CN1067252C - 化妆品或药物组合物及一种抗氧化系统在上述组合物中的应用 - Google Patents

化妆品或药物组合物及一种抗氧化系统在上述组合物中的应用 Download PDF

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CN1067252C
CN1067252C CN93119957A CN93119957A CN1067252C CN 1067252 C CN1067252 C CN 1067252C CN 93119957 A CN93119957 A CN 93119957A CN 93119957 A CN93119957 A CN 93119957A CN 1067252 C CN1067252 C CN 1067252C
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Q·L·恩奎恩
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Abstract

化妆品或药物组合物，其特征在于它含有由银杏树提取物和至少一种多酚化合物配合组成的增效作用抗氧化系统。银杏树提取物如银杏树叶已烷提取物。多酚化合物如黄酮类化合物。
用于预防和治疗尤其由空气污染和/或由紫外辐射引起的自由基在皮肤、头皮或粘膜上产生的细胞损伤，和/或用于抗皮肤加速衰老现象。

Description

化妆品或药物组合物及一种抗氧化系统在上述组合物中的应用
本发明的内容是关于含有银杏树提取物与至少一种多酚衍生物协同配合成抗氧化剂的化妆品或药物的组合物。
大部分化妆品或药物组合物都由一种其油性产品的脂肪相所组成，其具有被氧化的趋势，甚至在室温下也是如此，这种氧化作用的结果
使其组合物性质极大地改变，尤其是嗅觉性质，这使它在天气多变期间之后变得不能用了。
为了针对这种氧化现象而保护这些组合物，目前的做法是加入起抗氧化作用的保护剂。
如果抗氧化剂对良好保存化妆品或药物组合物中的脂肪物是特别有效的话，则人们现在就可知道：其中某些抗氧化剂还能抵抗氧化物质的有害作用，这些氧化物质尤其是在由空气污染物和紫外线所产生的自由基作用下生成的。这些有害的作用尤其作用于与外部介质接触的皮肤和粘膜细胞。
因而主要的是能够拥有可抑制自由基形成并能抗可引起不可逆细胞损伤的氧化现象的抗氧化剂。
现在发现在配合使用银杏树提取物和至少一种多酚化合物时有可能对含有易氧化脂肪物质的化妆品或药物组合物得到很好保存，同时能有效地保护皮肤或粘膜。此外还惊奇地发现这种配合具有协同的性质。
关于“多酚化合物”一词，可以理解为这些化合物含有至少一个二酚芳环，酚基可能醚化或酯化。在这种情况下，这样一种化合物也可简单称之为“多酚”。
本发明的内容是关于含有由银杏树提取物和至少一种多酚化合物组合构成的具有协同作用的抗氧化系统化妆品或药品组合物。
银杏树提取物的活性物质(或多种活性物质)是不知道的，但是采用非极性溶剂对植物原料尤其是叶子进行提取可以得到这种活性物质。下面所用“非极性提取物”一词是指这样一种提取物，即在这种提取物中含有并可采用较好纯化方法从中分离出一种或多种活性物质。在这里，一种活性物质是指具有抗氧化活性的物质(如后面实验部分所描述的那样，根据维生素F自(动)氧化试验能够加以证明)而且这种物质与多酚配合可显示出协同的抗氧化作用。
尤其使用二裂片银杏树叶的提取物。
将用非极性溶剂提取银杏树叶得到的部分蒸发至干可以得到银杏树非极性提取物。作为非极性溶剂可以列举直链、支链或环状C6-C14烷烃，正己烷是特别优选的。在日本专利91-014007中具体描述过这类提取物。
本发明组合物中所使用的多酚化合物可以选自于下述试验部分描述的那种维生索F自动氧化试验中具有抗氧化活性的那些多酚化合物。
例如；多酚可选自于：
a)黄酮类化合物
b)卡诺酸或卡诺醇(l′acide carnosique ou le carnosol)
c)(2,5-二羟基苯基)羧酸和(2,5-二羟基苯基)亚烃基羧酸类，可能被取代，以及它们的衍生物，尤其是它们的盐、酯或酰胺，
e)咖啡酸酯或酰胺
f)丹宁酸
在可使用的多酚中尤其可以列举黄酮类化合物，它们满足下述通式(1) 式中A″、B″、C″、和D″彼此独自代表H或OH，E″代表H，OH或OX′，其中X′代表
