常的组分,可用于治疗、护理和清洗皮肤和/或头发和用作修饰性化妆品方面的化妆产品。它们一般含有基于组合物总重量的0.01-15%,优选0.05-5%,更优选0.1-2.0%的至少一种式Ⅰ的稠合苯衍生物。
本发明的化妆品和皮肤科制剂以通常的化妆品的方式以适合的量施用于皮肤和/或头发。
本发明的化妆品和皮肤科制剂可以是多种形式。因此,例如它们可以是溶液、无水制剂、乳液或油包水型(W/O)的微乳液或水包油型(O/W)的多重乳液,多重乳液,例如油包水水包油(W/O/W)型、凝胶、固体条状物、软膏还有气溶胶。以胶囊化的形式给予式Ⅰ的稠合苯衍生物也是有利的,例如以胶原基质和其它通常的胶囊材料例如纤维素胶囊、明胶、蜡质或脂质体胶囊化的形式,这些在DE-A4308282中有描述,证明是有利的。
为了本发明,也可以往清洗皮肤和头发的含水系统或表面活性剂制剂中掺入式Ⅰ的稠合苯衍生物并且是有利的。
因此,本发明优选的实施方案也是使用至少一种式Ⅰ的稠合苯衍生物来保护皮肤和/或头发免于氧化压力,特别是在香波和洗涤配方中使用至少一种式Ⅰ的稠合苯衍生物。
本发明的化妆品和皮肤科制剂可含有通常用于该制剂中的化妆品辅料,例如防腐剂、杀菌剂、香料、防泡剂、染料、具有染色功能的色素、增稠剂、表面活性剂、乳化剂、软化剂、增水剂和/或湿润剂、脂肪、油、蜡或其它化妆品或皮肤病配方的常规成分,例如醇、多元醇、聚合物、泡沫稳定剂、电解质、有机溶剂或硅氧烷衍生物。
特别地,本发明的式Ⅰ的稠合苯衍生物也可以和其它抗氧化剂和/或自由基清除剂混合。
根据本发明,优选的抗氧化剂是所有常规的或适合于化妆品和/或皮肤病应用的抗氧化剂。
抗氧化剂优选选自氨基酸(例如甘氨酸、组氨酸、酪氨酸、色氨酸)和其衍生物、咪唑(例如咪唑丙烯酸)和其衍生物、肽例如D,L-肌肤、D-肌肽、L-肌肽和其衍生物(例如鹅肌肽)、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)和其衍生物、绿原酸及其衍生物、硫辛酸及其衍生物(二氢化硫辛酸)、金硫葡萄糖、丙硫尿嘧啶和其它硫醇(例如硫氧还蛋白、谷胱甘肽、半胱氨酸、胱氨酸、胱胺和其糖基酯、N-乙酰基酯、甲酯、乙酯、丙酯、戊酯、丁酯和月桂基酯、棕榈酰基酯、油基酯、γ-亚油基(linoleyl)酯、胆甾醇酯和甘油酯)及其盐、硫代二丙酸二月桂基酯、硫代二丙酸二硬脂基酯、硫代二丙酸和其衍生物(酯、醚、肽、类脂、核甘酸、核苷和盐)和硫砜亚胺化合物(例如低耐受量(例如pmol-μmol/kg)的buthionine硫砜亚胺、高半光氨酸硫砜亚胺、buthionine砜、五-、六-、七-硫堇硫砜亚胺)和(金属)螯合剂(例如α-羟基脂肪酸、棕榈酸、植酸、乳铁蛋白)、α-羟基酸(例如柠檬酸、乳酸、苹果酸)、腐殖酸、胆汁酸、胆汁提取物、胆红素、胆绿素、EDTA、EGTA和其衍生物、不饱和脂肪酸及其衍生物、(例如γ-亚麻酸、亚油酸、油酸)、叶酸及其衍生物、泛醌和泛醌醇和其衍生物、维生素C和其衍生物(例如棕榈酸抗坏血酸酯、磷酸抗坏血酸酯镁盐、醋酸抗坏血酸酯)、生育酚及其衍生物(例如维生素E醋酸酯)、维生素A及其衍生物(维生素A棕榈酸酯)和安息香树脂的苯甲酸松柏酯、芸香酸及其衍生物、丁基羟基甲苯、丁基羟基茴香醚、去甲二氢愈创木脂树脂酸、去甲二氢愈创木酸、三羟基丙基苯基甲酮、尿酸及其衍生物、甘露糖及其衍生物、芝麻酚、麻油酚、锌及其衍生物(例如ZnO,ZnSO4)、硒及其衍生物(例如蛋氨酸硒)、茋及其衍生物(例如茋氧化物、反式-茋氧化物)及其适合于本发明的这些提到的活性成分的衍生物(盐、酯、醚、糖、核苷酸、核苷、肽和类脂)。
