CN1185433A - 液体、油可混类胡萝卜素制剂 - Google Patents

液体、油可混类胡萝卜素制剂 Download PDF

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CN1185433A
CN1185433A CN97122957A CN97122957A CN1185433A CN 1185433 A CN1185433 A CN 1185433A CN 97122957 A CN97122957 A CN 97122957A CN 97122957 A CN97122957 A CN 97122957A CN 1185433 A CN1185433 A CN 1185433A
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E·卢德克
A-M·法伊弗
J·迈耶
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Abstract

液体、油可混类胡萝卜素制剂,它作为一个双分散系统,包括一个具有粒径小于100μm的水分散相,且其中一种或多种通过保护性胶体稳定的类胡萝卜素颗粒以分散体的形式存在于作为分散介质的油中。

Description

液体、油可混类胡萝卜素制剂
本发明涉及液体、油可混类胡萝卜素制剂、其制备方法,及其作为动物饲料、食品、化妆品和药品添加剂的用途。
类胡萝卜素构成具有从黄到红色的一组彩色颜料,它广泛存在于自然界中,并赋予许多食品特有的色彩。所涉及这类物质中最重要的代表是β-胡萝卜素、虾青素、β-阿朴-8’-胡萝卜醛、斑蝥黄质(canthaxanthin)、蕃茄红素和柠黄质(citranaxanthin)。对于食品和饲料工业和对于制药工业两者来说,这些可合成得到的物质是重要的着色剂,例如,作为合成染料的代用品,它们中的一些由于其维生素A原的活性而很具有意义。
所有的类胡萝卜素不溶于水,但在脂肪或油类中却有一些溶解性,虽然只是少量的溶解。这些有限的溶解性和对氧化的高敏感性,阻碍了在合成中得到的相对粗的产品在对食品和饲料染色中的直接应用,因为粗结晶形式的该物质只被很差地吸收,且因此产生很差的染色效果。
对食品的直接染色的改进只能通过系统制备的制剂而得到实现,其中活性成份以细分散形式存在,并且如果需要可通过保护性胶体进行保护以抗氧化。而且,这些用于饲料的制剂产生更高的类胡萝卜素生物利用率,从而间接地产生更好地染色效果,例如,对蛋黄和鱼的染色。
在饲料工业中,特别是鱼类养殖领域,特别是将类胡萝卜素中的虾青素和斑蝥黄质用作染色,特别是对大马哈鱼、鲟鱼和小虾染色。其中,活性成份以干粉的形式使用,其中分散的类胡萝卜素通过作为保护性胶体的例如明胶和糖进行保护以抗氧化分解。在饲料加工方法中,在挤压或压丸工艺中,干粉被直接混入,在该加工条件下所获得的应力因素例如热度、湿度和空气的影响经常对产品造成不合乎需要的损害,且因此造成活性成份的损失。
减少这些活性成份的损失是可能的,如WO 96/23420中所述,对于细磨碎的的虾青素将其悬浮于油中,接着喷涂到已经挤压或压丸的饲料上。在这种情况下,生物利用率和相应的染色效果以及活性成份的化学稳定性都是不令人满意的。
在描述于W094/19411的其它方法中,结晶β-胡萝卜素在含水保护性胶体溶液存在下被磨碎,且接着短暂加热至熔点,被转化成非晶形体。
这种制剂和常常被描述的水性类胡萝卜素分散体和O/W乳液(其中的活性成份伴随稳定保护性胶体存在)同样是不合适的,因为它们与油不可混。
GB993138描述了一种用于制备特别是含维生素A小球的方法,它包括将维生素A分散进水性的含明胶的保护性胶体溶液中,且该分散体又通过被悬浮于油中而以小球的形式被沉淀。由于超过300μm的过大粒径和这些悬浮液和乳液附带的物理不稳定性,对于液体类胡萝卜素制剂的上述应用,这样的系统是不合适的。
因此本发明的目的是开发一种类胡萝卜素制剂使其不具有上述缺点。
我们已经发现本发明目的可由液体、油可混类胡萝卜素制剂达到,作为双分散体系统,该制剂包括一个具有粒径小于100μm的水分散相,且其中通过保护性胶体稳定的一种或多种类胡萝卜素颗粒以分散体的形式存在于作为分散介质的油中。
本发明也涉及一种用于制备液体、油可混类胡萝卜素制剂的方法,其中水性的含保护性胶体的一种或多种类胡萝卜素的分散体在油中在乳化剂存在条件下被乳化。
