CN105524530A - 一种热交联型抗菌、防霉及分解甲醛的纳米涂层材料及其制备方法 - Google Patents
一种热交联型抗菌、防霉及分解甲醛的纳米涂层材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种热交联型抗菌、防霉及分解甲醛的纳米涂层材料及其制备方法,该涂层材料由以下质量百分比的成分组成:由0.2-7%的热交联剂或聚合物、0.1-10%的有机高分子、0-2%着色染料、2-15%纳米粒子、60-80%溶剂组成。其制备方法为:溶剂中加入热交联剂、有机高分子、着色染料,混匀后加入纳米氧化锌或者纳米氧化锌和纳米二氧化钛的纳米粒子,在500-10000转/分钟的转速下以搅拌、分散和乳化中的其中一种方式进行操作1小时,然后用高效研磨机研磨。本发明的有益效果:本发明可用挤压、喷涂,旋涂、刮涂等方式涂布在基材表面,通过热固化在基材表面形成一层耐磨性优良、可耐化学品腐蚀及耐候性极佳的具有抗菌、防霉及分解甲醛的纳米涂层。
Description
技术领域
本发明属于纳米涂层制备及应用技术领域,具体来说,涉及到一种热交联型抗菌、防霉及分解甲醛的纳米涂层材料及其制备方法。
背景技术
抗菌防霉涂料主要有两大类型:第一类是有机抗菌剂或有机防霉剂,其缺点是作用时间短,随着有机物的自行分解,抗菌或防霉作用逐渐消失,有害微生物会形成耐药性,并且某些有机物对人体和环境有负面影响。第二类是无机材料抗菌剂或防霉剂。而无机系列抗菌剂或防霉剂又分为两种:一种是以银、铜、锌等金属离子负载在无机载体上而制成的抗菌剂或防霉剂,其缺点是银、铜、锌等金属离子会流失,抗菌或防霉作用逐渐下降,并且难以做到抗菌和防霉同时兼顾;另一种是纳米氧化锌、二氧化钛等金属氧化的光催化作用来实现抗菌或防霉的无机抗菌剂或防霉剂,缺点是光催化作用必需借助紫外光、水、空气等条件。但是最新的研究表明,纳米氧化物的抗菌防霉活性主要取决于纳米粒子表面的缺陷数,该缺陷通过和空气中的水作用,形成氧负离子自由基。
中国专利CN200610157289.3中公开了一种纳米抗菌防霉涂料,按照重量百分比包括以下组分:水性涂料75-90%,纳米银3-7%,纳米铜或纳米锌3-7%,纳米氧化锌或纳米二氧化钛4-11%。但是该专利所述的纳米氧化物基本上都被水性涂料包覆,在表面裸露的纳米氧化物有限,非固化纳米涂层耐磨性、耐化学品腐蚀性,耐候性都很差,很容易脱落,其抗菌防霉性能有限。
中国专利CN101701120中公开了一种纳米氧化锌抗菌抗污涂料及其制备方法,但是根据该发明专利制作的纳米涂层很容易脱落,更重要的是这种纳米涂料做的非固化涂层耐磨性、耐化学品腐蚀性,耐候性都很差,很容易脱落,同时有大量的助溶剂挥发造成环境的污染。
氧化锌具有吸收紫外线(UV)特性,故含氧化锌的涂料具有极好的抗老化作用,延长涂层的使用寿命,并且一定数量的氧化锌还可以提高涂料的韧性和硬度如美国专利US41395150。另一方面,美国专利US7348029说明纳米氧化锌颗粒除了抗紫外线外还具备抑制病菌滋生的能力。纳米氧化锌作为理想的普适性抗菌能力,长效地抗污性,对环境质量无污染对环境质量无污染,具有环保型等特点。
发明内容
针对相关技术中的上述技术问题,本发明提出一种热交联型抗菌、防霉及分解甲醛的纳米涂层材料及其制备方法。
为实现上述技术目的,本发明的技术方案是这样实现的:
一种热交联型抗菌、防霉及分解甲醛的纳米涂层材料,其由以下质量百分比的成分组成:热交联剂或聚合物0.2-7%、有机高分子0.1-10%、着色染料0-2%、纳米粒子2-15%、溶剂60-80%。
