CN105566831B - 一种水发泡抗菌透气微孔薄膜母料、薄膜及制备方法 - Google Patents

一种水发泡抗菌透气微孔薄膜母料、薄膜及制备方法 Download PDF

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CN105566831B
CN105566831B CN201610126861.3A CN201610126861A CN105566831B CN 105566831 B CN105566831 B CN 105566831B CN 201610126861 A CN201610126861 A CN 201610126861A CN 105566831 B CN105566831 B CN 105566831B
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廖道权
谢太和
赵良知
林道宏
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Shenzhen Huanmeisheng Technology Co ltd
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Abstract

本发明涉及一种透气微孔薄膜母料，还涉及含有母料的塑料薄膜及其制备方法。一种水发泡抗菌透气微孔薄膜母料，包括聚烯烃聚合物，改性剂，微孔吸水无机发泡材料，引发剂，表面活性剂，塑料抗氧剂。一种水发泡抗菌透气微孔薄膜，含有上述的水发泡抗菌透气微孔薄膜母料以及吹塑薄膜塑料，制备方法为母料造粒后，吸水熟化，加入吹塑薄膜塑料混合并投入发泡挤出吹膜机挤出而成。本发明的水发泡抗菌透气微孔薄膜具有制备工艺简单稳定、加工性能良好等特点，发泡剂采用水发泡剂，环保安全，且有抗菌功能，挤出的抗菌透气薄膜微孔密度可控，具有开孔结构、泡孔尺寸细小均匀等特点，具有优良的综合力学性能、环保易回收等特点。

