CN103739916B - 一种抗紫外线抗静电聚烯烃母粒 - Google Patents

一种抗紫外线抗静电聚烯烃母粒 Download PDF

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CN103739916B
CN103739916B CN201310751271.6A CN201310751271A CN103739916B CN 103739916 B CN103739916 B CN 103739916B CN 201310751271 A CN201310751271 A CN 201310751271A CN 103739916 B CN103739916 B CN 103739916B
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王仲文
王执中
汤志龙
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ZHEJIANG QISELU MASTERBATCH CO Ltd
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Abstract

本发明公开了一种抗紫外线抗静电聚烯烃功能母粒。现有抗静电聚烯烃功能母粒虽有很好的抗静电效果，但会降低PO类塑料的热稳定性，且季胺盐类不符合FDA的规定。本发明抗紫外线抗静电聚烯烃母粒，它由以下质量百分比的原料组成：聚烯烃40‑60%，接枝聚烯烃10‑20%，聚乙烯醇20‑40%，复合抗氧剂1‑10%和纳米级四极晶须氧化锌4‑7%；所述的聚烯烃为熔融指数在0.1～25的均聚或共聚聚烯烃吹膜、流延或双向拉伸树脂；所述的接枝聚烯烃为同前述聚烯烃树脂吻合的接枝物，接枝率为0.8‑1.5%。本发明在聚烯烃树脂淋膜材料中添加量少，在保证良好的抗静电、抗老化性和力学性能的前提下，延长使用寿命，降低原料成本。