脂溶性活性成份的水分散方法与进一步的油包水乳化步骤的新组合,使得所得到的产物具有新的、令人惊异的特性。
由此可获得的液体类胡萝卜素制剂特别适合于作为染料或添加剂用于食品和/或饲料和用于化妆品或药物制剂。
其中包括通过保护性胶体稳定的一种或多种类胡萝卜素颗粒的水分散相的制备,是许多已公开的出版物和专利的主题,例如EP-B-0278284,EP-B-0065193,DE-A-3702030,DE-A-2534091和R.A.Morton,Fat Soluble Vitamins,Intern.Encyclopedia ofFood and Nutrition Vol.9,Pergamon Press 1970,pp.134-139中的摘要。
如上所述的许多水分散方法中,根据EP-B-0065193的微粒化方法对当前的目的来说特别适合。该方法区别点在于将一种类胡萝卜素溶于50℃至200℃之间的挥发性、水可混有机溶剂中小于10秒钟,且该类胡萝卜素立即从通过与水性保护性胶体溶液混合得到的溶液中以胶态分散形式沉淀。详细说明见EP-B-0065193。
在本发明范围内可以使用的类胡萝卜素是这类化合物中公知的可获得的天然或合成的代表物,它们适合作为着色剂,例如β-胡萝卜素、虾青素,蕃茄红素,胭脂树橙、玉米黄质、隐黄质,柠黄质,叶黄素、斑蝥黄质、β-阿朴-4’-胡萝卜醛,β-阿朴-8’-胡萝卜醛,β-阿朴-12’-胡萝卜醛,β-阿朴-8’-胡萝卜酸和这组中含羟基和羧基代表物的酯,例如低级烷基酯,且优选甲基和乙基酯。特别优选的是至今工业上容易获得的类胡萝卜素例如β-胡萝卜素、虾青素、斑蝥黄质、蕃茄红素、β-阿朴-8’-胡萝卜醛和β-阿朴-8’-胡萝卜酸酯,可使用其本身或使用其混合物,其中活性成份以油性的、非晶形和/或结晶的形式存在,油性和非晶形体是优选的以便于实现最佳生物利用率。
在执行上述微粒化方法中,为进行作为整个方法一部分的第一分散步骤,特别是可以用水可混的,热稳定的只含碳、氢和氧的挥发性溶剂,例如醇、醚、酯、酮和乙缩醛。优选使用乙醇、正丙醇、异丙醇、1-甲氧基-2-丁醇,1-正丙氧基-2-丙醇或丙酮。一般来说,有利的是这些溶剂水可混至少10%,具有低于200℃的沸点和/或含少于10个碳原子。
保护性胶体的例子是明胶、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。同样地,也可使用聚乙烯醇、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。对于进一步的细节见R.A.Morton,Fat SolubleVitamins.Intern.Encyclopedia of Food and Nutrition,Vol.9,PergamonPress 1970,pp.128-131。为了增加最终产品的机械稳定性,该胶体适合与增塑剂例如糖或糖醇,例如蔗糖、葡萄糖、乳糖、转化糖、山梨醇、甘露糖醇或甘油混合。
选择保护性胶体、增塑剂和类胡萝卜素的量以使提供的最终产品含有从0.01至10wt%,优选从0.5至5wt%的类胡萝卜素,从2至20wt%的保护性胶体,从2至20wt%的增塑剂,所有的百分数基于最终乳液的总量,和尽可能少量的稳定剂。
为了增加活性成份抗氧化分解的稳定性,加入稳定剂例如α-生育酚、叔丁基羟基甲苯、叔丁基羟基茴香醚、抗坏血酸或乙氧喹(ethoxyquin)是有益的,它们可以加入水相或溶剂相,但优选与染料和任何添加的乳化剂共溶于溶剂相。
可以用作初级分散体的乳化剂的例子包括抗坏血酸基(ascorbvl)棕榈酸酯,聚甘油脂肪酸酯、脱水山梨醇脂肪酸酯,丙二醇脂肪酸酯或卵磷脂,基于类胡萝卜素,以0至200wt%,优选10至150wt%,特别优选15至80wt%的浓度加入。
通过添加在食品和饲料工业上允许使用的防腐剂,可以防止不希望发生的水分散体的微生物降解,防腐剂例如有抗坏血酸,山梨酸钠,苯甲酸,苯甲酸钠或PHB酯例如4-羟基苯甲酸甲酯或4-羟基苯甲酸丙酯,基于类胡萝卜素,以0至200wt%,优选10至150wt%,特别优选15至80wt%的浓度加入。
