CN115257103A - 一种抗菌防雾bopp膜及其制备方法 - Google Patents
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Abstract
本发明涉及一种抗菌防雾BOPP膜,包括上表层、下表层和芯层的三层结构;上表层、下表层包含共聚聚丙烯、抗粘连剂、表层抗菌防雾剂;芯层包含均聚聚丙烯、芯层防雾剂;表层抗菌防雾剂包括共聚聚丙烯、改性锌离子和纳米氧化锌、单硬脂酸甘油酯、N‑N‑二(2羟基乙基)碳12‑碳18烷基氨基、聚乙二醇,二氧化碳基四元醇,抗氧化剂BHT;芯层防雾剂包括共聚聚丙烯、单硬脂酸甘油酯、N‑N‑二(2羟基乙基)碳12‑碳18烷基氨基、聚乙二醇、二氧化碳基二元醇。本发明制备得到的抗菌防雾BOPP膜具有高的防雾功能和抗菌效果。
Description
技术领域
本发明涉及一种抗菌防雾BOPP膜及其制备方法,属于薄膜制备技术领域。
背景技术
随着人们生活水平提高,存放于冰箱冷柜内的食用菌类产品、蔬菜水果、面包糕点越来越多。由于生鲜商品本身含水量较大,在储运及销售过程中温度会出现较大温差,在常规的复合袋中内层会产生一层不透明的水雾,导致用户看不清袋内的商品。且袋内的商品接触水雾后又易变质腐败,缩短了生鲜商品的保质期和上架期。一种抗菌防雾BOPP膜可以解决以上问题。
CN109094159B公开了一种防雾抗菌BOPP薄膜及其制备方法,其依次由上表层、芯层、下表层经双向拉伸制得,所述上表层为防雾层,其由以下组分按重量份组成:防雾母料3-4份、有机抗粘剂2-3份、热封料93-95份;所述芯层为均聚聚丙烯;所述下表层为防雾抗菌层,其是由以下组分按重量份组成:抗菌母料1-2份、有机抗粘剂2-3份、防雾母料4-5份、热封料90-93份。该发明可在双向拉伸生产线直接共挤产出防雾抗菌BOPP薄膜,相比传统涂布防雾抗菌薄膜,可省去涂布机的投入,同时避免后期涂布造成的污染及能耗损失。但是市场上类似的产品实际防雾能力并不是特别显著,特别是在忽冷忽热的潮气重的环境下,使用效果不佳。
发明内容
本发明的目的是为了解决上述背景问题中提出的问题,提供一种抗菌防雾BOPP膜及其制备方法,制备得到的抗菌防雾BOPP膜具有高的防雾功能和抗菌效果。
本发明的目的是这样实现的:
一种抗菌防雾BOPP膜,包括上表层、下表层和芯层的三层结构;上表层、下表层包含91-98质量份的共聚聚丙烯、1-5质量份的抗粘连剂、1-4份的表层抗菌防雾剂;芯层包含95-99.5质量份的均聚聚丙烯、0.5-5质量份的芯层防雾剂;所述的表层抗菌防雾剂包括70-90.5质量份的共聚聚丙烯、6-15质量份改性锌离子和纳米氧化锌、1.5-7质量份单硬脂酸甘油酯、1.5-7质量份N-N-二(2羟基乙基)碳12-碳18烷基氨基、0.5-1质量份聚乙二醇,1-5质量份的二氧化碳基四元醇,0.05-0.15质量份抗氧化剂BHT;所述的芯层防雾剂包括35-79质量份的共聚聚丙烯、10-30质量份单硬脂酸甘油酯、10-30质量份N-N-二(2羟基乙基)碳12-碳18烷基氨基、1-5质量份聚乙二醇、1-5质量份的二氧化碳基二元醇。
进一步地,所述抗粘连剂为以PP均聚物为载体含量为5w%的粒径为4-7μm的二氧化硅。
进一步地,所述三层结构中上表层厚度为0.9-1.1μm,芯层厚度为18-30μm,下表层厚度为0.9-1.1μm。
