CN108367178A - 具备稳定味道和气味的组合物 - Google Patents
具备稳定味道和气味的组合物 Download PDFInfo
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- CN108367178A CN108367178A CN201580085216.5A CN201580085216A CN108367178A CN 108367178 A CN108367178 A CN 108367178A CN 201580085216 A CN201580085216 A CN 201580085216A CN 108367178 A CN108367178 A CN 108367178A
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- acid
- oil
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Abstract
提出一种具备稳定味道和/或气味的组合物,含有(a)[6]‐姜酮酚和(b)至少一种单或多元不饱和C8‐C22脂肪酸或其单或多元C1‐C18脂肪醇酯。
Description
发明领域
本发明属于化妆产品和食品领域并且涉及含有[6]‐姜酮酚的组合物,[6]‐姜酮酚用于稳定组合物中所含脂肪酸及其酯的味道和/或气味,以及含有所述具备稳定味道和/或气味的组合物的个人护理产品和食品产品。
现有技术
脂肪酸(酯)是油和脂肪的主要成分。它们具备由含有约12‐22碳原子的长烃链和一个或多个羧酸(酰基)基团构成的简单结构。根据碳原子之间存在双键的数量脂肪酸(酯)通常分为饱和、单不饱和多不饱和脂肪酸(酯)。目前,大部分的脂肪酸(酯)由天然源包括植物和动物源得到,如硬动物脂肪、椰子油、棕榈仁油和豆油。最平常的天然产生的脂肪酸是棕榈酸、硬脂酸、油酸和亚油酸。除了热带油料如棕榈油和椰子油,有商业意义的植物和动物源油料中的大部分脂肪酸(酯)含有18个碳原子。其他脂肪酸(酯)属于由石油得到的合成化合物。由于有利的物理和生物性质,脂肪酸(酯)的用途是巨大的。
脂肪酸(酯)在化妆品工业非常重要并且在用于面部、身体和毛发日常护理的许多化妆制剂中是越来越常用的成分。天然产生的脂肪酸(酯)是皮肤的成分并且是构成最外层的复杂混合物的成分。由于其上油、软化、润滑和保护性能,脂肪酸(酯)可以防止水分由皮肤流失,主要通过在表皮上形成保护层。此外,它们软化角质层并减少皮肤发炎,从而减弱疼痛感受。然而随着年龄增长,皮肤脂肪酸(酯)的天然合成减少,这导致皮肤过量脱水。为了避免由于缺少脂肪酸(酯)导致的不想要的皮肤干燥,在大部分市售产品中将脂肪酸(酯)用作必要的化妆品成分。
除了在化妆品领域应用,由于其在人体适当功能中的生物效果—在新陈代谢中作为主要的代谢燃料(储存和运输能量)、作为所有膜的主要成分、作为基因调节剂—脂肪酸(酯)在食品和营养工业也十分重要。可食用脂肪酸(酯)大部分属于多元不饱和脂肪酸,其无法在哺乳动物中代谢合成并因此被成分“必需脂肪酸”。已经报道对于人类为了避免临床缺陷症状最小摄入量,以“ω‐3”脂肪酸(如二十二碳六烯酸(DHA)和二十碳五烯酸(EPA))为例,大约为每天0.5g。此外,许多流行病学和试验研究已经证明额外摄入“必须脂肪酸”具备显著的有益效果。为了满足消费者对必需脂肪酸(酯)巨大的需求,市场上有越来越多的各种食品和营养产品,提供足够量的必需脂肪酸(酯)。
尽管在化妆产品和食品中使用脂肪酸(酯)是成熟技术,仍然有一些没有解决的主要涉及原料的复杂储存以及最终产品的有限保质期的问题,这是由于所含不饱和脂肪酸(酯)的酸败所导致。酸败是导致物质变质的过程,即产生恶臭、令人不悦的气味或味道。具体地,被认为是脂肪水解和/或氧化为短链醛和酮,其大部分挥发并且具备令人反感的味道和气味。这一过程导致脂肪酸(酯)和最终产品变质。明显的是含有变质脂肪酸(酯)的油和脂肪不能被进一步加工为相应的最终产品,并且变质的最终产品不能再在市场上出售或被消费者使用。这都导致了生产成本的升高,这对于生产者和消费者都是不可以接受的。
为了避免或弱化脂肪酸(酯)的变质,已经采用了许多方法。例如在工业中通常在含有脂肪的食品或化妆品中使用抗氧化剂作为防腐剂,从而延迟氧化变质的出现或减慢氧化变质的进程。现有技术中也已知许多出版物解决变质问题。
专利申请KR 20100105234报道了一种组合物,用于防止不饱和脂肪酸的变质,其含有氯化钾、碳酸钾、氯化镁、乳酸钙和柠檬酸钠。
国际专利申请WO 92/22282公开用于化妆和/或药物制剂的油体成分。公开的油体成分完全或主要由Guerbet醇碳酸酯构成。这种油体成分不仅具备良好的皮肤和粘膜相容性,而且也具备相对于变质的高稳定性。
在专利申请US 2005/02445中记载了一种提高含油体食品氧化稳定性的方法。基于发现更大量油酸和更少量亚油酸用于改善氧化稳定性,公开方法的特征在于向含有高比例油酸与亚油酸的产品中加入富含ω‐3脂肪酸的油体。
专利申请GB 813,538 A的主题涉及5‐苊烯作为氧化剂用于减小氧化的有害影响,并改善含有固体脂肪、脂肪油体的可氧化组合物的稳定性的用途。
US 2521856 A提供了一种新的混合物,含有(a)丁基化氢醌单烷基醚,其中烷基含有1‐4个碳原子,(b)对苯二酚和(c)一种选自组包括柠檬酸、抗坏血酸、草酸、磷酸、乙基磷酸和磷酸三乙酯的酸性材料以改善材料—其由于含有脂肪酸甘油酯通常会氧化变质—的稳定性。
在专利申请GB 595838 A中提供了稳定的可食用植物、动物、鱼油、脂肪和蜡,其中将所述可食用材料与少量硫代二饱和脂肪酸或酯、酰胺、盐或酸酐接触。
GB 618409 A公开了植物源去甲二氢愈创木酸作为抗氧化剂将猪油、黄油、可食用油等长时间保持在新鲜和可食用的状态下,从而可以在密封容器中包装以及在热的气候条件下长时间储存。
尽管报道了一些含有脂肪酸(酯)的组合物具备抗变质的良好稳定性,其中大部分基于提高组合物中饱和脂肪酸的比例。然而,饱和脂肪酸相对于不饱和脂肪酸的比例对于人类营养特别重要。这意味着一方面需要高含量饱和脂肪酸以提高脂肪酸(酯)的稳定性,而另一方面营养上不需要,因为通常认为高含量饱和脂肪酸通过提高低密度脂蛋白(LDL),影响LDL与HDL(高密度脂蛋白)之间的比例,促进凝血和血管平滑肌增殖。
因此,亟需寻找一种新的含有脂肪酸(酯)的组合物,其具备稳定的味道和/或气味以及改善的抗氧化和抗变质性质。使用含有脂肪酸(酯)的组合物,可以实现脂肪酸(酯)作为原料更有效的储存和含有脂肪酸(酯)的最终产品的较长保质期,而不有意减少不饱和脂肪酸(酯)的含量。新的组合物应当保持所含脂肪酸(酯)的所有优异的物理和生物性能,并且进一步地具备优异的抗变质性能。优选地,组合物中使用的稳定剂应当具备确定的化学结构和纯度、使用中的毒理学安全性、良好的耐受性、低浓度下的有效性、易于制剂、无色并且无味。
基于化妆和食品工业中的含有脂肪酸(酯)的具备稳定味道和/或气味的组合物的一种重要优势,本发明解决的主要问题是提供一种含有脂肪酸(酯)的新组合物,其中所含不饱和脂肪酸仍然表现出其本身的物理和生物性能并且很好地抵抗氧化和变质。本发明解决的另一个问题是提供一种防止不饱和脂肪酸(酯)氧化和变质的新方法。此外,本发明解决的另一个问题是提供具备更优异抗变质性和更长保质期的化妆产品和食品。
发明内容
本发明的一个主题是一种具备稳定味道和/或气味的组合物,含有
(a)[6]‐姜酮酚和
(b)至少一种单或多元不饱和C8‐C22脂肪酸或其单或多元C1‐C18脂肪醇酯。
在根据本发明的组合物中[6]‐姜酮酚的含量为约0.0001至1wt.%,优选约0.001至0.1wt.%,并且特别优选0.005至0.05wt.%,相对于组合物的总量计。
已经令人惊讶地观察到,尽管[6]‐姜酮酚作为已知的抗氧化剂与常规抗氧化剂如α‐生育酚具备几乎等同的抗氧化活性,[6]‐姜酮酚甚至在低浓度下也表现出比其他抗氧化剂更优异地防止各种单或多元不饱和C8‐C22脂肪酸及其酯变质的活性。
[6]‐姜酮酚
[6]‐姜酮酚是一种已知的物质[IUPAC‐名称:1‐(4‐羟基‐3‐甲氧基苯基)‐癸‐3‐酮,CAS号:27113‐22‐0,FEMA 4665]。其可以例如根据H.D.Locksley等报道的方法(J.Chem.Soc.,Perkin Trans.I 1972,442,3001–3006)通过相应不饱和类似物的催化氢化合成或由天然源纯化。[6]‐姜酮酚根据温度(熔点31‐32℃,Dictionary of NaturalProducts)是淡黄色至无色固体或液体,尤其在根据本发明的组合物中所需的低使用量下具备低气味。
报道了[6]‐姜酮酚及其同系物的抗氧化和抗肿瘤促进效果(Mutation Research2001,400279,1–8)。[6]‐姜酮酚在体外使H2O2‐和UV诱导的氧化DNA碱基形成减弱。在用DBMA染色的隔日向DMBA‐处理的仓鼠口服施用30mg/kg(6)‐姜酮酚,显著改善了抗氧化物的状态,由该观察推断出[6]‐姜酮酚的抗氧化效率(Pharmacological reports,2010,62,1178‐1185)。
根据本发明[6]‐姜酮酚可单独或与其他已知稳定剂结合使用,所述稳定剂如生育酚和生育酚衍生物,例如乙酸生育酚、抗坏血酸和衍生物如抗坏血酸棕榈酸酯、Oxynex STLiquid(Merck,INCI名称:亚丁香基丙二酸二乙基己酯、辛酸/癸酸甘油三酯)、Tinogard AS(BASF,INCI名称:布美三唑)、Tinogard TT(BASF,INCI名称:季戊四醇四(双‐叔丁基羟基氢化肉桂酸)酯)、Tinogard TS(BASF,INCI名称:十八烷基二‐叔丁基‐4‐羟基氢化肉桂酸酯)、Tinogard TL(BASF,INCI名称:苯并三唑基十二烷基p‐甲酚)、BHT(丁基化羟基甲苯)、丁基羟基茴香醚(BHA)、酸如柠檬酸、酒石酸或草酸或EDTA及其盐。
不饱和脂肪酸及其酯
