CN113043695A - 一种改性pe膜及其制备方法 - Google Patents

一种改性pe膜及其制备方法 Download PDF

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CN113043695A
CN113043695A CN202110302197.4A CN202110302197A CN113043695A CN 113043695 A CN113043695 A CN 113043695A CN 202110302197 A CN202110302197 A CN 202110302197A CN 113043695 A CN113043695 A CN 113043695A
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film
film layer
antibacterial agent
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CN113043695B (zh
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张辉
李中明
李倩
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Sichuan Huili Industrial Co Ltd
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Abstract

本发明公开了一种改性PE材料及医用包装复合膜，改性PE膜包括外层PE膜层、中层PE膜层和内层PE膜层；所述外层PE膜层的原料包括：茂金属聚乙烯、乙丙共聚物和有机抗菌剂；所述有机抗菌剂采用羟苯甲酯；所述中层PE膜层的原料包括：低密度聚乙烯和复合抗菌剂；所述复合抗菌剂采用硅胶吸附羟苯甲酯的复合抗菌剂；所述内层PE膜层的原料包括：低密度聚乙烯、无机抗菌剂和润滑剂；所述无菌抗菌剂采用硅胶负载锌‑银抗菌剂。本发明提高了复合膜的阻隔性、抗菌性，同时保障热封性能。

Description

一种改性PE膜及其制备方法
技术领域
本发明涉及医用包装材料技术领域，具体涉及一种改性PE膜及其制备方法。
背景技术
目前，医药领域常用的液体药品包装均是硬包装，包括玻璃瓶和复合硬片制成的塑料容器，玻璃瓶存在重量大而且易碎的缺点，而塑料容器一般需要底托作为塑料容器的支撑，在使用时，需要拧开塑料容器的顶部，再进行挤压将液体挤出进行口服，用材多，且使用不方便。
为了提高液体包装使用的便利性，少数企业提出了液体包装用的条形复合膜袋，但是由于软包装盛装液体药品，对其阻隔性能要求高，因此，一般采用的是多层复合膜，一方面增加热封性，一方面要增加阻隔性，目前常用的是至少三层结构，即外层、阻隔层和热封层，代表性的复合膜有PET-AL-CPP和PET-AL-PE。
对于以PE为热封层的复合膜材料，PE层既作为热封层，又作为内层直接与药液接触。实际使用过程中，复合袋的大部分破损都产生在热封处，影响正常包装使用、同时影响药液质量；目前PE膜功能较为单一，PE膜阻隔性能和抗菌性能较差，使其经常局限用作一些复合软包装材料的内层薄膜材料使用，这严重限制了PE膜的实际应用。
发明内容
本发明所要解决的技术问题是：如何提高复合膜的阻隔性、抗菌性，同时保障热封性能，本发明提供了解决上述问题的一种改性PE材料及医用包装复合膜。
本发明通过下述技术方案实现：
一种改性PE膜，包括外层PE膜层、中层PE膜层和内层PE膜层；所述外层PE膜层的原料包括：茂金属聚乙烯、乙丙共聚物和有机抗菌剂；所述有机抗菌剂采用羟苯甲酯；所述中层PE膜层的原料包括：低密度聚乙烯和复合抗菌剂；所述复合抗菌剂采用硅胶吸附羟苯甲酯的复合抗菌剂；所述内层PE膜层的原料包括：低密度聚乙烯、无机抗菌剂和润滑剂；所述无菌抗菌剂采用硅胶负载锌-银抗菌剂。