优选的,所述的热交联剂选自双官能团的二环氧,如:二环氧化-1,3-丁二烯、二环氧甘油醚、二环氧己烷、1,2,7,8-二环氧酮、聚乙二醇二环氧乙烷甲基醚、二环戊二烯环氧化物等;或者所述的热交联剂选自双官能团的二乙烯基醚,如1,4-二环己烷二甲基二乙烯基醚、四(乙二醇)二乙烯基醚、1,6-己二醇二乙烯醚、三乙二醇二乙烯基醚、1,4-环己烷二甲醇二乙烯醚、1,4-丁二醇乙烯醚、二乙二醇二乙烯基醚等;或者所述的热交联剂选自双官能团的双苯酐,如4,4'-氧双邻苯二甲酸酐、均苯四甲酸酐、1,4,5,8-萘四甲酸酐、3,4,9,10-四羧酸酐等;或者所述的热交联剂选自双官能团的二异氰酸酯,如1,4-环己烷二异氰酸酯、1,5-奈二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、1,6-二异氰酸酯基己烷、反-1,4-环己基二异氰酸酯、二甲苯烷二异氰酸酯、L-赖氨酸二异氰酸酯、1,6-己二异氰酸酯、三甲基六亚甲基二异氰酸酯等;或者所述的热交联剂选自多官能团的环氧、氮丙啶、乙烯基醚、苯酐、异氰酸酯的单体,如:三(环氧丙基)异氰尿酸酯、异氰脲酸Β-三缩水甘油酯、缩水甘油醚、异氰脲酸Β-三缩水甘油酯、三羟甲基丙烷-三[3-(2-甲基吖丙啶基)丙酸酯]、三羟甲基丙烷-三(3-吖丙啶基丙酸酯)、季戊四醇三(3-氮丙啶基)丙酸酯等;或者所述的热交联剂选自多官能团的环氧、氮丙啶、乙烯基醚、苯酐、异氰酸酯的聚合物,如环氧树脂、酚醛环氧树脂、聚氮丙啶交联剂等。
优选的,所述有机高分子选自以下物质中的一种或多种:丙烯酸树脂或其酯类树脂、酚醛树脂、聚氨酯、脲醛树脂、聚乙烯醇、聚乙烯醇缩醛、氨基树脂、醇酸树脂、阿拉伯树胶、明胶、蛋白质、淀粉、纤维素。
优选的,所述的着色染料选用溶于溶剂的无色或者颜色为蓝色、黄色、紫色、红色的染料。
优选的,所述纳米粒子为纳米氧化锌或者纳米氧化锌和纳米二氧化钛的组合物,且粒径为1nm-1000nm。
优选的,所述的溶剂选自水或者以下物质中的一种或多种:四氢呋喃、丁酮、二乙醇甲醚、丙二醇甲醚、乙二醇乙醚、DMF、二乙二醇二甲醚、丁酮、N-甲基吡咯烷酮。
一种热交联型抗菌、防霉及分解甲醛的纳米涂层材料的制备方法,包括如下步骤:
溶剂中加入热交联剂、有机高分子、着色染料,混匀后加入纳米氧化锌或者纳米氧化锌和纳米二氧化钛的纳米粒子,在500-10000转/分钟的转速下以搅拌、分散和乳化中的其中一种方式进行操作1小时,用研磨机研磨至纳米粒子的粒径小于1000nm。
本发明的有益效果:本发明不但具有抗菌的性能,而且还具有很好的防霉及去除甲醛的特性,因此本发明提供一种含有纳米氧化锌的涂层材料,将其通过挤压、喷涂,旋涂、刮涂等方式涂布在基材表面,通过热交联固化在基材表面形成一层致密的三维网状结构,大幅提高了涂层的耐磨性、耐化学品腐蚀性及耐候性;同时由于表面被大量纳米粒子覆盖,因而该涂层具有抗菌、防霉及分解甲醛的纳米涂层;与光照交联固化比较,热固化使用范围更广,更适合于异形表面或者器件内部的涂层制备;该涂层使用范围广,可用于家装、油漆,外墙,码头和舰船等领域。
具体实施方式
为了使本发明实现的技术手段和创作特征易于明白了解,下面对本发明进一步阐述。
下面结合具体的实施例对本发明所述的热交联型抗菌、防霉及分解甲醛的纳米涂层材料做进一步说明,但是本发明的保护范围并不限于此。
实施例1
100g水中加入10g聚丙烯酸、8g水溶环氧树脂、0.5g甲基紫,混匀后加入50g初始粒径为20nm的氧化锌纳米粒子,4000转/分钟搅拌1小时,用高效研磨机研磨至粒度仪监控平均粒径小于200nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例2
100g水中加入10g聚乙烯醇缩醛、6g三羟甲基丙烷-三[3-(2-甲基吖丙啶基)丙酸酯]、1g甲基紫,混匀后加入41g初始粒径为20nm的二氧化钛和11g初始粒径为30nm的氧化锌纳米粒子,4000转/分钟分散1小时,用高效研磨机研磨至粒度仪监控平均粒径小于300nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例3
100g丁酮中加入8g脲醛树脂、4g二乙二醇二乙烯基醚、3g环氧树脂128、0.5g维多利亚纯蓝,混匀后加入45g初始粒径为20nm的氧化锌纳米粒子,4000转/分钟乳化1小时,用高效研磨机研磨至粒度仪监控平均粒径小于200nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例4