根据本发明作为成分(b)的不饱和脂肪酸及其酯是指单或多元不饱和脂肪酸及其单或多元C1‐C18脂肪醇酯。
优选地根据本发明的组合物的成分(b)包括
(b‐1)至少一种式(II)的酰基化合物
其中
R代表氢原子或C1‐C18烷基和
X代表单或多元不饱和C8‐C22酰基,
和/或
(b‐2)至少一种式(III)的酰基甘油化合物
其中
X’、X”和X”’相互独立地代表氢原子或者饱和或单或多元不饱和C8‐C22酰基,
前提是X’、X”和X”’不同时代表氢原子并且X’、X”和X”’中至少一个是不饱和酰基。
酰基化合物
根据本发明的作为成分(b‐1)的式(II)的酰基化合物包括单或多元不饱和C8‐C22脂肪酸和其C1‐C18醇的酯。
成分(b‐1)的C1‐C18的典型代表包括但不限于棕榈油酸(C16:1)、油酸(C18:1)、反油酸(C18:1)、蓖麻油酸(C18:1)、岩芹酸(C18:1)、11‐十八碳烯酸(C18:1)、亚油酸(C18:2)、α‐亚麻酸(C18:3)、γ‐亚麻酸(C18:3)、顺式‐亚麻酸(C18:3)、石榴酸(C18:3)、桐油酸(C18:3)、十八碳四烯酸(C18:4)、二十碳烯酸(C20:1)、二十碳‐9‐烯酸(C20:1)、二十烯酸(C20:1)、花生四烯酸(C20:4)、芥酸(C22:1)、EPA(C20:5)、二十二碳六烯酸(C20:5)、DHA(C22:6)、油酸肉豆蔻酯、芥酸肉豆蔻酯、油酸十六烷醇酯、芥酸十六烷醇酯、油酸十八烷醇酯、芥酸十八烷醇酯、油酸异十八烷醇酯、肉豆蔻酸油醇酯、棕榈酸油醇酯、硬脂酸油醇酯、异硬脂酸油醇酯、油酸油醇酯、山嵛酸油醇酯、芥酸油醇酯、油酸二十二烷醇酯、芥酸二十二烷醇酯、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。
在本发明的一个优选实施方案中,式(II)酰基化合物中R是氢原子,X是单或多元不饱和C16‐C22酰基。
在本发明的一个最优选实施方案中成分(b‐1)是油酸、亚油酸、γ‐亚麻酸、α‐亚麻酸、EPA和DHA。
亚油酸在葵花籽油、大豆油、红花油、玉米油、芝麻油、花生油、葡萄籽油和小麦胚芽油中产量最丰富。它对皮肤屏障功能至关重要。在干性皮肤中它强化表皮的脂肪屏障、抵抗水分的经表皮流失并且调节皮肤新陈代谢。在粉刺皮肤的人群中,观察到皮脂中亚油酸含量的减小,这导致毛孔堵塞以及形成粉刺和湿疹。在油性皮肤和问题皮肤使用亚油酸导致皮脂腺功能的改善,疏通毛孔并减少粉刺数量。
γ‐亚麻酸属于ω‐6系列并且可由天然源包括琉璃苣油、黑加仑油、月见草油和麻油得到。此外α‐亚麻酸是ω‐3组的代表物并且见于亚麻籽油、大豆油、菜籽油、小麦胚芽油、核桃油、藻类和海洋浮游植物。α‐和γ‐亚麻酸是细胞膜或人类细胞线粒体膜的生理成分。
多元不饱和脂肪酸如二十碳五烯酸(EPA)或二十二碳六烯酸(DHA)见于三文鱼、鳕鱼、鲱鱼、鲭鱼的鱼油中并且是藻类和海洋浮游植物的代谢产物。
酰基甘油化合物
在根据本发明的组合物中作为成分(b‐2)的式(III)的酰基甘油化合物涉及由甘油与C8‐C22脂肪酸形成的单、双或三甘油酯,其中脂肪酸包括但不限于辛酸(C8:0)、癸酸(C10:0)、月桂酸(C12:0)、肉豆蔻酸(C14:0)、棕榈酸(C16:0)、棕榈油酸(C16:1)、十七烷酸(C17:0)、硬脂酸(C18:0)、油酸(C18:1)、反油酸(C18:1)、蓖麻油酸(C18:1)、岩芹酸(C18:1)、11‐十八碳烯酸(C18:1)、亚油酸(C18:2)、α‐亚麻酸(C18:3)、γ‐亚麻酸(C18:3)、顺式‐亚麻酸(C18:3)、石榴酸(C18:3)、桐油酸(C18:3)、十八碳四烯酸(C18:4)、花生酸(C20:0)、二十碳烯酸(C20:1)、二十碳‐9‐烯酸(C20:1)、二十烯酸(C20:1)、花生四烯酸(C20:4)、芥酸(C22:1)、EPA(C20:5)、二十二碳六烯酸(C20:5)、二十二烷酸(C22:0)、DHA(C22:6)。
成分(b‐2)的典型代表包括但不限于棕榈油酸、油酸、亚油酸、亚麻酸、十八碳四烯酸、二十碳五烯酸、二十二碳六烯酸的单、二或三甘油酯,如甘油三油酸酯、甘油三亚油酸酯、甘油三亚麻油酸酯、1,3‐二油酸甘油酯、1,2‐二油酸甘油酯、1,3‐二亚油酸甘油酯、1,2‐二亚油酸甘油酯、1,3‐二亚麻酸甘油酯、1,2‐二亚麻酸甘油酯、1‐单油酸甘油酯、2‐单油酸甘油酯、1‐单亚麻酸甘油酯、2‐单亚麻酸甘油酯、1‐单亚麻酸甘油酯、2‐单亚麻酸甘油酯和混合的二或三甘油酯如1‐硬脂酸‐3‐油酸甘油酯、1‐硬脂酸‐2‐油酸甘油酯、2‐硬脂酸‐1‐油酸甘油酯、1‐硬脂酸‐3‐亚油酸甘油酯、1‐硬脂酸‐2‐亚油酸甘油酯、2‐硬脂酸‐1‐亚油酸甘油酯、1‐硬脂酸‐3‐亚麻酸甘油酯、1‐硬脂酸‐2‐亚麻酸甘油酯、2‐硬脂酸‐1‐亚麻酸甘油酯、1‐棕榈酸‐3‐油酸甘油酯、1‐棕榈酸‐2‐油酸甘油酯、2‐棕榈酸‐1‐油酸甘油酯、1‐棕榈酸‐3‐亚油酸甘油酯、1‐棕榈酸‐2‐亚油酸甘油酯、2‐棕榈酸‐1‐亚油酸甘油酯、1‐棕榈酸‐3‐亚麻酸甘油酯、1‐棕榈酸‐2‐亚麻酸甘油酯、2‐棕榈酸‐1‐亚麻酸甘油酯、1,2‐二硬脂酸‐3‐油酸甘油酯、1,3‐二硬脂酸‐2‐油酸甘油酯、2,3‐二硬脂酸‐1‐油酸甘油酯、1,2‐二硬脂酸‐3‐亚油酸甘油酯、1,3‐二硬脂酸‐2‐亚油酸甘油酯、2,3‐二硬脂酸‐1‐亚油酸甘油酯、1,2‐二硬脂酸‐3‐亚麻酸甘油酯、1,3‐二硬脂酸‐2‐亚麻酸甘油酯、2,3‐二硬脂酸‐1‐亚麻酸甘油酯、1,2‐二棕榈酸‐3‐油酸甘油酯、1,3‐二棕榈酸‐2‐油酸甘油酯、2,3‐二棕榈酸‐1‐油酸甘油酯、1,2‐二棕榈酸‐3‐亚油酸甘油酯、1,3‐二棕榈酸‐2‐亚油酸甘油酯、2,3‐二棕榈酸‐1‐亚油酸甘油酯、1,2‐二棕榈酸‐3‐亚麻酸甘油酯、1,3‐二棕榈酸‐2‐亚麻酸甘油酯、2,3‐二棕榈酸‐1‐亚麻酸甘油酯、1,2‐二油酸‐3‐硬脂酸甘油酯、1,3‐二油酸‐2‐硬脂酸甘油酯、1,2‐二亚油酸‐3‐硬脂酸甘油酯、1,3‐二亚油酸‐2‐硬脂酸甘油酯、1,2‐二亚麻酸‐3‐硬脂酸甘油酯、1,3‐二亚麻酸‐2‐硬脂酸甘油酯、1,2‐二油酸‐3‐棕榈酸甘油酯、1,3‐二油酸‐2‐棕榈酸甘油酯、1,2‐二亚油酸‐3‐棕榈酸甘油酯、1,3‐二亚油酸‐2‐棕榈酸甘油酯、1,2‐二亚麻酸‐3‐棕榈酸甘油酯、1,3‐二亚麻酸‐2‐棕榈酸。
在本发明的一个优选实施方案中式(III)的酰基化合物是源自植物油的单、二或三甘油酯。
在本发明的另一个优选实施方案中式(III)的酰基化合物是二甘油酯,其主要源自植物油,即式(III)的X’、X”和X”’中的两个相互独立地代表饱和或单或多元不饱和C8‐C22酰基,前提是其中之一是不饱和。
在本发明的另一个优选实施方案中式(III)的酰基化合物是单甘油酯,其主要源自植物油,即式(III)的X’、X”和X”’中的一个相互独立地代表单或多元不饱和C8‐C22酰基。
植物油是在室温下保持液体形式的液态植物脂肪。这些脂肪通常由植物各个部位,如种子、果实或植物幼苗提取。在化学术语中它们是较高饱和和不饱和脂肪酸三甘油酯的结合。换句话说,这些化合物是甘油和较高脂肪酸的酯,在其结构中含有长脂肪族碳链。根据本发明,植物油包括但不限于阿甘油、野樱莓(籽)油、牛油果油、桃(核)油、芥花油、黑籽油、南瓜(南瓜籽)油、野玫瑰(籽)油、石榴籽油、霍霍巴(液体蜡)油、可可/可可脂、小麦胚芽油、椰子/椰子油、红花油、玉米油、亚麻荠(Camelina)油、亚麻籽油、澳洲胡桃油、覆盆莓籽油、白芒花(Meadowfoam)籽油、西番莲(Passiflora)籽油、杏仁油、印度楝树(Neem)油、辣木(Moringa)油、琉璃苣(Borago)油、橄榄油、花生油、榛果油、核桃油、棕榈油、木瓜籽油、欧芹籽油、沙棘油、蓖麻油、米油、芝麻油、乳木果油/牛油果油、葵花籽油、大豆油、琼崖海棠(Tamanu)油、月见草油、葡萄籽油、蔓越莓籽油。
在本发明的一个最优选实施方案中式(III)的成分(b‐2)主要由在甘油分子上以各种结合酯化的油酸、亚油酸和亚麻酸构成。
此外,本发明要求[6]‐姜酮酚用于稳定不饱和脂肪酸(酯)的味道和/或气味的用途。
在一个优选实施方案中不饱和脂肪酸(酯)是单或多元不饱和C8‐C22脂肪酸或其单或多元C1‐C18脂肪醇酯。
在一个更优选实施方案中单或多元不饱和C8‐C22脂肪酸或其单或多元C1‐C18脂肪醇酯包括
(b‐1)至少一种式(II)的酰基化合物
其中
R代表氢原子或C1‐C18烷基和
X代表单或多不饱和C8‐C22酰基,
和/或
(b‐2)至少一种式(III)的酰基甘油化合物
其中
X’、X”和X”’相互独立地代表氢原子或者饱和或单或多元不饱和C8‐C22酰基,前提是X’、X”和X”’不同时代表氢原子并且X’、X”和X”’中至少一个是不饱和酰基。
在另一个优选实施方案中[6]‐姜酮酚的用量为0.0001至1wt.%,优选0.001至0.1wt.%,并且特别优选0.005至0.05wt.%,相对于组合物总量计。
进一步地,本发明要求[6]‐姜酮酚用于稳定至少部分不稳定—这是指氧气、温度和/或光敏感的—化妆品和/或食品成分以防止味道改变和/或变色的用途。含有[6]‐姜酮酚和这些不稳定化妆品成分的组合物也是本发明的主题。
不稳定的化妆品和/或食品成分是例如间苯二酚类如4‐(1‐苯乙基)‐1,3‐间苯二酚(INCI:苯乙基间苯二酚,商品名:Symrise的SymWhite 377)或4‐烷基间苯二酚类如4‐己基间苯二酚(INCI:己基间苯二酚,商品名例如Sytheon的Synovea HR或Kumar OrganicProd‐ucts的Kopnol)和4‐丁基间苯二酚(INCI:丁基间苯二酚,商品名例:Kuraray Co.的Rucinol或Vivimed Labs的Vivinol)以及其他易于变色的酚类化合物、维生素和维生素衍生物如维生素A、维甲酸、视黄酸及其衍生物、视黄醇及其衍生物,例如视黄醇乙酸酯、视黄醇丙酸酯、视黄醇棕榈酸酯、视黄醇油酸酯、视黄醇亚油酸酯、视黄醇视黄酸酯,。
