CN109267354A - 一种cvc面料的疏水整理方法 - Google Patents

一种cvc面料的疏水整理方法 Download PDF

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CN109267354A
CN109267354A CN201811041854.9A CN201811041854A CN109267354A CN 109267354 A CN109267354 A CN 109267354A CN 201811041854 A CN201811041854 A CN 201811041854A CN 109267354 A CN109267354 A CN 109267354A
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cvc
hydrophobic
cvc fabric
fabric
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潘学东
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Anhui Yayuan Printing And Dyeing Co Ltd
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Abstract

本发明公开了一种CVC面料的疏水整理方法，包括如下步骤：S1、将CVC面料表面进行预处理后，再在包含多元羧酸和次亚磷酸钠的水溶液中进行浸轧整理，接着进行预烘处理，得到表面包含‑COOH基团的CVC面料；S2、将步骤S1得到的表面包含‑COOH基团的CVC面料在包含氨基改性聚硅氧烷、氨基硅烷偶联剂和纳米粒子的乙醇溶液中进行浸轧整理，再进行烘干处理，得到疏水CVC面料。本发明提出的一种CVC面料的疏水整理方法，其不仅避免使用含氟整理剂，而且克服了传统疏水整理耐久性不佳的缺陷，整理得到的疏水CVC面料疏水效果优异，环保健康、性能突出、耐水洗性强。

Description

一种CVC面料的疏水整理方法
技术领域
本发明涉及功能面料技术领域，尤其涉及一种CVC面料的疏水整理方法。
背景技术
过去，大多使用含有长氟碳链的化合物作为疏水整理剂以得到低表面自由能的面料，虽然含氟体系的化合物整理后效果较好，但是此类整理剂价格昂贵，同时近些年的研究发现含氟化学物难以生物降解，对环境和人体健康造成潜在的危害，因此，如何使环境友好型的整理剂达到长氟碳链的化合物整理效果，是当今开发功能面料的一个重要课题。
目前也有文献报道采用二氧化硅、二氧化钛等无机纳米粒子构建粗糙结构，再通过化学表面改性方法将低表面能化合物接枝于基材表面，赋予其疏水性能。然而，由于引入的纳米涂层或颗粒与面料表面之间的结合力较弱，所制备的疏水织物的耐久性往往较差，经过洗涤或摩擦后，疏水性能容易丧失。
CVC面料是特指一类仅有涤与棉两种成分，且棉的含量大于涤的含量的面料，这类面料兼具纯棉织物的吸湿、透气、手感柔软和涤纶长丝织物的挺括、悬垂性好、外观平整度高等特点。然而，由于面料中棉成分是由亲水性的纤维素纤维组成，因此吸湿亲水性能好，非常易粘污，易吸附各种液体，影响其服用性能，因此，研究一种CVC面料的疏水整理方法，是当今开发多功能面料的一个重要课题。
发明内容
本发明提出了一种CVC面料的疏水整理方法，其不仅避免使用含氟整理剂，而且克服了传统疏水整理耐久性不佳的缺陷，整理得到的疏水CVC面料疏水效果优异，环保健康、性能突出、耐水洗性强。
本发明提出了一种CVC面料的疏水整理方法，包括如下步骤：