在制剂中上述抗氧化剂(一种或多种化合物)的量优选0.001-30%(重量),特别优选0.05-20%(重量),最优选1-10%(重量),以制剂的总重量计。
如果维生素E和/或其衍生物是抗氧化剂,优选其各自的浓度为0.001-10%(重量),以制剂的总重量计。
如果维生素A或维生素A衍生物或胡萝卜素或其衍生物是附加的抗氧化剂,优选其各自的浓度为0.001-10%(重量)是有利的,以制剂的总重量计。
优选本发明的乳液包含例如所述的脂肪、油、蜡和其它脂肪物质,还有常规由于该类型配方的水和乳化剂。
类脂相优选选自下面的物质:
-矿物油、矿物蜡;
-油,例如癸酸或辛酸的甘油三酸酯,还有天然油,例如蓖麻油;
-脂肪、蜡和其它天然和合成的脂肪物质,优选脂肪酸和低碳数的醇例如和异丙醇、丙二醇或甘油的酯,或脂肪醇和低碳数的链烷酸或和脂肪酸的酯;
-苯甲酸烷基酯;
-硅油,例如二甲基聚硅氧烷、二乙基聚硅氧烷、二苯基聚硅氧烷和其混合物的形式。
为了本发明的目的,乳液、油凝胶和水分散体或类脂分散体的油相优选选自由饱和的和/或不饱和的、支链的和/或非支链的链烷羧酸(链长为3-30个碳原子)和饱和的和/或非饱和的、支链的和/或非支链的醇(链长为3-30个碳原子)的酯组成的组,由芳香羧酸和饱和的和/或非饱和的、支链的和/或非支链的醇(链长为3-30个碳原子)的酯组成的组。此外这类酯油还可优选自由肉豆蔻酸异丙酯、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-乙基己基酯、月桂酸2-乙基己基酯、硬脂酸2-己基癸基酯、棕榈酸2-辛基十二烷酯、油酸油基酯、芥酸油基酯、油酸瓢儿菜酯、芥酸瓢儿菜酯和这类酯的合成、半合成的和天然混合物,例如霍霍巴油。
油相还可优选选自由支链的和非支链的烃和烃类蜡、硅油、二烷基醚组成的组,由饱和的或不饱和的、支链的或非支链的醇组成的组,还有脂肪酸甘油三酯,即饱和的和/或不饱和的、支链和/或非支链的链烷羧酸(链长为8-24,优选12-18个碳原子)的三甘油酯。例如脂肪酸甘油三酸酯优选选自合成的、半合成的和天然油,例如橄榄油、葵花油、大豆油、花生油、菜籽油、杏仁油、棕榈油、椰子油、棕榈仁油等等。
为了本发明的目的,还可优选使用这类油和蜡组分的任何混合物。当需要时,还可优选使用蜡如棕榈酸十六烷基酯,作为油相的唯一类脂组分。
油相优选选自异硬脂酸2-乙基己酯、辛基十二烷醇、异壬酸异三癸酯、异二十烷、可可酸2-乙基己酯、苯甲酸C12-C15烷基酯、辛酸/癸酸甘油三酸酯和二辛酰基醚。
苯甲酸C12-C15烷基酯和异硬脂酸2-乙基己酯的混合物、苯甲酸C12-C15烷基酯和异壬酸异三癸酯的混合物和苯甲酸C12-C15烷基酯、异硬脂酸2-乙基己酯和异壬酸异三癸酯的混合物是特别优选的。
为了本发明的目的,可优选使用烃、石蜡油、角鲨烷和角鲨烯。
优选油相还含有环状或线性硅油,或全部由这类油组成,尽管除了硅油之外优选使用附加的其它油相组分。
优选使用环甲基硅酮(八甲基环四硅氧烷)作为用于本发明的硅油。但是其它硅油也是本发明优选使用的,例如六甲基环三硅氧烷、聚二甲基硅氧烷、聚(甲基苯基硅氧烷)。
环甲基硅酮和异壬酸异三癸酯的混合物以及环甲基硅酮和异硬脂酸2-乙基己酯的混合物是特别优选的。
如果适当的话,本发明的含水相的制剂优选包含醇、二醇或低碳数的多元醇和其醚,优选乙醇、异丙醇、丙二醇、甘油、乙二醇、乙二醇一乙基或一丁基醚、丙二醇一甲基、一乙基或一丁基醚、二甘醇一甲基或一乙基醚和类似物,还可以含有低碳数醇例如乙醇、异丙醇、1,2-丙二醇和甘油,以及特别地含有一种或多种增稠剂,增稠剂优选选自二氧化硅、硅酸铝、多糖及其衍生物,例如透明质酸、黄原胶和羟丙基甲基纤维素,特别优选自聚丙烯酸酯,优选聚丙烯酸酯选自由Carbopol组成的组,例如980、981、1382、2984和5984型的Carbopol,每种情况下,单独使用或混合使用。
