CN107163349A - 三层复合保鲜膜及其制备方法和应用 - Google Patents
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Abstract
本发明属于包装材料领域,尤其涉及一种三层复合保鲜膜,还涉及上述的保鲜膜的制备方法,以及上述的保鲜膜的应用。本发明的三层复合保鲜膜,包括树脂基膜和活性成分;树脂基膜为由外层膜、中间层膜、内层膜所组成的三层复合薄膜,活性成分主要包括壳聚糖、茶多酚、银杏叶提取物、紫藤花提取物、鼠尾草提取物中的至少一种。本发明的保鲜膜选材合理,安全,在0~4 ℃冷藏条件下结合气调包装方式可有效延缓保藏食品的氧化及表面微生物的生长繁殖,能有效延长冷鲜羊肉的贮存时间,且最大程度的保持新鲜食品的原始风味和营养价值。
Description
技术领域
本发明属于包装材料领域,尤其涉及一种三层复合保鲜膜,还涉及上述的保鲜膜的制备方法,以及上述的保鲜膜的应用。
背景技术
目前关于食品尤其是肉制品的保鲜技术和标准化技术含量较低,而部分食品或肉制品销售时需要较长的货架期,相对冷冻肉制品贮藏温度高,其可能受到存在的一些腐败菌的影响,进而降低肉制品的营养价值,影响原始风味。
一般传统的保鲜技术主要是向食品中直接添加保鲜剂(防腐剂)或在其表面喷涂、浸泡防腐剂等,这不仅影响肉制品原有风味,同时也会带来食品安全等问题。而高效、安全的保鲜膜开发已成为食品尤其是肉制品生产企业的迫切要求。除保鲜膜开发外,气调包装技术在肉类保鲜中的应用也逐渐受到生产企业的关注。
CN 102501508 A披露了三层复合保鲜膜,其特征在于由内层、中层、外层组成,按质量百分比,所述外层的组分为线性低密度聚乙烯80%~ 90%,低密度聚乙烯5%~15%,可降解塑料2%~ 5% ;
所述中层的组分为高密度聚乙烯40%~ 80%,可降解塑料2%~ 5%,线性聚乙烯20~
55%组成;所述内层的组分为含芥末油的塑料2%~ 3%,聚丙烯93%~ 96%,可降解塑
料2%~ 5%,所述含芥末油的塑料由芥末油和聚丙烯组成,按质量百分比芥末油0.02%~
0.045%,聚丙烯99.955%~ 99.98%,所述芥末油的成分按质量百分比为异硫氰酸烯丙脂65%~ 75%,二硫化碳10%~ 15%,水分10%~ 25%。
以上的保鲜膜,最大的缺点是:保鲜效果无法保证。
其原因分析如下: 芥末油中的主要有效成分为异硫氰酸烯丙脂,该物质的沸点为151℃,该保鲜膜选用的树脂基材中有高密度聚乙烯、线性聚乙烯及聚丙烯,一般这些树脂的较佳加工温度在165℃以上,因此,该保鲜膜中加有的活性物质芥末油可能在加工过程中便已挥发,无法保证制备的保鲜膜有保鲜效果;
因此,需要针对上述的缺陷进行改进,设计一种具有良好的保鲜效果的保鲜膜。
发明内容
为了解决上述的技术问题,本发明提供了一种既能发挥天然活性成分抗菌及抗氧化特性,又安全、绿色的保鲜膜,尤其是该保鲜膜结合气调包装,能显著有效延长食品尤其是冷鲜食品的储存期。
三层复合保鲜膜,包括树脂基膜和活性成分;
树脂基膜为由外层膜、中间层膜、内层膜所组成的三层复合薄膜;
外层膜的材料为聚对苯二甲酸乙二醇酯;中间层膜的材料为乙烯-醋酸乙烯共聚物;内层膜的材料为低密度聚乙烯;
外层膜的厚度为15 μm,中间层膜的厚度为15 μm,内层膜的厚度为20 μm;
活性成分的总质量占内层膜低密度聚乙烯质量的1-5 %;
活性成分主要包括壳聚糖、茶多酚、银杏叶提取物、紫藤花提取物、鼠尾草提取物中的至少一种。
树脂基膜是以聚对苯二甲酸乙二醇酯、乙烯-醋酸乙烯共聚物和低密度聚乙烯为原料通过多层共挤流延装置制备而成。
三层复合保鲜膜的制备方法,包括如下步骤:
(1)制备活性成分
取壳聚糖、茶多酚、银杏叶提取物、紫藤花提取物、鼠尾草提取物混合均匀,得活性成分;
