CN108367852A - 抗氧化活性食品包装 - Google Patents
抗氧化活性食品包装 Download PDFInfo
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- CN108367852A CN108367852A CN201680068169.8A CN201680068169A CN108367852A CN 108367852 A CN108367852 A CN 108367852A CN 201680068169 A CN201680068169 A CN 201680068169A CN 108367852 A CN108367852 A CN 108367852A
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Abstract
本发明公开了包含聚合物材料和天然抗氧剂的食品包装材料。所述天然抗氧剂可以从植物材料中提取、分离和/或由此衍生。本发明还提供了一种用于形成食品包装材料的方法,包括形成包含天然抗氧剂和聚合物树脂的混合物以及处理该混合物以形成食品包装材料。
Description
技术领域
本发明涉及抗氧化活性食品包装。
背景技术
脂质氧化是食品变质、颜色变化和降解的主要原因,这显著限制了包装食品的保存期和货架期。非天然抗氧剂已被用于聚合物工业中以防止加工过程中聚合物的热降解。但是,这些抗氧剂对食品的潜在毒性使其不适用于食品包装。此外,消费者对食品中存在非天然物质具有强烈的偏见。
在此背景下,需要安全的、基于天然的抗氧化活性食品包装。
发明内容
根据本发明,提供了包含聚合物材料和天然抗氧剂的食品包装材料。
所述天然抗氧剂可以约0.00001wt%至20wt%的量或约0.0001wt%至5wt%的量,或约0.001wt%至1wt%的量或约0.005wt%至0.1wt%的量或约0.001wt%至0.01wt%的量存在于所述食品包装材料中。
所述天然抗氧剂可以约0.1ppm至20,000ppm,或约1ppm至50,000ppm,或约10ppm至10,000ppm,或约50ppm至1000ppm,或约10ppm至150ppm或约10ppm至100ppm的量,或以最高达约40ppm的量存在于所述食品包装材料中。
所述天然抗氧剂可以是从植物材料中提取的、分离的和/或由此衍生的。
所述植物材料可以选自水果/浆果、草本植物、香料、茶及其组合。
所述水果/浆果可以选自李子、西梅干、葡萄、葡萄干、蓝莓、覆盆子、黑莓、草莓、卡卡杜李、柠檬白杨、戴维森李子(Davidson's plum)、框东坚果(quandong)、蒲桃(riberry)、橙子、可可、樱桃、蔓越莓、欧洲越桔(bilberry)、猕猴桃、巴西莓、葡萄柚、梨、杏、香蕉、苹果、黑醋栗、鳄梨、波森莓、哈密瓜、椰子、火龙果、榴莲、海枣、接骨木果、枸杞莓、番石榴、美洲越橘(huckleberry)、菠萝蜜、杜松子、金橘、柠檬、酸橙、澳大利亚沙漠酸橙、灌木番茄、芒果、蜜瓜、西瓜、桑葚、油桃、橄榄、柑橘、番木瓜、桃子、柿子、石榴、菠萝、柚子、温桲、芒果、红酸栗、红毛丹果、杨桃、树番茄、乌吉尔果、咖啡及其组合。
所述草本植物可以选自叶、花、种子、树皮、球茎、假种皮(aril)和根,包括罗勒、莳萝、月桂叶、韭菜(chive)、水芹、苜蓿、蜀葵糖浆(marshmallow)、薰衣草、柠檬草、塔斯马尼亚胡椒、柠檬香桃木、茴香桃金娘(anise myrtle)、马郁兰、薄荷、艾蒿、柠檬香蜂草、土荆芥、咖喱叶、欧芹、紫苏、三叶叶、拉维纪草、牛膝草、缬草、西洋蓍草、酢浆草、龙蒿、山药、葱属(jimbu)、车叶草、***、芸香、鸭儿芹(mitsuba)、迷迭香、鼠尾草、牛至、百里香、留兰香、胡椒薄荷、香菜、肉桂、桂皮、茴香(fennel)、葫芦巴、莳萝芥末、丁香、番红花、洋葱、大蒜、韭葱、生姜、姜黄、葡萄籽、黑胡椒、八角茴香(star anise)、大豆、肉豆蔻干皮精油及其组合。
所述茶可以是绿茶、白茶、黄茶、药茶、后发酵茶、乌龙茶或黑茶。所述茶可以从野茶树(Camellia sinensis)获得。
所述草本植物可以是多年生草本植物。
所述草本植物可以选自迷迭香属(Rosmarinus)、鼠尾草属(Salvia)或牛至属(Origanum)。在一个实施方案中,所述草本植物可以选自迷迭香(Rosmarinusofficinalis)、鼠尾草(Salvia officinalis)、牛至(Origanum vulgaro)及其组合。在另一个实施方案中,所述草本植物可以是迷迭香。
所述香料可以选自叶、花、种子、树皮、球茎、假种皮(aril)和根,包括金合欢籽(Wattleseed)、藏红花、生姜、姜黄、葡萄籽、尖辣椒(chilli pepper)、小茴香(cumin)、多香果(allspice)、大茴香(anise)、葛缕子(carraway)、小豆蔻(cardamom)、肉桂、桂皮、丁香、香菜、小茴香(cumin)、茴香(fennel)、葫芦巴、高良姜、大蒜、生姜、辣根、野山竹汁(kokum)、芥末、肉豆蔻、罂粟种子、玫瑰、红辣椒(paprika)、藏红花、漆树、罗望子、姜黄、香草、芝麻、沙士(sarsaparilla)、檫树(sassafras)、零陵香豆(tonka bean)及其组合。
