CN111361248B - 一种消光pe材料及其制备方法和应用 - Google Patents

一种消光pe材料及其制备方法和应用 Download PDF

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CN111361248B
CN111361248B CN202010111814.8A CN202010111814A CN111361248B CN 111361248 B CN111361248 B CN 111361248B CN 202010111814 A CN202010111814 A CN 202010111814A CN 111361248 B CN111361248 B CN 111361248B
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extinction
layer
resin
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parts
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CN111361248A (zh
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李建军
李成
黄险波
叶南飚
李力
王斌
陈平绪
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Kingfa Science and Technology Co Ltd
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Abstract

本发明提供了一种消光PE材料，通过添加第三相热塑性弹性体，采用流延成型的技术方法，使其膜面均匀细腻、具有优异的消光性能和热封性能。消光层的单层雾值可达到80%以上；热封温度在120℃~135℃，且热封强度高，满足现有包材相关标准规定性能；可应用于塑料薄膜软包装领域。

Description

一种消光PE材料及其制备方法和应用
技术领域
本发明涉及软包装材料技术领域，具体涉及一种消光PE材料及其制备方法和应用。
背景技术
随着人们对包装品质要求的提高，消光聚乙烯（PE）材料受到越来越多的关注。消光膜是一种低光泽度呈漫反射消光效果的包装用膜。消光PE膜拥有良好的视觉呈现效果，能提升产品包装档次，而且相对于常见的PP、PET、NY等消光薄膜材质，其具备价格低廉的特点，有着很好的应用前景。常见的PE加工成型工艺有：吹胀法、流延法、双向拉伸法，其中，流延法是通过熔体流延骤冷生产一种无拉伸、非定向的平挤薄膜的方法。与吹胀法相比，其特点是生产速度快，产量高，厚度均匀。
为了保证商品在包装、运输、储存和消费过程中能承受一定的外力，保证商品不开裂、不泄露，达到保护商品的目的，要求封合部位有足够的强度和密封性能。因此对于包装材料的热封性能有一定的要求。热封强度反应了包装材料的各种综合物理机械性能，是包装材料的重要指标之一，热封强度越大，封口越牢固，运输保存过程中越不易发生破损，保存越良好。
现有市场上的消光PE产品主要来自于北欧化工（博禄）吹膜级双峰茂金属聚乙烯树脂，其形成了市场垄断，产品吹膜成型，原材料和产品单一，生产效率较低。相关流延消光PE包装材料的产品和技术，目前在市场上还十分少见，没有能兼顾良好热封性能、消光和膜面均匀细腻度的产品。
中国专利CN107351474A公开了一种单向拉伸可高速印刷的消光PE膜及其生产工艺，其消光PE膜包括电晕层、中间层和热封层，均采用吹膜级双峰茂金属聚乙烯FB2230和FB1520，单层消光有限需要多层共挤，原材料受限，材料成本较高，产品单一。
中国专利CN110305402A公开了一种消光流延PE膜及其生产工艺，包括热封层、中间层以及电晕层；主要通过在热封层使用流延PE专用的消光母粒(牌号为MF5050E)，同时由不相容的PP和PE形成的共混结晶体系，起到消光作用，该消光PE膜具有能适应凹版与柔版高速印刷的特点，但其雾度小于65%，无法达到理想的消光效果；而且其制备需使用特定原料，原材料受限。
中国专利CN108314818A公开了一种消光流延PE膜及其制备方法，其制备的流延PE膜具有内层、中层和外层的三层结构，通过在各层加入一定比例的无机填料，使其具有消光性的同时具有良好的拉伸强度、抗穿刺强度及阻燃性能；但热封问题没有得到解决。