优选地,不稳定化妆品成分选自间苯二酚类如SymWhite 377、4‐己基间苯二酚和4‐丁基间苯二酚和/或视黄醇和衍生物如视黄醇乙酸酯、视黄醇丙酸酯、视黄醇棕榈酸酯、视黄醇视黄酸酯。
工业应用
个人护理组合物
本发明的另一个主题是提供个人护理组合物或化妆品组合物,其含有根据本发明的具备稳定味道和/或气味的组合物。
个人护理或化妆品组合物可以含有研磨剂、抗痤疮剂、抗皮肤老化剂、抗橘皮组织剂、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、软化剂、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、驱污剂、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(re‐oiling agents)、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、冷却剂、皮肤冷却剂、加温剂、皮肤升温剂、稳定剂、紫外线吸收剂、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作为额外助剂和添加剂。
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是肥皂、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、脂肪族醇醚硫酸盐、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,但优选窄的同系物分布。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要著作,例如J.Falbe(ed.),“Surfactants in Con总量er Products”,Springer Verlag,Berlin,1987,pages 54to124or J.Falbe(ed.),“Katalysatoren,Tenside und(Catalysts,Surfactants and矿物油Additives)”,Thieme Verlag,Stuttgart,1978,pages 123‐217。表面活性剂在制剂中的百分比含量为0.1至10重量%,并且优选0.5至5重量%,基于制剂计。
油体
适当的油体,其为O/W乳液的成分,是例如基于含有6至18个,优选8至10个碳原子的Guerbet醇,直链饱和C6‐C22‐脂肪酸与直链或支链C6‐C22‐脂肪族醇的酯或支链饱和C6‐C13‐羧酸与直链或支链C6‐C22‐脂肪族醇的酯,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、山嵛酸十四烷酯、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、山嵛酸十六烷酯、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、山嵛酸十八烷酯、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、山嵛酸异十八烷酯、肉豆蔻酸油醇酯、棕榈酸油醇酯、硬脂酸油醇酯、异硬脂酸油醇酯、山嵛酸油醇酯、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、山嵛酸二十二烷酯、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、山嵛酸芥醇酯。此外适当的是饱和直链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‐C22‐脂肪族醇的酯,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、基于饱和C6‐C10‐脂肪酸的甘油三酯、基于饱和C6‐C18‐脂肪酸的液态单‐/二‐/三酸甘油酯混合物、C6‐C22‐脂肪族醇和/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、支链伯醇、取代环己烷、直链和支链C6‐C22‐脂肪族醇的碳酸酯,如例如碳酸二辛酯(CC)、基于具有6至18个优选8至10个碳原子的脂肪族醇的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
也可以将其他表面活性剂加入制剂作为乳化剂,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脂肪族醇、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摩尔环氧乙烷在甘油上的加成产物的C12/18脂肪酸单酯和二酯;
●含有6至22个碳原子的饱和和不饱和脂肪酸甘油单酯和二酯和脱水山梨糖醇单酯和二酯和它们的环氧乙烷加成产物;
●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,尤其是聚甘油酯例如,聚甘油聚蓖麻醇酸酯、聚甘油聚‐12‐羟基硬脂酸酯或聚甘油二聚合油异硬脂酸酯。同样适用的是多个这类化合物的混合物;
●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、蓖麻油酸以及12‐羟基硬脂酸和甘油、聚甘油、季戊四醇、二季戊四醇、糖醇(例如山梨糖醇)、烷基葡糖苷(例如:甲基葡糖苷、丁基葡糖苷、月桂基葡糖苷)以及多葡糖苷(例如纤维素)的偏酯;
●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、柠檬酸和脂肪族醇的混合脂和/或C6‐22脂肪酸、甲基葡萄糖和多元醇,优选丙三醇或聚甘油的混合脂;
●聚二醇类以及
●碳酸甘油酯。
环氧乙烷和/或环氧丙烷与脂肪族醇、脂肪酸和烷基酚的加成产物,脂肪酸或蓖麻油的甘油单酯和二酯和脱水山梨糖醇单酯和二酯是市场上可以买到的产品。在这里是指同系混合物,其平均烷氧基化度相当于进行加成反应的环氧乙烷和/或环氧丙烷和基质的用量比例。环氧乙烷与甘油加成产物的C12/18脂肪酸单酯和二酯已知用作化妆制剂的富脂剂。优选的乳化剂在下文详细列出:
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酯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C12‐22脂肪酸,如例如棕榈酸、硬脂酸或山嵛酸,以及C12‐22二羧酸,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,其中脂肪酸烷醇酰胺也可用作泡沫稳定剂。
使用的主要稠度因子是含有12至22个并且优选16至18个碳原子的脂肪族醇或羟基脂肪族醇以及偏甘油酯、脂肪酸或羟基脂肪酸。优选使用这些物质与烷基寡葡萄糖苷和/或相同链长的脂肪酸N‐甲基葡糖酰胺和/或聚甘油聚‐12‐羟基硬脂酸酯的结合物。
增稠剂和流变添加剂
适当的增稠剂是聚合物增稠剂,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和羟丙基纤维素、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、窄同系物分布的脂肪族醇乙氧基化物和电解质,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,例如由Amerchol得到商品名为Polymer JR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)、聚乙二醇类和胺类的缩合产物、季铵化胶原多肽如,例如月桂基二甲基铵羟丙基水解胶原(Lame‐L,)、季铵化小麦多肽、聚乙烯亚胺、阳离子硅氧烷聚合物,例如氨基二甲聚硅氧烷(氨基封端聚二甲基硅氧烷)、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,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),其以商品名CC或300市售。
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个碳原子的脂肪族醇的酯,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,如例如脂肪族醇、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个碳原子的脂肪族醇和/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。适当的挥发硅氧烷化合物的详细介绍见于Todd et al.in Cosm.Toil.91,27(1976)。
蜡和稳定剂
除了使用的天然油,制剂中还可以含有蜡,尤其是天然蜡例如,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(shellac wax)、鲸蜡、羊毛脂(wool wax)、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)、沙索蜡(sasolwaxes)、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。
作为稳定剂可以使用脂肪酸的金属盐,如例如硬脂酸或蓖麻酸镁、铝和/或锌盐。
主要防晒剂
在本发明中主要防晒剂是,例如在室温下是液态或结晶的有机物质(光过滤物质),其能够吸收紫外辐射并又以长波辐射的形式释放吸收的能量,例如热量。
根据本发明的制剂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/或宽带过滤物质和/或至少一种无机染料。根据本发明的制剂优选含有至少一种UV‐B过滤物质或一种宽带过滤物质,更特别是至少一种UV‐A过滤物质和至少一种UV‐B过滤物。
