CN116100887A - 一种抗腐蚀高阻隔片材 - Google Patents

一种抗腐蚀高阻隔片材 Download PDF

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CN116100887A
CN116100887A CN202211042569.5A CN202211042569A CN116100887A CN 116100887 A CN116100887 A CN 116100887A CN 202211042569 A CN202211042569 A CN 202211042569A CN 116100887 A CN116100887 A CN 116100887A
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heat
corrosion
resistant
layer
weight
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林武辉
符坚
庄远
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Suzhou Haishun Packaging Material Co ltd
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Abstract

本发明提供一种抗腐蚀高阻隔片材，从外至内至少包括耐热层、抗腐蚀阻隔层、热封层；其中，所述耐热层包括耐热聚烯烃树脂；所述抗腐蚀阻隔层包括30‑50重量份的聚烯烃树脂、5‑10重量份的POK聚酮树脂、5‑7重量份的纳米纤维素、5‑10重量份的相容剂。本发明还提供一种制备方法。设置抗腐蚀阻隔层，且抗腐蚀阻隔层中POK聚酮树脂具有耐化学性、耐磨、耐油、自润滑、耐冲击等诸多优良性能，纳米纤维素有很强的分子间与分子内氢键，可以大大地提高该层的机械性能，进而提高抗腐蚀高阻隔片材的阻隔性和耐腐蚀性。

Description

一种抗腐蚀高阻隔片材
技术领域
本发明涉及包装技术领域，尤其涉及一种抗腐蚀高阻隔片材。
背景技术
包装片材在各领域应用广泛，当包装片材应用在农药、生物制剂、工业化学液体、人用药液体、医疗液体等具有高腐蚀性内容物的包装时，包装片材和内容物之间发生反应导致包装片材受损及药物提前失效，进而使得内容物在存储过程中，使用功效下降，甚至有杂质产生。
目前市场上采用优化包装容器成分的做法，比如提高玻璃瓶中硼元素的含量，比如塑料瓶采用阿克拉三复氯乙烯或环状聚烯烃材料作为接触层，比如塑料瓶者内壁采用涂层镀层技术来实现高阻隔抗腐蚀的包装要求，但是从制造工艺上大大增加难度，成本也大幅增加，同时由于大多采用超惰性的材料，往往存在难以回收的问题。
发明内容
为了实现以上目的，本发明通过以下技术方案实现。
本发明提供一种抗腐蚀高阻隔片材，从外至内至少包括耐热层、抗腐蚀阻隔层、热封层；其中，
所述耐热层包括耐热聚烯烃树脂；
所述抗腐蚀阻隔层包括30-50重量份的聚烯烃树脂、5-10重量份的POK聚酮树脂、5-7重量份的纳米纤维素、5-10重量份的相容剂。
优选地，所述耐热聚烯烃树脂熔点＞130℃，密度大于0.9/cm3，熔融指数为0.5-10g/10min。
优选地，所述耐热层包括25-50重量份的耐热聚烯烃树脂、25-40重量份的阻隔树脂、25-70重量份的耐热功能填料、5-10重量份的相容剂。
