CN114211840A - 一种高阻隔输液膜及其制备方法 - Google Patents

一种高阻隔输液膜及其制备方法 Download PDF

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CN114211840A
CN114211840A CN202111398674.8A CN202111398674A CN114211840A CN 114211840 A CN114211840 A CN 114211840A CN 202111398674 A CN202111398674 A CN 202111398674A CN 114211840 A CN114211840 A CN 114211840A
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layer
barrier
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maleic anhydride
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CN114211840B (zh
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田仁和
张志辉
王亚楠
姜永
倪小琴
王永亮
刘如俊
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Jiangsu Best New Medical Material Co Ltd
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Abstract

本发明涉及输液材料领域，尤其涉及一种高阻隔输液膜及其制备方法，该高阻隔输液膜包括从内至外依次紧密贴合的阻湿层、阻气层、加强层和外层，相邻两层之间设有粘合层；通过上述层叠设置的多层结构以及每层组分的设计，使输液膜具备的优异气体和水汽的阻隔性能以及抗菌能力，同时还具备良好的韧性和耐刮擦性能，满足对输液膜材料的要求。

Description

一种高阻隔输液膜及其制备方法
技术领域
本发明涉及输液材料领域，尤其涉及一种高阻隔输液膜及其制备方法。
背景技术
目前我国市面上较常见的输液包装容器包括输液瓶、塑料瓶、聚氯乙烯软袋(简称PVC)以及非PVC软袋。作为传统包装容器的玻璃输液瓶具备价廉、化学稳定性、透明等优势，但其质量和体积较大，且存在不方便运输、生产工艺复杂、易碎等缺点，逐渐不能满足人们的需求。塑料瓶在一定程度上克服了玻璃瓶存在的缺点，但其透明度及耐高温性能较差，不适合氨基酸类药剂的使用。并且，玻璃瓶和塑料瓶在使用时需形成空气回路，通过外界空气进入瓶内形成内压来使药液滴出，这样会增加输液过程的二次污染。为解决这一问题PVC软袋应运而生，但是PVC软袋中含有聚氯乙烯单体，不利于人体的健康，且PVC软袋中含有一种增塑剂邻苯二甲酸二己酯(DEHP)，这种物质容易通过溶解渗入药剂中而进入人体，会对人体产生危害作用。
非PVC软袋是一种多层共挤式输液袋，具有较好的力学性能和稳定的理化性质，便于运输，广受市场的青睐，但目前国内使用的多层共挤输液袋的阻湿阻气性能较差，一般采用高阻隔外套袋放在输液袋外部，增加了工艺的复杂性。
发明内容
本申请的目的在于克服上述现有技术存在的不足，提供一种高阻隔输液膜及其制备方法，该高阻隔输液膜能够高效阻隔水蒸气、氧气、氮气、二氧化碳等气体，且能够满足输液膜材料在耐刮擦、耐折叠等方面的要求。
第一方面，本发明提供一种高阻隔输液膜，包括从内至外依次紧密贴合的阻湿层阻气层、加强层和外层，相邻两层之间设有粘合层；
所述阻湿层的材料包括线性低密度聚乙烯、环烯烃、马来酸酐接枝聚乙烯和纳米氧化锌；
所述阻气层的成分包括聚对苯二甲酸乙二醇酯和乙烯-乙烯醇共聚物；