优选的化妆品组合物,优选根据本发明的局部制剂含有一种、两种、三种或多种防晒剂,选自组包括4‐氨基苯甲酸及衍生物,水杨酸衍生物、二苯酮衍生物、二苯酰甲烷衍生物、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,有利的是将式(I)的化合物与活性物质—其渗透进入皮肤并从内部保护皮肤抵抗光线导致的损伤并减小皮肤基质金属蛋白酶的含量—结合。优选的成分,所谓的芳基烃受体拮抗剂,记载于WO 2007/128723,在本文引用。优选2‐亚苄基‐5,6‐二甲氧基‐3,3‐二甲基茚‐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‐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)(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‐甲氧基二苯甲酮(NeoBB)
●2‐羟基‐4‐甲氧基二苯甲酮‐5‐磺酸
●二羟基‐4‐甲氧基二苯甲酮
●2,4‐二羟基二苯甲酮
●四羟基二苯甲酮
●2,2'‐二羟基‐4,4'‐二甲氧基二苯甲酮
●2‐羟基‐4‐正辛氧基二苯甲酮
●2‐羟基‐4‐甲氧基‐4'‐甲基二苯甲酮
●羟基甲氧基二苯甲酮磺酸钠
●2,2'‐二羟基‐4,4'‐二甲氧基‐5,5'‐二磺基‐二苯甲酮二钠
●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
优选与一种或多种本发明制剂中的式(I)化合物结合的UV‐A过滤物质选自组包括
●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)‐苯甲酸己基酯(A Plus)
●根据DE 100 55 940A1(=WO 2002038537)的茚满亚基化合物
优选与一种或多种本发明制剂中的式(I)化合物结合的UV过滤物质选自组包括
●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‐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(NeoE1000)
●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‐甲氧基二苯甲酮‐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(Neo Heliopan MA)
●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。
二级防晒剂
有利的主要以及二级防晒剂记载于WO 2005 123101 A1。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)乳剂、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头发。
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、酪氨酸、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、氯原酸及其衍生物、硫辛酸及其衍生物(例如二氢硫辛酸)、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 123101 A1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)、镁的氧化物(例如MnO)、铝的氧化物(Al2O3)、铈的氧化物(例如Ce2O3)和/或其混合物。
抗衰老活性物
在本发明中抗衰老剂或生物活性剂是,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,特别是槲皮素及其衍生物,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。
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(TetradecylAminobutyroylvalylaminobutyric脲Trifluoroacetate)、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。
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。
植物提取物。组合物也可以含有各种植物提取物,如银杏(Ginkgo biloba)、橄榄树(Oleacea europensis)、Glyzyrrhiza glabra、越桔(Vaccinium myrtillus)、红三叶(Trifolium pratense)、荔枝(Litchi sinensis)、葡萄(Vitis)、酿酒葡萄(vinifera)、甘蓝(Brassica oleracea)、石榴(Punica granatum)、Petroselinium crispum、雷公根(Centella asiatica)、西番莲(Passiflora incarnata)、紫花苜蓿(Medicago sativa)、香蜂花(Melissa officinalis)、缬草(Valeriana officinalis)、欧洲板栗(Castaneasativa)、白柳(Salix alba)和Hapagophytum procumbens的提取物。
清凉剂
组合物可以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EP 2033688A2中描述的)。
抗微生物剂
适当的抗微生物剂理论上是能够抵抗革兰氏阳性菌的所有物质,如例如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、3‐碘‐2‐丙炔氨基甲酸丁酯、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。这些酶抑制剂优选柠檬酸三烷酯,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(HydagenCAT)。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。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(boisambrene forte)、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。
芳香油和芳香剂
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、鸢尾、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。
根据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)的化合物在皮肤和/或毛发上停留更长的时间,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5至99%b.w.,优选10至80%b.w.,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。
所述制剂还可至多含有99%b.w.,优选地,5至80%b.w.的水,基于制剂总量计。
食品组合物
本发明的另一个主题是提供食品组合物,其含有根据本发明的具备稳定味道和/或气味的组合物。
本发明的食品组合物是任何适用于消费并用于营养或享受目的的制剂或组合物,以及旨在被引入人类或动物口腔并在其中停留一段时间并随后被食用的产品(例如即食食品或饲料,见下文)或被由口腔移除的产品(例如口香糖)。这类产品包括任何在加工、部分加工或未加工状态下被人或动物消化的任何物质或产品。它们也包括在口服消费产品生产、制备或处理过程中加入并旨在引入人或动物口腔的物质。
本发明的食品组合物也包括在未改变、处理或制备状态下被人或动物吞下并消化的物质;在这方面本发明的口服消费产品也包括其他同时被吞食或预期被吞食的肠衣、糖衣或其他胶囊。表述“口服消费产品”是指即食食品和饲料,也就是对于味道重要的物质已经完成的食品和饲料。表述“即食食品”和“即食饲料”也包括饮料以及固体或半固体即食食品或饲料。可以提及的实例是冷冻产品,其在食用前必须解冻并加热至食用温度。产品如酸奶或冰激凌以及口香糖或硬焦糖也属于即食食品或饲料。
根据本发明优选的食品组合物也包括“半成产品”。在本发明中半成产品是指口服消费产品,其由于高含量的香料和味道赋予物质不适用作即食口服产品(特别是食品或饲料)。半成产品仅通过与至少一种其他成分混合(例如通过减少所述香料或味道赋予物质的浓度)并且任选进一步加工步骤(例如加热、冷冻)转化为即食口服产品(特别是食品或饲料)。半成产品的实例此处提到。
