CN114929194A - 包含类黑精的化妆品组合物 - Google Patents
包含类黑精的化妆品组合物 Download PDFInfo
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- CN114929194A CN114929194A CN202080088851.XA CN202080088851A CN114929194A CN 114929194 A CN114929194 A CN 114929194A CN 202080088851 A CN202080088851 A CN 202080088851A CN 114929194 A CN114929194 A CN 114929194A
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- melanoidin
- melanoidins
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Abstract
本申请涉及包含类黑精的化妆品组合物,其中所述类黑精具有200道尔顿至300kDa、优选1至300kDa且更优选1至100kDa,例如10至100kDa的重均分子量(Mw)。类黑精可通过或通过包括以下步骤的方法获得:a)提供包含类黑精的颗粒状食品;b)用pH大于7的水性提取剂溶液处理所述颗粒状食品,以通过使类黑精作为水相中的溶质而将其提取;c)将所述水相与所述残余的经处理的颗粒状食品进行物理分离;d)基于分子量分馏所述水相的分散或溶解组分;以及e)将所述经分馏的水相脱水以从中获得至少一种固体类黑精馏分。
Description
技术领域
本发明涉及类黑精在化妆品中的用途。更具体地,本发明涉及由分子量范围限定的类黑精在化妆品中的用途,该类黑精可从主要来源和诸如废咖啡渣的废物来源中提取。
发明背景
类黑精(melanoidins)是一类棕色、亲水性含氮聚合物,其在食品(如咖啡、可可、面包、麦芽、大麦、啤酒麦糟(Brewers Spent Grain)、大豆、肉类和蜂蜜)的热加工过程中形成,因此广泛分布于人类的饮食中。在这类食品的热加工过程中,氨基酸和还原糖(如醛糖和d-木糖)发生反应,形成所谓的初始美拉德(Maillard)反应产物。在持续加热的条件下,由这些初始美拉德反应产物的环化、脱水、逆醇醛缩合、重排、异构化和缩合形成类黑精。美拉德反应途径的复杂性导致了一系列最终反应产物,其中尤其是加热时间、加热类型、温度、系统的初始化学组成、含水量、水活性和pH是最终组成的决定因素。
举例来说,绿咖啡豆的烘焙过程可以表示为两个阶段的转化:i)豆类中游离水的蒸发;以及,ii)豆类内的热解,伴随着豆类的膨胀和变黑以及干重的损失。绿咖啡豆中存在的寡糖、多糖和蛋白质降解,然后可能参与美拉德反应。因此,在烘焙过程中,咖啡豆的化学组成发生了显著变化,其中类黑精是主要产物,但最终经烘焙的咖啡豆中也存在咖啡因和绿原酸。
技术分析表明,咖啡中的类黑精受到了极大的关注。当然,咖啡是相对富含类黑精的食品,含量高达28wt.%。咖啡酿造的类黑精是水溶性的,因此使得研究不太复杂;此外,鉴于全世界数百万人每天都在消费咖啡,咖啡具有巨大的商业价值。在此声明,虽然咖啡类黑精确实代表了本发明的优选重点,但本发明无意将衍生自其他食物来源的类黑精排除在本发明的范围之外。
虽然类黑精是发色团,即在给定组合物中是吸收特定波长的可见光并如此赋予所述组合物颜色的分子,但某些作者仅在化妆品组合物中间接使用了这种效用。
US 2003068286 A1(Stroud)描述了一种仿晒组合物,其包含0.01至10wt.%的1,3-二羟基丙酮(DHA)和0.01至10wt.%的3,5-二甲氧基-4-羟基苯甲醛。所应用的组合物不包含类黑精。相反,该引文提出,3,5-二甲氧基-4-羟基苯甲醛在皮肤上层产生橄榄绿颜色的类黑精,而DHA在皮肤上层产生橙棕色的类黑精,后者反应速率与3,5-二甲氧基-4-羟基苯甲醛大致相同。
US 2016128919 A1(Bjork)公开了一种用于涂抹皮肤暗化剂的装置,其中所述皮肤暗化剂选自:二羟基丙酮(DHA)、赤藓酮糖、指甲花、酪氨酸葡萄糖、乙酰酪氨酸、巴西木素、咖啡因、咖啡提取物、异丁基甲基黄嘌呤、甲基黄嘌呤、茶提取物、茶碱、靛红、四氧嘧啶、茚三酮、甘油醛、中酒石醛、戊二醛、4,5-二酮的吡唑啉衍生物、4,4-二羟基吡唑啉-5-酮的衍生物、或核桃提取物、可可提取物、香料提取物、水果提取物、蔬菜提取物和浆果提取物。施用的制剂不含类黑精,但认为皮肤内的氨基酸可能与施用的DHA反应形成类黑精发色团。
与这些引文相比,本发明涉及将类黑精直接包含在化妆品组合物中,其中所述类黑精可以全部或部分替代常用的有机颜料、矿物颜料和合成染料。例如,替代炭黑将是有益的,关于该种炭黑颜料对健康产生的有害影响,以及它衍生自尤其是不可再生的石炭纪资源的不完全燃烧,都存在争议。此外,在化妆品中替代偶氮染料将是有益的,因为某些类型的偶氮染料会引起过敏。此外,某些偶氮染料在紫外线辐射或皮肤微生物群落的作用下分解:芳香胺分解产物随后可能被皮肤吸收,这对皮肤是有害的。
本领域技术人员将进一步认识到,化妆品中发现的有机合成染料,即“FD&C”或“D&C”合成染料,通常作为煤焦油衍生物或从石油精炼中获得。这些是不可再生资源。此外,尽管此类有机合成染料可例如经美国食品和药物管理局认证使用,但这并不排除染料含有痕量的有毒重金属。本发明人已经认识到,从可再生资源和/或废弃食品中获得用于化妆品应用的类黑精着色剂将是一个巨大的益处。在这种情况下,据Mussatto等人,Separation andPurification Technology 83:173–179,2011所述,全世界近50%的咖啡生产被加工用于可溶性咖啡制备,这每年产生约600万吨的废咖啡渣。这种废咖啡渣将是一种极具吸引力的化妆品着色剂源材料。
Rodríguez等人,“Isolation and Characterization of Melanoidins fromDulce de Leche,A Confectionary Dairy Product”Molecules 2019,24,4163指出,类黑精可充当抗氧化剂,并可进一步表现出遗传毒性、细胞毒性和抗菌活性。例如,作者指出,类黑精可抑制病原菌的生长,如幽门螺杆菌(Helicobacter pylori)、大肠杆菌(Escherichiacoli)、蜡样芽孢杆菌(Bacillus cereus)、金黄色葡萄球菌(Staphylococcus aureus)、奇异变形杆菌(Proteus mirabilis)、铜绿假单胞菌(Pseudomonas aeruginosa)和鼠伤寒沙门氏菌(Salmonella typhimurium)。本发明人已经认识到,这些特性可以为将类黑精用作化妆品中的发色团提供补充活性,其中类黑精可以全部或部分替代添加的抗氧化剂和保鲜剂,例如甲醛、丁基化羟基甲苯(BHT)和丁基化羟基苯甲醚(BHA)。
发明内容
根据本发明的第一方面,提供了一种从食品中获得至少一种类黑精馏分的方法,所述方法包括以下步骤:
a)提供包含类黑精的颗粒状食品;
b)用pH大于7的水性提取剂溶液处理所述颗粒状食品,以将类黑精作为水相中的溶质而提取;
c)将所述水相从残余的经处理的颗粒状食品中物理分离;
d)基于分子量分馏所述水相的分散组分或溶解组分;以及
e)使所述经分馏的水相脱水以从中获得至少一种固体类黑精馏分。
颗粒状食品优选选自废咖啡渣和啤酒麦糟(BSG)。单独或附加地,在这种条件下,颗粒状食品可被微粉化。
