CN107847413A - 含有姜根提取物的化妆品组合物 - Google Patents
含有姜根提取物的化妆品组合物 Download PDFInfo
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- CN107847413A CN107847413A CN201680043381.9A CN201680043381A CN107847413A CN 107847413 A CN107847413 A CN 107847413A CN 201680043381 A CN201680043381 A CN 201680043381A CN 107847413 A CN107847413 A CN 107847413A
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Abstract
一种化妆品组合物,含有选自组包括姜根CO2提取物、E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮、香紫苏内酯、紫色黄雏菊榨汁或其混合物的抗污染制剂,其含量足以(a)减小或防止空气污染诱导的基因表达,和/或(b)减小或防止多环芳香烃诱导或可诱导的基因表达,和/或(c)减小或防止空气污染诱导或空气污染可诱导的皮肤损伤。
Description
发明领域
本发明属于化妆品领域并且涉及含有有效防止和治疗由于空气污染引发的人类皮肤和毛发疾病的特定制剂。
现有技术
人类皮肤是身体的外层覆盖。对于人类皮肤是外皮系统最大的器官。皮肤有多层表皮组织并且保卫底下的肌肉、骨骼、韧带和内部器官。除了没有被毛保护,人类皮肤类似于大部分其他哺乳动物的皮肤。尽管几乎所有人类皮肤都被毛囊覆盖,可能表现为无毛。皱纹是皮肤中的皱襞、凸起或皱褶。皮肤皱纹的出现通常是由于衰老过程如糖化、习惯的睡眠位置、体重减轻或暂时地,由于长时间浸泡在水里。皮肤的老化皱纹会由于习惯的面部表情、增龄、晒伤、抽烟、缺水和各种其他因素而加剧。已经进行了许多工作以确定可以抑制或至少减缓皮肤衰老的因素。事实上,化妆品市场上大量不同产品通常作为抗衰老或抗皱活性物质做广告。
另一方面,很少有工作涉及导致皮肤衰老、皱纹形成并且也可能引发感染和皮肤癌的另一重要因素:空气污染。
在本文中术语空气污染包括但不限于机动车尾气,以及工业废气。空气污染在本文中是指释放的气体污染物以及释放的颗粒。但也包括橡胶车轮摩擦的颗粒。与空气污染有关的颗粒可能结合多环芳香烃类(PAH)但并不限于富含PAH的那些。打印机释放的炭黑颗粒也是室内出现的空气污染问题。另一个问题是在室内用煤或木柴产生的空气污染。
在流行病学研究中,人类皮肤暴露于重复的空气污染中,以证明外部皮肤衰老与色斑和皱纹相关[Vierkoetter et al.,J Invest Dermatol 130(12),2719‐26,2010]。色斑的形成是由于角质化细胞和黑色素细胞—皮肤黑色素产生细胞—的相互响应。角质化细胞特别释放POMC(阿黑皮素原),其刺激黑色素细胞中的黑素形成。通过抑制POMC基因诱导,保护皮肤细胞抵抗过量黑色形成。皱纹的增多形成是由于皮肤中MMP1(基质金属蛋白酶‐1)—一种负责降解胶原蛋白的酶—增强的活性。通过抑制MMP1基因的诱导,保护皮肤细胞抵抗皱纹形成。不同的细胞激素,例如IL‐6(白细胞介素‐6)导致炎症,也通过炎症后色素沉着过度变成色斑。通过抑制IL‐6基因诱导,保护皮肤细胞抵抗炎症以及色斑形成。
某些机理示出空气污染物与人类皮肤和毛发相互作用并产生失调和官能不调,但是对于能够防止和治愈受损人类皮肤和毛发的活性物却知之甚少。因此,本发明的目的是确定用于同时抵抗空气污染物带给人类皮肤和毛发的消极结果,特别是抑制POMC基因诱导的适当的活性物和活性混合物,并因此保护皮肤细胞抵抗过量黑素形成。另一个抵抗空气污染物带给人类皮肤和毛发的消极结果的重点是提供特别抑制皮肤中MMP1(基质金属蛋白酶‐1)诱导的活性物和活性混合物,从而保护皮肤抵抗皱纹的增多形成。另一个目的是提供特别抑制IL‐6(白细胞介素‐6)诱导的活性物和活性混合物,从而保护皮肤细胞抵抗炎症以及色斑形成。最后一个目的是提供抑制AhR(芳香烃受体)活化—通过CYP1A1(细胞色素P450,家族1,亚家族A,多肽1)基因上调节的诱导,特别是颗粒诱导的CYP1A1基因表达测定—的活性物和活性混合物,并从而避免与AhR活化诱导的颗粒,特别是源自空气污染的气载颗粒相关的疾病。
发明内容
本发明的主题是化妆品组合物,含有选自组包括姜根CO2提取物、E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮、香紫苏内酯、紫色黄雏菊榨汁或其混合物的抗污染制剂,特别是姜根CO2提取物,其含量足以
(a)减小或防止空气污染诱导的基因表达,和/或
(b)减小或防止多环芳香烃诱导或可诱导的基因表达,和/或
(c)减小或防止空气污染诱导或空气污染可诱导的皮肤损伤,特别是皮肤癌、皮肤老化、皮肤炎症和过度色素沉着。
令人惊讶地观察到
·姜根CO2提取物和/或
·E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮和/或
·香紫苏内酯和/或
·紫色黄雏菊榨汁
单独使用,优选二元或三元混合物,在体外用模型颗粒—被描述为研究真实街道颗粒的适当替代品(Danielsen et al,Particle and Fibre Toxicology 2008,5:6)—处理的人类表皮角质化细胞上抑制了参与皮肤老化的基因上调节。同时在用与较少量PAHs结合的室内颗粒处理后诱导了基因表达。特别地,姜根CO2提取物也能够抑制上调节。
优选地,本发明的化妆品组合物含有姜根CO2提取物作为抗污染制剂,其含量足以
(a)减小或防止空气污染诱导的基因表达,和/或
(b)减小或防止多环芳香烃诱导或可诱导的基因表达,和/或
(c)减小或防止空气污染诱导或空气污染可诱导的皮肤损伤,特别是皮肤癌、皮肤老化、皮肤炎症和过度色素沉着。
二元或三元混合物
在一个优选实施方案中本发明的化妆品组合物含有所述制剂的二元混合物,其中二元混合物特别选自以下二元混合物:
(i)姜根CO2提取物和香紫苏内酯,或
(ii)姜根CO2提取物和E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮,或
(iii)姜根CO2提取物和紫色黄雏菊榨汁。
所述二元混合物特别有利地适合作为药物或非药物(特别是以化妆品的形式)用于保护皮肤和/或毛发,特别是上述(a)至(c)的效果。
因此,本发明的另一个方面是上述优选的二元混合物自身。
在二元混合物中姜根CO2提取物的含量优选为10重量%至70重量%,并且E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮的含量优选为30重量%至90重量%,前提是姜根CO2提取物和E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮的总量为100重量%。在姜根CO2提取物和香紫苏内酯或紫色黄雏菊榨汁的二元混合物中,这些活性物质各自在组合物中的含量优选为20重量%至80重量%,前提是所有活性物质的总量为100重量%。
最优选的是含有姜根CO2提取物和E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮或香紫苏内酯的二元混合物,其中E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮在最终产品中的含量为0.1重量%至0.5重量%,更优选0.3重量%至0.5重量%,并且香紫苏内酯或姜根CO2提取物在最终产品中的含量为0.05重量%至0.2重量%,更优选0.1重量%至0.2重量%,所述最终产品优选为化妆用或药物产品。
在另一个优选实施方案中组合物含有所述制剂的三元混合物,如
(i)姜根CO2提取物、香紫苏内酯和紫色黄雏菊榨汁;或
(ii)姜根CO2提取物、E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮和香紫苏内酯;或
(iii)姜根CO2提取物、E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮和紫色黄雏菊榨汁。
所述三元混合物特别有利地叠加影响和/或协同增效地影响混合物保护皮肤和/或毛发的性能,特别是上述(a)至(c)的效果。
因此,本发明的另一个方面是上述优选的三元混合物(i)至(iii)自身。
优选地在三元混合物(i)中姜根CO2提取物的含量为5重量%至60重量%,其中E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮的含量优选为20重量%至90重量%,并且香紫苏内酯的含量优选为5重量%至60重量%,前提是三种化合物的总量为100重量%。
优选地在三元混合物(ii)中姜根CO2提取物的含量为12.5重量%至75重量%,其中香紫苏内酯的含量优选为12.5重量%至75重量%,并且紫色黄雏菊榨汁的含量优选为12.5重量%至75重量%,前提是三种化合物的总量为100重量%。
优选地在三元混合物(iii)中姜根CO2提取物的含量为5重量%至60重量%,其中E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮的含量优选为20重量%至90重量%,并且紫色黄雏菊榨汁的含量优选为5重量%至60重量%,前提是三种化合物的总量为100重量%。
抗污染制剂,其二元或三元混合物的有效量是指0.01重量%至2.5重量%,优选约0.05重量%至1.0重量%的所述抗污染制剂,在二元或三元混合物的情况下,为混合物中所有抗污染制剂的总量——基于最终组合物计。
姜根CO2提取物
已知含有大量辛辣成分的姜根提取物用于为食品和饮料调味。用HPLC、GC和其他分析方法表征姜根提取物已充分记载。辛辣成分如姜酚、姜烯酚和姜油酮的定量是良好实验室操作。但是没有记载特征在于42‐50%体重量的大量辛辣成分的姜提取物用于化妆应用。
未知组成的姜根的水和/或乙醇和/或水/乙醇提取物记载为抗氧化剂和抗老化剂,并通常作为这些应用的优选提取物。JP 2009 073777 A1记载了这些提取物用于改善皱纹,JP 2000 319189 A1记载作为弹性蛋白酶抑制剂,Fujimura等人(Fragrance Journal(2002),30(6),38‐42)记载通过抑制弹性蛋白酶活性改善皱纹。JP 2007008847要求的提取物用20%乙醇制备,得到浓缩果糖基二肽作为活性成分。
已知姜酊、姜汁和上述姜根的水和/或乙醇和/或水/乙醇提取物施用于毛发和头皮。记载了这些提取物对于毛发和头皮的特别是增强的微循环的活性。例如,CN102451128A1提出防脱发洗发香波含有5%姜汁。JP 63 091315 A1记载了增强微循环的姜汁在用于刺激毛发生长的洗发香波中。EP 1281402 B1(Kao)涉及基本不含姜酚的姜提取物用于抑制毛发生长。
WO 2009 087578 A1(Foamix)公开了姜油在化妆品制剂中用作安抚、放松或温暖制剂。但是该文献没有公开姜油的组成。由于挥发性组分已知姜的精油具备强烈的辛辣气味和味道,并且与本发明的姜辛辣提取物不可比较。
分离姜的辛辣成分记载于不同文献。Ficker等人(Phytotherapy Research(2003),17(8),897‐902)评估了姜成分的抗真菌活性。
评估姜的辛辣成分的抗炎活性记载于不同文献,特别是Lantz等人(Phytomedicine(2007),14(2‐3),123‐128)。此外不同科研组,特别是Sang等人(Journalof Agricultural andFood Chemistry(2009),57(22),10645‐10650)评估了抗肿瘤活性和对于肿瘤细胞的增殖抑制活性。
CN 1840162 A1记载了姜根CO2提取物而没有明确辛辣成分如姜酚和姜烯酚的含量。该提取物被公开为抗炎提取物。应用实例是口服片剂、药丸和胶囊。没有记载局部施用于皮肤的实例。
在本发明中特别优选的姜根CO2提取物含有