优选地，所述阻隔树脂为EVOH或PVOH。
优选地，所述耐热功能填料选自碳酸钙、滑石粉、钛白粉中至少一种。
优选地，所述抗腐蚀阻隔层中所述聚烯烃树脂为POE或POP。
优选地，所述热封层包括75-80重量份的热封聚烯烃树脂、5-10重量份的POK聚酮树脂、10-15重量份的纳米片状填料。
优选地，所述热封聚烯烃树脂的熔融指数为0.5-50g/10min。
优选地，所述耐热层、所述抗腐蚀阻隔层、所述热封层的厚度比为(3-5)：(2-4)：(1-5)。
本发明还提供制备如上所述的抗腐蚀高阻隔片材的方法，包括如下步骤：
S1、称取耐热层原料，共混造粒，得耐热层母粒；
S2、称取抗腐蚀阻隔层原料，共混造粒，得抗腐蚀阻隔层母粒；
S3、称取热封层原料，共混造粒，得热封层母粒；
S4、将耐热层母粒、抗腐蚀阻隔层母粒、热封层母粒投入多层挤出流延设备，得抗腐蚀高阻隔片材。
相比现有技术，本发明的有益效果在于：
本发明提供一种抗腐蚀高阻隔片材，设置抗腐蚀阻隔层，且抗腐蚀阻隔层中POK聚酮树脂具有耐化学性、耐磨、耐油、自润滑、耐冲击等诸多优良性能，纳米纤维素有很强的分子间与分子内氢键，可以大大地提高该层的机械性能，进而提高抗腐蚀高阻隔片材的阻隔性和耐腐蚀性。
本上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合附图详细说明如后。本发明的具体实施方式由以下实施例及其附图详细给出。
附图说明
此处所说明的附图用来提供对本发明的进一步理解，构成本申请的一部分，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1为本发明的抗腐蚀高阻隔片材的结构剖视图；
图2为本发明的制备方法的步骤流程图。
图中：
100、抗腐蚀高阻隔片材；10、耐热层；20、抗腐蚀阻隔层；30、热封层。
具体实施方式
下面结合附图对本发明做进一步的详细说明，本发明的前述和其它目的、特征、方面和优点将变得更加明显，以令本领域技术人员参照说明书文字能够据以实施。在附图中，为清晰起见，可对形状和尺寸进行放大，并将在所有图中使用相同的附图标记来指示相同或相似的部件。在下列描述中，诸如中心、厚度、高度、长度、前部、背部、后部、左边、右边、顶部、底部、上部、下部等用词为基于附图所示的方位或位置关系。特别地，“高度”相当于从顶部到底部的尺寸，“宽度”相当于从左边到右边的尺寸，“深度”相当于从前到后的尺寸。这些相对术语是为了说明方便起见并且通常并不旨在需要具体取向。涉及附接、联接等的术语(例如，“连接”和“附接”)是指这些结构通过中间结构彼此直接或间接固定或附接的关系、以及可动或刚性附接或关系，除非以其他方式明确地说明。
下面，结合附图以及具体实施方式，对本发明做进一步描述，需要说明的是，在不相冲突的前提下，以下描述的各实施例之间或各技术特征之间可以任意组合形成新的实施例。
本发明提供一种抗腐蚀高阻隔片材，如图1所示，包括抗腐蚀高阻隔片材100，抗腐蚀高阻隔片材100从外至内至少包括耐热层10、抗腐蚀阻隔层20、热封层30；其中，
所述耐热层10包括耐热聚烯烃树脂；
所述抗腐蚀阻隔层20包括30-50重量份的聚烯烃树脂、5-10重量份的POK聚酮树脂、5-7重量份的纳米纤维素、5-10重量份的相容剂。
本实施例中，抗腐蚀阻隔层20中，POK聚酮树脂具有耐化学性、耐磨、耐油、自润滑、耐冲击等诸多优良性能，纳米纤维素有很强的分子间与分子内氢键，可以大大地提高该层的机械性能，进而提高抗腐蚀高阻隔片材100的阻隔性和耐腐蚀性。
