CN106192379B - 臭氧氧化法制备多价态银系抗菌纤维的方法及其抗菌纤维 - Google Patents

臭氧氧化法制备多价态银系抗菌纤维的方法及其抗菌纤维 Download PDF

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CN106192379B
CN106192379B CN201610575087.4A CN201610575087A CN106192379B CN 106192379 B CN106192379 B CN 106192379B CN 201610575087 A CN201610575087 A CN 201610575087A CN 106192379 B CN106192379 B CN 106192379B
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CN106192379A (zh
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张茂义
张华鹏
郭向红
虞树荣
陈建勇
汤战昌
方伟
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Zhejiang Jasan Group Jiangshan Knitting Co ltd
Zhejiang University of Technology ZJUT
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HANGZHOU JIANSHENG SOCKS Co Ltd
Zhejiang Sci Tech University ZSTU
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Abstract

本发明公开了一种臭氧氧化法制备多价态银系抗菌纤维的方法及其抗菌纤维。清洗纤维表面，除去油剂和杂质，将纤维置于酸性亚锡离子水溶液中浸渍，然后再用去离子水清洗纤维，置于银离子络合物水溶液中浸渍，浸渍于水中，同时通入臭氧进行氧化，清洗、干燥经过上述处理的纤维。本发明所制备的抗菌纤维具有高效、安全、广谱等特点，纤维上银的总含量在ppm级即可实现高效抗菌效果，该抗菌纤维可以与其他纤维混纺、交织，开发多种用途功能性抗菌纤维。