条件是姜酚总量为35至50%体重量,并且姜烯酚总量为1.5至6%体重量。这类提取物是EP 2772245 A1(SYMRISE)的主题,其在此通过引用提取物的性质以及得到提取物的方法结合进本文。该产品以商品名AgeRepair 3040由Symrise AG,Holzminden(DE)可得。
E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮
已知E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮用于防止UVB辐射导致的AhR上调节并且描述为以下化学式:
苄基茚二甲氧基二甲基茚满酮
该产品以商品名SymUrban TM可由Symrise AG,Holzminden(DE)得到。
香紫苏内酯
香紫苏内酯(CAS号564‐20‐5)
是通过λ类二萜香紫苏醇化学改性或生物转化制得的化合物。香紫苏醇存在于鼠尾草(Salvia sclarea L.)的根、叶和花部分并且其由所属源的分离已经记载(US 3,060,172)。根据本发明,香紫苏内酯的来源可以天然源自(提取)鼠尾草属,或可合成得到纯香紫苏内酯。根据本发明基本纯的香紫苏内酯含有多于百分之70的香紫苏内酯。
香紫苏内酯的同义词是(3aR,5aS,9aS,9bR)‐十氢‐3a,6,6,9a‐四甲基‐萘并[2,1‐b]呋喃‐2(1H)‐酮;3a,4,5,5aα,6,7,8,9,9a,9bα‐十氢‐3aβ,6,6,9aβ‐四甲基‐萘并[2,1‐b]呋喃‐2(1H)‐酮;[3aR‐(3aα,5aβ,9aα,9bβ)]‐十氢‐3a,6,6,9a‐四甲基‐萘并[2,1‐b]呋喃‐2(1H)‐酮;Norambreinolide;(+)‐Norambreinolide;(+)‐香紫苏内酯;(R)‐(+)‐香紫苏内酯;13,14,15,16‐Tetranorlabdano‐8α,12‐lactone;Norambreinolid。
香紫苏内酯是龙涎呋喃—一种香水中使用的有价值的龙涎香香料—的前体。但是香紫苏内酯自身也用作香料材料,其通常是化妆品中制剂的成分。
香紫苏醇和香紫苏内酯的抗炎活性记载于WO 200 230385A2(Henkel)。抗炎活性通过抑制5‐脂肪氧合酶以及环氧化酶‐1的活性得以证明。US 2003 072777(Color Access)给出了香紫苏内酯在五种成分的天然结合物中治疗痤疮的用途。香紫苏醇和香紫苏内酯的抗微生物活性已经记载于WO 1999 063978A1(Reynolds),包括香紫苏醇和香紫苏内酯用于治疗痤疮、皮炎和不想要的体味。WO 2001 074327A2(Color Access)公开了香紫苏内酯作为细胞分化增强剂的用途。根据该专利分化增强剂如香紫苏内酯用于刺激脂肪由表皮细胞产生,并同时提高屏障中的脂肪含量。作为所述组合物的一个用途提到了增强和延长仿晒产品。WO 2002060381A2(Color Access)记载了通过单独使用香紫苏内酯以及与白桦提取物结合增强屏障。US 2010 247692A1(Color Access)记载了香紫苏内酯在用于增强角质层功能的化妆品制剂中的用途。WO 2008 155048A1(Cognis)公开了单独含有香紫苏内酯或与甲基橙皮甙查尔酮结合的香紫苏内酯的化妆品组合物。记载了该化妆品组合物用于晒黑皮肤、染黑毛发或防止毛发变灰。
紫色黄雏菊榨汁
紫色黄雏菊是菊(Asteraceae)科开花植物紫松果菊(Echinacea purpurea)的常用名:
紫松果菊原产于北美东部。松果菊是19世纪中叶至20世纪早期的草本医学的基础抗微生物草药的一种,并且记载其用于蛇咬、炭疽病以及缓解疼痛。在19世纪30年代松果菊在欧洲和美洲作为草本药物流行。松果菊制剂的主要用途是预防和治疗上呼吸道感染(着凉和感冒)。紫色黄雏菊榨汁有价值的成分是咖啡酸衍生物(主要是菊苣酸和咖啡酰酒石酸)、多糖、蛋白质和氨基酸。该产品以商品名1298由Symrise AG,Holzminden(DE)可得。
化妆品组合物
本发明的另一个主题包括含有所述活性物的化妆品组合物。根据本发明的组合物可以是个人护理组合物、皮肤护理组合物、毛发护理组合物或防晒组合物,例如以洗剂、霜剂、乳液、泡沫、摩斯、油剂或棒剂。所述组合物可以含有约0.01重量%至约2.5重量%,且优选约0.05重量%至约1.0重量%的所述制剂、二元或三元混合物,基于最终组合物计。
优选地,该组合物可以进一步含有化妆品可接受载体,如水、C2‐C4醇、含有2至6个碳原子的多元醇和/或油体。
根据本发明的制剂可以含有研磨剂、抗痤疮剂、抗皮肤老化剂、溶脂剂、去头屑剂、抗炎剂、防刺激剂、抑制刺激剂,抗氧化剂、收敛剂、抑汗剂、杀菌剂、抗静电剂、粘合剂、缓冲剂、载体、螯合剂、细胞刺激剂、清洗剂、护理剂、脱毛剂、表面活性物质、除臭剂、止汗剂、柔软剂、乳化剂、酶、精油、纤维、成膜剂、固色剂、泡沫形成剂、泡沫稳定剂、消泡剂、泡沫促进剂、胶凝剂、凝胶形成剂、头发护理剂、毛发定型剂、头发拉直剂、增湿剂、润湿剂、保湿剂、漂白剂、加强剂、去污剂、光学增亮剂、浸溃剂、驱污剂、减摩剂、润滑剂、保湿霜、软膏、遮光剂、增塑剂、覆盖剂、上光剂、光泽剂、聚合物、粉末、蛋白质、加脂剂、磨蚀剂、硅酮、皮肤舒缓剂、皮肤清洁剂、护肤剂、皮肤愈合剂、皮肤光亮剂、皮肤保护剂、皮肤软化剂、增发剂、冷却剂、皮肤冷却剂、加温剂、皮肤升温剂、稳定剂、UV吸收剂、UV滤光剂、洗涤剂、织物柔顺剂、助悬剂、皮肤美黑剂、增稠剂、维生素、油、蜡、脂肪、磷脂、饱和脂肪酸、单或多不饱和脂肪酸、α‐羟基酸、多羟基脂肪酸、液化剂、染料、颜色保护剂、颜料、防蚀剂、芳香物质、调味物质、气味物质、多元醇、表面活性剂、电解质、有机溶剂或硅酮衍生物等额外助剂和添加剂。
表面活性剂
优选的助剂和添加剂是阴离子和/或两性或两性离子表面活性剂。阴离子表面活性剂的典型实例为皂类、烷基苯磺酸盐、烷烃磺酸盐、烯烃磺酸盐、烷基醚磺酸盐、甘油醚磺酸盐、甲酯磺酸盐、磺基脂肪酸、烷基硫酸盐、脂肪醇醚硫酸盐、甘油醚硫酸盐、脂肪酸醚硫酸盐、羟基混合醚硫酸盐、单甘油酯(醚)硫酸盐、脂肪酸酰胺(醚)硫酸盐、单‐和二烷基磺基丁二酸盐、单‐和二烷基磺基琥珀酰胺酸盐、磺基甘油三酯、酰胺皂、醚羧酸及其盐、脂肪酸羟乙磺酸盐、脂肪酸肌氨酸盐、脂肪酸牛磺酸盐、N‐酰氨酸如,例如酰基乳酸盐、酰基酒石酸盐、酰基谷氨酸盐和酰基天冬氨酸盐、烷基低聚葡糖苷硫酸盐、蛋白质脂肪酸缩合物(特别是小麦基植物产品)和烷基(醚)磷酸盐。如果阴离子表面活性剂含有聚乙二醇醚链,则它们可具有常规的同族分布,但优选具有窄同族分布。两性或两性离子表面活性剂的典型实例为烷基甜菜碱、烷基酰胺基甜菜碱、氨基丙酸盐、氨基甘氨酸盐、咪唑啉甜菜碱和磺基甜菜碱。所述表面活性剂均为已知化合物。其结构和制备信息可见于相关概述作品,参见,例如J.Falbe(编辑),“Surfactants in Consumer Products”,Springer Verlag,Berlin,1987,页54至124或J.Falbe(编辑),“Katalysatoren,Tenside und (Catalysts,Surfactants and Mineral Oil Additives)”,Thieme Verlag,Stuttgart,1978,pages 123‐217。表面活性剂在制剂中的百分含量可以为0.1至10重量%且优选0.5至5重量%,基于制剂计。
油体
适当的构成O/W乳液成分的油体是,例如,基于含有6至18个,优选8至10个碳原子的脂肪醇的Guerbet醇,直链C6‐C22‐脂肪酸与直链或支链C6‐C22‐脂肪醇的酯或支链C6‐C 13‐羧酸与直链或支链C6‐C 22‐脂肪醇的酯,如例如肉豆蔻酸十四烷酯、棕榈酸十四烷酯、硬脂酸十四烷酯、异硬脂酸十四烷酯、油酸十四烷酯、山嵛酸十四烷酯、芥酸十四烷酯、肉豆蔻酸十六烷酯、棕榈酸十六烷酯、硬脂酸十六烷酯、异硬脂酸十六烷酯、油酸十六烷酯、山嵛酸十六烷酯、芥酸十六烷酯、肉豆蔻酸十八烷酯、棕榈酸十八烷酯、硬脂酸十八烷酯、异硬脂酸十八烷酯、油酸十八烷酯、山嵛酸十八烷酯、芥酸十八烷酯、肉豆蔻酸异十八烷酯、棕榈酸异十八烷酯、硬脂酸异十八烷酯、异硬脂酸异十八烷酯、油酸异十八烷酯、山嵛酸异十八烷酯、油酸异十八烷酯、油醇肉豆蔻酸酯、棕榈酸油醇酯、油醇硬脂酸酯、油醇异硬脂酸酯、油酸油醇酯、山嵛酸油醇酯、芥酸油醇酯、肉豆蔻酸二十二烷酯、棕榈酸二十二烷酯、硬脂酸二十二烷酯、异硬脂酸二十二烷酯、油酸二十二烷酯、山嵛酸二十二烷酯、芥酸二十二烷酯、肉豆蔻酸芥醇酯、棕榈酸芥醇酯、硬脂酸芥醇酯、异硬脂酸芥醇酯、油酸芥醇酯、山嵛酸芥醇酯和芥酸芥醇酯。同样适当的是直链C6‐C22‐脂肪酸与支链醇,特别是2‐乙基己醇的酯、C18‐C38‐烷基羟基羧酸与直链或支链C6‐C 22‐脂肪醇的酯,特别是苹果酸二辛酯、直链和/或支链脂肪酸与多元醇(如,例如丙二醇、二聚二元醇(dimerdiol)或三聚三元醇(trimertriol))和/或Guerbet醇的酯、基于C6‐C10‐脂肪酸的甘油三酯、基于C6‐C18‐脂肪酸的液态单‐/二‐/三酸甘油酯混合物、C6‐C22‐脂肪醇和/或Guerbet醇与芳族羧酸,特别是苯甲酸的酯、C2‐C12‐二羧酸与具有1至22个碳原子的直链或支链醇或者具有2至10个碳原子和2至6个羟基的多元醇的酯、植物油、支链伯醇、取代环己烷、直链和支链C6‐C22‐脂肪醇的碳酸酯,如例如碳酸二辛酯(CC)、基于具有6至18个优选8至10个碳原子的脂肪醇的Guerbet碳酸酯、苯甲酸与直链和/或支链C6‐C22‐醇的酯(例如TN)、每个烷基具有6至22个碳原子的直链或支链、对称或非对称的二烷基醚,如例如二辛酰基醚(OE)、环氧化脂肪酸酯与多元醇的开环产物、硅油(环聚二甲基硅氧烷、硅酮甲基硅油等级,等)、和/或脂肪烃或环烷烃,如例如角鲨烷、角鲨烯或二烷基环己烷。
乳化剂
也可以向制剂中加入其他表面活性剂作为乳化剂,包括例如:
·2至30摩尔环氧乙烷和/或0至5摩尔环氧丙烷与直链C8‐22脂肪醇、与C12‐22脂肪酸、与烷基中具有8‐15个碳原子的烷基苯酚的加成产物;
·1至30摩尔环氧乙烷与甘油的加成产物的C12/18脂肪酸单酯和二酯;
·具有6至22个碳原子的饱和和不饱和脂肪酸的甘油单酯和二酯以及脱水山梨醇单酯和二酯,及其环氧乙烷加成产物;
·15至60摩尔环氧乙烷与蓖麻油和/或氢化蓖麻油的加成产物;
·多元醇酯以及,特别是聚甘油酯类如,例如,聚蓖麻酸聚甘油酯、聚‐12‐羟基硬脂酸聚甘油酯或聚甘油二聚合油异硬脂酸酯(polyglycerol dimerate isostearate)。本组中的一些化合物的混合物同样适当;
·2至15摩尔环氧乙烷与蓖麻油和/或氢化蓖麻油的加成产物;
·基于直链、支链、不饱和或饱和C6/22脂肪酸、蓖麻酸和12‐羟基硬脂酸和甘油、聚甘油、季戊四醇、二季戊四醇、糖醇类(例如山梨糖醇)、烷基糖苷类(例如甲基糖苷、丁基糖苷、月桂基糖苷)以及多苷类(例如纤维素)的偏酯类;
·磷酸单‐、二‐和三烷酯类以及磷酸单‐、二‐和/或三‐PEG烷酯类及其盐;
·羊毛蜡醇类;
·聚硅氧烷/聚烷基‐聚醚共聚物及相应衍生物;
·季戊四醇、脂肪酸、柠檬酸和脂肪醇的混合酯和/或C6‐22脂肪酸、甲基葡萄糖和多元醇类、优选甘油或聚甘油的混合酯;
·聚二醇类以及
·碳酸甘油酯。
环氧乙烷和/或环氧丙烷与脂肪醇、脂肪酸、烷基苯酚、脂肪酸的甘油单酯和二酯以及脂肪酸的脱水山梨醇单酯和二酯或与蓖麻油的加成产物是市售可得的公知产品。它们是同族混合物,其中烷氧基化的平均程度对应于进行加成反应的环氧乙烷和/环氧丙烷和底物的用量比例。环氧乙烷与甘油的加成产物的C12/18脂肪酸单酯和二酯已知用作化妆品制剂的脂质层强化剂。优选的乳化剂详细记载如下:
偏甘油酯。适当的偏甘油酯的典型实例是羟基硬脂酸单甘油酯、羟基硬脂酸二甘油酯、异硬脂酸单甘油酯、异硬脂酸二甘油酯、油酸单甘油酯、油酸二甘油酯、蓖麻酸单甘油酯、蓖麻酸二甘油酯、亚油酸单甘油酯、亚油酸二甘油酯、亚油酸单甘油酯、亚油酸二甘油酯、芥酸单甘油酯、芥酸二甘油酯、酒石酸单甘油酯、酒石酸二甘油酯、柠檬酸单甘油酯、柠檬酸二甘油酯、苹果酸单甘油酯、苹果酸二甘油酯及其仍含有少量源自生产过程的甘油三酯的技术混合物。1至30且优选5至10摩尔环氧乙烷与上述偏甘油酯的加成产物同样适当。