F″、G″、J″彼此独自代表H或OH，X1代表-CH2-、-CO-或-CHOH-，
A′、C′和D′彼此独自代表H、OH或CH3；E′代表H、CH、或OR′、其中R′代表式R′OH的糖的残基，B′、F′、G′和J″彼此独自代表H、OH、OCH3或-OCH2-CH2-OH。在糖R′OH中可以列举芸香糖。
化学式(Ⅰ)和(Ⅱ)的化合物都是已知的，它们可以根据在“The Flavonoids”Harborne J.B.,Mabry T.J.,Helga Mabry,1975,1-45页中描述的方法得到。
在本发明可使用的黄酮类化合物中，尤其可以列举：毒叶索、儿茶酸、表儿茶酚，l′criodictyol,la naringénine,路丁、la tro-xérutine、柯因.la tangérétine,la Intéoline,l′épigallocaté-chine和l′épigallocatéchine棓酸盐，la quercétine,非瑟酮.le kampférol,la galangine,la gallocatéchine,lépicatechine棓酸盐。
某些可使用的多酚存在于可用已知方法提取的植物中。可以利用茶叶提取物(Camellia sinensis或Camellia japonica)。尤其可以列举由Nikko公司以商品名Sunpnenon销售的绿茶提取物，它含有黄酮类化合物。
在可使用的多酚中，还可列举如卡诺酸和卡诺醇之类的多酚，比如它们可以从迷迭香中提取，或采用提取后蒸馏的方法(Chang等人，JOSC,vol.61,NO 6,六月，1984)提取，或者如EP-307626专利申请中所能描述的那样，采用如乙醇之类的极性溶剂提取，再采用如己烷之类的非极性溶剂提取以便除去嗅味物质。
可使用的多酚还可以选自于具有下述化学式(Ⅲ)的(2.5-二羟基苯基)烷基羧酸及其衍生物(尤其是酯和酰胺)；
Figure 9311995700081
式中；
R、″代表-OAlc、OH或-N(r′)(r″)，AIc是C1-C20直链或支链烷基，可能被一个或多个羟基或烷氧基取代，或Alc是C2-C20链烯基，
r′和r″独立地代表H、C1-C20烷基、C2-C6羟烷基或C3-C6多羟基烷基；或者r′和r″同其连接的氮原子一起构成杂环。
r是一个包括0(零)的数字，如链-(CH2)r-COR1含有至多21个碳原子。
R″2和R″3各自代表H或C1-C4烷基，R″2还可以代表C1-C4烷氧基。
化学式(Ⅲ)化合物是已知的，可以按照已知的方法，如类似于法国专利FR-2400358和FR2400359中描述的方法制备。
在本发明可使用的多酚中，还可列举咖啡酸酯或酰胺，在咖啡酸酯中尤其可以提及化学式(Ⅳ)化合物；式中Z代表C1-C8烷基，如甲基，或植醇残基，在咖啡酸酰胺中，尤其可以列举化学式(Ⅴ)化合物。
Figure 9311995700092
式中Z′代表C1-C8烷基，尤其C6-C8烷基。
化学式(Ⅳ)或(Ⅴ)的化合物是已知的，可按照已知的方法制备。
丹宁酸存在于由Sochibo公司以商品名Supextrat销售的Alep核桃提取物中。
在本发明化妆品或药物组合物中，银杏树非极性提取物的浓度一般是以该组合物总重量计为1-10％(重量)。
如上面限定的多酚的比例为以该组合物总重量计为0.1-1％(重量)。
对于通过简单实验程序的每种类型组合物可以确定银杏树非极性提取物与多酚的最佳相对比例。银杏树非极性提取物与多酚之重量比一般是1-100，尤其是约1n。
本发明的化妆品或药物组合物，除了上面叙述的活性成分组合物之外，还可以含有适宜的载体、在制备这种组合物中通常使用的活性组分或添加剂。它们尤其可以含有如水之类的溶剂、有机溶剂(如醇、油)或聚硅氧烷、增稠剂、表面活性剂、聚合物、固体脂肪物质(如蜡、羊毛脂)、清凉剂、防腐剂、PH调节剂、多价螯合剂、染色剂、香料、固体填料(粉末和颜料)、紫外吸收物质、autobronzants剂(如二羟基丙酮)等。
泡状分散形的组合物比如至少含有一种加入胶粒或类脂物双层系中的活性组分，它们可以封包含水相并分散在含水溶剂中。