在一实施例中，所述耐热聚烯烃树脂熔点＞130℃，密度大于0.9/cm3，熔融指数为0.5-10g/10min，以使得抗腐蚀高阻隔片材100具有良好的耐热性。
进一步地，所述耐热层10包括25-50重量份的耐热聚烯烃树脂、25-40重量份的阻隔树脂、25-70重量份的耐热功能填料、5-10重量份的相容剂，以使得耐热层10具有良好的耐热性的同时进一步地提高抗腐蚀高阻隔片材100的阻隔性。此外，抗腐蚀高阻隔片材100的各层的主体树脂均为聚烯烃树脂，构成单一材质体系，可回收。
进一步地，所述阻隔树脂为EVOH或PVOH。EVOH或PVOH含有大量的氢键，进一步地提高耐热层10的阻隔性。
进一步地，所述耐热层10中的相容剂为含酸性的聚烯烃树脂。
进一步地，所述耐热功能填料选自碳酸钙、滑石粉、钛白粉中至少一种。
在一实施例中，所述抗腐蚀阻隔层20中所述聚烯烃树脂为POE或POP。
在一实施例中，所述热封层30包括75-80重量份的热封聚烯烃树脂、5-10重量份的POK聚酮树脂、10-15重量份的纳米片状填料，以形成良好的热封性能的同时具备低吸附的优点。
进一步地，所述热封聚烯烃树脂的熔融指数为0.5-50g/10min，以保证良好的热封性能。
在一实施例中，所述耐热层10、所述抗腐蚀阻隔层20、所述热封层30的厚度比为(3-5)：(2-4)：(1-5)。
在一实施例中，抗腐蚀高阻隔片材100的厚度为100μm-5mm。
在一实施例中，所述抗腐蚀阻隔层20的相容剂为马来酸酐改性或者含有丙烯酸改性的聚烯烃树脂。
本发明还提供制备如上所述的抗腐蚀高阻隔片材的方法，如图2所示，包括如下步骤：
S1、称取耐热层10原料，共混造粒，得耐热层母粒；
S2、称取抗腐蚀阻隔层20原料，共混造粒，得抗腐蚀阻隔层母粒；
S3、称取热封层30原料，共混造粒，得热封层母粒；
S4、将耐热层母粒、抗腐蚀阻隔层母粒、热封层母粒投入多层挤出流延设备，得抗腐蚀高阻隔片材。
本发明的抗腐蚀高阻隔片材的制备方法简单、加工效率高。
在一实施例中，热封层30包括75-80重量份的热封聚烯烃树脂、5-10重量份的POK聚酮树脂、10-15重量份的纳米片状填料。步骤S4中，制备热封层母粒时，先将POK聚酮树脂、纳米片状填料共混形成包裹核壳结构，然后将包裹核壳结构均匀地分散于热封聚烯烃树脂中，依次经高速高温混合、密炼、造粒，得热封层母粒。
下面通过具体实施例对本发明的方法进行说明，应理解，这些实施例是用于说明本发明的基本原理、主要特征和优点，而本发明不受以下实施例的范围限制；实施例中采用的实施条件可以根据具体要求做进一步调整，未注明的实施条件通常为常规实验中的条件。
实施例1
抗腐蚀高阻隔片材的制备，包括如下步骤：
(1)称取25重量份的PP树脂BORMED HS850MO-11、25公斤的EVOH171(购自日本可乐丽)、25公斤的纳米碳酸钙、5公斤的无机有机粘结剂杜邦Nucrel EAA 30907，通过多螺杆混合造粒后烘干，得热封层母粒；
(2)称取30公斤的POE(购自Exxon Mobile公司)、5公斤的POK聚酮树脂M630A、5公斤的纳米纤维素(长度为100nm，长径比为10，结晶度为90％)、5公斤的相容剂AN4228C(购自杜邦)，通过多螺杆混合造粒后烘干，得抗腐蚀阻隔层母粒；