脱水山梨醇酯。适当的脱水山梨醇酯是脱水山梨醇单异硬脂酸酯、脱水山梨醇倍半异硬脂酸酯、脱水山梨醇二异硬脂酸酯、脱水山梨醇三异硬脂酸酯、脱水山梨醇单油酸酯、脱水山梨醇倍半油酸酯、脱水山梨醇二油酸酯、脱水山梨醇三油酸酯、脱水山梨醇单芥酸酯、脱水山梨醇倍半芥酸酯、脱水山梨醇二芥酸酯、脱水山梨醇三芥酸酯、脱水山梨醇单蓖麻酸酯、脱水山梨醇倍半蓖麻酸酯、脱水山梨醇二蓖麻酸酯、脱水山梨醇三蓖麻酸酯、脱水山梨醇单羟基硬脂酸酯、脱水山梨醇倍半羟基硬脂酸酯、脱水山梨醇二羟基硬脂酸酯、脱水山梨醇三羟基硬脂酸酯、脱水山梨醇单酒石酸酯、脱水山梨醇倍半酒石酸酯、脱水山梨醇二酒石酸酯、脱水山梨醇三酒石酸酯、脱水山梨醇单柠檬酸酯、脱水山梨醇倍半柠檬酸酯、脱水山梨醇二柠檬酸酯、脱水山梨醇三柠檬酸酯、脱水山梨醇单马来酸酯、脱水山梨醇倍半马来酸酯、脱水山梨醇二马来酸酯、脱水山梨醇三马来酸酯及其技术混合物。1至30且优选5至10摩尔环氧乙烷与上述脱水山梨醇的加成产物同样适当。
聚甘油酯。适当的聚甘油酯的典型实例是聚甘油‐2二聚羟基硬脂酸酯(PGPH)、聚甘油‐3‐二异硬脂酸酯(TGI)、聚甘油‐4异硬脂酸酯(GI 34)、聚甘油‐3油酸酯、聚甘油‐3二异硬脂酸酯(PDI)、聚甘油‐3甲基葡糖二硬脂酸酯(Tego450)、聚甘油‐3蜂蜡(Cera)、聚甘油‐4癸酸酯(聚甘油癸酸酯T2010/90)、聚甘油‐3鲸蜡基醚(NL)、聚甘油‐3二硬脂酸酯(GS 32)和聚甘油聚蓖麻酸酯(WOL 1403)、聚甘油二异硬脂酸(polyglyceryl dimerate isostearate)酯及其混合物。其它适当的多元醇酯的实例是任选与1至30摩尔环氧乙烷反应的月桂酸、椰油酸、牛油酸、棕榈酸、硬脂酸、油酸、山嵛酸等与三羟甲基丙烷或季戊四醇的单酯、二酯和三酯。
阴离子乳化剂。典型的阴离子乳化剂是脂肪族C12‐22脂肪酸,如例如棕榈酸、硬脂酸或山嵛酸,以及C12‐22的二羧酸,如例如壬二酸或癸二酸。
两性乳化剂。其他适当的乳化剂是两性或两性离子表面活性剂。两性离子表面活性剂是分子中含有至少一个季铵基团和至少一个羧酸酯基团和一个磺酸酯基团的表面活性化合物。特别适当的两性离子表面活性剂为所谓的甜菜碱,如N‐烷基‐N,N‐二甲基甘氨酸铵,例如椰油烷基二甲基甘氨酸铵、N‐酰胺基丙基‐N,N‐二甲基甘氨酸铵,例如椰油酰胺基丙基二甲基甘氨酸铵、和烷基或酰基中具有8‐18个碳原子的2‐烷基‐3‐羧甲基‐3‐羟乙基咪唑啉和椰油酰胺基乙基羟乙基羧甲基甘氨酸盐。特别优选已知CTFA名为椰油酰胺丙基甜菜碱的脂肪酸酰胺衍生物。同样适当的乳化剂为两性表面活性剂。两性表面活性剂是除了C8/18烷基或酰基外,分子中还含有至少一个游离氨基和至少一个‐COOH或‐SO3H‐基团且能形成内盐的表面活性化合物。适当的两性表面活性剂的实例为烷基中具有约8‐18个碳原子的N‐烷基甘氨酸、N‐烷基丙酸、N‐烷基氨基丁酸、N‐烷基亚氨基二丙酸、N‐羟乙基‐N‐烷基酰胺基丙基甘氨酸、N‐烷基牛磺酸、N‐烷基肌氨酸、2‐烷基氨基丙酸和烷基氨基乙酸。特别优选的两性表面活性剂为N‐椰油烷基氨基丙酸酯、椰油酰胺基乙基氨基丙酸酯和C12/18酰基肌氨酸。
富脂剂和稠度因子
富脂剂可以选自物质如例如,羊毛脂和卵磷脂以及聚乙氧基化或酰基化羊毛脂和卵磷脂衍生物、多元醇脂肪酸酯、单甘油酯和脂肪酸烷醇酰胺;脂肪酸烷醇酰胺也可用作泡沫稳定剂。
常用稠度因子是具有12至22个并且优选16至18个碳原子的脂肪醇或羟基脂肪醇以及偏甘油酯、脂肪酸或羟基脂肪酸。优选使用这些物质与烷基多糖苷和/或具有相同链长的脂肪酸N‐甲基葡糖酰胺和/或聚甘油聚‐12‐羟基硬脂酸酯的组合。
增稠剂和流变添加剂
适当的增稠剂是聚合增稠剂,如类(亲水性二氧化硅)、多糖,更特别是黄原胶、瓜尔胶、琼脂、藻酸盐和纤基乙酸钠(tyloses)、羧甲基纤维素和羟乙基纤维素、以及脂肪酸的相对高分子量聚乙二醇单酯和二酯、聚丙烯酸酯(例如[Goodrich]或[Sigma])、聚丙烯酰胺、聚乙烯醇和聚乙烯吡咯烷酮、表面活性剂如,例如乙氧基化脂肪酸甘油酯、脂肪酸与多元醇如季戊四醇或三羟甲基丙烷的酯、窄分布的脂肪醇乙氧基化物(fatty alcohol ethoxylates)和电解质如氯化钠和氯化铵。
聚合物
适当的阳离子聚合物是例如,阳离子纤维素衍生物,例如以商品名POLYMER JR由AMERCHOL得到的季铵化羟乙基纤维素、阳离子淀粉、二烯丙基铵盐和丙烯酰胺的共聚物、季铵化乙烯基吡咯烷酮/乙烯基咪唑聚合物如,例如(BASF)、聚乙二醇和胺的缩合产物、季铵化胶原多肽如,例如月桂基二甲基铵羟丙基胺水解胶原(L,)、季铵化小麦多肽、聚乙烯亚胺、阳离子硅氧烷聚合物如,例如氨基二甲聚硅氧烷(amo二甲基硅油)、己二酸和二甲基氨基羟丙基二亚乙基三胺的共聚物(SANDOZ)、丙烯酸与二甲基二烯丙基氯化铵的共聚物(550,CHEMVIRON)、聚氨基聚酰胺及其交联水溶性聚合物、阳离子角质素衍生物如,例如任选以微晶分布的季铵化壳聚糖、二卤代烷基如二溴丁烷与双二烷基胺的缩合产物,例如双‐二甲基氨基‐1,3‐丙烷、阳离子瓜尔胶如,例如CELANESE的CBS、C‐17、C‐16、季铵盐聚合物如,例如MIRANOL的A‐15、AD‐1、AZ‐1以及各种聚季铵盐类(例如6、7、32或37),其可以商品名CC或300由市场可得。
适当的阴离子、两性离子、两性和非离子聚合物是例如,乙酸乙烯酯/巴豆酸共聚物、乙烯基吡咯烷酮/丙烯酸乙烯酯共聚物、乙酸乙烯酯/马来酸丁酯/丙烯酸异冰片酯共聚物、甲基乙烯基醚/马来酸酐共聚物及其酯、未交联的和与多元醇交联的聚丙烯酸、丙烯酰胺基丙基三甲基氯化铵/丙烯酸酯共聚物、辛基丙烯酰胺/甲基丙烯酸甲酯/甲基丙烯酸叔丁基氨基乙酯/甲基丙烯酸2‐羟丙酯共聚物、聚乙烯吡咯烷酮、乙烯基吡咯烷酮/乙酸乙烯酯共聚物、乙烯基吡咯烷酮/甲基丙烯酸二甲基氨基乙酯/乙烯基己内酰胺三元共聚物和任选衍生的纤维素醚和硅氧烷。
珠光蜡
适当的珠光蜡是,例如,烷二醇酯,尤其是乙二醇二硬脂酸酯;脂肪酸烷醇酰胺,尤其是椰油脂肪酸二乙醇酰胺;偏甘油酯,尤其是硬脂酸单甘油酯;多元、任选羟基取代的羧酸与具有6‐22个碳原子的脂肪醇的酯,尤其是酒石酸的长链酯;具有总计至少24个碳原子的脂肪物质,如例如脂肪醇、脂肪酮、脂肪醛、脂肪醚和脂肪碳酸酯,尤其是月桂酮和二硬脂醚;脂肪酸如硬脂酸、羟基硬脂酸或山嵛酸、具有12‐22个碳原子的环氧烯烃与具有12‐22个碳原子的脂肪醇和/或具有2‐15个碳原子和2‐10个羟基的多元醇的开环产物、及其混合物。
硅氧烷化合物
适当的硅氧烷化合物是,例如二甲基聚硅氧烷、甲基苯基聚硅氧烷、环硅氧烷以及氨基、脂肪酸、醇、聚醚、环氧、氟、糖苷和/或烷基改性的硅氧烷化合物,在室温下它们可以是液态以及呈树脂态。其它适当的硅氧烷化合物是有机硅树脂,其为平均链长为200至300个二甲基硅氧烷单元的二甲基硅油与氢化硅酸盐的混合物。适当的挥发性硅氧烷的具体综述还可见于TODD等人的Cosm.Toil.91,27(1976)。
蜡和稳定剂
除了使用的天然油脂,制剂中也可以存在蜡,更特别是天然蜡如,例如小烛树蜡、巴西棕榈蜡、日本蜡、芦华草腊(ESPARTOGRASS WAX)、软木蜡、小冠椰子腊(GUARUMA WAX)、米糠油蜡、糖甘蔗蜡、小冠巴西棕蜡(OURICURY WAX)、褐煤蜡、蜂蜡、紫胶蜡(SCHELLACWAX)、鲸蜡、羊毛脂(羊毛蜡)、尾脂脂肪(UROPYGIAL FAT)、(纯)地蜡、地蜡(石蜡)、凡士林、石油蜡和微蜡;化学改性的蜡类(硬蜡类)如,例如,褐煤酯蜡(MONTAN ESTER WAXES)、德国沙索集团石油蜡(SASOL WAX)、氢化霍霍巴蜡(JOJOBA WAXES)以及合成蜡类如,例如,聚亚烷基蜡类和聚乙二醇蜡类。
脂肪酸的金属盐如,例如硬脂酸或蓖麻酸的镁盐、铝盐和/或锌盐用作稳定剂。
主要防晒剂
在本发明中主要防晒剂是,例如,在室温下是液体或晶体,并且能够吸收紫外辐射并以长波辐射,例如热的形式释放能量的有机物(滤光物质)。
本发明的制剂可有利地含有至少一种UV‐A过滤物质和/或至少一种UV‐B过滤物质和/或一种宽波过滤物质和/或至少一种无机颜料。本发明的制剂优选含有至少一种UV‐B过滤物质或一种宽波过滤物质,更特别优选至少一种UV‐A过滤物质和至少一种UV‐B过滤物质。
根据本发明优选的化妆品组合物,优选地,局部制剂,含有一种、两种、三种或更多种防晒剂,选自组包括4‐氨基苯甲酸和衍生物、水杨酸衍生物、二苯酮衍生物、二苯甲酰甲烷衍生物、丙烯酸二苯酯、3‐咪唑基‐4‐基丙烯酸及其酯、苯并呋喃衍生物、丙二酸亚苄酯衍生物、含有一个或多个有机硅自由基的聚合UV吸收剂、肉桂酸衍生物、樟脑衍生物、三苯胺基‐S‐三嗪衍生物、2‐羟基苯基苯并三唑衍生物、苯基苯并咪唑磺酸衍生物及其盐、邻氨基苯甲酸薄荷酯、苯并三唑衍生物和吲哚衍生物。
此外,有利地将式(I)的化合物与活性成分结合,所述活性成分渗透进入皮肤并由内保护细胞免受阳光导致的损害并降低皮肤基质金属蛋白酶水平。WO2007/128723记载了被称为芳香烃受体拮抗剂的各个优选成分,并在此引用。优选的是2‐亚苄基‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮。
下文引用的可在本发明中使用的UV过滤物质是优选的,但不限于这些物质。
优选使用的UV过滤物质选自组包括
·对氨基苯甲酸
·乙氧基化(25mol)对氨基苯甲酸乙酯(INCI名称:PEG‐25PABA)
·对二甲基氨基苯甲酸‐2‐乙基己酯
·N‐丙氧基化(2mol)对氨基苯甲酸乙酯
·对氨基苯甲酸甘油酯
·水杨酸高薄荷醇酯(胡莫柳酯)(NeoHMS)
·水杨酸‐2‐乙基己酯(NeoOS)
·三乙醇胺水杨酸酯
·水杨酸4‐异丙基苄酯
·邻氨基苯甲酸薄荷醇酯(NeoMA)
·二异丙基肉桂酸乙酯
·对甲氧基肉桂酸2‐乙基己酯(NeoAV)
·二异丙基肉桂酸甲酯
·对甲氧基肉桂酸异戊酯(NeoE 1000)
·对甲氧基肉桂酸二乙醇胺盐
·对甲氧基肉桂酸异丙酯
·2‐苯基苯并咪唑磺酸和盐(NeoHydro)
·3‐(4'‐三甲基铵)‐亚苄基‐莰基‐2‐酮硫酸甲酯
·β‐咪唑‐4(5)‐丙烯酸(尿刊酸)
·3‐(4'‐磺基)亚苄基‐莰基‐2‐酮和盐
·3‐(4'‐甲基亚苄基)‐D,L‐樟脑(NeoMBC)
·3‐亚苄基‐D,L‐樟脑
·N‐[(2和4)‐[2‐(氧代亚冰片‐3‐亚基)甲基]苄基]‐丙烯酰胺聚合物
·4,4'‐[(6‐[4‐(1,1‐二甲基)‐氨基羰基)苯基氨基]‐1,3,5‐三嗪‐2,4‐二基)二亚氨基]‐二‐(苯甲酸2‐乙基己酯)(Uvasorb HEB)
·亚苄基丙二酸酯‐聚硅氧烷(SLX)
·甘油基乙基己酸二甲氧基肉桂酸酯
·双丙二醇水杨酸酯
·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)(2,4,6‐三苯胺基‐(对‐羰基‐2'‐乙基己基‐1'‐氧基)‐1,3,5‐三嗪)(T150)
在本发明的制剂中优选与一种或多种式(I)的化合物结合的宽波过滤物质选自组包括
·2‐氰基‐3,3‐二苯基丙烯酸‐2‐乙基己酯(Neo303)
·2‐氰基‐3,3′‐二苯基丙烯酸乙酯
·2‐羟基‐4‐甲氧基二苯酮(NeoBB)
·2‐羟基‐4‐甲氧基二苯酮‐5‐磺酸
·二羟基‐4‐甲氧基二苯酮
·2,4‐二羟基二苯酮
·四羟基二苯酮
·2,2′‐二羟基‐4,4′‐二甲氧基二苯酮
·2‐羟基‐4‐正辛氧基二苯酮
·2‐羟基‐4‐甲氧基‐4′‐甲基二苯酮
·羟基甲氧基二苯酮磺酸钠
·2,2’‐二羟基‐4,4’‐二甲氧基‐5,5’‐二磺基‐二苯酮二钠
·苯酚,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)‐二甲硅氧基)‐丙基)(XL)
·2,2′‐亚甲基‐二‐(6‐(2H‐苯并三唑‐2‐基)‐4‐1,1,3,3‐四甲基丁基)‐苯酚)(M)
·2,4‐二‐[4‐(2‐乙基己氧基)‐2‐羟苯基]‐1,3,5‐三嗪
·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(S)