所述天然抗氧剂可以选自酚类,多酚类,酚酸类,酚酯类,酚单萜类,酚二萜类,类胡萝卜素,姜黄素,呫吨酮类(xanthones),维生素A、E和C,咖啡酰基衍生物,柠檬酸,抗坏血酸,单萜类,二萜类或三萜类,类黄酮,萜类,木脂素类,硫化物类,植物甾醇类,姜黄素类,茋类,苯酞类,生育三烯酚类,生育酚及其组合。
所述天然抗氧剂可以选自咖啡酸、迷迭香酸、鼠尾草酚、鼠尾草酸及其组合。
所述天然抗氧剂可以是包含酚二萜类的迷迭香提取物。
所述天然抗氧剂可以是包含鼠尾草酸和鼠尾草酚的迷迭香提取物。在一个实施方案中,所述天然抗氧剂可以是包含至少40wt%鼠尾草酸和鼠尾草酚的迷迭香提取物。
所述天然抗氧剂可以选自叶黄素、芦丁、花青素、α-蒎烯、冰片、(-)-莰烯、1,8-桉树脑、樟脑、马鞭草烯酮、乙酸冰片酯、12-O-甲基花生酸、咖啡酰基衍生物、羽扇烷、齐墩果烷、乌苏烷三萜、熊果酸、槲皮素、rofficerone、单萜、月桂烯、7-甲基吡啶并莽草酚、表迷迭香酚、樟脑、儿茶素、香芹酚、异高山黄芩素7-O-葡萄糖苷、芫花素、对伞花烃、里哪醇、γ-萜品烯、麝香草酚、β-蒎烯、桉叶油素、亚油酸、迷迭香醌(rosmariquinone)、单萜烃类、氧化单萜类、倍半萜烃类、(-)-茉莉酸甲酯、迷迭香酚、迷迭香双醛(rosmadial)、邻醌、对醌、圣草次苷、木犀草素3-O-β-D-葡萄糖醛酸苷、橙皮苷、香叶木苷、异高山黄芩素-7-O-葡萄糖苷、高车前素7-O-葡萄糖苷、姜醇、姜烯酚、姜油酮、4-羟基肉桂酰基甲烷、山奈酚、鼠李白素、辣椒素(capsaicin)、辣椒碱(capsaicinol)、酚挥发油类、丁子香酚、乙酰丁香酚、抗坏血酸棕榈酸酯、异丁子香酚、鞣质、β-胡萝卜素、β-谷甾醇、氢醌、乙酸芳樟酯植物3-17、月桂烯、松油烯-4-醇、茴香甲醇(cuminal)、γ-萜品烯、松香芹醇(pincarveol)、里哪醇、1-甲基-2-(1-甲基乙基)苯、胡萝卜次醇、异迷迭香酚、atuntzensin A、迷迭香酚-7-***、二甲氧基-迷迭香酚、迷迭香双醛(rosmadial)、safficinolide、sageone、rosmriquinone(Miltrone)、迷迭香二酚(rosmaridiphenol)、大黄素甲醚(physcion)、芹菜素、高车前素、蓟黄素、5,4’-二羟基-6,7,8-三甲氧基黄酮、5-羟基-7,4’-二甲氧基黄酮、鼠尾草酚的甲酯和乙酯、咖啡酸、原儿茶酸、2-咖啡酰氧基-3-[2-(4-羟基苄基)-4,5-二羟基]苯基丙酸、类黄酮、圣草酚、二氢槲皮素、二氢川芎酚、对茴香素-2,3-二醇、没食子酸、三裂鼠尾草素、木犀草素、泽兰叶黄素、木犀草素-7-O-葡萄糖苷、高车前苷、芹菜素-7-O-葡萄糖苷、6-O-咖啡酰基-β-D-呋喃果糖基-(2→1)-α-D-吡喃葡萄糖苷、1-O-咖啡酰基-β-D-呋喃芹糖基-(1→6)-β-D-吡喃葡萄糖苷、1-O-对羟基苯甲酰基-β-D-呋喃芹糖基-(1→6)-β-D-吡喃葡萄糖苷、1-O-(2-羟基-5-2-羟基-乙基)苯基-6-O-反式-咖啡酰基)-β-D-吡喃葡萄糖苷、4-O-(5-O-(3,5-二甲氧基-4-羟基苯甲酰基)-β-D-呋喃芹糖基-(1→2)-β-D-吡喃葡萄糖苷、6-O-E-亚铁酰基-(α和β)-吡喃葡萄糖苷、(+)-1-羟基松脂醇-1-β-D-吡喃葡萄糖苷、(+)-fraxiresinol-1-β-D-吡喃葡萄糖苷及其组合。儿茶酚化合物包括(-)-表儿茶素(EC),(-)-表儿茶素没食子酸酯(ECG),(-)-表没食子儿茶素(EGC)和(-)-表没食子儿茶素没食子酸酯(EGCG),香草酸、绿原酸和五环三萜类,例如乌索酸、齐墩果酸、桦木酸、肉毒碱、α-香树脂醇、β-香树脂醇及其组合。
所述天然抗氧剂可以是有机的。
所述天然抗氧剂可以掺入到所述食品包装材料的涂层(a coating)、层(alayer)、片(a sheet)或壁(a wall)中和/或其上。
所述天然抗氧剂可以在使用时迁移到食品上和/或其中。
所述食品包装材料可以进一步包含作为天然抗氧剂异构体的抗氧剂。所述异构体可以是立体异构体。
作为天然抗氧剂异构体的抗氧剂可以是异抗坏血酸钠。
所述聚合物材料可选自聚对苯二甲酸乙二醇酯(PET)、聚乳酸(PLA)、聚乙烯(PE)、乙烯乙烯醇共聚物(EVOH)、聚丙烯(PP)、聚偏二氯乙烯(PVdC)、聚苯乙烯(PS)、聚四氟乙烯(PTFE)、聚氯乙烯(PVC)、聚酰胺或尼龙(PA)及其组合。在一个实施方案中,所述聚合物材料是低密度聚乙烯(LDPE)或线性低密度聚乙烯(LLDPE)。
所述食品包装材料可以包括单个或多个聚合物层。在一个实施方案中,所述食品包装材料包括多个聚合物层。
所述食品包装材料可以包括第一层、第二层和聚合物阻挡层,其中所述第一层包含天然抗氧剂,所述第二层包含除氧剂,并且其中所述第二层位于所述第一层和所述阻挡层之间。
所述食品包装材料可以通过挤出生产。
所述食品包装材料可以是薄膜,例如保鲜膜。
本发明进一步提供由上述食品包装材料形成或包含上述食品包装材料的食品包装。
所述食品包装可以是包裹(a wrap)、包裹物件(a wrapper)、袋(可重新封闭的袋或冷冻袋)、容器、托盘、薄片、纸箱、盒子、瓶子、瓶盖、衬垫、管子、隔芯板、块及其组合。在一个实施方案中,所述食品包装材料是袋子,例如PE袋。