在本发明的一个实施方案中,所述分馏步骤d)通过以下方式进行:使用分子量截留膜进行超滤;离心;或者,尺寸排阻色谱法。在另一个但并非互斥的实施方案中,所述脱水步骤e)通过以下至少一种方式进行:冷冻干燥;喷雾干燥;对流干燥;辐射干燥;以及真空干燥。
根据本发明的第二方面,提供了一种包含类黑精的化妆品组合物,其中所述类黑精具有200道尔顿(Da)至300千道尔顿(kDa)的重均分子量(Mw)。类黑精的重均分子量(Mw)为1至300kDa,优选1至100kDa,且更优选10至100kDa。例如,所述类黑精应具有10至30kDa、30至50kDa、或50至100kDa的重均分子量(Mw)。优选的是,化妆品组合物中包含的所述类黑精通过上文和所附权利要求中限定的方法获得。所包含的类黑精可以非包封的形式存在于组合物中。
上文和所附权利要求中定义的化妆品组合物可以是非粉末状的固体化妆品组合物、粉饼式化妆品组合物或水性液体化妆品组合物。化妆品组合物的说明性且重要的实施方案包括以下:水性染发组合物;水性纹身油墨组合物;以及固体组合物,其可以用作面部化妆品,特别是眼部化妆品。
在特别优选的实施方案中,上述化妆品组合物的特征在于基本上不含咖啡因。
定义
如本文所用,除非上下文另有明确规定,否则单数形式“一个(a)”、“一个(an)”和“该(the)”包括复数指示物。
如本文所用,术语“包含(comprising)”、“包含(comprises)”和“由...组成(comprised of)”与“包括(including)”、“包括(includes)”、“包含(containing)”或“包含(contains)”同义,并且是包含式或开放式的,不排除附加的未列出的成员、要素或方法步骤。如果使用,短语“由...组成(consisting of)”将是封闭式的,并排除所有附加要素。此外,短语“基本上由...组成(consisting essentially of)”排除了附加的材料要素,但允许包含不会实质性改变本发明性质的非材料要素。
当量、浓度、尺寸和其他参数以范围、优选的范围、上限值、下限值或优选的上限值和限值的形式表示时,应当理解,还具体公开了通过将任何上限或优选值与任何下限或优选值相结合而获得的任何范围,无论上下文中是否明确提及获得的范围。
此外,根据标准理解,表示为“从0到x”的重量范围具体包括0wt.%:由所述范围定义的成分可能不存在于组合物中,或可能以高达x wt.%的量存在于组合物中。
如本文经常使用的,词语“优选的(preferable)”、“优选的(preferred)”、“优选(preferably)”、“特别地(particularly)”和“期望地(desirably)”是指在某些情况下可提供特定益处的本发明的实施方案。然而,叙述一个或多个优选的、优选的、特别的或期望的实施方案并不意味着其他实施方案不可用,也不打算将这些其他实施方案排除在本发明的范围之外。
如在整个本申请书中使用的,词语“可以(may)”以允许的含义使用,这意味着有可能——而不是强制性意义上的。
如本文所用,室温为23℃±2℃。
如本文所用,根据DIN 55672-1:2007-08,以四氢呋喃(THF)为洗脱剂,通过凝胶渗透色谱法(GPC)测定数均分子量(Mn)和重均分子量(Mw)。
当用于指代食物时,术语“微粉化”意指粒径为1至1500微米,通常为100至1250微米的粉末。术语“微粉化”旨在是指:通过精细分割材料产生的颗粒,其最初以大块状形式(bulk form)呈现;以及通过其他机械、化学或物理方法获得的颗粒,包括在溶液中形成或不形成晶种,以及通过一种或多种粉碎、碾磨、研磨、均质和超声粉碎获得的颗粒。
例如,可以使用具有研磨室的行星球磨机进行研磨,该研磨室包括用于旋转研磨介质的转子轴。可参考以下文献:Le Caer等人,Mechanical Alloying and High-EnergyBall-Milling:Technical Simplicity and Physical Complexity for the Synthesisof New Materials www.ademe.fr/recherche/manifestations/materiaux—2002/.。
碾磨可以在任何高能磨机中进行,例如:离心磨机;行星球磨机;喷射磨机,如旋转气流喷射磨机;以及流体能量磨机。期望地,高能磨机应能够向碾磨介质施加至少0.5G(例如0.5至25G)的冲击力。本发明中可能有用的磨机的非限制性示例公开于:美国专利号5,522,558;美国专利号5,232,169;美国专利号6,126,097;以及美国专利号6,145,765中。此外,应注意,本发明不排除在热(如WO00/56486所述)和/或在添加剂(如润滑剂、表面活性剂、分散剂和溶剂)存在下进行碾磨。
典型的超声处理首先包括将所述颗粒添加到至少一种溶剂和任选的至少一种反应物中。所用溶剂(多种)应包含或由选自以下各项的非极性溶剂组成:烷烃(R-H);环烷烃;支链烷烃;芳烃(Ar-H);卤代烷(R-X);及其混合物。示例性但非限制性的非极性溶剂包括正戊烷、正己烷、环己烷、正庚烷、异辛烷、三甲基戊烷、甲苯、二甲苯和苯。优选存在除所述溶剂之外的反应物:反应物如甲硅烷化剂和有机官能化硅烷用于缓和在起始颗粒的超声处理和破碎期间产生的新生成颗粒表面,从而产生非反应性颗粒。
然后,将超声能量应用于形成的介质。正如本领域技术人员将认识到的那样,超声频率、超声时间和所用功率是最终粒径分布的关键决定因素。仅用于说明,可提及ColeParmer Instrument Company提供的MisoNix3000作为进行超声处理的示例性声波探头。
在粉碎后,粉碎步骤中存在的任何液体都可与颗粒分离。在这方面可以采用一个或多个分离工艺,例如空气干燥、加热、过滤和蒸发,但优选在加热到足够温度的情况下去除流体,以防止颗粒在其干燥过程中团聚。
如本文所用,“d50粒径”是指粒径分布使得至少50%(按重量计)的颗粒具有小于规定值的粒径直径。除非另有说明,否则粒径由动态光散射确定。
除非另有规定,否则根据ASTM D3236,使用布氏粘度计在25℃和50%相对湿度(RH)的标准条件下测量本文所述的组合物的粘度。布氏粘度计的校准方法、主轴类型和转速根据制造商的说明进行选择,以适合待测量的组合物。
根据《美国联邦食品、药品和化妆品法案》(经P.L.修订,107–377,2002年12月19日)中应用的定义,本文使用的术语“化妆品”作为“旨在人体上摩擦、倾倒、喷洒或喷涂、引入或以其他方式涂抹的制品……用于清洁、美化、提升吸引力或改变外观”。在其最广泛的公开中,本发明的化妆品组合物的形式不受特别限制,可以是液体、乳液、糊状物(paste)、凝胶、固体或粉饼(compact powder)。化妆品组合物的具体示例包括:洗面奶;面部护理,如润肤液、护肤乳、面霜、凝胶、精华素和面膜;面部和眼部化妆制剂,如扑面粉、粉底、唇膏、胭脂、眼线笔、睫毛膏、眼影和眉笔;纹身,包括永久性化妆;毛发化妆品组合物,如洗发水、漱口水、护发素、毛发定型剂、焗油膏(hair treatment)和染发剂。本文定义中特别包括:眼部和面部化妆制剂;纹身剂,包括永久性化妆;和染发剂。
本文中关于化妆品组合物使用的术语“固体”指的是室温和大气压下组合物的状态:组合物具有高稠度,在储存期间保持其形式,并且不会在自身重量下流动。
