CN116554775A - 水性抗菌保护膜及其制备方法与应用 - Google Patents
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Abstract
本申请提供一种水性抗菌保护膜及其制备方法与应用,该水性抗菌保护膜包括按重量份计的如下组分:水性聚氨基甲酸乙酯60‑80份;分散剂1‑1.5份;抗菌剂1‑10份;消泡剂0.5份;水9‑32份;其中,所述水性聚氨基甲酸乙酯为阴离子脂肪族水性聚氨酯分散体;所述抗菌剂为纳米氧化锌水性浆状分散体。该水性抗菌保护膜成膜性好、韧性强、抗菌性能较佳、安全环保且可轻易撕除,还兼具防尘、防水油与污垢、防刮擦和耐磨耗等优异性能,能依据需求调整颜色;并且,所述水性抗菌保护膜可与物体表面完整贴合,不受物体形状大小或凹凸面或弧面等限制。该水性抗菌保护膜可广泛应用于公共设施、医疗器械和交通工具中。
Description
技术领域
本申请涉及抗菌膜技术领域,尤其涉及一种水性抗菌保护膜及其制备方法与应用。
背景技术
随着人们生活质量水平提高,对卫生意识越加重视,在医疗机构、商业设施、学校、公共设施、食品工厂、交通机构等物体表面具有抗菌性能也越加迫切。而近年来,喷涂式可撕保护膜在家具、金属、玻璃、陶瓷、木制品、塑料等物体表面被广泛应用,以免刮伤或附着脏污,并且可撕膜能直接撕除,还原物体干净表面。传统喷涂式的可撕保护膜具备日后可撕除的便利性,但其不具有抗菌性能,并且配方中通常都使用有机溶剂体系,而有机溶剂的挥发不利于人体健康和环境保护。
发明内容
有鉴于此,本申请提供一种水性抗菌保护膜,以解决上述问题。
另,本申请还提供一种制备水性抗菌保护膜的制备方法。
另,本申请还提供上述水性抗菌保护膜在公共设施、医疗器械和交通工具中的应用。
本申请一实施方式提供一种水性抗菌保护膜,包括按重量份计的如下组分:水性聚氨基甲酸乙酯60份-80份;分散剂1份-1.5份;抗菌剂1份-10份;消泡剂0.5份;水9份-32份;
其中,所述水性聚氨基甲酸乙酯为阴离子脂肪族水性聚氨酯分散体;所述抗菌剂为纳米氧化锌水性浆状分散体。
一种实施方式中,所述水性聚氨基甲酸乙酯的相对分子质量为10000-30000。
进一步地,所述水性聚氨基甲酸乙酯的固含量为30-50%,25℃下的粘度为10-200mPa·s,pH为8。
一种实施方式中,所述纳米氧化锌水性浆状分散体中纳米氧化锌的浓度为25000ppm,平均粒径为5-10nm。
一种实施方式中,所述分散剂为六偏磷酸钠。
一种实施方式中,所述消泡剂为聚醚改性硅油。
一种实施方式中,所述水性抗菌保护膜还包括水溶性颜料,所述水溶性颜料的重量份数为0.1份-5份。
本申请还提供一种制备上述水性抗菌保护膜的制备方法,包括如下步骤:
S1:将分散剂和抗菌剂加入水中,室温下搅拌混合均匀得到第一浆料;
S2:将水性聚氨基甲酸乙酯和消泡剂加入到所述第一浆料中,室温下继续搅拌混合均匀得到第二浆料;
S3:将S2中所述第二浆料干燥固化,即得所述水性抗菌保护膜。
一种实施方式中,S1中所述搅拌速度为500-1500rpm/min,搅拌时间为30-60min;S2中所述搅拌时间为60-80min。
一种实施方式中,S3中所述干燥温度为60-80℃,时间为5-10min。
一种实施方式中,S2步骤中还包括以下步骤:加入水溶性颜料,搅拌均匀后研磨,得到第二浆料。
上述水性抗菌保护膜在公共设施、医疗器械和交通工具中的应用也在本申请的保护范围内。
本申请中提供的水性抗菌保护膜以水性聚氨基甲酸乙酯树脂为基底,加入纳米氧化锌水性浆状分散体作为抗菌剂,配合调控分散剂和消泡剂的添加比例,并以水为溶剂,使得产品成膜性好、韧性强、抗菌性能较佳、安全环保且可轻易撕除,还兼具透明、光泽度佳、防尘、防水油与污垢、防刮擦和耐磨耗等优异性能。
