CN101312655B - 新颖的稳定的类胡萝卜素组合物 - Google Patents

新颖的稳定的类胡萝卜素组合物 Download PDF

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CN101312655B
CN101312655B CN2006800265171A CN200680026517A CN101312655B CN 101312655 B CN101312655 B CN 101312655B CN 2006800265171 A CN2006800265171 A CN 2006800265171A CN 200680026517 A CN200680026517 A CN 200680026517A CN 101312655 B CN101312655 B CN 101312655B
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卡尔·曼弗雷德·沃勒科
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Abstract

本发明涉及含有精细分散的类胡萝卜素的新颖组合物。本发明的新颖组合物能够被用作食物、饮料、动物饲料、化妆品或药物的着色剂或添加剂。着色剂组合物可以是液体或固体组合物。固体组合物包含至少一种被分散于基质中的类胡萝卜素,其中所述基质含有至少一种碳水化合物和/或一种被修饰的碳水化合物和可选的蛋白质、被修饰的蛋白质或其混合物,其中所述至少一种碳水化合物和/或一种被修饰的碳水化合物是淀粉或改性淀粉,其中所述淀粉或改性淀粉的用量是基质总重量的10wt.%到60wt.%,其中所述至少一种类胡萝卜素的浓度是组合物总重量的至少2%。优选使用β-胡萝卜素作为可在水中分散的固体着色剂组合物。