如本文所用,术语“结构化剂(structurant)”是指以任何已知的或以其他方式有效地为组合物提供悬浮、胶凝、增粘、固化和/或增稠特性的材料,或以其他方式为最终产品形式提供结构的那些材料。这些固体结构化剂包括一种或多种适于局部施用于人类皮肤的固体晶体或其他非聚合物悬浮剂。合适的悬浮剂是那些可以在组合物中形成结晶或其他基质的悬浮剂,该组合物中还含有挥发性溶剂、非挥发性溶剂或组合物的其他液体组分。此类材料通常在环境条件下为固体,包括有机固体、蜡、晶体或其他胶凝剂或其组合。结构化剂使颗粒状活性物均匀分布在整个产品中,并且还控制产品硬度或流变性。为完整性起见,适用于本文所公开的固体组合物中的晶体结构化剂特别在美国专利号5,552,136(Motley)、美国专利号5,976,514(Guskey等人)和美国专利号5,891,424(Bretzler等人)中进行了描述。
术语“粉饼”是指在制造过程中通过压实或压制至少部分提供内聚力(cohesion)的块状产品(a mass of product)。特别地,通过使用TA.XT.plus Texture Analyser质地计(可从Stable Micro Systems获得)进行测量,相对于所用主轴的表面积,粉饼应具有0.1至2.5kg的耐压力。通过将SMS P/3平头圆柱主轴(7.07mm2)以0.5mm/s的速度移动1.5mm的距离来测量该耐压力。
术语“纹身”是指哺乳动物身体上的不易消除的印记或图形,其通过使用针头、手术刀或其他相关设备在皮肤下插入色素而获得。该术语旨在包括表皮内纹身和真皮内纹身,这两种纹身尤其按其持久性区别。
如本文所用,“角质组织”是指被设置为哺乳动物最外层保护覆盖物的含角蛋白的层,其包括但不限于皮肤、毛发、指甲和角质层。没有特别的意图限制可应用本发明的化妆品组合物的角质组织的位点:可以提及暴露在面部、颈部、胸部、背部、手臂(包括腋下)、手、腿、脚、臀部和头皮上的角质组织。
如本文所用,术语“表皮”是指皮肤的外层,其主要细胞类型是角化细胞。正如本领域技术人员所理解的,表皮通常分为五层:角质层;颗粒层;棘层;和基底层。角质层通常被认为是不可存活的,并且含有许多层死掉的、无核的角化细胞,这些角化细胞基本上充满了角蛋白。透明层含有两到三层无核细胞。颗粒层包含两到四层细胞,这些细胞由含有透明角质颗粒的桥粒保持在一起。棘层包含八到十层适度活跃的分裂细胞,这些细胞也由桥粒保持在一起。基底层包含单层柱状细胞,这些细胞通过有丝分裂活跃分裂,并提供注定要通过上表皮层迁移到角质层的细胞。
如本文所用,术语“真皮”是指表皮和皮下组织之间的皮肤层。真皮为皮肤提供结构支撑,并包含衍生自成纤维细胞的非细胞胶原纤维。
本文中的术语“毛发”是指哺乳动物角蛋白纤维,包括头皮毛发、面部毛发和体毛发。此外,该术语还包括这样的毛发,包括附着在活体上的毛发,也包括从活体上去除的毛发。为完整起见,“毛发干”或“毛发纤维”是指单独的发束。
表述“头皮近端”意指延伸或基本拉直的毛发干中距离头皮比距离发梢更近的部分。因此,50%的毛发纤维长度将被视为靠近头皮,且50%的毛发纤维长度将被视为远离头皮。使用时,头皮近端的“x cm”意指从头皮作为端点开始测量的沿延伸或基本拉直的毛发的距离“x”。
“美容上可接受的”意指本文所述的组合物、制剂或组分适合与人类角质组织接触使用,而没有过度毒性、不相容性、不稳定性、过敏反应等。本文所述的所有旨在直接应用于角质组织的组合物和制剂仅限于美容上可接受的那些组合物和制剂。
如本文所用,术语“局部施用”意指将本发明的组合物施用或铺展到皮肤表面上。
本文中用作(共)溶剂的水旨在意指本领域普通技术人员所理解的低固体含量的水。例如,水可以是蒸馏水、脱矿物水、去离子水、反渗透水、锅炉冷凝水或超滤水。自来水在某些情况下是可以容忍的,但在本文所述的纹身油墨组合物中是不能容忍的。
如本文所用,“溶剂”是能够溶解另一种物质以形成均匀溶液的物质;在溶解过程中,溶剂和经溶解的物质都不会经历化学变化。溶剂可以是极性的或非极性的。术语“醇类溶剂”包括这样的溶剂,其是在25℃下在大气压力下为液体的任何水溶性单醇、二醇或多元醇。
如果有机液体产品具有沸点范围,则在大气压下沸点范围的起始点(最低温度)被视为标称沸点。如有必要,应根据ASTM标准测试方法D1078-95或其最新版本对材料的初始沸点进行任意测量。
如本文所用,术语“水可混溶的有机溶剂”是指在室温下与水完全混溶的有机溶剂。在这方面,可指出的特别优选的是可溶、自由可溶或极易溶于水的有机溶剂,由此其特征在于在室温下需要≤30ml的水以溶解1g的有机溶剂
(https://www.sigmaaldrich.com/united-kingdom/technical-services/ solubility.html)。
如本文所用,术语“水不混溶的有机溶剂”是指与水形成两相系统的有机溶剂。在这方面,可指出的特别优选的是微溶、极微溶或实际上不溶于水的有机溶剂,由此其特征在于在室温下需要≥100ml的水以溶解1g的有机溶剂
(https://www.sigmaaldrich.com/united-kingdom/technical-services/ solubility.html)。
如本文所用,术语“分散体”是指含有分布在连续液体介质中的离散颗粒的组合物。
如本文所用,术语“表面张力”是指增加液体表面或两种液体之间或液体与气体之间的界面的单位面积所需的力,通常以达因/厘米为单位。本文所述的表面张力是通过DuNoüy环法测量的,该方法使用Krüss USA,Matthews,N.C销售的EasyDyne张力计型号K20。
如本文所用,“C1-Cn烷基”是指包含1至n个碳原子的单价基团,其是烷烃的自由基,并且包括直链和支链有机基团。因此,“C1-C6烷基”是指包含1至6个碳原子的单价基团,其是烷烃的自由基,并且包括直链和支链有机基团。烷基的实例包括但不限于:甲基;乙基;丙基;异丙基;正丁基;异丁基;仲丁基;和叔丁基。在本发明中,此类烷基可为未取代的或可被一个或多个卤素取代。在适用的情况下,将在说明书中指出对给定取代基的偏好。
如本文所用,术语“C2-C6亚烷基”被定义为具有2至6个碳原子的饱和二价烃自由基。
本发明的组合物在本文中定义为“基本上不含”某些化合物、元素、离子或其他类似组分。术语“基本上不含”旨在意指化合物、元素、离子或其他类似组分未被故意添加到组合物中,并且至多仅以痕量存在,其对组合物的期望性质没有(不利)影响。示例性痕量按组合物的重量计为小于1000ppm。术语“基本上不含”包括那些实施方案,其中指定的化合物、元素、离子或其他类似组分完全不存在于组合物中,或不以可通过本领域一般使用的技术测量的任何量存在。
附图的简要说明
本发明将参考附图,其中:
图1示出了制备包含类黑精馏分的化妆品组合物的实施方案。
发明详述
本发明提供了以其分子量为特征的类黑精馏分在化妆品组合物中的用途。最广泛地说,所述类黑精的特征在于具有200道尔顿(Da)至300千道尔顿(kDa)的重均分子量(Mw)。类黑精可例如具有1至300kDa、例如1至200kDa、1至100kDa或期望的10至100kDa的重均分子量。例如,在期望特定色素或光吸收效果的情况下,使用具有更窄限定的分子量的类黑精馏分可能是可行的,例如10至30kDa、30至50kDa、50至100kDa或100至200kDa。还设想可能存在多于一种类黑精馏分:例如,可将基于具有10至30kDa的重均分子量的类黑精的第一馏分与基于具有50至100kDa或100至200kDa的重均分子量的类黑精的第二馏分组合在化妆品组合物中。
虽然本发明不排除获得所述类黑精馏分的其他手段,但本发明确实提供了一种用于从食品中获得至少一种类黑精馏分的方法,所述方法包括以下步骤:
a)提供包含类黑精的颗粒状食品;
b)用pH大于7的水性提取剂溶液处理所述颗粒状食品,以将类黑精作为水相中的溶质而提取;
c)将所述水相从残余的经处理的颗粒状食品中物理分离;
d)基于分子量分馏所述水相的分散组分或溶解组分;以及