Description

一种水发泡抗菌透气微孔薄膜母料、薄膜及制备方法
技术领域
本发明涉及一种透气微孔薄膜母料，特别涉及一种水发泡抗菌透气微孔薄膜母料，还涉及含有该水发泡抗菌透气微孔薄膜母料的塑料薄膜及其制备方法。具体说，涉及一种热塑性聚烯烃和无机材料混合物的抗菌透气微孔薄膜母料的制备及其这种母料直接加入塑料中制备抗菌微孔薄膜，而且这种薄膜具有透气抑菌防腐的作用。
背景技术
随着科学水平的发展和生活水平的提高，人们在生活上，利用透气微孔薄膜的透气而不透水的特性，制作防雨服，医院用一次性防护服，婴儿尿布，妇女卫生用品等；在工业上，塑料微孔薄膜用作水处理薄膜，制备饮用水、超纯净水，以及在酒业、药业上应用；在农副产品，如水果，蔬菜、食品、肉类和鲜花等的保鲜包装方面，透气微孔薄膜既能提供需要的氧气，又能保持水分，从而来延长其储存时间；在农业上，微孔保鲜膜可制成果套防止虫害和农药污染。因此，塑料透气微孔薄膜具有巨大的应用前景。
目前市场上的透气微孔薄膜存在透气性、保湿性差，保鲜效果不理想，保质时间较短，不具备杀菌效果等问题，迫切需要有一种透气性、保湿性好、抗菌保鲜效果更佳、保鲜时间更长的新型薄膜。
目前塑料透气薄膜的制造方法很多，主要有以下几种：
1.填料溶出法 是将热塑性树脂粉末与可溶性粉状填料共混压延成膜，或将树脂溶液与填料均匀混合后流延或涂刮成膜，待膜成形后，将膜中的填料用水或溶剂溶出，即成透气薄膜。此法可制得孔径大小均匀的薄膜。薄膜的微孔的孔径，由填料颗粒的大小及填料在树脂中的分散均匀程度决定。此法较简单易行，但填料粒子的溶出需要时间较长。
2.机械法 即机械制孔的方法，如用带针辊筒打孔等，而机械拉伸方法是制造微孔透气薄膜的新方法之一，但是这种方法工艺复杂，不确定因素很多，不容易控制。
3.溶剂成膜法 是将树脂溶于溶剂和小量非溶剂的混合液中,，通过流延或涂刮成膜，然后蒸发或浸泡，除去溶剂和非溶剂，干燥后可得微孔透气薄膜。但此法需用大量溶剂，需增加溶剂回收来解决环境污染问题。
4.发泡法 在高聚物溶胶或糊状物中加入有机或无机发泡剂，涂成膜后在适当温度下发泡可制得微孔透气薄膜。这种发泡方法必须控制发泡过程为开口发泡，而开孔发泡的开孔率过多又会影响薄膜强度，而且化学发泡剂会带来环保卫生问题。
这样就要想办法制作一种能既透气又能保持水分的微孔薄膜，这种微孔透气薄膜是在塑料薄膜上产生细微的小孔，根据用途不同，可以控制微孔的孔径大小来满足各种不同需要。
发明内容
本发明的目的在于克服现有技术的不足，提供一种高透气性、保水性，抗菌保鲜的水发泡抗菌透气微孔薄膜母料。
本发明的第二个目的在于提供一种将上述抗菌保鲜微孔薄膜母料加入聚烯烃塑料中加工而成的水发泡抗菌透气微孔薄膜。
本发明的第三个目的在于提供该水发泡抗菌透气微孔薄膜的制备方法。
为达到上述目的，本发明采取了如下的技术方案：
一种水发泡抗菌透气微孔薄膜母料，包括以下重量份的组分：聚烯烃聚合物70~90份，改性剂 0.5~10份，微孔吸水无机发泡材料10~30份，引发剂0.01~0.2份，表面活性剂1~3份，塑料抗氧剂 0.5~3份。
优选的，所述的聚烯烃聚合物为聚乙烯，聚丙烯，聚苯乙烯，乙烯-醋酸乙烯共聚物，乙烯-丙烯酸或丙烯酸酯的共聚物，丙烯共聚物、聚1-丁烯、聚4-甲基-1-戊烯、环烯烃聚合物中的至少一种。
优选的，所述的改性剂为聚乙烯醇，EVA，SBS，或POE中的至少一种。
优选的，所述的微孔吸水无机发泡材料为硅藻土，海泡石粉，木粉及壳粉，超细微孔硫酸钙，超细微孔硫酸镁，超细微孔碳酸钙，无机盐晶须（硫酸钙，碳酸钙等），金属晶须（氧化铝，氧化锌等）和微孔状纤维中的至少一种。
优选的，所述的引发剂由以下重量份的材料组成：接枝剂 0.01~0.1份，助接枝剂0.01~0.2份。进一步优选的，所述接枝剂为偶氮二异丁睛、过氧化苯甲酰、过氧化二异丙苯、过氧化十二酰、叔丁基过氧化碳酸-2-乙基己酯或过氧化苯甲酸叔丁酯中的至少一种；
优选的，所述助接枝剂为马来酸酐、二烯烃、苯乙烯、甲基苯乙烯、二乙烯基苯、丙烯酸酯或丙烯酸酯类衍生物中的至少一种。
优选的， 所述的抗氧剂由受阻酚类抗氧剂和亚磷酸酯抗氧剂组成，受阻酚类抗氧剂和亚磷酸酷抗氧剂的重量比是1:0.5~5份；所述表面活性剂为钛酸酯偶联剂、硅烷类偶联剂、铝钛复合偶联剂中的至少一种。
一种水发泡抗菌透气微孔薄膜，含有上述的水发泡抗菌透气微孔薄膜母料，以及吹塑薄膜塑料。
上述的水发泡抗菌透气微孔薄膜的制备方法，包括以下步骤：
S1.母料造粒：将微孔吸水无机发泡材料投入高速混合机，加入表面活性剂混合10~20分钟，接着投入聚烯烃聚合物，改性剂，引发剂，抗氧剂，，预混20~30分钟，然后将预混料投入双螺杆挤出机造粒成水发泡抗菌透气微孔薄膜母料；
S2.吸水熟化：将S1所得母料在高速混料机上，加入0.1~1.0%的水混合30~40分钟，放置2~4小时熟化；