Description

臭氧氧化法制备多价态银系抗菌纤维的方法及其抗菌纤维
技术领域
本发明涉及一种抗菌纤维及其制备方法，更具体的是一种臭氧氧化法制备多价态银系抗菌纤维的方法及其抗菌纤维，属于功能性纤维和纺织品及其制备领域。
背景技术
随着科学技术的发展和人们生活水平的提高，人们对纺织品的卫生功能提出了更好的要求，尤其在军事国防用纺织品、医疗卫生用纺织品、床上用品、公共场合用装饰纺织品、内衣、袜子等容易滋生微生物的纺织品上，纺织品的抗菌抑菌功能越来越受到人们的重视。
少量天然纤维或再生纤维本身具有一定的抗菌效果，如一些麻类纤维、壳聚糖纤维等。大部分普通纺织品没有抗菌功能，可以通过施加抗菌剂的方式实现：对于天然纤维和大部分合成纤维，可通过抗菌剂后整理的方式实现；对于合成纤维，还可以通过纺丝添加抗菌剂方式，实现纤维和纺织品的高效、耐久抗菌功能。其中抗菌剂为抗菌纺织品的有效成分，包括多种有机抗菌剂，如季铵盐类、胍类及卤胺类，和多种无机抗菌剂，如铜、锌、钛、钴、银等金属及其化合物。其中银系抗菌剂在高效性、广谱抗菌性、安全性、耐久性等方面具有十分优异的优势，在抗菌纤维和纺织品的开发和应用方面，具有十分重要的意义(银系纤维及其抗菌性能的研究进展，现代纺织技术，2014，(4)，p61-64)。申请号为201010285121.7的中国专利《纳米银抗菌纤维及其制备方法》、申请号为201310617323.0的中国专利《一种静电纺丝法制备纳米银抗菌纤维的方法》、申请号为201510662313.8的中国专利《一种制备银离子抗菌纤维的方法》、申请号为200810197275.3的中国专利《一种海藻酸盐纳米银抗菌纤维及其制备方法》、申请号为201110260091.9的中国专利《一种智能载银抗菌纤维及其制备方法和应用》等采用离子态银或金属态银作为抗菌有效成分来制备抗菌纤维。
已有研究表明不同价态的银均具有抗菌效果，总体而言，高价态银具有更好的抗菌活性。已有文献(四氧化四银药用研究进展，中国新药与临床杂志，2005，24(7):565-568；多价银氧化物Ag4O4的软化学制备、表征及抑菌性能评价，材料导报，2012,26(5):32-35)报道了高价态银优异的抗微生物性能和安全性。
发明内容
为了解决背景技术中存在的问题，本发明的目的是提供一种臭氧氧化法制备多价态银系抗菌纤维的方法及其抗菌纤维。
本发明是通过以下步骤来实现的：
一、一种臭氧氧化法制备多价态银系抗菌纤维的方法：
1)清洗纤维表面，除去油剂和杂质；
2)将纤维置于酸性亚锡离子水溶液中浸渍，然后再用浴比1:30的去离子水清洗纤维1-3次；
3)将经过步骤2)处理的纤维置于银离子络合物水溶液中浸渍；
4)将经过步骤3)处理的纤维浸渍于水中，同时通入臭氧进行氧化；
5)清洗、干燥经过上述处理的纤维。
所述步骤2)是将纤维在10-30℃、浓度为0.01-0.1mol/l的酸性亚锡离子水溶液中浸渍1-10分钟，纤维和酸性亚锡离子水溶液的浴比为1:10-1:50，酸性亚锡离子水溶液中添加有质量百分含量为36-38％的盐酸，盐酸添加量为5-100ml/l。
所述的酸性亚锡离子水溶液的亚锡离子采用氯化亚锡或硫酸亚锡中的一种。
所述步骤3)是将纤维置于10-40℃、浓度为0.001-0.05mol/l、pH 8-13的银离子络合物水溶液中浸渍0.1-10分钟，纤维与银离子络合物水溶液的浴比为1:10-1:50，所述的银离子络合物水溶液通过乙酸或氢氧化钠调节使其pH为8-13。
所述的银离子络合物水溶液中的银离子采用硝酸银、硫酸银、氯化银和氢氧化银中的一种。
所述的银离子络合物水溶液采用的络合剂为氨水与乙二胺四乙酸纳盐(EDTA)的复合络合剂或者乙二胺与乙二胺四乙酸纳盐(EDTA)的复合络合剂。
所述步骤4)具体是将纤维浸渍于pH 7-12、温度15-35℃的水浴中，纤维和水的浴比1:10-1:20，同时通入0.1-5g/h/l流量的臭氧1-60min。
所述的纤维为锦纶纤维，具体可为锦纶6或者锦纶66的短纤维或长丝。
二、多价态银系抗菌纤维
所述抗菌纤维由上述方法制备获得，该纤维表面含有Ag0、Ag+1、Ag+3多价态银。
所述抗菌纤维表面的Ag0、Ag+1、Ag+3多价态银含量为纤维质量的1-10000ppm。
本发明通过调节步骤3)的工艺条件可调节纤维表面Ag0价态银的量，通过步骤4)工艺条件调节纤维表面Ag+1和Ag+3价态银的获得量。
本发明的有益效果是：
(1)通过本发明技术方案，可方便制备表面含有Ag0、Ag+1、Ag+3多价态银的抗菌纤维，可调整不同价态银的含量，具有高效、安全和广谱抑菌性，可以单独或与其他常用纤维方便进行混纺、交织，制备和开发多种具有抗菌功能的纺织品。
(2)通过本发明技术方案所制备的抗菌纤维，具有耐久抗菌性，纤维抑菌率经水洗多次而不发生明显下降。
(3)本发明技术方案具有简单、易行、易批量制备等优点，银盐利用率高，纤维表面银含量在ppm级即可实现高效抗菌效果，所制备的抗菌纤维具有很高的性价比。
具体实施方式
下面结合实施例对本发明的内容作进一步的说明，本发明的实施例如下：