S1、将CVC面料进行预处理后，再在包含多元羧酸和次亚磷酸钠的水溶液中进行浸轧整理，接着进行预烘处理，得到表面包含-COOH基团的CVC面料；
S2、将步骤S1得到的表面包含-COOH基团的CVC面料在包含氨基改性聚硅氧烷、氨基硅烷偶联剂和纳米粒子的乙醇溶液中进行浸轧整理，再进行烘干处理，得到疏水CVC面料。
优选地，S1中，所述预处理的过程包括：将CVC面料依次用水、乙醚进行超声清洗。
优选地，S1中，所述包含多元羧酸和次亚磷酸钠的水溶液中，多元羧酸的含量为10-30wt％，次亚磷酸钠的含量为5-15wt％；优选地，多元羧酸为丁烷四羧酸或柠檬酸。
优选地，S1中，所述浸轧整理的过程包括：二浸二轧，浸轧温度为80-90℃，轧余率为80-130％；预烘处理的过程包括：90-100℃下预烘3-5min。
优选地，S2中，所述氨基改性聚硅氧烷是通过将α，ω-二羟基聚二甲基硅氧烷和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷进行缩聚反应得到；具体的，将α，ω-二羟基聚二甲基硅氧烷和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷按重量比18-25:1混合后，加热升温至85-95℃后加入浓度为3-5wt％的KOH溶液，KOH溶液的用量是α，ω-二羟基聚二甲基硅氧烷的0.06-0.1wt％，保温搅拌反应4-6h后，得到所述氨基改性聚硅氧烷。
优选地，S2中，所述氨基硅烷偶联剂为γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、N-(2-氨乙基)-3-氨丙基三甲氧基硅烷、苯胺甲基三乙氧基硅烷、苯胺甲基三甲氧基硅烷中的一种或多种的混合。
优选地，S2中，所述纳米粒子为纳米二氧化硅、纳米二氧化钛、纳米三氧化二铝、纳米二氧化锆、纳米氧化锌中的一种或多种的混合，优选地，所述纳米粒子的粒径为10-100nm。
优选地，所述包含氨基改性聚硅氧烷、氨基硅烷偶联剂和纳米粒子的乙醇溶液中，氨基改性聚硅氧烷的含量为5-25wt％，氨基硅烷偶联剂的含量为1-5wt％、纳米粒子的含量为2-10wt％。
优选地，所述浸轧整理的过程包括：一浸一轧，浸轧温度为50-60℃，轧余率为80-130％；所述烘干处理的过程包括：60-70℃下烘干3-5min。
本发明中，先对面料进行表面改性，利用多元羧酸在次亚磷酸钠的催化下与面料中纤维进行酯化反应，最终使面料表面产生大量的-COOH基团；然后再浸轧整理液处理，其浸轧整理液中包含氨基改性聚硅氧烷、氨基硅烷偶联剂，二者包含的氨基能与面料表面的-COOH极性基团产生定向吸附和反应，从而牢固的吸附在面料表面，因此面料表面可以有效包覆聚硅氧烷等疏水性物质，同时由于氨基硅烷偶联剂可以对纳米粒子进行定向吸附，因此也可以有效增强纳米粒子与面料表面的结合，从而使面料获得良好疏水性的同时还获得良好的耐洗性。
由此可知，本发明所述CVC面料的疏水整理方法，采用面料和疏水性物质之间的结合反应，显著提高低表面能化合物以及纳米粒子与面料的结合力，利用氨基长链聚硅氧烷形成疏水表面的同时，还借助于微纳米粒子构建粗糙结构的协同效应，最终水滴在面料表面易滚动，经多次皂洗后，面料仍然具有优异的疏水性能。此外本发明整理方法采用传统浸轧工艺，操作简单，耗时短，且无需高温焙烘。
具体实施方式
实施例1
一种CVC面料的疏水整理方法，包括如下步骤：
S1、将CVC面料表面依次用水、乙醚超声清洗后，再在包含多元羧酸和次亚磷酸钠的水溶液中进行浸轧整理，所述包含多元羧酸和次亚磷酸钠的水溶液中，多元羧酸的含量为10wt％，次亚磷酸钠的含量为15wt％，且多元羧酸为丁烷四羧酸，二浸二轧，浸轧温度为80℃，轧余率为130％，接着在90℃下预烘5min，得到表面包含-COOH基团的CVC面料；
