CN113480791A - 一种聚烯烃高透薄膜的紫外阻隔母粒及制备方法 - Google Patents
一种聚烯烃高透薄膜的紫外阻隔母粒及制备方法 Download PDFInfo
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Abstract
本发明公开了一种聚烯烃高透薄膜的紫外阻隔母粒,以重量份计,包含以下原料:聚烯烃载体树脂65~82份、紫外光吸收剂A 6~12份、紫外光吸收剂B 4~8份、无机纳米粒子5~10份、加工助剂3~5份;本发明的紫外阻隔母粒添加到树脂中制备成聚烯烃高透薄膜之后,所得的聚烯烃薄膜制品阻隔率大于98%,透明性大于90%,具有宽幅的紫外线阻隔效果,高透光性,高耐候性,在紫外光照射3000h之后仍可保持良好的紫外阻隔性能;本发明制备的紫外阻隔母粒可直接添加到聚烯烃树脂中进行制品的制造。
Description
技术领域
本发明涉及高分子材料技术领域,具体是涉及一种聚烯烃高透薄膜的紫外阻隔母粒及制备方法。
背景技术
聚烯烃薄膜由于其良好的气密性以及韧性、质轻、透明等特点,被广泛应用于包装行业,尤其是食品包装、日用品以及工业品包装。在塑料包装行业中,高透的塑料薄膜包装能够更好的展现内在商品的完好程度,但同时普通的高透塑料薄膜在使用过程中,容易使得内在商品受到紫外光的辐射而损坏,缩短商品的使用寿命。因此包装用薄膜通常需要添加紫外光吸收剂或者是紫外光屏蔽剂来实现薄膜的紫外阻隔效果,从而对商品进行保护。
紫外光吸收剂能够有效的吸收紫外光,但由于紫外光吸收剂结构的不同,特定的紫外光吸收剂只能吸收特定波长的紫外光,导致紫外光吸收剂的紫外吸收波长范围较短,无法对材料进行良好的紫外保护。三嗪类紫外光吸收剂由于其具有高效性、耐迁移性,常与受阻胺光稳定剂复配用于制品的耐候性能保护,例如,申请公布号为CN106589514B的发明专利申请公开了一种三嗪类紫外光吸收剂与受阻胺光稳定剂复配母粒的制备方法,该母粒在酸性条件下也具有良好的防老化效果。申请号为CN106977811A的发明专利申请公开了一种用于汽车内饰的聚丙烯母粒,将三嗪类紫外光吸收剂与两种受阻胺光稳定剂进行复配,具有低挥发性、高耐迁移性以及良好的耐候性能。但将三嗪类紫外光吸剂与其他紫外光吸收剂复配提高阻隔效果的专利目前还未发现。
紫外光屏蔽剂主要是无机纳米粒子,无机纳米粒子对紫外光的屏蔽作用最主要是通过对光的散射作用以及吸收光子的能量产生电子空穴对二者共同作用。当无机纳米粒子粒径远小于入射光波长时,会发生瑞利散射,瑞利散射对于短波长的光具有更强的散射作用。无机纳米粒子的电子结构是由充满电子的价态和没有电子的导带组成,禁带与导带之间的能带间隙称之为禁带,当入射光能量大于禁带宽度的时候,光子能够被吸收,价态上的电子将会发生跃迁到导带形成自由电子,而能量小于禁带宽度的光子则不能被吸收。无机纳米粒子具有持久的紫外光阻隔效果,能够作用较宽波长范围的紫外光。但在可见光波长范围内,无机纳米粒子也具有一定的散射作用,过多的添加无机纳米粒子会使薄膜的透光率下降,雾度大幅上升。
发明内容
本发明提供了一种聚烯烃高透薄膜的紫外阻隔母粒及制备方法,该紫外阻隔母粒所制备聚烯烃高透薄膜具有稳定的紫外阻隔性能以及对可见光的透明性、并具有持久的力学性能保护效果。
为实现上述目的,本发明采用的技术方案如下:
一种聚烯烃高透薄膜的紫外阻隔母粒,以重量份计,包含以下原料:聚烯烃载体树脂65~82份、紫外光吸收剂A 6~12份、紫外光吸收剂B 4~8份、无机纳米粒子5~10份、加工助剂3~5份。
优选的,聚烯烃载体树脂为聚乙烯树脂、聚丙烯树脂、聚氯乙烯树脂中的任意一种。
优选的,紫外光吸收剂A为三嗪类紫外光吸收剂;紫外光吸收剂B为苯并三唑类紫外光吸收剂、二苯甲酮类紫外光吸收剂、水杨酸酯类紫外光吸收剂中的任意一种。