壳聚糖、茶多酚、银杏叶提取物、紫藤花提取物、鼠尾草提取物的重量份数比为:1-4:1-5:1-5:1-5:1-3;
(2)改性
将经过烘干的内层膜原料低密度聚乙烯与活性成分混合,搅拌均匀,经双螺杆挤出机加热、剪切、挤出、切粒,得改性树脂;
活性成分的总质量占内层膜低密度聚乙烯质量的1-5 %;
(3)将聚对苯二甲酸乙二醇酯、乙烯-醋酸乙烯共聚物及步骤(2)中制备的改性树脂通过三层共挤流延装置制备出三层复合保鲜膜,控制外层膜厚度为15 μm,中间层膜厚度为15μm,内层膜的厚度为20 μm;
外层膜、中间层膜、内层膜重量比为1:1:1。
步骤(2)中,双螺杆挤出机的挤出条件如下:挤出机的7个加热区中,1区加热温度为165 ℃,2区加热温度为170 ℃,3区加热温度为175 ℃,4区加热温度为180 ℃,5区加热温度为180 ℃,6区加热温度为175 ℃,7区加热温度为170 ℃。
双螺杆挤出机的螺杆旋转的转速为40 rpm。
步骤(3)中多层共挤流延装置制备薄膜时,外层膜加热区温度设置为170℃-185℃,中间层膜加热区温度设置为165 ℃ - 180 ℃,内层膜加热区温度设置为170 ℃ - 180℃。
步骤(3)中多层共挤流延装置的转速为30 rpm,多层共挤流延装置的熔体泵转速为5 rpm。
活性成分中,茶多酚的纯度 ≥ 98%,壳聚糖的脱乙酰度 ≥ 90 %。
三层复合保鲜膜在羊肉保鲜中的应用,也是本发明所要保护的范围。
三层复合保鲜膜结合气调包装后在羊肉保鲜中的应用效果尤其显著,气调包装时,O2的体积浓度范围50-60%、CO2的体积浓度范围20-25%、N2的体积浓度范围20-25%。
本发明的构思如下:
以树脂基膜为基本原料,辅以天然的抗菌抗氧化剂,通过特定的工艺,将其制备成具有抗菌和保鲜功能的复合保鲜膜;
本发明所采用的原料,具有以下的特点:
树脂基膜材料选择:聚对苯二甲酸乙二醇酯(PET)、乙烯-醋酸乙烯共聚物(EVA)、低密度聚乙烯(LDPE);
聚对苯二甲酸乙二醇酯(PET)属线性的热塑性高聚物,拥有优异的物理机械性能,使用温度宽,具有光泽好,可回收,环保等优点。同时具有良好的透明性及较高的力学强度等特点,在包装市场中有较大的发展空间。
乙烯-醋酸乙烯共聚物(EVA)是一种热塑性弹性体,由于其大分子链上引入醋酸乙烯单体,因而具有优良的柔韧、耐冲击、耐环境应力开裂、透明、低温和易加工等性能。
低密度聚乙烯(LDPE)是用途较广泛的包装材料。LDPE有长支链和大量的短支链,物质的量较低,且分布较宽。LDPE具有较高的阻水性能,对气体如氧气、二氧化碳等也有一定的阻隔性能。
壳聚糖,又名脱乙酰甲壳素,由存在于海洋节肢动物甲壳中的甲壳素通过脱乙酰而制得。其抑菌机理主要为与细胞膜中的必须微量金属阳离子进行选择性螯合,改变细胞膜的通透性,影响细胞内外物质的转运和代谢;或者进入细胞基质与DNA结合,抑制DNA向RNA转录,通过干扰遗传物质的合成来影响细胞的分裂,从而达到抑制作用。由于壳聚糖具有良好的成膜性,使得其在食品、医疗领域都有较广泛的应用。
茶多酚为一种从茶叶中提取的天然多酚类物质,具有良好的抗氧化和抗菌能力。其主要是通过直接破坏微生物细胞结构、抑制病原菌的黏附等对微生物起到抑制作用。茶多酚除具有抗菌抗氧化作用外,其在改良色泽方面也发挥着作用。
银杏叶提取物是以银杏为原料,分离纯化提取的物质,其主要活性成分是黄酮类和萜内酯类,具有抗氧化作用。银杏叶提取物对食品中常见的污染菌具有光谱高效的抗菌活性,且其抗菌活性不受高温短时热处理的影响,因此起到有效防止食品腐败,延长食品保质期等作用。
紫藤花性微温,味甘,具有浓郁的香味,研究发现,紫藤花精油的主要成分为龙涎香精内酯、里哪醇、α-松油醇等。采用亚油酸氧化抑制作用等多个抗氧化评价体系评价紫藤花提取物的抗氧化能力时发现,在所有的测定方法中,紫藤花提取物均表现出了较强的抗氧化能力。
