CN1228937A - 类胡萝卜素聚集体作为着色剂的用途 - Google Patents
类胡萝卜素聚集体作为着色剂的用途 Download PDFInfo
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- CN1228937A CN1228937A CN99101364A CN99101364A CN1228937A CN 1228937 A CN1228937 A CN 1228937A CN 99101364 A CN99101364 A CN 99101364A CN 99101364 A CN99101364 A CN 99101364A CN 1228937 A CN1228937 A CN 1228937A
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- astaxanthin
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Abstract
本发明涉及类胡萝卜素聚集体作为食品和化妆及药用制品的着色剂的用途。
Description
本发明涉及类胡萝卜素聚集体作为着色剂的用途。
类胡萝卜素广泛存在于自然界中并已被以各种形式用于食品、化妆品和非食物用品的着色。但是由于类胡萝卜素一般对光和氧气非常敏感,其可能的用途受到了极大地限制。因此在实践中,类胡萝卜素着色的制品必须例如通过脱气或通过储存于不透明容器中来避光和避免与氧气接触。
本发明的目的是提供没有上述缺点的稳定的类胡萝卜素着色剂。
我们已经发现这个目的可按照本发明通过使用类胡萝卜素聚集体作为着色剂来达到。
类胡萝卜素的聚集是一种为人熟悉的现象,它已经被大量描述于文献中[P.Song,T.A.Moore,Photochemistry and Photobiology,19,435-441(1974);A.V.Ruban,P.Horton,A.J.Young,J.Photochem.Photobiol.B:Biol.,21,229-234(1993);V.R.Salares,N.M.Young,P.R.Carey,H.J.Bernstein,Journal of Raman Spectroscopy,6(6),282-288(1977)]。
类胡萝卜素聚集体可通过例如将类胡萝卜素在一种与水混溶的有机溶剂诸如像异丙醇、乙醇、丙酮或四氢呋喃与水的溶液中混合来制备。
正如在上述文献中所述的,根据所选的水与有机溶剂间混合比率的不同,用这种方法可制备出H-聚集体或者J-聚集体。
H-聚集体是一种多烯链的片垛(card-stack)排列,它在紫外/可见(UV/VIS)光谱中的特征在于在320-400nm范围内出现了一新谱带,这表示与其单体形式的吸收相比出现了紫移。J-聚集体正好相反,它表现出是多烯的线型头-尾排列结构,它导致了紫外吸收光谱的红移。
因此这些聚集体在颜色上与溶解的单体类胡萝卜素不同,它们不仅可通过目测其色移来鉴定,而且也可通过UV/VIS分光光度法鉴定。
现已惊异地发现这些类胡萝卜素聚集体比单体类胡萝卜素显示明显好得多的对光辐射如对氙灯辐射的稳定性。
由于其优良的耐光性,类胡萝卜素聚集体对于食品、化妆品制品和药物制品以及非食用物品的着色非常有用,对于染料暴露于光下的那些制品尤其有用。
在开始提及的类胡萝卜素聚集体中,对于用作着色剂来说,H-和/或J-聚集体是优选的,J-聚集体是特别优选的。
以聚集体形式用作着色剂的类胡萝卜素是已知的,天然或合成的这类物质的代表有例如β-胡萝卜素、番茄红素、胭脂树橙、玉米黄质、隐黄质、柑桔皮类胡萝卜素、叶黄素、斑蝥黄、虾青素。特别优选使用诸如β-胡萝卜素、虾青素或番茄红素等代表物,特别是虾青素和/或番茄红素,其现在已可方便地工业制备。
本发明的类胡萝卜素聚集体着色剂可单独使用,或者有利地在保护胶体的存在下使用。
保护胶体的例子有明胶、鱼明胶、淀粉、糊精、植物蛋白、果胶、阿拉伯树胶、酪蛋白、酪蛋白酸盐或其混合物。但是,也可能使用聚乙烯醇、聚乙烯吡咯烷酮、甲基纤维素、羧甲基纤维素、羟丙基纤维素和藻酸盐。更进一步的详情可参见R.A.Morton,Fat Soluble Vitamins,Intern.Encyclopedia of Food and Nutrition,Vol.9,Pergamon Press 1970,p128-131。
