CN114434916A - 一种抗光氧化的复合包装膜及其制备方法和应用 - Google Patents

一种抗光氧化的复合包装膜及其制备方法和应用 Download PDF

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CN114434916A
CN114434916A CN202210041120.0A CN202210041120A CN114434916A CN 114434916 A CN114434916 A CN 114434916A CN 202210041120 A CN202210041120 A CN 202210041120A CN 114434916 A CN114434916 A CN 114434916A
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photooxidation
layer film
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CN114434916B (zh
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陆柏益
杨博文
赵添
黄伟素
杨暄
柳岩
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Zhejiang University ZJU
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Abstract

本发明公开了一种抗光氧化的复合包装膜及其制备方法和应用，属于食品包装技术领域。所述复合包装膜包括外层膜和内层膜，所述外层膜包含基材和光阻隔材料；所述内层膜包含基材、色素和护色剂。外层膜中添加有光阻断材料，有效屏蔽280～470nm的可见光，内层膜添加有红色素，有效屏蔽620nm以上可见光，同时清除包装内部环境中的氧气，可应用于易受光氧化影响富含甾醇的食物、化妆品、保健品、生物制品中。本发明针对甾醇光氧化的发展路径，提供了一种提高植物甾醇光氧化稳定性的方法，利用复合包装膜的基础上配合使用复合抗氧化剂，阻断甾醇发生光氧化的链式反应，本发明具有较好的应用前景。

Description

一种抗光氧化的复合包装膜及其制备方法和应用
技术领域
本发明涉及食品包装技术领域，具体涉及一种利用抗光氧化的复合包装膜以提高植物甾醇光氧化稳定性的方法。
背景技术
植物甾醇(PS)，是以游离状态或与脂肪酸和糖等结合的状态存在的一种功能性成分，广泛存在于蔬菜、水果等各种植物的细胞膜中。甾醇类化合物，具有多种对人体有益的生理功能，研究发现，植物固醇有降低血液胆固醇、防治前列腺肥大、抑制肿瘤、抑制乳腺增生和调节免疫等作用。由于动物不能内源性地合成PS，人体只能通过摄取植物来源的食物来获得。
植物甾醇容易受到辐照、热、氧气、金属离子等环境因素的影响，生成植物甾醇氧化物(POPs)，并且POPs失去甾醇降低血浆LDL、总胆固醇和总甘油三酯及预防动脉粥样硬化的能力，同时POPs会扰乱肝脏脂质代谢进而加重肝脏损伤及促进动脉粥样硬化发展。其中光氧化是植物甾醇的主要氧化方式，在食品体系中光敏分子和氧气的参与下，导致甾醇氧化速度加快，营养价值损失，产品老化失效。
研究表明，食品中植物甾醇在紫外光、紫光、蓝光、红光等特定波长下氧化速度明显。例如豆奶中的植物甾醇在280～470nm和620～780nm波段发生氧化情况十分显著。同时食品基质中广泛存在光敏性分子，如核黄素、叶绿素、卟啉类分子等，也会在特定波长下促进光氧化的进行。
