CN110978702B - 一种热收缩膜及其制备方法和应用 - Google Patents
一种热收缩膜及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供了一种高性能的热收缩膜,该膜具有收缩温度低、收缩速度快、水蒸气透过率低及透明度高等优点。所述热收缩膜采用三层共挤吹膜法制备而成,包括外层、中层、内层;所述外层:中层:内层的质量比为1‑3:1‑3:1‑3;所述外层包括高压低密度聚乙烯、乙烯‑醋酸乙烯共聚物、防粘母粒、爽滑母粒和抗静电母粒;所述中层包括乙烯‑醋酸乙烯共聚物和丙烯基弹性体;所述内层包括高压低密度聚乙烯、茂金属低密度聚乙烯、丙烯基弹性体、防粘母粒、爽滑母粒、抗静电母粒。本发明热收缩膜提高了拉伸强度、弹性模量,有效降低了破包率;130℃处理20秒的热收缩率高达75%,透光率大于90%,雾度及光泽度都有很大改善。
Description
技术领域
本发明属于包装用聚合物材料技术领域,涉及一种热收缩膜,具体涉及一种收缩效率好与透明度高的热收缩膜及其制备方法、应用。
背景技术
随着国家环保节能力度的加大,一些采用纸箱包装的产品越来越多地被塑料包装所代替,塑料包装制品消费数量的提高,必将推动塑料包装机械业的技术进步与迅速发展,我国经济宏观面及微观面形势趋好,社会需求将会出现稳定增长局面,可望刺激塑料制品消费增长。为适应新时代的要求,也就要求塑料包装材料能够满足市场日益提高的包装质量和效益标准,那么热收缩膜也越来越多的应用到各个领域,目前市面的热收缩膜大概分2类,一类是PE收缩膜,另一类是POF收缩膜。
聚乙烯PE是透明的热塑性塑料,常用的PE有三大类,即低密度聚乙烯(LDPE)、高密度聚乙烯(HDPE)和线性低密度聚乙烯(LLDPE),三种材料性能具有较大的差异,PE热收缩膜广泛适用于酒类、易拉罐类、矿泉水类、各种饮料类、布匹等产品的整件集合包装。POF即为热收缩膜,POF全称多层共挤聚烯烃热收缩膜,它是将线性低密度聚乙烯作为中间层(LLDPE),共聚丙烯(PP)作为内、外层,通过三台挤出机塑化挤出,再经模头成型、膜泡吹胀等特殊工艺加工而成的。然而这2类收缩膜在使用过程中依然存在不少问题,例如POF收缩膜韧性很差、易破包;普通PE收缩膜收缩温度高,收缩速度慢,效率低,如果包装的外层是PE膜,在过烘道时容易出现熔融粘连,而且透明度差,不能对包装后的产品标签进行扫码识别,需要另打标签贴在膜外面,增加了工序,降低了效率。
发明内容
为了解决上述存在的技术问题,满足更多产品的包装要求,本发明目的是提供一种高性能的热收缩膜,该膜具有收缩温度低、收缩速度快、水蒸气透过率低及透明度高等优点。
基于上述目的,本发明解决上述技术问题所采用的技术方案是:
一种热收缩膜,所述热收缩膜采用三层共挤吹膜法制备而成,包括外层、中层、内层;
所述外层:中层:内层的质量比为1-3:1-3:1-3;
所述外层包括高压低密度聚乙烯、乙烯-醋酸乙烯共聚物、防粘母粒、爽滑母粒和抗静电母粒;
所述中层包括乙烯-醋酸乙烯共聚物和丙烯基弹性体;
所述内层包括高压低密度聚乙烯、茂金属低密度聚乙烯、丙烯基弹性体、防粘母粒、爽滑母粒、抗静电母粒。
本发明热收缩膜具有三层结构,外层用于印刷,采用的材料有利于进行电晕处理;内层作为热封层,要求其具有爽滑性,三层采用各种不同功能的聚乙烯以及其他材料,满足了收缩膜的各种要求。
优选地,按重量份数计,所述外层包括以下组分:高压低密度聚乙烯20-80份,乙烯-醋酸乙烯共聚物10-60份,防粘母粒0.5-5份,爽滑母粒0.1-3份和抗静电母粒0.3-6份。
