CN105694285A - 无机纳米复合抗菌pvc手套液态母料及其制备方法 - Google Patents

无机纳米复合抗菌pvc手套液态母料及其制备方法 Download PDF

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CN105694285A
CN105694285A CN201610103655.0A CN201610103655A CN105694285A CN 105694285 A CN105694285 A CN 105694285A CN 201610103655 A CN201610103655 A CN 201610103655A CN 105694285 A CN105694285 A CN 105694285A
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nano
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plasticizer
liquid concentrate
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林道宏
廖道权
谢太和
赵良知
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Huizhou Hongsheng Plastic Product Co Ltd
Huizhou Huanmeisheng New Material Co Ltd
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Huizhou Huanmeisheng New Material Co Ltd
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Abstract

本发明公开了一种抗菌PVC乳胶手套用无机纳米复合抗菌母料及其制备方法，所述无机纳米复合抗菌母料包括增塑剂、无机纳米复合抗菌剂、分散剂、表面活性剂、增稠剂，所述无机纳米复合抗菌液态母料易分散，且具有广谱抗菌效果。将所制备的无机纳米复合抗菌液态母料直接添加到制备PVC乳胶手套的原液中，然后经过常规PVC乳胶手套的生产工艺制作即可制得抗菌效果高效的PVC抗菌手套。