e)使所述经分馏的水相脱水以从中获得至少一种固体类黑精馏分。
可提供给步骤a)的示例性颗粒状食品源包括咖啡、可可、面包、麦芽、大麦、啤酒麦糟(BSG)、大豆、肉类和蜂蜜。所述咖啡本身可由烘焙咖啡豆、咖啡渣、废咖啡渣(SCG)、咖啡银皮(CS)和粒状咖啡提取物组成。啤酒麦糟(SBG)是将用于生产啤酒和其他麦芽产品,如麦芽提取物和麦芽醋的经过发芽和干燥的谷物进行加工后留下的固体残留物,:虽然大麦是用于酿造的主要谷物,但啤酒也由小麦、玉米、大米、高粱和小米制成。废咖啡渣(SCG)是在用热水或蒸汽处理用于制备速溶咖啡的咖啡渣的过程中获得的残留物质。咖啡银皮(CS)是绿咖啡豆外层的一层薄皮,作为烘焙过程的副产品获得。
在本发明中,优选将颗粒状食品微粉化。单独或另外地,优选颗粒状食品选自废咖啡渣和啤酒麦糟(BSG)。
可能会注意到对微粉化废咖啡渣的特别偏好。关于该实施方案,本方法可以包括步骤b)之前的至少一个预处理步骤。例如,将废咖啡渣暴露在高于室温的温度条件下进行干燥可能是有利的,例如50至100℃。或者,或除此之外,可以对废咖啡渣进行脱脂。可使用合适的溶剂以提取渣中存在的至少一部分脂质和/或油:所述合适的溶剂可提及在这样的压力和温度条件下施加的二氧化碳,使其为超临界流体。
处理步骤b)可使用提供以下阶段性能的任何方法进行:(1)水性提取剂渗透到所提供或经预处理的颗粒的固体基质中;(2)溶质在水性提取剂中的溶解;(3)溶质从固体基质中扩散出去;以及(4)经提取的溶质的收集。合适的方法包括但不限于:离心;浸渍;渗滤;煎煮;回流提取;加压液体提取;超声辅助提取;微波辅助提取;脉冲电场提取;以及水蒸馏。例如,合适的离心方法可包括向颗粒状食品中添加水性提取剂,然后在5至30℃的温度下施加500至5000重力(G),持续5至60分钟的时间:然后可收集含有类黑精的上清液。在另一个示例中,可通过在100℃至200℃的温度下进行10至120分钟(例如20至60分钟)时间段的加压液体提取来处理颗粒状食品。
提高类黑精的扩散率和溶解性的因素将有助于它们的提取。在本文中,优选的是水性处理溶液的pH高于7但小于或等于12或小于或等于10。替代地或除那些优选的pH范围之外,水性处理溶液可为碱性溶液,包括以下至少一种:氢氧化钠;氢氧化钾;氨(NH3(aq));以及氢氧化钙。
不排除水可混溶的溶剂存在于水性提取剂溶液中。然而,此类水可混溶的溶剂不应构成大于20wt.%的水性提取剂溶液。
将水相从残留的经处理的颗粒状食品的水相中分离出来(步骤c))(通过例如过滤、沉淀或倾析)之后,基于其分子量将经分散的组分或经溶解的组分进行分馏。该分馏(其任选地可在水溶液或分散体的浓缩之前进行)可通过使用必需的分子量截留膜的超滤来实现,该技术产生多个渗余物,然后其可被进一步处理。分馏也可通过离心或尺寸排阻色谱法进行。应认识到,通过适当选择要分馏的化合物的最小分子量,可以从所获得的渗余物中基本上消除咖啡因(Mw 194da)。
然后对经分馏的产物(如上述的渗余物)进行除水步骤,以产生固体形式的类黑精馏分。可提及的合适的脱水方法包括:冷冻干燥;喷雾干燥;对流干燥;辐射干燥;以及真空干燥。所获得的固体类黑精馏分可呈现为平均粒径(d50)为1至500μm的颗粒。必要时,可粉碎颗粒团聚体,以达到该粒径。
如本文所附的图1所示,基于分子量分馏的经分离和干燥的类黑精与其他成分结合以获得化妆品组合物。在附图中,其他成分被确定为粘合剂、溶剂和添加剂:这并不旨在是限制性的,因为添加的成分的确切性质取决于化妆品组合物的类型和形式。任何添加的成分都应导致形成美容上可接受的组合物。
通过以预定的量简单混合各种组分以及任何辅助成分来配制本发明的组合物。这可以使用本领域已知的任何混合技术来进行。然而,当然,优选不要手动混合成分,而是通过机器(例如静态或动态混合器)混合,以确保颗粒状成分、油质成分(其中所述化妆品组合物为水包油乳液)、以及水和水性成分(其中所述化妆品组合物为油包水乳液)的均匀分散。
如有必要,可在应用前充分制备组合物。然而,在水性化妆品组合物的一个有趣的替代实施方案中,可首先通过将组分仅与所施用的组合物中存在的一部分水混合来获得浓缩的组合物:然后可在施用前不久用剩余的水稀释浓缩的组合物。人们认为,此类浓缩的组合物可制备并储存为单包装浓缩物(可仅通过用水稀释转化);或多组分浓缩物,其中必须将两种或更多种组分结合并稀释以形成根据本发明的完整发挥功能的组合物。任何稀释都可以通过在混合下添加水,特别是去离子水和/或脱矿物水来实现。该组合物可在冲洗流中同样地制备,从而将一个或多个浓缩物的流注入连续的水流中。
在以下示例性实施方案中描述了本发明的各种特征,其旨在是说明性的而非限制本发明。
示例性实施方案1:水性染发组合物
在本发明的一个重要实施方案中,提供了一种水性染发组合物,其包含:
a)类黑精,其中所述类黑精具有200道尔顿至300kDa、优选1至300kDa且更优选1至100kDa、例如10至100kDa的重均分子量;和
b)至少一种助剂,该助剂选自:润湿剂;溶胀剂;渗透剂;pH调节剂;表面活性剂;增稠剂;抗微生物剂;和加香剂。
优选从上文和所附权利要求书中定义的提取工艺中获得组分a)。例如,基于组合物的重量,本发明的染发组合物可包括:
5至20wt.%的a)类黑精,所述类黑精的重均分子量为200道尔顿至300kDa,优选1至300kDa,更优选1至100kDa,例如10至100kDa;
5至40wt.%的b)至少一种助剂,该助剂选自:润湿剂;溶胀剂;渗透剂;pH调节剂;表面活性剂;增稠剂;抗微生物剂;和加香剂;和,
40至90wt.%的水。
应注意的是,基于试剂或试剂的假定作用模式提供的益处来对组分b)进行分类。进行这种分类是为了方便:特定的化学成分,例如氨,例如可能提供多于一种益处或通过多于一种作用模式进行操作。
关于水性染发组合物,基于组合物的重量,优选所述组合物含有40至90wt.%、优选40至80wt.%、且更优选55至75wt.%的水。在替代的但并非相互排斥的表征中,水性染发组合物可通过0.005至50Pa.s(如使用布氏粘度计在25℃下测量的)的粘度来限定。
可单独或组合使用的示例性润湿剂包括但不限于:甘油;丙二醇;山梨醇;1,3-丁二醇;聚乙烯吡咯烷酮(PVP);聚乙二醇(PEG);聚丙二醇(PPG);PEG/PPG嵌段共聚物;和PEG/PPG无规共聚物。示例性的PEG/PPG无规共聚物为PEG/PPG–8/17。
示例性的溶胀剂包括氨和单乙醇胺(MEA)。当包括氨时,氨将以氨水溶液NH3(aq)的形式存在于本发明的水性组合物中,该氨水溶液包含氨在水中的弱碱性溶液,其在本领域中可称为氢氧化铵、氨水(ammonia water,)、氨液、氨水(aqua ammonia)、氨水溶液(aqueous ammonia)或简称为氨(ammonia)。而术语“氢氧化铵”表示一种碱,其组成为[NH4 +][OH-],实际上不可能分离NH4OH样品,因为这些离子在氨溶液的氨总量中不占很大一部分,除非在极稀的氨溶液的情况下。
可单独或组合使用的示例性渗透剂包括:具有C1-C6烷基的一元醇,例如乙醇、1-丙醇、2-丙醇、1-丁醇和2-丁醇;具有3至8个碳原子的多元醇,例如丙二醇、丁二醇、戊二醇、己二醇、己三醇、庚二醇、庚三醇、辛二醇、辛三醇、异戊二烯二醇、丙二醇、甘油和二甘醇单乙醚;所述多元醇的酯;室温下为液体的N-烷基吡咯烷酮,例如N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-丙基-2-吡咯烷酮、N-丁基-2-吡咯烷酮和N-环己基-2-吡咯烷酮;C2-C6亚烷基碳酸酯,如碳酸乙烯酯和碳酸丙烯酯;芳香醇,如苄醇、苄氧基乙醇、肉桂醇、对茴香醇、对甲基苄醇、苯氧基乙醇、苯氧基异丙醇、2-苄基乙醇和β-苯乙醇。优选可以提及的是2-丙醇、1,2-己二醇和苄醇。