进一步优选，所述外层PE膜层的原料中，按重量份配比，茂金属聚乙烯100份，乙丙共聚物10份-20份，有机抗菌剂2-5份。
进一步优选，所述中层PE膜层的原料中，按重量份配比，低密度聚乙烯100份，复合抗菌剂3-8份。
进一步优选，所述内层PE膜层的原料中，按重量份配比，低密度聚乙烯100份，无机抗菌剂5-10份，润滑剂0.5-5份。
进一步优选，所述乙丙共聚物中乙烯含量为34-38％。
进一步优选，所述润滑剂采用聚乙烯蜡。
进一步优选，内层PE膜层、中层PE膜层和外层PE膜层的厚度比依次为：1:0.5-0.8:0.2-0.4。
一种改性PE膜的制备方法，用于制备上述的一种改性PE膜，包括以下步骤：步骤1：将茂金属聚乙烯、乙丙共聚物和有机抗菌剂混合、熔融造粒获得外层PE膜层物料；将低密度聚乙烯和复合抗菌剂混合、熔融造粒获得中层PE膜层物料；将低密度聚乙烯、无机抗菌剂和润滑剂混合、熔融造粒获得内层PE膜层物料；步骤2：将外层PE膜层物料、中层PE膜层物料和内层PE膜层物料三层共挤获得改性抗菌PE膜。
一种抗菌药品包装复合膜，由外向内依次包括耐候层PET、阻隔层Al和热封层PE；所述PE采用权利要求1至7任一项所述的一种改性PE膜、或采用权利要求8所述的一种改性PE膜的制备方法制备的改性PE膜。
一种抗菌药品包装复合膜的制备方法，用于制备上述的一种抗菌药品包装复合膜，包括以下步骤：
步骤1：将PET与铝箔通过粘接剂复合得到PET-AL复合膜；
步骤2：将步骤1得到的PET-AL复合膜通过粘接剂与改性PE膜复合；
步骤3：固化。
进一步优选，复合抗菌剂的制备方法包括：将硅胶浸泡于羟苯甲酯的乙醇溶液中，后经烘干获得复合抗菌剂。
进一步优选，硅胶负载锌-银抗菌剂的制备方法包括：采用硅胶浸泡于锌盐和银盐的水溶液中进行吸附，后经洗涤、干燥获得硅胶负载锌-银抗菌剂。
本发明具有如下的优点和有益效果：
现有技术中，对于以PE为热封层的复合膜材料，PE层既作为热封层，又作为内层直接与药液接触。实际使用过程中，复合袋的大部分破损都产生在热封处，影响正常包装使用、同时影响药液质量；目前PE膜功能较为单一，PE膜阻隔性能和抗菌性能较差，使其经常局限用作一些复合软包装材料的内层薄膜材料使用，这严重限制了PE膜的实际应用。
本发明采用多层PE改性膜复合获得最终的抗菌改性PE膜，具体地，通过采用无机抗菌剂改性PE膜与有机抗菌剂改性PE膜结合的方式、并采用复合抗菌剂作为过渡层，以提高整体抗菌效果、并保障热封及热封层与阻隔层的结合强度。对于聚乙烯种类的选择，也是基于与各抗菌剂结合的效果考虑进行优化设计的结果。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白，下面结合实施例，对本发明作进一步的详细说明，本发明的示意性实施方式及其说明仅用于解释本发明，并不作为对本发明的限定。
实施例1
本实施例提供了一种改性PE膜，包括外层PE膜层、中层PE膜层和内层PE膜层；各层组成如下所示：
所述外层PE膜层的原料为：茂金属聚乙烯、乙丙共聚物和有机抗菌剂；所述有机抗菌剂采用羟苯甲酯；按重量份配比，茂金属聚乙烯100份，乙丙共聚物15份，有机抗菌剂3份。其中，乙丙共聚物中乙烯含量为36％。
所述中层PE膜层的原料为：低密度聚乙烯和复合抗菌剂；所述复合抗菌剂采用硅胶吸附羟苯甲酯的复合抗菌剂；按重量份配比，低密度聚乙烯100份，复合抗菌剂5份。
所述内层PE膜层的原料为：低密度聚乙烯、无机抗菌剂和润滑剂；所述无菌抗菌剂采用硅胶负载锌-银抗菌剂；按重量份配比，低密度聚乙烯100份，无机抗菌剂9份，润滑剂4份；润滑剂采用聚乙烯蜡。