Description

一种抗紫外线抗静电聚烯烃母粒
技术领域
本发明涉及聚烯烃的改性，具体地说是一种抗紫外线抗静电聚烯烃功能母粒。
背景技术
聚乙烯、聚丙烯、聚醋酸乙烯为几种通用聚烯烃塑料，大量应用于各种电子电气、食药品、农副产品、纺织品、户内外装饰及广告等。由于PO材料不易消除静电集聚，生产过程中塑料薄膜会自动发生卷曲、撕裂和吸尘等现象；在复合和包装时，静电作用会导致粘接、封口困难，还有印刷性能不良、破损率高等现象。
只有在PO材料中加入抗静电剂才能有效解决上述问题。常用的抗静电剂根据所用的表面活性剂分为：阳离子、阴离子和非离子化合物及二性聚合物等，这些抗静电剂由于均系小分子量的化合物，虽有很好的抗静电效果，但会降低PO类塑料的热稳定性，且季胺盐类不符合FDA的规定，这些产品均为液体或低软化点的腊状固体，直接加入PO塑料中因熔点、粘度相差大，加入中的分散、分布困难，严重时影响挤出产生波动，另外由小分子决定它的迁移必然性，及环境温、湿差造成抗静电效果的强、弱差异，使它的抗静电性持久性缩短。选用金属导电物质的加入，如碳黑、金属粉、碳纳米管等均会在透明性、成色选择、加工、成本等因素上受到制约。
发明内容
本发明所要解决的技术问题是克服上述现有技术存在的缺陷，提供一种抗紫外线抗静电聚烯烃母粒。
为此，本发明采用如下的技术方案：一种抗紫外线抗静电聚烯烃母粒，它由以下质量百分比的原料组成：聚烯烃40-60%，接枝聚烯烃10-20%，聚乙烯醇20-40%，复合抗氧剂1-10%和纳米级四极晶须氧化锌4-7%；
所述的聚烯烃为熔融指数在0.1～25的均聚或共聚聚烯烃吹膜、流延或双向拉伸树脂；所述的接枝聚烯烃为同前述聚烯烃树脂吻合的接枝物，接枝率为0.8-1.5%；所述的聚乙烯醇为经过增塑改性的聚乙烯醇造粒料，熔融指数≥5；所述的复合抗氧剂为带胺基基团的受阻酚、亚磷酸酯和受阻胺的复配物。
在获得PO/PVA共混材料较好柔韧性的同时会导致PO/PVA共混材料刚性的大幅下降。为解决此现象，本发明引入刚性纳米级四极晶须氧化锌增韧，其能在提高韧性的同时不降低材料的强度与刚性，经多次试验检测，合理确定了本发明的具有抗紫外线老化、抗静电双功能的聚烯烃母粒配方。本发明的聚烯烃母粒具有高效的抗静电、抗老化性能，可用于电子，电气、喷墨印刷等包装、装饰、广告等领域，特别适用于挤出大型广告覆膜。
本发明所述各组分的研究和效果分析如下：
聚烯烃类（PP、PE）材料牌号众多，需根据用途与不同成膜方式选择不同牌号。大型广告上进行覆膜，由于聚烯烃塑料不易消除静集聚，生产过程中薄膜自动卷曲、撕裂和吸尘等现象；编织布覆合时，静电作用会导致粘合困难，还有喷墨或印刷性能不良、破损率高等问题。若在材料中混入抗静电剂后，就可有效解决上述问题。
经过增塑改性的聚乙烯醇造粒料属于亲水性高分子材料，它吸取空气中的水分在薄膜表面形成水膜，从而形成表面导电通路。
鉴于PO属非性材料而PVA是强极性材料，二者相容性不好。为避免降低淋膜的力学性能，引入带极性基团的接技PO材料作增容剂，促使二相间产生亲和力，达到海岛相PVA有良好的分散、分布均匀性及较好的二相接合力。
纳米级四极晶须氧化锌为抗静电剂引入、分散在混合材料中的氧化锌晶须形成了网架结构，根据隧道效应理论，能为静电荷的泄漏提供一个连续通路，从而降低表面电阻率和体积电阻率，阻止电荷的积累，该抗电剂的加入解决了一般小分子抗静电剂随环境温度、湿度变化抗静电性能强弱明显变化，随存放时间延长逐渐衰减的重大缺陷。另一方面钠米晶须氧化锌作为一种无机填充物，以纳米尺寸分散在混合塑料基体中形成的纳米效应使材料具有高强度、耐热性、高阻隔性和优良的加工性能，并且纳米晶须氧化锌是优良的紫外线屏蔽剂，能够较强地吸收及散射导致高聚物老化的长波和中波紫外线，阻止它们透入高聚物内部，减少激发反应，达到屏蔽紫外线、防止材料本身老化的目的。
带胺基基团的受阻酚、受阻胺和亚磷酸酯复配组成的复合抗氧剂的加入是因为它们可以与PVA相容，以使混合材料在加工过程中有良好的热氧稳定性，避免热氧分解产生变色及降低力学性能。
选用亲水性PVA聚合物作为抗静电剂，它是高分子材料、不会泄出、不会喷霜，加入到聚烯烃树脂因已经过改性并加混了增容剂－接技PO，所以它已变成由亲水基和亲油基两部分组成，其亲油基与高聚物相结合，而亲水基则面向空气排列到塑料表面，形成了肉眼看不到的“水膜层”（空气温度所致），提供了电荷向空气中传导的一层通路；同时因水分的吸收，为材料内部提供了电离条件，从而达到防止和消除静电的目的，达到不吸尘、不卷曲、防撕裂、封口好、印刷性佳、防老化而延长寿命等效果。
作为对上述技术方案的进一步完善和补充，本发明采取以下技术措施：
所述的接枝聚烯烃为马来酸酐接枝聚烯烃或丙烯酸接枝聚烯烃。
所述的四极晶须氧化锌采用硅烷活性剂改性，粒径≤400nm。
所述的复合抗氧剂为抗氧剂1098和TNPP的复配物。
所述的聚烯烃为EVA、HDPE、LDPE、LLDPE、PP中的任一种或二种以上的混合物。
聚乙烯醇增塑改性所用的增塑剂为40-60％甘油、20-40％PEG和10-30％TMS0的复配物。
上述抗紫外线抗静电聚烯烃母粒的制备方法如下：基料聚烯烃、接枝聚烯烃、经过增塑改性的聚乙烯醇造粒料、四极晶须氧化锌、复合抗氧化剂在高速搅拌机混合均匀后，即可上双螺杆挤出机挤出拉条造粒成具有抗紫外抗静电的双功能的聚烃母粒。
本发明的双抗聚烃母粒经实际应用、测试，具有以下优点和有益效果：
1.本色透明，可以为所有颜色共混生产；2.在聚烯烃中添加该母粒，表面阻率UL94标准测试达到106～109Ω/cm2；3.添加该母料后的薄膜在紫外线光照射480H后的断裂伸长保持率可达92%以上；4.在聚烯烃树脂淋膜材料中添加量少，可在保证良好的抗静电、抗老化性和力学性能的前提下，延长使用寿命，降低原料成本。
具体实施方式
下面结合实施例，对本发明作进一步详细说明。
实施例1和2
以经增塑改性的PVA造粒料为通道效应抗静剂并增强聚烯烃薄膜的极性，利于底板粘接与喷墨或印刷油墨的粘接。以纳米级晶须氧化锌为隧道效应抗静剂兼具抗紫外线屏蔽剂功效，防止在空气干燥情况下抗静电效果的丧失同时阻止了光老化反应的发生。
实施例1和2的配比（重量%）
原料名称 配比1 配比2
LDPE 45 /
HDPE / 45
接枝PO 6 8
PVA改性料 29 26
硅烷改性晶须ZnO 17 18
复合抗氧剂 3 2
上表中，实施例1中的复合抗氧剂由30%抗氧剂1098和70%的TNPP复配而成；实施例2中的复合抗氧剂由50%抗氧剂1098和50%的TNPP复配而成。实施例1中的PVA改性料改性所用的复合增塑剂为50％甘油、30％PEG和20％TMS0的复配物；实施例2中的PVA改性料改性所用的复合增塑剂为40％甘油、40％PEG和30％TMS0的复配物。
将配方中原料在高混机中混合5分钟出料，上双螺杆挤出机挤出造粒，挤出温度为200℃，螺杆转速为250转/分，得到抗紫外线抗静电聚烯烃母粒。
实施例1和实施例2所制得母粒在PP树脂应用中性能对比，按以下方式制得样品。
样品1，配比1：制得的母粒5%，PP树脂95%。
样品2，配比2：制得的母粒10%，PP树脂90%。
测试方法（1）薄膜材料经紫外光照射480h后断裂伸长的保持率；（2）按GB1410标准测试表面电阻率。
样品1和样品2性能对照表