所述加强层的成分包括己二酸-对苯二甲酸-丁二醇酯共聚物、聚乳酸和甲基丙烯酸缩水甘油酯；
所述外层的成分包括聚丙烯、聚酯弹性体和苯乙烯系嵌段共聚物；
所述粘合层的成分包括马来酸酐共聚酯和乙烯甲基丙烯酸酯。
相比于现有方法，本发明提供的高阻隔输液膜，具有以下优势：
阻湿层中通过线性低密度聚乙烯和环烯烃的复配为能够为输液膜提供水蒸气阻隔性能，通过加入纳米氧化锌能够使输液膜在常温或者高温下具备抗菌性能，加入马来酸酐接枝聚乙烯能够增强各组分之间的共融性，且四者复配得到的阻湿层能够达到双室袋虚焊的目的，具备良好的耐热性能，在灭菌后不发生粘连；阻气层通过聚对苯二甲酸乙二醇酯和乙烯-乙烯醇共聚物的复配使该输液膜能够有效阻隔二氧化碳、氮气、氧气等气体的渗透，而且聚对苯二甲酸乙二醇酯能够在一定程度上可阻挡紫外线，降低紫外线所导致的氧化；通过采用己二酸-对苯二甲酸-丁二醇酯共聚物、聚乳酸和甲基丙烯酸缩水甘油酯组成的加强层，使该输液膜不仅具备水蒸气阻隔性能，同时还具备抗撕裂的性能，弥补上述阻湿层易撕的缺陷，两层相互补充配合赋予输液膜双重的水蒸气阻隔性能，此外，将该层设计在阻气层的外层有效避免了阻气层中乙烯-乙烯醇共聚物在潮湿的环境下阻气性能下降的现象，使输液膜在较为潮湿的环境下仍对气体有较高的阻隔作用；聚丙烯和聚酯弹性体两种材料的极性相差较大，两者很难相容，加入苯乙烯系嵌段共聚物能够促进两者相容，通过聚丙烯、聚酯弹性体和苯乙烯系嵌段共聚物复配得到的外层具备抗折叠、耐刮擦的性能，同时能为薄膜提供耐低温性能；通过马来酸酐共聚酯和乙烯甲基丙烯酸酯组成的粘合层，不仅能够很好地粘合相邻两层，还能提高输液膜的柔韧性和断裂伸长率，同时含有酸酐基团的马来酸酐共聚酯能够与加强层中己二酸-对苯二甲酸-丁二醇酯共聚物以及外层中的聚酯弹性体具有更好的相容性，使相邻的两层更好的粘合。
通过上述层叠设置的多层结构以及每层中组分的设计，使该输液膜具备的优异气体和水汽的阻隔性能以及抗菌能力，同时还具备良好的韧性和耐刮擦性，满足对输液膜材料的要求。
优选地，所述阻湿层、阻气层、加强层、外层和粘合层的厚度比为(1～1.25):(1～1.25):(1.25～1.5)：(1.5～2.0)：(0.5～0.8)。
通过合理设计各层的厚度比例关系，使高阻隔输液膜不仅具备良好的阻湿阻气性能和力学性能，同时保证共挤吹膜过程中的加工性和加工稳定性。
优选地，所述输液薄膜的总厚度为200～260μm。
优选地，所述阻湿层中的所述线性低密度聚乙烯、环烯烃、马来酸酐接枝聚乙烯和纳米氧化锌的质量比为0.8～1.2：2：1.2～1.8：0.5～0.8；所述阻气层中的所述聚对苯二甲酸乙二醇酯和乙烯-乙烯醇共聚物的质量比为0.8～1.2：2.5；所述加强层中的所述己二酸-对苯二甲酸-丁二醇酯共聚物、聚乳酸和甲基丙烯酸缩水甘油酯的质量比为2：0.5～0.8：1～1.5；所述外层中所述聚丙烯、聚酯弹性体和苯乙烯系嵌段共聚物的质量比为3.5～4：2：0.8～1.2；所述粘合层中所述马来酸酐共聚酯和乙烯甲基丙烯酸酯的质量比为1：1～1.5。
优选地，所述苯乙烯系嵌段共聚物为苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物和苯乙烯-异戊二烯-苯乙烯二嵌段共聚物中的至少一种。
优选地，所述马来酸酐共聚酯为马来酸酐改性乙烯-醋酸乙烯酯、马来酸酐改性乙烯-丙烯酸酯共聚物和乙烯-丙烯酸酯-马来酸酐三元共聚物中的至少一种。
第二方面，本申请还提供了高阻隔输液膜的制备方法，具体包括以下步骤：采用共挤吹水冷工艺，将所述阻湿层、阻气层、加强层、外层和粘合层的成分分别混合均匀、熔融挤出，下吹成膜泡，依次经水环冷却、收卷成筒膜，再经分切得到高阻隔输液膜。
整个制备过程操作简便，上述成分结合该制备方法制得的输液膜在生产中不易出现破膜、厚度不均匀的情况，制备得到的输液膜力学性能优异，能够满足对输液膜的需求，而且具有高阻湿防潮、高阻气的性能，在输液薄膜领域具有广泛的应用前景。
优选地，所述水环冷却的工艺条件为：流速为500～700L/H，纯化水的温度为15～30℃。