进一步地,所述二氧化碳基二元醇的碳酸酯单元含量为45-75%,Mn=1500-5000Da;所述二氧化碳基四元醇的碳酸酯单元含量为45-75%,Mn=1500-5000Da。
一种抗菌防雾BOPP膜的制备方法,包括以下步骤:
(1)熔融塑化,制备三层共挤厚片,通过挤出机模头挤出激冷成型;所述三层共挤厚片各层中各组份的配比为:上表层、下表层包含91-98质量份的共聚聚丙烯、1-5质量份的抗粘连剂、1-4份的表层抗菌防雾剂,芯层包含95-99.5质量份的均聚聚丙烯、0.5-5质量份的芯层防雾剂;(2)双向拉伸 :将三层共挤厚片后经过纵向拉伸与横向拉伸;(3)牵引,电晕处理后收卷。
进一步地,所述熔融塑化温度为225-245℃。
进一步地,所述纵向拉伸比为4.50-5.50,横向拉伸比为8.0-10.0 。
进一步地,所述纵向拉伸过程中,预热温度为120-130℃,拉伸温度为110-125℃,定型温度为125-135℃;横向拉伸过程,预热温度为165-175℃,拉伸温度为150-160℃,定型温度为163-167℃。
生鲜食品在冷冻或者加工的过程中因为温差较大而产生冷雾或热雾,防雾机理就是加入薄膜芯层的防雾母料,因电晕处理的作用迁移到薄膜的表面,其中亲水基团因子对水进行亲和吸附、并降低水的表面张力,减小水分子与薄膜表面的接触角,使水汽还没有在薄膜表面集聚成细小水珠之前,就会润湿、扩散或者吸附于薄膜表面,形成一层超薄的透明亲水膜,并且不再对入射光线产生散射的作用,不干扰人的视线,从而达到防雾目的。
同时,薄膜表面含有改性锌离子和纳米氧化锌的抗菌剂,通过抗菌剂中的有效离子对细菌内蛋白质进行干扰破坏,可对大肠杆菌、金黄色葡萄球菌、白色念珠菌等各类致病菌进行高效广谱的抑制和杀灭。
要达到良好的防雾效果、起效快且要兼顾成本,本发明的技术方案:1、防雾分层添加,短效与长效兼顾。在两个表层采取加入抗菌剂和小比例防雾剂的复配方式,在芯层加入较大比例的防雾剂。表层防雾剂能使产品较快起效,而芯层的防雾剂通过电晕处理后亲水集团迁移到表面后,达到长效防雾的效果。2、抗菌剂只在表层加入,保证良好抗菌性能。3、采用双面电晕处理,使两个表面产生极性,使得两个表面都达到良好防雾。并且电晕功率比平常设定值低30%。
抗菌剂的选取,既要达到良好的抗菌效果,产品的雾度还要较低(保证视觉效果),且要保证薄膜耐高温不发黄。本发明选取了纳米锌离子体系抗氧剂,载体选用粒径较小的,从而不影响雾度性能。造粒时用耐热型抗氧剂,保证拉膜过程薄膜不发黄。
本发明的制备方法工艺中,为达到纵向拉伸环节厚片不粘辊,双面热封膜需要采用较低的加工工艺温度(预热温度为120-130℃,拉伸温度为110-120℃,定型温度为125-130℃,拉伸温度尽量在熔点下),生产速度需要降低20%,已达到充分加热。同时为了保证厚度,横拉的温度要适当提高,预热温度为165-175℃,拉伸温度为150-160℃,定型温度为163-167℃。保证生产稳定。2、双面电晕因薄膜两面都有极性,大卷收卷过紧卷底容易粘连。为解决该问题,一方面电晕功率要降低30%;另一方面要调节收卷张力,辊底1-3张力柱降低50N-20N,使大卷底部有合适的空气含量,促进母料的迁移。
所述的二氧化碳基二元醇采用二氧化碳、环氧丙烷、二元醇,在催化剂作用下,通过常规方法制备得到,其碳酸酯单元的含量为45-75%,Mn=1500-5000Da,为常规市售产品。二氧化碳基四元醇采用和二元醇类似的方法,只是二元醇替换为四元醇。