特别地,使用上述溶剂的混合物。在使用醇溶剂的情况下,水是另外的成分。
本发明的乳液是有利的,并含有例如所述的脂肪、油、蜡和其它脂肪物质,还有常规由于该类型配方的水和乳化剂。
本发明的凝胶通常在增稠剂存在下含有低碳数的醇,例如乙醇、异丙醇、1,2-丙二醇、甘油和水和/或上述的油,在油状醇凝胶的情况下,该增稠剂优选是二氧化硅或硅酸铝,在水-醇凝胶或醇凝胶的情况下,该增稠剂优选是聚丙烯酸酯。
适合本发明制剂的可从气溶胶容器中喷射出来的喷射剂是常规已知的易挥发的、液化的喷射剂,例如烃类(丙烷、丁烷、异丁烷),它们可以单独使用或混合使用。使用压缩空气也是有利的。
本发明的制剂也可有利地含有吸收UA-A和UV-B区域的UV辐射的物质,过滤物质的总量为例如0.1%-30%(重量),优选0.5%-10%(重量),特别优选1. 0-6.0%(重量),以制剂的总重量计,以便提供能保护皮肤或头发免于整个范围的紫外线辐射的化妆品制剂。它们也可用作头发或皮肤的防晒组合物。
如果本发明的制剂含有UV-B过滤物质,这些可以是油溶性的或水溶性的。有利的油溶性的UV-B过滤物质是,例如:-3-亚苄基樟脑衍生物,优选3-(4-甲基亚苄基)和3-亚苄基樟脑;-4-氨基苯甲酸衍生物,优选4-(二甲基氨基)苯甲酸(2-乙基己)酯和4-(二甲基氨基)苯甲酸戊酯;-肉桂酸酯,优选4-甲氧基肉桂酸2-乙基己酯和4-甲氧基肉桂酸异戊酯;-水杨酸酯,优选水杨酸2-乙基己酯、水杨酸4-异丙基苄酯和水杨酸高酯;-苯酮的衍生物,优选2-羟基-4-甲氧基苯酮,2-羟基4-甲氧基-4′-甲基苯酮和2,2′-二羟基-4-甲氧基苯酮;-亚苄基丙二酸的酯,优选4-甲氧基亚苄基丙二酸二(2-乙基己酯)和-2,4,6-三苯胺基(对-甲酰基(carbo)-2′-乙基-1′-己氧基)-1,3,5-三嗪。
有利的水溶性UV-B过滤物质是,例如:-2-苯基苯并咪唑-5-磺酸的盐,例如其钠盐、钾盐或其三乙醇铵盐和磺酸本身;-苯酮的磺酸衍生物,优选2-羟基-4-甲氧基苯酮-5-磺酸和其盐;-3-亚苄基樟脑的磺酸衍生物,例如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)磺酸和它们的盐,以及1,4-二(2-氧代-10-磺基-3-亚冰片基-甲基)苯和其盐(相应的10-硫酸根合化合物,例如相应的钠盐、钾盐或三乙醇铵盐),也称为苯-1,4-二(2-氧代-3-亚冰片基甲基)-10-磺酸。
可以和本发明的活性成分混合使用的上述UV-B过滤物质当然不限于上述所列的物质。
本发明还涉及至少一种式Ⅰ的稠合苯衍生物和至少一种UV-B过滤物质的混合物作为抗氧化剂的用途或至少一种式Ⅰ的稠合苯衍生物和至少一种UV-B过滤物质的混合物作为抗氧化剂在化妆品或皮肤科制剂中的用途。
至少一种式Ⅰ的稠合苯衍生物和迄今为止通常存在于化妆品制剂中的UV-A过滤物质混合也是有利的。这些物质优选是二苯甲酰基甲烷,特别是1-(4′-叔丁基苯基)-3-(4′-甲氧基苯基)-丙烷-1,3-二酮和1-苯基-3-(4′-异丙基苯基)丙烷-1,3-二酮。本发明还提供含有这些混合物的组合物和制剂。使用的量和UV-B混合物一样。
本发明还涉及至少一种式Ⅰ的稠合苯衍生物和至少一种UV-A过滤物质的混合物作为抗氧化剂的用途或至少一种式Ⅰ的稠合苯衍生物和至少一种UV-A过滤物质的混合物作为抗氧化剂在化妆品或皮肤科制剂中的用途。
本发明还涉及至少一种式Ⅰ的稠合苯衍生物和至少一种UV-A过滤物质以及至少一种UV-B过滤物质的混合物作为抗氧化剂的用途和至少一种式Ⅰ的稠合苯衍生物和至少一种UV-A过滤物质以及至少一种UV-B过滤物质的混合物作为抗氧化剂在化妆品或皮肤科制剂中的用途。