pH调节剂的实例包括:无机酸,如磷酸;羟基羧酸,如乳酸、乙醇酸、柠檬酸、3-羟基丁酸、4-羟基丁酸、2-羟基丁二酸、2,3-二羟基丁二酸、3-羟基戊酸、5-羟基戊酸、6-羟基己酸、及其碱金属或碱土金属盐;氨;碱金属氢氧化物;碱金属碳酸盐;碱金属碳酸氢盐;碱土金属氢氧化物;碱土金属碳酸盐;和碱土金属碳酸氢盐。
基于组合物的重量,本发明的水性染发组合物通常包含高达10wt.%、例如高达5wt.%或高达3wt.%的表面活性剂。本文中可使用多种表面活性剂,以用于分散相的乳化和用于提供所施用的组合物的可接受的铺展,但理想的表面活性剂选自:阴离子表面活性剂;非离子表面活性剂;两性表面活性剂;非起泡表面活性剂;乳化剂;及其混合物。美国专利号6,280,757(McAtee等人)提供了关于合适的表面活性剂的指导性公开。
阴离子表面活性剂:可用于本发明的组合物中的阴离子表面活性剂的非限制性示例公开于美国专利号3,929,678(Laughlin等人)和美国专利号4,557,853。可以提及的阴离子表面活性剂选自:i)基于具有8至36个或8至24个碳原子的脂肪酸的脂肪酸皂盐;ii)单烷基、二烷基和三烷基磷酸盐;iii)肌氨酸盐,如月桂酰肌氨酸钠、肉豆蔻酰肌氨酸钠和椰油酰肌氨酸钠;iv)硫酸盐,包括烷基和烷基醚硫酸盐,其中可能提及十二烷基硫酸钠、十二烷基硫酸铵、月桂醇聚醚硫酸铵、月桂醇聚醚硫酸钠、十三烷醇聚醚硫酸钠、十六烷基硫酸铵和十六烷基硫酸钠;v)羟乙基磺酸盐,如月桂酰羟乙基磺酸钠和椰油酰羟乙基磺酸铵;vi)牛磺酸盐,如月桂酰甲基牛磺酸钠和椰油酰甲基牛磺酸钠;vii)乳酸盐,如月桂酰乳酸钠、三乙醇胺月桂酰乳酸盐和己酰基乳酸钠;viii)谷氨酸盐,如月桂酰谷氨酸钠、肉豆蔻酰谷氨酸钠和椰油酰谷氨酸钠;及其混合物。
非离子表面活性剂:在本发明中具有实用性的合适非离子表面活性剂包括:烷基葡萄糖苷;烷基聚葡萄糖苷;多羟基脂肪酸酰胺;烷氧基化脂肪酸酯;蔗糖酯;胺氧化物;及其混合物。例如,可以提及:C8-C14葡萄糖酰胺、C8-C14烷基聚葡萄糖苷、蔗糖椰酸酯、蔗糖月桂酸酯、月桂胺氧化物、椰胺氧化物及其混合物。
两性表面活性剂:如本文所用,术语“两性表面活性剂”也旨在包括两性离子表面活性剂。可单独或组合使用的有用两性表面活性剂包括但不限于:脂肪族仲胺和叔胺的衍生物,优选其中氮处于阳离子状态,并且其中至少一个脂肪族自由基包含可电离的水溶性基团,例如羧基、磺酸盐、硫酸盐、磷酸盐或膦酸酯基团;甜菜碱;磺基甜菜碱;羟基磺基甜菜碱;烷基亚氨基乙酸酯或盐;亚氨基二链烷酸酯或盐;以及氨基链烷酸酯或盐。
非起泡表面活性剂:鉴于本发明的染发组合物在常规上不意图具有清洁功能,因此它们不需要是起泡体系,并且可以包含非起泡表面活性剂。在本文具有实用性的示例性非起泡表面活性剂包括:聚乙二醇20脱水山梨糖醇单月桂酸酯(聚山梨醇酯20);聚山梨醇酯60;聚山梨醇酯80;聚氧乙烯20脱水山梨糖醇三油酸酯(聚山梨醇酯85);硬脂醇聚醚-20;鲸蜡醇聚醚-10;鲸蜡硬脂醇聚醚-20;鲸蜡磷酸酯或盐;鲸蜡醇磷酸钾;二乙醇胺鲸蜡磷酸酯或盐;硬脂酸甘油酯;PPG-2-甲基葡萄糖醚二硬脂酸酯;和PEG-100硬脂酸酯或盐。
乳化剂体系:除上述内容外,本发明不排除使用乳化剂。可提及以下乳化剂混合物:从ISP获得的141(硬脂酸甘油酯、山嵛醇、棕榈酸、硬脂酸、卵磷脂、月桂醇、肉豆蔻醇和鲸蜡醇);从ISP获得的151(硬脂酸甘油酯、鲸蜡硬脂醇、硬脂酸、1-丙铵、3-氨基-N-(2-(羟乙基)-N-N-二甲基、N-C(16-18)酰基衍生物、氯化物);可从Croda获得的NF(乳化蜡NF);可从Croda获得的BEHENYLTMS(山嵛基三甲基硫酸铵和鲸蜡硬脂醇);以及从Gattefosse获得的DELTA(鲸蜡醇、硬脂酸甘油酯、聚乙二醇-75硬脂酸酯、鲸蜡醇聚醚-20和硬脂醇聚醚-20)。
基于组合物的重量,本发明的水性染发组合物可包含0至10wt.%,例如0至5wt.%的一种或多种增稠剂。所述增稠剂可选自:i)羧酸聚合物,例如从B.F.Goodrich获得的900系列的那些;ii)从B.F.Goodrich获得的丙烯酸酯/C10-C30烷基丙烯酸酯交联聚合物,如1342、1382、TR-1和TR-2;iii)交联的聚丙烯酸酯聚合物,其可以是阳离子聚合物或非离子聚合物;iv)聚丙烯酰胺聚合物,特别是非离子聚丙烯酰胺聚合物;iv)丙烯酰胺和取代的丙烯酰胺与丙烯酸和取代的丙烯酸的多嵌段共聚物;v)多糖,包括硬葡聚糖、纤维素和纤维素衍生物,如羧甲基纤维素和烷基羟烷基纤维素醚;vi)改性淀粉;vii)树胶,如黄原胶、阿拉伯胶、褐藻胶、海藻酸钠、槐豆胶和瓜尔胶;viii)蛋白,如胶原蛋白、白蛋白和明胶;及其混合物。
基于组合物的重量,本发明的水性染发组合物可包含0至5wt.%,优选0至2wt.%的至少一种抗微生物剂。优选的是组合物中包含的抗微生物剂或每种抗微生物剂都是不溶于水的结晶颗粒。示例性抗微生物剂包括但不限于:硫;吡罗克酮乙醇胺盐;硫化硒,如美国专利号2,694,668、美国专利号3,152,046和美国专利号4,089,945所述;以及吡啶硫酮盐(pyridinethione),如美国专利号3,753,196、美国专利号4,345,080、美国专利号4,323,683和美国专利号4,470,982所述。
可包括在水性染发组合物中的加香剂的实例包括香草醛、肉桂醇、天芥菜精、香豆灵、2-甲基-3-(3,4-亚甲基二氧基苯基)-丙醛、4-(4-羟基苯基)-2-丁酮、苯甲醛、茴香醇、3,4-二甲氧基苯甲醛、乙酸天芥菜酯、苯乙醛二甲基缩醛、苯氧乙醇、苯乙醛甘油缩醛、苄醇、苯乙醇、法尼醇(franeol)、糖内酯、薄荷醇、乙基二甘醇、乙酸苄酯、芳樟醇、樟脑、松油醇、香茅醇、香叶醇、2,6-壬二烯醇、碳酸甲基辛酯、3,7-二甲基-2,6-辛二烯醛和壬醛。
本发明的染发剂组合物可使用常规手段应用于毛发干的至少一部分,包括通过指触、通过手、通过刷子或通过另一器具,任选地与传递热能或适当电磁辐射的手段相配合。该组合物可应用于湿发或干发。应用的量有所不同,取决于毛发的厚度和长度以及期望的效果。
染发组合物可应用于基本上所有毛发或替代地应用于部分毛发。在一个实施方案中,该组合物可应用于毛发靠近头皮的部分,例如,距离头皮0至10cm或0至5cm。这对于使用者改良新生长的毛发根部的颜色可能是可取的。
示例性实施方案2:纹身油墨
在本发明的一个重要实施方案中,提供了一种水性纹身油墨组成组合物,该组合包括:
a)至少一种着色剂,其中所述至少一种着色剂包含类黑精,所述类黑精的重均分子量为200道尔顿至300kDa,优选1至300kDa,更优选1至100kDa,例如10至100kDa;
任选地b)至少一种共溶剂;和
c)至少一种助剂,该助剂选自:粘合剂;增稠剂;pH调节剂;表面活性剂;保湿剂;抗微生物剂;抗炎剂;抗氧化剂;防腐剂;和局部麻醉剂。
存在于着色剂组分a)中的类黑精优选从上文和所附权利要求书中定义的提取工艺中获得。注意,着色剂组分a)可包含所述类黑精、基本上由所述类黑精组成或由所述类黑精组成,取决于要获得的颜色效果。
在优选的实施方案中,基于组合物的重量,本发明的水性纹身油墨组合物包括:
10至40wt.%的水;
30至60wt.%的a)所述至少一种着色剂,其中所述至少一种着色剂包含类黑精,所述类黑精的重均分子量为200道尔顿至300kDa,优选1至300kDa,更优选1至100kDa,例如10至100kDa;
0至15wt.%的b)所述共溶剂;和
