CN109562055A - 用于对抗皮肤、头发和指甲老化迹象的组合物 - Google Patents
用于对抗皮肤、头发和指甲老化迹象的组合物 Download PDFInfo
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- CN109562055A CN109562055A CN201680087229.0A CN201680087229A CN109562055A CN 109562055 A CN109562055 A CN 109562055A CN 201680087229 A CN201680087229 A CN 201680087229A CN 109562055 A CN109562055 A CN 109562055A
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- skin
- polyphenol
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- extract
- dragon spruce
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Abstract
本发明涉及一种用于局部施用的组合物，其含有以下至少一种组合：(a)至少一种选自原花色素单体和低聚原花色素(OPC)、羟基芪、类黄酮单体和低聚物的多酚，其衍生物及其混合物，(b)云杉提取物，其包含至少一种选自以下的木脂素：羟罗汉脂素，亚麻木脂素，铁杉脂素，落叶松树脂醇和利欧委尔。本发明还涉及这种组合物用于对抗皮肤或毛发和指甲老化迹象或污染影响的美容用途，以及使用所述组合的美容治疗方法。
Description
背景技术
本发明涉及化妆品组合物和活性剂的组合，它们改善皮肤或皮肤附属物的外观，并且特别用作对抗皮肤或皮肤附属物的某些老化迹象的作用剂和/或抗污染剂。
本发明特别涉及增强皮肤对氧化剂的内在防御的组合。本发明还涉及其用于对抗皮肤或皮肤附属物老化迹象的化妆品用途，用于改善肤色的光泽或用于减少眼睛下方的黑眼圈。本发明还涉及化妆品处理方法，其包括局部施用组合物或含有其的组合物。
皮肤由两个隔层组成，表面一层，表皮，较深的一层，真皮，它们相互作用。人表皮主要由三种类型的细胞组成，即角质形成细胞，黑素细胞和朗格汉斯细胞；角质形成细胞非常占优势。这些细胞类型中的每一种都凭借其自身的功能有助于皮肤在生物体中的作用，特别是有助于防止外部攻击。
表皮通常被分成以下几层：构成表皮发芽层的角质形成细胞的基底层，称为有棘层的层，由置于发芽层上的若干层多面体细胞组成，一层至三层，称为颗粒层，由含有不同的细胞质内含物扁平细胞组成，它们是角质透明质颗粒，最后是角质层(或角质层)，由一组角质形成细胞在其分化的末期组成，称为角质细胞。
真皮给表皮提供了坚实的支撑。它也是它的供养部件。它主要由成纤维细胞和主要由胶原蛋白、弹性蛋白和称为基质的物质组成的细胞外基质组成。这些组分由成纤维细胞合成。其中也发现了白细胞、肥大细胞或其它组织巨噬细胞。最后，血管和神经纤维穿过真皮。
表皮和真皮之间的结合由真皮表皮连接确保。
细胞氧化和自由基积累在衰老过程中起重要作用。
自由基的来源可能是内源性的，由正常的代谢过程或呼吸引起；它们也可能因环境因素而增加，例如暴露于污染，吸烟或紫外线。这些自由基对皮肤的作用可导致氧化应激。
这些老化现象，无论是内在的还是外在的，都是自然的生理现象。然而，对于大量男性和女性，仍然需要改善其皮肤或皮肤附属物的外观并减少或延迟与衰老相关的体征。
申请JP2003160433描述了具有抗MMP(基质金属蛋白酶)活性的复合组合物，其含有可可(Theobroma cacao)与各种植物提取物的混合物。
细胞，特别是皮肤细胞，已经形成了针对这些氧化剂和氧化应激的防御机制，并且用于防止其有助于衰老的不利影响。
这一方面涉及谷胱甘肽的还原形式；另一方面，许多酶具有抗氧化活性，例如超氧化物歧化酶(SOD)，过氧化氢酶或血红素加氧酶。
在化妆品领域中已经提出使用抗氧化剂，特别是在局部施用中。例如，生育酚(维生素E)或其衍生物，维生素C或其衍生物，类胡萝卜素，泛醌或绿茶是已知的。
申请FR 3 017 289描述了具有强直接抗氧化能力的组合物，其含有多酚和维生素C的衍生物。
然而，仍然需要具有能够发挥整体抗氧化美容作用的新的活性剂，特别是对抗皮肤和/或头发的氧化应激及其效果。
发明内容
现在已经发现，在本发明的上下文中，具有直接抗氧化活性的植物云杉(Piceaabies)的提取物也能够促进细胞的两种内源性防御途径抵抗氧化应激。
此外，当这些提取物与葡萄树中存在的多酚类物质结合时，对细胞防御的抗氧化作用会协同增加；这些多酚可以是天然的或稳定的形式。
因此，本发明的主题是以下组合：
(a)至少一种选自原花色素单体和低聚原花青素(OPC)、羟基芪(hydroxystilbenes)、类黄酮单体和低聚物的多酚、其衍生物及其混合物，和