本发明的含有有效量活性成分的混合物的化妆品和皮肤科制剂还可含有通常用于化妆品中的无机色素,来保护皮肤免于UV射线。这些是钛、锌、锆、硅、锰、铈的氧化物和其混合物,以及其变型,其中氧化物是活性剂。特别优选基于二氧化钛的颜料。
本发明还提供这些UV-A过滤物质和色素的混合物以及含有该混合物的制剂。所使用的量如前混合物所述的。
本发明的保护头发免于UV射线的化妆品和皮肤科制剂是,例如洗发剂,洗发之前或之后,长效卷发之前或之后,染色或漂白之前或之后,当漂洗头发时,施用于头发的制剂,吹风干燥或定型头发的制剂,染色或漂白制剂、美发和治疗洗剂、发胶或长效卷发溶液。
化妆品和皮肤科制剂含有活性成分和通常用于该类型的头发护理和治疗的制剂的辅料。辅料包括防腐剂、表面活性剂、消泡剂、增稠剂、乳化剂、脂肪、油、蜡、有机溶剂、杀菌剂、香料、染料或色素(其任务是使头发或化妆品或皮肤科制剂本身染色)、电解质和抗油腻物质。
为了本发明的目的,术语“电解质”是指水溶性碱金属、铵、碱土金属(包括镁)和无机阴离子的锌盐和这类盐的混合物,必须保证这些盐是药物和化妆品上安全的。
本发明的阴离子优选选自氯化物、硫酸盐和硫酸氢盐、磷酸盐、磷酸氢盐和线性以及环状的低聚磷酸盐和碳酸盐及其碳酸氢盐。
皮肤清洁剂或洗发剂形式的化妆品制剂优选含有至少一种阴离子、非离子或两性表面活性剂或者该类物质的混合物、在含水介质中的式Ⅰ的稠合苯衍生物和通常用于该目的的辅料。表面活性剂和这些物质的混合物在洗发剂中的存在浓度是1wt%-50wt%。
如果化妆品或皮肤科制剂是洗剂的形式,该洗剂在例如漂白之前或之后,洗发之前或之后,在长效卷发之前或之后的两次洗发步骤之间被漂洗掉和涂敷,它们是例如水溶液或水-醇溶液,选择性地含有浓度为0.1-10wt%,优选0.2-5wt%的表面活性剂。
这些化妆品或皮肤科制剂也可以是含有常规用于该目的的的辅料的气溶胶的形式。
不被漂洗掉的洗剂,特别是定型头发的洗剂,用于吹风干燥头发的洗剂,美发和治疗的洗剂形式的化妆品制剂一般是水溶液、醇溶液或水-醇溶液的形式,含有至少一种阳离子、阴离子、非离子或两性聚合物或其混合物,也可以含有至少一种有效浓度的式Ⅰ的稠合苯衍生物。聚合物的用量是例如0.1-10wt%,优选0.1-3wt%。
含有至少一种式Ⅰ的稠合苯衍生物的治疗和护理头发的化妆品制剂可以是非离子或阴离子型的乳液形式。除水以外,非离子乳液含有油或也可以是例如聚乙氧基化的或聚丙氧基化的脂肪醇或这两种有机组分的混合物。这些乳液任选包含阳离子表面活性剂。
根据本发明,治疗和护理头发的化妆品制剂可以是凝胶的形式,除了有效量的至少一种式Ⅰ的稠合苯衍生物和通常用于该目的的溶剂,优选水,该凝胶还含有有机增稠剂,例如阿拉伯胶、黄原胶、海藻酸钠、纤维素衍生物优选甲基纤维素、羟甲基纤维素、羟乙基纤维素、羟丙基纤维素、羟丙基甲基纤维素或无机增稠剂,例如硅酸铝如膨润土或聚乙二醇和聚乙二醇硬脂酸酯或二硬脂酸酯的混合物。该增稠剂在凝胶中的存在量是0.1-30wt%,优选0.5-15wt%。
式Ⅰ的稠合苯衍生物在供头发用的产品中的量是0.01wt%-15wt%,优选0.05wt%-5wt%,特别是0.1wt%-2wt%,以产品的总重量计。
本发明的含水化妆品清洗剂或供水洗的低水或无水清洗剂浓缩物含有阴离子、非离子和/或两性表面活性剂,例如
-常规的皂,例如脂肪酸钠盐
-烷基硫酸盐、烷基醚硫酸盐、链烷磺酸盐和烷基苯磺酸盐
-磺基乙酸盐
-磺基甜菜碱
-肌氨酸盐
-氨基磺基甜菜碱
-磺基琥珀酸盐
-琥珀酸单酯
-烷基醚羧酸盐
-蛋白质-脂肪酸缩合物