Claims (5)

1.一种抗紫外线抗静电聚烯烃母粒，它由以下质量百分比的原料组成：聚烯烃40-60%，接枝聚烯烃10-20%，聚乙烯醇20-40%，复合抗氧剂1-10%和纳米级四极晶须氧化锌4-7%；
所述的聚烯烃为熔融指数在0.1～25的均聚或共聚聚烯烃吹膜、流延或双向拉伸树脂；所述的接枝聚烯烃为同前述聚烯烃树脂吻合的接枝物，接枝率为0.8-1.5%；所述的聚乙烯醇为经过增塑改性的聚乙烯醇造粒料，熔融指数≥5；所述的复合抗氧剂为抗氧剂1098和TNPP的复配物。
2.根据权利要求1所述的抗紫外线抗静电聚烯烃母粒，其特征在于，所述的接枝聚烯烃为马来酸酐接枝聚烯烃或丙烯酸接枝聚烯烃。
3.根据权利要求1或2所述的抗紫外线抗静电聚烯烃母粒，其特征在于，所述的四极晶须氧化锌采用硅烷活性剂改性，粒径≤400nm。
4.根据权利要求1或2所述的抗紫外线抗静电聚烯烃母粒，其特征在于，所述的聚烯烃为EVA、HDPE、LDPE、LLDPE、PP中的任一种或二种以上的混合物。
5.根据权利要求1或2所述的抗紫外线抗静电聚烯烃母粒，其特征在于，聚乙烯醇增塑改性所用的增塑剂为40-60％甘油、20-40％PEG和10-30％TMSO的复配物。
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