并且,本申请所述水性抗菌保护膜在干燥固化前是浆料状,可利用喷涂、含浸或刷涂等工艺设置在物体表面,可与物体表面完整贴合,不受物体形状大小或凹凸面或弧面等限制,应用场景较灵活。
另外,本申请所述水性抗菌保护膜使用水作为溶剂,水性环保,无VOC(挥发性有机物),不危害作业人员,对底材无损坏,覆盖在油漆、涂料、镀膜面等各种底材上也不会损坏,还能依据需求调整颜色。
具体实施方式
除非另有定义,本文所使用的所有的技术和科学术语与属于本申请实施例的技术领域的技术人员通常理解的含义相同。本文中所使用的术语只是为了描述具体的实施方式的目的,不是旨在限制本申请实施例。
另外,在本申请中如涉及“第一”、“第二”等的描述仅用于描述目的,而不能理解为指示或暗示其相对重要性或者隐含指明所指示的技术特征的数量。由此,限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在本申请的描述中,“多个”的含义是至少两个,例如两个、三个等,除非另有明确具体的限定。
如下采用具体实施方式进一步说明本申请的技术方案。
本申请一实施方式提供一种水性抗菌保护膜,包括按重量份计的如下组分:水性聚氨基甲酸乙酯60份-80份;分散剂1份-1.5份;抗菌剂1份-10份;消泡剂0.5份;水9份-32份;
其中,所述水性聚氨基甲酸乙酯为阴离子脂肪族水性聚氨酯分散体;所述抗菌剂为纳米氧化锌水性浆状分散体。
本申请中所述水性聚氨基甲酸乙酯为阴离子脂肪族水性聚氨酯分散体,可用水溶解稀释,是一种水稀释型聚氨酯(water-based PU)。
该水性聚氨基甲酸乙酯为以二苯甲烷二异氰酸酯(简称MDI,化学式为C15H10N2O2)和聚醚多元醇为原料制备得到的预聚物,使用二苯甲烷二异氰酸酯和聚醚多元醇为原料不会导致早期交联或凝胶化,使制得的水性聚氨基甲酸乙酯具有合适的粘度,有利于后续制备得到的浆料能干燥固化成膜,成膜后也可撕除剥离。另外,由于水性聚氨基甲酸乙酯包含二苯甲烷二异氰酸酯硬链段和聚醚多元醇软链段,两者共价偶联,能够抑制聚合物链段的流动,使得该水性抗菌膜具有良好的力学性能(如韧性)。
通过在反应体系中添加纳米氧化锌(ZnO)水性浆状分散体,赋予水性保护膜优异的抗菌性能。其中,纳米氧化锌的抗菌机理大致为:当纳米氧化锌与细菌接触时,因锌离子(Zn2+)具有强氧化还原特性,能够与有机物中的羧基(-COOH)、羟基(-OH)和磷酸脂质膜(PO3 2-)反应,从而破坏细菌的细胞膜结构进入细胞;进入细胞后能够进一步破坏电子传递系统的酶(功能性蛋白质)并与巯基(-SH,酶蛋白质序列内半膀胱酸侧链双硫键-Cys-S-S-Cys)反应,进而干扰酶的活性中心使其失活,从而达到杀菌目的;其反应机制如下:
ZnO+C2H5SH→ZnS+C2H4+H2O。
另外,相较于常规的抗菌剂,例如季铵盐类抗菌剂,其抗菌效果较差,银离子对于薄膜有后期黄化的风险。而纳米氧化锌水性分散体由于其一端具备有机分子链端(bindercompatible chain),能够形成空间位阻使纳米氧化锌彼此稳定分散不团聚,并且能与水性聚氨酯树脂端兼容并稳定分布于水性聚氨酯体系中。并且,纳米氧化锌无机粒子能在一定程度上增强保护膜的耐磨性。
本申请中提供的水性抗菌保护膜以水性聚氨基甲酸乙酯树脂为基底,加入纳米氧化锌水性浆状分散体作为抗菌剂,配合分散剂和消泡剂,并以水为溶剂,使得产品成膜性好、韧性强、抗菌性能较佳且安全环保。
一些实施例中,所述水性聚氨基甲酸乙酯的相对分子质量为10000-30000。
进一步地,所述水性聚氨基甲酸乙酯的固含量为30-50%,25℃下的粘度为10-200mPa·s,pH为8。