实施例1
采用规格为2.67dtex*38mm锦纶6短纤维6kg，经过如下方案进行抗菌纤维的制备：
(1)纤维清洗：AEO-9(脂肪醇聚氧乙烯醚)2g/l，Na2CO3 2g/l，温度90℃，时间30min，水洗3遍，烘干温度90℃，时间30min。
(2)在10℃、浓度为0.01mol/l、浴比为1:10的酸性氯化亚锡水溶液中浸渍纤维10分钟，溶液中质量百分含量为36-38％的盐酸5ml/l，之后用浴比1:30的去离子水清洗3道；
(3)将经过步骤(2)处理的纤维在10℃、浓度为0.001mol/l、浴比为1:50、pH 8的硝酸银络合物水溶液中0.1分钟；硝酸银所用络合剂为27％的氨水溶液与乙二胺四乙酸二钠盐的复合络合剂，硝酸银：氨(NH3)：乙二胺四乙酸二钠的摩尔比为1:4.5:0.05，乙酸调节络合液pH；
(4)将经过步骤(3)处理的纤维浸渍于浴比1:10、pH 7、温度15℃的水浴中，同时通入0.1g/h/l流量的臭氧1min；
(5)去离子水清洗上述纤维3道、85℃干燥经过上述处理的纤维1h。
经过上述处理后的纤维表面Ag0、Ag+1、Ag+3多价态银含量为纤维质量的1ppm。
将上述抗菌处理后的锦纶短纤维与棉纤维按照混纺比60:40纺纱得到32S混纺纱，织造成经纬密为78*65根/吋机织物试样，按照GB/T 20944.3标准震荡法进行抗菌测试，抑菌率测试结果如下表：
表1
测试微生物 水洗前 20次水洗后
大肠杆菌 88.7 87.5
金黄色葡萄球菌 83.6 80.3
白色念珠菌 80.3 75.1
实施例2
采用规格为70den/24f的锦纶66长丝10kg，经过如下方案进行抗菌纤维的制备：
(1)纤维清洗：AEO-9(脂肪醇聚氧乙烯醚)2g/l，Na2CO3 2g/l，温度90℃，时间30min，水洗3遍，烘干温度90℃，时间30min。
(2)在20℃、浓度为0.05mol/l、浴比为1:20的酸性硫酸亚锡水溶液中浸渍纤维5分钟，溶液中质量百分含量为36-38％的盐酸100ml/l，之后用浴比1:30的去离子水清洗2道；
(3)将经过步骤(2)处理的纤维在20℃、浓度为0.005mol/l、浴比为1:20、pH 10的硫酸银络合物水溶液中5分钟；硫酸银所用络合剂为27％的氨水溶液与乙二胺四乙酸二钠盐的复合络合剂，硝酸银：氨(NH3)：乙二胺四乙酸二钠的摩尔比为1:4.5:0.25，NaOH调节络合液pH；
(4)将经过步骤(3)处理的纤维浸渍于浴比1:15、pH 10、温度25℃的水浴中，同时通入2g/h/l流量的臭氧30min；
(5)去离子水清洗上述纤维3道、85℃干燥经过上述处理的纤维1h。
经过上述处理后的纤维表面Ag0、Ag+1、Ag+3多价态银含量为纤维质量的5320ppm。
将上述抗菌处理后的锦纶长丝与氨纶长丝原料制备20D+70D氨纶包芯纱，袜带小样机织造针织试样，按照GB/T 20944.3标准震荡法进行抗菌测试，抑菌率测试结果如下表：
表2
测试微生物 水洗前 50次水洗后
大肠杆菌 >99.9 >99.9
金黄色葡萄球菌 >99.9 >99.9
白色念珠菌 >99.9 99.5
实施例3
采用规格为2.67dtex*38mm锦纶6短纤维6kg，经过如下方案进行抗菌纤维的制备：
(1)纤维清洗：AEO-9(脂肪醇聚氧乙烯醚)2g/l，Na2CO3 2g/l，温度90℃，时间30min，水洗3遍，烘干温度90℃，时间30min。
(2)在30℃、浓度为0.1mol/l、浴比为1:50的酸性氯化亚锡水溶液中浸渍纤维1分钟，溶液中质量百分含量为36-38％的盐酸50ml/l，之后用浴比1:30的去离子水清洗3道；
(3)将经过步骤(2)处理的纤维在40℃、浓度为0.05mol/l、浴比为1:10、pH 13的氢氧化银络合物水溶液中10分钟；硫酸银所用络合剂为乙二胺与乙二胺四乙酸四钠盐的复合络合剂，硝酸银：乙二胺：乙二胺四乙酸四钠的摩尔比为1:0.6:0.5，NaOH调节络合液pH；
(4)将经过步骤(3)处理的纤维浸渍于浴比1:20、pH 12、温度35℃的水浴中，同时通入5g/h/l流量的臭氧60min；
(5)去离子水清洗上述纤维3道、85℃干燥经过上述处理的纤维1h。
经过上述处理后的纤维表面Ag0、Ag+1、Ag+3多价态银含量为纤维质量的9850ppm。
将上述抗菌处理后的锦纶短纤维与棉纤维按照混纺比95:5纺纱得到32S混纺纱，织造成经纬密为78*65根/吋机织物试样，按照GB/T 20944.3标准震荡法进行抗菌测试，抑菌率测试结果如下表：
表3
测试微生物 水洗前 50次水洗后
大肠杆菌 >99.9 >99.9
金黄色葡萄球菌 >99.9 >99.9
白色念珠菌 >99.9 >99.9
由以上实施例可见，本发明获得的表面含有Ag0、Ag+1、Ag+3多价态银的抗菌纤维具有高效、安全和广谱抑菌性，具有耐久抗菌性，纤维抑菌率经水洗多次而不发生明显下降。并且可调整不同价态银的含量，银盐利用率高，纤维表面银含量在ppm级即可实现高效抗菌效果。