本发明还提供一种方法,包括:
形成包含天然抗氧剂和聚合物树脂的混合物;和
处理所述混合物以形成食品包装材料。
所述处理可以包括挤出、模制、真空成形、铸造或层压。
附图说明
图1:显示从实施例2的样品1浸渍出来的鼠尾草酚和鼠尾草酸的峰的色谱图。
图2:显示从实施例2的样品2浸渍出来的鼠尾草酚和鼠尾草酸的峰的色谱图。
图3:显示从实施例2的样品3浸渍出来的鼠尾草酚和鼠尾草酸的峰的色谱图。
图4:显示从实施例2的样品4浸渍出来的鼠尾草酚和鼠尾草酸的峰的色谱图。
图5:显示从实施例2的样品5浸渍出来的鼠尾草酚和鼠尾草酸的峰的色谱图。
图6:显示从市售迷迭香提取物中浸渍出来的鼠尾草酚和鼠尾草酸的峰的色谱图。
图7:实施例3中使用的包括EVOO的袋子。
图8和9:储存在含有不同量的抗氧剂的冷冻袋中的EVOO的过氧化值。
具体实施方式
本发明涉及包含聚合物材料和天然抗氧剂的食品包装材料。如本文所用的术语“天然抗氧剂”应理解为是指抗氧剂是天然产物、化合物或化合物的混合物。天然产物、化合物或化合物的混合物通常是从天然来源获得。或者,天然存在的化合物可以在实验室中利用合成化学合成或从商业来源购买。
根据本发明的实施方案的抗氧化活性食品包装材料通常包含掺入到聚合材料中和/或其上的天然抗氧剂。聚合物材料可选自PET、PLA、PE、EVOH、PP、PVdC、PS、PVC、PA及其组合。典型地,基于所期望的包装材料的最终用途来选择聚合物材料。例如,PVC通常用于包装新鲜产品,包括肉类和预先烹制的食物。高密度PE通常用于冷冻食品的薄膜和容器中。
天然抗氧剂可以在以下一个或多个生产阶段中掺入到聚合物材料中和/或其上:
(i)在聚合阶段期间(即直接在聚合物材料的生产期间);
(ii)在随后的加工阶段(例如配混或混合阶段)中加入到成品颗粒中;
(iii)在处理机器本身,例如挤出机或注塑模具中;和/或
(iv)被施加到成品处理制品本身上,例如作为涂层(a coating)的一部分;
(v)在包封膜中,其提供对该过程的保护以掺入到聚合物材料中但是将抗氧剂释放到该材料中。
为了获得聚合物材料和天然抗氧剂的均匀混合物,天然抗氧剂可以在配混或混合阶段掺入聚合物材料中。在配混或混合阶段,天然抗氧剂可以作为固体、液体、油、粉末或作为乳液加入。在一个实施方案中,天然抗氧剂可以与聚合物树脂、载体和其他任选的添加剂例如粘附添加剂配混或混合以形成母料。该母料可以任选地包含适用于食品包装的其他常规功能性塑料添加剂,例如增粘剂、分散剂和化合物或着色剂。合适的载体包括多孔树脂,例如微孔LLDPE、高密度聚乙烯(HDPE)、LDPE、尼龙、聚苯乙烯或高结构或高表面积二氧化硅,或者蜡例如聚乙烯蜡(低分子量聚乙烯)、苯乙烯改性聚合物和共聚物,例如苯乙烯-乙烯-丁烯聚合物、苯乙烯-异戊二烯共聚物、苯乙烯-乙烯-丙烯嵌段共聚物和苯乙烯-丁二烯共聚物例如可从Chevron Philips获得的K树脂或者天然或合成沸石。
其他等同或替代的处理技术也可用于将天然抗氧剂添加剂掺入到聚合物材料中和/或其上。
随后可以通过例如挤出(包括流延薄膜挤出和吹塑薄膜挤出)、模塑或层压处理将天然抗氧剂添加剂掺入到聚合物树脂母料中,以形成食品包装材料。天然抗氧剂添加剂可以掺入到食品包装材料的涂层(a coating)、层(a layer)、片(a sheet)或壁(a wall)中和/或其上。食品包装材料的片(a sheet)或壁(a wall)可以包含一层或多层聚合物材料。
所述食品包装材料可以包含多个聚合物层。在一个实施方案中,所述食品包装材料包含外部阻隔层,包含天然抗氧剂的第一层和包含除氧剂的第二层。第二层位于阻挡层和第一层之间。在使用时,第一层旨在与食物接触以允许天然抗氧剂迁移到食物上和/或食物中。包含除氧剂的第二层有助于去除包装中的氧气或使其最少化。阻挡层防止氧气进入包装中或使其最少化。可以根据包装顶部空间中的氧气水平、最初食物中捕获氧气的多少以及储存过程中从周围空气输送到包装中的氧气量来选择合适的除氧剂。可掺入到聚合物中的合适的除氧剂的实例包括基于铁的化合物、抗坏血酸盐、金属盐、钴催化剂和儿茶酚。为了最大限度地减少金属污染物被传递到食物中的可能性,非铁化合物可能是优选的。
各聚合物层的厚度可足以执行该层的预期功能,例如用作阻挡层、用作除氧剂层或用作抗氧剂层。
多层包装材料可以通过例如挤出和层压来生产。制备多层膜的一个示例性方法包括共挤出聚合物层。然后可以通过首先冷却并随后层压将多层共挤出膜层压到阻挡层上,或者挤出到阻挡层上。
在一些实施方案中,所述食品包装材料可以是薄膜,例如保鲜膜。本发明还包括由本文所述的食品包装材料形成或包含此食品包装材料的食品包装。食品包装的非限制性实例包括包裹(a wrap)、包裹物件(a wrapper)、袋(可重新封闭的袋或冷冻袋)、容器、托盘、薄片、纸箱、瓶盖、盒子、瓶子、衬垫、隔芯板、块及其组合。
所述天然抗氧剂添加剂可以以使得其能够从聚合物材料迁移到食物上和/或食物中并从而抑制或延迟食物氧化的量掺入到聚合物材料中和/或其上。所述抗氧剂可以清除食品中或周围大气中产生的高活性物质,例如自由基、超氧化物和单线态氧,并参与脂质氧化。所述抗氧剂可以有助于氧化强化剂催化剂的中和。抗氧化作用可以控制、延缓或抑制食品质量的氧化和变质,保持食品的颜色、风味和香味,并且可以维持营养价值并延长食品的货架期。