-烷基甜菜碱和酰氨基甜菜碱
-脂肪酸链烷醇酰胺
-聚乙二醇醚衍生物。
是化妆用的皮肤清洗制剂的化妆品制剂可以是液体或固体形式。除了至少一种式Ⅰ的稠合苯衍生物,它们优选含有至少一种阴离子、非离子或两性表面活性剂或其混合物,和如果需要,一种或多种通常用于该目的的电解质和辅料。表面活性剂存在于清洗制剂中的浓度是1-94%(重量),以制剂的总重量计。
是洗发剂的化妆品制剂除了有效含量的至少一种式Ⅰ的稠合苯衍生物,优选含有至少一种阴离子、非离子或两性表面活性剂或其混合物,和如果需要,一种本发明的电解质和常规用于该目的辅料。表面活性剂存在于洗发剂中的浓度是1wt%-94wt%。
本发明的组合物除了上述表面活性剂和水以外,当需要时,含有常规用于化妆品中的添加剂,例如,香料、增稠剂、染料、除臭剂、抗菌物质、再加脂剂、配位剂和螯合剂、珠光剂、植物提取物、维生素、活性成分等等。
本发明还涉及保护皮肤和头发免于氧化和光氧化作用的美容方法,包括将足够量的化妆品组合物涂敷至皮肤或头发上,该组合物含有有效浓度的至少一种式Ⅰ的稠合苯衍生物。
本发明同样还涉及保护化妆品或皮肤科制剂免于氧化或光氧化的方法,这些制剂是例如治疗和护理头发的制剂,特别是染发剂、发胶、洗发剂、染发洗发精和化妆产品,例如指甲油、口红、粉底、洗涤和沐浴制剂、治疗或护理皮肤的乳剂或所有其它化妆品制剂,因为在贮存过程中的氧化或光氧化,其成分可能涉及稳定性问题,其中化妆品制剂含有有效含量的至少一种式Ⅰ的稠合苯衍生物。
在这些制剂中的式Ⅰ的稠合苯衍生物的量优选是0.01-15%(重量),较优选是0.05-5%(重量),特别是0.1-2.0%(重量),以制剂的总重量计。
本发明还涉及制备本发明的化妆品组合物的方法,包括将本发明的活性成分混合物以已知方式掺入化妆品或皮肤科制剂中。
下面的实施例用来说明本发明而不是限制本发明。除非另外说明,所有数量、份数和百分数是以重量计,以制剂的总量或总重量计。
实施例1O/W洗剂wt%石蜡油(GP9) 8.00棕榈酸异丙酯 3.00凡士林 4.00十六烷硬脂基醇 2.00PEG-40蓖麻油 0.50十六烷基硬脂基硫酸钠 0.5丙烯酸聚合物(carbomer)钠 0.40化合物Ⅰa 0.50甘油 3.00α-生育酚 0.20甲氧基肉桂酸辛酯 5.00丁基甲氧基二苯甲酰基甲烷 1. 00防腐剂、染料和香料 适量水 加至100.00
实施例2
唇膏wt%氢化蓖麻油 4.00纯地蜡 8.00蜂蜡 4.00巴西棕榈蜡 2.00凡士林 40.00化合物Ⅰa 0.50β-胡萝卜素 0.10防腐剂、染料和香料 适量石蜡油 加至100.00
实施例3
凝胶wt%Carbopol 934P 2.00三乙醇胺 3.00化合物Ⅰa 0.50α-乙酸生育酚酯 0.20聚氧乙烯失水山梨糖醇脂肪酸 0.50酯(吐温20)甘油 2.00PCA钠盐 0.50水解的胶原蛋白 2.00防腐剂、染料和香料 适量水 加至100.00
实施例4
防晒乳液
wt%环甲基硅酮 2.00十六烷基二甲基硅酮共聚醇 0.20PEG-22十二烷基共聚物 3.00石蜡油(GP9) 2.00辛酸/癸酸三甘油酯 5.80甲氧基肉桂酸辛酯 5.80丁基甲氧基二苯甲酰基甲烷 4.00化合物Ⅰa 0.50α-乙酸生育酚酯 0.50硫酸锌 0.70Na3HEDTA 0.3防腐剂、染料和香料 适量水 加至100.00
实施例5
头发洗剂
wt%乙醇 40.00己二酸二异丙酯 0.10PEG-40氢化蓖麻油 0.20化合物Ⅰa 0.50α-乙酸生育酚酯 0.10防腐剂、染料和香料 适量水 加至100.00
Claims (7)
1. 式Ⅰ的稠合苯衍生物作为抗氧化剂和/或自由基清除剂在化妆品或皮肤科制剂中的用途,