本发明的食品组合物优选包含一种或多种用于营养或享受目的的制剂。这特别包括(低卡路里)烘焙产品(例如面包、干饼干、蛋糕、其他烘烤产品)、糕饼(例如巧克力、巧克力棒、其他棒状产品、水果软糖、糖衣片、硬的和软的焦糖、口香糖)、无醇饮料(例如可可、咖啡、绿茶、红茶、富含(绿、红)茶提取物的(绿、红)茶饮品、rooibos茶、其他草本茶、含有水果的软饮、等张饮料、清爽饮料、甜美饮料(nectars)、水果和蔬菜果汁、水果或蔬菜果汁制品)、速溶饮料(例如速溶可可饮料、速溶茶饮料、速溶咖啡饮料)、肉质品(例如火腿、新鲜香肠或生香肠制品、五香或腌制的新鲜或腌肉制品)、蛋或蛋制品(干蛋、蛋白、蛋黄)、谷物制品(例如早餐谷物、麦片棒、预煮即食米饭制品)、奶制品(例如全脂或低脂或脱脂奶饮料、米粉布丁、酸奶、克菲尔(kefir)、奶油奶酪、软奶酪、硬奶酪、干燥奶粉、乳清、黄油、白脱牛奶、含有部分或全部水解乳蛋白的制品)、由大豆蛋白或其他大豆馏分得到的制品(例如豆奶和由其制得的制品、含有分离的或酶加工的大豆蛋白的饮料、含有大豆粉的饮料、含有大豆卵磷脂的制品、发酵产品如豆腐或豆豉或由其制得的制品和与水果制品以及任选香料的混合物)、水果制品(例如果酱、果汁冰糕(sorbets)、蜜饯、水果馅料)、蔬菜制品(例如番茄酱、调味汁、干燥蔬菜、冷冻蔬菜、预煮蔬菜、熬煮蔬菜)、小吃(例如烤制或炸制薯片或土豆球产品、玉米或花生为主的挤出物)、脂肪或油基制品或其乳液(例如蛋黄酱、加料蛋黄酱、调料、各个均为全脂或低脂)、其他即食菜品和汤(例如汤粉、速溶汤粉、预煮汤)、香料、香料混合物以及特别是在例如小吃领域使用的佐料、甜味剂制品、片剂或袋剂、其他用于将饮料或其他食品调成甜味或调白的制品。本发明范围内的制品也可以半成品的形式用于生产其他用于营养或享受目的的制品。本发明范围内的制品也可以胶囊、片剂(未包衣和包衣片剂,例如肠溶衣)、糖衣片、颗粒、丸剂、固体混合物、液体相中分散体的形式、乳液形式、粉末形式、溶液形式、浆剂或其他可以被吞食或咀嚼的制剂的形式,以及食品添加剂的形式。
半成品通常用于生产用于营养或享受目的的即用或即食制剂。
用于营养或享受目的的即食制剂或半成品制品的其他成分可以是用于食品或享受食品的常规底物、辅助物质和添加剂,例如水、新鲜或加工的蔬菜或动物为主或生料混合物(例如生的、烘烤、干燥、发酵、熏制和/或煮制肉类、骨头、软骨、鱼、蔬菜、草药、坚果、蔬菜汁、蔬菜泥或其混合物)、易消化或不易消化的碳水化合物(例如蔗糖、麦芽糖、果糖、葡萄糖、糊精、直链淀粉、支链淀粉、菊粉、木聚糖、纤维素、塔格糖)、糖醇(例如山梨糖醇、赤藻糖醇)、天然或硬化脂肪(例如牛脂、猪油、棕榈脂、椰子油、氢化植物脂肪)、油(例如向日葵油、花生油、玉米油、橄榄油、鱼油、豆油、芝麻油)、脂肪酸或其盐(例如硬脂酸钾)、蛋白或非蛋白氨基酸和相关化合物(例如γ‐氨基丁酸、牛磺酸)、肽(例如谷胱甘肽)、天然或加工蛋白质(例如明胶)、酶(例如肽酶)、核酸、核苷酸、令人不愉快味道印象的味道矫正剂、用于其它通常不是令人不愉快味道印象的其它味道调节剂、其它味道调节物质(例如环己六醇磷酸酯、核苷酸如鸟苷单磷酸盐、腺苷单磷酸盐或其它物质,如谷氨酸钠或2‐苯氧基丙酸)、乳化剂(例如卵磷脂、甘油二酯、阿拉伯胶)、稳定剂(例如角叉菜胶、藻酸盐)、防腐剂(例如苯甲酸及其盐、山梨糖酸及其盐)、抗氧化剂(例如生育酚、抗坏血酸)、螯合剂(例如柠檬酸)、有机或无机酸(例如乙酸、磷酸)、苦味素(例如奎宁、咖啡因、柠檬苦素、苦龙胆脂苷、律草酮(humolone)、蛇麻酮(lupolone)、儿荼酚、鞣酸)、防止酶促褐变的物质(例如亚硫酸盐、抗坏血酸)、醚油、植物提取物、天然或合成的着色剂或着色颜料(例如类胡萝卜素、类黄酮、花色素、叶绿素及其衍生物)、辛香料、三叉神经活性物质或包含这种三叉神经活性物质的植物提取物、合成的、天然的或等同天然的香料或芳香剂以及气味矫正剂。
本发明的食品组合物,例如以制品或半成品形式的那些,优选含有调味组合物用于完善和改良味道和/或气味。一种制品可以含有固体载体和调味组合物成分。适当的调味组合物包括,例如,合成、天然或等同天然的香料、香精和味道赋予物质、反应香料、烟熏香料或其他香味赋予制品(例如蛋白(部分)水解物,优选具有高精氨酸含量的蛋白(部分)水解物、烤肉香料、植物提取物、辛香料、调味制品、蔬菜和/或蔬菜制品)以及适当的辅助物质和载体。此处特别适当的是产生烘烤、肉香(特别是鸡肉、鱼肉、海鲜、牛肉、猪肉、羔羊肉、羊肉、山羊肉)、类蔬菜(特别是番茄、洋葱、大蒜、芹菜、韭菜、蘑菇、茄子、海藻)、香辛料(特别是黑胡椒和白胡椒、小豆蔻、肉豆蔻、西班牙甘椒、芥末和芥末制品)、炸制、类酵母、煮制、脂肪、咸味和/或辛辣的味道印象并因此可以增强辣味印象。香料组合物通常含有多于一种所述的成分。
本发明的食品组合物优选自组包括
●糕饼,优选低热量或无热量糕饼,优选自组包括麦片棒产品、水果糖、糖衣片、硬焦糖和口香糖,
●无醇饮料,优选自组包括绿茶、红茶、富含(绿、红)茶提取物的(绿、红)茶饮品、rooibos茶、其他草本茶、含有水果的低糖或无糖软饮、等张饮料、甜美饮料(nectars)、水果和蔬菜果汁、水果或蔬菜果汁制品,
●速溶饮料,优选自组包括速溶(绿、红、rooibos、草本)茶饮料,
●谷物制品,优选自组包括低糖和无糖早餐谷物和麦片棒,
●奶制品,优选自组包括低脂和脱脂奶饮料、酸奶、克菲尔、乳清、白脱牛奶或冰激凌,
●由大豆蛋白或其他大豆馏分得到的制品,优选自组包括豆奶、由豆奶制得的制品、含有分离的或酶加工的大豆蛋白的饮料、含有大豆粉的饮料、含有大豆卵磷脂的制品、由含有大豆卵磷脂和水果制品以及任选香料的混合物的制品制得的产品,●甜味剂制品、片剂或袋剂,
●无糖糖衣
●冰激凌,含有或不含奶基成分,优选无糖。
香味或香料化合物
本领域熟知的香味化合物和香料制剂(成分d)可以加入本发明的香料组合物。这些香料制剂可以选自合成香料液体和/或源自植物叶、花、果实等的油及其结合。香料液体的代表包括:人工、天然或合成水果香料如桉树油、柠檬油、橙油、香蕉油、葡萄油、白柠檬油、杏仁油和葡萄柚油和水果香精包括苹果、草莓、樱桃、橙子、菠萝等;豆类和坚果产生的味道如咖啡、可可、可乐、花生、杏仁等;以及根产生的味道如甘草或姜。
香料制剂优选自组包括精油和提取物、酊剂和香膏,例如茴香醚、罗勒油、佛手柑油、苦杏仁油、樟脑油、香茅油、柠檬油;柠檬桉油、桉树油、茴香油、葡萄柚油、洋甘菊油、荷兰薄荷油、蒿子油、白柠檬油、橘子油、肉豆蔻油(特别是肉豆蔻花油)、没药油、丁香油、丁香花油、橙油、牛至油、欧芹(籽)油、辣薄荷油、迷迭香油、鼠尾草油(香鼠尾草油、达尔马提亚或西班牙鼠尾草油)、八角油、百里香油、香草精、桧油(特别是杜松子油)、冬青油、肉桂叶油、桂皮油及其馏分,或由其分离的成分。
特别有利是本发明的香料组合物含有至少一种,优选两种、三种、四种、五种、六种、七种、八种或更多种香料制剂,其选自以下组:薄荷醇(优选左旋薄荷醇和/或消旋薄荷醇)、茴香脑、茴香醚、茴香醛、茴香醇、(外消旋)新薄荷醇、桉树脑(1,8‐桉油醇)、薄荷酮(优选左旋薄荷酮)、异薄荷酮(优选D‐异薄荷酮)、异胡薄荷醇、乙酸薄荷酯(优选L‐乙酸薄荷酯)、丙酸薄荷酯、香芹酮(优选(‐)‐香芹酮,任选作为荷兰薄荷油的组分)、水杨酸甲酯(任选作为冬青油的组分)、丁香酚乙酸酯、异丁香酚甲醚、β‐环高柠檬醛、丁香酚、异丁醛、3‐辛醇、二甲基硫醚、己醇、己醛、反式‐2‐己醛、顺式‐3‐己烯醇、4‐萜品醇、薄荷烯酮、里哪醇、乙酸8‐罗勒烯酯、异戊醇、异戊醛、α‐蒎烯、β‐蒎烯、苧烯(优选D‐苧烯,任选作为精油的组分)、薄荷酮、反式‐水合桧烯、薄荷呋喃、石竹烯、大根香叶烯D、肉桂醛、薄荷内酯、百里酚、γ‐辛内酯、γ‐壬内酯、γ‐癸内酯、(1,3E,5Z)‐十一烷三烯、2‐丁酮、甲酸乙酯、乙酸3‐辛酯、异戊酸异戊酯、顺式‐和反式‐乙酸香芹酯、对聚伞花素、大马酮、突厥酮、顺式‐氧化玫瑰、反式‐氧化玫瑰、葑醇、乙醛二乙缩醛、乙酸1‐乙氧基乙酯、顺式‐4‐庚烯醛、顺式‐茉莉酮、二氢茉莉酸甲酯、2'‐羟基苯丙酮、薄荷基甲基醚、乙酸桃金娘烯酯、2‐苯乙醇、异丁酸2‐苯乙酯、异戊酸2‐苯乙酯、香叶醇、橙花醇和绿花白千层醇。
特别优选的香味或香料化合物含有薄荷醇、桉油酚、丁香酚、麝香草酚、肉桂醛、辣薄荷油、荷兰薄荷油、桉树油、百里香油、肉桂油、丁香油、云杉针油、茴香油、鼠尾草油、茴香油、八角油、春黄菊油、和蒿子油及其混合物。
甜味剂
术语“甜味剂”代表基于蔗糖甜度(因此甜度为1)的相对甜度至少为25的物质。根据本发明(a)在口服消费产品(特别是食品、饲料或药品)中使用的甜味剂优选防龋齿和/或每克口服消费产品的热量不大于5kcal。
在本发明优选的口服消费产品中有利的甜味剂选自下组:
天然存在的甜味剂,优选自组包括
●神秘果素、莫内林、马宾灵、奇异果甜蛋白、仙茅甜蛋白、布拉齐因、皮泰亭(pentaidin)、D‐苯丙氨酸、D‐色氨酸以及获自含有这些氨基酸和/或蛋白质的自然资源中得到的提取物或馏分,以及这些氨基酸和/或蛋白质的生理上可接受的盐,尤其是钠、钾、钙或铵盐;
●新橙皮苷二氢查尔酮、柚苷二氢查尔酮、甜菊苷、甜菊双糖苷、莱鲍迪苷,尤其是莱鲍迪苷A、莱鲍迪苷B、莱鲍迪苷C、莱鲍迪苷D、莱鲍迪苷E、莱鲍迪苷F、莱鲍迪苷G、莱鲍迪苷H,杜尔可苷和甜叶悬钩子苷、甜茶苷A、甜茶苷B、甜茶苷G、甜茶苷H、甜茶苷I、甜茶苷J、白元参苷1、白元参苷2、糙苏苷1、糙苏苷2、糙苏苷3和糙苏苷4、相思子三萜苷A、相思子三萜苷B、相思子三萜苷C、相思子三萜苷D、奥斯雷丁、聚波朵苷A、strogin 1、strogin 2、strogin 4、selligueain A、二氢槲皮素‐3‐醋酸酯、紫苏葶、telosmoside A15、巴西甘草甜素I‐V、蝶卡苷(pterocaryoside)、cyclocaryosides、木库罗苷(mukurozioside)、反式茴香脑、反式肉桂醛、bryosides、bryonosides、bryonodulcosides、肉质雪胆阜苷、scandenosides、绞股蓝皂苷、三叶苷、根皮苷、二氢黄酮醇、苏木精、青色素、绿原酸、合欢皂苷、telosmosides、gaudichaudioside、罗汉果苷、罗汉果糖苷V、hernandulcins、莽那亭(monatin)、叶甜素、甘草次酸及其衍生物,尤其是其苷类例如甘草甜素,以及这些化合物的生理上可接受的盐,尤其是钠、钾、钙盐或铵盐;
●提取物或提取物的富集馏分,选自组包括奇异果提取物(卡特莫夫灌木)、甜叶菊种(Stevia ssp.)(尤其是Stevia rebaudiana)的提取物、swingle提取物(苦瓜属Momordica或Siratia grosvenorii、罗汉果)、Glycyrrhiza ssp.(尤其是Glycyrrhiza glabra)的提取物、悬钩子属(Rubus ssp.)(尤其是Rubus suavissimus)的提取物、柑橘提取物以及Lippia dulcis的提取物。