所述天然抗氧剂可以约0.00001wt%至20wt%的量或约0.0001wt%至5wt%的量,或约0.001wt%至1wt%的量或约0.005wt%至0.1wt%的量或约0.001wt%至0.01wt%的量存在于所述食品包装材料中。
所述天然抗氧剂可以约0.1ppm至20,000ppm,或约1ppm至50,000ppm,或约10ppm至10,000ppm,或约50ppm至1000ppm,或约10ppm至150ppm或约10ppm至100ppm的量,或以最高达约40ppm的量存在于所述食品包装材料中。
在一些实施方案中,天然抗氧剂被组合以实现协同效应。例如,鼠尾草抗氧剂的自由基清除活性可以与柠檬酸的螯合能力相结合。该方法利用不同的抗氧化机理途径,从而能够实现与使用单一抗氧剂相比更高的功效。每种抗氧剂的量可以相同或不同。在一个实施方案中,维生素C可以通过再生后一种分子而与生育酚协同相互作用。在另一个实施方案中,来自迷迭香草的酚酸例如迷迭香酸可以与β-生育酚协同作用。包括酚酸和类黄酮的多酚类可以与维生素抗氧剂协同作用,从而增强抗氧化作用。
所述天然抗氧剂可以从植物材料中提取、分离和/或由此衍生。通常,所述天然抗氧剂是植物材料的提取物。所述天然抗氧剂可以是有机的。
如本文所用的术语“提取物”是指源自植物材料的活性制剂。在本说明书的上下文中,“活性”是指提取物能够产生如本文所公开的所期望的抗氧化作用。通过“提取”过程获得提取物是本领域技术人员理解的提取活性成分的方法。提取过程可以包括用液体或超临界流体处理植物材料以溶解活性制剂并将其与残余的不想要的植物材料相分离。提取物可以是液体形式(例如作为煎液、溶液、输液或酊剂)或固体形式(例如作为粉末或颗粒)。
示例性的提取过程包括用包括己烷、丙酮、乙醇、水或其混合物的食用级溶剂进行处理,通过将植物碾压进行机械提取,与油混合,然后加热,搅拌并加压过滤,在多个步骤中进行超临界二氧化碳萃取,通过加压热水萃取,使用少量乙醇、超声辅助甲醇萃取和水蒸馏,并用乙醇浸渍。
适用于食品包装材料的提取物可以是通过单一、组合和/或连续提取任何可用的植物材料获得的基于水、凝胶、油和/或有机溶剂的提取物。合适的提取方法以及合适的用于提取的溶剂和液体是本领域技术人员已知的。用于提取的水溶剂(例如水、酸、碱);油(例如椰子);有机溶剂(例如己烷、乙醇、甲醇、丙酮、四氢呋喃和氯仿)可以依次或以组合混合物用于提取。使用例如超临界氮气或二氧化碳的超临界流体萃取也可用于获得提取物。
此外,本领域技术人员将理解的是,可以对提取物进行一个或多个后提取步骤,以例如增加或维持提取物的稳定性,改变或变动提取物的物理形式或者协助将提取物配制成食品包装材料。
提取物可以来自任何合适的植物材料。合适的植物材料包括但不限于叶、根、树皮、果实、枝条、坚果(例如榛子、花生、杏仁核桃等)、种子和花。植物材料可以是例如新鲜的、干燥的或冷冻干燥的。对于任何给定的植物物种,可以使用多于一种植物材料来生产提取物。本领域技术人员将理解的是,天然抗氧剂提取物也可以从商业来源获得。
所述植物材料可以选自水果/浆果、草本植物、香料、茶及其组合。所述草本植物可以是多年生草本植物。
所述水果/浆果可以选自李子、西梅、葡萄、葡萄干、蓝莓、覆盆子、黑莓、草莓、卡卡杜李、柠檬白杨、戴维森李子(Davidson's plum)、框东坚果(quandong)、蒲桃(riberry)、橙子、可可、樱桃、蔓越莓、欧洲越桔(bilberry)、猕猴桃、巴西莓、葡萄柚、梨、杏、香蕉、苹果、黑醋栗、鳄梨、波森莓、哈密瓜、椰子、火龙果、榴莲、海枣、接骨木果、枸杞莓、番石榴、美洲越橘(huckleberry)、菠萝蜜、杜松子、金橘、柠檬、酸橙、澳大利亚沙漠酸橙、灌木番茄、芒果、蜜瓜、西瓜、桑葚、油桃、橄榄、柑橘、番木瓜、桃子、柿子、石榴、菠萝、柚子、温桲、芒果、红酸栗、红毛丹果、杨桃、树番茄、乌吉尔果、咖啡及其组合。
所述草本植物可以选自叶、花、种子、树皮、球茎、假种皮(aril)和根,包括罗勒、莳萝、月桂叶、韭菜(chive)、水芹、苜蓿、蜀葵糖浆(marshmallow)、薰衣草、柠檬草、塔斯马尼亚胡椒、柠檬香桃木、茴香桃金娘(anise myrtle)、马郁兰、薄荷、艾蒿、柠檬香蜂草、土荆芥、咖喱叶、欧芹、紫苏、三叶叶、拉维纪草、牛膝草、缬草、西洋蓍草、酢浆草、龙蒿、山药、葱属(jimbu)、车叶草、***、芸香、鸭儿芹(mitsuba)、迷迭香、鼠尾草、牛至、百里香、留兰香、胡椒薄荷、香菜、肉桂、桂皮、茴香(fennel)、葫芦巴、莳萝芥末、丁香、番红花、洋葱、大蒜、韭葱、生姜、姜黄、葡萄籽、黑胡椒、八角茴香(star anise)、大豆、肉豆蔻干皮精油及其组合。
所述茶可以是绿茶、白茶、黄茶、药茶、后发酵茶、乌龙茶或黑茶。所述茶可以从野茶树(Camellia sinensis)获得。
所述草本植物可以选自迷迭香属(Rosmarinus)、鼠尾草属(Salvia)或牛至属(Origanum)。在一个实施方案中,所述草本植物可以选自迷迭香(Rosmarinusofficinalis)、鼠尾草(Salvia officinalis)、牛至(Origanum vulgaro)及其组合。在另一个实施方案中,所述草本植物可以是迷迭香。