类脂物，尤其离子或非离子两性类脂物的泡状分散物可按已知方法制备，例如在含水溶液中使类脂物溶胀以便生成分散在含水介质中的微球体，如同Banghan,Standish和Watkins,J.Mol.Biol.13,238(1965)文章或法国专利FR2315991和2416008中所描述的那样。在″Les Liposomes en biologie cellulaireet pharmacologie”中，Edition(出版)INSERM/John LibberyEurotext,1987,6至18页，也描述过不同的制备方式。
这些组合物可以呈细小微粒分散液形式。术语“细小微粒”一方面包含微小球体之意，另一方面也为微小胶囊的意思；术语“微小球体”系指由其上吸收和/或吸附活性组分的多孔的聚合物基体组成的细小微粒，关于“微小胶囊”术语系指由聚合物薄膜(它包住由活性成分生成的核)构成的细小微粒。这些组合物的形式比如在EP-27496l和FR2659554专利申请中都有描述。
本发明的组合物尤其是保护人的表皮、头发和粘膜的化妆品或药物组合物；皮肤和表皮性组织的化妆用组合物；口腔-牙齿用的组合物，如牙膏，或治疗眼炎的组合物如眼药。
为保护头发而使用本发明化妆组合物时，它能以香波、洗涤剂、凝胶形式或以在洗发前后，染色或脱色前后、烫发或弄直卷发之前、之中和之后的冲洗、涂用组合物的形式使用。它们还能以适合或治疗的洗剂或者凝胶形式；刷子卷发或成褶皱的洗剂或者凝胶的形式；头发发浆形式；烫发或弄直卷发的组合物形式；或以头发染色或脱色组合物形式使用。
当本发明组合物用作睫毛、眉毛或皮肤化妆品时，例如该组合物都是以处理皮膏、染色底子、口红、面用脂粉、de lignuers(即称之“眼线”)或染睫毛和眉毛美容等形式出现。
当本发明组合物是药物组合物时，该组合物尤其能够以乳剂(乳状液或香脂)、凝胶、洗液、软膏、泡状分散液或细小微粒分散状的形式出现，除了上面叙述的组合之外它还可能含有其它药物活性成分。
由于这些组合物有协同组合作用，所以本发明的组合物成为特别是能涂到皮肤、表面性组织和粘膜上，例如能预防和治疗尤其由空气污染和紫外辐射引起的自由基所致损伤的化妆或药物组合物。尤其是，本发明化妆品组合物可以预防或治疗皮肤加速衰老的现象。
本发明还一个内容在于：作为在制备化妆品或药物组合物用作预防或治疗在皮肤上、头皮或粘膜上的细胞损伤，尤其是由空气污染和/或紫外辐射引起的自由基所造成的细胞损伤，和/或用作抗皮肤加速衰老现象时的协同活性组合，而配合使用至少一种银杏树提取物和至少一种多酚。
本发明还有一个内容是关于化妆品的治疗方法，它能抵抗对皮肤和头发由于空气污染物和紫外辐射引起的自由基所造成的美感损伤，其特征在于：将含有前面描述的协同配合的组合物涂到皮肤或头发上。
下面的实施例对本发明作了说明。
在这些实施例中，其使用的银杏树提取物按下面指出的方法制备。“Sunphenon“绿茶提取物由Nikko化学公司销售。Alep胡桃稀酒精提取物由Sochibo公司以商品名Supextrat销售。
银杏树提取物制取方式
把成为植物粉末状的两裂片银杏树叶装入用多孔纤维纸板作成的圆柱形器皿中。
将该圆柱形器皿放入“索氏抽提器”型的抽提器中：该抽提器在其底部装一个含有加热沸腾己烷( 69℃)的圆底烧瓶。溶剂蒸汽经分流通过、冷凝在冷却器中并在圆柱形器皿中回复到液态，逐渐浸没其器皿。在完全浸没之后，其含有植物提取物的溶剂经虹吸而流到开始的圆底烧瓶中。其过程连续进行，烧瓶中的液体含植物提取物越来越多。
提取进行12小时。
然后在减压下将己烷部分蒸发至干。
实施例1：H/E乳状液
这种乳状液具有下述组成(％(重量))。
-硬脂酸甘油酯                      2％
-由ICI公司销售的Tween 60(具有20摩尔
环氧乙烷的山梨糖醇酐单硬脂酸酯)    1％
-硬脂酸                            1.4％
-三乙醇胺                          0.7％
-Carbopol 940(用三乙醇胺中和)      0.2％
-甜杏仁油                          3％
-凡士林油                          8％
-Alep核桃的稀酒精提取物            0.1％
-银杏树提取物                      1％