·2,4‐二‐[{(4‐(3‐磺酸基)‐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‐[{(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‐甲氧乙基羰基)苯基氨基]‐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‐乙基羰基)苯基氨基]‐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‐(三甲基硅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″‐甲基丙氧烯基)‐2‐羟基}苯基]‐6‐(4‐甲氧基苯基)‐1,3,5‐三嗪
·2,4‐二‐[{4‐(1′,1′,1′,3′,5′,5′,5′‐七甲基硅氧基‐2″‐甲基丙氧基)‐2‐羟基}苯基]‐6‐(4‐甲氧基苯基)‐1,3,5‐三嗪
组合物可以含有其他典型的洗涤剂和清洁组合物成分如UV‐A过滤物质,其在本发明的制剂中优选与一种或多种式(I)的化合物结合,选自组包括
·4‐异丙基二苯甲酰甲烷
·对苯二亚甲基‐二莰烷磺酸和盐(SX)
·4‐叔丁基‐4′‐甲氧基二苯甲酰基甲烷(阿伏苯宗)/(Neo357)
·亚苯基‐二‐苯并咪唑基‐四磺酸二钠盐(NeoAP)
·2,2′‐(1,4‐亚苯基)‐二‐(1H‐苯并咪唑‐4,6‐二磺酸),一钠盐
·2‐(4‐二乙氨基‐2‐羟基苯甲酰基)‐苯甲酸己酯(A Plus)
·根据DE 100 55 940 A1(=WO 2002038537)的茚满亚基化合物
组合物可以含有其他典型的洗涤剂和清洁组合物成分如UV过滤物质,其在本发明的制剂中优选与一种或多种式(I)的化合物结合,选自组包括
·对氨基苯甲酸
·3‐(4′‐三甲基铵)‐亚苄基莰基‐2‐酮硫酸甲酯
·水杨酸高薄荷醇酯(NeoHMS)
·2‐羟基‐4‐甲氧基二苯酮(NeoBB)
·2‐苯基苯并咪唑磺酸(NeoHydro)
·对苯二亚甲基‐二莰烷磺酸和盐(SX)
·4‐叔丁基‐4′‐甲氧基二苯甲酰基甲烷(Neo357)
·3‐(4′‐磺基)亚苄基‐莰基‐2‐酮和盐
·2‐氰基‐3,3‐二苯基丙烯酸‐2‐乙基己酯(Neo303)
·N‐[(2和4)‐[2‐(氧代亚冰片‐3‐亚基)甲基]苄基]‐丙烯酰胺聚合物
·对甲氧基肉桂酸2‐乙基己酯(NeoAV)
·乙氧基化(25mol)对氨基苯甲酸乙酯(INCI名称:PEG‐25PABA)
·对甲氧基肉桂酸异戊酯(NeoE 1000)
·2,4,6‐三苯胺基‐(对‐羰基‐2′‐乙基己基‐1′‐氧基)‐1,3,5‐三嗪(T150)
·苯酚,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)‐二甲硅氧基)‐丙基)(XL)
·4,4′‐[(6‐[4‐(1,1‐二甲基)‐氨基羰基)苯基氨基]‐1,3,5‐三嗪‐2,4‐二基)二亚氨基]‐二‐(苯甲酸2‐乙基己基酯)(Uvasorb HEB)
·3‐(4′‐甲基亚苄基)‐D,L‐樟脑(NeoMBC)
·3‐亚苄基‐樟脑
·水杨酸‐2‐乙基己酯(NeoOS)
·4‐二甲基氨基苯甲酸‐2‐乙基己酯(Padimate O)
·羟基‐4‐甲氧基二苯酮‐5‐磺酸和钠盐
·2,2′‐亚甲基‐二‐(6‐(2H‐苯并三唑‐2‐基)‐4‐1,1,3,3‐四甲基丁基)‐苯酚)(M)
·亚苯基‐二‐苯并咪唑基‐四磺酸二钠盐(NeoAP)
·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(S)
·亚苄基丙二酸酯‐聚硅氧烷(SLX)
·邻氨基苯甲酸薄荷醇酯(NeoMA)
·2‐(4‐二乙氨基‐2‐羟基苯甲酰基)‐苯甲酸己酯(A Plus)
·根据DE 100 55 940(=WO 02/38537)的茚满亚基化合物
有利的主要以及二级防晒剂记载于WO 2005 123101A1。有利地这些制剂含有至少一种UVA过滤物质和/或至少一种UVB过滤物质和/或至少一种无机颜料。该制剂在本发明中可以各种形式存在,如通常用于防晒制剂的形式。因此,它们的形式可以为溶液、油包水型(W/O)或水包油型(O/W)乳剂或多重乳剂,例如水包油包水型(W/O/W)、凝胶、水分散体、固体棒或气雾剂。
在另一个优选实施方案中本发明的制剂含有遮光剂,即,特别是UV过滤物质和/或无机颜料(UV过滤颜料)的总量能够使本发明的制剂具备大于或等于2的光照防护系数(优选大于或等于5)。本发明的该制剂特别适用于保护皮肤和毛发。
二级防晒剂
除了上述主要防晒剂组,也可以使用抗氧化剂型的二级防晒剂。抗氧化剂型的二级防晒剂阻断了当紫外线渗透进入皮肤时引发的光化学反应链。典型实例是氨基酸类(例如甘氨酸、组氨酸、酯氨酸、色氨酸)及其衍生物、咪唑类(例如尿刊酸)及其衍生物、肽类例如D,L‐肌肽、D‐肌肽,L‐肌肽及其衍生物(例如鹅肌肽)、类胡萝卜素类、胡萝卜素类(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、脂酮酸及其衍生物(例如二氢脂酮酸)、金硫葡糖、丙基硫氧嘧啶和其他硫醇(例如硫氧还蛋白、谷胱甘肽、半胱氨酸、胱氨酸、胱胺及其糖基、N‐乙酰基、甲基、乙基、丙基、戊基、丁基和月桂基、棕榈酰基、油烯基、α‐亚油酰基、胆甾醇基和其甘油酯)及其盐、硫代二丙酸二月桂酯、硫代二丙酸双十八酯、硫代二丙酸及其衍生物(酯类、醚类、肽类、脂类、核苷酸类、核苷类和盐)以及非常低的耐药剂量的亚砜亚胺化合物(例如丁硫氨酸亚砜亚胺、同型半胱氨酸亚砜亚胺、丁硫氨酸砜、五‐、六‐和七‐硫氨酸亚砜亚胺)、以及(金属)螯合剂类(例如,Α‐羟基脂肪酸类、棕榈酸、植酸、乳铁蛋白)、Α‐羟基酸类(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及其衍生物、不饱和脂肪酸及其衍生物(例如亚油酸、油酸)、叶酸及其衍生物、泛醌和泛醇及其衍生物、维生素C及其衍生物(例如抗坏血酸棕榈酸酯、抗坏血酸磷酸镁、抗坏血酸乙酸酯)、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)以及安息香树脂的苯甲酸松酯、芸香十烯酸及其衍生物、糖基芦丁、阿魏酸、亚糠基山梨醇、肌肽、丁基羟甲苯、丁基羟基茴香醚、去甲二氢愈创木酸木脂酸、去甲二氢愈创木酸、三羟基丁酰苯、尿酸及其衍生物、甘露糖及其衍生物、超氧化物歧化酶、二氧化钛(例如乙醇中的分散体)、锌及其衍生物(例如ZNO、ZNSO4)、硒及其衍生物(例如蛋氨酸硒)、芪类及其衍生物(例如均二苯乙烯氧化物、反‐均二苯乙烯氧化物)及这些活性化合物的适合本发明目的的衍生物(盐类、酯类、醚类、糖类、核苷酸类、核苷类、肽类和脂类)。
有利的无机二级光照防护颜料精细分散于金属氧化物和金属盐中,其记载于WO2005 123101A1中。无机颜料,特别是疏水性无机微颜料,在本发明的最终化妆品制剂中的总量有利地是0.1至30重量%,优选0.5至10.0重量%,基于制剂总量计。
同样优选的是使用微粒状UV过滤物质或无机颜料,其可任选为疏水性的,如钛的氧化物(TiO2)、锌的氧化物(ZnO)、铁的氧化物(Fe2O3)、锆的氧化物(ZrO2)、硅的氧化物(SiO2)、锰的氧化物(例如MnO)、铝的氧化物(Al2O3)、铈的氧化物(例如Ce2O3)和/或其混合物。
调节皮肤和/或毛发染色的活性物质
用于提亮皮肤和/或毛发的优选活性成分选自组包括:曲酸(5‐羟基‐2‐羟甲基‐4‐吡喃酮)、曲酸衍生物,优选曲酸双棕榈酸酯、熊果苷、抗坏血酸、抗坏血酸衍生物,优选抗坏血酸磷酸镁、氢醌、氢醌衍生物、间苯二酚、间苯二酚衍生物、优选4‐烷基间苯二酚和4‐(1‐苯乙基)1,3‐间苯二酚(苯乙基间苯二酚)、环己基氨基甲酸甲酯(优选WO 2010/122178和WO2010/097480中公开的一种或多种环己基氨基甲酸甲酯)、含硫分子,优选谷胱甘肽或半胱氨酸、α‐羟基酸(优选柠檬酸、乳酸、苹果酸)及其盐和酯、N‐乙酰酪氨酸及其衍生物、十一碳烯酰基苯丙氨酸、葡萄糖酸、色酮衍生物,优选芦荟苦素、黄酮类化合物、1‐氨基乙基次膦酸、硫脲衍生物、鞣花酸、烟酰胺(nicotinamide)、锌盐类,优选氯化锌或葡萄糖酸锌、崖柏素和衍生物、三萜类,优选山楂酸、甾醇类,优选麦角甾醇、苯并呋喃酮类,优选川芎内酯、乙烯基愈疮木酚、乙基愈疮木酚、二酸类(dionic acids),优选十八烯二酸和/或壬二酸,氮氧化物合成抑制剂,优选L‐硝基精氨酸及其衍生物、2,7‐二硝基吲唑或硫瓜氨酸、金属螯合剂(优选a‐羟基脂肪酸类、植酸、腐殖酸、胆酸、胆汁提取物、EDTA、EGTA及其衍生物)、维甲酸类化合物、豆奶和提取物、丝氨酸蛋白酶抑制剂或硫辛酸或者用于皮肤和毛发提亮的其他合成或天然活性成分,后者优选地以提植物提取物的形式使用,优选熊果提取物、大米提取物、番木瓜提取物、姜黄提取物、桑果提取物、凉薯提取物、香附提取物、甘草提取物或由其浓缩或分离的组成成分,优选光甘草定或甘草查尔酮甲、桂木提取物、酸模属的提取物、松属(松树)的提取物、葡萄属的提取物或者由其分离或浓缩的芪类衍生物、虎耳草提取物、黄芩提取物(scutelleria extract)、葡萄提取物和/或微藻提取物,特别是四肩突四鞭藻提取物。
作为成分(b)的优选皮肤提亮剂是曲酸和苯乙基间苯二酚作为酪氨酸酶抑制剂、β‐和α‐熊果苷、对苯二酚、烟酰胺、二酸、抗坏血酸磷酸镁和维生素C及其衍生物、桑果提取物、凉薯提取物、番木瓜提取物、姜黄提取物、香附提取物、甘草提取物(含有甘草甜素)、α‐羟基酸类、4‐烷基间苯二酚类、4‐羟基苯甲醚。由于非常好的活性,特别是与根据本发明的香紫苏内酯结合,优选这些这些皮肤提亮剂。此外,所述优选皮肤提亮剂易于获得。
对此有利的皮肤和毛发仿晒活性成分是类似酪氨酸酶的物质如L‐酪氨酸、N‐乙酰基酪氨酸、L‐DOPA或L‐二羟基苯丙氨酸、黄嘌呤生物碱如如咖啡因、可可碱和茶碱及其衍生物、阿黑皮素原肽类如ACTH、α‐MSH、其肽类似物和与黑皮质素受体结合的其他物质、肽类如Val‐Gly‐Val‐Ala‐Pro‐Gly、Lys‐Ile‐Gly‐Arg‐Lys或Leu‐Ile‐Gly‐Lys、嘌呤类、嘧啶类、叶酸、铜盐类如葡萄糖酸铜、氯化铜或吡咯烷酸铜、1,3,4‐噁二唑‐2‐硫醇如5‐吡嗪‐2‐基‐1,3,4‐噁二唑‐2‐硫醇、姜黄素、锌二甘氨酸盐(Zn(GIy)2)、碳酸氢锰(II)络合物(“拟过氧化氢酶”),如例如EP0584178中所描述、四取代的环己烯衍生物,例如W02005/032501中所描述、异戊二烯萜类,如WO2005/102252和W02006/010661中所描述、黑色素衍生物如Melasyn‐100和MelanZe、二酰基丙三醇类、脂肪族或环状二醇类、补骨脂素类、前列腺素及其类似物、腺苷酸环化酶的活化剂和激活毛发黑素小体转化成角蛋白细胞的化合物如丝氨酸蛋白酶或者PAR‐2受体激动剂、菊属的植物和植物部分的提取物、地榆属、核桃提取物、urucum提取物、大黄提取物、微藻提取物,尤其是球等鞭金藻、海藻糖、赤藓酮糖和二羟基丙酮。也可以使用引起皮肤和毛发染色或变褐色的黄酮类化合物(例如槲皮素、鼠李醚、山奈酚、漆黄素、染料木黄酮、黄豆苷元、白杨素和芹菜素、表儿茶素、香叶木苷和香叶木素、桑色素、槲皮苷、柚皮素、橙皮苷、根皮苷和根皮素)。
上述额外的用于皮肤调节和毛发染色的活性成分的实例在根据本发明的产品中的含量优选0.00001至30重量%,优选0.0001至20重量%,特别优选0.001至5重量%,基于制剂的总重计。
抗老化活性物
在本发明中抗老化剂或生物活性剂是,例如抗氧化剂、基质金属蛋白酶抑制剂(MMPI)、皮肤保湿剂、粘多糖刺激剂(glycosaminglycan stimulkators)、抗炎剂、TRPV1拮抗剂和植物提取物。