随着包装工业的发展，具有保湿、保鲜、避光、防渗透等功能的复合膜得到广泛使用，通过食品外包装的光阻断将是一种提高甾醇抗氧化稳定性的有效阻控手段。
专利文献CN 106750556 A公开了一种抗光氧化的可食用包装膜，将具有抗氧化活性的天然色素与护色剂添加到可食用膜基质中，孵育其抗光氧化及抗氧化的功效。具体的，所述天然色素为紫甘蓝红色素、甜菜红、萝卜红、葡萄皮红和甘蓝红的一种或几种，花色苷具有较高的抗氧化活性。同时护色剂的使用提高色素薄膜的稳定性。
然而不同的天然色素仅对特定范围内的光具有光阻隔作用，目前未见有能够特异性阻隔植物甾醇光氧化的包装膜报道。因此，开发一种提高甾醇氧化稳定性，实现体系抗氧化性能及稳定性调控的包装膜就成为了亟需解决的问题。
发明内容
本发明的目的在于针对植物甾醇易光氧化的特点以及氧化路径中关键影响因素，提供一种提高植物甾醇光氧化稳定性的方法。
为实现上述目的，本发明采用如下技术方案：
本发明提供了一种抗光氧化的复合包装膜，所述复合包装膜包括外层膜和内层膜，所述外层膜包含基材和光阻隔材料，所述光阻隔材料包括二氧化钛、氧化铁和氧化锌中的至少一种；所述内层膜包含基材、色素和护色剂，所述色素为甜菜红、萝卜红、葡萄皮红、甘蓝红、伊红和商用红色染料中的一种或几种。
本发明前期研究发现，植物甾醇在特定波长(尤其是280～470nm和620～780nm)下氧化速度明显，因此，本发明提供了一种能够特异性阻断上述波段可见光的复合包装膜，通过外包装膜来遮蔽上述容易导致甾醇氧化的波长，从源头减少植物甾醇与导致其氧化的光接触。
本发明研究表明，薄膜中添加二氧化钛(TiO2)、氧化铁(Fe2O3)和氧化锌(ZnO)可以有效屏蔽280～470nm的可见光，添加红色素及染料可以有效屏蔽620nm以上可见光，二者形成的包装膜能够有效提高植物甾醇的光氧化稳定性。而且红色素及染料具有脱氧功能，通过清除光氧化的中间物质-氧气，起到阻断光氧化路径的作用。
本发明在不影响包装膜自身阻隔性能的基础上，添加了光阻隔材料制得光阻隔基膜，添加色素、护色剂、脱氧剂制得抗氧化色素膜，两种膜复合制备出具有抗光氧化能力的包装材料。具体的，通过在可熔融加工的树脂材料中添加光阻隔材料或者脱氧材料共混后，采用共挤、流延、涂布、静电纺丝等方式成型，制备出多层包装膜。或者将一层或多层光阻隔层、一层或多层抗氧化层和基膜采用复合机、胶粘剂将进行黏合复合，制备多层复合膜。
作为优选，所述基材为乙烯-乙烯醇共聚物(EVOH)、聚偏二氯乙烯(PVDC)、聚对苯二甲酸乙二醇酯(PET)、二醇类改性PET(PETG)、聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)、聚氯乙烯(PVC)、聚乳酸(PLA)、聚碳酸酯(PC)、聚丙烯酸甲酯、聚酰胺中的一种或几种的共混物。上述材料制备的包装膜具有透明、均匀、抗拉的特点，根据包装对象的需求，可以选取有相应特性的材料，如阻氧性、亲水性。
作为优选，所述外层膜由一层或多层可熔融树脂加工制备，其中包含占质量百分比为1～5的光阻隔材料；所述内层膜由一层或多层可熔融树脂加工制备，其中包含占质量百分比为1～4的色素。更为优选，光阻隔材料占比3～4％；色素占比2～3％。
作为优选，所述光阻隔材料还包括商用红色染料。本发明通过在外层膜添加TiO2和红色染料，同时实现对280～470nm和620～780nm波长可见光的阻隔。商用红色染料可采用人工合成色素。