(b)云杉提取物，其包含至少一种选自以下的木脂素：羟罗汉脂素(hydroxymatairesinol)，亚麻木脂素(secoisolariciresinol)，铁杉脂素(conidendrin)，落叶松树脂醇(lariciresinol)和利欧委尔(liovil)。
本发明的主题还是组合物，特别是用于局部施用的组合物，例如化妆品组合物，其至少含有所述组合。
本发明的主题还是本申请中定义的组合，或包含其的组合物，用于预防或减少与氧化应激相关的皮肤病，和/或用于刺激皮肤细胞抵抗氧化应激的防御。
本发明的主题还是以下组合或含有其的化妆品组合物的非治疗性美容用途：(a)至少一种选自原花色素单体和低聚原花青素(OPC)、羟基芪(hydroxystilbenes)、类黄酮单体和低聚物的多酚、其衍生物及其混合物；和(b)云杉提取物，其包含至少一种选自以下的木脂素：羟罗汉脂素，亚麻木脂素，铁杉脂素，落叶松树脂醇和利欧委尔，用于对抗皮肤或皮肤附属物的老化迹象和/或对抗与环境特别是污染有关的影响皮肤迹象。
本发明还涉及云杉(Picea abies)(或云杉(spruce))提取物用于刺激皮肤细胞的内源性防御和改善皮肤细胞对氧化应激的抗性的用途。云杉提取物将用作这些应用的作用剂，特别是含有它们的组合或组合物，旨在改善皮肤对氧化应激的抵抗力，对抗衰老的迹象或改善皮肤的光泽。
在申请WO2009/101261中描述了根据本发明使用的云杉(或云杉)提取物的抗菌活性和作为抗UV产品中的光保护剂。这些提取物的活性主要基于氧化还原反应，该反应可以中和自由基，或者通过捕获这些自由基。
出乎意料的是，现在已经发现，云杉(Picea abies)或云杉(spruce)提取物通过皮肤细胞增加GSH产生，从而改善它们的抗性和皮肤对氧化应激的抗性。
谷胱甘肽是存在于基础状态的细胞中的抗氧化剂，主要以还原形式GSH存在。一小部分是氧化形式的GSSG。与未与所述提取物接触的皮肤细胞相比，本发明的云杉提取物能够使GSH合成增加至少10％；该增加可以是至少20％，或甚至至少30％，并且可以大于或等于60％，特别是等于大约66％。
此外，根据本发明的云杉提取物在无毒剂量下激活血红素加氧酶1或HO-1酶的细胞合成。
血红素加氧酶是一种参与血红蛋白降解的酶。血红素加氧酶同种型1(HO-1)是存在于正常人皮肤中的II期酶；它在皮肤的解毒和抗氧化保护的生理系统中起作用，响应于应激诸如氧化应激。
因此，云杉提取物用于通过两种互补途径促进皮肤对氧化物质的内源性防御。
此外，在本发明的上下文中，已发现多酚，特别是从葡萄树中提取的多酚或其衍生物，对HO-1酶的合成也具有刺激作用。
出乎意料的是，云杉提取物与葡萄树中提取的多酚的组合或与葡萄树中提取的多酚衍生物的组合对细胞，特别是皮肤细胞的HO-1产生(合成)的增加具有协同作用。
因此，云杉提取物和多酚的组合，特别是从葡萄树提取的多酚或从这些多酚的衍生物，将通过谷胱甘肽途径在两个互补水平上刺激皮肤细胞对氧化物质的内源性防御具有改善的活性，通过谷胱甘肽途径(GSH合成增加)和通过酶解毒途径(HO-1合成增加)。
大气污染物，例如颗粒物质或气态污染物，例如二氧化硫，臭氧和氮氧化物，或香烟烟雾，对自由基具有引发剂活性，自由基是导致生物细胞损伤的氧化现象的来源。与外界环境直接和永久接触的器官细胞，如皮肤、头皮和某些粘膜，对污染物的这些影响特别敏感，特别是导致皮肤加速老化，一种肤色，缺乏光泽，色素斑以及皱纹和细纹的早期形成，以及头发的活力的减少和暗淡外观。
因此，本发明涉及组合(或含有它们的组合物)的用途，用于对抗皮肤或皮肤附属物的衰老迹象，无论所述衰老是内在的还是外在的，以及用于对抗与环境和污染的影响相关的皮肤迹象。
除皱纹和细纹外，色素斑的出现，皮肤厚度的减少，皮肤弹性的丧失和皮肤的下垂也是在衰老过程中观察到的变化。除了持续老化之外，皮肤也会随着个体的疲劳状态而不断变化，从而导致眼睛下方的眼袋和黑眼圈，疲惫的容貌和暗淡的肤色。
该组合或含有其的组合物特别可用于减少或预防皮肤病，例如肤色暗沉，皮肤色素沉着或色素沉着的异质性和色素斑，皱纹和细纹，皮肤变薄以及皮肤紧致度和/或皮肤的弹性的丧失。
术语“皮肤”旨在表示面部和/或身体皮肤，头皮和粘膜或半粘膜(例如嘴唇)。术语“皮肤附属物”旨在表示头发，体毛，睫毛，指甲，优选头发。
此外，眼睛下方黑眼圈的存在是导致疲劳或老化的外观的迹象，并且希望减少它们。在导致它们存在的原因中，可以提及位于眼睛下方的薄且高度血管化区域中血红蛋白的积累。在该区域中血红蛋白降解的刺激有助于暗区的消失，从而导致黑眼圈的减少或消失。
因此，本发明的主题还是根据本发明的云杉提取物和多酚的组合或含有它们的组合物用于改善皮肤和肤色的光泽和/或防止或减少眼睛周围和/或眼睛下方的黑眼圈外观的用途。
本发明还涉及如本文所定义的云杉或云杉冷冻提取物用于预防或减少眼睛下方黑眼圈的存在的用途。
在本说明书中，对于表示“在......和......之间”或“从......到......”的范围，应理解包括端点。
