CN110667217A - 对称式高阻隔聚三氟氯乙烯复合硬片 - Google Patents

对称式高阻隔聚三氟氯乙烯复合硬片 Download PDF

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CN110667217A
CN110667217A CN201910984989.7A CN201910984989A CN110667217A CN 110667217 A CN110667217 A CN 110667217A CN 201910984989 A CN201910984989 A CN 201910984989A CN 110667217 A CN110667217 A CN 110667217A
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layer
barrier
polychlorotrifluoroethylene
hard sheet
composite
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李俊
林武辉
伍秋涛
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SUZHOU HAISHUN PACKAGING MATERIAL CO Ltd
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Abstract

本发明公开了一种对称式高阻隔聚三氟氯乙烯复合硬片，为复合膜结构，复合膜从外到内依次是热成型强度支撑层、填充层、第一粘接层、阻隔层、第二粘接层、热封层。在不提高阻隔层厚度的前提下，通过层间的优化组合，使热成型后阻隔层拉伸厚度更均匀，具有更优异的成型泡罩阻隔性。

Description

对称式高阻隔聚三氟氯乙烯复合硬片
技术领域
本发明涉及一种层合包装材料，更具体地说，涉及一种对称式高阻隔药用包装复合材料。
背景技术
含氟聚合物具有非常优良的水汽阻隔性、化学稳定性和耐气候性。特别用来适合包装那些易吸潮的贵昂的新特药，是欧美近几年来比较流行的药用高阻隔包装材料。
聚三氟氯乙烯是三氟氯乙烯的均聚物，具有在主链碳周围含有氟原子和氯原子结构，分子结构中的氟原子使聚合物具有化学惰性，氯原子使聚合物具有透明性，热塑性以及硬度，因此，聚三氟氯乙烯具有良好的化学惰性、耐化学腐蚀性和耐热性，机械强度高、韧性大、光学性能和介电性能优异。由于聚三氟氯乙烯薄膜具有最低的水-汽渗透率，不渗透任何气体，具有光学透明性、耐超低温性，可以在绝对零度的苛刻条件下使用，长期使用温度在-200-300℃，因此聚三氟氯乙烯薄膜作为性能优异的包装材料是其他材料无法取代的。但是，传统聚三氟氯乙烯硬片的阻隔层聚三氟氯乙烯薄膜在热成型时位于外层，因而存在不同位置拉伸均匀性差或局部阻隔层聚三氟氯乙烯薄膜在热成型时被拉伸过薄的现象，出现经热成型后整体阻隔性不理想的问题，不能满足现代社会对包装材料高阻隔性的要求。
发明内容
本发明所要解决的技术问题在于针对上述现有技术中的不足，提供一对称式高阻隔聚三氟氯乙烯复合硬片，为复合膜结构，复合膜从外到内依次是热成型强度支撑层、填充层、第一粘接层、阻隔层、第二粘接层、热封层。
优选的是，热成型强度支撑层为聚氯乙烯硬片、聚酯硬片、聚丙烯硬片中的一种或多种的组合，其中，所述热成型强度支撑层的厚度为100～300μm。
优选的是，填充层设置于两强度支撑层之间。
优选的是，填充层以重量计份包括如下成分：
Figure BDA0002236420040000021
四氟乙烯-六氟丙烯共聚物具有优异的力学强度、化学稳定性、电绝缘性、润滑性、耐磨性、不粘性、耐老化性和不燃性，其中引入的氟原子使其基本上保持了聚四氟乙烯的优异性能，且加工性能较好，相对密度低，在四氟乙烯-六氟丙烯共聚物中引入ABS树脂、醋酸纤维素丁酸酯、聚砜时，由于ABS树脂、醋酸纤维素丁酸酯、聚砜之间的协同配合作用，降低了共聚物分子链的结晶度，另外，引入的ABS树脂、醋酸纤维素丁酸酯、聚砜在四氟乙烯-六氟丙烯共聚物分子链上引入支链，降低四氟乙烯-六氟丙烯共聚物链与链之间的作用力，青铜粉末可以提高材料的拉伸强度、硬度、耐磨性，热传导率，降低冷流性，惰性氧化铝填料球具有纯度高、强度大、耐高温的特性、热震稳定性好，化学性能稳定等特点，增加液体的分布点，对材料起支撑和保护强度作用，同时惰性氧化铝填球是惰性的，不会与物料发生反应，晶须和炭黑的添加能够大幅度提高材料的拉伸力学性能。
优选的是，复合相容剂为热塑性弹性体与聚碳酸酯的混合物。