合成的甜味物质,优选地选自组包括唛甘浦(magap)、环拉酸钠或环拉酸的其它生理上可接受的盐、安赛蜜K或其它生理上可接受的盐、新橙皮苷二氢查尔酮、柚苷二氢查尔酮、沙卡林(saccharin)、沙卡林钠盐、阿斯巴甜、超级阿斯巴甜、纽甜、阿力甜、糖精、紫苏葶、三氯蔗糖、胍乙酸、卡瑞来、苏洛内特和苏洛奥内特(sucrooctate)。
增稠剂
在本发明优选的口服消费产品(特别是食品、饲料或药品)中有利的增稠剂选自下组包括:交联聚丙烯酸及其衍生物、多糖及其衍生物,如黄原胶、琼脂、海藻酸盐或tyloses、纤维素衍生物,例如羧甲基纤维素和羟基羧甲基纤维素、脂肪醇、甘油单酯和脂肪酸、聚乙烯醇和聚乙烯吡咯烷酮。
根据本发明优选的口服消费产品(特别是食品或饲料)含有使用乳酸菌增稠的奶和/或使用乳酸菌增稠的奶油,并优选自组包括酸奶、克菲尔和夸克。
根据本发明的含有使用乳酸菌增稠奶和/或使用乳酸菌增稠奶油的食品组合物有利地是含有益生菌的口服消费产品,其中益生菌优选自组包括动物双歧杆菌乳亚种BB‐12、动物双歧杆菌乳亚种DN‐173 010、动物双歧杆菌乳亚种HN019、嗜酸乳杆菌LA5、NCFM、约氏乳酸杆菌La1、干酪乳酸杆菌immunitass/defensis、干酪乳酸杆菌代田菌(DSM 20312)、干酪乳酸杆菌CRL431、罗伊氏乳酸杆菌(ATCC 55730)和鼠李糖乳酸杆菌(ATCC 53013)。
口香糖添加剂
根据本发明特别优选的口服消费产品(特别是食品、饲料或药品)是口香糖并包括口香糖胶基。口香糖胶基优选自组包括口香糖或泡泡糖胶基。后者更软,从而可以形成泡泡。根据本发明优选的口香糖胶基,除了常规使用的天然树脂或天然latex树胶,包括弹性体如聚乙酸乙烯酯(PVA)、聚乙烯(低分子量和中等分子量)、聚异丁烯(PIB)、聚丁二烯、异丁烯‐异戊二烯共聚物(丁基橡胶)、聚乙烯基乙醚(PVE)、聚乙烯基丁醚、乙烯基酯和乙烯基醚的共聚物、苯乙烯‐丁二烯共聚物(苯乙烯‐丁二烯橡胶,SBR)或乙烯基弹性体,例如基于乙酸乙烯酯/月桂酸乙烯酯、乙酸乙烯酯/硬脂酸乙烯酯或乙酸亚乙酯/乙酸乙烯酯,及所述弹性体的混合物,例如如EP 0 242 325、US 4,518,615、US 5,093,136、US 5,266,336、US5,601,858或US 6,986,709中所述。此外,根据本发明优选的口香糖胶基还包含其他组分,例如(矿物)填料、增塑剂、乳化剂、抗氧化剂、蜡、脂肪或脂肪油,如硬化(氢化)植物或动物脂肪、甘油单酯、甘油二酯或甘油三酯。适合的(矿物)填料有例如碳酸钙、二氧化钛、二氧化硅、滑石、氧化铝、磷酸二钙、磷酸三钙、氢氧化镁及其混合物。适合的增塑剂或防粘剂(脱粘剂)是例如羊毛脂、硬脂酸、硬脂酸钠、乙酸乙酯、二醋精(二乙酸甘油酯)、三醋精(三乙酸甘油酯)、柠檬酸三乙酯。适合的蜡是例如石蜡、小烛树蜡、巴西棕榈蜡、微晶蜡和聚乙烯蜡。适合的乳化剂是例如磷脂如卵磷脂、脂肪酸的甘油单酯和甘油二酯,例如单硬脂酸甘油酯。
本发明的口香糖(特别是上文公开的)优选包含成分如不同类型的糖、糖替代品、其他甜味物质、糖醇(特别是山梨糖醇、木糖醇、甘露醇)、具有清凉效果的成分、令人不愉快味道印象的味道矫正剂、其他味道矫正物质(例如磷酸肌醇、核苷酸如单磷酸鸟苷、单磷酸腺苷或其他物质如谷氨酸钠或2‐苯氧基丙酸)、保湿剂、增稠剂、乳化剂、稳定剂、气味校正剂和香料(例如桉树‐薄荷脑、樱桃、草莓、葡萄柚、香草、香蕉、柑橘、桃、黑醋栗、热带水果、姜、咖啡、肉桂、(所述香料)与薄荷香料的结合以及单独的荷兰薄荷和辣薄荷)。特别优选的是香料与其他具有清凉、温暖和/或令人垂涎特性物质的结合。
用于稳定脂肪酸(酯)味道和/或气味的方法
本发明的另一个主题是提供一种稳定不饱和脂肪酸(酯)味道和/或气味的方法,其中将[6]‐姜酮酚加至不饱和脂肪酸(酯)。
在一个优选实施方案中不饱和脂肪酸(酯)是单或多元不饱和C8‐C22脂肪酸或其单或多元C1‐C18脂肪醇酯。
在一个更优选实施方案中单或多元不饱和C8‐C22脂肪酸或其单或多元C1‐C18脂肪醇酯包括
(b‐1)至少一种式(II)的酰基化合物
其中
R代表氢原子或C1‐C18烷基和
X代表单或多元不饱和C8‐C22酰基,
和/或
(b‐2)至少一种式(III)的酰基甘油化合物
其中
X’、X”和X”’相互独立地代表氢原子或者饱和或单或多元不饱和C8‐C22酰基,
前提是X’、X”和X”’不同时代表氢原子并且X’、X”和X”’中至少一个是不饱和酰基。
在另一个优选实施方案中[6]‐姜酮酚的用量为0.0001至1wt.%,优选0.001至0.1wt.%,并且特别优选0.005至0.05wt.%,相对于组合物总量计。
实施例
实施例1
抗氧化活性的评估
6‐姜酮酚是已知的抗氧化剂。借助ABTS‐试验比较[6]‐姜酮酚和α‐生育酚的抗氧化能力。
通过过硫酸钾2,2’‐连氮基双‐(3‐乙基苯并噻唑啉6‐磺酸)(ABTS)转变为蓝绿色自由基ABTS·+。通过加入[6]‐姜酮酚和α‐生育酚该自由基被还原并且观察到变色,通过在734nm的吸光度测定。通过以下公式计算测试物质对自由基形成的抑制:
其中缩写有以下含义:
●A测试物质:含有测试物质[6]‐姜酮酚和α‐生育酚的光井的吸光度
●A对比样:不含测试物质光井的吸光度
由一系列测试样本稀释液中自由基形成的抑制[%]计算IC50。其为自由基形成被抑制50%的浓度。结果示于表1。
表1
基于自由基形成抑制的活性(至少两次独立试验的平均值)
测试物质 | IC50(μM) |
[6]‐姜酮酚 | 17,4 |
α‐生育酚 | 26,8 |
结果示出[6]‐姜酮酚和α‐生育酚表现出相似的IC50值,表示相似的自由基消除活性,而[6]‐姜酮酚稍微好于α‐生育酚(1.5倍)。
实施例2
阿甘油的嗅觉评估
如表2给出制备含有阿甘油和[6]‐姜酮酚(A)以及不含[6]‐姜酮酚(B)的油体样本以评估[6]‐姜酮酚的气味保护效果。
表2
油体样本A和B的组成(含量以%b.w.计)
通常阿甘油(INCI:刺阿干树(ARGANIA SPINOSA)仁油)是透明、黄至橙色液体,特征在于酰基甘油含有42‐50%油酸(C18:1)、30‐36%亚油酸、12‐16%棕榈酸(C16:0)和4‐6%硬脂酸(C18:0)。它具备非常特有并且强烈的气味。
在本实验中使用的阿甘油特征在于,通过各自脂肪酸甲酯的甲醇醇解后GC分析测定,酰基甘油化合物含有51%油酸(C18:1)、35%亚油酸、14%棕榈酸(C16:0)和6%硬脂酸(C18:0)。进一步地,通过分别具备光散射检测和二极管阵列检测的HPLC分析测定,其含有0.29%油酸(C18:1)和0.25%亚油酸作为自由脂肪酸。
通过HPLC‐MS表征酰基化合物和酰基甘油化合物并列于表3:
HPLC‐MS:YMC ODS‐AQ,5μm,150x3mm带预柱,温度:40℃,流速:0,4ml/分钟,梯度为100%甲醇至100%异丙醇,检测波长205nm,柱后通过注射泵加入100mM甲醇铵甲酸溶液,流速:0.150μl/h,MS离子阱,带有自动MS/MS碎片的正离子和负离子模式的ESI,扫描200至1500。
表3
在负离子(研究自由脂肪酸)和正离子(研究酰基甘油化合物)模式下通过HPLC‐MS测定表征酰基化合物和甘油酯化合物
(1)M‐1代表[M‐H]‐离子
(2)M+18代表[M+NH4]+离子
(3)M+23代表[M+Na]+离子
列表中酰基自由基缩写为:
O=油酸,L=亚油酸,P=棕榈酸,和S=硬脂酸.
分别将油体样品A和B分为2部分。将各油体样本的一份放置在室温下(A1和B1)。使用Mikrolab Aarhus的低压(Oxypress)设备将另一部分在5bar氧气和60℃下放置72h(A2和B2)。
氧气处理后,通过18名测试人员在直接比较中(A1至A2和B1至B2)评估油体样本A和B的两部分。为了嗅觉评估,要求测试人员通过使用以下2级评分决定两个氧气处理的油体样本(A2和B2)中哪个样品闻起来最类似于保持在室温下的样本(A1和B1)
1=更可比,更少异味
0=不太可比,更多异味
为了统计分析使用khi2试验,评估结果在表4中给出。
表4
评估结果
结果证明2%的[6]‐姜酮酚在中性油中的1%溶液(=0.02%纯[6]‐姜酮酚)表现出抵抗酸败臭味产生的显著保护。
实施例3
鳄梨油的稳定
如表5给出制备含有鳄梨油和[6]‐姜酮酚(A)以及不含[6]‐姜酮酚(B至D)的油体样本以评估[6]‐姜酮酚的气味保护效果。
表5
油体样本A至D的组成(用量以%b.w.计)
通常鳄梨油(INCI:鳄梨(Persea Gratissima)油)是透明或浑浊、无色至黄绿液体,特征在于甘油酯含有65%油酸(C18:1)和6‐10%亚油酸(C18:2)(L.Roth and K.Kormann ecomed 2000,page 117)。
在本实验中使用的鳄梨油特征在于,通过各自脂肪酸甲酯的甲醇醇解后GC分析测定,甘油酯化合物含有63%油酸(C18:1)、21%棕榈酸(C16:0)、11%亚油酸、和10%棕榈油酸(C16:1)。
通过HPLC‐MS表征酰基化合物和酰基甘油化合物并列于表6:
HPLC‐MS:YMC ODS‐AQ,5μm,150x3mm带预柱,温度:40℃,流速:0,4ml/分钟,梯度为100%甲醇至100%异丙醇,检测波长205nm,柱后通过注射泵加入100mM甲醇铵甲酸溶液,流速:0.150μl/h,MS离子阱,带有自动MS/MS碎片的正离子和负离子模式的ESI,扫描200至1500。
表6
在负离子(研究自由脂肪酸)和正离子(研究甘油酯化合物)模式下通过HPLC‐MS测定表征酰基化合物和甘油酯化合物
(1)M‐1代表[M‐H]‐离子
(2)M+18代表[M+NH4]+离子
(3)M+23代表[M+Na]+离子
列表中酰基自由基缩写为:
O=油酸,L=亚油酸,P=棕榈酸,和P=棕榈油酸.