云杉或普通云杉(Picea abies)是松科(Pinaceae)和云杉属(Picea)的一种树脂树。适用于实施本发明的提取物优选从木材和树皮中获得，特别是从木材结中存在的木材或与结相邻的区域中获得。
用于实施本发明的云杉提取物优选含有相对于提取物重量(表示为固体)至少5％，特别是5％至15％的木脂素，其中至少一种木脂素选自：羟罗汉脂素，亚麻木脂素，铁杉脂素，落叶松树脂醇和利欧委尔。特别适用于实施本发明的提取物含有至少4％，特别是4％至10％，特别是约5％至6％的羟罗汉脂素。提取物中每种其他木脂素的含量通常为0.01％至5％，特别是约0.1％至2％。特别使用溶解在甘油中的提取物(具有8％木脂素含量)。
适用于实施本发明的多酚选自原花青素单体和低聚原花青素(OPC)、羟基芪和类黄酮单体和低聚物。这种多酚例如从各种植物中提取，特别是从葡萄树中提取。它们可以从葡萄(Vitis vinifera)植物的各个部分获得，例如从果实或从果实的部分例如种子或表皮获得，但也可以从葡萄蔓中获得。
多酚可以特别地选自单体或低聚物形式的羟基芪(hydroxystilbene)，特别是白藜芦醇(顺式和/或反式)，土大黄苷(rhapontin)，脱氧土大黄苷(deoxyrhapontin)，白皮杉醇(piceatannol)，云杉新甙(piceid)和白藜芦醇低聚物(Viniferins)。
适用于本发明的其它多酚是类黄酮，例如黄烷-3-醇的单体和低聚物，特别是儿茶素，表儿茶素，没食子儿茶素，表没食子儿茶素(例如表没食子儿茶素没食子酸酯)和低聚原花色素或OPC，花色素苷或黄烷酮；提及还可以由黄酮醇、二氢黄酮醇、黄酮和异黄酮组成。
有利地，多酚或多酚衍生物包括白藜芦醇和/或儿茶素，和/或儿茶素或白藜芦醇低聚物，或这些化合物的衍生物。
儿茶素低聚物优选包含2-6个儿茶(儿茶素或表儿茶素)单元，也称为OPC。
这些多酚可以是天然的或稳定的形式。
术语“多酚衍生物”旨在表示更特别稳定的分子，其中所有或一些羟基被醚化或酯化。根据一个优选的实施方案，酯化用饱和或不饱和脂肪酸形成。脂肪酸可特别选自丁酸，戊酸，己酸，山梨酸，月桂酸，棕榈酸，硬脂酸，油酸，亚油酸，亚麻酸，α-亚麻酸，花生四烯酸，二十碳五烯酸(ecosapentaenoic)和二十二碳六烯酸。
类黄酮的单体单元对应于下面的结构(I)
其中-R1代表-OR2基团、氢原子或取代基R3；R2和R3可以相同或不同，如下面对R4的定义，
-至少大部分取代基R代表-COR4基团，R4是具有至少两个碳原子的直链或支链、饱和或不饱和烷基，或芳基，芳烷基或芳基亚烷基，
-不表示-COR4基团的其他取代基R是氢原子或烷基，和
-n1和n2可以彼此相同或不同，是1至3的数字，对应于环上取代基的数目，
单体单元通过碳-碳键和/或单元之间的醚桥连接在低聚物和聚合物中。
在本发明的低聚物和聚合物中，连续单元的碳原子之间的键位于一个单元的C-4和另一个单元的C-6或C-8之间。
在其他低聚物和聚合物中，至少两个单元也通过氧桥连接。
在一种相应的组合物中，多酚低聚物或聚合物对应于下式
其中R1和R如上所定义，n1至n6可以相同或不同，是1至3的数字，m是0至100的数字，更特别是1至10。
在式(II)中，m优选为11至100的数，或者在一个变体中，m等于0。
本发明特别涉及一种组合物，其特征在于R代表饱和或不饱和脂肪酸基团，更特别选自丁酸，戊酸，己酸，山梨酸，月桂酸，棕榈酸，硬脂酸，油酸，亚油酸，亚麻酸，α-亚麻酸，花生四烯酸，二十碳五烯酸和二十二碳六烯酸自由基。
在式(II)的其它多酚中，R2表示苯基或芳基烷基或芳基亚烷基，烷基或亚烷基更具体是C1-C8，具体是C1-C4。作为芳基烷基或芳基亚烷基的实例，将提及苄基和苯乙烯基。
本发明特别涉及黄烷醇衍生物，特别是其中R1是-OR2基团的那些，R2如上所定义的那些。优选属于儿茶素系列的黄烷醇衍生物的酯的问题。
在这些酯中，每个黄烷醇单元通常有五个含氧基团，并且所述基团位于3,5,7,3'和4'位。
在一种优选的组合物中，多酚是植物来源的类黄酮提取物，特别是葡萄树，更特别是葡萄籽(OPC)，含有对应于式(I)的单元的单体、低聚物和/或聚合物。
根据第二方面，用于本发明组合的多酚是植物来源的二苯烯酸(stilbenoic)提取物，特别是葡萄树，尤其是葡萄蔓，含有对应于式(III)的单元的单体、低聚物和/或聚合物。
这些单元的特征在于同时存在间苯二酚型核(核A)和对苯酚型核(核B)，它们通过碳基连接体如C相互连接。在最简单的情况下，两个核A和B结合在一起，而C部分不存在，这与间苯三酚的情况相对应。这些单元的核A和B通常是不同的，并且C部分由两个碳组成，这两个碳可以是sp2-杂化的并形成乙烯基：这是白藜芦醇的情况。
C部分可以很容易地由sp3-杂化的碳组成，并且尤其可以用作单体之间的连接点以形成聚合物。与类黄酮类似，这些芪化合物通过-OR基团稳定(对应于-OH官能团的酯化)。
本发明还涉及一种组合物，其特征在于多酚对应于所述类黄酮和芪多酚的非对映异构体和/或区域异构体。