抗氧化剂。适当的抗氧化剂包括氨基酸类(优选甘氨酸,组氨酸,酪氨酸,色氨酸)及其衍生物、咪唑类(优选尿刊酸)及其衍生物、肽类,优选D,L‐肌肽、D‐肌肽、L‐肌肽及其衍生物(优选鹅肌肽)、肉碱、肌酸、马曲金(MATRIKINE)肽类(优选赖氨酰‐苏氨酰‐苏氨酰‐赖氨酰‐丝氨酸)和棕榈酰化五肽类、类胡萝卜素类、胡萝卜素类(优选Α‐胡萝卜素、Β‐胡萝卜素、番茄红素)及其衍生物、硫辛酸及其衍生物(优选二氢硫辛酸)、金硫葡萄糖、丙基硫氧嘧啶和其他硫醇(优选硫氧还蛋白、谷胱甘肽、半胱氨酸、胱氨酸、胱胺和糖基、N‐乙酰基、甲基、乙基、丙基、戊基、丁基和月桂基、棕榈酰基、油烯基、Γ‐亚油烯基、胆甾醇基、甘油基及其寡甘油酯)及其盐、硫代二丙酸二月桂酯、硫代二丙酸二硬脂酯、硫代二丙酸及其衍生物(优选酯类、醚类、肽类、脂类、核苷酸类、核苷类和盐)和非常低的耐药剂量(例如pmol至μmol/kg)的亚砜亚胺化合物(优选丁硫氨酸亚砜亚胺、同型半胱氨酸亚砜亚胺、丁硫氨酸砜、五‐、六‐和七‐硫氨酸亚砜亚胺)、以及(金属)螯合剂(优选α‐羟基脂肪酸、棕榈酸、植酸、乳铁蛋白)、α‐羟基酸(优选柠檬酸、乳酸、苹果酸)、腐殖酸、胆汁酸、胆汁提取物、单宁类、胆红素、胆绿素、EDTA、EGTA及其衍生物、不饱和脂肪酸及其衍生物(优选γ‐亚麻酸,亚油酸,油酸)、叶酸及其衍生物、泛醌及其衍生物,泛醇及其衍生物、维生素C及衍生物(优选抗坏血酸棕榈酸酯、抗坏血酸磷酸镁、抗坏血酸基乙酸酯、抗坏血酸葡糖苷)、生育酚及衍生物(优选维生素E乙酸酯)、维生素A及衍生物(维生素A棕榈酸酯)以及安息香树脂的苯甲酸松酯、芸香十烯酸及其衍生物、黄酮类及其糖基化前体,具体而言,槲皮素及其衍生物,优选α‐葡糖基芦丁、迷迭香酸、鼠尾草酚、卡诺酸、白藜芦醇、咖啡酸及其衍生物、芥子酸及其衍生物、阿魏酸及其衍生物、姜黄素类、绿原酸及其衍生物、类视黄醇类,优选类视黄醇棕榈酸酯、视黄醇或维甲酸、乌索酸、乙酰丙酸、丁基羟基甲苯、丁基羟基茴香醚、去二氢愈创木酸、去甲二氢愈创木酸、三羟基丁酰苯、尿酸及其衍生物、甘露糖及其衍生物、锌及其衍生物(优选ZnO、ZnSO4)、硒及其衍生物(优选硒蛋氨酸)、超氧化物歧化酶、二苯乙烯类及其衍生物(优选二苯乙烯氧化物、反式‐二苯乙烯氧化物)及这些引用的活性成分的适合本发明的衍生物(盐、酯类、醚类、糖类、核苷酸类、核苷类、肽类和脂类)或者具有抗氧化作用的植物的提取物或馏分,优选绿茶、路易波士(rooibos)茶、蜜树茶、葡萄、迷迭香、鼠尾草、蜜蜂花、百里香、薰衣草、橄榄、燕麦、可可、银杏、人参、甘草、金银花、苦参、葛根、松、柑橘、余甘子或ST.JOHN麦汁、葡萄籽、小麦胚芽、余甘子、辅酶,优选辅酶Q10、质体醌和甲基萘醌。优选的抗氧化剂选自组包括维生素A及衍生物,维生素C及衍生物,生育酚及衍生物,优选生育酚醋酸酯、以及泛醌。
如果使用维生素E和/或其衍生物作为抗氧化剂,有利的选择其浓度为约0.001至约10%体重量,基于制剂总重计。如果使用维生素A或胡萝卜素或其衍生物作为抗氧化剂,有利的选择其浓度为约0.001至约10%体重量,基于制剂总重计。
基质金属蛋白酶抑制剂(MMPI)。优选的组合物包含基质金属蛋白酶抑制剂,尤其是那些抑制基质金属蛋白酶裂解胶原的抑制剂,选自组包括:熊果酸、视黄醇棕榈酸酯、没食子酸丙酯、早熟素类、6‐羟基‐7‐甲氧基‐2,2‐二甲基‐1(2H)‐苯并吡喃、3,4‐二氢‐6‐羟基‐7‐甲氧基‐2,2‐二甲基‐1(2H)‐苯并吡喃、盐酸苯甲脒、半胱氨酸蛋白酶抑制剂N‐乙基马来酰胺和丝氨酸蛋白酶抑制剂的ε‐氨基‐正己酸:苯基甲基磺酰基氟化物、collhibin(Pentapharm公司;INCI:水解大米蛋白)、oenotherol(Soliance公司;INCI:丙二醇、水、月见草根提取物、鞣花酸和鞣花单宁类,例如来自石榴的提取物)、磷酸阿米酮桧木醇、EDTA、加拉定(galardin)、Equistat(Collaborative Group公司;苹果提取物、大豆种子提取物、熊果酸、大豆异黄酮类和大豆蛋白类)、鼠尾草提取物、MDI(Atrium公司;INCI:粘多糖(glycosaminoglycans)),fermiskin(Silab/MAWI公司;INCI:水和香菇提取物)、actimp1.9.3(Expanscience/Rahn公司;INCI:水解羽扇豆蛋白),lipobelle大豆糖苷配基(Mibelle公司;INCI:醇、聚山梨醇酯80、卵磷脂和大豆异黄酮)、绿茶和黑茶提取物以及WO02069992A1中列出的其它植物提取物(见其中的表1‐12,通过引用并入本文)、大豆蛋白或大豆糖蛋白、来自大米、豌豆或羽扇豆的水解蛋白、抑制MMP的植物提取物,优选香菇提取物、蔷薇科、蔷薇亚科的叶提取物,特别是黑莓叶提取物(优选地,如WO2005123101A1中所述,通过引用并入本文),例如SymMatrix(Symrise公司,INCI:麦芽糖糊精、欧洲黑莓(RubusFruticosus)叶提取物)。优选的活性物质选自组包括视黄醇棕榈酸酯、熊果酸、蔷薇科、蔷薇亚科的叶提取物、染料木素和黄豆苷元。
皮肤保湿剂。优选的皮肤保湿剂选自组包括含有3至12个碳原子的烷二醇或烷三醇,优选C3‐C10‐烷二醇和C3‐C10‐烷三醇。更优选地,所述皮肤保湿剂选自组包括:甘油、1,2‐丙二醇、1,2‐丁二醇、1,3‐丁二醇、1,2‐戊二醇、1,2‐己二醇、1,2‐辛二醇和1,2‐癸二醇。
粘多糖刺激剂。优选的组合物含有刺激粘多糖合成的物质,选自组包括透明质酸和衍生物或盐,Subliskin(Sederma,INCI:苜蓿中华根瘤菌发酵滤液、十六烷基羟乙基纤维素、卵磷脂)、Hyalufix(BASF,INCI:水、丁二醇、高良姜叶提取物、黄原胶、辛酸/癸酸甘油三酯、Stimulhyal(Soliance,INCI:酮葡糖酸钙(Calcium ketogluconate))、Syn‐Glycan(DSM,INCI:十四烷基氨基丁酸基缬氨酰氨基丁脲三氟乙酸酯、甘油、氯化镁)、Kalpariane(Biotech Marine)、DC Upregulex(Distinctive Cosmetic成分,INCI:水、丁二醇、磷脂质类、水解丝胶蛋白)、葡萄糖胺、N‐乙酰基葡萄糖胺、类视黄醇类,优选视黄醇和维生素A、牛蒡果提取物、枇杷提取物、芫花素、N‐甲基‐L‐丝氨酸、(‐)‐α‐没药醇或合成的α‐没药醇,例如Symrise的Dragosantol和Dragosantol100、燕麦葡聚糖、松果菊提取物和大豆蛋白水解物。优选的活性物质选自组包括透明质酸和衍生物或盐、视黄醇和衍生物、(‐)‐α‐没药醇或合成的Α‐没药醇,例如Symrise的Dragosantol和Dragosantol100、燕麦葡聚糖、松果菊提取物、苜蓿根瘤菌发酵滤液、酮葡糖酸钙、高良姜叶提取物和十四烷基氨基丁酸基缬氨酰氨基丁脲三氟醋酸酯。
抗炎剂。所述组合物还可含有抗炎和/或抗发红和/或瘙痒缓解成分,特别是,选自以下的皮质类固醇的甾类物质有利地用作抗炎活性成分或缓解发红和瘙痒的活性成分:皮质醇(hydrocortisone)、地塞美松、磷酸地塞美松、甲基脱氢皮质或可的松,还包括其它甾类抗炎剂。还可使用非甾类抗炎剂。本文可引用的实例为昔康类,如吡罗昔康或替诺昔康;水杨酸盐类如阿司匹林、双水杨酸(disalcid)、solprin或芬度柳;乙酸衍生物如双氯芬酸、氯芬酸、吲哚美辛、舒林酸、托美丁或clindanac;灭酸酯类如甲灭酸、甲氯灭酸、氟芬那酸或尼氟灭酸;丙酸衍生物如布洛芬、萘普生、苯恶洛芬或吡唑类如保泰松、羟保松、非普拉宗(febrazone)或阿扎丙宗。邻氨基苯甲酸衍生物,特别是WO 2004047833A1中描述的燕麦蒽酰胺(avenanthramides),为本发明的组合物中的优选的抗瘙痒成分。
同样有用的是天然或天然生成的抗炎物质混合物或缓解发红和/或瘙痒的物质混合物,特别是洋甘菊、芦荟、没药类、茜草类、柳树、柳叶菜、燕麦、金盏花、山金车、St John’s麦汁、金银花、迷迭香、西番莲、金缕梅、姜或紫锥菊的提取物或馏分;优选地选自组包括洋甘菊、芦荟、燕麦、金盏花、山金车、金银花、迷迭香、金缕梅、姜或紫锥菊的提取物或馏分、和/或纯物质,优选地α‐没药醇、芹黄素、芹黄素‐7‐葡萄糖苷、姜酚类、姜烯酚类、姜二醇类、脱氢姜二酮类、姜酮酚类(paradols)、天然或天然生成的燕麦蒽酰胺,优选曲尼司特(tranilast)、燕麦蒽酰胺A、燕麦蒽酰胺B、燕麦蒽酰胺C、非天然或非天然生成的燕麦蒽酰胺,优选二氢燕麦蒽酰胺D、二氢燕麦蒽酰胺E、燕麦蒽酰胺D、燕麦蒽酰胺E、燕麦蒽酰胺F、乳香脂酸、植物甾醇、甘草甜素、光甘草定和甘草查尔酮A;优选地,选自组包括α‐没药醇、天然燕麦蒽酰胺、非天然燕麦蒽酰胺,优选二氢燕麦蒽酰胺D(如WO2004047833A1中描述)、乳香脂酸、植物甾醇、甘草甜素、和甘草查尔酮A、和/或尿囊素、泛醇、羊毛脂、(假‐)神经酰胺类[优选神经酰胺2、羟丙基双棕榈酰胺MEA、十六基氧丙基甘油基甲氧基丙基十四酰胺、N‐(1‐十六酰)‐4‐羟基‐L‐脯氨酸(1‐十六基)酯、羟乙基棕榈基氧羟丙基棕榈酰胺]、鞘糖脂、植物甾醇、壳聚糖、甘露糖、乳糖和β‐葡聚糖,特别是燕麦的1,3‐1,4‐β‐葡聚糖。
当在本发明中使用没药醇时,其可以为天然或合成源,并且优选α‐没药醇。优选地,使用的没药醇合成制得或为天然(‐)‐α‐没药醇和/或α‐没药醇的合成混合异构体。如果使用天然(‐)‐α‐没药醇,其可作为精油或植物提取物或其馏分的组分采用,例如作为甘菊或Vanillosmopsis(特别是香子兰菊(Vanillosmopsis erythropappa)或Vanillosmopsisarborea)的油或提取物(的馏分)的组分采用。合成的α‐没药醇可例如从Symrise名称"Dragosantol"得到。
如果在本发明的中使用姜提取物,优选使用新鲜或干姜根的提取物,其通过用甲醇、乙醇、异丙醇、丙酮、乙酸乙醋、二氧化碳(CO2)、己烷、二氯甲烷、氯仿或其他溶剂或类似极性的溶剂混合物提取制得。提取物的特征在于,存在有效缓解皮肤刺激的量的组分如姜辣素、姜烯酚、姜二醇、脱氢姜二酮类和/或副姜油酮。
TRPV1拮抗剂。基于作为TRPV1拮抗剂的作用减轻皮肤神经过敏性的适当化合物包括例如WO2009087242A1中描述的反式‐4‐叔丁基环己醇,或者通过活化μ‐受体的TRPV1间接调节剂,例如乙酰基四肽‐15,是优选的。
脱屑剂。组合物可以含有脱屑剂(成分B5),含量为约0.1至约30%体重量,优选约0.5至约15%体重量,特别优选约1至约10%体重量,基于制剂总重量计。术语“脱屑剂”是指能够起以下作用的任何化合物:
·通过促进剥离而直接地作用于脱屑,如β‐羟基酸类,特别是水杨酸及其衍生物(包括5‐正辛酰基水杨酸);α‐羟基酸类,如乙醇酸、柠檬酸、乳酸、酒石酸、苹果酸或扁桃酸;尿素;龙胆酸;低聚果糖;肉桂酸;槐树的提取物;白藜芦醇和茉莉酸的一些衍生物;
·或者参与涉及以下物质的剥离或者降解的酶:角化桥粒、糖苷酶类、角质层胰凝乳蛋白酶(SCCE)或其他蛋白酶(胰蛋白酶、糜蛋白酶样)。可以提及螯合无机盐类的试剂:EDTA;N‐酰基‐N,N',N'‐乙二胺四乙酸;氨基磺酸化合物并且特别是(N‐2‐羟乙基哌嗪‐N‐2‐乙烷)磺酸(HEPES);2‐氧代噻唑烷‐4‐羧酸的衍生物(前半胱氨酸);甘氨酸类型的α‐氨基酸类的衍生物(如EP‐0852949中所述,以及由BASF公司以商品名称TRILON M销售的甲基甘氨酸二乙酸钠);蜂蜜;糖衍生物,如O‐辛酰基‐6‐D‐麦芽糖和N‐乙酰葡萄糖胺;如由SILAB公司以商品名称销售的板栗提取物、诸如由SILAB公司以商品名称销售的刺梨提取物、或者由Degussa公司销售的植物鞘氨醇(与水杨酸接枝的植物鞘氨醇)。
适用于本发明的脱屑剂特别地选自组包括磺酸类、钙螯合剂、α‐羟基酸类如乙醇酸、柠檬酸、乳酸、酒石酸、苹果酸或扁桃酸;抗坏血酸及其衍生物如抗坏血酸葡萄糖苷和抗坏血酸磷酸镁;烟酰胺;尿素;(N‐2‐羟基乙基哌嗪‐N‐2‐乙烷)磺酸(HEPES)、β‐羟基酸类如水杨酸及其衍生物、维甲酸类化合物如视黄醇及其酯类、视黄醛、维甲酸及其衍生物、专利文件FR 2570377A1、EP0199636A1、EP0325540A1、EP0402072A1中描述的那些、板栗或刺梨提取物,尤其是由SILAB公司销售的产品;还原化合物如半胱氨酸或半胱氨酸前体。
可以使用的脱屑剂还是烟酸及其酯类和烟酰胺,也被称为维生素B3或维生素PP、和抗坏血酸及其前体,特别是如专利申请EP1529522A1中所描述。
抗橘皮组织剂。抗橘皮组织剂和脂解剂优选地是选自WO2007/077541中所描述的那些、和β‐肾上腺素能受体激动剂如辛弗林及其衍生物、和WO2010/097479中所描述的氨基甲酸环己基酯类。增强或提高抗橘皮组织剂活性的制剂,尤其是刺激和/或去极化C神经纤维的制剂,优选地是选自组包括辣椒素及其衍生物、香草基‐壬酰胺和其衍生物、L‐肉碱,辅酶A、异黄酮类、大豆提取物、菠萝提取物和共轭亚油酸。
加脂剂。根据本发明的制剂和产品也可包含一种或多种加脂剂和/或成脂剂以及增强或提高加脂剂活性的制剂。加脂剂是例如羟基甲氧基苯基丙基甲基甲氧基苯并呋喃(商品名称:)。