所述内层膜中的红色素不仅能够阻断620nm以上波长，还具有抗氧化性能，能够阻断光氧化路径。在抵抗光氧化的同时，包装膜中的抗氧化剂缓慢释放，在包装储存过程中抑制内部商品的氧化过程，延长其货架期。本发明进一步添加护色剂提高色素稳定性，持续发挥内层膜的抗氧化效果。作为优选，所述护色剂为DL-苹果酸、蔗糖、乳糖、单宁酸、阿魏酸、柠檬酸和对羟基苯甲酸中的一种或几种；所述护色剂占质量百分比为5％～10％。
作为优选，所述内层膜中还包含占质量百分比为5％～10％的脱氧剂，所述脱氧剂为抗坏血酸，主要起到稳定色素和清除体系内氧气的作用。抗坏血酸通过还原反应清除单线态氧、超氧自由基和羟自由基等活性氧基团，以达到抗氧化、保鲜效果。
本发明还提供了一种制备所述复合包装膜的方法，所述方法包括：分别往制膜机中加入外层膜原料和内层膜原料制得外层膜和内层膜，其中外层膜的加工温度为：挤出机140～220℃，机头200～240℃，内层膜的加工温度为：挤出机130～180℃，机头170～190℃；再采用水性胶粘剂将外层膜和内层膜进行复合，制得厚度为60～120μm的膜，40～80℃熟化制得所述复合包装膜。
具体的，将光阻隔材料或色素材料与树脂母粒共混，采用双螺杆挤出机、吹膜机或多层共挤流延机挤出、吹塑、流延成膜，或者采用静电纺丝制膜。
作为优选，所述制备方法包括：1)将可熔融加工的树脂材料和光阻隔材料混合，通过双螺杆挤出机或者流延机制成光阻隔基膜；2)将可熔融加工的树脂材料和色素、抗氧化剂、护色剂混合，采用挤压、流延或铸膜的方法制膜，获得抗氧化色素膜；3)采用复合机、胶粘剂将上述光阻隔基膜与抗氧化色素膜复合，并在40～80℃温度下熟化24～48小时。
本发明还提供了所述的复合包装膜作为包装材料以提高食品、化妆品、保健品、生物制品中植物甾醇光氧化稳定性中的应用。
本发明针对植物甾醇发生光氧化反应的主要节点，对植物甾醇进行保护，应用于易受光氧化影响的食品包装中，提高食品的稳定性。通过改变成膜基质和色素的种类及比例，可以抵抗特定波长的光照，无论在光照还是避光条件下，能表现出稳定的抗光氧化能力。所述包装膜同样适用于其他富含甾醇的化妆品、保健品、生物制品等产品的包装。
进一步的，本发明提供了一种提高植物甾醇光氧化稳定性的方法，包括以下步骤：
(1)往含有植物甾醇的食品、化妆品、保健品、生物制品中添加复配抗氧化剂，所述复配抗氧化剂的组成包括：白藜芦醇、番茄红素、鼠尾草酸和抗坏血酸；
(2)再采用所述的复合包装膜对步骤(1)的产品进行包装。
本发明通过在富含甾醇的食品、化妆品、保健品、生物制品中添加复配抗氧化剂，以清除存在体系内的活性氧自由基。
作为优选，以食品、化妆品、保健品、生物制品的总质量计，所述复配抗氧化剂的组成为白藜芦醇0.4mg/g、番茄红素0.1mg/g、鼠尾草酸0.2mg/g、抗坏血酸0.2mg/g。
上述方法利用所述复合包装膜配合使用复合抗氧化剂，阻断食品、化妆品、保健品、生物制品中甾醇发生光氧化的链式反应，即从引发反应的特定波长光照、光氧化的主要中间媒介-氧气，到氧化形成的自由基各个环节进行了逐一保护，切断了光氧化的链式反应，起到了防止甾醇氧化的作用。
本发明具备的有益效果：
(1)本发明针对甾醇光氧化的发展路径，提供了一种具备抗光氧化能力的活性包装膜，在屏蔽引发光氧化的特定波长的同时，对于光氧化的基本物质氧气进行阻断。具体的，外层膜中添加有光阻断材料，对特定波长可见光进行阻断，内层膜添加有红色素，在阻断特定波长可见光的同时清除包装内部环境中的氧气，使单线态氧的生成降低，阻断光氧化的进行。
(2)本发明制备出的抗氧化包装膜具有透明、均匀、阻隔氧气和抗拉的特点，并且能够持续稳定的发挥抗氧化作用。本发明充分利用了无机材料和有机高分子材料各自的特性，使得包装膜在保持其透明可视的情况下，依旧具有优秀的光线屏蔽性。此外由于本发明通过释放抗氧化剂的形式提高了食品的氧化稳定性，因此食品安全性更高，对食品风味和营养价值的保持更为有利。