更优选地,外层组分中所述高压低密度聚乙烯的熔融指数为0.2-2.0g/10min,密度为0.918-0.933g/cm3。
更优选地,外层组分中所述乙烯-醋酸乙烯共聚物的熔融指数为0.2-2.0g/10min,密度为0.928-0.950g/cm3,醋酸乙烯(VA)含量为6-20%。
优选地,按重量份数计,所述中层包括以下组分:乙烯-醋酸乙烯共聚物22-85份和丙烯基弹性体10-60份。
更优选地,中层组分中所述乙烯-醋酸乙烯共聚物的熔融指数为0.3-1.8g/10min,密度为0.928-0.950g/cm3,VA含量为6-20%。
更优选地,中层组分中所述丙烯基弹性体的熔融指数为0.2-3.5g/10min,密度为0.860-0.890g/cm3。
优选地,按重量份数计,所述内层包括以下组分:高压低密度聚乙烯20-80份,茂金属低密度聚乙烯5-25份,丙烯基弹性体10-60份,防粘母粒0.8-6份,爽滑母粒0.1-5份和抗静电母粒0.5-6份。
更优选地,内层组分中所述高压低密度聚乙烯的熔融指数为0.2-2.0g/10min,密度为0.918-0.933g/cm3。
更优选地,内层组分中所述茂金属低密度聚乙烯的熔融指数为0.2-1.0g/10min,密度0.910-0.935g/cm3。
更优选地,内层组分中所述丙烯基弹性体熔融指数为0.2-3.5g/10min,密度为0.860-0.890g/cm3。
优选地,所述防粘母粒为硅酸盐类无机物。更优选地,所述防粘母粒为沸石、天然二氧化硅或合成二氧化硅中的一种或几种。
优选地,所述爽滑母粒包含芥酸酰胺和/或油酸酰胺。
优选地,所述抗静电母粒为长效抗静电剂。具体地,所述长效抗静电剂优选舒尔曼生产的VLA55。
为解决现有技术的收缩膜缺口敏感性、耐低温冲击强度低、易老化、收缩不均匀等性能缺点,为了对收缩膜进行改性以满足高韧性要求,现有技术往往通过加入热塑性弹性体或橡胶弹性体来改善抗冲击性能,目前常用的弹性体包括茂金属聚乙烯(POE),但POE增韧改性的收缩膜产品也有一些不足之处——影响收缩膜的透明度、应力发白现象明显。申请人前期研究基础发现利用丙烯基弹性体进行改性的收缩膜收缩率比利用普通低密度聚乙烯和茂金属聚乙烯改性提高了约30%,同时能够降低收缩温度和缩短收缩时间。
本发明为了降低收缩温度,还加入乙烯-醋酸乙烯共聚物(EVA),其熔点约为70-90℃,而其他低密度聚乙烯材料熔点约为110-125℃。同时其具有很好的耐低温性能,热分解温度较低,约为230℃左右,随着分子量的增大,其强度、冲击韧性和耐环境应力开裂性提高。EVA的性能与乙酸乙烯酯(VA)的含量有很大的关系,当VA的含量增加时,它的回弹性、柔韧性、黏合性、透明性、溶解性、耐应力开裂性和冲击性能都会提高;当VA的含量降低时EVA的刚性、耐磨性及电绝缘性都会增加。一般来说,VA含量小于10%时比聚乙烯柔软,耐冲击强度好;在10-20%范围时透明性良好,耐寒耐应力开裂;而VA含量超过30%时为弹性材料,具有良好的黏合性。
本发明还提供了一种热收缩膜的制备方法,包括以下步骤:
将三层的组分分别熔融,输出并形成三层融合成一层的膜坯再挤出,经冷却得到膜泡;
将所得膜泡夹成筒膜,将筒膜展平后冷却,得到热收缩膜。
优选地,将三层的组分分别加入外层挤出机、中层挤出机、内层挤出机进行熔融,输出并形成三层的融合成一层的膜坯再经过模口挤出,经冷却得到膜泡。
更优选地,挤出机各区挤出温度分别为:一区温度为135-150℃,二区温度为145-155℃,三区温度为140-160℃,四区温度为135-155℃,五区温度为135-145℃,模头温度为145-160℃。