根据一个具体实施方案，多酚的所有羟基被酯化或醚化；因此多酚衍生物不再具有游离OH官能团。
这些醚或酯尤其可以通过申请WO2011/128714中描述的方法制备。
特别使用从葡萄蔓中提取的多酚，特别是白藜芦醇及其衍生物。特别适用于实施本发明的多酚是儿茶素，儿茶素低聚物或OPC，例如从葡萄籽中提取的那些，以及这些多酚的衍生物，特别是其酯。
应当理解，在本发明的上下文中，可以使用任何比例的各种多酚及其衍生物的混合物，其可以是如上所述的部分或完全酯化或醚化的。
有利地，在根据本发明的一种组合物中，(a)中提到的多酚是从葡萄树中提取的，并且包含从葡萄籽中提取的OPC；特别地，该组合或组合物包含多酚衍生物，其是多酚酯。
根据一个具体实施方案，多酚以葡萄籽提取物的形式存在于组合或组合物中，任选地稳定化以便在所述提取物中获得多酚衍生物。
这些多酚通常占儿茶素单体和/或二聚体的至少20％(相对于总多酚的重量)；例如，原花色素二聚体含量大于或等于20％(相对于总多酚的重量)，和/或[儿茶素和表儿茶素]含量大于或等于20％(按重量计，相对于总多酚的重量)。
根据本发明的一个实施方案，葡萄籽提取物基本上不含多酚以外的组分。
根据本发明的组合物，特别是化妆品组合物，特别可以包含(a)中提到的多酚或多酚衍生物，其浓度相对于组合物的总重量为0.01％-10％重量，并且在特别是大于或等于0.05％。根据本发明的一个实施方案，在组合物中，(a)中提到的多酚或多酚衍生物例如以0.1％至5％的浓度存在；特别地，该组合物含有0.1％至5％的葡萄籽多酚的酯化衍生物。
根据本发明的组合物，特别是化妆品组合物，可特别包含云杉提取物，特别是云杉木提取物，其存在浓度为相对于组合物总重量的0.01％至10％重量。云杉提取物可以例如以大于或等于0.05％，特别是大于或等于0.1％的浓度存在。因此，相对于组合物的总重量，如上所述的云杉木提取物可以以0.1％至5％，或甚至0.5％至5％或0.5％至3％的浓度存在。
根据本发明的组合物含有例如葡萄籽提取物，其任选地通过多酚的酯化来稳定，其浓度为相对于组合物总重量的0.01％至10％重量，和云杉木提取物，其以其浓度为相对于组合物总重量的0.01％至10％重量浓度存在，例如，浓度大于或等于0.05％。
有利地，在根据本发明的化妆品组合物中，特别是从葡萄树的多酚(特别是富含OPC的葡萄籽多酚)或其衍生物和云杉提取物中之间的重量比为0.1％至5％，表示为多酚/云杉木脂素(或从葡萄树提取的多酚/云杉木脂素中)，优选葡萄多酚/云杉木脂素的比例在0.5和3之间。这是因为已经观察到，在这些比例中，协同活性对由HO-1酶介导的内源性抗氧化防御是最佳的。
特别地，在人皮肤成纤维细胞上，与通过添加组合的两种组分中的每一种的简单效果所预期的增加相比，HO-1合成增加至少30％，特别是至少40％；与组合的每种组分的效果之和相比，这种协同作用可以导致增加超过70％。
根据本发明的组合物优选是化妆品组合物，或适用于施用到皮肤或皮肤附属物的皮肤病学组合物。根据本发明的组合物含有如上定义的多酚和云杉提取物的组合，以及生理学上可接受的介质。
术语“生理学上可接受的介质”旨在表示与皮肤或皮肤附属物相容的介质。它特别是化妆品可接受的介质。因此，其旨在表示皮肤良好耐受并具有令人愉快的气味和外观的介质或赋形剂。
术语“化妆品或组合物”旨在表示指与人体表面部分或与牙齿和颊粘膜接触的物质或混合物，仅用于或仅主要用于清洁它们，使它们变得芳香，改变它们的外观，保护它们，使它们保持良好状态或改善体味。
该组合物可以或多或少是流体的，并且可以具有白色或彩色乳膏，软膏，乳，洗液，精华素，糊剂或泡沫的外观。它也可以是固体形式，特别是棒状。它可以用作护理产品和/或用作皮肤或皮肤附属物的化妆产品和/或卫生产品。
根据本发明的组合物可以是化妆品领域中通常使用的任何药物形式，并且它可以特别是任选的两相洗剂类型的分散体的任选胶凝的水性或油性溶液的形式。通过将脂肪相分散在水相(O/W)或反之亦然(W/O)，或三重乳液(W/O/W或O/W/O)或离子和/或非离子型的囊状分散体。根据常规方法制备这些组合物。
当根据本发明使用的组合物是乳液时，相对于组合物的总重量，脂肪相的比例可以为0.5重量％至80重量％，优选为5重量％至50重量％。乳液形式的组合物中使用的油、乳化剂和助乳化剂选自本领域常规使用的那些。相对于组合物的总重量，乳化剂和助乳化剂在组合物中的存在比例为0.1％至30％重量，优选0.5％至20％重量。
作为可以在本发明中使用的油，提及的是烃或矿物来源(矿物油)或合成来源(液体凡士林，异十六烷)，植物油(杏仁油，葡萄籽油，乳木果液体部分，黄油，鳄梨油，大豆油)，动物油(羊毛脂)，合成油(全氢化角鲨烯，季戊四醇四辛酸)，硅氧烷衍生物(环戊硅氧烷，环己硅氧烷和硅氧烷聚合物)和氟油(全氟聚醚)。作为脂肪物质，还可以使用脂肪醇(十六烷基或硬脂基醇)，脂肪酸(硬脂酸)，蜡(巴西棕榈蜡，地蜡，蜂蜡)，黄油和氢化油。