发明内容
本发明目的在于，提供一种消光PE材料，该PE材料膜面均匀细腻，同时具有优异的消光性能和热封性能。
本发明另一目的在于，提供上述消光PE材料的制备方法。
本发明是通过以下技术方案实现的：
一种消光PE材料，包含消光层、基材层和电晕层；
其中，所述消光层，按重量份计，包括组分：25份~75份PP树脂；30份~70份HDPE树脂；4份~34份相容剂；0-5份助剂；
所述相容剂，按重量百分比计，包括80%~100%热塑性弹性体；0~20%马来酸酐接枝相容剂；
所述基材层，按重量份计，包括组分：95~100份LLDPE树脂；0~5份助剂；
所述电晕层，按重量份计，包括组分：30~70份LLDPE树脂；30~70份LDPE树脂；0~5份助剂。
优选的，所述消光PE材料的厚度为48~52μm，其中所述消光层：基材层：电晕层的厚度比为1~2:2~3:1~2。
所述的热塑性弹性体选自乙丙橡胶EPR、乙烯-醋酸乙烯共聚物EVA、三元乙丙橡胶EPDM、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物SEBS、乙烯基聚烯烃弹性体POE、嵌段乙烯基聚烯烃弹性体OBC、丙烯基聚烯烃弹性体Vistamaxx中的任意一种或几种。所述的马来酸酐接枝相容剂选自聚乙烯接枝马来酸酐PE-g-MA、聚丙烯接枝马来酸酐PP-g-MA中的一种或几种。
优选的，所述热塑性弹性体在相容剂中所占的重量百分比为80%~90%，马来酸酐接枝相容剂在相容剂中所占的重量百分比为10%~20%。
PP树脂包括均聚PP和共聚PP；共聚PP包括二元无规共聚PP和三元无规共聚PP，所述共聚PP的熔融指数MFI在230℃、2.16kg下为6g/10min~11g/10min，热封温度为114℃~165℃；优选熔融指数MFI在230℃、2.16kg下为8g/10min~10g/10min，热封温度为116℃~125℃。
HDPE树脂为高粘挤出级高密度聚乙烯，熔融指数MFI在190℃、2.16kg下为0.01g/10min~2g/10min，数均分子量为25000~60000，分子量分布为3~6；优选熔融指数MFI在190℃、2.16kg下为0.05g/10min~1g/10min，数均分子量为35000~50000，分子量分布为4~5。
本发明可以根据各层的加工情况以及需求选择助剂，所述助剂包括抗氧剂、抗静电剂、爽滑剂；添加量为0~5份。所述抗氧剂包括受阻酚类抗氧剂、亚磷酸酯类抗氧剂；抗静电剂包括季铵盐类抗静电剂；爽滑剂包括芥酸酰胺爽滑剂、油酸酰胺爽滑剂。所述助剂可以复配使用。
所述LLDPE树脂和LDPE树脂的熔融指数MFI在190℃、2.16kg下为1.0~3.0g/10min。
本发明的一种消光PE材料的制备方法，包括以下步骤：
（1）消光层母粒的制备：按照配比，将HDPE树脂与相容剂共混，得到共混物1；将PP树脂与助剂共混，得到共混物2；再将共混物1和共混物2共混并放入共混机，经过挤出造粒得到消光层母粒；
（2）基材层母粒的制备：按照配比，将LLDPE树脂与助剂共混，经过挤出造粒得到基材层母粒；
（3）电晕层母粒的制备：按照配比，将LLDPE树脂、 LDPE树脂和助剂在高混机中均匀混合，经过挤出造粒得到电晕层母粒；
（4）将上述造粒得到的消光层母粒、基材层母粒、电晕层母粒分别放入流延机的消光层料筒、基材层料筒、电晕层料筒；随后根据设定的流量计量进行分配器分配，将消光层母粒同基材层母粒和电晕层母粒吸入三台挤出机下料口，依次经
过挤出、冷却、测厚、电晕和牵引收卷系统，在设定工艺下流延共挤成消光PE薄膜材料。
所述步骤（4）中所述挤出机采用单螺杆挤出机，挤出机螺杆长径比为29~36；流延共挤的温度为150~240℃。
本发明的一种消光PE材料可应用于塑料薄膜软包装领域。
本发明与现有技术相比，具有如下有益效果：
（1）本发明通过添加第三相热塑性弹性体，改善了膜面均匀性、消光性能以及热封性能，制备得到的消光PE薄膜材料膜面均匀细腻、具有优异的消光性能和热封性能。
（2）本发明消光层的单层雾值可达到80%以上，成本更优；热封温度在120℃~ 135℃，且热封强度高，满足现有包材相关标准规定；而且原材料容易获取，选材范围更广，打破北欧化工FB2230和FB1520树脂在行业内的垄断。
（3）本发明提供了消光PE包装材料流延成型的技术方法，能够在消光PE材料领域填补空白，提供技术引导作用；丰富后期产品的多样性，对行业发展极其重要。