更优选地,挤出机压力为155-335bar。
优选地,冷却得到膜泡的具体操作为通过自动风环的10-25℃的冷却风冷却得到膜泡。
优选地,冷却得到膜泡后,利用稳泡架稳定膜泡,由在线测厚仪360℃旋转测量整个膜泡的厚度分布,并由厚度调节系统将信息反馈至自动风环调节,调节以得到符合要求的厚度。
优选地,将所得膜泡进入人字排夹成扁平的筒膜进入上牵引旋转装置,将筒膜展平后进入导辊进一步冷却,得到热收缩膜。
优选地,将所得热收缩膜经过电晕处理后切边,分成单张收成包装。
更优选地,将所得热收缩膜进入电晕处理装置,经过电晕处理后切边,进入下牵引装置分成单张进入前后收卷装置收卷后包装。
具体地,一种热收缩膜的制备方法,包括以下步骤:
(1)将三层的组分分别加入外层挤出机、中层挤出机、内层挤出机进行熔融,输出并形成三层的融合成一层的膜坯再经过模口挤出;
(2)通过自动风环的10-25℃的冷却风冷却得到膜泡;
(3)将所得膜泡进入人字排夹成扁平的筒膜进入上牵引旋转装置,将筒膜展平后进入导辊进一步冷却,得到热收缩膜。
更具体地,一种热收缩膜的制备方法,包括以下步骤:
(1)将三层的组分分别加入外层挤出机、中层挤出机、内层挤出机进行熔融塑化后输出,将各挤出机输出的材料输送至模头,三层融合成一层的膜坯再经过模口挤出;
(2)通过自动风环的10-25℃的冷却风冷却成需要的膜泡;
(3)冷却后经过稳泡架稳定膜泡,由在线测厚仪360℃旋转测量整个膜泡的厚度分布,并由厚度调节系统将信息反馈至自动风环,调节以得到符合要求的厚度;
(4)将膜泡进入人字排夹成扁平的筒膜进入上牵引旋转装置,将筒膜展平后依次进入导辊进一步冷却,得到热收缩膜;
(5)将所得热收缩膜进入电晕处理装置,经过电晕处理后切边,进入下牵引装置分成单张进入前后收卷装置收卷后包装。
本发明采用高新技术设备,通过多层共挤工艺技术制备高性能热收缩膜,推动了塑料共混技术、塑料助剂新品及应用技术的进步和发展,在保证塑料包装材料无毒、卫生、环保的前提下,利用低成本技术使塑料包装材料性能提升,实现包装材料减量化。
本发明还提供了一种热收缩膜作为包装膜的应用,本发明热收缩膜用于纸巾、药品、饮料、日化等其它包装。本发明热收缩膜收缩率高、收缩速度快,适用于流水线运行较快的产品,尤其适用于要避免热处理会影响质量的产品,因此本发明尤其适用于纸巾、饮料、食品包装、医疗药品市场。
本发明还提供了一种应用热收缩膜的方法,包括以下步骤:将所述热收缩膜包裹在产品或包装件外面,经过加热,使所述热收缩膜裹紧产品或包装件。
优选地,利用热收缩膜包装机使所述热收缩膜裹紧产品或包装件。
本发明的有益效果是:
(1)本发明通过改进配方降低热收缩膜膜的收缩温度,改进配方后热收缩膜韧性大大提高,具有收缩温度低、收缩速度快、水蒸气透过率低及透明度高等优点,在膜厚度为50μm下,拉伸强度33-38Mpa,弹性模量87-98Mpa,有效降低了破包率;130℃处理20秒的热收缩率高达75%,透光率大于90%,雾度及光泽度都有很大改善,可直接扫码。
(2)本发明热收缩膜具有三层结构,外层用于印刷,采用的材料有利于进行电晕处理;内层作为热封层,要求其具有较低的起封温度和较高的热封强度,还要有较好的爽滑性,容易包装;三层采用各种不同功能的聚乙烯以及其他材料,在保证塑料包装材料无毒、卫生、环保的前提下,利用低成本技术使塑料包装材料性能提升,满足了热收缩膜的各种要求,实现包装材料减量化,并实现热收缩膜快速包装,降低了成本,提高了效率。