为提高类胡萝卜素制剂的机械稳定性,将所述胶体与一种增塑剂混合可能是有益的,所述增塑剂的例子有糖或糖醇如蔗糖、葡萄糖、乳糖、转化糖、山梨糖醇、甘露糖醇或甘油。
所选保护胶体、增塑剂和类胡萝卜素聚集体的量一般是能使终产物包含0.1-100ppm,优选0.5-50ppm,特别优选1-20ppm的类胡萝卜素(优选虾青素或番茄红素),20-200ppm的保护胶体,20-200ppm的增塑剂(所有的ppm数据均是基于最终制剂的总质量)和任选少量的稳定剂的量。
为提高类胡萝卜素对氧化降解的稳定性,最好加入稳定剂诸如α-生育酚、叔丁基羟基甲苯、叔丁基羟基茴香醚、抗坏血酸或乙氧基喹。
也可使用乳化剂,例如抗坏血酰棕榈酸酯、聚甘油脂肪酸酯、山梨糖醇酐脂肪酸酯、丙二醇脂肪酸酯或卵磷脂,其基于类胡萝卜素的使用浓度为0-200%(重量),优选10-150%(重量),特别优选15-80%(重量)。
在某些情况下,除类胡萝卜素聚集体外,也可以使用生理上可接受的油诸如像芝麻油、玉米油、棉花籽油、豆油或花生油以及中等长度链植物脂肪酸酯也可能是有益的,其基于类胡萝卜素的使用浓度为0-500%(重量),优选10-300%(重量),特别优选20-100%(重量)。
本发明还提供包含类胡萝卜素聚集体,特别是虾青素和/或番茄红素的聚集体的食品,其含量是0.1-100ppm,优选0.5-50ppm,特别优选1-20ppm(基于制品的总量)。
所述食品特别是指乳品、脂肪如人造黄油以及优选为饮料如软饮料。
所述着色的饮料可以是透明制品,也可以是不透明即浑浊制品。所述类胡萝卜素聚集体优选用于着色透明饮料制品。本发明的类胡萝卜素聚集体可作为干粉或作为一种加溶物以乳液或悬浮液的形式混入到饮料中。
当类胡萝卜素聚集体用于食品中时,不被食品所接受的有机溶剂如丙酮或四氢呋喃可首先在不引起聚集体形式变化的情况下小心蒸馏掉。
本发明还提供含有0.1-100ppm,优选含有0.5-50ppm,特别优选含有1-20ppm(基于所述化妆品或药品的总量)的类胡萝卜素聚集体的化妆品和药物制品。
这些化妆品和药物制品一般基于一种包括至少一种油相的载体。但是,在具有亲水性取代基的化合物的使用中,仅具有水基的制品也是可能的。因此,油、水包油和油包水乳液、乳油和糊剂、防护性口红基料或脱脂凝胶体均是适合的。
这种化妆品或药品因此可以以液体、糊或固体的形式出现,例如油包水乳油、水包油乳油和洗剂、气溶胶发泡乳油、油、润滑棒(greasesticks)、粉末、喷雾剂或水醇洗剂(hydroalcoholic lotions)。
在化妆品中常用的油组份的例子有液体石蜡、硬脂酸甘油酯、肉豆蔻酸异丙酯、己二酸二异丙酯、2-乙基己酸十六烷基十八烷酯、氢化聚异丁烯、凡士林、辛酸/癸酸三甘油酯、微晶蜡、羊毛脂和硬脂酸。
用作添加剂的常规化妆品辅剂包括例如辅助乳化剂、脂肪和蜡、稳定剂、增稠剂、活性生物物质、成膜剂、香料、附加染料、珠光剂、保存剂、颜料、电解质(如硫酸镁)和pH调节剂。适合的辅助乳化剂优选包括已知的水/油乳化剂以及油/水乳化剂诸如聚甘油酯、脱水山梨醇酯或部分酯化的甘油酯。脂肪的典型例子有甘油酯;适合的蜡包括蜂蜡、石蜡或与亲水蜡混合的微蜡(micro wax)。可用的稳定剂有脂肪酸的金属盐诸如镁、铝和/或锌的硬脂酸盐。适合的增稠剂包括例如交联的聚丙烯酸和其衍生物,多糖,尤其是黄原胶、瓜尔豆胶、琼脂、藻酸盐和纤基乙酸钠、羧甲基纤维素和羟乙基纤维素、以及脂肪醇、单甘油酯和脂肪酸、聚丙烯酸酯、聚乙烯醇和聚乙烯吡咯烷酮。活性生物物质的例子有植物提取物、蛋白质水解物和维生素复合体。常规的成膜剂包括例如亲水胶体诸如脱乙酰壳多糖、微晶脱乙酰壳多糖或季铵化脱乙酰壳多糖、聚乙烯吡咯烷酮、乙烯基吡咯烷酮/乙酸乙烯酯共聚物、丙烯酸系列的聚合物、季纤维素衍生物和类似化合物。适合的保存剂有例如甲醛溶液、对羟基苯甲酸盐或山梨酸。适合的珠光剂包括例如二元醇的二硬脂酸酯如乙二醇二硬脂酸酯以及脂肪酸和脂肪酸单甘油酯。除了类胡萝卜素聚集体外,可用的染料是适用并符合化妆品目的的物质,诸如列表说明于例如在下列出版物中的染料:“Kosmetische Farbemittel”of the Farbstoffkommission der DeutschenForschungsgemeinschaft,published in Verlag Chemie,Weinheim,1984。这些染料的一般使用浓度是基于总混合物的0.001-0.1%(重量)。