内层PE膜层、中层PE膜层和外层PE膜层的厚度比依次为：1:0.6:0.3。
其中，复合抗菌剂采用如下方法制备获得：将硅胶浸泡于羟苯甲酯的乙醇溶液中进行充分吸附，后经烘干获得复合抗菌剂，过程中可采用多次吸附和/或超声震荡等手段促进分散和吸附；最终硅胶与羟苯甲酯的质量比为1:3。
硅胶负载锌-银抗菌剂采用如下方法制备获得：采用硅胶浸泡于锌盐和银盐的水溶液中进行充分吸附，后经洗涤、干燥获得硅胶负载锌-银抗菌剂，过程中可采用多次吸附和/或超声震荡等手段促进分散和吸附；具体地，锌盐和银盐分别可采用硝酸锌和硝酸银的水溶液，最终的硅胶、锌离子和银离子的质量比为：1:5:5。
改性PE膜的制备方法，具体步骤如下所示：
步骤1：将茂金属聚乙烯、乙丙共聚物和有机抗菌剂混合、熔融造粒获得外层PE膜层物料；将低密度聚乙烯和复合抗菌剂混合、熔融造粒获得中层PE膜层物料；将低密度聚乙烯、无机抗菌剂和润滑剂混合、熔融造粒获得内层PE膜层物料；
步骤2：将外层PE膜层物料、中层PE膜层物料和内层PE膜层物料三层流延共挤获得改性抗菌PE膜。
实施例2
本实施例提供了一种抗菌药品包装复合膜，由外向内依次包括耐候层PET、阻隔层Al和热封层PE；热封层PE采用实施例1提供的改性PE膜；耐候层PET的厚度为20μm，阻隔层Al的厚度为15μm，改性PE膜的厚度为50μm。
抗菌药品包装复合膜的制备方法具体如下所示：
步骤1：铝箔复合
将PET与铝箔通过粘接剂复合得到PET-Al复合膜。首先，将外层印刷完成的PET基材转移至干法复合机放卷部，控制放后，进入涂胶工序；在PET基材的里层涂胶，涂胶前应用乙酸乙酯调节粘合剂粘度至15PaS，上胶量控制在3.8g/m2；涂胶完成后的中间品进入四段干燥箱进行干燥(干燥温度控制：一区50℃±5℃；二区60℃±5℃；三区75℃±5℃；四区85℃±5℃)，保证有机溶剂能完全挥发，PET基材进入复合部与铝箔复合，复合完成后收卷。
步骤2：PE薄膜复合
PET-Al复合膜通过粘接剂与改性PE膜复合。首先，将第一次复合完后的中间品转移至干法复合机放卷部，控制放卷后，进入涂胶工序，在铝箔层上涂胶，涂胶前应用乙酸乙酯调节粘合剂粘度于16S，上胶量控制在4.2g/m2，涂胶完成后的中间品进入四段干燥箱进行干燥(干燥温度控制：一区50℃±5℃；二区60℃±5℃；三区75℃±5℃；四区85℃±5℃)，保证有机溶剂能完全挥发，中间品进入复合部与PE薄膜复合。复合完成后控制收卷。
步骤3：固化
将外观合格的产品转移至温度为42±3℃的固化室固化90h。
其中，粘接剂采用75％的聚氨酯复合粘接剂主剂GM8160和25％聚氨酯复合粘接剂固化剂GM8160B配合使用，并用于乙酸乙酯调节粘接剂的粘度。
实施例3
本实施例与实施例2的区别在于，各层组成配比不同：
所述外层PE膜层的原料：按重量份配比，茂金属聚乙烯100份，乙丙共聚物11份，有机抗菌剂3份。其中，乙丙共聚物中乙烯含量为36％。
所述中层PE膜层的原料：按重量份配比，低密度聚乙烯100份，复合抗菌剂5份。
所述内层PE膜层的原料：按重量份配比，低密度聚乙烯100份，无机抗菌剂7份，润滑剂3份；润滑剂采用聚乙烯蜡。
实施例4
本实施例与实施例2的区别在于：以外层PE膜层作为整体的单层膜结构，整体厚度与实施例1相同。即PE膜层的原料为：茂金属聚乙烯、乙丙共聚物和有机抗菌剂；所述有机抗菌剂采用羟苯甲酯；按重量份配比，茂金属聚乙烯100份，乙丙共聚物15份，有机抗菌剂3份。其中，乙丙共聚物中乙烯含量为36％。
实施例5
本实施例与实施例2的区别在于：以中层PE膜层作为整体的单层膜结构，整体厚度与实施例1相同。即PE膜层的原料为：低密度聚乙烯和复合抗菌剂；所述复合抗菌剂采用硅胶吸附羟苯甲酯的复合抗菌剂；按重量份配比，低密度聚乙烯100份，复合抗菌剂5份。
