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CN109955569B - 一种可重叠热封的收缩膜、其制备方法及由其制备的包装袋 - Google Patents

一种可重叠热封的收缩膜、其制备方法及由其制备的包装袋 Download PDF

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Publication number
CN109955569B
CN109955569B CN201711434628.2A CN201711434628A CN109955569B CN 109955569 B CN109955569 B CN 109955569B CN 201711434628 A CN201711434628 A CN 201711434628A CN 109955569 B CN109955569 B CN 109955569B
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Prior art keywords
heat
layer
ethylene
shrink film
copolymer
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CN201711434628.2A
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CN109955569A (zh
Inventor
宋建新
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Shenghui New Material Co ltd
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Shenghui New Material Co ltd
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Priority to CN201711434628.2A priority Critical patent/CN109955569B/zh
Priority to MX2020006743A priority patent/MX2020006743A/es
Priority to KR1020207020156A priority patent/KR102418822B1/ko
Priority to US16/958,128 priority patent/US11633945B2/en
Priority to JP2020536782A priority patent/JP7457651B2/ja
Priority to PCT/CN2018/105915 priority patent/WO2019128320A1/zh
Publication of CN109955569A publication Critical patent/CN109955569A/zh
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Abstract

本发明公开了一种可重叠热封的收缩膜，其包括外表层和热封层，外表层中含有低分子量化合物且经过电子交联处理，所述低分子量化合物选自石蜡、油酰胺、硬脂酸以及它们的衍生物中的一种或两种以上。其中外表层中的低分子量化合物在重叠热封时受热的作用下不仅可以在聚合物中迁移影响聚合物分子链的移动，而且可迁移到两个熔融的界面，阻碍聚合物分子链的互相穿透。本发明还通过对外表层进行电子交联处理，促使外表层形成聚合物分子链交联结构，进一步降低聚合物分子链的移动。进而使得收缩膜外表层之间不易熔融粘结，形成可剥离的界面，使得该收缩膜可适用于多个袋子重叠热封。本发明还公开了可重叠热封的收缩膜的制备方法以及尤其制备的包装袋。