S3. 挤出制备抗菌透气微孔薄膜：在吹塑薄膜塑料中加入占整个加工材料的总重量3~5%的S2熟化的水发泡抗菌透气微孔薄膜母料，一起混合20~40分钟，投入发泡挤出吹膜机的加料口，料筒温度为150~210℃，模头温度为100~150℃，螺杆转速为20~150转/分钟，挤出后为水发泡抗菌透气微孔薄膜。
本发明具有以下优点：
本发明的水发泡抗菌透气微孔薄膜具有制备工艺简单稳定、加工性能良好等特点，发泡剂采用水发泡剂，环保安全，且有抗菌功能，挤出的抗菌透气薄膜微孔密度可控，具有开孔结构、泡孔尺寸细小均匀等特点，具有优良的综合力学性能、环保易回收等特点。
具体实施方式
下面结合具体实施例进一步详细说明本发明。
实施例1
一种水发泡抗菌透气微孔薄膜母料，由以下重量份的材料组成：聚乙烯90份，EVA3份，海泡石粉+硫酸钙晶须10份，叔丁基过氧化碳酸-2-乙基己酯 0.04份，丙烯酸酯0.08份，硅烷类偶联剂1份，塑料抗氧剂 0.5份，。
含有上述水发泡抗菌透气微孔薄膜母料的水发泡抗菌透气微孔薄膜的制备方法，包括以下步骤：
S1.将微孔吸水无机发泡材料投入高速混合机，加入表面活性剂混合15分钟，接着投入聚乙烯原料，改性剂，引发剂，抗氧剂，预混25分钟，然后将预混料投入双螺杆挤出机造粒成水发泡抗菌透气微孔薄膜母料；
S2.将母料在高速混料机上，加入0.5%的水混合30分钟，放置2小时熟化；
S3.在吹塑薄膜塑料中加入占整个加工材料的总重量3%的S2熟化的水发泡抗菌透气微孔薄膜母料，一起混合30分钟，投入发泡挤出吹膜机的加料口，料筒温度为150~180℃，模头温度为100~130℃，螺杆转速为40转/分钟，挤出后为抗菌透气微孔薄膜。
根据ISO22196-2011的标准方法测试薄膜抗菌产品性能指标：金黄色葡萄球菌的杀菌率为99.75%，大肠杆菌的杀菌率为99.88%。
实施例2
一种水发泡抗菌透气微孔薄膜，通过以下重量份的材料制成：聚丙烯80份，POE 5份，超细微孔碳酸钙+氧化锌晶须20份，过氧化苯甲酰0.03份，二乙烯基苯0.15份，铝钛复合偶联剂2份，塑料抗氧剂3份。
含有上述水发泡抗菌透气微孔薄膜母料的水发泡抗菌透气微孔薄膜的制备方法，包括以下步骤：
S1.将吸水微孔无机发泡材料投入高速混合机，加入表面活性剂混合20分钟，接着投入原料，改性剂，引发剂，抗氧剂，预混30分钟，然后将预混料投入双螺杆挤出机造粒成水发泡制备抗菌透气微孔薄膜母料；
S2.将母料在高速混料机上，加入0.8%的水混合40分钟，放置4小时熟化；
S3. 在吹塑薄膜塑料中加入占整个加工材料的总重量5%的S2熟化的水发泡抗菌透气微孔薄膜母料，一起混合30分钟，投入发泡挤出吹膜机的加料口,料筒温度为180~210℃,模头温度为120~150℃，螺杆转速为60转/分钟，挤出后为抗菌透气微孔薄膜。
根据ISO22196-2011的标准方法测试薄膜抗菌产品性能指标:金黄色葡萄球菌的杀菌率为99.62%,大肠杆菌的杀菌率为99.84%。
实施例3
一种水发泡抗菌透气微孔薄膜，通过以下重量份的材料制成：乙烯-醋酸乙烯共聚物70份，聚乙烯醇2份，硅藻土+硫酸钙晶须30份，过氧化苯甲酰0.02份，苯乙烯0.2份，表面活性剂1.5份，塑料抗氧剂2份。
含有上述水发泡抗菌透气微孔薄膜母料的水发泡抗菌透气微孔薄膜的制备方法，包括以下步骤：
S1.将吸水微孔无机发泡材料投入高速混合机，加入表面活性剂混合20分钟，接着投入原料，改性剂，引发剂，抗氧剂，预混25分钟，然后将预混料投入双螺杆挤出机造粒成水发泡制备抗菌透气微孔薄膜母料；
S2.将母料在高速混料机上，加入1.0%的水混合30分钟，放置2小时熟化；
S3. 在吹塑薄膜塑料中加入占整个加工材料的总重量4%的S2熟化的水发泡抗菌透气微孔薄膜母料，一起混合30分钟，投入发泡挤出吹膜机的加料口，料筒温度为150~190℃，模头温度为110~140℃，螺杆转速为65转/分钟，挤出后为抗菌透气微孔薄膜。
根据ISO22196-2011的标准方法测试薄膜抗菌产品性能指标:金黄色葡萄球菌的杀菌率为99.60%,大肠杆菌的杀菌率为99.82%
性能测试
将实施例1~3制成的抗菌透气微孔薄膜进行性能测试，测试结果完全符合国家规定，且过程中没有使用任何的毒性物质。
表 1各实施例抗菌透气微孔薄膜性能
发泡片材性能 单位 实施例1 实施例2 实施例3
厚度 （μm） 69 72 80
密度 （g*cm-3） 0.75 0.73 0.78
拉伸强度（纵向） （MPa） 35 38 32
拉伸强度（横向） （MPa） 26 25 22
断裂伸长率（纵向） （%） 98 102 137
断裂伸长率（横向） （%） 86 82 80
弹性模量（纵向） N/mm2 983 962 1000
弹性模量（横向） N/mm2 1105 985 1078
泡孔平均直径 （μm） 70 68 72
熔体强度 （cN） 12 13.5 10
水汽透过率 g/(m2•24h) 13 11 9
气体通过率(O2) cm3/m2daybar >30000 >30000 >30000
气体通过率(CO2) cm3/m2daybar >30000 >30000 >30000