5至15wt.%的c)至少一种助剂,该助剂选自:粘合剂;增稠剂;pH调节剂;表面活性剂;保湿剂;抗微生物剂;抗炎剂;抗氧化剂;防腐剂;和局部麻醉剂。
应注意的是,基于试剂或试剂的假定作用模式提供的益处对组分c)进行分类。制作这种分类是为了方便:而特定的化学成分,例如聚乙二醇,例如可能提供多于一种益处或通过多于一种作用模式操作。在这方面,这里重申,类黑精本身提供色素功能,并充当抗微生物剂、抗炎剂和抗氧化剂,因此可以最大限度地减少对于具有这些功能的辅助成分的需要。
本发明的水性纹身油墨组合物可包括除上述类黑精之外的其他着色剂。所述着色剂必须是水溶性或水分散性的,并且可以选自:无机颜料;有机颜料;天然染料;合成染料;及其组合。还设想使用有机、涂漆(lacqucered)颜料或漆颜料(“色淀颜料(lakepigment)”),其通过用金属盐使天然或合成染料沉淀获得。然而,优选的是制剂基本上不含金属颗粒和/或基本上不含微胶囊化的着色剂。
为完整性起见,示例性无机颜料包括但不限于:金属氧化物,例如氧化铁红、氧化铁黄、氧化铁黑、锐钛矿、板钛矿、金红石、氧化铝、氧化锆、氧化钴、氧化铈、氧化镍、氧化铬、氧化镍铬、氧化锌;和复合氧化物;金属氢氧化物,如氢氧化钙、氢氧化铁、氢氧化铝、氢氧化铬、氢氧化镁;和复合金属氢氧化物;普鲁士蓝;硫化铁;锰紫;炭黑;云母;和高岭土。
水性纹身油墨组合物可包含至少一种水可混溶的有机共溶剂。当存在时,水和所述至少一种水可混溶的有机溶剂应以20:80至80:20的重量比混合,例如30:70至70:30。在附加的并非旨在与上述那些比例相互排斥的优选声明中,优选选择本部分中包括水可混溶的有机溶剂或水可混溶的有机溶剂的混合物,并以足以在室温下将水/溶剂组合的表面张力降低至小于64达因/厘米的量添加到水中。
本发明的至少一种水可混溶的有机溶剂可选自:C1-6烷醇,如甲醇、乙醇、正丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇、正戊醇;环戊醇;环己醇;二醇,特别是具有2至12个碳原子的二醇,例如乙二醇、丙二醇、丁二醇、1,5-戊二醇、戊二醇、己二醇,但也包括硫代二甘醇和低聚二醇及聚亚烷基二醇,例如二乙二醇、三乙二醇、二丙二醇、聚乙二醇和聚丙二醇;三醇,如1,2,6-己三醇;酮和酮醇,如丙酮、甲乙酮、2-戊酮、3-戊酮、甲基异丁基酮、环己酮和二丙酮醇;四氢呋喃;二氧六环;具有2至12个碳原子的二醇的单C1-4-烷基醚,例如乙二醇单-(C1-C4)-烷基醚、丙二醇单-(C1-C4)-烷基醚,特别是乙二醇单甲基醚、乙二醇单丁基醚、丙二醇单甲基醚、丙二醇单丙基醚、丙二醇单丁基醚;二乙二醇单-(C1-C4)-烷基醚,如二乙二醇单甲基醚和二乙二醇单丁基醚;二丙二醇单-(C1-C4)烷基醚,例如二丙二醇N-丙基醚、二丙二醇单丙基醚和二丙二醇单丁醚;丙二醇苯醚;线性酰胺,如N,N-二甲基甲酰胺和N,N-二甲基乙酰胺;环酰胺,如2-吡咯烷酮、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、己内酰胺和1,3-二甲基咪唑啉酮;糖酯,如二甲基异山梨醇酯;环酯,如己内酯;和亚砜,如二甲基亚砜和环丁砜。所述至少一种水可混溶的溶剂优选选自丙酮、二丙酮醇、异丙醇及其混合物。
不严格排除该制剂中存在水不混溶的有机溶剂,但它不代表优选实施方案。相反,优选的是制剂基本上不含水不混溶的有机溶剂,因此呈现为单一的连续水相。
就上述组分c)而言,粘合剂(binders)或粘合剂(binding agents)确实代表水性纹身油墨组合物的常规成分,基于组合物的重量,所述粘合剂含量可以高达5wt.%。粘合剂是非挥发性成分,其将颗粒状着色剂彼此粘合,并且在这样做时,促进使用针头和类似注射手段将油墨引入真皮内或表皮内。可单独或组合使用的示例性粘合剂包括但不限于:聚乙烯吡咯烷酮(PVP),特别是重均分子量为1至3000kDa的聚乙烯吡咯烷酮;聚乙二醇(PEG),特别是重均分子量为0.2至6kDa的聚乙二醇;聚丙二醇(PPG),特别是重均分子量为0.2至6kDa的聚丙二醇;PEG/PPG嵌段共聚物,特别是重均分子量为5至15kDa的PEG/PPG嵌段共聚物;PEG/PPG无规共聚物;和Shellac树脂。
基于组合物的重量,所述水性纹身油墨组合物通常包含高达5wt.%,例如高达3wt.%的表面活性剂。本文中可使用多种表面活性剂以用于分散相的乳化和提供所施用的组合物的可接受的铺展,但理想的表面活性剂将选自:阴离子表面活性剂;非离子表面活性剂;两性表面活性剂;非起泡表面活性剂;乳化剂;及其混合物。认为示例性实施方案1提供的关于表面活性剂的公开是适用的,其在此通过引用并入。
pH调节剂的实例:无机酸,如磷酸;羟基羧酸,如乳酸、乙醇酸、柠檬酸、3-羟基丁酸、4-羟基丁酸、2-羟基丁二酸、2,3-二羟基丁二酸、3-羟基戊酸、5-羟基戊酸、6-羟基己酸及其碱金属或碱土金属盐;氨;碱金属氢氧化物;碱金属碳酸盐;碱金属碳酸氢盐;碱土金属氢氧化物;碱土金属碳酸盐;和碱土金属碳酸氢盐。
基于组合物的重量,本实施方案的制剂可包含0至5wt.%,例如0至3wt.%的一种或多种增稠剂。所述增稠剂可选自:i)羧酸聚合物,例如从B.F.Goodrich获得的900系列的那些;ii)从B.F.Goodrich获得的丙烯酸酯/C10-C30烷基丙烯酸酯交联聚合物,如1342、1382、TR-1和TR-2;iii)交联的聚丙烯酸酯聚合物,其可以是阳离子聚合物或非离子聚合物;iv)聚丙烯酰胺聚合物,特别是非离子的聚丙烯酰胺聚合物;iv)丙烯酰胺和取代丙烯酰胺与丙烯酸和取代丙烯酸的多嵌段共聚物;v)多糖,包括硬葡聚糖、纤维素和纤维素衍生物,如羧甲基纤维素和烷基羟烷基纤维素醚;vi)改性淀粉;vii)树胶,如黄原胶、阿拉伯胶、褐藻胶、海藻酸钠、槐豆胶和瓜尔胶;viii)蛋白,如胶原蛋白、白蛋白和明胶;及其混合物。
如本领域所知,保湿剂或补水剂是具有水结合特性的化妆品组合物,其能够保留相对于其重量的大量水。保湿剂通常比油更易溶于水。关于本制剂中使用的合适保湿剂的指导性参考文献包括WO98/22085、WO98/18444和WO97/01326。本文使用的示例性保湿剂包括:氨基酸;胶原蛋白氨基酸或肽;角蛋白氨基酸;丝氨基酸;尿素;糖胺聚糖;N-乙酰氨基葡萄糖;甘油;甘油的聚乙二醇醚;透明质酸、乙酰透明质酸、天冬氨酸、葡糖醛酸和谷氨酸的碱金属盐。
基于组合物的重量,本实施方案的制剂可包含0至5wt.%,优选0至2wt.%的至少一种抗微生物剂。优选的是组合物中包含的抗微生物剂或每种抗微生物剂都是不溶于水的结晶颗粒。示例性抗微生物剂包括但不限于:硫;吡罗克酮乙醇胺盐;硫化硒,如美国专利号2,694,668、美国专利号3,152,046和美国专利号4,089,945所述;以及吡啶硫酮盐,如美国专利号3,753,196、美国专利号4,345,080、美国专利号4,323,683和美国专利号4,470,982所述。
基于组合物的重量,本实施方案的制剂可包含0至2wt.%的至少一种抗炎剂。可单独或组合使用的合适抗炎剂包括:维生素F;维生素E;不饱和脂肪酸;芦丁;生物类黄酮;咖啡酸苯乙酯;沙棘油;橄榄油;荷荷巴油;洋甘菊精油;洋甘菊提取物;金缕梅(Hamamelisvirginiana)提取物;甜菜根提取物;辣根提取物;蒲公英提取物;野菊花(Chrysanthemumindicum)提取物;Sukbagui提取物;倍他米松;地塞米松;及其混合物。上述提取物可通过包括热水或醇类提取工艺的已知方法获得。可提及对金缕梅提取物的偏好。
示例性抗氧化剂包括维生素E、维生素F、维生素C、芦丁、白藜芦醇、鼠尾草酸、壳聚糖、类黄酮、没食子酸盐、花色素苷和类胡萝卜素。示例性防腐剂包括克菌丹、洗必太、六氯酚、三氯生、三醋精及其混合物。