S2、将步骤S1得到的表面包含-COOH基团的CVC面料在包含氨基改性聚硅氧烷、氨基硅烷偶联剂和纳米粒子的乙醇溶液中进行浸轧整理，所述包含氨基改性聚硅氧烷、氨基硅烷偶联剂和纳米粒子的乙醇溶液中，氨基改性聚硅氧烷的含量为5wt％，氨基硅烷偶联剂的含量为5wt％、纳米粒子的含量为2wt％，一浸一轧，浸轧温度为60℃，轧余率为80％，再在70℃下烘干3min，得到疏水CVC面料；
其中所述氨基改性聚硅氧烷是通过将α，ω-二羟基聚二甲基硅氧烷和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷进行缩聚反应得到，具体的，将α，ω-二羟基聚二甲基硅氧烷和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷按重量比18:1混合后，加热升温至95℃后加入浓度为3wt％的KOH溶液，KOH溶液的用量是α，ω-二羟基聚二甲基硅氧烷的0.1wt％，保温搅拌反应4h后，得到所述氨基改性聚硅氧烷；所述氨基硅烷偶联剂为γ-氨丙基三乙氧基硅烷，所述纳米粒子为纳米二氧化硅，且粒径为100nm。
实施例2
一种CVC面料的疏水整理方法，包括如下步骤：
S1、将CVC面料表面依次用水、乙醚超声清洗后，再在包含多元羧酸和次亚磷酸钠的水溶液中进行浸轧整理，所述包含多元羧酸和次亚磷酸钠的水溶液中，多元羧酸的含量为30wt％，次亚磷酸钠的含量为5wt％，且多元羧酸为柠檬酸，二浸二轧，浸轧温度为90℃，轧余率为80％，接着在100℃下预烘3min，得到表面包含-COOH基团的CVC面料；
S2、将步骤S1得到的表面包含-COOH基团的CVC面料在包含氨基改性聚硅氧烷、氨基硅烷偶联剂和纳米粒子的乙醇溶液中进行浸轧整理，所述包含氨基改性聚硅氧烷、氨基硅烷偶联剂和纳米粒子的乙醇溶液中，氨基改性聚硅氧烷的含量为25wt％，氨基硅烷偶联剂的含量为1wt％、纳米粒子的含量为10wt％，一浸一轧，浸轧温度为50℃，轧余率为130％，再在60℃下烘干5min，得到疏水CVC面料；
其中所述氨基改性聚硅氧烷是通过将α，ω-二羟基聚二甲基硅氧烷和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷进行缩聚反应得到，具体的，将α，ω-二羟基聚二甲基硅氧烷和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷按重量比25:1混合后，加热升温至85℃后加入浓度为5wt％的KOH溶液，KOH溶液的用量是α，ω-二羟基聚二甲基硅氧烷的0.06wt％，保温搅拌反应6h后，得到所述氨基改性聚硅氧烷；所述氨基硅烷偶联剂为N-(2-氨乙基)-3-氨丙基三甲氧基硅烷，所述纳米粒子为纳米二氧化钛、三氧化二铝的混合，且所述纳米粒子的粒径为10nm。
实施例3
一种CVC面料的疏水整理方法，包括如下步骤：
S1、将CVC面料表面依次用水、乙醚超声清洗后，再在包含多元羧酸和次亚磷酸钠的水溶液中进行浸轧整理，所述包含多元羧酸和次亚磷酸钠的水溶液中，多元羧酸的含量为20wt％，次亚磷酸钠的含量为10wt％，且多元羧酸为丁烷四羧酸，二浸二轧，浸轧温度为85℃，轧余率为100％，接着在95℃下预烘4min，得到表面包含-COOH基团的CVC面料；
S2、将步骤S1得到的表面包含-COOH基团的CVC面料在包含氨基改性聚硅氧烷、氨基硅烷偶联剂和纳米粒子的乙醇溶液中进行浸轧整理，所述包含氨基改性聚硅氧烷、氨基硅烷偶联剂和纳米粒子的乙醇溶液中，氨基改性聚硅氧烷的含量为15wt％，氨基硅烷偶联剂的含量为3wt％、纳米粒子的含量为6wt％，一浸一轧，浸轧温度为55℃，轧余率为100％，再在65℃下烘干4min，得到疏水CVC面料；