100gDMF中加入8g环氧树脂、10g酚醛树脂、0.5g结晶紫,混匀后加入68g初始粒径为20nm的氧化锌纳米粒子,4000转/分钟分散1小时,用高效研磨机研磨至粒度仪监控平均粒径小于400nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例5
100g乙二醇乙醚中加入9g酚醛树脂、4g1,6-二异氰酸酯基己烷、4g环氧树脂、1g染料黄,混匀后加入61g初始粒径为25nm的氧化锌纳米粒子,4000转/分钟分散1小时,用高效研磨机研磨至粒度仪监控平均粒径小于200nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例6
100g水中加入8g卵清蛋白、9g水性环氧,混匀后加入51g初始粒径为50nm的氧化锌纳米粒子,4000转/分钟分散1小时,用高效研磨机研磨至粒度仪监控平均粒径小于500nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例7
100g丙烯酸异辛酯中加入8g丙烯酸马来酸酐共聚物、6g缩水甘油醚、0.5g纯蓝,混匀后加入40g初始粒径为50nm的氧化锌纳米粒子、11g初始粒径为30nm的氧化钛,4000转/分钟乳化1小时,用高效研磨机研磨至粒度仪监控平均粒径小于600nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例8
100gN-甲基吡咯烷酮中加入7g丙烯酸-丙烯酸羟乙酯共聚物、6g异氰脲酸Β-三缩水甘油酯,混匀后加入50g初始粒径为20nm的氧化锌纳米粒子,4000转/分钟分散1小时,用高效研磨机研磨至粒度仪监控平均粒径小于300nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例9
100gN,N-二乙基甲酰胺中加入10g聚氨酯、7g三(环氧丙基)异氰尿酸酯、0.5g纯蓝、0.5g燃料黄,混匀后加入53g初始粒径为20nm的氧化锌纳米粒子4000转/分钟搅拌1小时,用高效研磨机研磨至粒度仪监控平均粒径小于400nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例10
100g丙二醇甲醚中加入8g酚醛树脂、6g3,4,9,10-四羧酸酐等、1g染料黄,混匀后加入46g初始粒径为20nm的氧化锌纳米粒子4000转/分钟分散1小时,用高效研磨机研磨至粒度仪监控平均粒径小于200nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例11
100g甲基丙烯酸羟乙酯中加入10g脲醛树脂、7g季戊四醇三(3-氮丙啶基)丙酸酯,混匀后加入41g初始粒径为30nm的氧化锌纳米粒子、10g初始粒径为50nm的二氧化钛纳米粒子,4000转/分钟搅拌1小时,用高效研磨机研磨至粒度仪监控平均粒径小于200nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例12
100g异戊二烯中加入5g醇酸树脂、12g酚醛环氧树脂、0.8g结晶紫,混匀后加入35g初始粒径为20nm的氧化锌纳米粒子,4000转/分钟乳化1小时,用高效研磨机研磨至粒度仪监控平均粒径小于200nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例13
100g二乙醇甲醚中加入12g阿拉伯树胶、6g三羟甲基丙烷-三(3-吖丙啶基丙酸酯)、0.5g维多利艳蓝,混匀后加入42g初始粒径为40nm的氧化锌纳米粒子、6g初始粒径为20nm的二氧化钛纳米粒子,4000转/分钟搅拌1小时,用高效研磨机研磨至粒度仪监控平均粒径小于400nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例14