Description

无机纳米复合抗菌PVC手套液态母料及其制备方法
技术领域
本发明涉及高分子材料领域，具体的，涉及一种无机纳米复合抗菌PVC手套液态母料及其制备方法。
背景技术
PVC手套广泛用于日常生活，具有卫生防护作用，使用方便，防护性能好，安全无毒，深受用户欢迎，产品在发达国家及地区拥有广阔的市场。
随着人们自我防护意识的增强，越来越多的人在医院，食品加工等场合使用手套，手套的应用保护了外界病毒、细菌对人的侵袭，但随着穿戴时间的增加，手部出汗量增多，穿的者的手表面容易滋生细菌、病菌、真菌，会对穿戴者的健康造成危害。而且在摘除手套、放置手套时，会产生二次污染、扩大感染范围等问题。抗菌PVC乳胶手套除了特有的防护功能以外，对穿戴者的手表面具有杀菌保健功能，而且可以防止造成二次污染。
抗菌PVC乳胶手套就是在PVC乳胶上添加一定量的抗菌剂，使得PVC手套产品具有抗菌效果。抗菌剂主要有有机抗菌剂、无机抗菌剂和天然抗菌剂三大类。无机抗菌剂具有耐热性好，不产生耐药性等优势，现有的无机抗菌剂以银离子抗菌剂效果最好，但银离子易被还原而变色，还原后抗菌效果显著降低，且价格较昂贵，并易在人体中蓄积对人体造成危害。
与以上几种抗菌材料相比，不含银离子的纳米无机复合抗菌剂具有如下优点：
1）比有机、天然抗菌剂具有更好的长效性和稳定性；
2）容易控制粒径及形貌；
3）可被人体降解，不会在人体中慢性蓄积造成危害；
4）有较广泛的抗菌谱；
5）生产成本较低廉；
6）细胞毒性较小，不会引起银质沉着症、银中毒等。
目前纳米无机抗菌粉体由于粒径太小，具有很大的比表面积，易团聚，难分散。因此制备一种在生产手套过程中易分散的纳米无机复合抗菌剂是迫切需要的。
发明内容
本发明旨在克服上述现有技术的缺陷，提供一种无机纳米复合抗菌PVC手套液态母料，该纳米无机复合抗菌液态母料添加到PVC乳胶手套原液材料中，起到抗菌作用，其中的抗菌液态母料为纳米级，抗菌效果强，且分散性好，不团聚。
本发明的另一目的在于提供所述无机纳米复合抗菌PVC手套液态母料的制备方法。
本发明所要解决的技术问题通过以下技术方案予以实现。
一种无机纳米复合抗菌母料,包括以下按重量份计算的组分：
增塑剂50～80份；
无机纳米复合抗菌剂20～50份；
分散剂0.1～3份；
表面活性剂0.1～1份；
增稠剂0.1～2份。
本发明的无机纳米复合抗菌母料用分散剂、表面活性剂、增稠剂等对复合抗菌剂进行加工处理，制备出了纳米级的复合抗菌液态母料，其不易团聚，具有显著的抗菌效果。所述无机复合抗菌液态母料抗菌效果显著增加的机理为：（1）接触吸附机理，纳米复合抗菌剂晶体的粒径较小，对细菌表面的吸附能力很强，这种吸附增强了纳米复合抗菌剂与细菌表面发生相互作用的能力；（2）金属离子溶出机理，带负电的细菌会使带正电的R2+逐渐溶出，二者在细胞膜表面通过库伦力结合，之后，R2+穿透细胞膜进入细胞，与细胞中的巯基反应，使蛋白质变性，从而使细胞丧失分裂增殖能力而死亡，当菌体被杀灭后，R2+通过沉淀平衡又游离出来，与其他菌落接触，继续发挥抗菌作用；（3）光催化抗菌机理，当能量大于抗菌剂禁带宽度（约3.3eV）的光照射到抗菌剂表面时，价带上的电子被激发跃迁到导带，留下带正电的空穴，从而在抗菌剂表面产生了电子（e－）-空穴（h+）对。空穴与水分子发生反应生成强氧化性的·OH以及H+，吸附在抗菌剂表面的O2俘获电子生成O2 －·，O2 －·与H+反应生成HO2·，HO2·进一步与电子反应生成HO2 －，HO2 －与H+反应从而产生H2O2，H2O2能够渗透到细胞中，从而杀灭或抑制细菌生长。
优选地，所述复合抗菌剂为纳米氧化锌、纳米氧化铜、纳米二氧化硅、纳米二氧化钛、纳米碳酸钙、纳米三氧化二铝、碳酸钙晶须、四针状氧化锌晶须的两种或两种以上混合物。
优选地，所述增塑剂为邻苯二甲酸酯类增塑剂、脂肪酸酯类增塑剂、磷酸酯类增塑剂、环氧酯类增塑剂、聚酯类增塑剂、偏苯三酸酯类增塑剂、含氦增塑剂、烷基磺酸酯类增塑剂、多元醇酯类增塑剂、柠檬酸酯类增塑剂的一种或多种。
优选地，所述分散剂为脂肪酸类分散剂、脂肪族酰胺类分散剂、酯类分散剂、石蜡类分散剂、金属皂类分散剂、低分子蜡类分散剂、聚磷酸盐分散剂、硅酸盐分散剂、聚马来酸类分散剂、聚丙烯酸酯类分散剂的一种或多种。
优选地，所述表面活性剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂或锆类偶联剂。
优选地，所述增稠剂为无机增稠剂、纤维素醚、天然高分子及其衍生物、合成高分子、络合型有机金属化合物、印花增稠剂的一种或多种。
所述纳米复合抗菌母料的制备方法包括如下步骤：
S1.将增塑剂与分散剂加热到70～100℃，混合均匀；
S2.加入复合抗菌剂混合均匀，用研磨机研磨1～4h，制备粒径为20～100nm的纳米材料；
S3.加入表面活性剂和增稠剂，研磨20分钟～60分钟,得到纳米抗菌PVC手套液态母料。
优选地，所述步骤S2.为加入原始粒径为5μm～20μm复合抗菌剂，混合均匀后用恒温型纳米研磨机研磨1～4小时，制备粒径为20～100nm的纳米材料。
本发明还公开了所述无机纳米复合抗菌液态母料在制备抗菌PVC乳胶手套中的应用。在制造PVC手套原液中，添加PVC乳胶手套的原液重量的3%～5%的纳米复合抗菌液态母料，然后经过常规PVC手套的生产工艺即可制得PVC抗菌乳胶手套。
与现有技术相比，本发明的创新点在于：本发明抗菌PVC乳胶手套所添加的纳米复合抗菌液态母料的抗菌成分为无机抗菌剂，不含银离子，不会在人体沉积，安全无毒害，且抗菌效果好；所述的复合抗菌剂经处理后变为纳米级，在具有较大比表面积的同时不团聚，易分散，从而能够发挥高效的抗菌效果；所制备的纳米复合抗菌母料为液态，可直接加入到制备PVC乳胶手套的原液中，工艺简便，可与制备乳胶手套的原液充分混合均匀。
具体实施方式
以下各实施例的份数均按重量份计。
实施例1
首先将80份乙酰柠檬酸三丁酯（ATBC）和0.1份聚乙二醇2000加热到70℃，充分混合均匀，然后按比例加入20份粒径为5μm～20μm的复合抗菌剂（氧化锌:氧化铜1:0.5），进一步混合均匀，用恒温型纳米研磨机研磨2小时，使得复合抗菌剂粒径达到20～100nm，然后加入0.3份硅烷偶联剂KH550和0.1份甲基纤维素，再研磨20分钟得到纳米复合抗菌液态母料。
在生产PVC手套的原液中加入原液量3%的纳米复合抗菌液态母料，经过常规PVC乳胶手套的生产工艺制作成PVC抗菌手套。
根据ISO22196-2011的标准方法测试PVC抗菌手套产品性能指标：金黄色葡萄球菌的杀菌率为99.71%，大肠杆菌的杀菌率为99.82%。
实施例2
首先将70份环氧大豆油和2.5份乙烯－丙烯酸共聚物加热到80℃，充分混合均匀，然后按比例加入30份粒径为5μm～20μm的复合抗菌剂（四针状氧化锌晶须:二氧化硅1:0.5），进一步混合均匀，用恒温型纳米研磨机研磨3小时，使得复合抗菌剂粒径达到20～100nm，然后加入0.8份单烷氧基焦磷酸酯型偶联剂和0.8份大豆蛋白胶，再研磨30分钟得到纳米复合抗菌液态母料。
在生产PVC手套的原液中加入原液量5%的纳米复合抗菌液态母料，经过常规PVC乳胶手套的生产工艺制作成PVC抗菌手套。
根据ISO22196-2011的标准方法测试PVC抗菌手套产品性能指标：金黄色葡萄球菌的杀菌率为99.86%，大肠杆菌的杀菌率为99.93%。
实施例3
首先将75份邻苯二甲酸二异壬酯（DINP）和1.5份硬脂酸单甘油酯（GMS）加热到100℃，充分混合均匀，然后按比例加入25份粒径为5μm～20μm的复合抗菌剂（氧化锌:二氧化钛1:1），进一步混合均匀，用恒温型纳米研磨机研磨2.5小时，使得复合抗菌剂粒径达到20～100nm，然后加入0.3份铝酸酯偶联剂（ASA）和1.0份聚丙酸酯共聚乳液，再研磨25分钟得到纳米复合抗菌液态母料。
在生产PVC手套的原液中加入原液量4%的纳米复合抗菌液态母料，经过常规PVC乳胶手套的生产工艺制作成PVC抗菌手套。
根据ISO22196-2011的标准方法测试PVC抗菌手套产品性能指标：金黄色葡萄球菌的杀菌率为99.68%，大肠杆菌的杀菌率为99.83%。
以上所述实施例仅表达了本发明的实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制，但凡采用等同替换或等效变换的形式所获得的技术方案，均应包括在本发明权利要求的保护范围之内。