作为可用于本发明的乳化剂和助乳化剂，提及的是例如聚乙二醇的脂肪酸酯，例如PEG-100硬脂酸酯和PEG-20硬脂酸酯，和甘油的脂肪酸酯，例如硬脂酸甘油酯，蔗糖酯和磷脂。
以已知的方式，根据本发明使用的组合物还可含有化妆品领域中常用的佐剂，例如亲水或亲脂胶凝剂，亲水或亲脂活性剂，防腐剂，抗氧化剂，溶剂，芳香剂，填充剂，遮蔽剂，颜料，气味吸收剂，螯合剂和染料。这些各种佐剂的量是在所讨论的领域中常规使用的那些，并且例如占组合物总重量的0.01％至20％。根据它们的性质，可以将这些佐剂引入脂肪相，水相或脂质囊泡中。在任何情况下，将选择这些佐剂以及它们的比例，以便不损害抗氧化剂组合的所需性质。
作为亲水性胶凝剂，尤其可以提及羧乙烯基聚合物(卡波姆)，丙烯酸共聚物如丙烯酸酯/丙烯酸烷基酯共聚物，聚丙烯酰胺，多糖，天然树胶和粘土，并且作为亲脂性胶凝剂，可以提及改性的粘土如膨润土，脂肪酸金属盐，疏水二氧化硅和聚乙烯。
作为填料，提及的是例如由以下制成：球形或微纤维形式的聚丙烯的聚酰胺(尼龙)颗粒；聚(甲基丙烯酸甲酯)微球；乙烯/丙烯酸酯共聚物粉末；膨胀粉末，例如空心微球，特别是由偏二氯乙烯、丙烯腈和甲基丙烯酸酯的三元共聚物形成的微球，由KemanordPlast公司以Expancel的名称出售；天然有机材料的粉末，例如淀粉，特别是玉米、小麦或米粉淀粉，它们可以交联或不交联，例如辛烯基琥珀酸酐交联的淀粉粉末；硅树脂微珠，例如由Toshiba Silicone公司以Tospearl的名称销售的那些；二氧化硅；金属氧化物，如二氧化钛或氧化锌；云母；及其混合物。
根据本发明使用的组合物还可含有其它活性剂，特别是至少一种选自以下的化合物：保湿剂；脱色剂；抗糖化剂；NO-合成酶抑制剂；刺激皮肤或表皮大分子合成和/或防止其降解的作用剂；刺激成纤维细胞和/或角质形成细胞增殖或刺激角质形成细胞分化的作用剂；肌肉松弛剂；张紧剂；防污剂和/或自由基清除剂，防晒剂及其混合物。
作为抗氧化剂，尤其可以提及生育酚及其酯，特别是生育酚乙酸酯；抗坏血酸及其衍生物，特别是抗坏血酸磷酸镁，抗坏血酸葡糖苷和抗坏血酸四异棕榈酸酯；阿魏酸；丝氨酸；鞣花酸，根皮素，螯合剂，如BHT，BHA或N，N'-双(3,4,5-三甲氧基苄基)乙二胺及其盐，以及它们的混合物。
特别地，根据本发明的化妆品组合物还含有至少一种选自维生素C及其衍生物和维生素E或其衍生物如乙酸生育酚的活性剂。
另外的活性剂可以以相对于组合物总重量的0.001％至20％重量的含量存在于根据本发明的组合物中，优选0.01％至10％重量，甚至更优选0.5％至0.5％重量，和更优选0.1％-1％重量，相对于组合物的总重量。
本发明的主题还是一种美容治疗方法，包括向皮肤或皮肤附属物施用本发明的组合或组合物的步骤。
特别是用于预防或减少由氧化应激引起的皮肤病的美容治疗方法，包括至少一个步骤，其包括向皮肤或皮肤附属物施用以下组合或包含所述组合的美容组合物的至少一个步骤：(a)至少一种选自原花色素单体和低聚原花青素(OPC)、羟基芪、类黄酮单体和低聚物的多酚、其衍生物及其混合物，和(b)一种云杉提取物，其包含至少一种选自以下的木脂素：羟罗汉脂素(hydroxymatairesinol)，亚麻木脂素(secoisolariciresinol)，铁杉脂素(conidendrin)，落叶松树脂醇(lariciresinol)和利欧委尔(liovil)。
因此，美容治疗过程旨在预防或减少皮肤症状，例如肤色暗沉，皮肤色素沉着或色素沉着的不均匀性和色素斑，皱纹和细纹，皮肤变薄和紧致度丧失，和/或皮肤的弹性。
通过施用云杉提取物、含有其的组合或如上所述的组合物，美容处理方法还可用于改善皮肤和肤色的光泽和/或防止或减少眼睛周围和/或眼睛下方的黑眼圈的出现。
根据本发明的组合物可以直接施用于皮肤，或者可选地，施用于闭合或非闭塞类型的化妆品或皮肤病学支持物，旨在以局部方式施用于皮肤，例如水凝胶面膜，擦拭物，织物或生物纤维素。
该施用可以例如是每天，每天或每周几次。它可能会持续数天和/或数周，甚至更长；它可以是连续的，或者可选地，例如，持续1至2个月，然后在中断后重新开始。
本发明还涉及以下组合用于制备化妆品组合物的用途：
(a)至少一种选自原花色素单体和低聚原花青素(OPC)、羟基芪、类黄酮单体和低聚物的多酚、其衍生物及其混合物，
(b)如本文所定义云杉提取物，其包含至少一种选自以下的木脂素：羟罗汉脂素，亚麻木脂素，铁杉脂素，落叶松树脂醇和利欧委尔。
该组合物适合施用于皮肤或皮肤附属物。该组合物有利地使得可以对抗与皮肤或皮肤附属物上的自由基的作用相关的体征成为可能。
本发明进一步涉及制备化妆品组合物的方法，包括混合下列物质的步骤：
(a)至少一种选自原花色素单体和低聚原花青素(OPC)、羟基芪、类黄酮单体和低聚物的多酚、其衍生物及其混合物，
(b)如本文所定义云杉提取物，其包含至少一种选自以下的木脂素：羟罗汉脂素，亚麻木脂素，铁杉脂素，落叶松树脂醇和利欧委尔，
和任选的生理学上可接受的赋形剂。
具体实施方式
在下面的实施例中说明了本发明的其他特征和优点。
实施例1：云杉提取物对抗氧化剂防御的活性