鼠尾草,又名洋苏叶,可以作为香辛料来调味和保藏食物。植物化学研究表明鼠尾草提取物中富含二萜、三萜、黄酮和各种酚类化合物,由于共轭环状结构和羟基的存在使得这类化合物具有很强的抗氧化能力,可以清除氧化过程中的自由基,还可以通过螯合金属离子来减缓氧化过程。
本发明的有益效果在于,本发明提供的保鲜膜在0 ~ 4 ℃冷藏条件下结合气调包装可有效延缓鲜食品的氧化及表面微生物的生长繁殖,抑制其食品中的汁液流失,可有效延长冷鲜食品的贮存时间,降低成本,且最大程度的保持食品尤其是肉制品的原始风味和营养价值。
附图说明
图1为本发明羊肉保鲜膜的剖视图;
图2为本发明羊肉保鲜膜A-C与对照组保鲜膜O在相同贮藏时间下的pH值对比曲线图;
图3为本发明羊肉保鲜膜A-C与对照组保鲜膜O在相同贮藏时间下的挥发性盐基氮(TVB-N)对比曲线图;
图4为本发明羊肉保鲜膜A-C与对照组保鲜膜O在相同贮藏时间下的菌落总数对比曲线图。
具体实施方式
下面结合附图和具体实施方式来对本发明作更进一步的说明,以便本领域的技术人员更了解本发明,但并不以此限制本发明。
基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
以下实施例中所提到的简称具体如下:
聚对苯二甲酸乙二醇酯PET;
乙烯-醋酸乙烯共聚物EVA;
低密度聚乙烯LDPE;
本发明所用的设备及原料的生产厂家或来源如下:
双螺杆挤出机:上海科创橡塑机械设备有限公司
多层共挤流延装置:浙江精诚模具机械有限公司;
壳聚糖:购自国药集团化学试剂有限公司,脱乙酰度为 92%;
茶多酚:购自国药集团化学试剂有限公司,茶多酚的纯度为98.5%;
银杏叶提取物:购自上海谱振生物科技有限公司;
紫藤花提取物:购自陕西斯诺特生物技术有限公司;
鼠尾草提取物:购自西安赛奥生物技术有限公司。
实施例1
(1)取活性成分壳聚糖、茶多酚、银杏叶提取物、紫藤花提取物、鼠尾草提取物与LDPE树脂(预先在60℃烘箱中烘干的)充分混合、搅拌均匀,经双螺杆挤出机加热、剪切、挤出、切粒制备出改性LDPE树脂;
壳聚糖、茶多酚、银杏叶提取物、紫藤花提取物、鼠尾草提取物的重量份数比为1:1:1:1:1;活性成分的总重量占内层膜LDPE的1%;
双螺杆挤出机的挤出条件如下:挤出机的7个加热区中,1区加热温度为165 ℃,2区加热温度为170 ℃,3区加热温度为175 ℃,4区加热温度为180 ℃,5区加热温度为180 ℃,6区加热温度为175 ℃,7区加热温度为170 ℃;
双螺杆挤出机的螺杆旋转转速为40 rpm;
(2)将PET树脂、EVA树脂及制备的改性LDPE树脂通过多层共即流延装置制备三层复合羊肉保鲜膜A。经气体渗透仪测试,三层复合羊肉保鲜膜A的氧气透过率为9.40±0.12e-2(Cm3/m2.d.Pa)。
外层膜、中间层膜及内层膜重量比为1:1:1。
多层共挤流延装置的转速为30 rpm,多层共挤流延装置的熔体泵转速为5 rpm;多层共挤流延装置制备薄膜时,外层PET膜加热区温度设置为170℃-185℃,中间层EVA膜加热区温度设置为165 ℃ - 180 ℃,内层LDPE膜加热区温度设置为170 ℃ - 180 ℃。
外层膜为15 μm,中间层为15 μm,内层膜为20 μm。
实施例2
(1)将活性成分壳聚糖、茶多酚、银杏叶提取物、紫藤花提取物、鼠尾草提取物与LDPE树脂(预先在60℃烘箱中烘干的)充分混合、搅拌均匀,经双螺杆挤出机加热、剪切、挤出、切粒制备出改性LDPE树脂;
壳聚糖、茶多酚、银杏叶提取物、紫藤花提取物、鼠尾草提取物的重量比依次是3:1:5:5:1;活性成分总重量占LDPE树脂总重量的5%;双螺杆挤出的条件同实施例1(实施例3中双螺杆挤出的条件也同实施例1);
