CN107652884A - 一种抗菌环保薄膜及其制备方法 - Google Patents

一种抗菌环保薄膜及其制备方法 Download PDF

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CN107652884A
CN107652884A CN201710969085.8A CN201710969085A CN107652884A CN 107652884 A CN107652884 A CN 107652884A CN 201710969085 A CN201710969085 A CN 201710969085A CN 107652884 A CN107652884 A CN 107652884A
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张佳斌
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Ningbo Hi Tech Zone Xia Yuan Technology Co Ltd
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Abstract

本发明公开了一种抗菌环保薄膜及其制备方法，所述抗菌环保膜由内及外依次是PET层、抗菌层、PE层、杀菌凃层，其中，所述抗菌层是由聚乳酸、丙烯酸羟丙酯、丙烯酰氯、三氟丙基甲基二氯硅烷、乙烯基三异丙氧基硅烷、羟丙基甲基纤维素、壳聚糖、丁香酚、聚乙烯醇、乳化剂、引发剂和去离子水配制而成的，所述杀菌涂层是由乙醇、聚乙二醇、去离子水、肉桂醛、β‑环糊精、钛酸酯偶联剂、纳米二氧化钛、有机硅树脂、分散剂和消泡剂制备而成的。本发明所制备的抗菌环保薄膜具有更好的杀菌杀毒效果，耐用性好，使用寿命长，对环境无污染等优点。