Description

新颖的稳定的类胡萝卜素组合物
本发明涉及含有精细分散的类胡萝卜素的新颖组合物。本发明的新颖组合物能够被用作食物、饮料、动物饲料、化妆品或药物的着色剂或添加剂。 
着色剂组合物可以是液体或固体组合物。优选使用β-胡萝卜素作为可在水中分散的固体着色剂组合物。液体着色剂组合物可以是β-胡萝卜素的稳定水分散体系。为了获得中等彩色色相(hue),这些组合物可选地含有另一着色化合物,例如另一类胡萝卜素,如β-玉米胡萝卜素(β-zeacarotene)、角黄素、8′-脱-β-胡萝卜素醛、8′-脱-β-类胡萝卜素酸乙酯、番茄红素、虾青素、叶黄素和玉米黄素。 
可在水中分散的固体着色剂组合物是其中β-胡萝卜素精细地分散于基质或载体中的组合物。基质或载体可以是常规用于配制类胡萝卜素的任何基质或载体。例如,载体可以是碳水化合物、经修饰的碳水化合物、蛋白质、经修饰的蛋白质或其混合物。 
用于本发明的这类着色剂组合物的制备可以以本身已知的用于制备食品和饮料中使用的类胡萝卜和脂溶性维生素组合物的方式完成,例如如欧洲专利公开号0 347 751、0 966 889、1066 761、1 106 174和国际专利申请WO 98/15195中所公开的,这些专利文献内容通过参考并入本文。 
制备本发明着色剂组合物的优选步骤是制备β-胡萝卜素和油溶性抗氧化剂在甘油和可选的有机溶剂(例如氯化烃)中的溶液,并在水性溶液中将油性溶液乳化,如果需要,则例如通过蒸发去除有机溶剂,所述水性溶液制备自保护性的水胶体载体如蛋白质、多肽或经修饰的多糖或其混合物、碳水化合物和任选的水溶性抗氧化剂。 
这样获得的水包油分散体系可以使用常规技术被转化为固体组合物例如干粉,所述常规技术如喷雾干燥、喷雾干燥结合流化床造粒(后一技术通常已知为流化喷雾干燥或FSD),或粉末捕获(powder-catch)技术,所述 粉末捕获技术中喷雾出的乳剂微滴被吸收剂(如淀粉)床捕获并随后干燥。 
公知的固体着色剂组合物以约1wt.%的含量含有β-胡萝卜素并具有橙色色度(shade)。这类组合物可在水中分散,并在食物、饮料、动物饲料、化妆品或药物中产生黄色色度。出于经济原因考虑,提高可在水中分散的该类型组合物中类胡萝卜素的浓度会是有利的。因此,本发明的一个目的是提出一种新的可在水中分散的着色剂组合物,其具有相当的色度但是具有提高的类胡萝卜素浓度。 
通常已知用于饮料中的着色剂组合物应具有高的色彩亮度(colorintensity)以及相对高的浑浊度(turbidity)。我们已出人意料地发现,如果该化合物被用作载体或基质的一部分时,淀粉或改性淀粉含量的变化对色彩亮度和浑浊度、红色值和颗粒尺寸具有影响。还发现通过使用占载体或基质总重量10%到60%的淀粉或改性淀粉,可以将β-胡萝卜素的浓度提高到至少2%、优选2%到10%、更优选2%到5%(根据组合物的总重量计算),其中最终组合物仍然具有涉及足够的色彩亮度和浑浊度特性。 
因此通过根据权利要求1的着色剂组合物达成本发明的所述目的。 
本发明的有利实施方案由从属权利要求阐明。 
本文使用术语“类胡萝卜素”包括胡萝卜素和结构相关的多烯化合物,其可用作食物、饮料、动物饲料、化妆品或药物的着色剂。这类类胡萝卜素的实例是α-或β-胡萝卜素、8′-脱-β-胡萝卜素醛、8′-脱-β-胡萝卜素酸酯如乙酯、角黄素、虾青素、番茄红素、叶黄素、玉米黄素或藏红花素或其混合物。如已经提到的,优选的类胡萝卜素是β-胡萝卜素。 
存在于本发明组合物中的载体或基质除了食物淀粉或改性食物淀粉(例如辛烯琥珀酰钠淀粉)外,还含有辛烯基丁二酸酯淀粉糊精(octenylbutanedioate amylodextrin,CapsulTM),多糖胶质如阿拉伯胶,或麦芽糖糊精,或蛋白质如明胶(例如鱼明胶或猪或牛明胶),或植物蛋白,或乳蛋白或磺酸木质素(ligninsulfonate)或其混合物。 
本发明的新颖组合物还合适地含有佐剂和/或赋形剂,如一种或多种单、双、寡或多糖,甘油三酯,水溶性抗氧化剂,和/或一种或多种脂溶性 抗氧化剂。固体组合物也可含有抗结块剂,如硅酸和水。 
可存在于本发明组合物中的单糖和二糖实例为蔗糖、转化糖、葡萄糖、果糖、乳糖、麦芽糖和糖醇。 
可存在于本发明组合物中的甘油三酯的实例是中等链甘油三酯,植物油如玉米油、葵花子油、大豆油、红花油、油菜籽油、花生油、棕榈油、棕榈仁油、棉籽油或椰子油。 
水溶性抗氧化剂可以是抗坏血酸及其盐,例如抗坏血酸钠等。脂溶性抗氧化剂可以是生育酚,例如dl-α-生育酚(即合成的生育酚)、d-α-生育酚(即天然生育酚)、β-和γ-生育酚及其混合物;丁羟基甲苯、丁基羟基苯甲醚、没食子酸丙酯、t-丁羟基喹啉或脂肪酸的抗坏血酸酯,如抗坏血酸棕榈酸酯或硬脂酸酯。根据水性基质溶液的pH,后两种化合物可以被可选地加入水相中。 
典型地,根据本发明的粉末组合物包含 
-约10到约60wt.%、优选地约20到约30wt.%的糖聚合物,例如麦芽糖糊精; 
-约5到约50wt.%、优选地约10到约40wt.%的阿拉伯胶; 
-约0.2到约10wt.%、优选地约1.5到约10wt.%的类胡萝卜素; 