在一些情况下,不仅在第一分散步骤中溶解类胡萝卜素或多种类胡萝卜素的混合物,而且溶解生理上允许使用的油例如芝麻油、玉米油、棉籽油、豆油或花生油和中长链植物脂肪酸的酯(基于类胡萝卜素,以从0至500wt%,优选从10至300wt%,特别优选从20至100wt%的浓度加入)也是有益的,当与水相混合时,油与活性成份和所述的添加剂以非常细的分散形式共沉淀。
根据使用的保护性胶体的类型和数量,得到的水性类胡萝卜素分散体是深色的粘性液体,在可凝胶胶体的情况下,它象凝胶一样固化,且其中的类胡萝卜素的平均粒径小于0.2mm。
根据沸点,以已知的方法,例如通过蒸馏,可能的话在减压下蒸馏,或通过与水不混溶的溶剂萃取,可以除去溶剂。
与上述现有技术相反,在现有技术中活性成份含水分散体转化成颜料粉末,在新的方法中额外的油包水乳化导致以双分散体形式存在的新的液体制剂。
在该方法中,伴随着使用乳化剂,形成一种其中水相含有通过保护性胶体稳定的类胡萝卜素微细颗粒的油包水乳液。适合的乳化剂是具有HLB值低于10,特别是从2至6(cf.H.P.Fiedler,Lexikon der Hilfsstoffefr Pharmazie,Kosmetik und angrenzende Gebiete,1996,pp.753 etseq.)的已知的W/O乳化剂。这类乳化剂典型的代表是多元醇的脂肪酸部分酯,例如甘油单硬脂酸酯或甘油一、二和三酸酯的混合物,脱水山梨醇的脂肪酸部分酯和/或优选的聚甘油脂肪酸酯,例如聚甘油多聚蓖酸酯,基于类胡萝卜素以从10至1000wt%,优选从100至900wt%,特别优选从400至800wt%的浓度使用。
该分散介质可以是来源于矿物质,植物和动物的。典型的代表是食用油,特别是芝麻油、玉米油、棉籽油、豆油或花生油,中长链植物脂肪酸酯,和各种鱼油例如鲭鱼油、黍鲻油或鲑鱼油。基于最终乳液总量,该分散介质的量一般是30至95,优选50至80wt%。
乳化可以连续进行或间歇进行。
该双分散系统的物理稳定性,例如沉积稳定性是通过水相在油相中非常良好的细分散,例如通过在20至80,优选40至70℃条件下用转子/定子分散器,或用诸如APV Gaulin的高压均化器,或用诸如在700至1000bar压力范围的微流化器(microfluidizer)的超高压均化器进行充分处理得以实现的。从而对于水分散相所实现的平均粒径小于100μm,优选小于10μm,特别是小于1μm。
此外,在分散相中,通过保护性胶体稳定的该微细颗粒的类胡萝卜素确保该液体制剂具有与根据EP-B-0065193中所述干粉同样的生物利用率和化学稳定性。
在水产养殖中为了染色,可以将如此制得的含类胡萝卜素活性成分的新型液体制剂直接或一般在用油稀释后喷到已挤压的鱼食品上。
在食品领域,该液体类胡萝卜素制剂可以用于染色,特别是对人造奶油,焙烤产品,面食制品,甜食等,如果该染色方法要求制剂是油可溶的,则该新型的W/O乳液特别适合。从使用着眼,该液体制剂具有另外的好处,即与类胡萝卜素干粉相比,可以更容易地配制。
这同样适用于在化妆品和药品领域该新型类胡萝卜素液体制剂以染色为目的应用。
下述实施例进一步解释该新方法是怎样进行的。
实施例1
通过根据EP-B-0065193中的混合室微粒化方法制备具有虾青素颗粒的平均粒径是约100nm的85g虾青素分散体,其中除6wt%的虾青素以外含有55wt%的水,20wt%的蔗糖,15wt%的明胶,2wt%的乙氧喹,1wt%的防腐剂和1wt%的抗坏血酸基棕榈酸酯,且接着在50℃条件下经过5分钟乳化进300g豆油和30g聚甘油多聚蓖酸酯的混合物中。得到的稳定乳液具有的活性成分含量约为1.2wt%。
当使用齿环分散器(Ultraturax)作为均化器时能实现分散相的平均滴径约为2μm。如果,再使用1000bar的高压均化器;能成功地实现平均滴径约为1μm。
实施例2
通过根据EP-B-0065193中的混合室微粒化方法制备具有斑蝥黄质颗粒的平均粒径是约150nm的193g斑蝥黄质分散体,其中除了4wt%的斑蝥黄质以外含70wt%的水、14wt%的蔗糖,9wt%的明胶、1wt%的乙氧喹、1wt%的防腐剂和1wt%的抗坏血酸基棕榈酸酯,且接着在60℃条件下经过2分钟,借助于11000rpm下的Ultraturax乳化进400g豆油和40g聚甘油多聚蓖酸酯的混合物中。为了改善该细分散体,该乳液在约26℃下,用900bar的超高压均化器(微流化器)进行另外的两次均化。得到的稳定乳液具有的活性成份含量约是1.2wt%,平均滴径是0.85μm。