毛发生长激活剂或抑制剂
根据本发明的制剂和产品还可含有一种或一种毛发生长激活剂,即刺激毛发生长的制剂。优选地,毛发生长激活剂优选自组包括嘧啶衍生物如2,4‐二氨基嘧啶‐3‐氧化物(Aminexil)、2,4‐二氨基‐6‐哌啶并嘧啶‐3‐氧化物(Minoxidil)及其衍生物、6‐氨基‐1,2‐二氢‐1‐羟基‐2‐亚氨基‐4‐哌啶并嘧啶及其衍生物、黄嘌呤生物碱类如咖啡因、可可碱和茶碱及其衍生物、槲皮素及衍生物、二氢槲皮素(花旗松素)及衍生物、钾通道开放剂、抗雄激素剂、合成的或天然的5‐还原酶抑制剂、烟酸酯如烟酸生育酚酯、烟酸苄酯和C1‐C6烷基烟酸盐、蛋白质例如三肽Lys‐Pro‐Val、diphencypren、激素、非那雄胺、度他雄胺、氟他胺、比卡鲁胺、孕烷衍生物、黄体酮及其衍生物、醋酸环丙孕酮、安体舒通和其他利尿剂、钙调磷酸酶抑制剂如FK506(他克莫司(Tacrolimus)、藤霉素(Fujimycin))及其衍生物、环孢菌素A及其衍生物、锌和锌盐、多酚、前花青素、原花青素、植物甾醇如β‐谷甾醇、生物素、丁子香酚、(±)‐β‐香茅醇、泛醇、糖原例如来源于贻贝、来源于微生物的提取物、藻类、植物和以下属的植物的植物部分,例如:蒲公英(狮齿菊属或蒲公英属)、直管草属(Orthosiphon)、牡荆(Vitex)、咖啡、泡林藤(Paullinia)、可可(Theobroma)、萍叶细辛(Asiasarum)、南瓜属(Cucurbita)或槐(Styphnolobium)、锯叶棕(Serenoa repens)(锯棕榈)、苦参(Sophoraflavescens)、非洲臀果木(Pygeum africanum)、黍(Panicum miliaceum)、美类叶升麻(Cimicifuga racemosa)、大豆(Glycine max)、丁香(Eugenia caryophyllata)、黄栌(Cotinus coggygria)、扶桑(Hibiscus rosa‐sinensis)、茶树(Camellia sinensis)、巴拉圭茶(Ilex paraguariensis)、等鞭藻(Isochrysis galbana)、甘草(licorice)、葡萄、苹果、大麦或啤酒花的提取物,或/和大米或小麦水解产物。
可选地,根据本发明的制剂和产品可包含一种或多种毛发生长抑制剂(如上所述),即减缓或防止毛发生长的制剂。毛发生长抑制剂优选自组包括激活素,激活素衍生物或激活素激动剂、鸟氨酸脱羧酶抑制剂如α‐二氟甲基鸟氨酸或五环三萜类化合物例如熊果酸、桦木醇、桦木酸、齐墩果酸及其衍生物、5α‐还原酶抑制剂、雄激素受体拮抗体、S‐腺苷甲硫氨酸脱羧酶抑制剂、γ‐谷氨酰转肽酶抑制剂、谷氨酰胺转胺酶抑制剂、大豆来源的丝氨酸蛋白酶抑制剂、来自微生物,海藻,不同微藻或植物和植物部分,例如豆科(Leguminosae)、茄科(Solanaceae)、禾本科(Graminae)、萝蘑科(Asclepiadaceae)或葫芦科(Cucurbitaceae)、角叉菜属(Chondrus)、海萝属(Gloiopeltis)、仙菜属(Ceramium)、杜尔维勒属(Durvillea)、大豆属(Glycine max)、地榆属(Sanguisorba officinalis)、金盏花属(Calendula officinalis)、金缕梅属(Hamamelis virginiana)、蒙大纳山金车属(Arnica montana)、白柳属(Salix alba)、贯叶连翘属(Hypericum perforatum)或匙羹藤属(Gymnema sylvestre)的提取物。
清凉剂
所述组合物还可含有一种或多种具有生理清凉作用的物质(清凉剂),其优选自以下列表:薄荷醇和薄荷醇衍生物(例如L‐薄荷醇、D‐薄荷醇、外消旋薄荷醇、异薄荷醇、新异薄荷醇、新薄荷醇)、薄荷基醚(例如(I‐薄荷氧基)‐1,2‐丙二醇、(I‐薄荷氧基)‐2‐甲基‐1,2‐丙二醇、I‐薄荷基‐甲醚)、薄荷酯(例如甲酸薄荷酯、乙酸薄荷酯、异丁酸薄荷酯、乳酸薄荷酯、L‐乳酸L‐薄荷酯、D‐乳酸L‐薄荷酯、(2‐甲氧基)‐乙酸薄荷酯、(2‐甲氧基乙氧基)乙酸薄荷酯、焦谷氨酸薄荷酯)、碳酸薄荷酯(例如丙二醇碳酸薄荷酯、乙二醇碳酸薄荷酯、甘油碳酸薄荷酯或其混合物)、薄荷醇与二元羧酸的半酯或其衍生物(例如琥珀酸单薄荷酯、戊二酸单薄荷酯、丙二酸单薄荷酯、O‐薄荷基琥珀酸酯‐N,N‐(二甲基)酰胺、O‐薄荷基丁二酸酯酰胺)、薄荷烷羧酸酰胺(在这种情况下优选如US 4,150,052中所描述的薄荷烷羧酸‐N‐乙酰胺[WS3]或NΑ‐(薄荷烷羰基)甘氨酸乙酯[WS5]、如WO2005049553A1中描述的薄荷烷羧酸‐N‐(4‐氰基苯基)酰胺或薄荷烷羧酸‐N‐(4‐氰基甲基苯基)酰胺、甲烷羧酸‐N‐(烷氧基烷基)酰胺类)、薄荷酮和薄荷酮衍生物(例如L‐薄荷酮甘油缩酮)、2,3‐二甲基‐2‐(2‐丙基)‐丁酸衍生物(例如2,3‐二甲基‐2‐(2‐丙基)‐丁酸‐N‐甲酰胺[WS23])、异胡薄荷醇或其酯(I‐(‐)‐异胡薄荷醇、I‐(‐)‐异胡薄荷醇乙酸酯)、薄荷烷衍生物(例如P‐薄荷烷‐3,8‐二醇)、荜澄茄醇或含有荜澄茄醇的合成或天然混合物、环烷基二酮衍生物的吡咯烷酮衍生物(例如3‐甲基‐2(1‐吡咯烷基)‐2‐环戊烯‐1‐酮)或四氢嘧啶‐2‐酮(例如WO2004/026840中描述的ICILINE或相关化合物)、其它甲酰胺(例如N‐(2‐(吡啶‐2‐基)乙基)‐3‐P‐薄荷烷甲酰胺或相关化合物)、(1R,2S,5R)‐N‐(4‐甲氧基苯基)‐5‐甲基‐2‐(1‐异丙基)环己烷‐甲酰胺[WS12]、草氨酸酯(优选EP2033688A2中描述的)。
抗微生物剂
适当的抗微生物剂原则上是对革兰氏阳性细菌有效的所有物质,例如4‐羟基苯甲酸及其盐和酯、N‐(4‐氯苯基)‐N'‐(3,4‐二氯苯基)脲、2,4,4'‐三氯‐2'‐羟基‐二苯基醚(三氯生)、4‐氯‐3,5‐二甲基‐苯酚、2,2'‐亚甲基双(6‐溴‐4‐氯苯酚)、3‐甲基‐4‐(1‐甲基乙基)苯酚、2‐苄基‐4‐氯‐苯酚、3‐(4‐氯苯氧基)‐1,2‐丙二醇、丁基氨基甲酸3‐碘‐2‐丙炔酯、氯己定、3,4,4'‐三氯碳酰替苯胺(TTC)、抗菌芳香剂、麝香草酚、麝香草油、丁香酚、丁香油、薄荷醇、薄荷油、金合欢醇、苯氧乙醇、甘油单癸酸酯、单辛酸甘油酯、月桂酸单甘油酯(GML)、双甘油单癸酸酯(DMC)、水杨酸N‐烷基胺,例如,正辛基水杨酰胺或正癸基水杨酰胺。
酶抑制剂
适当的酶抑制剂是例如酯酶抑制剂。这些酶抑制剂优选为柠檬酸三烷酯,例如柠檬酸三甲酯、柠檬酸三丙酯、柠檬酸三异丙酯、柠檬酸三丁酯和,特别是,柠檬酸三乙酯(Hydagen CAT)。上述物质抑制酶活性,由此减少气味的生成。适合作为酯酶抑制剂的其它物质为甾醇硫酸酯或甾醇磷酸酯,例如,羊毛甾醇硫酸酯或磷酸酯、胆固醇硫酸酯或磷酸酯、菜油甾醇硫酸酯或磷酸酯、豆甾醇硫酸酯或磷酸酯和谷甾醇硫酸酯或磷酸酯;二羧酸和其酯,例如戊二酸、戊二酸单乙酯、戊二酸二乙酯、己二酸、己二酸单乙酯、己二酸二乙酯、丙二酸和丙二酸二乙酯;羟基羧酸及其酯,例如柠檬酸、苹果酸、酒石酸或酒石酸二乙酯,以及甘氨酸锌。
气味吸收剂和止汗活性剂
适当的气味吸收剂是能够吸收并在很大程度上保留形成味道的化合物的物质。它们降低各成分的分压,由此还可降低其扩散速率。重要的是在该过程中芳香剂必须保持未受损害。气味吸收剂对细菌没有作用。它们含有例如作为主成分的蓖麻油酸的复合锌盐,或作为“固香剂”为本领域技术人员所知晓的特定的主要中和气味的芳香剂,例如,岩蔷薇或苏合香的提取物或一些松香酸衍生物。气味掩蔽剂为芳香剂或芳香油,除了其作为气味掩蔽剂的功能之外,还向除臭剂提供其各自香味。可以提及的芳香油是例如天然和合成芳香剂的混合物。天然芳香剂为花、茎和叶、果实、果皮、根、木材、草本植物和禾本植物、松针和树枝以及树脂和香脂的提取物。还适当的是动物产品,例如麝猫香和海狸香。典型的合成芳香化合物为酯、醚、醛、酮、醇和烃类产物。酯类芳香剂化合物是例如,乙酸苄基酯、乙酸P‐叔丁基环己酯、乙酸芳樟酯、乙酸苯乙酯、苯甲酸芳樟酯、甲酸苄酯、环己基丙酸烯丙酯、丙酸苏合香酯和水杨酸苄酯。醚类包括,例如苄基乙基醚;醛类包括,例如含有8至18个碳原子的直链烷醛、柠檬醛、香茅醛、香茅基氧基乙醛、仙客来醛、羟基香茅醛、铃兰醛和波洁红醛(bourgeonal);酮包括,例如紫罗兰酮和甲基柏木酮;醇包括茴香脑、香茅醇、丁香酚、异丁香酚、香叶醇、芳樟醇,苯乙醇和松油醇;烃类主要包括萜烯和香脂。然而,优选使用不同芳香剂化合物的混合物,它们一起产生令人愉快的香味。通常用作芳香成分的挥发性较低的精油也适用作芳香油,例如鼠尾草油、甘菊油、丁香油、蜂花油、薄荷油、肉桂叶油、椴树花油、杜松子油、香根草油、乳香油、白松香油(galbanum oil)、岩蔷薇油和熏衣草油。优选单独使用或以混合物使用佛手柑油、二氢月桂烯醇、铃兰醛、新铃兰醛、香茅醇、苯乙醇、α‐己基肉桂醛、香叶醇、苄丙酮、仙客来醛、芳樟醇、乙氧基甲氧基环十一烷(boisambreneforte)、龙涎呋喃、吲哚、二氢茉莉酮酸甲酯、sandelice、柠檬油、柑橘油、橙油、异戊氧基乙酸烯丙酯、cyclovertal、熏衣草油、鼠尾草油、β‐大马酮、波旁香叶油、水杨酸环己酯、Vertofix Coeur、Iso‐E‐Super、Fixolide NP、evernyl、iraldein gamma、苯乙酸、乙酸香叶酯、乙酸苄酯、玫瑰醚、romilat、2‐乙基‐己酸乙酯(irotyl)和2‐叔丁基环己基乙基碳酸酯(floramat)。
适当的收敛止汗活性成分主要是铝,锆或锌的盐。这类适当的antihydrotic活性成分是例如,氯化铝、氢氯酸铝、二氢氯酸铝、倍半氢氯酸铝及其络合物,例如与1,2‐丙二醇的络合物、尿囊素羟基铝(aluminium hydroxyallantoinate)、酒石酸氯化铝、三氢氯酸铝锆、四氢氯酸铝锆、五氢氯酸铝锆及其络合物,例如与氨基酸如甘氨酸的络合物。
成膜剂和抗头皮屑剂
标准成膜剂是例如,壳聚糖、微晶壳聚糖、季铵壳聚糖、聚乙烯吡咯烷酮、乙烯基吡咯烷酮/乙酸乙烯酯共聚物、丙烯酸系聚合物、季纤维素衍生物、胶原、透明质酸及其盐和类似化合物。
适当的抗头皮屑剂是Pirocton Olamin(1‐羟基‐4‐甲基‐6‐(2,4,4‐三甲基戊基)‐2‐(1H)‐吡啶酮单乙醇胺盐)、(氯咪巴唑)、(4‐乙酰基‐1‐{4‐[2‐(2,4‐二氯苯基)r‐2‐(1H‐咪唑‐1‐基甲基)‐1,3‐二氧戊(dioxylan)‐c‐4‐基甲氧基苯基}‐哌嗪、酮康唑、新康唑、二硫化硒、胶体硫、硫聚乙二醇脱水山梨醇单油酸酯、硫蓖麻醇聚乙氧基化物、硫磺焦油馏分、水杨酸(或结合六氯酚)、十一碳烯酸、单乙醇酰胺磺基琥珀酸钠盐、UD(蛋白质/十一烯酸浓缩物)、吡啶硫酮锌、吡啶硫酮铝和吡啶硫酮镁/双吡硫翁硫酸镁。
载体和助水溶物
优选的化妆品载体材料在25℃和1013mbar下为固体或液体(包括高粘度物质),例如甘油、1,2‐丙二醇、1,2‐丁二醇、1,3‐丙二醇、1,3‐丁二醇、乙醇、水以及两种或多种所述液体载体物质与水的混合物。任选地,本发明的这些制剂可使用防腐剂或助溶剂制备。可作为本发明制剂的成分的其它优选的液体载体物质选自组包括油类,例如植物油、中性油和矿物油。
可作为本发明制剂的成分的优选的固体载体物质为水胶体,例如淀粉、降解淀粉、化学或物理改性淀粉、糊精、(粉末状)麦芽糊精(优选地具备葡糖值为5至25,优选10‐20)、乳糖、二氧化硅、葡萄糖、改性纤维素、阿拉伯树胶、印度树胶、胺黄树胶、梧桐胶、卡拉胶、普鲁兰多糖、凝胶多糖、黄原胶、结冷胶、瓜尔豆胶、角豆粉、藻酸盐、琼脂、果胶和菊粉以及两种或两种以上这些固体物质的混合物,特别是,麦芽糊精(优选地,葡糖值为15至20)、乳糖,二氧化硅和/或葡萄糖。
此外,助水溶物,例如乙醇、异丙醇或多元醇,可用于改善流动性。适当的多元醇优选含有2至15个碳原子和至少两个羟基。这种多元醇可含有其它官能团,更具体地为氨基,或可被氮修饰。典型实例为:
·甘油;
·烷二醇,例如乙二醇、二乙二醇、丙二醇、丁二醇、己二醇和平均分子量为100至1000道尔顿的聚乙二醇;
·自缩合度为1.5至10的寡甘油技术混合物,如二甘油含量为40至50重量%的二甘油技术混合物;
·羟甲基化合物,特别是,例如三羟甲基乙烷、三羟甲基丙烷、三羟甲基丁烷、季戊四醇和二季戊四醇;