所述香料可以选自叶、花、种子、树皮、球茎、假种皮(aril)和根,包括金合欢籽(Wattleseed)、藏红花、生姜、姜黄、葡萄籽、尖辣椒(chilli pepper)、小茴香(cumin)、多香果(allspice)、大茴香(anise)、葛缕子(carraway)、小豆蔻(cardamom)、肉桂、桂皮、丁香、香菜、小茴香(cumin)、茴香(fennel)、葫芦巴、高良姜、大蒜、生姜、辣根、野山竹汁(kokum)、芥末、肉豆蔻、罂粟种子、玫瑰、红辣椒(paprika)、藏红花、漆树、罗望子、姜黄、香草、芝麻、沙士(sarsaparilla)、檫树(sassafras)、零陵香豆(tonka bean)及其组合。
在其它一些实施方案中,所述天然抗氧剂可以选自酚类,多酚类,酚酸类,酚酯类,酚单萜类,酚二萜类,类胡萝卜素,姜黄素,呫吨酮类(xanthones),维生素A、E和C,咖啡酰基衍生物,柠檬酸,抗坏血酸,单萜类、二萜类或三萜类,类黄酮,萜类,木脂素类,硫化物类,植物甾醇类,姜黄素类,茋类,苯酞类,生育三烯酚类,生育酚、萜烯化合物中的一种或多种及其组合。
在一个实施方案中,所述天然抗氧剂可以是迷迭香醇、7-甲基-迷迭香醇、鼠尾草酚、鼠尾草酸或12-甲基鼠尾草酸。在一些实施方案中,所述天然抗氧剂可以选自咖啡酸、迷迭香酸、鼠尾草酚、鼠尾草酸及其组合。
在又一个实施方案中,所述天然抗氧剂可以选自叶黄素、芦丁、花青素、α-蒎烯、冰片、(-)-莰烯、1,8-桉树脑、樟脑、马鞭草烯酮、乙酸冰片酯、12-O-甲基花生酸、咖啡酰基衍生物、羽扇烷、齐墩果烷、乌苏烷三萜、熊果酸、槲皮素、rofficerone、单萜、月桂烯、7-甲基吡啶并莽草酚、表迷迭香酚、樟脑、儿茶素、香芹酚、异高山黄芩素7-O-葡萄糖苷、芫花素、对伞花烃、里哪醇、γ-萜品烯、麝香草酚、β-蒎烯、桉叶油素、亚油酸、迷迭香醌(rosmariquinone)、单萜烃类、氧化单萜类、倍半萜烃类、(-)-茉莉酸甲酯、迷迭香酚、迷迭香双醛(rosmadial)、邻醌、对醌、圣草次苷、木犀草素3-O-β-D-葡萄糖醛酸苷、橙皮苷、香叶木苷、异高山黄芩素-7-O-葡萄糖苷、高车前素7-O-葡萄糖苷、姜醇、姜烯酚、姜油酮、4-羟基肉桂酰基甲烷、山奈酚、鼠李白素、辣椒素(capsaicin)、辣椒碱(capsaicinol)、酚挥发油类、丁子香酚、乙酰丁香酚、抗坏血酸棕榈酸酯、异丁子香酚、鞣质、β-胡萝卜素、β-谷甾醇、氢醌、乙酸芳樟酯植物3-17、月桂烯、松油烯-4-醇、茴香甲醇(cuminal)、γ-萜品烯、松香芹醇(pincarveol)、里哪醇、1-甲基-2-(1-甲基乙基)苯、胡萝卜次醇、异迷迭香酚、atuntzensinA、迷迭香酚-7-***、二甲氧基-迷迭香酚、迷迭香双醛(rosmadial)、safficinolide、sageone、rosmriquinone(Miltrone)、迷迭香二酚(rosmaridiphenol)、大黄素甲醚(physcion)、芹菜素、高车前素、蓟黄素、5,4’-二羟基-6,7,8-三甲氧基黄酮、5-羟基-7,4’-二甲氧基黄酮、鼠尾草酚的甲酯和乙酯、咖啡酸、原儿茶酸、2-咖啡酰氧基-3-[2-(4-羟基苄基)-4,5-二羟基]苯基丙酸、类黄酮、圣草酚、二氢槲皮素、二氢川芎酚、对茴香素-2,3-二醇、没食子酸、三裂鼠尾草素、木犀草素、泽兰叶黄素、木犀草素-7-O-葡萄糖苷、高车前苷、芹菜素-7-O-葡萄糖苷、6-O-咖啡酰基-β-D-呋喃果糖基-(2→1)-α-D-吡喃葡萄糖苷、1-O-咖啡酰基-β-D-呋喃芹糖基-(1→6)-β-D-吡喃葡萄糖苷、1-O-对羟基苯甲酰基-β-D-呋喃芹糖基-(1→6)-β-D-吡喃葡萄糖苷、1-O-(2-羟基-5-2-羟基-乙基)苯基-6-O-反式-咖啡酰基)-β-D-吡喃葡萄糖苷、4-O-(5-O-(3,5-二甲氧基-4-羟基苯甲酰基)-β-D-呋喃芹糖基-(1→2)-β-D-吡喃葡萄糖苷、6-O-E-亚铁酰基-(α和β)-吡喃葡萄糖苷、(+)-1-羟基松脂醇-1-β-D-吡喃葡萄糖苷、(+)-fraxiresinol-1-β-D-吡喃葡萄糖苷及其组合。儿茶酚化合物包括(-)-表儿茶素(EC),(-)-表儿茶素没食子酸酯(ECG),(-)-表没食子儿茶素(EGC)和(-)-表没食子儿茶素没食子酸酯(EGCG),香草酸、绿原酸和五环三萜类,例如乌索酸、齐墩果酸、桦木酸、肉毒碱、α-香树脂醇、β-香树脂醇及其组合。
所述天然存在的化合物可以使用例如上述提取技术从天然来源获得,或者可选地从商业来源购买。所述天然抗氧剂可以是食用级或通常被公认安全(GRAS)特别批准的抗氧剂、填料、混合物、香料。这增加了天然抗氧剂可安全用于食品包装的可能性。
在一些实施方案中,所述食品包装材料可以进一步包含抗氧剂,其为天然抗氧剂的异构体。所述异构体可以是结构异构体或立体异构体。在一个实施方案中,作为天然抗氧剂的异构体的抗氧剂可以是异抗坏血酸钠。
所述食品包装材料可以包含多种天然抗氧剂。在一些实施方案中,所述天然抗氧剂可协同相互作用,使得多种抗氧剂的抗氧化活性大于单独抗氧剂活性的总和。所述天然抗氧剂也可以具有抗微生物活性。