(3)本发明提供的抗光氧化膜作为一种安全有效的抗光氧化包装材料，包装原料均为食品级材料，可应用于易受光氧化影响富含甾醇的食物、化妆品、保健品、生物制品中，具有较好的应用前景。
(4)本发明所采用的生产制造方法和制造设备易于操作和推广，所采用的原料简单易得，安全环保，无需纸张、铝箔等资源消耗和环境成本极高的材料加入，废弃的包装物可直接回收利用。因此，本发明有着极大的应用价值。
具体实施方式
下面结合具体实施例对本发明做进一步说明。以下实施例仅用于说明本发明，不用来限制本发明的适用范围。在不背离本发明精神和本质的情况下，对本发明方法、步骤或条件所做的修改或替换，均属于本发明的范围。
下述实施例中所使用的试验方法如无特殊说明，均为常规方法；所使用的材料、试剂等，如无特殊说明，为可从商业途径得到的试剂和材料。
具体的，下述实施例中采用的设备、原料如下：
塑料吹膜机型号FBVI-20/28；塑料共挤流延机型号FDCI-20/28。
乙烯-乙烯醇共聚物(EVOH)，CAS：25067-34-9，天津希恩思奥普德科技；聚乙烯，CAS：9002-88-4，Sigma-Aldrich；高密度聚乙烯(HDPE)，CAS：9002-88-4，麦克林；丙烯酸，CAS：79-10-7，上海阿拉丁；TiO2，CAS：13463-67-7，麦克林；红色商用颜料，贝临特；甜菜红，上海蓝平；甘蓝红，上海蓝平；柠檬酸，CAS：77-92-9；抗坏血酸，CAS：50-81-7。
实施例1
一、制膜
1、用塑料吹膜机进行制膜，在吹膜机的进料口中加入成膜材料：取一定量的乙烯-乙烯醇共聚物(EVOH)，添加0.5％、1％、2％、3％、4％、5％(w/w)的TiO2，吹膜机加工温度为：挤出机180℃，机头220℃。
2、关于包装膜透光率的测定，使用UV-VIS扫描分光光度计测试薄膜处理的透光率百分比，设置2nm狭缝宽度，从280到700nm扫描，采样间隔为1nm。在300、370、400、470、535、580、650nm处记录每个包装膜的透光率测量。结果如表1所示。
表1
Figure BDA0003470260110000061
如表1所示，添加TiO2可以有效屏蔽280～470nm的可见光，当TiO2含量为4％，对于特定可见光的阻断效果最好。
二、包装膜对植物甾醇光氧化的影响
1、将50g大豆种子冲洗干净，并在室温下于150mL水中浸泡12h。将浸泡过的大豆种子在破壁机中用400mL的水高于70℃研磨1.0分钟，以制成大豆浆，然后过400目筛过滤。将豆浆90℃煮沸10分钟，备用。采用121℃高温灭菌，20min。
2、在豆浆中加入0.05％的核黄素和叶绿素，使用包装膜袋装样品，热塑封口，将包装好的样品置于30℃反应，加速光氧化反应，光照强度为30000lux。
3、14天后检测使用GC-MS检测甾醇含量变化，具体方法参考doi.org/10.1016/j.foodchem.2020.127430，评价包装膜抗氧化效果。结果如表2所示。
表2
Figure BDA0003470260110000071
实施例2
1、制膜：用塑料吹膜机进行制膜，按照表3配方在吹膜机的进料口中加入成膜材料：取一定量的高密度聚乙烯(HDPE)，添加红色商用颜料、TiO2，吹膜机加工温度为：挤出机180℃，机头220℃。
2、测定包装膜透光率，结果如表3所示。
表3
Figure BDA0003470260110000072
由表3可知，红色染料可以有效屏蔽620nm以上可见光，红色染料为4％，对于特定可见光的阻断效果最好。
3、检测包装膜对植物甾醇光氧化的影响，操作步骤同实施例1。结果如表4所示。