100g二乙二醇二甲醚中加入9g聚乙烯醇、7g聚氮丙啶交联剂、0.5g艳蓝、0.5g甲基紫,混匀后加入46g初始粒径为40nm的氧化锌纳米粒子,4000转/分钟分散1小时,用高效研磨机研磨至粒度仪监控平均粒径小于200nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例15
100g四氢呋喃中加入10g纤维素、6g季戊四醇三(3-氮丙啶基)丙酸酯,混匀后加入56g初始粒径为40nm的氧化锌纳米粒子,4000转/分钟分散1小时,用高效研磨机研磨至粒度仪监控平均粒径小于200nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例16
80g丙二醇甲醚、50gDMF中加入14g丙烯酸甲酯-丙烯酸羟乙酯共聚物、8g二乙二醇二乙烯基醚、0.5g结晶紫、0.8g纯蓝,混匀后加入61g初始粒径为20nm的氧化锌纳米粒子,4000转/分钟分散1小时,用高效研磨机研磨至粒度仪监控平均粒径小于200nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
实施例17
80g丙二醇甲醚中加入1g醇酸树脂、2g酚醛环氧树脂、15g结晶紫,混匀后加入2g初始粒径为20nm的氧化锌纳米粒子,4000转/分钟分散1小时,用高效研磨机研磨至粒度仪监控平均粒径小于200nm,即可得到热交联型抗菌、防霉及分解甲醛的纳米涂层材料。
综上所述,借助于本发明的上述技术方案,本发明可用挤压、喷涂,旋涂、刮涂等方式涂布在基材表面,通过热交联固化在基材表面形成一层致密的三维网状结构,大幅提高了涂层的耐磨性、耐化学品腐蚀性及耐候性;同时由于表面被大量纳米粒子覆盖,因而该涂层具有抗菌、防霉及分解甲醛的纳米涂层;与光照交联固化比较,热固化使用范围更广,更适合于异形表面或者器件内部的涂层制备;该涂层使用范围广,可用于家装、油漆,外墙,码头和舰船等领域。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种热交联型抗菌、防霉及分解甲醛的纳米涂层材料,其特征在于,其由以下质量百分比的成分组成:热交联剂或聚合物0.2-7%、有机高分子0.1-10%、着色染料0-2%、纳米粒子2-15%、溶剂60-80%。
2.根据权利要求1所述的热交联型抗菌、防霉及分解甲醛的纳米涂层材料,其特征在于,所述的热交联剂选自双官能团的二环氧单体、二氮丙啶单体、二乙烯基醚单体、双苯酐单体、二异氰酸酯单体;或者所述的热交联剂选自多官能团的环氧单体、氮丙啶单体、乙烯基醚单体、苯酐单体、异氰酸酯单体;或者所述的热交联剂选自多官能团的环氧、氮丙啶、乙烯基醚、苯酐、异氰酸酯的聚合物。
3.根据权利要求1所述的热交联型抗菌、防霉及分解甲醛的纳米涂层材料,其特征在于,所述有机高分子选自以下物质中的一种或多种:丙烯酸树脂或其酯类树脂、酚醛树脂、聚氨酯、脲醛树脂、聚乙烯醇、聚乙烯醇缩醛、氨基树脂、醇酸树脂、阿拉伯树胶、明胶、蛋白质、淀粉、纤维素。
4.根据权利要求1所述的热交联型抗菌、防霉及分解甲醛的纳米涂层材料,所述的着色染料选用溶于溶剂的无色或者颜色为蓝色、黄色、紫色、红色的染料。
5.根据权利要求1所述的热交联型抗菌、防霉及分解甲醛的纳米涂层材料,其特征在于,所述的纳米粒子为纳米氧化锌或者纳米氧化锌和纳米二氧化钛的组合物,所述纳米粒子的粒径为1nm-1000nm。
6.根据权利要求1所述的热交联型抗菌、防霉及分解甲醛的纳米涂层材料,其特征在于,所述的溶剂选自水或者以下物质中的一种或多种:四氢呋喃、丁酮、二乙醇甲醚、丙二醇甲醚、乙二醇乙醚、DMF、二乙二醇二甲醚、丁酮、N-甲基吡咯烷酮。
7.一种热交联型抗菌、防霉及分解甲醛的纳米涂层材料的制备方法,其特征在于,包括如下步骤:
溶剂中加入热交联剂、有机高分子、着色染料,混匀后加入纳米氧化锌或者纳米氧化锌和纳米二氧化钛的纳米粒子,在500-10000转/分钟的转速下以搅拌、分散和乳化中的其中一种方式进行操作1小时,用研磨机研磨至纳米粒子的粒径小于1000nm。
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