其中取代基分别独立地是如下定义的:
R1是氢,C1-C12-酰基;
R2是氢,C1-C12-烷基;
R3和R4是C1-C12-烷基;
R5和R6是氢,C1-C12-烷基;
X是-CH2-,-(CH2)2-。
2.如权利要求1的用途,其中取代基分别独立地是如下定义的:
R1是氢;
R2是氢,C3-C6-烷基;
R3和R4是C3-C8-烷基;
R5是氢;
R6是C3-C6-烷基;
X是-CH2-。
3.如权利要求1或2之一所述的用途,其中至少一种式Ⅰ的化合物以有效量存在于化妆品或皮肤科制剂中。
4.如权利要求1-3中任一项所述的用途,其中至少一种式Ⅰ的化合物以0.01-15wt%浓度存在于化妆品或皮肤科制剂中。
6.如权利要求5的化妆品或皮肤科制剂,含有作为抗氧化剂或自由基清除剂的式Ⅰ的化合物,其中变量如权利要求2定义的。
7.如权利要求5或6之一的化妆品或皮肤科制剂,含有作为抗氧化剂或自由基清除剂的式Ⅰa的化合物,
Applications Claiming Priority (2)
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DE19941595.1 | 1999-09-01 | ||
DE19941595A DE19941595A1 (de) | 1999-09-01 | 1999-09-01 | Verwendung von anellierten Benzolderivaten als Antioxidans oder Radikalfänger in kosmetischen Zubereitungen |
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CN1291468A true CN1291468A (zh) | 2001-04-18 |
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CN00126881A Pending CN1291468A (zh) | 1999-09-01 | 2000-09-01 | 稠合苯衍生物作为抗氧化剂或自由基清除剂在化妆品制剂中的用途 |
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Country | Link |
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EP (1) | EP1080716A1 (zh) |
JP (1) | JP2001089369A (zh) |
CN (1) | CN1291468A (zh) |
DE (1) | DE19941595A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9889080B2 (en) | 2015-05-07 | 2018-02-13 | Celeb LLC | Color depositing shampoo |
US10245221B2 (en) | 2015-05-07 | 2019-04-02 | Celeb LLC | Stabilized color depositing shampoo |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US4144325A (en) * | 1976-11-10 | 1979-03-13 | Voyt Walter F | Method of and composition for preventing sunburn while affording tanning |