优选的,紫外光吸收剂A为紫外光吸收剂UV-1164、紫外光吸收剂UV-1577、紫外光吸收剂UV-400、紫外光吸收剂UV-1600中的任意一种。
优选的,紫外光吸收剂B为紫外光吸收剂UV-326、紫外光吸收剂UV-328、紫外光吸收剂UV-329、紫外光吸收剂UV-234、紫外光吸收剂UV-360中的任意一种。
优选的,无机纳米粒子为纳米氧化锌、纳米氧化铈、纳米二氧化钛、纳米氧化锡锑、纳米蒙脱土、纳米滑石粉中的任意一种;无机纳米粒子的粒径为10~100nm。
优选的,无机纳米粒子为经过表面包覆处理过的无机纳米粒子,其中,表面包覆剂为硅烷偶联剂、硬脂酸、酞酸酯、二氧化硅中的任意一种。
优选的,加工助剂为硬脂酸钙、硬脂酸锌、EBS、PE蜡、氧化PE蜡、抗氧剂1010、抗氧剂168的任意一种或几种。
一种聚烯烃高透薄膜的紫外阻隔母粒的制备方法,步骤如下:
(1)按照上述原料组分及质量份数称取各原料;
(2)将称取的各原料加入至高混机中进行搅拌5min;
(3)将混合后的物料加入到双螺杆挤出机中,经熔融挤出,得到聚烯烃高透薄膜的紫外阻隔母粒。
由于采用了以上技术,本发明较现有技术相比,具有的有益效果如下:
(1)本发明公开的紫外阻隔母粒使用三嗪类紫外光吸收剂与另外一种紫外光吸收剂复配可长宽幅、持久的阻隔紫外光,再复配无机纳米粒子,可达高效的紫外阻隔作用;本发明的紫外阻隔母粒添加到树脂中制备成聚烯烃高透薄膜之后,初始薄膜的紫外阻隔率在98%以上,透光率90%以上,并且在紫外光照射3000h之后仍具有良好的紫外阻隔效果,同时具有良好的力学性能保护效果;
(2)本发明公开的紫外阻隔母粒只需将各种助剂与聚烯烃载体树脂混合均匀进行挤出造粒即可,制备工艺简单,成本较低。
附图说明
图1是实施例1中组2紫外阻隔母粒制备得到的聚烯烃高透薄膜的阻隔率图。
具体实施方式
下面结合附图和具体实施方式,进一步阐明本发明。
实施例1:
本实施例步骤如下:
(1)组1~4聚乙烯高透薄膜的紫外阻隔母粒原料配方如表1所示。
表1组1~4聚乙烯高透薄膜的紫外阻隔母粒原料配方(单位:重量份)
原料 | 组1 | 组2 | 组3 | 组4 |
聚乙烯树脂 | 82 | 77 | 72 | 67 |
三嗪类紫外光吸收剂 | 6 | 9 | 9 | 12 |
苯并三唑类紫外光吸收剂 | 4 | 6 | 6 | 8 |
无机纳米粒子 | 5 | 5 | 10 | 10 |
加工助剂 | 3 | 3 | 3 | 3 |
所用聚乙烯树脂的融指为10~20g/10min,密度为0.9~0.93g/cm3。
所用三嗪类紫外光吸收剂为紫外光吸收剂UV-1164。
所用苯并三唑类紫外光吸收剂为紫外光吸收剂UV-328。
所用无机纳米粒子为经过硅烷偶联剂包覆处理的纳米氧化锌。经过包覆处理后无机纳米粒子的粒径为30nm。
所用加工助剂为硬脂酸钙、EBS、抗氧剂1010、抗氧剂168的混合物。
(2)组1~4的一种聚乙烯高透薄膜的紫外阻隔母粒的制备方法,包含以下步骤:
S1.将聚乙烯树脂、紫外光吸收剂(三嗪类紫外光吸收剂、苯并三唑类紫外光吸收剂)、无机纳米粒子、加工助剂按重量份比进行称重,然后使用高混机搅拌5min左右,使其混合均匀、然后出料;
S2.将S1经高混机混合均匀的物料加入到双螺杆挤出机中,经熔融挤出,得到聚乙烯高透薄膜的紫外阻隔母粒。
上述组1~4母粒制备过程中,双螺杆挤出机挤出造粒工艺如表2所示。
表2组1~4母粒制备过程中挤出造粒工艺
实施例2:对比例1~3
对比例1~3阻隔母粒的制备方法与实施例1中组2的制备方法相同,其区别如表3所示。
表3对比例1~3阻隔母粒的原料配方(单位:重量份)
原料 | 对比例1 | 对比例2 | 对比例3 |
聚乙烯树脂 | 77 | 77 | 82 |
三嗪类紫外光吸收剂 | 15 | 9 | |
苯并三唑类紫外光吸收剂 | 15 | 6 | |