-5到约15wt.%、优选地约5到约10wt.%的单糖或二糖; 
-10到约50wt.%、优选地约15到约50wt.%的淀粉和改性淀粉; 
-约5到约50wt.%、优选地约10到约20wt.%的甘油三酯; 
-0到约5%、优选地约0.1到约2wt.%的水溶性抗氧化剂; 
-0到约5%、优选地约0.01到约1wt.%的脂溶性抗氧化剂; 
-0到约2wt.%优选地约0.1到约1wt.%的硅酸;和 
-0到约10wt.%、优选地约1到约5wt.%的水; 
所有成分的百分比总计为100。 
本发明的新颖组合物可用作食物、饮料、动物饲料、化妆品或药物的着色剂。通过本发明,优选地提供包含β-胡萝卜素作为着色剂的组合物。其中β-胡萝卜素可以被用作着色剂的饮料可以是碳酸饮料(例如调味的苏打水)、软饮或矿物饮品,以及非碳酸饮料,例如调味的水、果汁、混合 果汁(fruit punches)和这些饮料的浓缩形式。他们可以基于天然水果汁或蔬菜汁或基于人造香料。还包括酒精饮料和方便饮料粉。此外还包括含糖的饮料,无热量的含人造甜味剂的健康饮料。 
另外,得自天然来源或合成来源的乳制品属于食品的范围,其中根据本发明的组合物可以被用作着色剂。这类产物的典型实例是乳饮品、冰激凌、乳酪、酸乳等。乳替代产品如酸乳饮品和豆腐产品也包含在本申请的范围内。 
本发明的新颖组合物也可用作甜食产品、糖果、口香糖、甜点(例如冰激凌、果冻、布丁、方便布丁粉)等等以及谷物、小吃、曲奇、意大利面、汤和沙司、蛋黄酱、沙拉酱等等的着色剂。 
为了对食物或药物产品着色,本发明的组合物可根据本身已知的方法以可分散于水或油的固体或液体类胡萝卜素形式被应用。 
通常,β-胡萝卜素着色剂组合物可作为水性储存溶液、干粉混合物被添加,或根据特定的应用与其他合适的食品成分预混合。根据最终应用的配方,可例如使用干粉搅拌机、低剪力混合机、高压匀化器或高剪力混合机来完成混合。混合方法和油性成分或水性成分的用量可影响最终应用的颜色。显而易见地,这类技术属于本领域技术人员的技能范围之内。 
以下的实施例进一步阐述本发明。 
实施例1:含β-胡萝卜素的着色剂组合物的物理特征对以Capsul和阿拉伯胶混合物为基础的CapsulTM(淀粉衍生物)含量的依赖性 
典型地,用于本发明用途的粉末组合物对应于494nm的色彩亮度E11在1300到1900范围内,优选地在1350到1600范围内,以NTU测量的浑浊度在70到250NTU的范围内,优选地在70到120NTU的范围内。 
在本发明一个优选的实施方案中,粉末组合物包含以Capsul和阿拉伯胶混合物计约25wt.%到约80wt.%、优选地60wt.%到80wt.%的CapsulTM。 
实施例2:着色剂组合物的制备
a)溶液A的制备: 
在80℃下,向1.5升反应管中530g去离子水中加入80.8g阿拉伯胶和244.7g改性淀粉(CapsulTM)的干燥预混合物。在惰性气氛中72℃下搅拌混合物,并将水性溶液的pH保持在约3.9。固体完全溶解后,向混合物中加入7.2g抗坏血酸钠、43.4g蔗糖和175.0g麦芽糖糊精DE-2023。 
b)溶液B的制备: 
向反应烧瓶中加入144.6g的中等链甘油三酯(Berg+Schmidt的Bergabest MCT-Oil 60/40)和0.72g的dl-α-生育酚。在惰性气氛中,加入25.3g的晶体β-胡萝卜素和磁性搅拌棒。柔和地搅拌悬浮液,同时加热至170℃。将混合物在该温度下保持60秒后将混合物再次冷却至85℃。 
c)乳剂的制备: 
在强力搅拌下,在72℃向溶液A中加入溶液B,并将乳剂强力搅拌约15到20分钟。通过将前乳剂在50/300bar的压强下三次高压匀化处理(APV-La 1000匀化器)获得精细的乳剂。 
d)喷雾干燥: 
向乳剂中加入0.2wt.%的硅酸(Aerosil 200),然后在65℃下在实验室喷雾干燥器中将乳剂喷雾干燥约1小时,使用约200℃的入口温度和约80℃的出口温度。在真空烘箱中室温下将喷雾干燥的粉末干燥过夜。 
e)分析: 
通过光子相关光谱学(Coulter N4 Plus)测量的前乳剂的平均颗粒尺寸约 为500-600nm,通过分光光度法和HPLC分析测定的粉末的β-胡萝卜素含量为2.9%。根据CIE-体系针对5ppm分散体系测量的色值L*=87.6、a*=-8、b*=54。根据a*和b*的值,可以计算出饱和度c*=55下的色相角h*=82°。 
*)Copenhagen果胶A/S的GENU果胶型VIS 
根据上述制备法的组合物特征如下: 
    物质     含量wt.%
    晶体抗坏血酸钠     1.0
    蔗糖     6.0
    麦芽糖糊精DE-2023**     24.2
    Capsul**     33.8
    阿拉伯胶**(GA)     11.2
    MCT中等链甘油三酯     20.0
    dl-α-生育酚     0.10
    β-胡萝卜素     3.5
    Aerosil 200     0.20
   