其中所述氨基改性聚硅氧烷是通过将α，ω-二羟基聚二甲基硅氧烷和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷进行缩聚反应得到，具体的，将α，ω-二羟基聚二甲基硅氧烷和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷按重量比21:1混合后，加热升温至90℃后加入浓度为4wt％的KOH溶液，KOH溶液的用量是α，ω-二羟基聚二甲基硅氧烷的0.08wt％，保温搅拌反应5h后，得到所述氨基改性聚硅氧烷；所述氨基硅烷偶联剂为苯胺甲基三乙氧基硅烷，所述纳米粒子为纳米二氧化锆、氧化锌的混合，且所述纳米粒子的粒径为50nm。
实施例4
一种CVC面料的疏水整理方法，包括如下步骤：
S1、将CVC面料表面依次用水、乙醚超声清洗后，再在包含多元羧酸和次亚磷酸钠的水溶液中进行浸轧整理，所述包含多元羧酸和次亚磷酸钠的水溶液中，多元羧酸的含量为15wt％，次亚磷酸钠的含量为8wt％，且多元羧酸为柠檬酸，二浸二轧，浸轧温度为86℃，轧余率为110％，接着在92℃下预烘4.5min，得到表面包含-COOH基团的CVC面料；
S2、将步骤S1得到的表面包含-COOH基团的CVC面料在包含氨基改性聚硅氧烷、氨基硅烷偶联剂和纳米粒子的乙醇溶液中进行浸轧整理，所述包含氨基改性聚硅氧烷、氨基硅烷偶联剂和纳米粒子的乙醇溶液中，氨基改性聚硅氧烷的含量为20wt％，氨基硅烷偶联剂的含量为2wt％、纳米粒子的含量为5wt％，一浸一轧，浸轧温度为56℃，轧余率为90％，再在66℃下烘干3.5min，得到疏水CVC面料；
其中所述氨基改性聚硅氧烷是通过将α，ω-二羟基聚二甲基硅氧烷和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷进行缩聚反应得到，具体的，将α，ω-二羟基聚二甲基硅氧烷和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷按重量比20:1混合后，加热升温至88℃后加入浓度为4.5wt％的KOH溶液，KOH溶液的用量是α，ω-二羟基聚二甲基硅氧烷的0.09wt％，保温搅拌反应5.5h后，得到所述氨基改性聚硅氧烷；所述氨基硅烷偶联剂为γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷的混合，所述纳米粒子为纳米氧化锌，且粒径为600nm。
将实施例1-4得到的疏水CVC面料进行如下疏水性测试测试：
疏水性测试：
(1)淋湿实验：参照GB4745纺织织物表面抗湿性测定沾水试验标准，其中，1级--受淋表面全部润湿；2级--受淋表面有一半润湿，这通常是指小块不连接的润湿面积的总和；3级--受淋表面仅有不连接的小面积润湿；4级--受淋表面没有润湿，但在表面沾有小水珠；5级--受淋表面没有润湿，在表面也未沾有小水珠。
(2)接触角测试：将水滴滴于疏水CVC面料表面，通过扫描电镜获得水滴在该疏水CVC面料表面的形态，计算出水滴在疏水CVC面料表面的接触角；按照AATCC测试方法61-2003将疏水CVC面料洗涤50次后，获得水滴在疏水CVC面料表面的接触角。
上述实施例1-4得到的疏水CVC面料的性能测试结果如下表所示：
本发明中，先对面料进行表面改性，利用多元羧酸在次亚磷酸钠的催化下与面料中纤维进行酯化反应，最终使面料表面产生大量的-COOH基团；然后再浸轧整理液处理，其浸轧整理液中包含氨基改性聚硅氧烷、氨基硅烷偶联剂，二者包含的氨基能与面料表面的-COOH极性基团产生定向吸附和反应，从而牢固的吸附在面料表面，因此面料表明可以有效包覆聚硅氧烷等疏水性物质，同时由于氨基硅烷偶联剂可以对纳米粒子进行定向吸附，因此也可以有效增强纳米粒子与面料表面的结合，从而是面料获得良好疏水性的同时还获得良好的耐洗性。