将油体样本分别分为3部分,其中一部分在日光检测设备(Original Hanau–Xenonlamp)中暴露于550‐600W/m2的人工UV光线(300至800nm)8小时。其他两部分分别在暴露于室温下的常规光线下(RTL)或在50℃的加热仓中储存一个月。处理后,在232nm下测定吸光度,因为其与通过检测作为特定氧化化合物的共轭二烯的氧化状态正相关。通过以下公式计算相对于起始t=0的调节并列于表7。
表7
232nm下吸光度和相对于t=0时的调节作用。
由列表可以看出,1%和2%的[6]‐姜酮酚在中性油中的1%溶液,对应于0.01和0.02%纯[6]‐姜酮酚,当与不含添加剂的阿甘油比较时,导致在232nm的吸光度较小增大。在所有三个处理中观察到[6]‐姜酮酚的保护效果。令人惊异地是,0.02%[6]‐姜酮酚(C)比25倍浓度的0.5%的α‐生育酚(D)表现出更好的保护,尽管其抗氧化能力—如实施例1中给出—仅稍微不同。
实施例4
阿甘油的稳定
为了评估保护油体抵抗氧化的影响,如表8所列出,制备含有阿甘油而不含不同添加剂(A)以及含有各种添加剂(B至D)的油体样本。
表8
油体样本A至D的组成(用量以%b.w.计)
将油体各分成三份。将一份在在日光检测设备(Original Hanau–Xenon lamp)中暴露于550‐600W/m2的人工UV光线(300至800nm)8小时。其他两部分分别在暴露于室温下的常规光线下(RTL)或在50℃的加热仓中储存一个月(50℃)。处理后,在232nm下测定吸光度,因为其与通过检测作为特定氧化化合物的共轭二烯的氧化状态正相关。通过以下公式计算相对于起始t=0的调节并列于表9。
表9
232nm下吸光度和相对于t=0时的调节作用。
232nm下吸光度 | A | B | C | D |
初始t=0 | 0.1581 | 0.1677 | 0.1898 | 0.2655 |
RTL,1个月 | 0.4993 | 0.5267 | 0.4175 | 0.8717 |
50℃,1个月 | 0.3749 | 0.3964 | 0.4191 | 0.8642 |
日光检测 | 0.2877 | 0.2903 | 0.2965 | 0.4615 |
相对于t=0时的调节作用[%] | A | B | C | D |
RTL,1个月 | 216 | 214 | 120 | 228 |
50℃,1个月 | 137 | 136 | 121 | 225 |
日光检测 | 82 | 73 | 56 | 74 |
由列表可以看出,1%和2%的[6]‐姜酮酚在中性油中的1%溶液,对应于0.01和0.02%纯[6]‐姜酮酚,当与不含添加剂阿甘油比较时,导致在232nm的吸光度较小增大。在所有三个处理中观察到[6]‐姜酮酚的保护效果。令人惊异地是,0.02%[6]‐姜酮酚(C)比25倍浓度的0,5%的α‐生育酚(D)表现出更好的保护,尽管其抗氧化能力—如实施例1中给出—仅稍微不同。
如表2给出表征阿甘油(INCI:刺阿干树(ARGANIA SPINOSA)仁油)。
实施例5
紧致抗橘皮油的气味稳定性
如表10中给出制备含有[6]‐姜酮酚(A)以及不含[6]‐姜酮酚(B至D)的抗橘皮油。
表10
油体样本A和B的组成(用量以%b.w.计)
将A相的成分混合并在35℃下加热直到得到澄清溶液。将B相的成分逐一加入并持续搅拌直到均匀。将含有(A)和不含(B)[6]‐姜酮酚的油体分别分为4部分并在40℃和50℃的加热箱中分别放置1和2个月。放置后,将油体冷却至室温并由22名测试人员评估。为了嗅觉评估要求测试人员在直接比较中基于以下2级评分评价每个时间点油体A和B的气味:
1=变质严重
0=较少变质
为了统计分析使用khi2试验,评估结果在表11中给出。
表11
评估结果
可以清楚看出,含有0.02%[6]‐姜酮酚的油体(A)通常表现出更好的嗅觉性能。放置温度越高,时间越长,这种气味保护效果(p<0.05=统计上显著)越显著(较少的测试人员给出1分)。在50℃下放置2个月后100%的测试人员认为含有[6]‐姜酮酚的油具备最少的变质气味。
实施例6
脸部护理凝霜的嗅觉评估
如表12中给出制备含有[6]‐姜酮酚(A和B)以及不含[6]‐姜酮酚(C和D)的凝霜
表12
油体样本A至B的组成(用量以%b.w.计)
将A相和B相的成分分别混合。将C相的成分分散在B相中,并在高剪切下加入混合的A相。在高剪切下加入D相的成分。将pH值调节至6。
将含有和不含[6]‐姜酮酚的凝霜样本A至D分别分为2份。将各个凝霜中的一份保存于无光照的室温下(A1‐D1),另一份使用Mikrolab Aarhus氧压设备在60℃下暴露于5bar氧气72小时(A2–D2)。
氧气处理后,在直接比较中由20名测试人员评估凝霜A2–D2和C1。为了嗅觉评估,要求测试人员根据变质气味用1=变质最严重和5=变质最少评价5个样品。评估结果在表13中给出。
表13
嗅觉评估结果
结果清楚证明了[6]‐姜酮酚的气味稳定效率。100%的志愿者将氧压处理的对比样C2评价为变质最严重(60%分数1)和较严重(40%分数2)。如预期,几乎所有志愿者(95%)将对比参考C1—其未经氧压处理在无光照室温下储存—评价为变质最少(分数5)。
[6]‐姜酮酚的气味保护作用通过以下事实清楚示出,大部分的志愿者将含有0.02%[6]‐姜酮酚的样品B2和含有0.01%[6]‐姜酮酚的样品A2分别评价为4分(55%)和3分(70%)。样本D2被30%的志愿者评为1分(变质最严重),40%的志愿者评为2分(变质较严重),因此在防止产生变质气味时0.5%的生育酚没有[6]‐姜酮酚有效。
实施例7
富含亚油酸的面部护理凝霜的嗅觉评估
如表14给出制备含有(A)和不含(B)[6]‐姜酮酚的凝霜。
表14
油体样本A至B的组成(用量以%b.w.计)
将A相和B相的成分分别混合。将C相的成分分散在B相中,并在高剪切下加入混合的A相。在高剪切下加入D相的成分。将pH值调节至6。
根据GC分析使用的亚油酸由67.96%亚油酸(C18:2)和25.92%油酸(C18:1)的构成。
将含有(A)和不含(B)[6]‐姜酮酚的凝霜样本分为2份。将各个凝霜中的一份保存于无光照的室温下(RT)(A1和B1),另一份使用Mikrolab Aarhus氧压设备在60℃下暴露于5bar氧气72小时(A2和B2)。
氧气处理后,在直接比较中由20名测试人员评估凝霜A2,B2和B1。为了嗅觉评估,要求测试人员根据变质气味用1=变质最严重和2=变质最少评价3个样品。评估结果在表15中给出。
表15
嗅觉评估的结果
结果清楚证明了[6]‐姜酮酚的稳定效率。70%的志愿者将氧压处理的对比样B2评价为变质最严重。如预期,大部分志愿者(85%)将对比参考B1—其未经氧压处理在无光照室温下储存—评价为变质最少(分数5)。
[6]‐姜酮酚的气味保护作用通过以下事实清楚示出,55%的志愿者将样本A2评价为2分(55%),15%的志愿者评价为3分(变质最少)。
实施例8
亮肤O/W霜的稳定
已知间苯二酚如4‐(1‐苯乙基)‐1,3‐苯二酚(苯乙基间苯二酚)在光照和较高温度下(例如>30℃)长时间发放置时易于变色。为了研究[6]‐姜酮酚是否也对这类不稳定化妆品成分有稳定作用,如表16给出制备含有3%阿甘油和0.5%美白活性物SymWhite 377(苯乙基间苯二酚)而不含(A)以及含有(B和C)[6]‐姜酮酚的亮肤O/W霜,用于评估气味和颜色变化。
表16
油体样本A至C的组成(用量以%b.w.计)
将A相和B相加热至80℃。乳化前将Aristoflex AVC分散在A相。在高剪切下将B相的成分加入A相。将pH值调节至约5。将霜剂样本分别分为2份,将一份在日光检测设备(Original Hanau–Xenon lamp)中暴露于550‐600W/m2的人工UV光线(300至800nm)8小时。其他部分在无光室温下(RTD)放置一个月。处理后,在直接比较中由19名测试人员评估6个凝霜的气味。结果示于表17。
表17
嗅觉评估的结果
*0.2%SymDecanox HA对应于0.002%[6]‐姜酮酚
**2%SymDecanox HA对应于0.02%[6]‐姜酮酚
由表格可以看出,气味变质最少的样本是在RTD下放置1个月的含有2%SymDecanox HA的样本(C)(63%的测试人员给出6分),随后是在RTD下放置1个月的含有0.2%SymDecanox的样本(B)(21%的测试人员给出6分)以及在RTD放置1个月的对比样(11%的测试人员给出6分)。100%的测试人员将通过日光检测的对比样(A)评估为变质最多的气味(47%和53%的测试人员分别给出1分和2分)。加入SymDecanox HA导致显著改善,74%和16%的测试人员分别对含有2%(C)和0.2%(B)该组份的样本给出了3分。
除了嗅觉评估,由于含有SymWhite 377,也评估日光检测的样本的变色。可以使用基于对立色系统(opponent color system)的CIELAB颜色模型描述颜色。CIELAB通过三轴上的数值描述颜色:L*,a*,和b*,其中维度L用于亮度,a*和b*用于红/绿和黄/蓝的对立色维度,基于非线性压缩的坐标。L*轴由黑(0)延伸至白(100),a*轴由绿(‐a)延伸至红(+a),b*轴由蓝(‐b)延伸至黄(+b)。