可以理解地,可以选取具有更高粘度(如500mPa·s)的水性聚氨基甲酸乙酯,后续可根据不同粘度选择不同的成膜方式,如喷涂、刷涂或含浸等。
一些实施例中,所述纳米氧化锌水性浆状分散体中纳米氧化锌的浓度为25000ppm,平均粒径为5-10nm。
一些实施例中,所述分散剂为六偏磷酸钠。
一些实施例中,所述消泡剂为聚醚改性硅油。
一些实施例中,所述水性抗菌保护膜还包括水溶性颜料,所述水溶性颜料的重量份数为0.1份-5份。根据需求,可以通过添加不同的水溶性颜料来得到不同颜色的水性抗菌保护膜,起到识别和装饰作用。
一些实施例中,水性抗菌保护膜包括按重量份计的如下组分:水性聚氨基甲酸乙酯70份;分散剂1份;抗菌剂1份;消泡剂0.5份;水27.5份。
一些实施例中,水性抗菌保护膜包括按重量份计的如下组分:水性聚氨基甲酸乙酯60份;分散剂1.5份;抗菌剂5份;消泡剂0.5份;水溶性颜料1份;水32份。
一些实施例中,水性抗菌保护膜包括按重量份计的如下组分:水性聚氨基甲酸乙酯80份;分散剂1.5份;抗菌剂9份;消泡剂0.5份;水9份。
本申请还提供一种上述水性抗菌保护膜的制备方法,包括如下步骤:
S1:将分散剂和抗菌剂加入水中,室温下搅拌混合均匀得到第一浆料;
S2:将水性聚氨基甲酸乙酯和消泡剂加入到所述第一浆料中,室温下继续搅拌混合均匀得到第二浆料;
S3:将S2中所述第二浆料干燥固化,即得所述水性抗菌保护膜。
一些实施例中,S1中所述搅拌速度为500-1500rpm/min,搅拌时间为30-60min;S2中所述搅拌时间为60-80min。
进一步地,所述搅拌速度为1000-1200rpm/min。
一些实施例中,S3中所述干燥温度为60-80℃,时间为5-10min。
一些实施例中,S2步骤中还包括以下步骤:加入水溶性颜料,搅拌均匀后研磨,得到第二浆料。
一些实施例中,所述水性抗菌保护膜的膜厚为20-100μm。
上述水性抗菌保护膜可广泛应用于公共设施、医疗器械和交通工具等。
因本申请中提供的水性抗菌保护膜在干燥固化前是浆料状,可利用喷涂、含浸或刷涂等工艺设置在基体表面,可根据需要喷覆多层以控制膜厚。该水性抗菌保护膜可广泛应用于各种公共设施、医疗器械和交通工具中,诸如门把、电梯按钮、公用推车手把、扶手、桌面、设备按键或触控面上,以及护理站工作推车、病人轮椅扶手支架、楼梯手扶架、病床扶手、柜台桌面,公交车内手拉环与手扶杆等,实现抗菌保护功能。
以下将结合具体实施例和对比例对本申请中的水性抗菌保护膜的制备方法和性能作进一步说明。
对实施例和对比例中所用到的部分试剂作如下说明:
水性聚氨基甲酸乙酯:国新科技,WU-3021(固含量30%,粘度15-100mPa·s@25℃,pH 8);
分散剂:六偏磷酸钠三福化工;
抗菌剂:纳米氧化锌水性浆状分散体安峰实业,WZnO-2110(水性纳米氧化锌);
消泡剂:聚醚改性硅油,安峰实业,IOTA1100;
水溶性颜料:酞青蓝科莱恩,100。
各项性能测试的检测方法和/或测试标准如下:
(1)抗菌性:按照日本工业标准JIS Z 2801-2010(国际标准ISO 22196-2011)进行测试;选用的金黄色葡萄球菌的菌株编号为BCRC 10451,大肠杆菌的菌株编号为BCRC11634,作用时间为24h;当抗菌值(R)≥2时,表示有抗菌效果。
(2)耐冲击性:按照CNS 10757-1995测试标准,测试设备为落球式冲击试验机(HV-0105),冲击头的直径为25.4mm,试验荷重为300g,试验高度为300mm。
(3)耐磨耗性(RCA):测试设备为RCA耐磨耗试验机(NORMAN,7-IBB),试验荷重为55g,循环100次。
(4)光泽度:按照ASTM D523-14-2018测试标准,测试设备为micro-TRI-gloss光泽计(BYK,4446),试验射角为60°。