·低级烷基糖苷,尤其是烷基中含有1至8个碳原子的那些烷基糖苷,例如甲基糖苷和丁基糖苷;
·含有5至12个碳原子的糖醇,例如山梨醇或甘露糖醇;
·含有5至12个碳原子的糖,例如葡萄糖或蔗糖;
·氨基糖,例如葡糖胺;
·二醇胺,例如二乙醇胺或2‐氨基丙烷‐1,3‐二醇。
防腐剂
适当的防腐剂是例如,苯氧基乙醇、甲醛溶液、对羟基苯甲酸酯类、戊二醇或山梨酸以及Kosmetikverordnung(“化妆品指南”)中附录6,A和B部分中列举的其它类别的化合物。
芳香油和香料
适当的芳香油是天然芳香剂与合成芳香剂的混合物。天然芳香剂包括花(百合、薰衣草、玫瑰、茉莉、橙花、依兰)、茎和叶(天竺葵、广藿香、苦橙)、果实(茴香、胡荽、香菜、杜松)、果皮(佛手柑、柠檬、橙)、根(肉豆蔻、当归、芹菜、小豆蔻、木香、虹膜、菖蒲)、木材(松木、檀香、愈创木、雪松木、花梨木)、草本植物和禾本植物(龙蒿、柠檬草、鼠尾草、百里香)、松针和树枝(云杉、冷杉、松树、矮松)、树脂和香脂(格蓬、榄香脂、安息香、没药、乳香、红没药)的提取物。还可使用动物原料,例如麝猫香和海狸香。典型的合成芳香剂化合物是酯、醚、醛、酮、醇和烃类产物。酯类芳香剂化合物实例是乙酸苄酯,异丁酸苯氧基乙酯、环己基乙酸p‐叔丁酯、乙酸芳樟酯、乙酸二甲基苄基原酯(dimethyl benzyl carbinyl acetate)、乙酸苯乙酯、苯甲酸芳樟酯、甲酸苄酯、苯基甘氨酸乙基甲酯、环己基丙酸烯丙酯、丙酸苏合香酯和水杨酸苄酯。醚类包括,例如苄基乙基醚;而醛类包括,例如含有8至18个碳原子的直链烷醛、柠檬醛、香茅醛、香茅基氧基乙醛、仙客来醛、羟基香茅醛、铃兰醛和波洁红醛。适当的酮类的实例是紫罗兰酮、α‐异甲基紫罗酮和甲基柏木酮。适当的醇类是茴香脑、香茅醇、丁香酚、异丁香酚、香叶醇、芳樟醇、苯乙醇和松油醇。烃类主要包括萜烯类和香脂类。然而,优选使用不同芳香剂化合物的混合物,它们一起产生令人愉快的香味。其它适当的芳香油为大多用作芳香成分的挥发性较低的精油。实例是鼠尾草油、甘菊油、丁香油、蜂花油、薄荷油、肉桂叶油、莱姆花油、杜松子油、香根草油、乳香油、白松香油、岩蔷薇油和熏衣草油。以下为单独或以混合形式优选使用的物质:佛手柑油、二氢月桂烯醇、铃兰醛、新铃兰醛、香茅醇、苯乙醇、己基肉桂醛、香叶醇、苄丙酮、仙客来醛、芳樟醇、乙氧基甲氧基环十一烷、龙涎呋喃、吲哚、二氢茉莉酮酸甲酯(hedione)、sandelice、柑橘类精油、柑橘油、橙油、乙醇酸烯丙基戊酯、cyclovertal、醒目熏衣草油、鼠尾草油、大马酮、波旁香叶油、水杨酸环己酯、Vertofix Coeur、Iso‐E‐Super、Fixolide NP、evernyl、iraldein gamma、苯乙酸、乙酸香叶酯、乙酸苄酯、玫瑰醚、romilat、2‐乙基‐己酸乙酯(irotyl)和2‐叔丁基环己基乙基碳酸酯(floramat)。
染料
适合的染料是例如德国研究学会染料协会(Farbstoff‐kommission derDeutschen Forschungsgemeinschaft)的公开物“Kosmetische ”,VerlagChemie,Weinheim,1984,页81至106中列举的适于并批准用于化妆品的物质中的任何一种。实例包括胭脂红A(C.I.16255)、专利蓝V(C.I.42051)、靛蓝(C.I.73015)、叶绿酸(C.I.75810)、喹啉黄(C.I.47005)、二氧化钛(C.I.77891)、阴丹士林蓝RS(C.I.69800)和茜草红(C.I.58000)。鲁米诺(Luminol)也可用作荧光染料。有利的着色颜料是例如二氧化钛、云母、铁氧化物(例如Fe2O3、Fe3O4、FeO(OH))和/或氧化锡。有利的染料是例如胭脂红、柏林蓝、氧化铬绿、群青和/或锰紫。
制剂
本发明的优选组合物选自用于治疗、防护、护理和清洁皮肤和/或毛发的产品或作为化妆产品,优选地,作为滞留(leave‐on)产品(是指与洗去(rinse‐off)产品相比,一种或多种式(I)的化合物停留在皮肤和/或毛发上持续更长的时间,从而使其保湿和/或抗老化和/或伤口治愈的促进作用更显著)。
本发明的制剂优选以乳剂形式,例如W/O(油包水)、O/W(水包油)、W/O/W(水包油包水)、O/W/O(油包水包油)乳剂、PIT乳剂、皮克林(Picking)乳剂、油含量低的乳剂、微米乳剂或纳米乳剂;溶液,例如在油(脂肪油或脂肪酸酯,特别是C6‐C32脂肪酸C2‐C30酯)或硅油、分散体、悬浮液、乳霜、乳液或奶液中的溶液,取决于制备方法和成分;凝胶(包括水凝胶、水分散凝胶、油凝胶);喷雾剂(例如泵喷雾剂或含有推进剂的喷雾剂)或用于擦拭化妆品的泡沫或浸渍溶液;洗涤剂,如肥皂、合成洗涤剂、洗涤液、淋浴和沐浴制剂、沐浴产品(胶囊、油剂、片剂、盐、浴盐、肥皂等);泡腾制剂、皮肤护理产品,如乳剂(如上所述)、软膏剂、糊剂、凝胶(如上所述)、油、香油、乳清、粉末(如擦脸粉、身体粉)、面膜、眉笔、唇膏、走珠、泵剂、气雾剂(发泡、非发泡或后发泡)、除臭剂和/或止汗剂、漱口水和口腔清洗剂、足部护理产品(包括去角质、除臭剂)、驱虫剂、防晒霜、晒后用品、剃须产品、须后膏、剃须前和剃须后洗剂、脱毛剂、头发护理产品,如洗发香波(包括2合1香波,去屑香波,婴儿香波,干性发质香波,浓缩香波)、护发素、生发油、生发水、染发液、造型膏、润发油、烫发和卷发药水、发胶、定型助剂(如凝胶或蜡)、头发光滑剂(护发剂、松弛剂)、染发剂如短时直接染发剂、半永久性染发剂、永久性染发、护发素、护发摩丝、眼睛护理产品、化妆、卸妆或婴儿产品。
本发明的制剂尤其优选以乳剂形式,特别是W/O、O/W、W/O/W、O/W/O乳剂形式、PIT乳剂、皮克林乳剂、油含量低的乳剂、微米乳剂或纳米乳剂、凝胶(包括水凝胶、水分散凝胶、油凝胶)、溶液,例如在油(脂肪油或脂肪酸酯,特别是C6‐C32脂肪酸C2‐C30酯)或硅油中的溶液、或喷雾剂(例如泵喷雾剂或具有推进剂的喷雾剂)。
辅助物质和添加剂的含量为占总重量5至99%,优选10至80%,基于制剂总量计。本领域技术人员容易根据特定产品的性质通过简单试凑法确定在各情况下所使用的化妆品或护肤用品助剂和添加剂以及芳香剂的的量。
所述制剂还可含有占总重量99%,优选地,5至80%的水,基于制剂总量计。
药物
本发明的另一个目的涉及一种用于保护、防止、处理和/或治疗与
(a)空气污染诱导的基因表达,和/或
(b)多环芳香烃诱导或可诱导的基因表达,和/或
(c)空气污染诱导或空气污染可诱导的皮肤损伤
相关的人类皮肤和/或毛发失调和官能不调的药物,其含有选自组包括姜根CO2提取物、E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮、香紫苏内酯、紫色黄雏菊榨汁,特别优选姜根CO2提取物或上述优选的二元或三元混合物的抗污染制剂。
特别地,保护和防止空气污染诱导的皮肤和/或毛发失调和官能不调特别是指抑制
1)POMC基因诱导,并从而保护皮肤细胞抵抗过量黑素形成,和/或
2)皮肤中MMP1(基质金属蛋白酶‐1)诱导以保护皮肤抵抗皱纹的增多形成,和/或
3)IL‐6(白细胞介素‐6)诱导以保护皮肤细胞抵抗炎症以及色斑形成,其中炎症特别地不基于真菌感染和/或
4)CYP1A1基因表达以保护皮肤细胞抵抗由于AhR活化,特别是颗粒诱导的CYP1A1基因表达的损伤。
非治疗方法
本发明的另一个主题涉及一种用于保护人类皮肤和/或毛发抵抗空气污染诱导的损伤的非治疗方法,通过施用有效量的至少一种选自组包括姜根CO2提取物、E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮、香紫苏内酯、紫色黄雏菊榨汁,特别优选姜根CO2提取物或上述优选的二元或三元混合物的抗污染制剂。
优选地,将0.1mg/cm2至约5mg/cm2,优选2mg/cm2至3mg/cm2的制剂,其含有约0.1重量%至0.5重量%,优选0.3重量%至0.5重量%所述的本发明的活性制剂,施用至人类皮肤和/或毛发,其中所述制剂的有效量为约8μg/cm2至约10μg/cm2。
用途
本发明的最后的一个主题是一种选自组包括姜根CO2提取物、E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮、香紫苏内酯、紫色黄雏菊榨汁,特别优选姜根CO2提取物或上述优选的二元或三元混合物的抗污染制剂用于保护人类皮肤和/或毛发抵抗空气污染的用途。
特别地,保护人类皮肤和/或毛发抵抗空气污染是指通过诱导某些基因诱导的空气污染,其导致黑素形成和/或皱纹形成和/或炎症,色斑形成,其中炎症特别地不基于真菌感染和/或与AhR活化—通过CYP1A1基因上调节,特别是颗粒诱导的CYP1A1基因表达测定—相关的疾病。
因此更优选地本发明涉及选自组包括姜根CO2提取物、E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮、香紫苏内酯、紫色黄雏菊榨汁,特别优选姜根CO2提取物或上述优选的二元或三元混合物的抗污染制剂用于保护和/或抑制和/或减少人类皮肤和/或毛发失调和官能不调,其分别与POMC基因诱导和/或MMP1基因诱导和/或IL‐6基因诱导和/或颗粒诱导的CYP1A1基因表达相关,此处特别优选姜根CO2提取物。
本发明的一个特别优选方面是上述优选的二元或三元混合物用于保护和/或抑制和/或减少人类皮肤和/或毛发失调和官能不调,其分别与POMC基因表达诱导和/或MMP1基因表达诱导和/或IL‐6基因表达诱导和/或颗粒诱导的CYP1A1基因表达相关,特别优选含有姜根CO2提取物和香紫苏内酯或E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮的二元混合物,并且特别优选含有姜根CO2提取物和香紫苏内酯的二元混合物。
优选地,将0.1mg/cm2至约5mg/cm2,优选2mg/cm2至3mg/cm2的制剂,其含有约0.1重量%至0.5重量%,优选0.3重量%至0.5重量%所述的本发明的活性制剂,施用至人类皮肤和/或毛发,其中所述制剂的有效量为约8μg/cm2至约10μg/cm2。
本发明的另一个主题是选自姜根CO2提取物、E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮、香紫苏内酯、紫色黄雏菊榨汁的化合物,特别优选姜根CO2提取物或上述二元混合物或上述三元混合物分别作为抗污染制剂和抗污染混合物,用于保护人类皮肤和毛发,特别是保护和/或抑制和/或减少人类皮肤和/或毛发失调和官能不调,其分别与POMC基因表达诱导和/或MMP1基因表达诱导和/或IL‐6基因表达诱导和/或颗粒诱导的CYP1A1基因表达相关的用途。特别地优选姜根CO2提取物或含有姜根CO2提取物和香紫苏内酯或E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮的二元混合物或优选含有姜根CO2提取物和香紫苏内酯和紫色黄雏菊榨汁的三元混合物。
本发明的另一个主题是含量为约0.01重量%至约2.5重量%,优选约0.05重量%至约1.0重量%的至少一种选自组包括姜根CO2提取物、E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮、香紫苏内酯、紫色黄雏菊榨汁,特别优选姜根CO2提取物或如上所述这些制剂的二元混合物或三元混合物在化妆品组合物中分别作为抗污染制剂和抗污染混合物,用于保护人类皮肤和毛发,特别是保护和/或抑制和/或减少人类皮肤和/或毛发失调和官能不调,其分别与POMC基因表达诱导和/或MMP1基因表达诱导和/或IL‐6基因表达诱导和/或颗粒诱导的CYP1A1基因表达相关的非治疗用途。特别优选姜根CO2提取物或含有姜根CO2提取物和香紫苏内酯或E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮的二元混合物或优选含有姜根CO2提取物和香紫苏内酯和紫色黄雏菊榨汁的三元混合物。
实施例
___________________________________________________________________________
实施例1
模型颗粒