优选地，所述膜泡内充填百级净化空气进行吹胀。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
现有技术中常采用环烯烃单一组分作为阻隔层，韧性较差，容易开裂，进而影响阻隔性能。发明人研究发现加入适量的线性低密度聚乙烯，一方面能提高阻湿层的韧性，另一方面还能协同环烯烃使输液膜具备水蒸气阻隔性能。此外，发明人在阻湿层中加入了纳米氧化锌，使输液膜具备抗菌性能，保证输液膜内液体的洁净度，同时还能在一定程度上提高拉伸强度，但实际研究中发现纳米氧化锌与线性低密度聚乙烯以及环烯烃之间的共融性较差，发明人通过大量的实验研究发现马来酸酐接枝聚乙烯的加入能够提高纳米氧化锌与线性低密度聚乙烯以及环烯烃之间的结合度，从而使阻湿层具有良好的稳定性能，同时通过各组分的复配使阻湿层能够达到双室袋虚焊的目的，具备良好的耐热性能，在灭菌后不发生粘连。
对于阻气层中的成分，本发明通过大量实验研究得到的阻气层，其组成为聚对苯二甲酸乙二醇酯和乙烯-乙烯醇共聚物两种成分的复配，发明人发现两者能够相互协同、促进，为该输液膜提供优异的阻气性能，优于单一组分对于二氧化碳、氮气、氧气等气体的阻隔效果，同时聚对苯二甲酸乙二醇酯能在一定程度上可阻挡紫外线，降低紫外线所导致的氧化。
对于加强层中的成分，发明人通过在加强层中加入聚乳酸，一方面协同阻湿层中的纳米氧化锌，为输液膜提供抗菌性能，另一方面还发现聚乳酸与己二酸-对苯二甲酸-丁二醇酯共聚物和甲基丙烯酸缩水甘油酯混合能够阻隔水蒸气，同时己二酸-对苯二甲酸-丁二醇酯共聚物还能改善聚乳酸的力学性能，三者复配使输液膜具备优良的抗撕裂性能，弥补上述阻湿层易撕的缺陷，两层相互补充配合赋予输液膜双重的水蒸气阻隔性能，而且还能有效避免阻气层中乙烯-乙烯醇共聚物在潮湿的环境下阻气性能下降的现象，使该输液膜在较为潮湿的环境下仍对气体有较高的阻隔作用。
对于外层中的成分，鉴于聚丙烯和聚酯弹性体两种材料的极性相差较大，两者很难相容，发明人通过大量的实验发现加入适量的苯乙烯系嵌段共聚物能够促进两者相容，使外层的稳定性大幅提高，具备抗折叠、耐刮擦的性能，同时还能为该输液膜提供耐低温性能。
此外，发明人还对粘合层进行了实验研究，发现通过马来酸酐共聚酯和乙烯甲基丙烯酸酯两者协同、复配得到的粘合层，能够很好地粘合相邻两层，还能提高输液膜的柔韧性和断裂伸长率，同时含有酸酐基团的马来酸酐共聚酯能够与加强层中己二酸-对苯二甲酸-丁二醇酯共聚物以及外层中的聚酯弹性体具有更好的相容性，使相邻层更好的粘合。
发明人通过上述层叠设置的多层结构以及每层组分的配合，使该输液膜具备优异的气体和水汽阻隔性能以及抗菌能力，同时还具备良好的韧性和耐刮擦性，满足对输液膜材料的要求。
以下实施例所用原料生产厂家及型号如下：
线性低密度聚乙烯为日本东曹公司；
环烯烃为日本三井化学APL 5014DP；
马来酸酐接枝聚乙烯为默克250G；
聚对苯二甲酸乙二醇酯为美国伊斯曼PETG；
乙烯-乙烯醇共聚物为日本可乐丽H171B。
己二酸-对苯二甲酸-丁二醇酯共聚物为德国巴斯夫C1200；
聚乳酸为美国Natureworks 4032D；
甲基丙烯酸缩水甘油酯为默克2506；
聚丙烯为埃克森1014H1；
聚酯弹性体为美国杜邦5526；
苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物SEBS为美国科腾G1645；苯乙烯-异戊二烯-苯乙烯二嵌段共聚物SEPS为可乐丽7311F；
马来酸酐改性乙烯-醋酸乙烯酯为法国阿科玛18211；
马来酸酐改性乙烯-丙烯酸酯共聚物为法国阿科玛5500；
乙烯-丙烯酸酯-马来酸酐三元共聚物为法国阿科玛4700；
乙烯甲基丙烯酸酯为法国阿科玛AX8900；
聚乳酸为日本三井化学M-133A。
实施例1：
本实施例提供的高阻隔输液膜，包括从内至外依次紧密贴合的阻湿层阻气层、加强层和外层，相邻两层之间设有粘合层；