无机纳米粒子 | 5 | 5 | |
加工助剂 | 3 | 3 | 3 |
组1~4与对比例1~3的性能测试结果
将组1~4及对比例1~3按照1.5%的重量百分比添加量制备80μm厚的PE膜,参照GB/T 2410-2008、ASTM G154对初始以及紫外光老化3000h之后的薄膜性能进行测试,测试结果如表4、表5所示。
表4初始薄膜性能的测试结果
初始 | 组1 | 组2 | 组3 | 组4 | 对比例1 | 对比例2 | 对比例3 |
透光率 | 91.3% | 90.8% | 90.5% | 90.3% | 91.6% | 90.9% | 91.1% |
紫外阻隔率 | 98.1% | 98.7% | 99.2% | 99.9% | 87.2% | 82.2% | 89.7% |
表5紫外光老化3000h之后的薄膜性能的测试结果
3000h | 组1 | 组2 | 组3 | 组4 | 对比例1 | 对比例2 | 对比例3 |
透光率 | 89.0% | 88.6% | 88.4% | 88.1% | 87.5% | 87.1% | 87.3% |
紫外阻隔率 | 92.5% | 95.4% | 98.1% | 99.6% | 75.3% | 70.5% | 79.3% |
强度保留率 | 80.3% | 82.2% | 85.5% | 88.7% | 70.5% | 66.3% | 72.5% |
实施例3:
本实施例步骤如下:
(1)组5~8聚丙烯高透薄膜的紫外阻隔母粒原料配方如表6所示。
表6组5~8聚丙烯高透薄膜的紫外阻隔母粒原料配方(单位:重量份)
原料 | 组5 | 组6 | 组7 | 组8 |
聚丙烯树脂 | 82 | 77 | 72 | 67 |
三嗪类紫外光吸收剂 | 6 | 9 | 9 | 12 |
苯并三唑类紫外光吸收剂 | 4 | 6 | 6 | 8 |
无机纳米粒子 | 5 | 5 | 10 | 10 |
加工助剂 | 3 | 3 | 3 | 3 |
所用聚丙烯树脂的融指为8~15g/10min,密度为0.9~0.95g/cm3。
所用三嗪类紫外光吸收剂为紫外光吸收剂UV-1577。
所用苯并三唑类紫外光吸收剂为紫外光吸收剂UV-326。
所用无机纳米粒子为经过硬脂酸包覆处理的纳米氧化铈。经过包覆处理后无机纳米粒子的粒径为50nm。
所用加工助剂为硬脂酸钙、EBS、抗氧剂1010、抗氧剂168的混合物。
(2)上述组5~8的一种聚丙烯高透薄膜的紫外阻隔母粒的制备方法,其制备方法与实施例1中的制备方法相同;不同之处在于,组5~8母粒制备过程中,双螺杆挤出机挤出造粒工艺如表7所示。
表7组5~8母粒制备过程中挤出造粒工艺
实施例4:对比例4~6
对比例4~6阻隔母粒的制备方法与实施例3中组6的制备方法相同,其区别如表8所示。
表8对比例4~6阻隔母粒原料配方(单位:重量份)
原料 | 对比例4 | 对比例5 | 对比例6 |
聚丙烯树脂 | 77 | 77 | 82 |
三嗪类紫外光吸收剂 | 15 | 9 | |
苯并三唑类紫外光吸收剂 | 15 | 6 | |
无机纳米粒子 | 5 | 5 | |
加工助剂 | 3 | 3 | 3 |
组5~8与对比例4~6的性能测试结果
将组5~8与对比例4~6按照1.5%的重量百分比添加量制备80μm厚的PE膜,参照GB/T2410-2008、ASTM G154对初始以及紫外光老化3000h之后的薄膜性能进行测试,测试结果如表9、表10所示。
表9初始薄膜性能的测试结果
初始 | 组5 | 组6 | 组7 | 组8 | 对比例4 | 对比例5 | 对比例6 |
透光率 | 91.0% | 90.8% | 90.5% | 90.4% | 91.1% | 90.7% | 91.3% |