(2)然后将PET树脂、EVA树脂及制备的改性LDPE树脂通过多层共即流延装置制备三层复合羊肉保鲜膜B。经气体渗透仪测试,三层复合羊肉保鲜膜B的氧气透过率为8.30±0.21e-2(Cm3/m2.d.Pa)。(多层共挤流延的条件同实施例1,在此不再赘述)。
外层膜为15 μm,中间层为15 μm,内层膜为20 μm。
外层膜、中间层膜及内层膜重量比为1:1:1。
实施例3
(1)将活性成分壳聚糖、茶多酚、银杏叶提取物、紫藤花提取物、鼠尾草提取物与LDPE树脂(预先在60℃烘箱中烘干的)充分混合、搅拌均匀,经双螺杆挤出机加热、剪切、挤出、切粒制备出改性LDPE树脂;
壳聚糖、茶多酚、银杏叶提取物、紫藤花提取物、鼠尾草提取物的重量比依次是3:1:5:5:1;
活性成分总重量占LDPE树脂总重量的3%; (实施例3中双螺杆挤出的条件也同实施例1);
(2)然后将PET树脂、EVA树脂及制备的改性LDPE树脂通过多层共即流延装置制备三层复合羊肉保鲜膜C。经气体渗透仪测试,三层复合羊肉保鲜膜C的氧气透过率为8.80±0.16e-2(Cm3/m2.d.Pa)。(实施例3中的多层共挤流延的条件也同实施例1)。
外层膜为15 μm,中间层为15 μm,内层膜为20 μm。
外层膜、中间层膜及内层膜重量比为1:1:1。
实施例4
对照组保鲜膜:
将PET树脂、EVA树脂及LDPE树脂通过多层共即流延装置制备对照组薄膜O。经气体渗透仪测试,对照组薄膜O的氧气透过率为10.30±0.27e-2(Cm3/m2.d.Pa)。
外层膜为15 μm,中间层为15 μm,内层膜为20 μm;
三层树脂用量比例为1:1:1;
取适量(等分,保证每个包装袋内装有30g冷鲜羊肉即可)冷鲜羊肉,等分,分别对应冷鲜羊肉A,冷鲜羊肉B,冷鲜羊肉C、冷鲜羊肉O,同时分别采用实施例1-3中的保鲜膜A-C(试验组)及对照组保鲜膜O包装,按照不同气体比例(O2为55%、CO2为25%、N2为25%)进行气调包装,维持肉样良好的色泽。
分别检测0 ~ 4 ℃条件下储藏0 d、2 d、4 d、6 d、8 d、10 d、12 d后试验组和对照组的pH值、TVB-N值及菌落总数。
实验结果如附图2所示;
由图2可知,在0 ~ 4 ℃条件下储藏期间,各组的pH值呈先下降后上升的趋势。这主要是屠宰后的羊肉在0-5天内由于血液供应停止,这时进行无氧酵解,导致乳酸的积累使得羊肉的pH值降低。随着贮藏时间的延长,乳酸逐步分解成水、酒精及二氧化碳进而使得pH值上升;同时,随着肉成熟过程的进行,羊肉中的蛋白质逐步分解为氨基酸,这也使得羊肉的pH值上升。一般,新鲜羊肉浸出液的pH值为5.8 ~ 6.2。对照组保鲜膜包装的羊肉第6天其pH值已超过6.2,试验组羊肉的pH值上升较缓慢,A组保鲜膜包装的羊肉在第8天pH值超过6.2,而B、C组保鲜膜包装的羊肉pH值在第10天才超过6.2。这表明在相同气调包装的冷藏条件下(O2为55%、CO2为25%、N2为25%),活性成分达到3 % - 5 %的保鲜效果优于1% - 3 %。
按照GB 2707-2016《鲜(冻)畜肉卫生标准》规定,鲜肉评价标准为TVB-N值≤ 15mg/100g。由附图3中曲线变化可知,各组的TVB-N值都呈上升的趋势,其中试验组A-C组TVB-N值升高速率低于对照组O,第4天时对照组的TVB-N值达14.6 mg/100g,第6天时已超标。试验组A-C组第10天的TVB-N值分别为15.4 mg/100g、13.2 mg/100g、14.6 mg/100g,这表明加有活性成分的保鲜膜其保鲜效果优于不添加活性成分的对照组保鲜膜;此外,试验组中C组保鲜膜包装的羊肉其TVB-N值低于A、B组保鲜膜,这表明在相同气调包装的冷藏条件下(O2为55%、CO2为25%、N2为25%),活性成分达到3 - 5 %的保鲜效果优于1 - 3 %。该结果与各组羊肉的pH值数据变化吻合。