附图说明
图1为实施例1的消光PE薄膜材料膜面的SEM图。
图2为对比例1的消光PE薄膜材料膜面的SEM图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
本发明实施例中使用的原料及试剂均来源于市售。
PP树脂1：二元无规共聚聚丙烯，MFI(230℃/2.16kg)：8.5g/10min，热封温度116℃；
PP树脂2：二元无规共聚聚丙烯，MFI(230℃/2.16kg)：11g/10min，热封温度135℃；
HDPE树脂1：高粘挤出级高密度聚乙烯，MFI(190℃/2.16kg)：0.04g/10min，数均分子量为53820，分子量分布为5.5；
HDPE树脂2：高粘挤出级高密度聚乙烯，MFI(190℃/2.16kg)：1g/10min，数均分子量为42180，分子量分布为4.5；
LLDPE树脂： MFI(190℃/2.16kg)：2.0g/10min；
LDPE树脂： MFI(190℃/2.16kg)：2.0g/10min；
热塑性弹性体：乙烯基聚烯烃弹性体POE；
丙烯基聚烯烃弹性体Vistamaxx；
苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物SEBS；
三元乙丙橡胶EPDM；
嵌段乙烯基聚烯烃弹性体OBC；
乙烯-醋酸乙烯共聚物EVA；
马来酸酐接枝相容剂：聚乙烯接枝马来酸酐PE-g-MA；
复配抗氧剂：受阻酚抗氧剂1010和亚磷酸酯抗氧剂168按2：1复配的混合物；
复配助剂：复配抗氧剂、季铵盐抗静电剂和芥酸酰胺爽滑剂按照3：3：4复配的混合物；
实施例1~10和对比例1~3的消光PE材料的制备方法：（按照表1~3各组分配比）
（1）消光层母粒的制备：按照配比，将HDPE树脂与相容剂共混，得到共混物1；将PP树脂与复配抗氧剂共混，得到共混物2；再将共混物1和共混物2共混并放入共混机，经过挤出造粒得到消光层母粒；
（2）基材层母粒的制备：按照配比，将LLDPE树脂与复配抗氧剂共混，经过挤出造粒得到基材层母粒；
（3）电晕层母粒的制备：按照配比，将LLDPE树脂、LDPE树脂和复配助剂，在高混机中均匀混合，经过挤出造粒得到电晕层母粒；
（4）将上述造粒得到的消光层母粒、基材层母粒、电晕层母粒分别放入流延机的消光层料筒、基材层料筒、电晕层料筒；随后根据设定的流量计量进行分配器分配，将消光层母粒同基材层母粒和电晕层母粒吸入三台挤出机下料口，依次经过挤出、冷却、测厚、电晕和牵引收卷系统，在设定工艺下流延共挤成消光PE薄膜材料。制备得到的消光PE薄膜材料的厚度为48μm，消光层：基材层：电晕层的比例为1:2:1。
流延共挤的设定温度从下料口段至模头依次为150℃、230℃、230℃、230℃、230℃、230℃、240℃、240℃。
各项性能测试方法：
雾度值测试：参照标准ASTM D1003-13，检测塑料薄膜材料雾度值；
热封温度测试：参照标准ASTM F2029-2016，检测塑料薄膜材料热封温度(2kg，0.8s)，试样尺寸为100mm*15mm*0.4mm；
热封强度测试：参照标准YBB00122003-2015，检测塑料薄膜材料热封强度(2kg，0.8s)，试样尺寸为100mm*15mm*0.4mm；
产品外观：使用扫描电子显微镜（SEM）观察产品膜面。
表1：实施例1~6各组分配比（按重量份计）及产品各项性能测试结果
Figure 331371DEST_PATH_IMAGE002
表2：实施例7~10各组分配比（按重量份计）及产品各项性能测试结果
Figure 982933DEST_PATH_IMAGE004
表3：对比例1~4各组分配比（按重量份计）及产品各项性能测试结果
Figure DEST_PATH_IMAGE005
对实施例1~10的消光PE薄膜材料通过肉眼观察，膜面均匀细腻；使用扫描电子显微镜（SEM）观察膜面，实施例1的消光PE薄膜（图1）与对比例1的消光PE薄膜（图2）比较，添加了热塑性弹性体的消光PE薄膜的膜面明显更加均匀细腻。
由实施例1~6与对比例1~3比较可知，添加了热塑性弹性体的实施例1~6的雾度和热封强度明显较高，热封温度较低；说明热塑性弹性体的加入对材料的热封性能起正向作用，能够降低热封温度，同时可以提高热封强度；而且能够提升材料的消光性能；相容剂PE-g-MA对热封、消光和均一性等有增效作用。