表4
Figure BDA0003470260110000081
实施例3
1、制膜：用塑料共挤流延机进行制膜：在外层加入阻隔气体层原材料聚乙烯75％(w/w)和丙烯酸25％(w/w)混合物，或添加一定量的光阻隔材料TiO2；内层加入一定量的色素/染料、脱氧剂和聚乙烯的混合物进行制膜；内外层同时挤出成膜，提供的膜厚度为110μm，流延机加工温度为：挤出机200℃，机头220℃，冷却辊温度为25℃。
2、测定包装膜透光率，结果如表5所示。
表5
Figure BDA0003470260110000082
由表5可知，添加TiO2和红色素及染料形成的包装膜能够有效屏蔽280～470nm和620nm以上的可见光，有效提高植物甾醇的光氧化稳定性。当TiO2含量为4％，红色染料为4％或者色素含量为3％，抗坏血酸含量为5％时，对于特定可见光的阻断效果最好。
3、检测包装膜对植物甾醇光氧化的影响，操作步骤同实施例1。结果如表6所示。
表6
Figure BDA0003470260110000091
实施例4
1、制膜：用塑料共挤流延机进行制膜：在外层加入阻隔气体层原材料EVOH 75％(w/w)和聚乙烯25％(w/w)混合物，并添加一定量的光阻隔材料TiO2；内层加入一定量的色素/染料、脱氧剂和聚乙烯的混合物进行制膜；内外层同时挤出成膜，提供的膜厚度为110μm，流延机加工温度为：挤出机200℃，机头220℃，冷却辊温度为25℃。
2、检测包装膜对植物甾醇光氧化的影响，操作步骤同实施例1。结果如表7所示。
表7不同类型的包装对植物甾醇光氧化的影响
Figure BDA0003470260110000092
Figure BDA0003470260110000101
由表1-7的结果可知，采用光阻隔包装可以有效地提升植物甾醇的光稳定性。单独使用TiO2、红色染料或色素可以提升植物甾醇的光稳定性，但是效果有限。同时使用两种包装膜时，有着明显的协同效果，两者协同可以阻隔大部分280～470nm和620～780nm的可见光，破坏光氧化反应条件。同时配合脱氧剂的使用，清除内环境的氧气，切断氧化的链式反应，起到防止脂质过氧化的作用，进一步提升了植物甾醇的光氧化稳定性。
实施例5
一、复配抗氧化剂的添加量优化。
1、称取大豆分离蛋白4g、大豆油20g(含有0.5％w/w的植物甾醇混合物)、去离子水180g。将上述称取的大豆分离蛋白、大豆油置于60℃的温度下，以7000rpm的转速进行搅拌混合均匀后得到乳液。
2、在步骤1制备的乳液中加入不同配比的白藜芦醇、番茄红素、鼠尾草酸、抗坏血酸，配比如表8所示。
3、在样品中加入0.1％亚甲基蓝加速光氧化，置于30℃反应，光照强度为30000lux，反应72小时。
4、检测甾醇含量变化。
表8不同配比的抗氧化剂对植物甾醇光氧化的影响
Figure BDA0003470260110000102
Figure BDA0003470260110000111
如表8所示，不同配比抗氧化剂提高植物甾醇光氧化稳定性的效果，其中白藜芦醇的效果更为明显，番茄红素和鼠尾草酸处于高剂量时，拮抗植物甾醇光氧化的效果反而有所下降。抗坏血酸对于复合抗氧化剂有着明显的协同增效，故作为增效剂添加。因此，抗氧化剂的最佳复配组合为白藜芦醇0.4mg/g、番茄红素0.1mg/g、鼠尾草酸0.2mg/g、抗坏血酸0.2mg/g。
二、制膜
1、用塑料吹膜机进行制膜，在吹膜机的进料口中加入成膜材料：取一定量的乙烯-乙烯醇共聚物(EVOH)，添加4％的TiO2和4％的红色商用染料，吹膜机加工温度为：挤出机200℃，机头220℃。