其中，阻湿层的成分为质量比为1：2：1.5：0.5的线性低密度聚乙烯、环烯烃、马来酸酐接枝聚乙烯和纳米氧化锌的混合物；阻气层的成分为质量比为1.2：2.5的聚对苯二甲酸乙二醇酯和乙烯-乙烯醇共聚物的混合物；加强层的成分为质量比为2：0.8：1.2的己二酸-对苯二甲酸-丁二醇酯共聚物、聚乳酸和甲基丙烯酸缩水甘油酯的混合物；外层的成分为质量比为4：2：1的聚丙烯、聚酯弹性体和苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物SEBS的混合物；粘合层的成分为质量比为1：1.2的马来酸酐改性乙烯-醋酸乙烯酯和乙烯甲基丙烯酸酯的混合物；阻湿层、阻气层、加强层、外层和粘合层的厚度比为1:1:1.5:2.0:0.8；输液膜的总厚度为240μm。
其制备方法按照以下步骤制备：采用共挤吹水冷工艺，将所述阻湿层、阻气层、加强层、外层和粘合层的成分分别混合均匀、熔融挤出，下吹成膜泡，依次经水环冷却、收卷成筒膜，再经分切得到高阻隔输液膜，其中，水环冷却的工艺条件为：流速为600L/H，纯化水的温度为25℃，膜泡内充填百级净化空气。
实施例2：
本实施例提供的高阻隔输液膜，包括从内至外依次紧密贴合的阻湿层阻气层、加强层和外层，相邻两层之间设有粘合层；
其中，阻湿层的成分为质量比为1.2：2：1.5：0.6的线性低密度聚乙烯、环烯烃、马来酸酐接枝聚乙烯和纳米氧化锌的混合物；阻气层的成分为质量比为0.8：2.5的聚对苯二甲酸乙二醇酯和乙烯-乙烯醇共聚物的混合物；加强层的成分为质量比为2：0.8：1.2的己二酸-对苯二甲酸-丁二醇酯共聚物、聚乳酸和甲基丙烯酸缩水甘油酯的混合物；外层的成分为质量比为3.5：2：1的聚丙烯、聚酯弹性体和苯乙烯系嵌段共聚物的混合物；粘合层的成分为质量比为1：1～1.5的马来酸酐共聚酯和乙烯甲基丙烯酸酯的混合物；阻湿层、阻气层、加强层、外层和粘合层的厚度比为1.25:1:1.25:1.8:0.8；输液膜的总厚度为220μm。
其制备方法按照以下步骤制备：采用共挤吹水冷工艺，将所述阻湿层、阻气层、加强层、外层和粘合层的成分分别混合均匀、熔融挤出，再下吹成膜筒、膜泡，最后依次经水环冷却、收卷成筒膜，再经分切得到高阻隔输液膜，其中，水环冷却的工艺条件为：流速为700L/H，纯化水的温度为22℃，膜泡内充填百级净化空气。
实施例3：
本实施例提供的高阻隔输液膜，包括从内至外依次紧密贴合的阻湿层阻气层、加强层和外层，相邻两层之间设有粘合层；
其中，阻湿层的成分为质量比为0.8：2：1.5：0.5的线性低密度聚乙烯、环烯烃、马来酸酐接枝聚乙烯和纳米氧化锌的混合物；阻气层的成分为质量比为1.2：2.5的聚对苯二甲酸乙二醇酯和乙烯-乙烯醇共聚物的混合物；加强层的成分为质量比为2：0.8：1.2的己二酸-对苯二甲酸-丁二醇酯共聚物、聚乳酸和甲基丙烯酸缩水甘油酯的混合物；外层的成分为质量比为3.5：2：1的聚丙烯、聚酯弹性体和苯乙烯系嵌段共聚物的混合物；粘合层的成分为质量比为1：1.5的马来酸酐共聚酯和乙烯甲基丙烯酸酯的混合物；阻湿层、阻气层、加强层、外层和粘合层的厚度比为1.2:1:1.2：2.0：0.8；输液膜的总厚度为260μm。
其制备方法按照以下步骤制备：采用共挤吹水冷工艺，将所述阻湿层、阻气层、加强层、外层和粘合层的成分分别混合均匀、熔融挤出，下吹成膜泡，依次经水环冷却、收卷成筒膜，再经分切得到高阻隔输液膜，其中，水环冷却的工艺条件为：流速为700L/H，纯化水的温度为30℃，膜泡内充填百级净化空气。
对比例1：
在实施例1的基础上去掉阻湿层的马来酸酐接枝聚乙烯，其他成分及制备方法均不变。
对比例2：
在实施例1的基础上将阻气层的聚对苯二甲酸乙二醇酯替换为乙烯-乙烯醇共聚物，其他成分及制备方法均不变。
对比例3：
在实施例1的基础上将加强层的聚乳酸替换为环烯烃，其他成分及制备方法均不变。
对比例4：
在实施例1的基础上将粘合层的马来酸酐共聚酯替换为甲基丙烯酸缩水甘油酯，其他成分及制备方法均不变。
对比例5：