Description

一种抗菌环保薄膜及其制备方法
本申请为分案申请，原案专利号为：201610264755.1，申请日为2016年04月22日，发明名称为：一种抗菌环保薄膜及其制备方法。
技术领域
本发明属于薄膜技术领域，特别是涉及一种抗菌环保薄膜及其制备方法。
背景技术
随着科技进步及现代工业的迅猛发展，环境问题日趋严重。随着人们更加关注健康和对环保意识的逐渐提高，对建筑玻璃膜的抗菌、净化空气的需求日益迫切。现有的无机金属抗菌涂料虽然具有抗菌性能，如以纳米银作为杀菌成分，但抗菌时间短，易发生氧化而失，且很容易染灰尘，易吸水变质，硬度低容易损坏，易于脱落，且环保性能较差。传统杀菌剂中通常具有有毒物质，涂覆后会产生甲醛这种致癌物质。
发明内容
为了克服现有技术中存在的不足，本发明公开了一种抗菌环保薄膜及其制备方法，旨在提供一种即可抗菌又对环境无污染的薄膜材料。
本发明是通过如下技术实现的：
一种抗菌环保膜，所述抗菌环保膜由内及外依次是PET层、抗菌层、PE层、杀菌凃层。
作为对本发明的进一步改进，所述抗菌层的厚度不小于PET层与PE层的厚度之和，所述杀菌涂层的厚度不小于抗菌层的厚度，通过对PET层、抗菌层、PE层、杀菌凃层叠覆顺序及各层厚度关系的设计，进一步保证抗菌环保薄膜的抗菌性能。
作为一种优选实施方式，所述抗菌层所用的涂料是由如下重量份的原料配制而成的：
较佳地，所述乳化剂优选为三苯乙基酚聚氧乙烯醚，所述引发剂优选为硫酸钾。
所述的聚乳酸具有良好的机械性质和物理性质。聚乳酸适用于吹塑、热塑等各种加工方法，应用十分广泛，也拥有良好的光泽度和透明度，聚乳酸薄膜具有良好的透气性、透氧性及透二氧化碳性，它也具有隔离气味的特性。病毒及霉菌易依附在生物可降解膜的表面，故有安全及卫生的疑虑，然而，聚乳酸是唯一具有优良抑菌及抗霉特性的生物可降解膜。
所述的壳聚糖来自于甲壳素，它是一种植物抗毒素，具有天然抗菌性，可抑制多种食品表面的真菌、细菌。
所述的丙烯酰氯，不仅增强了抗菌层的耐热性，同时丙烯酰氯可以和壳聚糖进行交联作用，增强壳聚糖的杀菌作用。
所述的醋酸可以很好的溶解壳聚糖将壳聚糖溶解到聚合物中，优选浓度为0.1mol/L。
所述的丁香酚是丁香油的主要成分，主要功效就是抗菌杀毒。
所述的聚乙烯醇可以使壳聚糖和甲基丁香酚在聚乳酸中的接枝效率提高，通过甲基丁香酚和壳聚糖的协同作用，提高抗菌杀毒的效果。
所述的三氟丙基甲基二氯硅烷提高了抗菌层的耐热性。
作为对本发明的进一步改进，所述抗菌剂层所用的涂料是通过如下方法制备而成的：
(1)预乳液制备
将相应重量份的聚乳酸、丙烯酸羟丙酯、乳化剂、引发剂、三氟丙基甲基二氯硅烷、乙烯基三异丙氧基硅烷、聚乙烯醇与1/2-3/4重量份的去离子水混合，预乳化得到预乳液；
(2)乳液聚合
将相应重量份的羟丙基甲基纤维素、壳聚糖、醋酸(0.1M)、丁香酚及剩余的去离子水加入到反应器中，将反应器中的物料在300-400r/min条件下搅拌升温至75-85℃，再将上述步骤(1)制得的预乳液滴加到所述反应器中，1-2h滴完，滴完之后保持温度反应1-2h，然后升温至85-90℃，继续保温反应1h，降至室温、出料、过滤，得到抗菌层涂料。
作为一种优选实施方式，所述杀菌涂层所用的涂料是由如下重量份的原料制备而成的：
较佳地，所述分散剂为柠檬酸钠，所述消泡剂为有机硅高效消泡剂，由多种改性聚二甲基硅氧烷与其它高效消泡组分精制而成的高效改性有机硅高效消泡剂，来自德丰消泡剂厂。
所述的肉桂醇又名3-苯基丙烯醛，肉桂醛作为食品防霉剂对人体无毒或低毒，而对微生物的生长繁殖能起到较强的抑制作用，对黄曲霉、黑曲霉、橘青霉、串珠镰刀菌、白地霉、酵母等均有强烈的抑菌效果。
所述的纳米二氧化钛对光有催化作用，可以降解一部分的微生物。
所述杀菌涂层所用的涂料是通过如下方法制备而成的：
(1)将相应重量份的乙醇、聚乙二醇、柠檬酸钠加入到去离子水中，再加入相应重量份的肉桂醛、纳米二氧化钛、β-环糊精，在300-500rpm条件下分散10-30min，然后逐滴滴加钛酸酯偶联剂，继续在300-500rpm条件下反应30min后，再用球磨机研磨20-30min，制成浆料；
(2)向上述步骤(1)所得的浆料中加相应重量份的有机硅树脂，在800rpm条件下继续分散20-30min后，加入消泡剂，继续分散20-30min后得到抗菌涂层所用的涂料。
与现有技术相比，本发明制备的薄膜具有更好的杀菌杀毒效果，且对环境无污染，耐用性更好好，使用寿命更长。
具体实施方式
为了使本技术领域人员更好地理解本发明的技术方案，并使本发明的上述特征、目的及优点更加清晰易懂，现结合实施例对本发明做进一步解释说明，应当指出的是，在此列出的所有实施例仅仅是说明性的，并不意味着对本发明范围进行限定。
实施例1