Claims (7)

1.一种臭氧氧化法制备多价态银系抗菌纤维的方法，其特征在于，
1)清洗纤维表面，除去油剂和杂质；
2)将纤维置于酸性亚锡离子水溶液中浸渍，然后再用浴比1:30的去离子水清洗纤维1-3次；
所述步骤2)是将纤维在10-30℃、浓度为0.01-0.1mol/L 的酸性亚锡离子水溶液中浸渍1-10分钟，纤维和酸性亚锡离子水溶液的浴比为1:10-1:50，酸性亚锡离子水溶液中添加有质量百分含量为36-38％的盐酸，盐酸添加量为5-100mL /L ；
3)将经过步骤2)处理的纤维置于银离子络合物水溶液中浸渍；
所述步骤3)是将纤维置于10-40℃、浓度为0.001-0.05mol/L 、pH 8-13的银离子络合物水溶液中浸渍0.1-10分钟，纤维与银离子络合物水溶液的浴比为1:10-1:50，所述的银离子络合物水溶液通过乙酸或氢氧化钠调节使其pH为8-13；
4)将经过步骤3)处理的纤维浸渍于水中，同时通入臭氧进行氧化；
所述步骤4)具体是将纤维浸渍于pH 7-12、温度15-35℃的水浴中，纤维和水的浴比1:10-1:20，同时通入0.1-5g/h/L 流量的臭氧1-60min；
5)清洗、干燥经过上述处理的纤维，所述纤维表面含有Ag0、Ag+1、Ag+3多价态银。
2.根据权利要求1所述的一种臭氧氧化法制备多价态银系抗菌纤维的方法，其特征在于：所述的酸性亚锡离子水溶液的亚锡离子采用氯化亚锡或硫酸亚锡中的一种。
3.根据权利要求1所述的一种臭氧氧化法制备多价态银系抗菌纤维的方法，其特征在于：所述的银离子络合物水溶液中的银离子采用硝酸银、硫酸银、氯化银和氢氧化银中的一种。
4.根据权利要求1所述的一种臭氧氧化法制备多价态银系抗菌纤维的方法，其特征在于：所述的银离子络合物水溶液采用的络合剂为氨水与乙二胺四乙酸钠 盐(EDTA)的复合络合剂或者乙二胺与乙二胺四乙酸钠 盐(EDTA)的复合络合剂。
5.根据权利要求1～4任一所述的一种臭氧氧化法制备多价态银系抗菌纤维的方法，其特征在于：所述的纤维为锦纶纤维。
6.多价态银系抗菌纤维，其特征在于：所述抗菌纤维由权利要求1～4任一所述方法制备获得，该纤维表面含有Ag0、Ag+1、Ag+3多价态银。
7.根据权利要求6所述的一种多价态银系抗菌纤维，其特征在于：所述抗菌纤维表面的Ag0、Ag+1、Ag+3多价态银含量为纤维质量的1-10000ppm。
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