Claims (9)

1.一种无机纳米复合抗菌液态母料，其特征在于，包括以下按重量份计算的组分：
增塑剂50～80份；
无机纳米复合抗菌剂20～50份；
分散剂0.1～3份；
表面活性剂0.1～1份；
增稠剂0.1～2份。
2.根据权利要求1所述无机纳米复合抗菌液态母料，其特征在于，所述无机纳米复合抗菌剂为纳米氧化锌、纳米氧化铜、纳米二氧化硅、纳米二氧化钛、纳米碳酸钙、纳米三氧化二铝、碳酸钙晶须、四针状氧化锌晶须的两种或两种以上混合物。
3.根据权利要求1所述无机纳米复合抗菌液态母料，其特征在于，所述增塑剂为邻苯二甲酸酯类增塑剂、脂肪酸酯类增塑剂、磷酸酯类增塑剂、环氧酯类增塑剂、聚酯类增塑剂、偏苯三酸酯类增塑剂、含氦增塑剂、烷基磺酸酯类增塑剂、多元醇酯类增塑剂、柠檬酸酯类增塑剂的一种或多种。
4.根据权利要求1所述无机纳米复合抗菌液态母料，其特征在于，所述分散剂为脂肪酸类分散剂、脂肪族酰胺类分散剂、酯类分散剂、石蜡类分散剂、金属皂类分散剂、低分子蜡类分散剂、聚磷酸盐分散剂、硅酸盐分散剂、聚马来酸类分散剂、聚丙烯酸酯类分散剂的一种或多种。
5.根据权利要求1所述无机纳米复合抗菌液态母料，其特征在于，所述表面活性剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂或锆类偶联剂。
6.根据权利要求1所述无机纳米复合抗菌液态母料，其特征在于，所述增稠剂为无机增稠剂、纤维素醚、天然高分子及其衍生物、合成高分子、络合型有机金属化合物、印花增稠剂的一种或多种。
7.如权利要求1～6任意一项权利要求所述无机纳米复合抗菌液态母料的制备方法，其特征在于，包括如下步骤：
S1.将增塑剂与分散剂加热到70～100℃，混合均匀；
S2.加入无机复合抗菌剂混合均匀，用研磨机研磨1～4h，制备粒径为20～100nm的纳米材料；
S3.加入表面活性剂和增稠剂，研磨20分钟～60分钟,得到无机纳米复合抗菌液态母料。
8.根据权利要求7所述无机纳米复合抗菌液态母料的制备方法，其特征在于，所述步骤S2.为：加入原始粒径为5μm～20μm的无机复合抗菌剂，混合均匀后，用恒温型纳米研磨机研磨1～4小时，制备粒径为20～100nm的纳米材料。
9.权利要求1至6任意一项权利要求所述无机纳米复合抗菌液态母料在制备抗菌PVC乳胶手套中的应用。
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CN108041722A (zh) * 2018-01-18 2018-05-18 蓝帆医疗股份有限公司 一种儿童抗菌手套及其制备方法
CN110527215A (zh) * 2019-09-02 2019-12-03 华南理工大学 一种具有自抗菌性能的pvc塑料及其制备方法
CN116003936A (zh) * 2023-01-08 2023-04-25 欣润新材料科技(江苏)有限公司 一种新型防护面罩用防雾软质pvc透明材料
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CN108041722A (zh) * 2018-01-18 2018-05-18 蓝帆医疗股份有限公司 一种儿童抗菌手套及其制备方法
CN110527215A (zh) * 2019-09-02 2019-12-03 华南理工大学 一种具有自抗菌性能的pvc塑料及其制备方法
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CN116003936A (zh) * 2023-01-08 2023-04-25 欣润新材料科技(江苏)有限公司 一种新型防护面罩用防雾软质pvc透明材料

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