一种抗菌环保膜，所述抗菌环保膜由内及外依次是PET层、抗菌层、PE层、杀菌凃层，其中，PET层与PE层的厚度均为25μm，杀菌涂层与抗菌层的厚度均为50μm。
所述抗菌层所用的涂料是由如下重量份的原料配制而成的：
所述抗菌剂层所用的涂料是通过如下方法制备而成的：
(1)预乳液制备
将相应重量份的聚乳酸、丙烯酸羟丙酯、乳化剂、引发剂、三氟丙基甲基二氯硅烷、乙烯基三异丙氧基硅烷、聚乙烯醇与1/2重量份的去离子水混合，预乳化得到预乳液；
(2)乳液聚合
将相应重量份的羟丙基甲基纤维素、壳聚糖、醋酸(0.1M)、丁香酚及剩余的去离子水加入到反应器中，将反应器中的物料在300r/min条件下搅拌升温至75℃，再将上述步骤(1)制得的预乳液滴加到所述反应器中，1h滴完，滴完之后保持温度反应2h，然后升温至85℃，继续保温反应1h，降至室温、出料、过滤，得到抗菌层涂料。
所述杀菌涂层所用的涂料是由如下重量份的原料制备而成的：
所述杀菌涂层所用的涂料是通过如下方法制备而成的：
(1)将相应重量份的乙醇、聚乙二醇、柠檬酸钠加入到去离子水中，再加入相应重量份的肉桂醛、纳米二氧化钛、β-环糊精，在500rpm条件下分散10min，然后逐滴滴加钛酸酯偶联剂，继续在500rpm条件下反应30min后，再用球磨机研磨20min，制成浆料；
(2)向上述步骤(1)所得的浆料中加相应重量份的有机硅树脂，在800rpm条件下继续分散20min后，加入消泡剂，继续分散30min后得到抗菌涂层所用的涂料。
实施例2
一种抗菌环保膜，所述抗菌环保膜由内及外依次是PET层、抗菌层、PE层、杀菌凃层，其中，PET层的厚度为22μm，抗菌层厚度为50μm，PE层厚度为25μm、杀菌凃层厚度为53μm。
所述抗菌层所用的涂料是由如下重量份的原料配制而成的：
所述抗菌剂层所用的涂料是通过如下方法制备而成的：
(1)预乳液制备
将相应重量份的聚乳酸、丙烯酸羟丙酯、乳化剂、引发剂、三氟丙基甲基二氯硅烷、乙烯基三异丙氧基硅烷、聚乙烯醇与3/4重量份的去离子水混合，预乳化得到预乳液；
(2)乳液聚合
将相应重量份的羟丙基甲基纤维素、壳聚糖、醋酸(0.1M)、丁香酚及剩余的去离子水加入到反应器中，将反应器中的物料在400r/min条件下搅拌升温至85℃，再将上述步骤(1)制得的预乳液滴加到所述反应器中，2h滴完，滴完之后保持温度反应1h，然后升温至90℃，继续保温反应1h，降至室温、出料、过滤，得到抗菌层涂料。
所述杀菌涂层所用的涂料是由如下重量份的原料制备而成的：
所述杀菌涂层所用的涂料是通过如下方法制备而成的：
(1)将相应重量份的乙醇、聚乙二醇、柠檬酸钠加入到去离子水中，再加入相应重量份的肉桂醛、纳米二氧化钛、β-环糊精，在300rpm条件下分散30min，然后逐滴滴加钛酸酯偶联剂，继续在300rpm条件下反应30min后，再用球磨机研磨30min，制成浆料；
(2)向上述步骤(1)所得的浆料中加相应重量份的有机硅树脂，在800rpm条件下继续分散30min后，加入消泡剂，继续分散20min后得到抗菌涂层所用的涂料。
实施例3
一种抗菌环保膜，所述抗菌环保膜由内及外依次是PET层、抗菌层、PE层、杀菌凃层，其中，PET层的厚度为30μm，抗菌层厚度为55μm，PE层厚度为24μm、杀菌凃层厚度为60μm。。
所述抗菌层所用的涂料是由如下重量份的原料配制而成的：
所述抗菌剂层所用的涂料是通过如下方法制备而成的：
(1)预乳液制备
将相应重量份的聚乳酸、丙烯酸羟丙酯、乳化剂、引发剂、三氟丙基甲基二氯硅烷、乙烯基三异丙氧基硅烷、聚乙烯醇与3/5重量份的去离子水混合，预乳化得到预乳液；
(2)乳液聚合
将相应重量份的羟丙基甲基纤维素、壳聚糖、醋酸(0.1M)、丁香酚及剩余的去离子水加入到反应器中，将反应器中的物料在350r/min条件下搅拌升温至80℃，再将上述步骤(1)制得的预乳液滴加到所述反应器中，1.5h滴完，滴完之后保持温度反应1.5h，然后升温至87℃，继续保温反应1h，降至室温、出料、过滤，得到抗菌层涂料。
所述杀菌涂层所用的涂料是由如下重量份的原料制备而成的：
所述杀菌涂层所用的涂料是通过如下方法制备而成的：
(1)将相应重量份的乙醇、聚乙二醇、柠檬酸钠加入到去离子水中，再加入相应重量份的肉桂醛、纳米二氧化钛、β-环糊精，在400rpm条件下分散20min，然后逐滴滴加钛酸酯偶联剂，继续在400rpm条件下反应30min后，再用球磨机研磨25min，制成浆料；
(2)向上述步骤(1)所得的浆料中加相应重量份的有机硅树脂，在800rpm条件下继续分散23min后，加入消泡剂，继续分散26min后得到抗菌涂层所用的涂料。
所获得的样品依据JIS Z2801:2000标准进行抗菌检测，其金黄色葡萄球菌抗菌率为99.9％。