在某些实施方案中,基于组合物的重量,本实施方案的制剂可包含高达1wt.%的至少一种局部麻醉剂。如本领域已知的,局部麻醉剂降低敏感神经纤维的兴奋性,通过与钠离子通道膜内侧上的结合位点相互作用阻止钠离子的流入,从而阻止产生用于传导兴奋所需的动作电位。本文中优选的局部麻醉剂选自:利多卡因、甲哌卡因、丙胺卡因、阿替卡因、布比卡因、二丁卡因、罗哌卡因、依替卡因、达克罗宁、普鲁卡因、苯佐卡因、2-氯普鲁卡因、奥布卡因、丁卡因、福莫卡因、依替卡因、普莫卡因、左旋布比卡因、氧普鲁卡因、海克卡因、地布卡因、哌罗卡因、氨苯丁酯、苦味酸氨苯丁酯、盐酸二甲异喹、地哌冬、达克罗宁、克他命、对丁基氨基苯甲酸、普莫卡因、及其药学上可接受的盐、及其混合物。可提及对于利多卡因和苯佐卡因的偏好:该偏好旨在涵盖这些化合物的药学上可接受的盐。
本发明的纹身油墨组合物可通过任何常规技术应用。如本领域技术人员所认识到的,纹身的应用可在皮肤准备之前进行,通过清洁以去除表面污染物和/或应用麻醉剂来提供局部和暂时的疼痛缓解。如上文所述,局部麻醉剂的预施用可补充油墨组合物本身中包含的任何麻醉剂。
表皮内纹身可被视为“半永久性着色剂”,因为着色剂位于表皮内,不会扩散出皮肤,并且在没有皮肤物理破坏或自然脱皮的情况下无法从皮肤上去除。特别地,表皮内纹身不能在水、肥皂、醇类溶剂或其组合的作用下被洗掉。
本发明的组合物的表皮施用可通过例如:针;微针;喷射注射;热致微孔;电穿孔;声穿孔;或其组合进行。此外,表皮施用的部位可能是角质层、透明层、颗粒层、棘层和基底层中的一个或多个。
不旨在限制本发明,认为真皮内施用技术的特点应在于使用具有至少三个细尖的针在毛细血管作用下将油墨引入真皮,这些细尖以50至5000min-1的频率轴向前后移动。在这种引入模式下,作为一种防御反应,巨噬细胞在真皮内释放:然而,鉴于油墨颗粒比巨噬细胞大得多,油墨颗粒被吞噬细胞包围的后果是将油墨颗粒固定在真皮内。在这种引入模式下,还可以确定一部分油墨颗粒将被成纤维细胞吸收,且另外部分将保留在真皮中胶原纤维的细胞外基质中。然而,由于表皮细胞都会脱落,一方面是自然的一方面是对于针造成的损伤的愈合反应,因此任何沉积在表皮内的油墨都会损失掉。
用于真皮内应用的示例性纹身针包括但不限于在:EP 2454966 A1;US 2007/0038181 A(Melamud);US 2004/0186501 A(Kuei);美国专利号8,764,784(Crockett);美国设计专利号866950S1(Schubert);和美国设计专利号888240S1(Importla)中描述的那些。
虽然纹身旨在是永久性的,但人们认识到,人们经常试图将其从身体上去除。因此将类黑精用作颜料被认为是有益的,因为这些化合物可以通过引入到真皮或表皮中的酶和化学物质(如过氧化氢和臭氧)的靶向作用进行降解。类黑精的降解使颜料成为“可去除的”。
示例性实施方案3:用作眼部化妆品的固体化妆品组合物
在本发明的一个重要实施方案中,提供了一种固体化妆品组合物,所述组合物包括:
a)至少一种着色剂,其中所述至少一种着色剂包含类黑精,所述类黑精的重均分子量为200道尔顿至300kDa,优选1至300kDa,更优选1至100kDa,例如10至100kDa;
b)至少一种结构化剂;和
c)至少一种增稠剂。
本发明提出,如上所定义的固体化妆品组合物可具有作为面部化妆品(例如眼部化妆品)的特定用途。存在于着色剂组分a)中的类黑精优选从上文和所附权利要求书中定义的提取工艺中获得。注意,着色剂组分a)可包含所述类黑精、基本上由所述类黑精组成或由所述类黑精组成,取决于要获得的颜色效果。
在优选的实施方案中,基于组合物的重量,本发明的固体化妆品组合物包括:
2至30wt.%的a)至少一种着色剂,其中所述至少一种着色剂包含类黑精,所述类黑精的重均分子量为200道尔顿至300kDa,优选1至300kDa,更优选1至100kDa,例如10至100kDa;
4至50wt.%的b)至少一种结构化剂;
4至50wt.%的c)至少一种增稠剂;和
0至90wt.%的d)至少一种助剂,该助剂选自:载体;稳定剂;表面活性剂;和保鲜剂。
应注意的是,基于试剂或试剂的假定作用模式提供的益处对组分d)进行分类。制作这种分类是为了方便:而特定的化学成分可能提供多于一种益处或通过多于一种作用模式操作。
基于组合物的重量,本发明的固体化妆品组合物包含4至50wt.%,例如5至40wt.%或5至30wt.%的一种或多种结构化剂。
不旨在限制本发明,在本发明中具有实用性的所述结构化剂应包括或由软化点为50至150℃的蜡组成,并可包括以下一种或多种:i)数均分子量(Mn)为500至7500的聚乙烯;ii)石油蜡,如石蜡、地蜡、纯地蜡、粗地蜡、土蜡和微晶蜡;iii)由一氧化碳和氢气聚合而成的合成蜡,如费-托蜡;iv)聚烯烃蜡;v)氢化动物油、鱼油或植物油;以及vi)植物和动物源性蜡,如蜂蜡、巴西棕榈蜡、小烛树蜡、鲸蜡和月桂果蜡。
基于组合物的重量,本实施方案的固体化妆品组合物可包含4至50wt.%,例如5至40wt.%或5至30wt.%的一种或多种增稠剂。所述增稠剂可选自:i)羧酸聚合物,例如从B.F.Goodrich获得的900系列的那些;ii)从B.F.Goodrich获得的丙烯酸酯/C10-C30烷基丙烯酸酯交联聚合物,如1342、1382、TR-1和TR-2;iii)交联的聚丙烯酸酯聚合物,其可以是阳离子聚合物或非离子聚合物;iv)聚丙烯酰胺聚合物,特别是非离子聚丙烯酰胺聚合物;iv)丙烯酰胺和取代的丙烯酰胺与丙烯酸和取代的丙烯酸的多嵌段共聚物;v)多糖,包括硬葡聚糖、纤维素和纤维素衍生物,如羧甲基纤维素和烷基羟烷基纤维素醚;vi)改性淀粉;vii)树胶,如黄原胶、阿拉伯胶、褐藻胶、海藻酸钠、槐豆胶和瓜尔胶;viii)蛋白质,如胶原蛋白、白蛋白和明胶;及其混合物。
固体化妆品组合物可包含高达50wt.%的载体,其具有在施用时留下包含类黑精组分作为着色剂的膜的功能。示例性载体包括:水;水可混溶的溶剂;水不可混溶的溶剂;挥发性硅氧烷,如Todd等人,“Volatile Silicone Fluids for Cosmetics”,Cosmetics andToiletries,91:27-32(1976)所述的;非挥发性有机液体;以及非挥发性所述类黑精液体。术语“挥发性所述类黑精”是指在环境条件下具有可测量蒸汽压的所述类黑精材料:环状聚甲基硅氧烷是一个重要的实例。
为完整起见,非挥发性有机液体的非限制性实例包括矿物油、PPG-14丁基醚、肉豆蔻酸异丙酯、矿脂、硬脂酸丁酯、辛酸十六酯、肉豆蔻酸丁酯、肉豆蔻酸肉豆蔻酯、C12-15烷基苯甲酸酯(例如Finsolv.TM.)、二丙二醇二苯甲酸酯、PPG-15硬脂基醚苯甲酸酯及其共混物(例如Finsolv TPP)、新戊二醇二庚酸酯(例如,由Inolex提供的Lexfeel 7)、辛基十二醇、异硬脂酸异硬脂醇酯、苯甲酸十八酯、乳酸异硬脂醇酯、棕榈酸异硬脂醇酯、异壬酸异壬酯、异二十烷、新戊酸辛基十二醇酯、氢化聚异丁烷和硬脂酸异丁酯。认为美国专利号6,013,248(Luebbe等人)和美国专利号5,968,489(Swaile等人)在这方面提供了指导性参考。
基于组合物的重量,固体化妆品组合物通常包含高达5wt.%,例如高达3wt.%的表面活性剂。本文中可使用多种表面活性剂,用于分散相的乳化和提供所施用的组合物的可接受铺展,但理想的表面活性剂将选自:阴离子表面活性剂;非离子表面活性剂;两性表面活性剂;非起泡表面活性剂;乳化剂;及其混合物。对示例性实施方案1提供的关于表面活性剂的公开被认为是适用的,并通过引用在此并入。