(3)本发明热收缩膜可100%回收利用,同时符合GB/4806.6-2016食品接触用塑料树脂和GB/4806.7-2016食品接触用塑料材料及制品等食品、药品相关安全质量标准要求,本发明热收缩膜绿色环保,原料安全健康。
具体实施方式
现结合具体实施例对本发明作进一步说明,以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1
本实施例热收缩膜,具有三层结构,分别为外层、中层和内层,三层材料之间的重量百分比分别为:外层33%,中层34%,内层为33%;各层组成组分如下表1所示:
表1
外层组分中所述高压低密度聚乙烯的熔融指数为0.25g/10min,密度为0.924g/cm3,具体地优选中海壳牌石油化工有限公司生产的2420D;所述乙烯-醋酸乙烯共聚物的熔融指数为0.25g/10min,密度为0.930g/cm3,醋酸乙烯(VA)含量为12%,具体地优选美国杜邦公司生产的3135。
中层组分中所述乙烯-醋酸乙烯共聚物的熔融指数为1.5g/10min,密度为0.930g/cm3,VA含量为15%,具体地优选日本东曹公司生产的EVA630;所述丙烯基弹性体的熔融指数为1.3g/10min,密度为0.862g/cm3,具体地优选美国埃克森公司生产的Vistamaxx6102FL。
内层组分中所述高压低密度聚乙烯的熔融指数为0.25g/10min,密度为0.924g/cm3,具体地优选中海壳牌石油化工有限公司生产的2420D;内层组分中所述茂金属低密度聚乙烯的熔融指数为0.2g/10min,密度0.916g/cm3,具体地优选美国埃克森公司生产的XP6026;内层组分中所述丙烯基弹性体熔融指数为0.9g/10min,密度为0.874g/cm3,具体地优选美国埃克森公司生产的Vistamaxx3020FL。
所述爽滑母粒优选华谊科技发展有限公司生产的SAB-8078;所述抗静电剂优选舒尔曼生产的VLA55。
一种热收缩膜的制备方法,包括以下步骤:
(1)将三层的组分分别加入外层挤出机、中层挤出机、内层挤出机进行熔融塑化后输出,将各挤出机输出的材料输送至模头,三层融合成一层的膜坯再经过模口挤出;
(2)通过自动风环的10-25℃的冷却风冷却成需要的膜泡;
(3)冷却后经过稳泡架稳定膜泡,由在线测厚仪360℃旋转测量整个膜泡的厚度分布,并由厚度调节系统将信息反馈至自动风环,调节以得到符合要求的厚度;
(4)将膜泡进入人字排夹成扁平的筒膜进入上牵引旋转装置,将筒膜展平后依次进入导辊进一步冷却,得到热收缩膜;
(5)将所得热收缩膜进入电晕处理装置,经过电晕处理后切边,进入下牵引装置分成单张进入前后收卷装置收卷后包装。
挤出机工艺参数如表2所示:
表2
温度 | 1区 | 2区 | 3区 | 4区 | 5区 | 压力(bar) |
外层 | 141 | 145 | 147 | 143 | 142 | 182-238 |
中层 | 135 | 138 | 140 | 136 | 135 | 155-236 |
内层 | 142 | 148 | 151 | 146 | 143 | 201-327 |
模头 | 148 | 151 | 155 | 152 |
实施例2
本实施例热收缩膜,具有三层结构,分别为外层、中层和内层,三层材料之间的重量百分比分别为:外层33%,中层45%,内层为22%;各层组成组分如下表3所示:
表3
除防粘母粒为天然二氧化硅外,本实施例热收缩膜各层组成组分的熔融指数、密度和厂家等同实施例1。本实施例热收缩膜的制备方法同实施例1,挤出机工艺参数如表4所示:
表4