由不同模型颗粒诱导的基因表达。SRM 1650b和SRM 2975是真实街道颗粒物质的替代品(Danielson et al,2008)。细炭黑是用于室内污染,例如激光打印机的颗粒的模型颗粒。细节列于表1:
表1
体外使用的模型颗粒以诱导基因表达或蛋白质的生物合成
实施例2
E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮的抗空气污染活性
在不含BPE和EGF的角化细胞介质中培养成年人类表皮角质化细胞24h,随后加入模型颗粒(参见表1.1)。将模型颗粒悬浮于磷酸盐缓冲盐水并超声处理1分钟,随后直接将其以1.5μg/cm2加入角质化细胞。将E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮(BDDI)溶解于DMSO并在介质中稀释。施用含有化合物和最多0.1%DMSO的溶液,2h后用模型颗粒处理。通过qRT‐PCR分析基因表达。对于各个基因,设计特定的PCR引物对并在表2总结:
表2
用于RT‐PCR的特定引物对(正向/反向)
CYP1A1:细胞色素P450 1A1;IL‐6:白细胞介素6;POMC:阿黑皮素原;MMP1:基质金属蛋白酶1
下表3和4示出用室外和室内颗粒诱导后CYP1A1基因表达结果,表5是POMC、IL‐6和MMP1表达。
表3:用室外颗粒诱导后CYP1A1基因表达
表4:用室内颗粒诱导后CYP1A1基因表达
表5:POMC,IL‐6和MMP1基因表达
E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮能够抑制颗粒诱导的Cyp1A1基因表达。对于室内和室外模型颗粒同样示出。E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮也可以抑制颗粒诱导的POMC、IL‐6和MMP1基因表达。
实施例3:
香紫苏内酯的抗空气污染活性
在不含BPE和EGF的角化细胞介质中培养成年人类表皮角质化细胞24h,随后加入模型颗粒(参见表1.1)。将模型颗粒悬浮于磷酸盐缓冲盐水并超声处理1分钟,随后将其以1.5μg/cm2加入角质化细胞。将香紫苏内酯溶解于DMSO并在介质中稀释。施用含有化合物和最多0.1%DMSO的溶液,2h后用模型颗粒处理。通过qRT‐PCR分析基因表达。对于各个基因,设计特定的PCR引物(参见表2)。表6总结了香紫苏内酯改变POMC基因表达的结果。
表6:香紫苏内酯改变POMC基因表达
香紫苏内酯能够抑制颗粒诱导的POMC基因表达。
实施例4a
姜根CO2提取物的抗空气污染活性
I)在不含BPE和EGF的角化细胞介质中培养成年人类表皮角质化细胞24h,随后加入模型颗粒(参见表1.1)。将模型颗粒悬浮于磷酸盐缓冲盐水并超声处理1分钟,随后将其以1.5μg/cm2直接加入角质化细胞。将姜根CO2提取物溶解于DMSO并在介质中稀释。施用含有化合物和最多0.1%DMSO的溶液,2h后用模型颗粒处理。通过qRT‐PCR分析基因表达。对于各个基因,设计特定的PCR引物对(参见表2)。表7总结了姜根CO2提取物改变POMC和IL‐6基因表达的结果。
表7:姜根CO2提取物改变的POMC和IL‐6基因表达
姜根CO2提取物能够抑制颗粒诱导的POMC和IL‐6基因表达。
II)在RPMI中培养HaCaT角质形成细胞24h,随后加入模型颗粒(参见表1.1)。将模型颗粒悬浮于磷酸盐缓冲盐水并超声处理1分钟,随后将其以3.75μg/cm2直接加入HaCaT角质形成细胞。将姜根CO2提取物溶解于DMSO并在介质中稀释。施用含有化合物和最多0.1%DMSO的溶液,2h后用模型颗粒处理。表8总结了姜根CO2提取物改变IL‐1α、IL‐6和IL‐8蛋白质表达的结果。
表8:姜根CO2提取物改变IL‐1‐α、IL‐6和IL‐8蛋白质表达
姜根CO2提取物能够抑制颗粒诱导的IL‐1α、IL‐6和IL‐8蛋白质表达。
实施例4b
姜根CO2提取物对于毛发的抗空气污染活性
将由人类皮肤得到的毛囊纤维显微解刨并在培养液中保持20天。将模型颗粒SRM1649b悬浮、超声并以0.1mg/ml的浓度加入毛囊。姜根CO2提取物加入1天后,用模型污染物刺激。通过图像分析研究毛囊伸长,并且通过毛球的形态观察评估毛囊存活。
表9:姜根CO2提取物改变毛囊凋亡(特别优选姜根CO2提取物)
姜根CO2提取物能够抵抗颗粒诱导的毛囊凋亡。
表10:与第0天相比姜根CO2提取物改变毛囊伸长[μm]
姜根CO2提取物能够抵抗颗粒诱导的毛囊伸长。
实施例5
紫色黄雏菊榨汁的抗空气污染活性
在不含BPE和EGF的角化细胞介质中培养成年人类表皮角质化细胞24h,随后加入模型颗粒(参见表1.1)。将模型颗粒悬浮于磷酸盐缓冲盐水并超声处理1分钟,随后将其以1.5μg/cm2直接加入角质化细胞。将紫色黄雏菊榨汁直接溶解于介质。施用该溶液,2h后用模型颗粒处理。通过qRT‐PCR分析基因表达。对于各个基因,设计特定的PCR引物对(参见表2)。表11总结了紫色黄雏菊榨汁改变POMC和IL‐6基因表达的结果。
表11:紫色黄雏菊榨汁改变的POMC和IL‐6基因表达
紫色黄雏菊榨汁能够抑制颗粒诱导的POMC和IL‐6基因表达。
实施例6
二元混合物的抗空气污染活性
在不含BPE和EGF的角化细胞介质中培养成年人类表皮角质化细胞24h,随后加入模型颗粒(参见表1.1)。将模型颗粒悬浮于磷酸盐缓冲盐水并超声处理1分钟,随后将其以1.5μg/cm2直接加入角质化细胞。将姜根CO2提取物和香紫苏内酯的混合物直接溶解于介质。施用该溶液,2h后用模型颗粒处理。通过qRT‐PCR分析基因表达。对于各个基因,设计特定的PCR引物对(参见表2)。表12总结了姜根CO2提取物和香紫苏内酯二元混合物改变的POMC和IL‐6基因表达的结果。
表12:姜根CO2提取物和香紫苏内酯二元混合物改变的POMC和IL‐6基因表达
二元混合物能够抑制颗粒诱导的POMC和IL‐6基因表达。
实施例7至17:皮肤和毛发护理制剂
在下文本发明通过各种制剂实施例更详细地说明:
7=皮肤护理凝胶(SPF 6)
8=防晒乳液SPF 24(UVA/UVB平衡)
9=有色抗衰老膏剂,SPF 15
10=身体乳液,SPF 15
11=皮肤舒缓晚霜O/W
12=霜W/O
13=护肤安瓿
14=护肤油
15=沐浴露&香波
16=有色护肤棒剂SPF 50
17=发胶
在制剂实施例7–17中以下两种芳香油PFO1和PFO2用作芳香剂(DPG=二丙二醇)。
表A:玫瑰香味的芳香油PFO1(用量以份数计)
表B:具备白花香和麝香的芳香油PFO2(用量以份数计)
表9:空气污染保护组合物
序列表
<110> 西姆莱斯股份公司
<120> 化妆品组合物
<130> C 3485 EP
<160> 10
<170> BiSSAP 1.3
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<211> 22
<212> DNA
<213> 巨大芽孢杆菌
<400> 1
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<210> 2
<211> 21
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<213> 巨大芽孢杆菌
<400> 2
cattcttggc aaatgctttc g 21
<210> 3
<211> 24
<212> DNA
<213> 巨大芽孢杆菌
<400> 3
agatggtcaa ggagcactac aaaa 24
<210> 4
<211> 22
<212> DNA
<213> 巨大芽孢杆菌
<400> 4
gctcaatcag gctgtctgtg at 22
<210> 5
<211> 20
<212> DNA
<213> 巨大芽孢杆菌
<400> 5
cctcgagccc accgggaacg 20
<210> 6
<211> 22
<212> DNA
<213> 巨大芽孢杆菌
<400> 6
aactggaccg aaggcgcttg tg 22
<210> 7
<211> 18
<212> DNA
<213> 巨大芽孢杆菌
<400> 7
tggaagtgcg tggctggt 18
<210> 8
<211> 19
<212> DNA
<213> 巨大芽孢杆菌
<400> 8
tgcactccag caggttgct 19
<210> 9
<211> 21
<212> DNA
<213> 巨大芽孢杆菌
<400> 9
tgaaaggtgg accaacaatt t 21
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<212> DNA
<213> 巨大芽孢杆菌
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ccaagagaat ggccgagttc 20
Claims (15)
1.一种化妆品组合物,含有选自组包括姜根CO2提取物、E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮、香紫苏内酯、紫色黄雏菊榨汁或其混合物的抗污染制剂,其含量足以
(a)减小或防止空气污染诱导的基因表达,和/或
(b)减小或防止多环芳香烃诱导或可诱导的基因表达,和/或
(c)减小或防止空气污染诱导或空气污染可诱导的皮肤损伤。
2.根据权利要求1所述的组合物,其中皮肤损伤是皮肤癌、皮肤炎症或过度色素沉着。
3.根据权利要求1所述的组合物,含有
(i)姜根CO2提取物和香紫苏内酯,或
(ii)姜根CO2提取物和E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮,或
(iii)姜根CO2提取物和紫色黄雏菊榨汁的二元混合物。
4.根据权利要求1所述的组合物,含有
(i)姜根CO2提取物、香紫苏内酯和紫色黄雏菊榨汁,或
(ii)姜根CO2提取物、E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮和香紫苏内酯,或
(iii)姜根CO2提取物、E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮和紫色黄雏菊榨汁的三元混合物。
5.根据权利要求1所述的组合物是个人护理组合物、皮肤护理组合物、毛发护理组合物或防晒组合物。
6.根据权利要求1所述的组合物是洗剂、霜剂、乳液、泡沫、摩斯、油剂或棒剂。
7.根据权利要求1所述的组合物,其中所述制剂的含量为约0.01至约2.5重量%,基于最终组合物计。
8.根据权利要求7所述的组合物,其中所述制剂的含量为约0.05重量%至约1.0重量%—基于最终组合物计。
9.根据权利要求1所述的组合物,还含有化妆可接受的载体。
10.根据权利要求3所述的组合物,其中所述化妆可接受的载体选自组包括水、C2‐C4醇、含有2至6个碳原子的多元醇和油体。
11.一种用于保护、处理和/或治疗人类皮肤和/或毛发抵抗
(a)空气污染诱导的基因表达,和/或
(b)多环芳香烃诱导或可诱导的基因表达,和/或
(c)空气污染诱导或空气污染可诱导的皮肤损伤的药物,其含有选自组包括姜根CO2提取物、E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮、香紫苏内酯、紫色黄雏菊榨汁或其二元或三元混合物的抗污染制剂。
12.一种用于保护人类皮肤和/或毛发抵抗空气污染诱导的损伤的非治疗方法,通过施用有效量的至少一种选自组包括姜根CO2提取物、E/Z‐2‐苄基茚‐5,6‐二甲氧基‐3,3‐二甲基茚满‐1‐酮、香紫苏内酯、紫色黄雏菊榨汁或其二元或三元混合物的抗污染制剂。
13.根据权利要求12所述的方法,其中将约0.1至约5mg/cm2有效量的所述制剂施用至人类皮肤和/或毛发。
14.姜提取物或根据权利要求3所述的二元混合物或根据权利要求4所述的三元混合物分别作为抗污染制剂和抗污染混合物用于保护人类皮肤和/或毛发的用途。
15.根据权利要求14所述的用途,所述制剂以约0.1至约5mg/cm2的有效量施用至人类皮肤和/或毛发。
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