基于制品的总量,辅剂和添加剂物质的总比例可以为1-80%(重量),优选6-40%(重量),其非水部分(活性组份)可以为20-80%(重量),优选30-70%(重量)。所述制品可用常规方式例如通过热、冷、热-热/冷或转相温度(PIT)乳化来制备。
优选的化妆或药用制品包括例如透明乳剂、加溶物、凝胶或水醇洗剂形式的透明制剂。
下文的实施例说明按照本发明的类胡萝卜素聚集体的用途。
实施例1
将5ml每升丙酮含50mg虾青素的分子溶液在室温下与95ml的水(70ml)和丙酮(30ml)的混合物混合。从橙色到粉红色的颜色变化直接指示出在约30分钟内形成了J-聚集体。将这种聚集体溶液在一个照射装置(来自Heraeus的Suntest)中照射10分钟,没有观察到颜色的变化。将分子态溶解的虾青素的对比溶液(2.5ppm的虾青素丙酮溶液)在相同条件下照射,10分钟后颜色完全消失。
照射前和照射后测量的UV/VIS光谱说明:与单体形式相比,虾青素的J-聚集体提高了耐光性[参见图1:(1)照射前的虾青素单体形式;(2)照射后的单体形式;(3)照射前的虾青素J-聚集体;(4)照射后的J-聚集体]。
实施例2
将5ml每升异丙醇含50mg番茄红素的分子溶液与95ml的水(30ml)和异丙醇(70ml)的混合物混合。从橙色到橙黄色的色移直接指示出在数秒钟内形成了H-聚集体。将这种聚集体溶液在一个照射装置(来自Heraeus的Suntest)中照射10分钟,只观察到少许颜色的变化。将分子态溶解的番茄红素的对比溶液(2.5ppm的番茄红素异丙醇溶液)在相同条件下照射,颜色强度更明显地下降。通过将所述照射溶液稀释和加热,可以将其转化成分子溶解态供定量分析。在所述溶液中以聚集体形式存在的番茄红素比单体形式的番茄红素稳定1.5倍。
Claims (12)
1.类胡萝卜素聚集体作为着色剂的用途。
2.权利要求1的用途,其中所述类胡萝卜素聚集体是H-聚集体和/或J-聚集体。
3.权利要求1的用途,其中所述类胡萝卜素聚集体是J-聚集体。
4.所述以H-和/或J-形式的类胡萝卜素聚集体在食品、化妆品和药品着色上的用途。
5.按照权利要求1-4中任一项的类胡萝卜素聚集体的用途,其中所述类胡萝卜素是虾青素或番茄红素。
6.包含类胡萝卜素聚集体的饮料。
7.权利要求6的透明饮料,包含作为类胡萝卜素的虾青素和/或番茄红素。
8.权利要求6和7中任一项的饮料,具有基于饮料总量0.1-100ppm的类胡萝卜素含量。
9.包含类胡萝卜素聚集体的化妆或药用制品。
10.权利要求9的化妆或药用制品,包含作为类胡萝卜素的虾青素和/或番茄红素。
11.权利要求9和10中任一项的透明化妆或药用制品。
12.按照权利要求9-11中任一项的化妆或药用制品,具有基于制品总量0.1-100ppm的类胡萝卜素含量。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19802134A DE19802134A1 (de) | 1998-01-21 | 1998-01-21 | Verwendung von Carotinoid-Aggregaten als Färbemittel |
DE19802134.8 | 1998-01-21 |
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CN1228937A true CN1228937A (zh) | 1999-09-22 |
CN1121153C CN1121153C (zh) | 2003-09-17 |
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CN99101364A Expired - Lifetime CN1121153C (zh) | 1998-01-21 | 1999-01-21 | 类胡萝卜素聚集体作为着色剂的用途 |
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US (1) | US6827941B1 (zh) |
EP (1) | EP0930022B1 (zh) |
JP (1) | JP3921305B2 (zh) |
CN (1) | CN1121153C (zh) |
CA (1) | CA2257552C (zh) |