Description

一种可重叠热封的收缩膜、其制备方法及由其制备的包装袋
技术领域
本发明属于包装薄膜技术领域，涉及一种可重叠热封的收缩膜及其制备方法。
背景技术
收缩膜袋广泛应用于食品，主要用于鲜肉制品、加工肉制品、海产品、奶酪包装，尤其是在不规则形体物品或商品的组合式(集束)包装方面，既能保证食品的安全，防止交叉感染等功能，又能延长食品保质期。应用于食品包装的收缩膜袋一般要求具有如下性能：合适的收缩率、阻氧性、防湿性、耐冲击性(抗穿刺能力)、耐寒性、耐热性和耐油性等。
为了提高自动或半自动包装设备的包装效率，需要将多个袋子同时热封，而多个袋子同时热封时，在热封边重叠的情况下，会出现袋子之间熔合的现象。为解决袋子之间熔合这一问题，现有收缩膜的外表层和内侧热封层这两个表层使用不同的材质，目的是扩大熔融温度差，已有外表层比热封层的温度高65℃～150℃，其中热封层通常使用聚乙烯，外表层通常使用尼龙6，66/尼龙6等酰胺共聚物或其混合物、均聚丙烯材料、聚对苯二甲酸乙二醇酯等高熔点材质，因此多个袋子重叠热封时，内层形成不可剥离的界面，而外表层形成可剥离不熔合的界面，达到袋子重叠热封的效果。但是，由于外表层和热封层材质熔点温差较大，使得收缩膜在多层共挤加工生产中的操作难度增加，可控性不高。另外，由于上述外表层材质的熔点较高，加工时不仅能耗较大，而且对设备的要求较高，加工设备的螺杆及模具清洗不易。
发明内容
因此，针对现有技术中收缩膜袋外表层和热封层熔点温差较大，对加工设备要求高且生产操控不易的技术问题，本发明的第一目的在于提供一种可重叠热封的收缩膜，该可重叠热封的收缩膜的外表层和热封层材料熔点差尽管较低，但多个袋子重叠热封时，同样可达到袋子内层形成不可剥离的界面，且两个袋子的外表层形成可剥离不熔合的界面。
本发明的可重叠热封的收缩膜包括外表层和热封层，其特征在于，外表层中含有低分子量化合物且经过电子交联处理，所述低分子量化合物选自石蜡、油酰胺、硬脂酸以及它们的衍生物中的一种或两种以上(包括两种，下同)。
本发明在外表层中加入石蜡、油酰胺、硬脂酸以及它们的衍生物等低分子量化合物，一方面由于其在重叠热封时受热的作用下，这类化合物运动速度大于聚合物分子链的速度，因此其在聚合物中可迁移，影响聚合物分子链的移动，另一方面在相同的压力下，石蜡、油酰胺或硬脂酸等低分子量化合物更多的迁移到两个熔融的界面，可阻碍聚合物分子链的互相穿透。而且本发明还通过对外表层进行电子交联处理，促使外表层形成聚合物分子链交联结构，进一步降低聚合物分子链的移动。在上述多种因素的共同作用下，当多层收缩膜重叠进行加热挤压时，若两层收缩膜相邻的面为外表层时，由于聚合物分子链的互相穿透受到阻碍，不易熔融粘结，因此形成可剥离的界面。在上述情形下，外表层材料的熔点不需要比热封层熔点高出太多(只需高出0～64℃甚至更低)即可适用于多个袋子重叠热封。
油酰胺的衍生物包括羟基、卤素、C1～C6烷基等取代的油酰胺类化合物。
石蜡的衍生物包括羟基、卤素、C1～C6烷基等取代的石蜡类化合物。
硬脂酸的衍生物包括硬脂酸酯、硬脂酸盐、取代的硬脂酸、取代的硬脂酸酯、取代的硬脂酸盐；其中硬脂酸酯包括硬脂酸甲酯、硬脂酸乙酯、硬脂酸丙酯、硬脂酸丁酯等等，硬脂酸盐包括钠盐、钾盐、铵盐等等，取代的硬脂酸、取代的硬脂酸酯、取代的硬脂酸盐中的取代基包括羟基、卤素、C1～C6烷基等等。
较佳的，外表层中所述低分子量化合物的含量为0.5～50wt％，优选0.5～30wt％。
较佳的，外表层材料(不包括所述低分子量化合物)为聚烯烃和乙烯共聚物中的一种或两种以上。
在加入石蜡、油酰胺、硬脂酸以及它们的衍生物之后，聚烯烃材料的表面(外表面)形成此化合物诸多的分布点，在这些分布点上，此类化合物可阻止聚烯烃材料分子链之间的有效融合，随着此类化合物量的增加，聚烯烃分子链间的不融合点随之增加。而当聚烯烃材料受到加速电子束的撞击时，分子链形成交联结构，电子束剂量越高，交联密度越高，而大分子的交联点是不融不溶的。当上述两个因素共同作用时，即当弱化的融合点(化合物作用)增多时(是指因为加入此类化合物之后，外表面原可融合作用点被弱化)，交联点也增多时(电子剂量的作用)，一个可融合，不可剥离的界面被破坏，形成一个新的不融合，可剥离的聚烯烃热封界面(外表面)。