在37℃下，在补充有1％胎牛血清的DMEM培养基中，用不同浓度的云杉提取物处理人成纤维细胞的铺满培养物。
测试具有以下木脂素组成(重量％)的云杉属提取物：
总木脂素：6-8.4％
羟罗汉脂素 5-6％
亚麻木脂素 0.3-0.4％
铁杉脂素 0.2-0.4％
利欧委尔 0.2-0.4％
落叶松树脂醇 0.1-0.2％
其他木脂素 0.2-1％。
-细胞裂解物中GSH的定量
GSH/GSSG-Glo测试基于用于检测和定量总谷胱甘肽(GSH+GSSG)，GSSG和GSH/GSSG比率的发光系统。该测定基于通过谷胱甘肽S-转移酶与荧光素酶反应结合将荧光素-NT探针转化为荧光素的反应。检测到的发光与存在的GSH的量成比例。
在一种情况下，测量谷胱甘肽的总量。为此，将存在于细胞裂解物中的所有谷胱甘肽转化为GSH，然后通过测试进行测量。在仅测量GSSG氧化形式的情况下，在将GSSG转化为GSH之前，存在的GSH被试剂阻断。
温育后，除去细胞培养基，用PBS洗涤细胞，然后用裂解缓冲液替换。
将细胞在环境温度下裂解5分钟。
加入50μl“产生荧光素的培养基”。
将板在环境温度下孵育30分钟。
加入100μl/孔的检测试剂。
将板在环境温度下平衡15分钟。
用具有以下参数的Tecan M200仪器测量发光：积分时间＝1秒，静止时间＝1秒。
结果：云杉冷冻提取物浓度范围为100至500μg/ml(0.01％-0.05％)显著增加正常人真皮成纤维细胞中GSH的合成，相对于未处理的细胞基础水平，从11％上升至66％。
这些数据在第二个实验中得到证实，该实验表明富含羟罗汉脂素的云杉提取物浓度范围为250-500μg/ml(0.025％-0.05％)能够在正常人真皮成纤维细胞中诱导GSH的显著细胞合成。相对于未处理细胞的基础水平，从33％开始至64％。
此外，在这些实验条件下不存在细胞毒性，并且可以得出结论，在防御刺激上观察到的效果不是毒性作用的结果。
-定量细胞裂解物中的HO-1酶
用化合物刺激24小时后，分离细胞，以1200rpm离心10分钟并重悬于裂解缓冲液中。在液氮/解冻中进行两个冷冻循环，然后通过离心除去细胞碎片。然后将细胞裂解物在使用前储存在-80℃。
根据生产者的说明，使用BCA试剂盒(Sigma)测定样品中的总蛋白质浓度。对于每个样品，测量一式三份进行。在显示的结果中报告平均值。
使用人总HO-1/HMOX1ELISA试剂盒，通过ELISA测定法测量细胞裂解物中HO-1的量，如下：
-用8μg/ml浓度的捕获抗体包被ELISA板，并在环境温度下孵育过夜。
-将板用PBS-0.05％Tween 20洗涤三次，并在室温下用PBS-1％BSA封闭1小时。
-用PBS-0.05％Tween 20洗涤板三次。
-将100μl未稀释的样品加入到板和HO-1标准样品中，浓度范围为0.15-10ng/ml。在环境温度下孵育2小时。
-在用PBS-0.05％Tween 20三次洗涤步骤后，在环境温度下加入100μl HRP结合的检测抗体(200ng/ml)2小时。
-在三个洗涤步骤后，在环境温度下加入链霉抗生物素蛋白-HRP溶液20分钟。
-在三次洗涤步骤后，加入TMB HRP底物。在15-20分钟的温育时间后，在环境温度和黑暗中，通过加入2N H2SO4终止反应。
-用Tecan Infini酶标仪在450nm处读取光密度(OD)，在570nm处校正。
用Magellan软件分析结果。
HO-1浓度相对于每个样品的总蛋白质浓度标准化。
在这些实验条件下没有细胞毒性得到进一步验证，并且可以得出结论，观察到对防御的刺激所产生的效果不是毒性作用的结果。
结果：HO-1浓度(总蛋白质的pg/μg)
实施例2：云杉和葡萄籽提取物的组合对抗氧化防御的活性
根据与实施例1相同的方案，用各种浓度的云杉提取物和葡萄籽提取物处理37℃下在补充有1％胎牛血清的DMEM培养基中的人成纤维细胞的铺满培养物。
相对于总多酚，葡萄籽提取物具有原花青素含量，如下：
总多酚 100％
儿茶素+表儿茶素 22.6％
原花青素二聚体 25.1％
细胞裂解物中的HO-1浓度相对于每个样品中的总蛋白质浓度标准化。结果如下表所示：
此外，在这些实验条件下没有细胞毒性得到验证，并且可以得出结论，观察到对防御的刺激所产生的效果不是毒性作用的结果。
添加剂效应的活性百分比增加率为34％+68％，即102％。对云杉提取物和葡萄籽提取物的组合测量的活性比该理论总和大76％。
这表明富含原花青素(的葡萄籽提取物和富含羟基山羊草醇(hydroxymatairesinol)的云杉提取物能够以协同方式显着诱导正常人皮肤成纤维细胞中HO-1抗氧化酶的产生。实际上，对于组合测量的活性大于单独测量的每种化合物的活性总和。
结果总结在下表中：
实施例3：根据本发明的组合物
洗剂
将组合物的各种成分混合以获得洗剂。所述洗剂将在早晨和/或晚上施用于所有面部和颈部。
凝胶霜
凝胶霜将在早晨和/或晚上施用于面部，颈部和手部。
乳液
该组合物将在早晨和/或晚上施用于面部和颈部。
Claims (14)