DE (2) | DE19802134A1 (zh) |
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US20060088904A1 (en) * | 2004-10-01 | 2006-04-27 | Lockwood Samuel F | Methods for the synthesis of astaxanthin |
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US20070134173A1 (en) * | 2005-12-09 | 2007-06-14 | The Procter & Gamble Company | Personal care compositions |
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JP6426902B2 (ja) * | 2014-03-20 | 2018-11-21 | 株式会社コーセー | カロテノイド含有組成物、並びにカロテノイドの劣化抑制剤及びカロテノイドの劣化抑制方法 |
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1998
- 1998-01-21 DE DE19802134A patent/DE19802134A1/de not_active Withdrawn
- 1998-11-24 DE DE59809639T patent/DE59809639D1/de not_active Expired - Lifetime
- 1998-11-24 EP EP98122311A patent/EP0930022B1/de not_active Expired - Lifetime
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1999
- 1999-01-07 US US09/226,143 patent/US6827941B1/en not_active Expired - Lifetime
- 1999-01-14 CA CA002257552A patent/CA2257552C/en not_active Expired - Lifetime
- 1999-01-19 JP JP01040199A patent/JP3921305B2/ja not_active Expired - Lifetime
- 1999-01-21 CN CN99101364A patent/CN1121153C/zh not_active Expired - Lifetime
Cited By (1)
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CN101951871B (zh) * | 2007-12-21 | 2013-05-22 | 荷兰联合利华有限公司 | 包含着色抗氧化剂的局部组合物 |
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Publication number | Publication date |
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CN1121153C (zh) | 2003-09-17 |
CA2257552A1 (en) | 1999-07-21 |
CA2257552C (en) | 2007-10-30 |
EP0930022B1 (de) | 2003-09-17 |
EP0930022A3 (de) | 2001-09-05 |
JPH11285359A (ja) | 1999-10-19 |
JP3921305B2 (ja) | 2007-05-30 |
DE19802134A1 (de) | 1999-07-22 |
EP0930022A2 (de) | 1999-07-21 |
US6827941B1 (en) | 2004-12-07 |
DE59809639D1 (de) | 2003-10-23 |
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