实施例1
S1:将1份分散剂(六偏磷酸钠),1份抗菌剂(纳米氧化锌水性浆状分散体)和27.5份纯水加入搅拌机,室温下边搅拌边加入,搅拌速度为1000rpm/min,分散45min,得到第一浆料;
S2:向第一浆料中加入70份水性聚氨基甲酸乙酯,0.5份消泡剂(聚醚改性硅油),室温下继续分散55min,得到第二浆料;
S3:将第二浆料凉风干燥5min后烘烤,烘烤温度为80℃,烘烤时间为5min,烘烤后于室温静置5min,得到水性抗菌保护膜。
实施例2
S1:将1.5份分散剂(六偏磷酸钠),5份抗菌剂(纳米氧化锌水性浆状分散体)和32份纯水加入搅拌机,搅拌速度为1000rpm/min,分散45min,得到第一浆料;
S2:向第一浆料中加入60份水性聚氨基甲酸乙酯,0.5份消泡剂(聚醚改性硅油),室温下继续分散55min;再加入1份水溶性颜料(酞青蓝),边搅拌边加入,室温分散30min,再以三轮研磨机充分研磨使良好着色,即得到第二浆料;
S3:将第二浆料凉风干燥5min后烘烤,烘烤温度为80℃,烘烤时间为5min,烘烤后于室温静置5min,得到水性抗菌保护膜。
实施例3
S1:将1.5份分散剂(六偏磷酸钠),9份抗菌剂(纳米氧化锌水性浆状分散体)和9份纯水加入搅拌机,搅拌速度为1000rpm/min,分散45min,得到第一浆料;
S2:向第一浆料中加入80份水性聚氨基甲酸乙酯,0.5份消泡剂(聚醚改性硅油),室温下继续分散55min,得到第二浆料;
S3:将第二浆料凉风干燥5min后烘烤,烘烤温度为80℃,烘烤时间为5min,烘烤后于室温静置5min,得到水性抗菌保护膜。
对比例1
S1:将1.5份分散剂(六偏磷酸钠),10份抗菌剂(纳米氧化锌水性浆状分散体)和28份纯水加入搅拌机,搅拌速度为1000rpm/min,分散45min,得到第一浆料;
S2:向第一浆料中加入60份水性聚氨基甲酸乙酯,0.5份消泡剂(聚醚改性硅油),室温下继续分散55min,得到第二浆料;
S3:将第二浆料凉风干燥5min后烘烤,烘烤温度为80℃,烘烤时间为5min,烘烤后于室温静置5min,得到水性抗菌保护膜。
对比例2
S1:将1份分散剂(六偏磷酸钠),0.5份抗菌剂(纳米氧化锌水性浆状分散体)和18份纯水加入搅拌机,搅拌速度为1000rpm/min,分散45min,得到第一浆料;
S2:向第一浆料中加入80份水性聚氨基甲酸乙酯,0.5份消泡剂(聚醚改性硅油),室温下继续分散55min,得到第二浆料;
S3:将第二浆料凉风干燥5min后烘烤,烘烤温度为80℃,烘烤时间为5min,烘烤后于室温静置5min,得到水性抗菌保护膜。
上述实施例1-3及对比例1-2中的配方见表1。
表1实施例1-3及对比例1-2配方(份)
组分 | 实施例1 | 实施例2 | 实施例3 | 对比例1 | 对比例2 |
水性聚氨基甲酸乙酯 | 70 | 60 | 80 | 60 | 80 |
分散剂 | 1 | 1.5 | 1.5 | 1.5 | 1 |
抗菌剂 | 1 | 5 | 9 | 10 | 0.5 |
水溶性颜料 | 0 | 1 | 0 | 0 | 0 |
消泡剂 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
水 | 27.5 | 32 | 9 | 28 | 18 |
实施例1-3和对比例1-2中水性抗菌保护膜采用喷涂方式制备得到,单层厚度为22.4μm左右,分别对其进行性能测试,结果见表2。
表2实施例1-3和对比例1-2性能测试结果
注:表中分散性对应性能,“+”表示可分散或分散性好,“-”表示不可分散或分散性不佳。