温度 | 1区 | 2区 | 3区 | 4区 | 5区 | 压力(bar) |
外层 | 141 | 145 | 147 | 143 | 142 | 182-238 |
中层 | 135 | 138 | 143 | 141 | 137 | 165-256 |
内层 | 142 | 148 | 151 | 146 | 143 | 178-307 |
模头 | 148 | 155 | 158 | 155 |
实施例3
本实施例热收缩膜,具有三层结构,分别为外层、中层和内层,三层材料之间的重量百分比分别为:外层25%,中层50%,内层为25%;各层组成组分如下表5所示:
表5
除防粘母粒为合成二氧化硅外,本实施例热收缩膜各层组成组分的熔融指数、密度和厂家等同实施例1。本实施例热收缩膜的制备方法同实施例1,挤出机工艺参数如表6所示:
表6
温度 | 1区 | 2区 | 3区 | 4区 | 5区 | 压力(bar) |
外层 | 141 | 145 | 147 | 143 | 142 | 172-218 |
中层 | 135 | 138 | 143 | 141 | 137 | 195-286 |
内层 | 142 | 148 | 151 | 146 | 143 | 178-277 |
模头 | 148 | 155 | 158 | 155 |
实施例4
本实施例热收缩膜,具有三层结构,分别为外层、中层和内层,三层材料之间的重量百分比分别为:外层20%,中层60%,内层为20%;各层组成组分如下表7所示:
表7
除防粘母粒为合成二氧化硅外,本实施例热收缩膜各层组成组分的熔融指数、密度和厂家等同实施例1。本实施例热收缩膜的制备方法同实施例1,挤出机工艺参数如表8所示:
表8
温度 | 1区 | 2区 | 3区 | 4区 | 5区 | 压力(bar) |
外层 | 141 | 145 | 147 | 143 | 142 | 172-208 |
中层 | 138 | 141 | 143 | 141 | 138 | 195-305 |
内层 | 142 | 148 | 151 | 146 | 143 | 178-237 |
模头 | 148 | 155 | 158 | 155 |
对比例1
对比例1为现有技术的一种热收缩膜,具有三层结构,分别为外层、中层和内层,三层材料之间的重量百分比分别为:外层30%,中层40%,内层为30%;各层组成组分如下表9所示:
表9
对比例1挤出机工艺参数如表10所示:
表10
温度 | 1区 | 2区 | 3区 | 4区 | 5区 | 压力(bar) |
外层 | 165 | 168 | 172 | 168 | 166 | 286-423 |
中层 | 188 | 195 | 198 | 195 | 193 | 330-542 |
内层 | 177 | 182 | 186 | 185 | 181 | 318-528 |
模头 | 198 | 205 | 208 | 203 |
根据《GBT13519-92-聚乙烯热收缩薄膜》对实施例1-4所制得的热收缩膜与对比例1热收缩膜的各项性能参数进行测试,其中热收缩率以130℃处理20秒进行测试,所得结果如表11所示。
表11 热收缩膜性能测试