2、在吹膜机的进料口中加入成膜材料：甜菜红(3％)、抗坏血酸(5％)、柠檬酸(5％)和聚乙烯的混合物；吹膜机加工温度为：挤出机160℃，机头185℃。
3、将上述步骤1与步骤2制备的薄膜采用干式复合机、水性胶粘剂，制造出总厚度为95um的膜。而后在温度设定为45℃的熟化室内熟化48小时。
三、包装膜和复配抗氧化剂联合使用
1、豆浆制备同实施例1。
2、往制备的豆浆中加入白藜芦醇0.4mg/g、番茄红素0.1mg/g、鼠尾草酸0.2mg/g、抗坏血酸0.2mg/g，然后采用步骤二制备的包装膜进行包装。
3、性能检测
往样品中添加0.05％的核黄素和叶绿素，再将包装好的样品置于30℃反应，光照强度为30000lux。14天后检测甾醇含量变化。
结果显示，经过14天加速氧化处理后，植物甾醇的留存率在97.21％，极大的提升了植物甾醇的氧化稳定性。

Claims (10)

1.一种抗光氧化的复合包装膜，其特征在于，包括外层膜和内层膜，所述外层膜包含基材和光阻隔材料，所述光阻隔材料包括二氧化钛、氧化铁和氧化锌中的至少一种；所述内层膜包含基材、色素和护色剂，所述色素为甜菜红、萝卜红、葡萄皮红、甘蓝红、伊红和商用红色染料中的一种或几种。
2.如权利要求1所述的抗光氧化的复合包装膜，其特征在于，所述基材为乙烯-乙烯醇共聚物、聚偏二氯乙烯、聚对苯二甲酸乙二醇酯、二醇类改性的聚对苯二甲酸乙二醇酯、聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、聚乳酸、聚碳酸酯、聚丙烯酸甲酯、聚酰胺中的任意一种或几种的共混物。
3.如权利要求1所述的抗光氧化的复合包装膜，其特征在于，所述外层膜由一层或多层可熔融树脂加工制备，其中包含占质量百分比为1～5％的光阻隔材料；所述内层膜由一层或多层可熔融树脂加工制备，其中包含占质量百分比为1～4％的色素。
4.如权利要求1所述的抗光氧化的复合包装膜，其特征在于，所述光阻隔材料还包括商用红色染料。
5.如权利要求1所述的抗光氧化的复合包装膜，其特征在于，所述护色剂为DL-苹果酸、蔗糖、乳糖、单宁酸、阿魏酸、柠檬酸和对羟基苯甲酸中的一种或几种；所述护色剂占质量百分比为5％～10％。
6.如权利要求1所述的抗光氧化的复合包装膜，其特征在于，所述内层膜中还包含占质量百分比为5％～10％的脱氧剂，所述脱氧剂为抗坏血酸。
7.如权利要求1-6任一项所述的复合包装膜的制备方法，其特征在于，包括：分别往制膜机中加入外层膜原料和内层膜原料制得外层膜和内层膜，其中外层膜的加工温度为：挤出机140～220℃，机头200～240℃，内层膜的加工温度为：挤出机130～180℃，机头170～190℃；再采用水性胶粘剂将外层膜和内层膜进行复合，制得厚度为60～120μm的膜，40～80℃下熟化制得所述复合包装膜。
8.如权利要求1-6任一项所述的复合包装膜作为包装材料以提高食品、化妆品、保健品、生物制品中植物甾醇光氧化稳定性中的应用。
9.一种提高植物甾醇光氧化稳定性的方法，其特征在于，包括以下步骤：
(1)往含有植物甾醇的食品、化妆品、保健品、生物制品中添加复配抗氧化剂，所述复配抗氧化剂的组成包括：白藜芦醇、番茄红素、鼠尾草酸和抗坏血酸；
(2)再采用如权利要求1-6任一项所述的复合包装膜对步骤(1)的产品进行包装。
10.如权利要求9所述的提高植物甾醇光氧化稳定性的方法，其特征在于，步骤(1)中，以食品、化妆品、保健品、生物制品的总质量计，所述复配抗氧化剂的组成为白藜芦醇0.4mg/g、番茄红素0.1mg/g、鼠尾草酸0.2mg/g、抗坏血酸0.2mg/g。
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