较佳的，热封层材料为聚烯烃、乙烯共聚物和沙林树脂中的一种或两种以上。
本发明的一些较佳实施例中，为提高所述可重叠热封收缩膜的阻隔性，其还包括中间层，中间层材料为偏二氯乙烯共聚物(PVdC)、乙烯乙烯醇共聚物、聚烯烃、乙烯共聚物和沙林树脂(Surlyn)中的一种或两种以上的混合物。优选阻隔性能好的偏二氯乙烯共聚物。
本发明中，较佳的，聚烯烃选自的聚丙烯(PP)、低密度聚乙烯(LDPE)和线性低密度聚乙烯(LLDPE)；聚烯烃优选熔点为80～170℃，比如，熔点为80～130℃的线形低密度聚乙烯的，再比如熔点为158～165℃的嵌段共聚聚丙烯。
较佳的，乙烯共聚物选自乙烯-乙酸乙烯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸共聚物和乙烯-马来酸酐共聚物，乙烯共聚物中乙烯含量优选72～96wt％。乙烯共聚物优选熔点为60～110℃，比如乙烯-乙酸乙烯酯共聚物中乙酸乙烯酯含量为9～28％时，熔点为70～110℃，乙酸乙烯酯含量为9～20％时，熔点为85～100℃。
本发明进一步的一些较佳实施例中，所述可重叠热封的收缩膜由外到内依次包括：
外表层，包含60～95wt％聚烯烃、3～10wt％乙烯共聚物和2～30wt％低分子量化合物；
中间层，材料为偏二氯乙烯共聚物、乙烯乙烯醇共聚物、聚烯烃、乙烯共聚物、沙林树脂中的一种或两种以上；
热封层，包含50～100wt％聚乙烯和0～50wt％乙烯-乙酸乙烯酯共聚物。
较佳的，外表层和中间层之间、中间层和热封层之间还可分别通过一层或两层粘接层粘接，粘接层材料为聚烯烃、乙烯共聚物和沙林树脂中的一种或两种以上。
粘接层主要起过渡粘结及辅助阻隔的作用，便于多层共挤生产工艺的操作。
较佳的，外表层和中间层之间的粘接层包含两层，紧邻外表层的一层材料为聚乙烯和乙烯-乙酸乙烯酯共聚物的混合物，或者聚乙烯、乙烯-乙酸乙烯酯共聚物和沙林树脂的混合物；紧邻中间层的另一层材料为乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸乙酯聚合物或乙烯-马来酸酐共聚物。
较佳的，中间层和热封层之间的粘接层包含两层，紧邻热封层的一层材料为乙烯-乙酸乙烯酯共聚物和沙林树脂的混合物，或者聚乙烯和乙烯-乙酸乙烯酯共聚物的混合物；紧邻中间层的另一层材料为乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸乙酯聚合物或乙烯-马来酸酐共聚物。
本发明更进一步的一些较佳实施例中，所述可重叠热封的收缩膜由外到内依次包括：
外表层，包含60～95wt％聚乙烯、3～10wt％乙烯-乙酸乙烯酯共聚物和2～30wt％低分子量化合物；
外表粘接层，包含15～25wt％聚乙烯和75～85wt％乙烯-乙酸乙烯酯共聚物；
粘接层，材料为乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸乙酯聚合物或乙烯-马来酸酐共聚物；
中间层，材料为偏二氯乙烯共聚物；
粘接层，材料为乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸乙酯聚合物或乙烯-马来酸酐共聚物；
热封粘接层，包含15～25wt％聚乙烯和75～85wt％乙烯-乙酸乙烯酯共聚物；
热封层，包含50～60wt％聚乙烯和40～50wt％乙烯-乙酸乙烯酯共聚物。
本发明的第二目的在于提供一种制备所述的可重叠热封的收缩膜的方法，其包括以下加工步骤：
S1：挤出膜管；
S2：共挤膜管经加热后，吹塑形成膜泡，获得双向取向结构，再经冷却定型，制成多层共挤收缩薄膜；