Claims (5)

1.一种抗菌环保膜，其特征在于：所述抗菌环保膜由内及外依次是PET层、抗菌层、PE层、杀菌凃层，所述抗菌层的厚度不小于PET层与PE层的厚度之和，所述杀菌涂层的厚度不小于抗菌层的厚度，所述抗菌层所用的涂料是由如下重量份的原料配制而成的：
其中，所用醋酸的浓度为0.1mol/L，
所述乳化剂为三苯乙基酚聚氧乙烯醚，所述引发剂为硫酸钾，所述抗菌层所用的涂料是通过如下方法制备而成的：
(1)预乳液制备
将相应重量份的聚乳酸、丙烯酸羟丙酯、乳化剂、引发剂、三氟丙基甲基二氯硅烷、乙烯基三异丙氧基硅烷、聚乙烯醇与1/2-3/4重量份的去离子水混合，预乳化得到预乳液；
(2)乳液聚合
将相应重量份的羟丙基甲基纤维素、壳聚糖、醋酸(0.1M)、丁香酚及剩余的去离子水加入到反应器中，将反应器中的物料在300-400r/min条件下搅拌升温至75-85℃，再将上述步骤(1)制得的预乳液滴加到所述反应器中，1-2h滴完，滴完之后保持温度反应1-2h，然后升温至85-90℃，继续保温反应1h，降至室温、出料、过滤，得到抗菌层涂料。
2.如权利要求1所述的抗菌环保膜，其特征在于：所述杀菌涂层所用的涂料是由如下重量份的原料制备而成的：
3.如权利要求2所述的抗菌环保膜，其特征在于：所述分散剂为柠檬酸钠。
4.如权利要求2所述的抗菌环保膜，其特征在于：所述消泡剂为有机硅高效消泡剂。
5.如权利要求2所述的抗菌环保膜，其特征在于：所述杀菌涂层所用的涂料是通过如下方法制备而成的：
(1)将相应重量份的乙醇、聚乙二醇、柠檬酸钠加入到去离子水中，再加入相应重量份的肉桂醛、纳米二氧化钛、β-环糊精，在300-500rpm条件下分散10-30min，然后逐滴滴加钛酸酯偶联剂，继续在300-500rpm条件下反应30min后，再用球磨机研磨20-30min，制成浆料；
(2)向上述步骤(1)所得的浆料中加相应重量份的有机硅树脂，在800rpm条件下继续分散20-30min后，加入消泡剂，继续分散20-30min后得到抗菌涂层所用的涂料。
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