Claims (10)

1.一种消光PE材料，其特征在于，包括消光层、基材层和电晕层；
其中，所述消光层，按重量份计，包括组分：25份~75份PP树脂；30份~70份HDPE树脂；4份~34份相容剂；0~5份助剂；
所述相容剂，按重量百分比计，包括80%~95.1%热塑性弹性体；4.9%~20%马来酸酐接枝相容剂；
所述的热塑性弹性体选自乙丙橡胶EPR、乙烯-醋酸乙烯共聚物EVA、三元乙丙橡胶EPDM、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物SEBS、乙烯基聚烯烃弹性体POE、嵌段乙烯基聚烯烃弹性体OBC、丙烯基聚烯烃弹性体Vistamaxx中的任意一种或几种；
所述的PP树脂包括均聚PP和共聚PP；所述共聚PP包括二元无规共聚PP和三元无规共聚PP；所述共聚PP的熔融指数MFI在230℃、2.16kg下为6g/10min~11g/10min，热封温度为114℃~165℃；
所述的HDPE树脂为高黏挤出级高密度聚乙烯，熔融指数MFI在190℃、2.16kg下为0.01g/10min~2g/10min，数均分子量为25000~60000，分子量分布为3~6；
所述基材层，按重量份计，包括组分：95~100份LLDPE树脂，0~5份助剂；
所述电晕层，按重量份计，包括组分：30~70份LLDPE树脂；30~70份LDPE树脂；0~5份助剂；
所述LLDPE树脂和LDPE树脂的熔融指数MFI在190℃、2.16kg下为1.0~3.0g/10min。
2.根据权利要求1所述的一种消光PE材料，其特征在于，所述消光PE材料的厚度为48~52μm，其中所述消光层：基材层：电晕层的厚度比为1~2:2~3:1~2。
3.根据权利要求1所述的一种消光PE材料，其特征在于，所述热塑性弹性体在相容剂中所占的重量百分比为80%~90%，马来酸酐接枝相容剂在相容剂中所占的重量百分比为10%~20%。
4.根据权利要求1所述的一种消光PE材料，其特征在于，所述的马来酸酐接枝相容剂选自聚乙烯接枝马来酸酐PE-g-MA、聚丙烯接枝马来酸酐PP-g-MA中的一种或几种。
5.根据权利要求1所述的一种消光PE材料，其特征在于，所述共聚PP的熔融指数MFI在230℃、2.16kg下为8g/10min~10g/10min，热封温度为116℃~125℃。
6.根据权利要求1所述的一种消光PE材料，其特征在于，所述的HDPE树脂的熔融指数MFI在190℃、2.16kg下为0.05g/10min~1g/10min，数均分子量为35000~50000，分子量分布为4~5。
7.根据权利要求1所述的一种消光PE材料，其特征在于，所述助剂为抗氧剂、抗静电剂或爽滑剂中的一种或几种的复配。
8.根据权利要求1~7任一项所述的一种消光PE材料的制备方法，其特征在于，包括以下步骤：
（1）消光层母粒的制备：按照配比，将HDPE树脂与相容剂共混，得到共混物1；将PP树脂与助剂共混，得到共混物2；再将共混物1和共混物2共混并放入共混机，经过挤出造粒得到消光层母粒；
（2）基材层母粒的制备：按照配比，将LLDPE树脂与助剂共混，经过挤出造粒得到基材层母粒；
（3）电晕层母粒的制备：按照配比，将LLDPE树脂、LDPE树脂和助剂在高混机中均匀混合，经过挤出造粒得到电晕层母粒；
（4）将上述造粒得到的消光层母粒、基材层母粒、电晕层母粒分别放入流延机的消光层料筒、基材层料筒、电晕层料筒；随后根据设定的流量计量进行分配器分配，将消光层母粒同基材层母粒和电晕层母粒吸入三台挤出机下料口，依次经
过挤出、冷却、测厚、电晕和牵引收卷系统，在设定工艺下流延共挤成消光PE薄膜材料。
9.根据权利要求8所述的一种消光PE材料的制备方法，其特征在于，步骤（4）中所述挤出机采用单螺杆挤出机，所述挤出机螺杆长径比为29~36；所述流延共挤的温度为150~240℃。
10.根据权利要求1~7任一项所述的一种消光PE材料的应用，其特征在于，应用于塑料薄膜软包装领域。
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