在实施例1的基础上将加强层中的己二酸-对苯二甲酸-丁二醇酯共聚物、聚乳酸和甲基丙烯酸缩水甘油酯的质量比为2:0.8:1.2替换为1:0.8:1.2，其他成分及制备方法均不变。
对比例6：
在实施例1的基础上将外层中聚丙烯、聚酯弹性体和苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物SEBS的质量比为4：2：1替换为2：1：2，其他成分及制备方法均不变。
试验例：
对本申请实施例1～3和对比例1～6制备的高阻隔输液膜根据国家标准YBB0112005-2015进行如下性能测试，以进一步对本申请的技术效果做详细描述，测试结果详见表1。
表1测试结果
Figure BDA0003364317420000091
Figure BDA0003364317420000101
从表1的测试结果来看，本发明实施例所提供的高阻隔输液膜，具备优异的高阻湿阻气性能，且拉伸强度和透光率良好，因此，本发明制备得到的高阻隔膜能够满足输液膜材料的需求。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换或改进等，均应包含在本发明的保护范围之内。

Claims (9)

1.一种高阻隔输液膜，其特征在于，包括从内至外依次紧密贴合的阻湿层、阻气层、加强层和外层，相邻两层之间设有粘合层；
所述阻湿层的成分包括线性低密度聚乙烯、环烯烃、马来酸酐接枝聚乙烯和纳米氧化锌；
所述阻气层的成分包括聚对苯二甲酸乙二醇酯和乙烯-乙烯醇共聚物；
所述加强层的成分包括己二酸-对苯二甲酸-丁二醇酯共聚物、聚乳酸和甲基丙烯酸缩水甘油酯；
所述外层的成分包括聚丙烯、聚酯弹性体和苯乙烯系嵌段共聚物；
所述粘合层的成分包括马来酸酐共聚酯和乙烯甲基丙烯酸酯。
2.如权利要求1所述的高阻隔输液膜，其特征在于，所述阻湿层、阻气层、加强层、外层和粘合层的厚度比为(1～1.25):(1～1.25):(1.25～1.5)：(1.5～2.0)：(0.5～0.8)。
3.如权利要求1所述的高阻隔输液膜，其特征在于，所述输液膜的总厚度为200～260μm。
4.如权利要求1所述的高阻隔输液膜，其特征在于，所述阻湿层中的所述线性低密度聚乙烯、环烯烃、马来酸酐接枝聚乙烯和纳米氧化锌的质量比为0.8～1.2：2：1.2～1.8：0.5～0.8；所述阻气层中的所述聚对苯二甲酸乙二醇酯和乙烯-乙烯醇共聚物的质量比为0.8～1.2：2.5；所述加强层中的所述己二酸-对苯二甲酸-丁二醇酯共聚物、聚乳酸和甲基丙烯酸缩水甘油酯的质量比为2：0.5～0.8：1～1.5；所述外层中所述聚丙烯、聚酯弹性体和苯乙烯系嵌段共聚物的质量比为3.5～4：2：0.8～1.2；所述粘合层中所述马来酸酐共聚酯和乙烯甲基丙烯酸酯的质量比为1：1～1.5。
5.如权利要求1所述的高阻隔输液膜，其特征在于，所述苯乙烯系嵌段共聚物为苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物和苯乙烯-异戊二烯-苯乙烯二嵌段共聚物中的至少一种。
6.如权利要求1所述的高阻隔输液膜，其特征在于，所述马来酸酐共聚酯为马来酸酐改性乙烯-醋酸乙烯酯、马来酸酐改性乙烯-丙烯酸酯共聚物和乙烯-丙烯酸酯-马来酸酐三元共聚物中的至少一种。
7.权利要求1～6任一项所述的高阻隔输液膜的制备方法，其特征在于，具体包括以下步骤：采用共挤吹水冷工艺，将所述阻湿层、阻气层、加强层、外层和粘合层的成分分别混合均匀、熔融挤出，下吹成膜泡，依次经水环冷却、收卷成筒膜，再经分切得到高阻隔输液膜。
8.如权利要求7所述的高阻隔输液膜的制备方法，其特征在于，所述水环冷却的工艺条件为：流速为500～700L/H，纯化水的温度为15～30℃。
9.如权利要求7所述的高阻隔输液膜的制备方法，其特征在于，所述膜泡内充填百级净化空气进行吹胀。
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