S3：对此收缩膜进行电子交联处理，使表面层形成聚合物分子链交联结构。
较佳的，步骤S3中电子加速处理时，电压范围为125-500kev，电子辐射剂量为3-20Mrad。
一些实施例中，步骤S1中挤出膜管具体指：将可重叠热封的收缩膜各层对应的原料置于配有多层共挤模头的挤出机中共挤制得膜管。
本发明的第三目的在于提供一种包装袋，所述包装袋由所述的可重叠热封的收缩膜制成。所述包装袋可用于鲜肉制品、加工肉制品、海产品、乳酪等产品的热封保存。
本发明的积极进步效果在于：
1、本发明在外表层中加入石蜡、油酰胺、硬脂酸以及它们的衍生物等低分子量化合物，一方面由于其在热封时在受热作用下，运动速度大于聚合物分子链的速度，因此其在聚合物中迁移，影响聚合物分子链的移动，另一方面在相同的压力下，加入的低分子量化合物更多的迁移到两个熔融的界面，可阻碍聚合物分子链的互相穿透。而且本发明还通过对外表层进行电子交联处理，促使外表层形成聚合物分子链交联结构，进一步降低聚合物分子链的移动。在上述多种因素的共同作用下，当多层收缩膜重叠进行加热挤压时，若两层收缩膜相邻的面为外表层时，由于聚合物分子链的互相穿透受到阻碍，不易熔融粘结，因此形成可剥离的界面。在上述情形下，外表层材料的熔点不需要比热封层材料熔点高出太多(只需高出0～64℃甚至更低)即可适用于多个袋子重叠热封。
2、本发明的一些较佳实施例中，外表层使用熔点较低的树脂比如聚丙烯，聚乙烯或和乙烯-乙酸乙烯酯共聚物的混合物等，同时加入石蜡、油酰胺、硬脂酸以及它们的衍生物；热封层则使用或聚乙烯和乙烯-乙酸乙烯酯共聚物的混合物，熔融粘结性能较好。外表层比热封层的材料熔点之差虽然只高0～64℃，同样可实现多个袋子重叠热封而袋子间外表层可剥离不熔合的效果。以此使用更低熔点、更容易加工的树脂在薄膜外表层，一是降低了对设备的要求，合理降低了能耗；二是低熔点的树脂在薄膜加工生产中具有更强的可控性；三是低熔点的树脂材料在加工设备螺杆及模具中更易清洗。
3、实验表明，本发明的可重叠热封的收缩膜的优选实施例中，热封层采用50～60wt％聚乙烯和40～50wt％乙烯-乙酸乙烯酯共聚物的混合物，具有较佳的熔融粘合性能，可有效提高袋子的热封性；而对应的外表层的材质采用60～95wt％或聚乙烯，3～10％乙烯-乙酸乙烯酯共聚物以及2～30％的石蜡、油酰胺或硬脂酸时，其中或聚乙烯可以和乙烯-乙酸乙烯酯共聚物协同作用，添加的化合物可有效降低外表层的熔融粘合，三种材质的混合可使外表层材料熔点不高但不易粘合，此为实现多个袋子重叠热封而袋子间外表层可剥离不熔合的效果的基础，同时保证外表层比热封层的材料熔点之差只高0～39℃，有效降低能耗并更加便于加工。外表粘接层采用15～25wt％聚乙烯和75～85wt％乙烯-乙酸乙烯酯共聚物的混合物，同时粘接层采用乙烯-乙酸乙烯酯共聚物，分两层过渡使得外表层与中间层有效粘接；同样的中间层和热封层之间也采用两层过渡粘接。
附图说明
图1为本发明实施例2～7的可重叠热封的收缩膜的结构示意图。
具体实施方式
为了进一步说明本发明，给出以下系列具体实施例，但本发明并不受这些具体实施例的限制，任何了解该领域的技术人员对本发明的些许改动将可以达到类似的结果，这些改动也包含在本发明之中。
实施例1～7和对比例1～8
表1原料
Figure BDA0001525569370000051
表2实施例1～7和对比例1～8的各层的原料及质量百分含量
Figure BDA0001525569370000052
Figure BDA0001525569370000061
实施例1～7以及对比例1～7分别按照以下步骤S1～S3制备收缩膜：
S1：将表2所示各层对应的原料置于配有多层共挤模头的挤出机中共挤制得膜管，对膜管冷却处理；
S2：共挤膜管经加热后，吹塑形成膜泡，获得双向取向结构，再经冷却定型，制成多层共挤收缩薄膜；
S3：对此收缩膜进行电子交联处理，电压范围为125-500kev，电子辐射剂量为3-20Mrad，使表面层形成聚合物分子链交联结构。