现在将参照下面的实施例仅通过例举说明的方式来更详细地描述本发明。所述实施例旨在用于举例说明本发明,并且不应将其解释为在整个说明书中限制说明书公开内容的一般性。
实施例
实施例1-含抗氧剂的薄膜的制备
制备包含食用级迷迭香提取物和聚乙烯树脂的母料。迷迭香提取物包含:24-26wt%总抗氧化酚二萜类,其中>16wt%鼠尾草酸、1-4wt%精油、<1wt%水、小于2wt%酒精、向日葵油(有机)和角质层蜡。将母料加入到聚合物树脂中,然后挤出形成薄膜。
实施例2-抗氧剂从薄膜中迁移
进行迁移测试以验证天然抗氧化活性化合物从抗氧化活性薄膜中迁移出来。
制备下列样品:
样品1:包含含有约7,500ppm酚二萜的食用级迷迭香提取物的LDPE薄膜。
样品2:包含含有约125ppm酚二萜的食用级迷迭香提取物的LDPE薄膜。
样品3:包含含有约112.5ppm酚二萜的食用级迷迭香提取物的LDPE薄膜。
样品4:包含含有约112.5ppm酚二萜的食用级迷迭香提取物的HDPE薄膜。
样品5:包含含有约25ppm酚二萜的食用级迷迭香提取物的LDPE薄膜。
市售的迷迭香提取物也作为对照进行测试(样品6)。
根据澳大利亚标准AS2070-1999,使用模拟方案对样品1至6进行模拟。模拟物是50%乙醇。制备50%乙醇溶液(50:50v/v乙醇:milliQ水)。对10cm×10cm的薄膜子样品称重,并且然后在柔和照明下用50%乙醇溶液提取。通过液相色谱串联质谱(LCQQQ)分析这些提取物并监测特征离子(鼠尾草酚和鼠尾草酸的m/z分别为285和287)的存在。
检测所有样品1至6的特征离子,由此提供成功地证实从测试薄膜迁移的鼠尾草酚和鼠尾草酸。结果如图1至6所示。
在10分钟的接触时间之后,模拟溶液中鼠尾草酚和鼠尾草酸的浓度能够被半定量测定。浓度在下表1中给出。
*约值
实施例3-薄膜的抗氧化性质
使用真正的食品***对样品1、2和4进行模拟以测量薄膜的抗氧化性质。食品模拟物是特级初榨橄榄油(EVOO)。
模拟的目的是测定含抗氧剂的薄膜是否能够保护食品模拟物免于氧化。
将由对应于样品1和2的薄膜制成的袋子和样品4制成的袋子放置成与EVOO接触,然后在环境条件或加热条件下储存。目的是为EVOO样品提供氧化机会,从而允许在一段时间内测量过氧化值的变化。然后将EVOO氧化(过氧化值增加)与不含抗氧剂的对照薄膜进行比较。
每个袋子都装有EVOO。在0时(t=0)测量EVOO的过氧化值以建立基线值。在不同的氧化阶段使用两种不同的EVOO样品。澳大利亚EVOO(红岛品牌)的基线过氧化值为12.57毫克当量(milli Eq)过氧化物/Kg。西班牙EVOO(Moro品牌)的基线过氧化值为7.92毫当量过氧化物/kg。选择EVOO样品进行试验以确保在14天的测试时间内可以测量薄膜的任何抗氧化效果。
每个EVOO模拟***的过氧化值(PV)以3个时间间隔进行,t=0天、t=7天和t=14天。为了加速EVOO样品的氧化并测量任何抗氧化效果,暴露于光、空气和热进行试验。
已知曝光对氧化过程有贡献。在测试期间(t=14天),环境测试样品在全光下保持打开。图7显示了袋子装满EVOO,在室温(21℃)下储存并暴露于光下的情况。图8和9显示了获得的PV。“低剂量”对应于样品1,“中等剂量”对应于样品2,并且“高剂量”对应于样品4。图8和9显示了含有不同量的抗氧剂的袋子始终延迟氧化而不依赖于量。
本发明的实施方案提供抗氧化活性食品包装,其显著抑制氧化反应并主动释放抗氧剂化合物作为氧自由基的清除剂以保护食品免受由脂质氧化引起的变质、颜色变化和降解。
为了本说明书的目的,词语“包括(comprising)”意味着“包括但不限于”,并且词语“包含(comprises)”具有相应的含义。
仅通过举例说明的方式描述了以上实施方案,并且在随后的权利要求的范围内可以进行修改。
Claims (37)
1.包含聚合物材料和天然抗氧剂的食品包装材料。
2.根据权利要求1所述的食品包装材料,其中所述天然抗氧剂以约0.00001wt%至20wt%的量或约0.0001wt%至5wt%的量,或约0.001wt%至1wt%的量或约0.005wt%至0.1wt%的量或约0.001wt%至0.01wt%的量存在于所述食品包装材料中。
3.根据权利要求1所述的食品包装材料,其中所述天然抗氧剂以约0.1ppm至20,000ppm的量或约1ppm至50,000ppm的量,或约10ppm至10,000ppm,或约50ppm至1000ppm的量,或约10ppm至100ppm的量存在于所述食品包装材料中。
4.根据权利要求1至3中任一项所述的食品包装材料,其中所述天然抗氧剂是从植物材料中提取的、分离的和/或由此衍生的。
5.根据权利要求1至4中任一项所述的食品包装材料,其中所述植物材料选自水果/浆果、草本植物、香料、茶及其组合。
6.根据权利要求5所述的食品包装材料,其中所述水果/浆果选自李子、西梅干、葡萄、葡萄干、蓝莓、覆盆子、黑莓、草莓、卡卡杜李、柠檬白杨、戴维森李子(Davidson's plum)、框东坚果(quandong)、蒲桃(riberry)、橙子、可可、樱桃、蔓越莓、欧洲越桔(bilberry)、猕猴桃、巴西莓、葡萄柚、梨、杏、香蕉、苹果、黑醋栗、鳄梨、波森莓、哈密瓜、椰子、火龙果、榴莲、海枣、接骨木果、枸杞莓、番石榴、美洲越橘(huckleberry)、菠萝蜜、杜松子、金橘、柠檬、酸橙、澳大利亚沙漠酸橙、灌木番茄、芒果、蜜瓜、西瓜、桑葚、油桃、橄榄、柑橘、番木瓜、桃子、柿子、石榴、菠萝、柚子、温桲、芒果、红酸栗、红毛丹果、杨桃、树番茄、乌吉尔果、咖啡及其组合。