    基质中的%Capsul     48.8
    GA+Capsul中的%Capsul     75.1
   
    分析数据  
    UV/%     2.9
    HPLC/%     2.9
    E11对应/494nm     1642
    E11对应/463nm     1732
    L*/a*/b*-5ppm     87/8/54
    L*/c*/h*-5ppm     87/55/82
    浑浊度/NTU-5ppm     117
**基质 
实施例3:根据上述步骤制备的其他两种组合物(2,3)与本发明范围之外的组合物(对照)比较:
    物质     对照    含量wt.%     2)    含量wt.%     3)    含量wt.%
    晶体抗坏血酸钠     1.0     1.0     1.0
    蔗糖     7.0     7.0     6.0
    麦芽糖糊精DE-    2023**     39.9     28.9     28.9
    Capsul**     0.0     11.0     30.0
    阿拉伯胶**(GA)     33.0     33.0     15.0
    MCT     15.3     15.3     15.3
    dl-α-生育酚     0.1     0.1     0.1
    β-胡萝卜素晶体     3.5     3.5     3.5
    Aerosil 200     0.2     0.2     0.2
       
    基质中的%Capsul     0.0     15.1     40.6
    GA+Capsul中的%    Capsul     0.0     25.0     66.7
       
    分析数据      
    UV/%     3.5     3.2     3.2
    HPLC/%     35     3.1     3.3
    E11对应/494nm     1282     1392     1518
    E11对应/463nm     1196     1435     1714
    L*/a*/b*-5ppm     88/10/44     88/9/55     88/7/66
    L*/c*/h*-5ppm     88/45/77     88/56/81     88/66/84
  红色值%     18     14     10
  浑浊度/NTU-5ppm     125     104     71
**基质 

Claims (8)

1.包含分散于基质中的类胡萝卜素的着色剂组合物,其中所述基质含有改性淀粉,特征是所述组合物包含
-10到60wt.%的糖聚合物;
-5到50wt.%的阿拉伯胶;
-0.2到10wt.%的类胡萝卜素;
-5到10wt.%的单糖或二糖;
-10到20wt.%的甘油三酯;
-0.1到2wt.%的水溶性抗氧化剂;
-0.01到1wt.%的脂溶性抗氧化剂;
-0.1到1wt.%的硅酸;和
-1到5wt.%的水,并且其中
所述基质的改性淀粉包含以辛烯基丁二酸酯淀粉糊精和阿拉伯胶的混合物为基础25wt.%到80wt.%用量的辛烯基丁二酸酯淀粉糊精,足以为着色剂组合物赋予在1300到1900范围内的对应于494nm的色彩亮度和70到250NTU的浊度。
2.如权利要求1所述的组合物,其中所述类胡萝卜素是β-胡萝卜素。
3.如权利要求1或2中所述的组合物,其中所述甘油三酯是衍生自脂肪酸的具有6到12个碳原子的中等链甘油三酯。
4.如权利要求1到3中任一项所述的组合物,其中所述脂溶性抗氧化剂是生育酚或脂肪酸酯或其混合物。
5.如权利要求4所述的组合物,其中所述水溶性抗氧化剂是抗坏血酸。
6.如权利要求1到5中任一项所述的组合物,其为粉末。
7.如权利要求1到6中任一项所述的组合物,其包含:
a)20到30wt.%的麦芽糖糊精;
b)10到40wt.%的阿拉伯胶;
c)1.5到10wt.%的类胡萝卜素。
8.含有如权利要求1到7中任一项所述的组合物的食物、饮料、动物饲料、化妆品或药物。
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