-无菌的去矿化水+防腐剂适量至       100％
H/E意指：水包油型乳化液
Carbopol 940是由Goodrich销售的交联聚丙烯酸
在75-80℃加热硬脂酸甘油酯、Tween 60、硬脂酸、所述油。加入三乙醇胺。将这种混合物倒入有60克水的中和Carbopol中。将温度降到40℃，加入提取物，剩余的水和防腐剂。
实施例2：用于身体的H/E治疗蜡状物
以类似的方法制备下述蜡状物：
-硬脂酸甘油酯                            2％
-由ICI公司销售的Tween 60(具有20摩尔
 环氧乙烷的山梨糖醇酐单硬脂酸酯)         1％
-十六烷醇                                0.5％
-硬脂酸                                  1.4％
-三乙醇胺                                0.7％
-Carbopol 940(用三乙醇胺中和)            0.4％
-乳油术油脂的液体部分                    12％
-合成的全氢化角鲨烯                      12％
-Alep核桃稀酒精提取物                    0.1％
-银杏树提取物                            1％
-无菌去矿化水+防腐剂适量至               100％
实施例3：手用洗剂
-银杏树提取物                            1％
-绿茶提取物                              0.1％
-Lecinol S10                             0.375％
-Generol 122 ES                         0.625％
-由Dow公司销售的D5(Cyclométhicone)      2％
-甘油                                    10％
-对羟基苯甲酸甲酯                        0.3％
-水，适量至                              100％
Lecinol S10是由Nikko公司销售的氢化卵磷脂商品名：
Cenerol 122 ES是由Henkel公司销售的具有5摩尔环氧乙烷的氧乙基化植物甾醇商品名。
实施倒4：泡状分散液
-非离子amphiphile*                 1.5％
-胆固醇                            1.5％
-酰基谷氨酸钠HS21(AjinoBoto)       0.5％
-甘油                              3％
-绿茶提取物(Sunphenon)             0.1％
-两裂片银杏树提取物                l％
-全氢化角鲨烯                      10％
-对羟基苯甲酸甲酯                  0.2％
-Carbopol 940(Goodrich)            0.4％
-三乙醇胺    适量PH7
-水适量至                          100％
(*)非离子amphiphile是满足下述化学式的产品混合物：
C12H25-[OC2 H3(R)-O-C3 H5(OH)-O]n-H式中：
n代表该单位的统计数字，等于2.7，-OC2H3(R)-基代表
Figure 9311995700151
和
Figure 9311995700152
基团。-C3H5(OH)-O-基代表
R基代表C14H29和C16H33基等摩尔混合物
以“酰基谷氨酸盐 HS 21”商品名销售的产品是硬脂酰基谷氨酸二钠。
该泡状分散液按以下方法制备：
将非离子amphiphile化合物加到胆固醇和温度为100C的酰基谷氨酸盐中。
温度降低到90℃，在这个温度下加甘油、绿茶提取物、银杏树提取物和水(10克)。
混合物冷却至50℃，然后用Virtis 60均化器(40,000转/分)均化二次，每次4分钟。