紫外阻隔率 | 98.3% | 98.5% | 98.9% | 99.8% | 84.3% | 81.8% | 90.6% |
表10紫外光老化3000h之后的薄膜性能的测试结果
3000h | 组5 | 组6 | 组7 | 组8 | 对比例4 | 对比例5 | 对比例6 |
透光率 | 89.3% | 88.7% | 88.5% | 88.4% | 86.9% | 86.7% | 87.2% |
紫外阻隔率 | 92.1% | 94.2% | 96.2% | 99.3% | 77.1% | 71.8% | 78.2% |
强度保留率 | 80.2% | 82.7% | 84.8% | 87.1% | 71.2% | 66.9% | 73.7% |
从表4、表5、表9、表10,组1~8以及对比例1~6可知本发明的紫外阻隔母粒所制聚烯烃高透薄膜具有极高的紫外阻隔效果、良好的透明性,阻隔率最高可达99.9%,且在紫外光老化3000h之后,紫外阻隔效果依然维持在90%以上,透明度下降程度较小,拉伸强度保留率在80%以上。
本发明实施例1中组2紫外阻隔母粒所制备聚烯烃高透薄膜样品的阻隔率图详见附图1,通过附图1可知该薄膜样品在280nm到380nm之间的紫外阻隔率为98.7%,透明性在90%以上。
本发明制备的紫外阻隔母粒可直接添加到聚烯烃树脂中进行制品的制造。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (10)
1.一种聚烯烃高透薄膜的紫外阻隔母粒,其特征在于,以重量份计,包含以下原料:聚烯烃载体树脂65~82份、紫外光吸收剂A 6~12份、紫外光吸收剂B 4~8份、无机纳米粒子5~10份、加工助剂3~5份。
2.根据权利要求1所述的一种聚烯烃高透薄膜的紫外阻隔母粒,其特征在于:聚烯烃载体树脂为聚乙烯树脂、聚丙烯树脂、聚氯乙烯树脂中的任意一种。
3.根据权利要求1所述的一种聚烯烃高透薄膜的紫外阻隔母粒,其特征在于:紫外光吸收剂A为三嗪类紫外光吸收剂;紫外光吸收剂B为苯并三唑类紫外光吸收剂、二苯甲酮类紫外光吸收剂、水杨酸酯类紫外光吸收剂中的任意一种。
4.根据权利要求3所述的一种聚烯烃高透薄膜的紫外阻隔母粒,其特征在于:紫外光吸收剂A为紫外光吸收剂UV-1164、紫外光吸收剂UV-1577、紫外光吸收剂UV-400、紫外光吸收剂UV-1600中的任意一种。
5.根据权利要求3述的一种聚烯烃高透薄膜的紫外阻隔母粒,其特征在于:紫外光吸收剂B为紫外光吸收剂UV-326、紫外光吸收剂UV-328、紫外光吸收剂UV-329、紫外光吸收剂UV-234、紫外光吸收剂UV-360中的任意一种。
6.根据权利要求1所述的一种聚烯烃高透薄膜的紫外阻隔母粒,其特征在于:无机纳米粒子为纳米氧化锌、纳米氧化铈、纳米二氧化钛、纳米氧化锡锑、纳米蒙脱土、纳米滑石粉中的任意一种。
7.根据权利要求6所述的一种聚烯烃高透薄膜的紫外阻隔母粒,其特征在于:无机纳米粒子的粒径为10~100nm。
8.根据权利要求6所述的一种聚烯烃高透薄膜的紫外阻隔母粒,其特征在于:无机纳米粒子为经过表面包覆处理过的无机纳米粒子,其中,表面包覆剂为硅烷偶联剂、硬脂酸、酞酸酯、二氧化硅中的任意一种。
9.根据权利要求1所述的一种聚烯烃高透薄膜的紫外阻隔母粒,其特征在于:加工助剂为硬脂酸钙、硬脂酸锌、EBS、PE蜡、氧化PE蜡、抗氧剂1010、抗氧剂168的任意一种或几种。
10.一种用于制备权利要求1-9中任一项所述的聚烯烃高透薄膜的紫外阻隔母粒的方法,其特征在于,步骤如下:
(1)按照上述原料组分及质量份数称取各原料;
(2)将称取的各原料加入至高混机中进行搅拌5min;
(3)将混合后的物料加入到双螺杆挤出机中,经熔融挤出,得到聚烯烃高透薄膜的紫外阻隔母粒。
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