其中，实施例1为两层结构，实施例2～6以及对比例1～7均为七层结构，对比例1～7的外表层未添加硬脂酸等低分子量化合物。
对比例8的原料与实施例3的相同，但是对比例8按照步骤S1～S2制备收缩膜，未进行步骤S3的电子交联处理。
对实施例1～7以及对比例1～8制得的收缩膜进行性能测试和重叠热封性测试。
重叠热封性测试为：将两个或三个袋子重叠在一起进行抽真空热封，进行10次重复试验；粘合指的是两个袋子重叠热封后，两个袋子之间接触的外表面熔融粘结不易分开的次数，次数越多，重叠热封效果越差；密合是指两个袋子重叠热封后，两个袋子之间接触的外表面贴合在一起但是热收缩后能分开的次数，次数越少，重叠热封效果越好。
性能测试和重叠热封性测试结果如表3所示。
表3施例1～6和对比例1～8的性能测试结果
Figure BDA0001525569370000071
由表3可知，在重叠热封性方面，对比例1、2、4和8内外层材料熔点相差不大，但是在未添加低分子量化合物(对比例1和2)或者外表层未电子交联处理(对比例8)的情况下，重叠热封效果较差，袋子之间出现严重的粘连。对比例3和5的内外层熔融温差较大，具有较佳的防粘合性能，但是在密合性能较差。对比例6和7也出现重叠密封时密合性能较差的问题。可见对比例1～8均不能同时满足较佳的密合和防粘合性能要求，不能适用于多个袋子重叠密封。实施例1～7在外表层添加有低分子量化合物并经电子交联处理后，加热时不易粘合，虽然内外层材料熔点差为0～64℃，但是仍具有较佳的密合性能，同时可有效地防止两个袋子之间的粘合，外表面贴合在一起袋子热收缩后依然能很容易地分开，可适用于多个袋子重叠密封。
另外，在收缩性能方面，包括纵向(MD)和横向(TD)的，以及雾度(透明度)和拉伸强度方面实施例1～7与对比例1～8无明显差异。
以上已对本发明创造的较佳实施例进行了具体说明，但本发明创造并不限于所述实施例，熟悉本领域的技术人员在不违背本发明创造精神的前提下还可做出种种的等同的变型或替换，这些等同的变型或替换均包含在本申请权利要求所限定的范围内。

Claims (5)

1.一种可重叠热封的收缩膜，其包括外表层和热封层，其特征在于，外表层的组成为聚烯烃、乙烯共聚物和低分子量化合物且经过电子交联处理，所述低分子量化合物选自油酰胺、硬脂酸或硬脂酸丁酯，所述乙烯共聚物选自乙烯-乙酸乙烯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸共聚物和乙烯-马来酸酐共聚物；
其由外到内依次包括：
外表层，由60～95wt％聚烯烃、3～10wt％乙烯共聚物和2～30wt％低分子量化合物组成；
中间层材料为偏二氯乙烯共聚物或乙烯乙烯醇共聚物；
热封层，包含50～100wt％聚乙烯和0～50wt％乙烯-乙酸乙烯酯共聚物；
所述可重叠热封的收缩膜的方法，包括以下加工步骤：
S1：挤出膜管；
S2：共挤膜管经加热后，吹塑形成膜泡，获得双向取向结构，再经冷却定型，制成多层共挤收缩薄膜；
S3：对此收缩膜进行电子交联处理，使表面层形成聚合物分子链交联结构。
2.如权利要求1所述的可重叠热封的收缩膜，其特征在于，外表层和中间层之间、中间层和热封层之间分别通过一层或两层粘接层粘接，粘接层材料为聚烯烃、乙烯共聚物和沙林树脂中的一种或两种以上。
3.一种制备权利要求1～2任一项所述的可重叠热封的收缩膜的方法，其特征在于，包括以下加工步骤：
S1：挤出膜管；
S2：共挤膜管经加热后，吹塑形成膜泡，获得双向取向结构，再经冷却定型，制成多层共挤收缩薄膜；
S3：对此收缩膜进行电子交联处理，使表面层形成聚合物分子链交联结构。
4.如权利要求3所述的方法，其特征在于，步骤S3中电子加速处理时，电压范围为125-500kev，电子辐射剂量为3-20Mrad。
5.一种包装袋，其由权利要求1～2任一项所述的可重叠热封的收缩膜制成。
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