所得的产品冷却至室温，再用20克水稀释。加入油相(全氢化角鲨烯和对羟基苯甲酸甲酯)，然后以40,000转/分均化二次，每次4分钟。
Carbopol胶(Carbopol 940和水适量至100)在30秒钟内以10,000转/分使其分散，然后整个溶液用三乙醇胺中和。
得到平滑光亮的膏状物，在头皮上使用这种膏状物以保护头发不受自由基的有害作用。
抗氧化剂活性的研究
采用一种对氧化作用特别敏感的物质维生素F加速氧化的方法证明本发明抗氧化系统的效果。
为了研究起见，使用METROHM公司的“RANCIMAT”自动装置(A.Scher等人，Fette,Scifen.Anstrichmitte 88(1)1-6,1986)。
采用单独的“SUNPHENON”绿茶提取物、单独的银杏树己烷提取物、并且采用绿茶提取物与银杏树己烷提取物的混合物，制备维生素F混合物。
在空气鼓泡(20升/小时)下将每个试样加热到100℃，接着连续浓缩由装有水的容器中的过氧化氢与维生素F醛降解所生成的挥发性酸，容器中插入一根铂电投，这个电极按照时间的变化测量由挥发酸浓度增加所引起的电导增加。由所得到的氧化指数曲线的两条渐近线相交来决定其诱发时间。
这个时间相应于在维生素F自氧化之前的潜在时间。
该潜在时间越长，维生素F抗自氧化则越好。
其结果如下：
试验的产品              诱发时间
0.1％绿茶               33分
1％银杏树               48分
0.1％绿茶，1％银杏树    258分

Claims (10)

1．化妆品或药物组合物，其特征在于：它含有协同作用的抗氧化系统，该系统由银杏树提取物与至少一种多酚化合物组合构成，所述的银杏树提取物是可溶于非极性溶剂的银杏叶子提取物。
2．根据权利要求1所述的组合物，其特征在于：所述的非极性溶剂是C6-C14链烷。
3．根据权利要求2所述的组合物，其特征在于所述的非极性溶剂是正己烷。
4．根据权利要求1所述的组合物，其特征在于：所述的多酚化合物含有至少一个二酚芳环，酚基可能被醚化或酯化。
5．根据权利要求1所述的组合物，其特征在于：银杏树提取物的浓度以该组合物的总重量计为1-10％(重量)。
6．根据权利要求1所述的组合物，其特征在于：多酚化合物的比例以该组合物的总重量计为0.1-1％(重量)。
7．根据权利要求1所述的组合物，其特征在于：银杏树提取物与多酚化合物之重量比为1-100。
8．根据权利要求1-7任一项所述的组合物，其特征在于：所述的多酚化合物选自于黄酮类化合物，卡诺酸、卡诺醇、取代或未取代的(2,5-二羟基苯基)羧酸和(2,5-二羟基苯基)亚烷基羧酸类，以及它们的衍生物，咖啡酸酯或酰胺或丹宁酸。
9．至少一种银杏树提取物和至少一种多酚化合物作为协同作用的抗氧化系统在制备用于预防或治疗由空气污染和/或由紫外辐射产生的自由基在皮肤、头皮或粘膜上引起的细胞损伤和/或用于抗皮肤加速衰老现象的化妆品或药物组合物中的应用。
10．根据权利要求9的应用，其特征在于：所述组合物的特性如权利要求2-8中任一权利要求所限定的那样。
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FR2699818B1 (fr) 1995-02-03
JP3538425B2 (ja) 2004-06-14
CN1097616A (zh) 1995-01-25
US5686082A (en) 1997-11-11
CA2130449A1 (fr) 1994-07-07
WO1994014414A1 (fr) 1994-07-07
FR2699818A1 (fr) 1994-07-01
DE69323733T2 (de) 1999-10-21
KR950700048A (ko) 1995-01-16
KR100302226B1 (ko) 2001-11-22
ES2129118T3 (es) 1999-06-01
DE69323733D1 (de) 1999-04-08
EP0627909B1 (fr) 1999-03-03
JPH07504209A (ja) 1995-05-11

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