实施例6
本实施例与实施例2的区别在于：以内层PE膜层作为整体的单层膜结构，整体厚度与实施例1相同。即PE膜层的原料为：低密度聚乙烯、无机抗菌剂和润滑剂；所述无菌抗菌剂采用硅胶负载锌-银抗菌剂；按重量份配比，低密度聚乙烯100份，无机抗菌剂9份，润滑剂4份；润滑剂采用聚乙烯蜡。
实施例7
本实施例与实施例2的区别在于：以外层PE膜层和内层PE膜层复合，无中间PE膜层。
实施例8
本实施例与实施例2的区别在于：各PE膜层中的抗菌剂加入量不同：
外层PE膜层：有机抗菌剂5份；
中层PE膜层：复合抗菌剂5份；
内层PE膜层：无机抗菌剂5份。
性能测试
对上述实施例2-8制备的复合膜进行性能测试，测试如下所示：
一、测试方法
1、水蒸气透过量(袋)：取复合膜产品适量，置于热封仪，先三边封袋，热合温度150℃-170℃，压力0.2-0.3MPa，时间1秒。使袋子热合成(10±0.5cm)*(5±0.25cm)的三边长方形热封袋。灌入8ml-20ml水，排干气体，热封第四边。同法制备8个袋，按照水蒸气透过量法(YBB00092003)第三法(1)在温度40±2℃，相对湿度25％±5％的条件下，放置14天，计算获得。
水蒸气透过量是考察复合膜防潮性的重要指标，通过控制该指标能保证药品的装量差异合格，药品有效成分不挥发。
2、氧气透过量：取复合膜产品，按照气体透过量测定法(YBB00082003-2015)第一法或第二法的规定进行。氧气透过量是考察复合膜的重要指标，通过控制该指标确保复合膜的气体阻隔性，保证药品不发生氧化反应，能有效控制药品质量的稳定。
3、Al层与PE层剥离强度：取复合膜产品，按照国家食品药品监督管理局发布的方法标准剥离强度测定法(YBB00102003-2015)的方法检查。Al层与PE层剥离强度考察包装材料在生产过程中是否保证粘合的牢固性和粘合剂涂布的均匀性。
4、热合强度：取复合膜产品，裁取100mm*100mm试片四片，将任意两个试片复合膜面叠合，置热封仪上进行热合(热合温度150℃-170℃，压力0.2-0.3MPa，时间1秒)，按热合强度测定法(YBB00122003-2015)进行检测。热合强度考察复合膜、袋在装药后封口处的强度，直接关系到包装材料对所装药品的保护能力的大小。
5、微生物限度：取复合膜产品，用开孔面积为20cm2的消毒过的金属模板压在内层面上，将无菌棉签用氯化钠注射液稍沾湿，在半孔范围内擦抹5次，换1支棉签再擦抹5次，每个位置用2支棉签共擦抹10次，共擦抹5个位置100cm2。每支棉签抹完后立即剪短(或烧断)，投入盛有30ml无菌生理盐水放入锥形瓶(或大试管)中。全部擦抹棉签投入瓶中后，将瓶迅速摇晃1分钟，即得供试液。取提取液按照微生物限度法(《中国药典》2015版四部通则1105、1106)测定。微生物限度检测用来检验产品被微生物污染的程度，从而确保产品的卫生安全。
6、稳定性测试
按照《塑料和橡胶类药包材料稳定性研究指导原则》(征求意见稿)和本品的稳定性进行考察。采用《指导原则》加速等效的条件，本次实验选择60℃/10％，考察了0d/20d/40d/60d/80d/96d。具体温湿度设置：60℃±2℃/10％±5％RH。
二、测试结果
1、阻隔性和强度性能测试结果
表1实施例2-实施例8制备的复合膜的性能测试结果
Figure BDA0002986699710000061
备注：各性能指标单位为：
水汽阻隔性，即水蒸气透过量，g/(m2·24h)；
氧气阻隔性，即氧气透过量，cm3/(m2·24h·0.1MPa)；
Al层与PE层的剥离强度N/15mm(纵向/横向)；
热合强度N/15mm(纵向/横向)；
需氧菌总数cfu/100cm2；
霉菌和酵母菌总数cfu/100cm2；
大肠埃希菌cfu/100cm2。
2、稳定性测试结果