Claims (8)

1.一种液体、油可混类胡萝卜素制剂,它作为双分散系统,包括一个具有粒径小于100μm的水分散相,且其中通过保护性胶体稳定的一种或多种类胡萝卜素颗粒以分散体的形式存在于作为分散介质的油中。
2.根据权利要求1的液体、油可混类胡萝卜素制剂,其中的水分散相包括以油性的、非晶形和/或晶体形式存在的、通过保护性胶体稳定的一种或多种类胡萝卜素颗粒。
3.根据权利要求1和2的液体、油可混类胡萝卜素制剂,它包括HLB值低于10的乳化剂。
4.根据权利要求1至3的液体、油可混类胡萝卜素制剂,其中的水分散相还包括诸如乳化剂、抗氧化剂和/或防腐剂的添加剂。
5.根据权利要求1至4的液体、油可混类胡萝卜素制剂,其中的水分散含类胡萝卜素相的粒径小于10μm。
6.根据权利要求1至5的液体、油可混类胡萝卜素制剂,其具有的类胡萝卜素含量为0.01至10wt%。
7.一种制备根据权利要求1至6的液体、油可混类胡萝卜素制剂的方法,其中一种或多种类胡萝卜素的水性、含保护性胶体的分散体在乳化剂存在下在油中乳化。
8.根据权利要求1至6的液体、油可混类胡萝卜素制剂用作动物饲料、食品、化妆品和/或药品的添加剂的用途。
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