固体组合物中也可存在保鲜剂。其实例包括:苯氧基乙醇;C1-C6烷基对羟基苯甲酸酯;咪唑啉基脲;二甲基二羟甲基乙内酰脲;N-(3-氯烯丙基)氯化六铵;西曲溴铵;乙二胺四乙酸三钠;和丁羟茴醚(BHA)。当存在时,基于组合物的重量,保鲜剂通常以高达0.5wt.%,例如0.01至0.1wt.%的量添加。然而,鉴于类黑精的防腐功能,还设想所述固体化妆品组合物可基本上不含保鲜剂。
本发明的固体化妆品组合物可配制为任何已知或其他有效的产品形式,以用于将类黑精活性物局部应用于皮肤的所需区域。此类产品形式的非限制性实例包括块状物、棒状、铅笔状和走珠式,但前提是所选形式包含本文定义的所有必需要素。固体组合物通常存储在适当的包装或涂抹器装置中并从中分配,该包装或涂抹器装置应可关闭以防止在施用之前和施用之间任何组成挥发性化合物的损失。
鉴于上述描述和示例性实施方案,对于本领域技术人员来说,显而易见的是,可以在不脱离权利要求书范围的情况下对其进行等效修改。
Claims (19)
1.一种包含类黑精的化妆品组合物,其中所述类黑精具有200道尔顿至300千道尔顿(kDa)、优选1至300kDa且更优选1至100kDa的重均分子量(Mw)。
2.根据权利要求1所述的化妆品组合物,其中所述组合物为非粉末状固体化妆品组合物、粉饼化妆品组合物或水性液体化妆品组合物。
3.一种水性染发组合物,其包含:
a)类黑精,其中所述类黑精具有200道尔顿至300kDa、优选1至300kDa且更优选1至100kDa的重均分子量;和,
b)至少一种助剂,所述助剂选自:润湿剂;溶胀剂;渗透剂;pH调节剂;表面活性剂;增稠剂;抗微生物剂;和加香剂。
4.根据权利要求3所述的水性染发组合物,其中基于所述组合物的重量,所述水性染发组合物包含:
5至20wt.%的a)类黑精,所述类黑精的重均分子量为200道尔顿至300kDa,优选1至300kDa且更优选1至100kDa;
5至40wt.%的b)至少一种助剂,所述助剂选自:润湿剂;溶胀剂;渗透剂;pH调节剂;表面活性剂;增稠剂;抗微生物剂;和加香剂;和,
40至90wt.%的水。
5.一种水性纹身油墨组成组合物,其包含:
a)至少一种着色剂,其中所述至少一种着色剂包含类黑精,所述类黑精的重均分子量为200道尔顿至300kDa,优选1至300kDa且更优选1至100kDa;
任选地,b)至少一种共溶剂;和
c)至少一种助剂,所述助剂选自:粘合剂;增稠剂;pH调节剂;表面活性剂;保湿剂;抗微生物剂;抗炎剂;抗氧化剂;防腐剂;和局部麻醉剂。
6.根据权利要求5所述的水性纹身油墨组合物,其中基于所述组合物的重量,所述水性纹身油墨组合物包含:
10至40wt.%的水;
30至60wt.%的a)所述至少一种着色剂,其中所述至少一种着色剂包含类黑精,所述类黑精的重均分子量为200道尔顿至300kDa,优选1至300kDa且更优选1至100kDa;
0至15wt.%的b)所述共溶剂;和
5至15wt.%的c)至少一种助剂,所述助剂选自:粘合剂;增稠剂;pH调节剂;表面活性剂;保湿剂;抗微生物剂;抗炎剂;抗氧化剂;防腐剂;和局部麻醉剂。
7.一种固体化妆品组合物,所述组合物包含:
a)至少一种着色剂,其中所述至少一种着色剂包含类黑精,所述类黑精的重均分子量为200道尔顿至300kDa,优选1至300kDa且更优选1至100kDa;
b)至少一种结构化剂;和
c)至少一种增稠剂。
8.根据权利要求7所述的固体化妆品组合物,其中基于所述组合物的重量,所述固体化妆品组合物包含:
2至30wt.%的a)至少一种着色剂,其中所述至少一种着色剂包含类黑精,所述类黑精的重均分子量为200道尔顿至300kDa,优选1至300kDa且更优选1至100kDa;
4至50wt.%的b)至少一种结构化剂;
4至50wt.%的c)至少一种增稠剂;和,
0至90wt.%的d)至少一种助剂,所述助剂选自:载体;稳定剂;表面活性剂;和保鲜剂。
9.根据权利要求1至8中任一项所述的化妆品组合物,其中所述类黑精具有10至100kDa的重均分子量(Mw)。
10.根据权利要求1至9中任一项所述的化妆品组合物,其中所述类黑精具有10至30kDa、30至50kDa或50至100kDa的重均分子量(Mw)。
11.根据权利要求1至10中任一项所述的化妆品组合物,其特征在于基本上不含咖啡因。
12.一种从食品中获得至少一种类黑精馏分的方法,所述方法包括以下步骤:
a)提供包含类黑精的颗粒状食品;
b)用pH大于7的水性提取剂溶液处理所述颗粒状食品,以通过使类黑精作为水相中的溶质而提取所述类黑精;
c)将所述水相与残余的经处理的颗粒状食品物理分离;
d)基于分子量分馏所述水相的分散组分或溶解组分;以及
e)将所述经分馏的水相脱水以从中获得至少一种固体类黑精馏分。
13.根据权利要求12所述的方法,其中所述颗粒状食品选自废咖啡渣和啤酒麦糟(BSG)。
14.根据权利要求12或权利要求13所述的方法,其中将所述颗粒状食品微粉化。
15.根据权利要求12至14中任一项所述的方法,其中步骤b)包括用氢氧化钠水溶液处理所述颗粒状食品。
16.根据权利要求12至15中任一项所述的方法,其中步骤b)在离心下进行。
17.根据权利要求12至16中任一项所述的方法,其中所述分馏步骤d)通过以下方式进行:使用分子量截留膜进行超滤;离心;或者,尺寸排阻色谱。
18.根据权利要求12至17中任一项所述的方法,其中所述脱水步骤e)通过以下至少一种方式进行:冷冻干燥;喷雾干燥;对流干燥;辐射干燥;以及真空干燥。
19.根据权利要求1至11中任一项所述的化妆品组合物,其中所述类黑精通过权利要求12至18中任一项所定义的方法获得。
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EP19020723.3 | 2019-12-23 | ||
PCT/EP2020/087838 WO2021130349A1 (en) | 2019-12-23 | 2020-12-23 | Cosmetic compositions comprising melanoidins |
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EP (1) | EP4081185A1 (zh) |
JP (1) | JP2023508343A (zh) |
KR (1) | KR20220119451A (zh) |
CN (1) | CN114929194A (zh) |
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EP4108094A1 (en) * | 2021-06-23 | 2022-12-28 | Kaffee Bueno ApS | Coffee melanoidin nanoparticles and nanofibers |
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US20220347083A1 (en) | 2022-11-03 |
EP4081185A1 (en) | 2022-11-02 |
WO2021130349A1 (en) | 2021-07-01 |
AU2020412821A1 (en) | 2022-06-30 |
CA3160760A1 (en) | 2021-07-01 |
KR20220119451A (ko) | 2022-08-29 |
JP2023508343A (ja) | 2023-03-02 |
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