Claims (7)

1.一种水发泡抗菌透气微孔薄膜，其特征在于：含有水发泡抗菌透气微孔薄膜母料，以及吹塑薄膜塑料；
所述水发泡抗菌透气微孔薄膜母料，包括以下重量份的组分：聚烯烃聚合物70~90份，改性剂 0.5~10份，微孔吸水无机发泡材料10~30份，引发剂0.01~0.2份，表面活性剂1~3份，塑料抗氧剂 0.5~3份；
所述水发泡抗菌透气微孔薄膜的制备方法，包括以下步骤：
S1.母料造粒：将微孔吸水无机发泡材料投入高速混合机加入表面活性剂混合10~20分钟，接着投入聚烯烃聚合物，改性剂，引发剂，抗氧剂，预混20~30分钟，然后将预混料投入双螺杆挤出机造粒成水发泡抗菌透气微孔薄膜母料；
S2.吸水熟化：将S1所得母料在高速混料机上，加入0.1~1.0%的水混合30~40分钟，放置2~4小时熟化；
S3. 挤出制备抗菌透气微孔薄膜：在吹塑薄膜塑料中加入占整个加工材料的总重量3~5%的S2熟化的水发泡抗菌透气微孔薄膜母料，一起混合20~40分钟，投入发泡挤出吹膜机的加料口，料筒温度为150~210℃，模头温度为100~150℃，螺杆转速为20~150转/分钟，挤出后为水发泡抗菌透气微孔薄膜；
所述的微孔吸水无机发泡材料为硅藻土，海泡石粉，木粉及壳粉，超细微孔硫酸钙，超细微孔硫酸镁，超细微孔碳酸钙，无机盐晶须，金属晶须，微孔状纤维中的至少一种。
2.根据权利要求1所述的水发泡抗菌透气微孔薄膜，其特征在于：所述的聚烯烃聚合物为聚乙烯，聚丙烯，聚苯乙烯，乙烯-醋酸乙烯共聚物，乙烯-丙烯酸或丙烯酸酯的共聚物，丙烯共聚物、聚1-丁烯、聚4-甲基-1-戊烯、环烯烃聚合物中的至少一种。
3.根据权利要求1所述的水发泡抗菌透气微孔薄膜，其特征在于：所述的改性剂为PVA，EVA，SBS，POE中的至少一种。
4.根据权利要求1所述的水发泡抗菌透气微孔薄膜，其特征在于：所述的引发剂由以下重量份的材料组成：接枝剂 0.01~0.1份，助接枝剂0.01~0.2份。
5.根据权利要求4所述的水发泡抗菌透气微孔薄膜，其特征在于：；所述接枝剂为偶氮二异丁睛、过氧化苯甲酰、过氧化二异丙苯、过氧化十二酰、叔丁基过氧化碳酸-2-乙基己酯或过氧化苯甲酸叔丁酯中的至少一种。
6.根据权利要求4所述的水发泡抗菌透气微孔薄膜，其特征在于：所述助接枝剂为马来酸酐、二烯烃、苯乙烯、甲基苯乙烯、二乙烯基苯、丙烯酸酯或丙烯酸酯类衍生物中的至少一种。
7.根据权利要求1所述的水发泡抗菌透气微孔薄膜，其特征在于：所述的抗氧剂由受阻酚类抗氧剂和亚磷酸酯抗氧剂组成，受阻酚类抗氧剂和亚磷酸酯抗氧剂的重量比是1:0.5~5份；所述表面活性剂为钛酸酯偶联剂、硅烷类偶联剂、铝钛复合偶联剂中的至少一种。
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