表2实施例2制备的复合膜稳定性测试结果
Figure BDA0002986699710000071
基于表1的实验数据可知，实施例2和实施例3获得的复合膜综合性能最好，表现出良好的水气阻隔性、氧气阻隔性，同时兼具良好的热合强度、Al层与PE层的剥离强度，抗菌效果明显。实施例4制备的单独采用有机抗菌剂改性的PE膜、以及实施例6制备的单独使用无机抗菌剂改性的PE膜，最终的产品综合性能较差，且实施例5单独使用复合抗菌剂改性的PE膜用于复合膜，其整体效果却低于实施例4和实施例6制备复合膜。
对于实施例7和实施例8制备的物种间过渡层的改性PE膜，其整体性能低于实施例2和实施例3的产品，尤其是实施例制备的复合膜的热合强度、Al层与PE层的剥离强度方面较差。
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (8)

1.一种改性PE膜，其特征在于，包括外层PE膜层、中层PE膜层和内层PE膜层；
所述外层PE膜层的原料包括：茂金属聚乙烯、乙丙共聚物和有机抗菌剂；所述有机抗菌剂采用羟苯甲酯；
所述中层PE膜层的原料包括：低密度聚乙烯和复合抗菌剂；所述复合抗菌剂采用硅胶吸附羟苯甲酯的复合抗菌剂；
所述内层PE膜层的原料包括：低密度聚乙烯、无机抗菌剂和润滑剂；所述无菌抗菌剂采用硅胶负载锌-银抗菌剂。
2.根据权利要求1所述的一种改性PE膜，其特征在于，所述外层PE膜层的原料中，按重量份配比，茂金属聚乙烯100份，乙丙共聚物10份-20份，有机抗菌剂2-5份。
3.根据权利要求1所述的一种改性PE膜，其特征在于，所述中层PE膜层的原料中，按重量份配比，低密度聚乙烯100份，复合抗菌剂3-8份。
4.根据权利要求1所述的一种改性PE膜，其特征在于，所述内层PE膜层的原料中，按重量份配比，低密度聚乙烯100份，无机抗菌剂5-10份，润滑剂0.5-5份。
5.根据权利要求1所述的一种改性PE膜，其特征在于，所述乙丙共聚物中乙烯含量为34-38％。
6.根据权利要求1所述的一种改性PE膜，其特征在于，所述润滑剂采用聚乙烯蜡。
7.根据权利要求1所述的一种改性PE膜，其特征在于，内层PE膜层、中层PE膜层和外层PE膜层的厚度比依次为：1:0.5-0.8:0.2-0.4。
8.一种改性PE膜的制备方法，用于制备权利要求1至7任一项所述的一种改性PE膜，其特征在于，包括以下步骤：
步骤1：将茂金属聚乙烯、乙丙共聚物和有机抗菌剂混合、熔融造粒获得外层PE膜层物料；将低密度聚乙烯和复合抗菌剂混合、熔融造粒获得中层PE膜层物料；将低密度聚乙烯、无机抗菌剂和润滑剂混合、熔融造粒获得内层PE膜层物料；
步骤2：将外层PE膜层物料、中层PE膜层物料和内层PE膜层物料三层共挤获得改性抗菌PE膜。
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CN111269483A (zh) * 2020-04-07 2020-06-12 上海冠宝塑胶有限公司 一种抗菌pe收缩膜及其加工方法
CN111716858A (zh) * 2020-07-03 2020-09-29 四川汇利实业有限公司 一种改性流延聚丙烯膜及易撕pet-al-cpp药品包装复合膜的制备方法
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CN117429128A (zh) * 2023-12-20 2024-01-23 杭州神彩包装印业有限公司 一种自吸潮包装袋及其制造工艺
CN117429128B (zh) * 2023-12-20 2024-03-12 杭州神彩包装印业有限公司 一种自吸潮包装袋及其制造工艺

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