复合相容剂主要是改善各个成分之间的兼容性，提高各个成分之间的界面强度，保证应力有效地通过基体传递到四氟乙烯-六氟丙烯共聚物晶体上，从而提高填充层的外界应力，模量得到提高、塑性和拉伸强度。
优选的是，第一粘接层和第二粘接层为聚氨酯层，聚氨酯层的厚度为3～5μm。
优选的是，阻隔层为聚三氟氯乙烯-氯乙烯-丙烯酸叔丁酯共聚物膜。
优选的是，聚三氟氯乙烯-氯乙烯-丙烯酸叔丁酯共聚物中，聚三氟氯乙烯的质量、氯乙烯、丙烯酸叔丁酯的摩尔比为7:3:1。
优选的是，热封层为聚乙烯层或聚氯乙烯层。
优选的是，热封层的两侧壁均涂设镀铝层或者镀锌层。
本发明的有益效果是：(1)本发明提供的高阻隔聚三氟氯乙烯复合硬片，由多层薄膜构成，起阻隔层作用的聚三氟氯乙烯薄膜位于中间层，在热成型时其上下均有支撑层，热成型时阻隔层拉伸更均匀，具有更优异的成型泡罩阻隔性；(2)两强度支撑层之间设置填充层，进一步提高强度支撑层的拉伸力学性能，从而改善复合硬片的拉伸强度和均匀度，避免硬片厚度不均匀和过薄过厚的缺陷，在兼顾聚三氟氯乙烯复合硬片高阻隔性的前提下，提高复合硬片的力学性能和表观质量。
具体实施方式
下面结合实施例对本发明做进一步的详细说明，以令本领域技术人员参照说明书文字能够据以实施。
应当理解，本文所使用的诸如“具有”、“包含”以及“包括”术语并不排除一个或多个其它元件或其组合的存在或添加。
实施例1：
一种对称式高阻隔聚三氟氯乙烯复合硬片，为复合膜结构，复合膜从外到内依次是热成型强度支撑层、填充层、第一粘接层、阻隔层、第二粘接层、热封层，其中，填充层设置于两热成型强度支撑层之间，热成型强度支撑层为聚氯乙烯硬片，聚氯乙烯硬片的厚度为100μm，第一粘接层和第二粘接层为聚氨酯层，所述聚氨酯层的厚度为3μm。
填充层以重量计份包括如下成分：
Figure BDA0002236420040000031
Figure BDA0002236420040000041
其中，复合相容剂为热塑性弹性体与聚碳酸酯的混合物。
其中，阻隔层为聚三氟氯乙烯-氯乙烯-丙烯酸叔丁酯共聚物膜，聚三氟氯乙烯-氯乙烯-丙烯酸叔丁酯共聚物中，聚三氟氯乙烯的质量、氯乙烯、丙烯酸叔丁酯的摩尔比为7:3:1
其中，热封层为聚乙烯层，热封层的两侧壁均涂设镀铝层。
实施例2：
本实施例与实施例1的原料和工艺基本相同，唯一不同之处在于，填充层以重量计份包括如下成分：
Figure BDA0002236420040000042
实施例3：
本实施例与实施例1的原料和工艺基本相同，唯一不同之处在于，热成型强度支撑层为聚酯硬片,聚酯硬片的厚度为100μm。
实施例4：
本实施例与实施例1的原料和工艺基本相同，唯一不同之处在于，热封层为聚氯乙烯层。
对比例1：
本对比例与实施例1的原料和工艺基本相同，唯一不同之处在于，两强度支撑层之间不设填充层。
对比例2:
本对比例与实施例1的原料和工艺基本相同，唯一不同之处在于，将复合相容剂改为单一热塑性弹性体或聚碳酸酯。
对比例3：
本对比例与实施例1的原料和工艺基本相同，唯一不同之处在于，将阻隔层的聚三氟氯乙烯-氯乙烯-丙烯酸叔丁酯共聚膜改为聚三氟氯乙烯薄膜。
以上实施例1-4及对比例1-3的产品性能如下表所示，以下为性能测试结果：
Figure BDA0002236420040000051
拉伸强度：按照GB/T528-1998标准进行测试。
断裂伸长率:按照GB/T3923.1-1997标准进行测试。
水蒸气透过量:按照GB/T21529标准进行测试。
氧气透过率:按照GB/T19789标准进行测试。
实施例1与对比例1相比，复合膜的抗拉伸强度和断裂伸长率均得到明显的提高，这表明强度支撑层之间设置的填充层可以提高支撑层的抗拉伸强度和断裂伸长率，减少不同位置拉伸均匀性差或局部热成型时拉伸过薄的现象，从而提高薄膜整体的拉伸均匀度。
实施例1与对比例2相比，复合膜的拉伸强度和断裂伸长率均显著高于对比例2，这表明复合相容剂热塑性弹性体与聚碳酸酯之间的协同配位作用改善各个成分之间的兼容性，提高各个成分之间的界面强度和应力，从而提高填充层的外界应力、模量、塑性和拉伸强度。
实施例1与对比例3相比，聚三氟氯乙烯-氯乙烯-丙烯酸叔丁酯共聚膜阻隔层水蒸气透过量和氧气透过率明显低于以聚三氟氯乙烯薄膜阻隔层，这表明聚三氟氯乙烯-氯乙烯-丙烯酸叔丁酯共聚物的阻隔性能优于聚三氟氯乙烯，三氟氯乙烯、氯乙烯、丙烯酸叔丁酯成分之间协同配合，减少膜层中大尺寸以及微孔的缺陷，提高薄膜的致密性，从而提高薄膜的阻隔性。
因此，本发明制备的对称式高阻隔聚三氟氯乙烯复合硬片通过层间的优化组合，提高热成型后阻隔层拉伸均匀性，具有更优异的成型泡罩阻隔性。
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节。