1.一种化妆品组合物，其含有以下至少一种组合：
(a)至少一种选自原花色素单体和低聚原花色素(OPC)、羟基芪、类黄酮单体和低聚物的多酚、其衍生物及其混合物，
(b)云杉提取物，其包含至少一种选自以下的木脂素：羟罗汉脂素，亚麻木脂素，铁杉脂素，落叶松树脂醇和利欧委尔。
2.如权利要求1所述的化妆品组合物，其特征在于，(a)中提到的一种或多种多酚是从葡萄树中提取的。
3.如权利要求1和2中至少一项所述的化妆品组合物，其特征在于，多酚衍生物是多酚酯。
4.如权利要求1至3中至少一项所述的化妆品组合物，其特征在于，多酚或多酚衍生物(a)的存在浓度为相对于所述组合物总重量的0.01％至10％重量。
5.如权利要求1至4中至少一项所述的化妆品组合物，其特征在于，云杉提取物是云杉木提取物，并且相对于所述组合物的总重量，所述云杉提取物浓度为0.01％至10％重量。
6.如权利要求1至5中至少一项所述的化妆品组合物，其特征在于它至少含有：
(a)一种含有多酚的葡萄籽提取物，其通过酯化稳定，所述提取物的浓度为0.01％-10％重量，
(b)一种云杉提取物，其浓度为0.01％-10％重量。
7.如权利要求2至6中至少一项所述的化妆品组合物，其特征在于，从葡萄树或其衍生物中提取的多酚与云杉提取物之间的浓度的重量比为0.1至5，表示为多酚/云杉木脂素。
8.如权利要求1至7中至少一项所述的化妆品组合物，其特征在于，它还含有至少一种选自以下的活性剂：抗氧化剂，保湿剂，脱屑剂，改善屏障功能的作用剂，脱色剂和改善了皮肤微循环作用剂。
9.如权利要求1至8中至少一项所述的化妆品组合物，其特征在于，它含有至少一种选自维生素C及其衍生物和维生素E及其衍生物的活性剂。
10.组合的美容用途，所述组合：(a)至少一种选自原花色素单体和低聚原花色素(OPC)、羟基芪、类黄酮单体和低聚物的多酚，其衍生物及其混合物，和(b)云杉提取物，其包含至少一种选自以下的木脂素：羟罗汉脂素，亚麻木脂素，铁杉脂素，落叶松树脂醇和利欧委尔，或含有所述组合的化妆品组合物的用途，所述组合物如权利要求1至9之一所定义，用于对抗皮肤或皮肤附属物的老化迹象或对抗与污染有关的皮肤迹象。
11.组合的美容用途，所述组合：(a)至少一种选自原花色素单体和低聚原花色素(OPC)、羟基芪、类黄酮单体和低聚物的多酚，其衍生物及其混合物，和(b)云杉提取物，其包含至少一种选自以下的木脂素：羟罗汉脂素，亚麻木脂素，铁杉脂素，落叶松树脂醇和利欧委尔，或含有所述组合的化妆品组合物的用途，所述组合物如权利要求1至9之一所定义，用于改善皮肤的光泽和/或减少眼睛周围黑眼圈的外观。
12.如权利要求10和11中至少一项所述的组合的美容用途，其特征在于，所述组合或含有其的组合物用作对抗选自以下病症的作用剂：皱纹和细纹，暗沉肤色，色素斑，皮肤紧致度下降，眼睛下方有黑眼圈。
13.一种用于预防或减少由氧化应激诱导的皮肤病的美容治疗方法，包括至少一个步骤，其包括向皮肤或头皮施用至少以下组合或含有它的化妆品组合物：(a)至少一种选自原花色素单体和低聚原花色素(OPC)、羟基芪、类黄酮单体和低聚物的多酚，其衍生物及其混合物，和(b)云杉提取物，其包含至少一种选自以下的木脂素：羟罗汉脂素，亚麻木脂素，铁杉脂素，落叶松树脂醇和利欧委尔。
14.如权利要求1至5中任一项所述的云杉提取物作为改善皮肤对氧化应激的抵抗力、改善皮肤光泽和/或防止或减少眼睛下存在的黑眼圈的用途。
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| FR1656318 | 2016-07-01 | ||
| FR1656318A FR3053251A1 (fr) | 2016-07-01 | 2016-07-01 | Composition pour lutter contre les signes du vieillissement de la peau et des phaneres |
| PCT/FR2016/052294 WO2018002453A1 (fr) | 2016-07-01 | 2016-09-12 | Composition pour lutter contre les signes du vieillissement de la peau et des phaneres |
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| CN109562055A true CN109562055A (zh) | 2019-04-02 |
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| US (1) | US11607379B2 (zh) |
| EP (1) | EP3478368B1 (zh) |
| KR (1) | KR20190055060A (zh) |
| CN (1) | CN109562055B (zh) |