本发明使用的二氧化碳基多元醇,可以提高了与低极性的聚丙烯材料的结合力,制备过程中制备得到的产品表面更加光滑平整,能够大幅减少水雾的挂壁。在表层添加二氧化碳基四元醇,而在芯层添加二元醇,可以更好的结合多层结构,同时可以促进迁移的效果。
本发明在表层中添加抗氧化剂BHT,也可以一定程度上提高抗菌性和防雾效果。
具体实施方式
下面结合实施例对本发明作进一步说明。
二氧化碳基二元醇和二氧化碳基四元醇为定制产品,采用二氧化碳、环氧丙烷、二元醇和四元醇,在催化剂作用下,通过常规方法制备得到,两者碳酸酯单元的含量为45-75%,Mn=1500-5000Da。其余原料均为市售常规原料。
实施例1
1)厚片制备
在两个表层配置挤出机,加入上、下表层包含94质量份的共聚聚丙烯、2质量份的抗粘连剂、4份的表层抗菌防雾剂;芯层配置挤出机加入芯层包含97.5质量份的均聚聚丙烯、2.5质量份的芯层防雾剂,分别通过熔融塑化,制得熔融状态下的PP熔体,经过模头分配器与芯层汇合,经衣架型模头流出,挤出厚片,熔融挤出温度在230度,铸片。铸片系统,冷却水温在22.5度,冷辊温度在25度。
2)纵向拉伸和横向拉伸
其中所述纵向拉伸比为5,横向拉伸比为9 ,纵向拉伸过程中,预热温度为125℃,拉伸温度为120℃,定型温度为130℃;横向拉伸过程,预热温度为170℃,拉伸温度为155℃,定型温度为165℃。
3)电晕处理及收卷。
采取双面电晕处理,主面电晕功率为130kw,次面电晕功率为60kw。
所述的表层抗菌防雾剂包括80质量份的共聚聚丙烯、10质量份改性锌离子和纳米氧化锌、4质量份单硬脂酸甘油酯、4质量份N-N-二(2羟基乙基)碳12-碳18烷基氨基、0.75质量份聚乙二醇,3质量份的二氧化碳基四元醇,0.1质量份抗氧化剂BHT;所述的芯层防雾剂包括50质量份的共聚聚丙烯、20质量份单硬脂酸甘油酯、20质量份N-N-二(2羟基乙基)碳12-碳18烷基氨基、3质量份聚乙二醇、3质量份的二氧化碳基二元醇。
所述抗粘连剂为以PP均聚物为载体含量为5w%的粒径为4-7μm的二氧化硅。所述三层结构中上表层厚度为1μm,芯层厚度为24μm,下表层厚度为1μm。所述二氧化碳基二元醇的碳酸酯单元含量为55%,Mn=3000Da;所述二氧化碳基四元醇的碳酸酯单元含量为55%,Mn=4000Da。
实施例2:按实施例1的制备方法制备,表层抗菌防雾剂为质量份1,芯层防雾剂为质量份5。
实施例3:按实施例1的制备方法制备,表层抗菌防雾剂为质量份4,芯层防雾剂为质量份0.5。
对比例1:按实施例1的制备方法制备,除了各表层不加抗菌防雾剂。
对比例2:按实施例1的制备方法制备,除了表层不添加二氧化碳基四元醇,芯层不添加二氧化碳基二元醇。
对比例3:按实施例1的制备方法制备,除了表层不添加二氧化碳基四元醇。
对比例4:按实施例1的制备方法制备,除了表层不添加二氧化碳基二元醇。
对比例5:按实施例1的制备方法制备,除了表层不添加抗氧化剂。
对比试验条件与结果见附表。
性能测试:按照GB/T31026-2015 塑料薄膜防雾性试验方法 检测防雾性能,按照GB/T 31402-2015塑料表面抗菌性能试验方法 测试抗菌性能。
表1:实施例1-3和对比例1-5的性能测试结果
实施例1 | 实施例2 | 实施例3 | 对比例1 | 对比例2 | 对比例3 | 对比例4 | 对比例5 | |
抗菌率 | ≥99.9 | ≥99.9 | ≥99.9 | 17.2 | ≥99.9 | ≥99.9 | ≥99.9 | 65.8 |