7.根据权利要求5所述的食品包装材料,其中所述草本植物选自叶、花、种子、树皮、球茎、假种皮(aril)和根,包括罗勒、莳萝、月桂叶、韭菜(chive)、水芹、苜蓿、蜀葵糖浆(marshmallow)、薰衣草、柠檬草、塔斯马尼亚胡椒、柠檬香桃木、茴香桃金娘(anisemyrtle)、马郁兰、薄荷、艾蒿、柠檬香蜂草、土荆芥、咖喱叶、欧芹、紫苏、三叶叶、拉维纪草、牛膝草、缬草、西洋蓍草、酢浆草、龙蒿、山药、葱属(jimbu)、车叶草、***、芸香、鸭儿芹(mitsuba)、迷迭香、鼠尾草、牛至、百里香、留兰香、胡椒薄荷、香菜、肉桂、桂皮、茴香(fennel)、葫芦巴、莳萝芥末、丁香、番红花、洋葱、大蒜、韭葱、生姜、姜黄、葡萄籽、黑胡椒、八角茴香(star anise)、大豆、肉豆蔻干皮精油及其组合。
8.根据权利要求5所述的食品包装材料,其中所述茶是绿茶、白茶、黄茶、药茶、后发酵茶、乌龙茶或黑茶。
9.根据权利要求5所述的食品包装材料,其中所述茶从野茶树(Camellia sinensis)获得。
10.根据权利要求5所述的食品包装材料,其中所述草本植物是多年生草本植物。
11.根据权利要求5所述的食品包装材料,其中所述草本植物选自迷迭香属(Rosmarinus)、鼠尾草属(Salvia)或牛至属(Origanum)。
12.根据权利要求11所述的食品包装材料,其中所述草本植物选自迷迭香(Rosmarinusofficinalis)、鼠尾草(Salvia officinalis)、牛至(Origanum vulgaro)及其组合。
13.根据权利要求12所述的食品包装材料,其中所述草本植物是迷迭香。
14.根据权利要求5所述的食品包装材料,其中所述香料选自叶、花、种子、树皮、球茎、假种皮(aril)和根,包括金合欢籽(Wattleseed)、藏红花、生姜、姜黄、葡萄籽、尖辣椒(chilli pepper)、小茴香(cumin)、多香果(allspice)、大茴香(anise)、葛缕子(carraway)、小豆蔻(cardamom)、肉桂、桂皮、丁香、香菜、小茴香(cumin)、茴香(fennel)、葫芦巴、高良姜、大蒜、生姜、辣根、野山竹汁(kokum)、芥末、肉豆蔻、罂粟种子、玫瑰、红辣椒(paprika)、藏红花、漆树、罗望子、姜黄、香草、芝麻、沙士(sarsaparilla)、檫树(sassafras)、零陵香豆(tonka bean)及其组合。
15.根据权利要求1所述的食品包装材料,其中所述天然抗氧剂选自酚类,多酚类,酚酸类,酚酯类,酚单萜类,酚二萜类,类胡萝卜素,姜黄素,呫吨酮类(xanthones),维生素A、E和C,咖啡酰基衍生物,柠檬酸,抗坏血酸,单萜类,二萜类或三萜类,类黄酮,萜类,木脂素类,硫化物类,植物甾醇类,姜黄素类,茋类,苯酞类,生育三烯酚类,生育酚及其组合。
16.根据权利要求1所述的食品包装材料,其中所述天然抗氧剂选自咖啡酸、迷迭香酸、鼠尾草酚、鼠尾草酸及其组合。
17.根据权利要求1所述的食品包装材料,其中所述天然抗氧剂是包含酚二萜类的迷迭香提取物。
18.根据权利要求1所述的食品包装材料,其中所述天然抗氧剂是包含鼠尾草酸和鼠尾草酚的迷迭香提取物。
19.根据权利要求1所述的食品包装材料,其中所述天然抗氧剂是包含至少40wt%鼠尾草酸和鼠尾草酚的迷迭香提取物。
20.根据权利要求1所述的食品包装材料,其中所述天然抗氧剂选自叶黄素、芦丁、花青素、α-蒎烯、冰片、(-)-莰烯、1,8-桉树脑、樟脑、马鞭草烯酮、乙酸冰片酯、12-O-甲基花生酸、咖啡酰基衍生物、羽扇烷、齐墩果烷、乌苏烷三萜、熊果酸、槲皮素、rofficerone、单萜、月桂烯、7-甲基吡啶并莽草酚、表迷迭香酚、樟脑、儿茶素、香芹酚、异高山黄芩素7-O-葡萄糖苷、芫花素、对伞花烃、里哪醇、γ-萜品烯、麝香草酚、β-蒎烯、桉叶油素、亚油酸、迷迭香醌(rosmariquinone)、单萜烃类、氧化单萜类、倍半萜烃类、(-)-茉莉酸甲酯、迷迭香酚、迷迭香双醛(rosmadial)、邻醌、对醌、圣草次苷、木犀草素3-O-β-D-葡萄糖醛酸苷、橙皮苷、香叶木苷、异高山黄芩素-7-O-葡萄糖苷、高车前素7-O-葡萄糖苷、姜醇、姜烯酚、姜油酮、4-羟基肉桂酰基甲烷、山奈酚、鼠李白素、辣椒素(capsaicin)、辣椒碱(capsaicinol)、酚挥发油类、丁子香酚、乙酰丁香酚、抗坏血酸棕榈酸酯、异丁子香酚、鞣质、β-胡萝卜素、β-谷甾醇、氢醌、乙酸芳樟酯植物3-17、月桂烯、松油烯-4-醇、茴香甲醇(cuminal)、γ-萜品烯、松香芹醇(pincarveol)、里哪醇、1-甲基-2-(1-甲基乙基)苯、胡萝卜次醇、异迷迭香酚、atuntzensinA、迷迭香酚-7-***、二甲氧基-迷迭香酚、迷迭香双醛(rosmadial)、safficinolide、sageone、rosmriquinone(Miltrone)、迷迭香二酚(rosmaridiphenol)、大黄素甲醚(physcion)、芹菜素、高车前素、蓟黄素、5,4’-二羟基-6,7,8-三甲氧基黄酮、5-羟基-7,