(3)称取75公斤的三元和二元共聚的PP树脂(购自韩国乐天SFC-750M)、5公斤的POK聚酮树脂M630A、10公斤的纳米三氧化二铝(购自福建闽江学院)，先将POK聚酮树脂M630A、纳米三氧化二铝共混形成包裹核壳结构，然后将包裹核壳结构均匀地分散于PP树脂中，依次经高速高温混合、密炼、造粒，得热封层母粒；
(4)将耐热层母粒、抗腐蚀阻隔层母粒、热封层母粒投入多层挤出流延设备，得抗腐蚀高阻隔片材；其中，耐热层10厚度为60μm，抗腐蚀阻隔层20厚度为60μm，热封层厚度为20μm。
实施例2
抗腐蚀高阻隔片材的制备，包括如下步骤：
(1)称取40重量份的PP树脂BORMED HS850MO-11、30公斤的EVOH171(购自日本可乐丽)、50公斤的纳米碳酸钙、8公斤的无机有机粘结剂杜邦Nucrel EAA 30907，通过多螺杆混合造粒后烘干，得热封层母粒；
(2)称取40公斤的POE(购自Exxon Mobile公司)、8公斤的POK聚酮树脂M630A、6公斤的纳米纤维素(长度为100nm，长径比为10，结晶度为90％)、7公斤的相容剂AN4228C(购自杜邦)，通过多螺杆混合造粒后烘干，得抗腐蚀阻隔层母粒；
(3)称取78公斤的三元和二元共聚的PP树脂(购自韩国乐天SFC-750M)、7公斤的POK聚酮树脂M630A、12公斤的纳米三氧化二铝(购自福建闽江学院)，先将POK聚酮树脂M630A、纳米三氧化二铝共混形成包裹核壳结构，然后将包裹核壳结构均匀地分散于PP树脂中，依次经高速高温混合、密炼、造粒，得热封层母粒；
(4)将耐热层母粒、抗腐蚀阻隔层母粒、热封层母粒投入多层挤出流延设备，得抗腐蚀高阻隔片材；其中，耐热层10厚度为60μm，抗腐蚀阻隔层20厚度为60μm，热封层厚度为20μm。
实施例3
抗腐蚀高阻隔片材的制备，包括如下步骤：
(1)称取50重量份的PP树脂BORMED HS850MO-11、40公斤的EVOH171(购自日本可乐丽)、60公斤的纳米碳酸钙、9公斤的无机有机粘结剂杜邦Nucrel EAA 30907，通过多螺杆混合造粒后烘干，得热封层母粒；
(2)称取50公斤的POE(购自Exxon Mobile公司)、10公斤的POK聚酮树脂M630A、7公斤的纳米纤维素(长度为100nm，长径比为10，结晶度为90％)、10公斤的相容剂AN4228C(购自杜邦)，通过多螺杆混合造粒后烘干，得抗腐蚀阻隔层母粒；
(3)称取80公斤的三元和二元共聚的PP树脂(购自韩国乐天SFC-750M)、10公斤的POK聚酮树脂M630A、15公斤的纳米三氧化二铝(购自福建闽江学院)，先将POK聚酮树脂M630A、纳米三氧化二铝共混形成包裹核壳结构，然后将包裹核壳结构均匀地分散于PP树脂中，依次经高速高温混合、密炼、造粒，得热封层母粒；
(4)将耐热层母粒、抗腐蚀阻隔层母粒、热封层母粒投入多层挤出流延设备，得抗腐蚀高阻隔片材；其中，耐热层10厚度为60μm，抗腐蚀阻隔层20厚度为60μm，热封层厚度为20μm。
对比例1
与实施例1的不同之处在于，抗腐蚀阻隔层原料中去掉POK聚酮树脂。
对比例2
与实施例1的不同之处在于，抗腐蚀阻隔层原料中去掉纳米纤维素。
实施例4
将实施例1至实施例3、对比例1和对比例2制得的片材进行阻隔性能测试，透水透氧测试方法按照YBB000152002-2015测试。测试结果见表一。
表一
Figure BDA0003821093150000081