由实施例1-3及对比例1的结果可知,该水性抗菌保护膜具有良好的抗菌性能,对金黄色葡萄球菌和大肠杆菌的抗菌值>2,具有至少99%的抗菌活性;并且具有很好的耐冲击性(即韧性),耐磨耗性能和较好的光泽度。另外,可通过加入水溶性颜料对外观颜色进行调整,使其容易被识别。对比例1中,抗菌剂添加量过多,于树脂溶液中分散性不佳且影响成膜。对比例2中抗菌剂添加量过少,所制备得到的膜抗菌性很差。
本申请的水性抗菌保护膜以水性聚氨基甲酸乙酯为基底,加入纳米氧化锌水性浆状分散体作为抗菌剂,配合分散剂和消泡剂,并以水为溶剂,使得产品成膜性好、韧性强、抗菌性能佳、安全环保且可轻易撕除,还兼具透明、光泽度佳、防尘、防水油与污垢、防刮擦和耐磨耗等优异性能。并且,本申请所述水性抗菌保护膜在干燥固化前是浆料状,可利用喷涂、含浸或刷涂等工艺设置在物体表面,可与物体表面完整贴合,不受物体形状大小或凹凸面或弧面等限制,应用场景较灵活。另外,本申请所述水性抗菌保护膜使用水作为溶剂,水性环保,无VOC(挥发性有机物),不危害作业人员,对底材无损坏,覆盖在油漆、涂料、镀膜面等各种底材上也不会损坏,还能依据需求调整颜色。
以上说明是本申请一些具体实施方式,但在实际的应用过程中不能仅仅局限于这些实施方式。对本领域的普通技术人员来说,根据本申请的技术构思做出的其他变形和改变,都应该属于本申请的保护范围。
Claims (10)
1.一种水性抗菌保护膜,其特征在于,包括按重量份计的如下组分:
其中,所述水性聚氨基甲酸乙酯为阴离子脂肪族水性聚氨酯分散体;所述抗菌剂为纳米氧化锌水性浆状分散体。
2.如权利要求1所述的水性抗菌保护膜,其特征在于,所述水性聚氨基甲酸乙酯的相对分子质量为10000-30000。
3.如权利要求1所述的水性抗菌保护膜,其特征在于,所述纳米氧化锌水性浆状分散体中纳米氧化锌的浓度为25000ppm,平均粒径为5-10nm。
4.如权利要求1所述的水性抗菌保护膜,其特征在于,所述分散剂为六偏磷酸钠;所述消泡剂为聚醚改性硅油。
5.如权利要求1所述的水性抗菌保护膜,其特征在于,所述水性抗菌保护膜还包括水溶性颜料,所述水溶性颜料的重量份数为0.1份-5份。
6.一种如权利要求1-5任一项所述的水性抗菌保护膜的制备方法,其特征在于,包括如下步骤:
S1:将分散剂和抗菌剂加入水中,室温下搅拌混合均匀得到第一浆料;
S2:将水性聚氨基甲酸乙酯和消泡剂加入到所述第一浆料中,室温下继续搅拌混合均匀得到第二浆料;
S3:将S2中所述第二浆料干燥固化,即得所述水性抗菌保护膜。
7.如权利要求6所述的制备方法,其特征在于,S1中所述搅拌速度为500-1500rpm/min,搅拌时间为30-60min;S2中所述搅拌时间为60-80min。
8.如权利要求6所述的制备方法,其特征在于,S3中所述干燥温度为60-80℃,时间为5-10min。
9.如权利要求6所述的制备方法,其特征在于,S2步骤中还包括以下步骤:加入水溶性颜料,搅拌均匀后研磨,得到第二浆料。
10.一种如权利要求1-5任一项所述的水性抗菌保护膜在公共设施、医疗器械和交通工具中的应用。
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CN107337977A (zh) * | 2017-08-28 | 2017-11-10 | 四川省蓝扬科技有限公司 | 一种具有抗菌环保功能的水性涂料组合物 |
CN109021550A (zh) * | 2018-06-22 | 2018-12-18 | 同济大学 | 一种超支化水性聚氨酯纳米氧化锌复合材料及其制备方法 |
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