为了测定测试制剂的L*a*b*数值,搅拌日光检测处理后的样本并随后装入培养皿。使用Chroma Meter CR 410(Konica/Minolta)进行色度测量。使用以下公式计算两种颜色的色差ΔE:
其中p=样本1,v=样本2。受训评估者可以通过裸眼目视观察到0.5‐1的色差ΔE。2‐4的色差也可以被未训练评估者目视观察到。结果列于表19:
表19
含有或不含SymDecanox HA的日光检测样本的颜色测量结果
*0.2%SymDecanox HA对应于0.002%[6]‐姜酮酚
**2%SymDecanox HA对应于0.02%[6]‐姜酮酚
结果清楚示出[6]‐姜酮酚对间苯二酚SymWhite 377(4‐(1‐苯乙基)‐1,3‐间苯二酚)的颜色稳定作用。日光检测处理后不含SymDecanox HA的对比样(A)比含有SymDecanoxHA的凝霜更暗(较小的L*值)更黄(较大的正b*值)。加入对应于0.02%[6]‐姜酮酚的2%SymDecanox HA(C),通过最大的L*值和最小的正a*和b*值以及相对于对比样最大的色差ΔE,证明得到了最好的颜色保护。
实施例9
含有维甲酸的抗老化霜的稳定
维甲酸如视黄醇是有效的抗老化化妆制剂,其已知不稳定并且在光照和较高温度下(例如>30℃)长时间发放置时易于变色。为了研究[6]‐姜酮酚是否也对这类不稳定化妆品成分有稳定作用,如表20给出制备含有0.2%视黄醇10SU(BASF,9.9–11.1%all‐E‐retinol)而不含(A)以及含有(B和C)[6]‐姜酮酚的抗老化霜,用于评估颜色变化。
表20
样本A至D的组成(用量以%b.w.计)
将A相加热至80℃。对于B相,将Carbopol Ultrez 21撒在水表面以膨胀。随后,加入甘油并将B相加热至80℃。随后在使用Ultra Turra剧烈搅拌下将B相加入A相。将制剂冷却并在约40℃加入C相。随后,使用氢氧化钠中和制剂以得到5‐5.5的pH值。当制剂达到室温时,在搅拌下加入E相。检测最终pH值为5‐5.5。
将霜剂在日光检测设备(Original Hanau–Xenon lamp)中暴露于550‐600W/m2的人工UV光线(300至800nm)8小时。随后通过测定L*a*b*数值和计算色差ΔE,如实施例8所述,评估变色。结果示于表21。
表21
日光检测样本的颜色测量结果
*1%SymDecanox HA对应于0.01%[6]‐姜酮酚
**2%SymDecanox HA对应于0.02%[6]‐姜酮酚
结果清楚示出[6]‐姜酮酚对维甲酸视黄醇的颜色稳定作用。日光检测处理后对比样(A)比含有[6]‐姜酮酚(B和C)的霜剂更暗(较小的L*值)更蓝(较大的负b*值)。加入对应于0.01%和0.02%[6]‐姜酮酚的2%SymDecanox HA,通过相对于对比样类似的色差ΔE,证明得到了类似的颜色保护。
与SymDecanox HA相比,证明已知的稳定剂生育酚不适用于保护视黄醇免于变色。与之相反,与不向制剂加入稳定剂相比,甚至导致了更强烈的变色,如通过比较霜剂A和D的L*a*b*数值所示出。在日光检测处理后,与对比样(A)相比霜剂D通过更高的负a*数值说明更绿,并且通过更高的正b*数值说明更黄。
化妆品制剂实施例
表22a和22b给出了一系列根据本发明的制剂
1=抗衰老面部精油
2=用于身体和毛发的闪亮干性油
3=发油
4=BB霜SPF 15
5=婴儿尿布疹护理霜‐W/O
6=柔软清新沐浴露
7=护发油
8=口红
9=唇膏
10=遮瑕棒
11=日霜SPF 20
12=沐浴油
13=洁面啫喱
14=睫毛膏
15=洗发香波
16=按摩霜
17=沐浴油
18=亮肤霜
19=面部凝胶
20=O/W婴儿护理湿巾的浸泡乳液
21=抗老化霜
22=APD滚涂乳液
表22a
化妆制剂(含量以%b.w.计)
表22b
化妆品制剂(含量以%b.w.计)
表16和17给出芳香油PFO1和PFO2的组成(DPG=二丙二醇)。
表23
芳香油PFO1
表24
芳香油PFO2
实施例10
明胶胶囊
直接食用明胶胶囊
表25
直接食用明胶胶囊
明胶胶囊中使用的香料具备以下组成(以wt.%计):0.1%纽甜粉、0.05%阿斯巴甜、29.3%野生薄荷油、29.3%辣薄荷油Willamette、2.97%三氯蔗糖、2.28%三乙酸甘油酯、5.4%酒石酸二乙酯、12.1%薄荷油yakima、0.7%乙醇、3.36%2‐羟乙基薄荷基碳酸酯、3.0%2‐羟丙基薄荷基碳酸酯、0.27%香草醛、5.5%D‐柠檬烯、5.67%L‐乙酸薄荷酯。
用于直接食用的明胶胶囊(以类似于WO 2004/050069的方法制备)直径为5mm并且核材料和壳材料之间的重量比为90:10。胶囊在口腔中在少于10秒的时间内打开并在少于50秒的时间内完全溶解。
实施例11
用于烹饪的调香植物油
表26
用于烹饪的调香植物油
这些植物油可用于为各种热食或冷食调味。
Claims (15)
1.一种具备稳定味道和/或气味的组合物,含有
(a)[6]‐姜酮酚和
(b)至少一种单或多元不饱和C8‐C22脂肪酸或其单或多元C1‐C18脂肪醇酯。
2.根据权利要求1所述的组合物,其中成分(b)包括
(b‐1)至少一种式(II)的酰基化合物
其中
R代表氢原子或C1‐C18烷基和
X代表单或多元不饱和C8‐C22酰基,
和/或
(b‐2)至少一种式(III)的酰基甘油化合物
其中
X’、X”和X”’相互独立地代表氢原子或者饱和或单或多元不饱和C8‐C22酰基,前提是X’、X”和X”’不同时代表氢原子并且X’、X”和X”’中至少一个是不饱和酰基。
3.根据权利要求2所述的组合物,其中在成分(b‐1)中R是氢原子并且X是单或多元不饱和C16‐C22酰基。
4.根据权利要求2所述的组合物,其中成分(b‐1)选自组包括油酸、亚油酸、γ‐亚麻酸、α‐亚麻酸、EPA和DHA。
5.根据权利要求2所述的组合物,其中成分(b‐2)由甘油分子上以各种结合酯化的油酸、亚油酸和亚麻酸构成。
6.根据权利要求1所述的组合物,其中组合物含有0.0001至1wt.%的成分(a),基于组合物总量计。
7.一种含有根据权利要求1所述的组合物的化妆品组合物。
8.一种含有根据权利要求1所述的组合物的食品组合物。
9.[6]‐姜酮酚用于稳定单或多元不饱和C8‐C22脂肪酸或其单或多元C1‐C18脂肪醇酯的味道和/或气味的用途。
10.根据权利要求9所述的用途,其中单或多元不饱和C8‐C22脂肪酸或其单或多元C1‐C18脂肪醇酯包括
(b‐1)至少一种式(II)的酰基化合物
其中
R代表氢原子或C1‐C18烷基和
X代表单或多元不饱和C8‐C22酰基,
和/或
(b‐2)至少一种式(III)的酰基甘油化合物
其中
X’、X”和X”’相互独立地代表氢原子或者饱和或单或多元不饱和C8‐C22酰基,前提是X’、X”和X”’不同时代表氢原子并且X’、X”和X”’中至少一个是不饱和酰基。
11.根据权利要求9或10所述的用途,其中[6]‐姜酮酚的加入量为0.0001 to 1wt.%,基于总重量计。
12.一种稳定不饱和脂肪酸(酯)味道和/或气味的方法,其中将[6]‐姜酮酚加至不饱和脂肪酸(酯)。
13.根据权利要求12所述的方法,其中[6]‐姜酮酚的加入量为0.0001 to 1wt.%,基于总重量计。
14.[6]‐姜酮酚用于稳定不稳定化妆品和/或食品成分的气味、味道和颜色的用途。
15.根据权利要求14所述的用途,其中不稳定化妆品和/或食品成分选自间苯二酚类和维甲酸类。
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KR20240065168A (ko) | 2024-05-14 |
MX2018006868A (es) | 2018-09-21 |
US20250143988A1 (en) | 2025-05-08 |
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CN108367178B (zh) | 2024-09-27 |
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JP6896732B2 (ja) | 2021-06-30 |
US12226501B2 (en) | 2025-02-18 |
ES2855176T3 (es) | 2021-09-23 |
JP2018537477A (ja) | 2018-12-20 |
MX379850B (es) | 2025-03-11 |
EP3386595A1 (en) | 2018-10-17 |
KR20180094000A (ko) | 2018-08-22 |
EP3386595B1 (en) | 2020-11-25 |
BR112018011372A2 (pt) | 2018-12-04 |
US20190380934A1 (en) | 2019-12-19 |
BR112018011372B1 (pt) | 2021-05-04 |
KR102662345B1 (ko) | 2024-04-29 |
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