Claims (10)

1.一种对称式高阻隔聚三氟氯乙烯复合硬片，为复合膜结构，其特征在于，所述复合膜从外到内依次是热成型强度支撑层、填充层、第一粘接层、阻隔层、第二粘接层、热封层。
2.根据权利要求1所述的对称式高阻隔聚三氟氯乙烯复合硬片，其特征在于，热成型强度支撑层为聚氯乙烯硬片、聚酯硬片、聚丙烯硬片中的一种或多种的组合，其中，所述热成型强度支撑层的厚度为100～300μm。
3.根据权利要求1所述的对称式高阻隔聚三氟氯乙烯复合硬片，其特征在于，所述填充层设置于两强度支撑层之间。
4.根据权利要求1所述的对称式高阻隔聚氯乙烯复合硬片，其特征在于，所述填充层以重量计份包括如下成分：
Figure FDA0002236420030000011
5.根据权利要求所4述的对称式高阻隔聚三氟氯乙烯复合硬片，其特征在于，所述复合相容剂为热塑性弹性体与聚碳酸酯的混合物。
6.根据权利要求1所述的对称式高阻隔聚三氟氯乙烯复合硬片，其特征在于，所述第一粘接层和第二粘接层为聚氨酯层，所述聚氨酯层的厚度为3～5μm。
7.根据权利要求1所述的对称式高阻隔聚三氟氯乙烯复合硬片，其特征在于，所述阻隔层为聚三氟氯乙烯-氯乙烯-丙烯酸叔丁酯共聚物膜。
8.根据权利要求7所述的对称式高阻隔聚三氟氯乙烯复合硬片，其特征在于，所述聚三氟氯乙烯-氯乙烯-丙烯酸叔丁酯共聚物中，聚三氟氯乙烯、氯乙烯、丙烯酸叔丁酯的摩尔比为7:3:1。
9.根据权利要求1所述的对称式高阻隔聚三氟氯乙烯复合硬片，其特征在于，所述热封层为聚乙烯层或聚氯乙烯层层。
10.根据权利要求1所述的对称式高阻隔聚三氟氯乙烯复合硬片，其特征在于，所述热封层的两侧壁均涂设镀铝层或者镀锌层。
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