由表一可知，实施例1、实施例2、实施例3制得的抗腐蚀高阻隔片材具备优异的阻隔性能。由实施例1与对比例1、对比例2可知，在抗腐蚀阻隔层中添加POK聚酮树脂、纳米纤维素能够大大地提高片材的阻隔性。
将实施例1至实施例3、对比例1和对比例2制得的片材进行耐腐蚀性能测试。各实施例分别取20片5×5cm的片材，浸泡于浓度为5％的氯化钠溶液中，氯化钠溶液在35℃的PH为6.9-7.2，浸泡一周，观察片材表面有无气泡、起皮。测试结果见表二。
表二
Figure BDA0003821093150000082
由表二可知，实施例1、实施例2、实施例3制得的抗腐蚀高阻隔片材具备良好的抗腐蚀性能。由实施例1与对比例1、对比例2可知，在抗腐蚀阻隔层中添加POK聚酮树脂、纳米纤维素能够提高片材的抗腐蚀性能。
以上，仅为本发明的较佳实施例而已，并非对本发明作任何形式上的限制；凡本行业的普通技术人员均可按说明书附图所示和以上而顺畅地实施本发明；但是,凡熟悉本专业的技术人员在不脱离本发明技术方案范围内，利用以上所揭示的技术内容而做出的些许更动、修饰与演变的等同变化，均为本发明的等效实施例；同时,凡依据本发明的实质技术对以上实施例所作的任何等同变化的更动、修饰与演变等，均仍属于本发明的技术方案的保护范围之内。

Claims (10)

1.一种抗腐蚀高阻隔片材，其特征在于，从外至内至少包括耐热层(10)、抗腐蚀阻隔层(20)、热封层(30)；其中，
所述耐热层(10)包括耐热聚烯烃树脂；
所述抗腐蚀阻隔层(20)包括30-50重量份的聚烯烃树脂、5-10重量份的POK聚酮树脂、5-7重量份的纳米纤维素、5-10重量份的相容剂。
2.根据权利要求1所述的一种抗腐蚀高阻隔片材，其特征在于，所述耐热聚烯烃树脂熔点＞130℃，密度大于0.9/cm3，熔融指数为0.5-10g/10min。
3.根据权利要求1或2所述的一种抗腐蚀高阻隔片材，其特征在于，所述耐热层(10)包括25-50重量份的耐热聚烯烃树脂、25-40重量份的阻隔树脂、25-70重量份的耐热功能填料、5-10重量份的相容剂。
4.根据权利要求3所述的一种抗腐蚀高阻隔片材，其特征在于，所述阻隔树脂为EVOH或PVOH。
5.根据权利要求3所述的一种抗腐蚀高阻隔片材，其特征在于，所述耐热功能填料选自碳酸钙、滑石粉、钛白粉中至少一种。
6.根据权利要求1所述的一种抗腐蚀高阻隔片材，其特征在于，所述抗腐蚀阻隔层(20)中所述聚烯烃树脂为POE或POP。
7.根据权利要求1所述的一种抗腐蚀高阻隔片材，其特征在于，所述热封层(30)包括75-80重量份的热封聚烯烃树脂、5-10重量份的POK聚酮树脂、10-15重量份的纳米片状填料。
8.根据权利要求7所述的一种抗腐蚀高阻隔片材，其特征在于，所述热封聚烯烃树脂的熔融指数为0.5-50g/10min。
9.根据权利要求1所述的一种抗腐蚀高阻隔片材，其特征在于，所述耐热层(10)、所述抗腐蚀阻隔层(20)、所述热封层(30)的厚度比为(3-5)：(2-4)：(1-5)。
10.制备如权利要求1-9任意一所述的抗腐蚀高阻隔片材的方法，其特征在于，包括如下步骤：
S1、称取耐热层(10)原料，共混造粒，得耐热层母粒；
S2、称取抗腐蚀阻隔层(20)原料，共混造粒，得抗腐蚀阻隔层母粒；
S3、称取热封层(30)原料，共混造粒，得热封层母粒；
S4、将耐热层母粒、抗腐蚀阻隔层母粒、热封层母粒投入多层挤出流延设备，得抗腐蚀高阻隔片材。
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