防雾 | Ⅰ | Ⅰ | Ⅱ | Ⅲ | Ⅳ | Ⅲ | Ⅲ | Ⅱ |
雾度% | 1.35 | 1.37 | 1.36 | 1.25 | 1.45 | 1.58 | 1.62 | 1.98 |
以上描述仅为本申请的较佳实施例以及对所运用技术原理的说明。本领域技术人员应当理解,本申请中所涉及的发明范围,并不限于上述技术特征的特定组合而成的技术方案,同时也应涵盖在不脱离所述发明构思的情况下,由上述技术特征或其等同特征进行任意组合而形成的其它技术方案。例如上述特征与本申请中公开的(但不限于)具有类似功能的技术特征进行互相替换而形成的技术方案。
Claims (8)
1.一种抗菌防雾BOPP膜,其特征在于,包括上表层、下表层和芯层的三层结构;上表层、下表层包含91-98质量份的共聚聚丙烯、1-5质量份的抗粘连剂、1-4份的表层抗菌防雾剂;芯层包含95-99.5质量份的均聚聚丙烯、0.5-5质量份的芯层防雾剂;所述的表层抗菌防雾剂包括70-90.5质量份的共聚聚丙烯、6-15质量份改性锌离子和纳米氧化锌、1.5-7质量份单硬脂酸甘油酯、1.5-7质量份N-N-二(2羟基乙基)碳12-碳18烷基氨基、0.5-1质量份聚乙二醇,1-5质量份的二氧化碳基四元醇,0.05-0.15质量份抗氧化剂BHT;所述的芯层防雾剂包括35-79质量份的共聚聚丙烯、10-30质量份单硬脂酸甘油酯、10-30质量份N-N-二(2羟基乙基)碳12-碳18烷基氨基、1-5质量份聚乙二醇、1-5质量份的二氧化碳基二元醇。
2.根据权利要求1所述的一种抗菌防雾BOPP膜,其特征在于,所述抗粘连剂为以PP均聚物为载体含量为5w%的粒径为4-7μm的二氧化硅。
3.根据权利要求1所述的一种抗菌防雾BOPP膜,其特征在于,所述三层结构中上表层厚度为0.9-1.1μm,芯层厚度为18-30μm,下表层厚度为0.9-1.1μm。
4.根据权利要求1所述的一种抗菌防雾BOPP膜,其特征在于,所述二氧化碳基二元醇的碳酸酯单元含量为45-75%,Mn=1500-5000Da;所述二氧化碳基四元醇的碳酸酯单元含量为45-75%,Mn=1500-5000Da。
5.根据权利要求1至4任一项所述的一种抗菌防雾BOPP膜的制备方法,其特征在于包括以下步骤:
(1)熔融塑化,制备三层共挤厚片,通过挤出机模头挤出激冷成型;所述三层共挤厚片各层中各组份的配比为:上表层、下表层包含91-98质量份的共聚聚丙烯、1-5质量份的抗粘连剂、1-4份的表层抗菌防雾剂,芯层包含95-99.5质量份的均聚聚丙烯、0.5-5质量份的芯层防雾剂;(2)双向拉伸 :将三层共挤厚片后经过纵向拉伸与横向拉伸;(3)牵引,电晕处理后收卷。
6.根据权利要求5所述的一种抗菌防雾BOPP膜的制备方法,其特征在于,所述熔融塑化温度为225-245℃。
7.根据权利要求5所述的一种抗菌防雾BOPP膜的制备方法,其特征在于,其中,所述纵向拉伸比为4.50-5.50,横向拉伸比为8.0-10.0 。
8.根据权利要求5所述的一种抗菌防雾BOPP膜的制备方法,其特征在于,所述纵向拉伸过程中,预热温度为120-130℃,拉伸温度为110-125℃,定型温度为125-135℃;横向拉伸过程,预热温度为165-175℃,拉伸温度为150-160℃,定型温度为163-167℃。
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