| CA (1) | CA3029435A1 (zh) |
| ES (1) | ES2950111T3 (zh) |
| FR (1) | FR3053251A1 (zh) |
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| CN115137662A (zh) * | 2022-07-22 | 2022-10-04 | 广州洁雅日化科技有限公司 | 一种乌发育发组合物及其制备和应用 |
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| ES2913623T3 (es) * | 2018-01-09 | 2022-06-03 | Tomcat International Ltd | Composiciones útiles para el tratamiento cosmético de las pieles grasas |
| CN108464417A (zh) * | 2018-04-10 | 2018-08-31 | 湖北娅安科技开发有限公司 | 一种用于护眼饮品的营养强化剂的合成方法 |
| AU2020326319A1 (en) * | 2019-08-02 | 2022-03-17 | Oy Granula Ab Ltd | A method and a compound for preventing mammalian cancer cell proliferation and for treating cancer |
| WO2023144120A1 (en) | 2022-01-25 | 2023-08-03 | Planbio Cosmetics Srl | Composition containing nero di troia pomace extract |
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2016
- 2016-07-01 FR FR1656318A patent/FR3053251A1/fr active Pending
- 2016-09-12 EP EP16774531.4A patent/EP3478368B1/fr active Active
- 2016-09-12 PL PL16774531.4T patent/PL3478368T3/pl unknown
- 2016-09-12 ES ES16774531T patent/ES2950111T3/es active Active
- 2016-09-12 WO PCT/FR2016/052294 patent/WO2018002453A1/fr unknown
- 2016-09-12 CA CA3029435A patent/CA3029435A1/fr not_active Abandoned
- 2016-09-12 US US16/314,521 patent/US11607379B2/en active Active
- 2016-09-12 CN CN201680087229.0A patent/CN109562055B/zh active Active
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| CN115137662A (zh) * | 2022-07-22 | 2022-10-04 | 广州洁雅日化科技有限公司 | 一种乌发育发组合物及其制备和应用 |
| CN115137662B (zh) * | 2022-07-22 | 2023-08-11 | 广东中科中研生物工程有限公司 | 一种乌发育发组合物及其制备和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20190201318A1 (en) | 2019-07-04 |
| EP3478368C0 (fr) | 2023-06-07 |
| FR3053251A1 (fr) | 2018-01-05 |
| EP3478368A1 (fr) | 2019-05-08 |
| US11607379B2 (en) | 2023-03-21 |
| ES2950111T3 (es) | 2023-10-05 |
| EP3478368B1 (fr) | 2023-06-07 |
| WO2018002453A1 (fr) | 2018-01-04 |
| KR20190055060A (ko) | 2019-05-22 |
| CN109562055B (zh) | 2023-04-04 |
| PL3478368T3 (pl) | 2023-08-28 |
| CA3029435A1 (fr) | 2018-01-04 |
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