从附图4中可以看出,菌落总数随着贮藏时间的延长逐渐升高,其中对照组的菌落总数值增加的较快。贮藏前期,较低的pH值抑制了微生物的滋生与繁殖,使得菌落总数增长速率较后期慢,后期随着pH值的逐渐升高,微生物大量繁殖导致菌落总数增长较快。
以上详细描述了本发明的部分具体实例。应当理解为,本领域的普通技术无需创造性劳动就可以根据本发明的构思做出诸多修改和变化。因此,凡本技术领域的技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案,皆应在由权利要求书所确定的保护范围内。
Claims (10)
1.三层复合保鲜膜,其特征在于,所述的保鲜膜包括树脂基膜和活性成分;
树脂基膜为由外层膜、中间层膜、内层膜所组成的三层复合薄膜;
外层膜的材料为聚对苯二甲酸乙二醇酯;中间层膜的材料为乙烯-醋酸乙烯共聚物;内层膜的材料为低密度聚乙烯;
外层膜的厚度为15 μm,中间层膜的厚度为15 μm,内层膜的厚度为20 μm;
活性成分的总质量占内层膜低密度聚乙烯质量的1-5 %;
活性成分主要包括壳聚糖、茶多酚、银杏叶提取物、紫藤花提取物、鼠尾草提取物中的至少一种。
2.如权利要求1所述的三层复合保鲜膜,其特征在于,树脂基膜是以聚对苯二甲酸乙二醇酯、乙烯-醋酸乙烯共聚物和低密度聚乙烯为原料通过多层共挤流延装置制备而成。
3.如权利要求1所述的三层复合保鲜膜的制备方法,包括如下步骤:
(1)制备活性成分
取壳聚糖、茶多酚、银杏叶提取物、紫藤花提取物、鼠尾草提取物混合均匀,得活性成分;
壳聚糖、茶多酚、银杏叶提取物、紫藤花提取物、鼠尾草提取物的重量份数比为:1-4:1-5:1-5:1-5:1-3;
(2)改性
将经过烘干的内层膜原料低密度聚乙烯与活性成分混合,搅拌均匀,经双螺杆挤出机加热、剪切、挤出、切粒,得改性树脂;
活性成分的总质量占内层膜低密度聚乙烯质量的1-5 %;
(3)将聚对苯二甲酸乙二醇酯、乙烯-醋酸乙烯共聚物及步骤(2)中制备的改性树脂通过三层共挤流延装置制备出三层复合保鲜膜,控制外层膜厚度为15 μm,中间层膜厚度为15μm,内层膜的厚度为20 μm;
外层膜、中间层膜、内层膜重量比为1:1:1。
4.根据权利要求3所述三层复合保鲜膜的制备方法,其特征在于,步骤(2)中,双螺杆挤出机的挤出条件如下:挤出机的7个加热区中,1区加热温度为165 ℃,2区加热温度为170℃,3区加热温度为175 ℃,4区加热温度为180 ℃,5区加热温度为180 ℃,6区加热温度为175 ℃,7区加热温度为170 ℃。
5.如权利要求4所述三层复合保鲜膜的制备方法,其特征在于,双螺杆挤出机的螺杆旋转的转速为40 rpm。
6.如权利要求5所述三层复合保鲜膜的制备方法,其特征在于,步骤(3)中多层共挤流延装置制备薄膜时,外层膜加热区温度设置为170℃-185℃,中间层膜加热区温度设置为165 ℃ - 180 ℃,内层膜加热区温度设置为170 ℃ - 180 ℃。
7.如权利要求5所述三层复合保鲜膜的制备方法,其特征在于,步骤(3)中多层共挤流延装置的转速为30 rpm,多层共挤流延装置的熔体泵转速为5 rpm。
8.如权利要求5所述三层复合保鲜膜的制备方法,其特征在于,活性成分中,茶多酚的纯度 ≥ 98%,壳聚糖的脱乙酰度 ≥ 90 %。
9.如权利要求1所述三层复合保鲜膜在羊肉保鲜中的应用。
10.如权利要求1所述三层复合保鲜膜结合气调包装后在羊肉保鲜中的应用,气调包装时,O2的体积浓度范围50-60%、CO2的体积浓度范围20-25%、N2的体积浓度范围20-25%。
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