4’-二甲氧基黄酮、鼠尾草酚的甲酯和乙酯、咖啡酸、原儿茶酸、2-咖啡酰氧基-3-[2-(4-羟基苄基)-4,5-二羟基]苯基丙酸、类黄酮、圣草酚、二氢槲皮素、二氢川芎酚、对茴香素-2,3-二醇、没食子酸、三裂鼠尾草素、木犀草素、泽兰叶黄素、木犀草素-7-O-葡萄糖苷、高车前苷、芹菜素-7-O-葡萄糖苷、6-O-咖啡酰基-β-D-呋喃果糖基-(2→1)-α-D-吡喃葡萄糖苷、1-O-咖啡酰基-β-D-呋喃芹糖基-(1→6)-β-D-吡喃葡萄糖苷、1-O-对羟基苯甲酰基-β-D-呋喃芹糖基-(1→6)-β-D-吡喃葡萄糖苷、1-O-(2-羟基-5-2-羟基-乙基)苯基-6-O-反式-咖啡酰基)-β-D-吡喃葡萄糖苷、4-O-(5-O-(3,5-二甲氧基-4-羟基苯甲酰基)-β-D-呋喃芹糖基-(1→2)-β-D-吡喃葡萄糖苷、6-O-E-亚铁酰基-(α和β)-吡喃葡萄糖苷、(+)-1-羟基松脂醇-1-β-D-吡喃葡萄糖苷、(+)-fraxiresinol-1-β-D-吡喃葡萄糖苷及其组合。儿茶酚化合物包括(-)-表儿茶素(EC),(-)-表儿茶素没食子酸酯(ECG),(-)-表没食子儿茶素(EGC)和(-)-表没食子儿茶素没食子酸酯(EGCG),香草酸、绿原酸和五环三萜类,例如乌索酸、齐墩果酸、桦木酸、肉毒碱、α-香树脂醇、β-香树脂醇及其组合。
21.根据权利要求1所述的食品包装材料,其中所述天然抗氧剂是有机的。
22.根据权利要求1至21中任一项所述的食品包装材料,其中所述天然抗氧剂掺入到所述食品包装材料的涂层(a coating)、层(a layer)、片(a sheet)或壁(a wall)中和/或其上。
23.根据权利要求1至22中任一项所述的食品包装材料,其中所述天然抗氧剂在使用时迁移到食品上和/或其中。
24.根据权利要求1至23中任一项所述的食品包装材料,其进一步包含作为天然抗氧剂异构体的抗氧剂。
25.根据权利要求24所述的食品包装材料,其中所述作为天然抗氧剂异构体的抗氧剂是异抗坏血酸钠。
26.根据权利要求1至25中任一项所述的食品包装材料,其中所述聚合物材料选自聚对苯二甲酸乙二醇酯(PET)、聚乳酸(PLA)、聚乙烯(PE)、乙烯乙烯醇共聚物(EVOH)、聚丙烯(PP)、聚偏二氯乙烯(PVdC)、聚苯乙烯(PS)、聚四氟乙烯(PTFE)、聚氯乙烯(PVC)、聚酰胺或尼龙(PA)及其组合。
27.根据权利要求1至26中任一项所述的食品包装材料,其包括单个或多个聚合物层。
28.根据权利要求27所述的食品包装材料,其包括多个聚合物层。
29.根据权利要求28所述的食品包装材料,其包括第一层、第二层和聚合物阻挡层,其中所述第一层包含天然抗氧剂,所述第二层包含除氧剂,并且其中所述第二层位于所述第一层和所述阻挡层之间。
30.根据权利要求1至29中任一项所述的食品包装材料,其通过挤出生产。
31.根据权利要求1至30中任一项所述的食品包装材料,其中所述食品包装材料为薄膜形式。
32.由权利要求1至31中任一项所述的食品包装材料形成或包含所述食品包装材料的食品包装。
33.根据权利要求32所述的食品包装,其为包裹(a wrap)、包裹物件(a wrapper)、袋、容器、托盘、薄片、纸箱、盒子、瓶子、瓶盖、衬垫、管子、隔芯板或块。
34.根据权利要求33所述的食品包装,其中所述袋是可重新封闭的袋或冷冻袋。
35.根据权利要求33所述的食品包装,其为包裹(a wrap)。
36.一种方法,包括:
形成包含天然抗氧剂和聚合物树脂的混合物;和
处理所述混合物以形成食品包装材料。
37.根据权利要求36所述的方法,其中所述处理包括挤出、模制、真空成形、铸造或层压。
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CN110564040A (zh) * | 2019-09-23 | 2019-12-13 | 泉州宁遇新材料有限公司 | 一种天然防腐蚀、抗氧化hdpe塑料及其制备方法 |
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CN114957744B (zh) * | 2022-04-25 | 2024-02-20 | 贵州省材料产业技术研究院 | 一种仿生pva保鲜膜的制备方法和产品及其应用 |
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EP3353090A1 (en) | 2018-08-01 |
US10723536B2 (en) | 2020-07-28 |
CN108367852B (zh) | 2020-11-20 |
JP2018537369A (ja) | 2018-12-20 |
EP3353090A4 (en) | 2019-05-22 |
AU2016325872A1 (en) | 2018-04-12 |
US20180290811A1 (en) | 2018-10-11 |
AU2016325872B2 (en) | 2021-05-06 |
WO2017049364A1 (en) | 2017-03-30 |
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