US4248861A (en) * | 1979-02-21 | 1981-02-03 | Schutt Steven R | Skin treatment methods |
JPH02121975A (ja) * | 1988-10-28 | 1990-05-09 | Eisai Co Ltd | 2,3−ジヒドロベンゾフラン誘導体 |
JPH03261705A (ja) * | 1990-03-09 | 1991-11-21 | Sansho Seiyaku Co Ltd | メラニン生成抑制外用剤 |
TW393475B (en) * | 1992-10-16 | 2000-06-11 | Chugai Pharmaceutical Co Ltd | 4-alkoxyl-2,6-di-t-butyl phenol derivatives |
EP0640609A1 (en) * | 1993-08-24 | 1995-03-01 | Ono Pharmaceutical Co., Ltd. | Fused phenol derivatives having inhibitory activity on TXA2 synthetase, and 5-lipoxygenase and scavenging activity on oxygen species |
ES2154560B1 (es) * | 1998-09-16 | 2001-12-01 | Lipotec Sa | Composicion a base de derivados de cromanos y su uso para reducir quimicamente las reacciones oxidativas o inducidas por radicales libres. |
-
1999
- 1999-09-01 DE DE19941595A patent/DE19941595A1/de not_active Withdrawn
-
2000
- 2000-08-09 EP EP00117050A patent/EP1080716A1/de not_active Withdrawn
- 2000-08-29 JP JP2000259130A patent/JP2001089369A/ja not_active Withdrawn
- 2000-09-01 CN CN00126881A patent/CN1291468A/zh active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9889080B2 (en) | 2015-05-07 | 2018-02-13 | Celeb LLC | Color depositing shampoo |
US10245221B2 (en) | 2015-05-07 | 2019-04-02 | Celeb LLC | Stabilized color depositing shampoo |
Also Published As
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DE19941595A1 (de) | 2001-03-08 |
EP1080716A1 (de) | 2001-03-07 |
JP2001089369A (ja) | 2001-04-03 |
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