本发明通过改进配方降低热收缩膜的收缩温度,改进配方后热收缩膜韧性大大提高,具有收缩温度低、收缩速度快、水蒸气透过率低及透明度高等优点。因对比例1热收缩膜的配方中使用的材料有部分茂金属中密度及高密度聚乙烯,所以膜的加工温度高,收缩温度高,材料挺度高,柔韧性差、收缩后膜很脆、易破包;由于高密度聚乙烯结晶度高透明度差,收缩后透明更差。从表11可以看出,膜的厚度相同,对比例1的雾度高达32,而4个实施例的雾度都在12以下,可在包装后扫内包装的二维码;减少了外贴标签的工序,降低了成本。光泽度大于85,较高的光泽度使印刷图案更鲜艳,货架展示效果更好。通过表11可以看出,在膜厚度为50μm下实施例的拉伸强度33-38Mpa,弹性模量87-98Mpa,强度高,而弹性模量低,膜有较高的韧性和抗刺穿性能,有效的降低了破包率。130℃处理20秒的热收缩率纵向高达75%,横向48%;大大提高了包装速度,降低了收缩时间,使包装的夹持力更高,物品更牢固。
以上所述,仅是本发明的较佳实施例而已,并非对本发明的技术方案作任何形式上的限制。凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明的技术方案的范围内。
Claims (5)
1.一种热收缩膜,其特征在于,所述热收缩膜采用三层共挤吹膜法制备而成,包括外层、中层、内层;
所述外层:中层:内层的质量比为1-3:1-3:1-3;
所述外层包括高压低密度聚乙烯、乙烯-醋酸乙烯共聚物、防粘母粒、爽滑母粒和抗静电母粒;
所述中层包括乙烯-醋酸乙烯共聚物和丙烯基弹性体;
所述内层包括高压低密度聚乙烯、茂金属低密度聚乙烯、丙烯基弹性体、防粘母粒、爽滑母粒、抗静电母粒;
外层组分中所述高压低密度聚乙烯的熔融指数为0.2-2.0g/10min,密度为0.918-0.933g/cm3;外层组分中所述乙烯-醋酸乙烯共聚物的熔融指数为0.2-2.0g/10min,密度为0.928-0.950g/cm3,VA含量为6-20%;
所述中层组分中所述乙烯-醋酸乙烯共聚物的熔融指数为0.3-1.8g/10min,密度为0.928-0.950g/cm3,VA含量为6-20%;中层组分中所述丙烯基弹性体的熔融指数为0.2-3.5g/10min,密度为0.860-0.890g/cm3;
按重量份数计,所述外层包括以下组分:高压低密度聚乙烯20-80份,乙烯-醋酸乙烯共聚物10-60份,防粘母粒0.5-5份,爽滑母粒0.1-3份和抗静电母粒0.3-6份;
按重量份数计,所述中层包括以下组分:乙烯-醋酸乙烯共聚物22-85份和丙烯基弹性体10-60份;
按重量份数计,所述内层包括以下组分:高压低密度聚乙烯20-80份,茂金属低密度聚乙烯5-25份,丙烯基弹性体10-60份,防粘母粒0.8-6份,爽滑母粒0.1-5份和抗静电母粒0.5-6份。
2.根据权利要求1所述的热收缩膜,其特征在于,内层组分中所述高压低密度聚乙烯的熔融指数为0.2-2.0g/10min,密度为0.918-0.933g/cm3;内层组分中所述茂金属低密度聚乙烯的熔融指数为0.2-1.0g/10min,密度0.910-0.935g/cm3;内层组分中所述丙烯基弹性体熔融指数为0.2-3.5g/10min,密度为0.860-0.890g/cm3。
3.权利要求1-2任一项所述的热收缩膜的制备方法,其特征在于,包括以下步骤:
将三层的组分分别熔融,输出并形成三层融合成一层的膜坯再挤出,经冷却得到膜泡;
将所得膜泡夹成筒膜,将筒膜展平后冷却,得到热收缩膜。
4.根据权利要求3所述的制备方法,其特征在于,冷却得到膜泡后,利用稳泡架稳定膜泡,由在线测厚仪360℃旋转测量整个膜泡的厚度分布,并由厚度调节系统将信息反馈至自动风环调节,调节以得到符合要求的厚度。
5.权利要求1-2中任一项所述的热收缩膜作为包装膜的应用。
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