由此可知，本发明所述CVC面料的疏水整理方法，采用面料和疏水性物质之间的结合反应，显著提高低表面能化合物以及纳米粒子与面料的结合力，利用氨基长链聚硅氧烷形成疏水表面的同时，还借助于微纳米粒子构建粗糙结构的协同效应，最终水滴在面料表面易滚动，经多次皂洗后，面料仍然具有优异的疏水性能。此外本发明整理方法采用传统浸轧工艺，操作简单，耗时短，且无需高温焙烘。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (9)

1.一种CVC面料的疏水整理方法，其特征在于，包括如下步骤：
S1、将CVC面料进行预处理后，再在包含多元羧酸和次亚磷酸钠的水溶液中进行浸轧整理，接着进行预烘处理，得到表面包含-COOH基团的CVC面料；
S2、将步骤S1得到的表面包含-COOH基团的CVC面料在包含氨基改性聚硅氧烷、氨基硅烷偶联剂和纳米粒子的乙醇溶液中进行浸轧整理，再进行烘干处理，得到疏水CVC面料。
2.根据权利要求1所述的CVC面料的疏水整理方法，其特征在于，S1中，所述预处理的过程包括：将CVC面料依次用水、乙醚超声清洗。
3.根据权利要求1或2所述的CVC面料的疏水整理方法，其特征在于，S1中，所述包含多元羧酸和次亚磷酸钠的水溶液中，多元羧酸的含量为10-30wt％，次亚磷酸钠的含量为5-15wt％；优选地，多元羧酸为丁烷四羧酸或柠檬酸。
4.根据权利要求1-3任一项所述的CVC面料的疏水整理方法，其特征在于，S1中，所述浸轧整理的过程包括：二浸二轧，浸轧温度为80-90℃，轧余率为80-130％；预烘处理的过程包括：90-100℃下预烘3-5min。
5.根据权利要求1-4任一项所述的CVC面料的疏水整理方法，其特征在于，S2中，所述氨基改性聚硅氧烷是通过将α，ω-二羟基聚二甲基硅氧烷和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷进行缩聚反应得到；具体的，将α，ω-二羟基聚二甲基硅氧烷和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷按重量比18-25:1混合后，加热升温至85-95℃后加入浓度为3-5wt％的KOH溶液，KOH溶液的用量是α，ω-二羟基聚二甲基硅氧烷的0.06-0.1wt％，保温搅拌反应4-6h后，得到所述氨基改性聚硅氧烷。
6.根据权利要求1-5任一项所述的CVC面料的疏水整理方法，其特征在于，S2中，所述氨基硅烷偶联剂为γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、N-(2-氨乙基)-3-氨丙基三甲氧基硅烷、苯胺甲基三乙氧基硅烷、苯胺甲基三甲氧基硅烷中的一种或多种的混合。
7.根据权利要求1-6任一项所述的CVC面料的疏水整理方法，其特征在于，S2中，所述纳米粒子为纳米二氧化硅、纳米二氧化钛、纳米三氧化二铝、纳米二氧化锆、纳米氧化锌中的一种或多种的混合，优选地，所述纳米粒子的粒径为10-100nm。
8.根据权利要求1-7任一项所述的CVC面料的疏水整理方法，其特征在于，所述包含氨基改性聚硅氧烷、氨基硅烷偶联剂和纳米粒子的乙醇溶液中，氨基改性聚硅氧烷的含量为5-25wt％，氨基硅烷偶联剂的含量为1-5wt％、纳米粒子的含量为2-10wt％。
9.根据权利要求1-8任一项所述的CVC面料的疏水整理方法，其特征在于，所述浸轧整理的过程包括：一浸一轧，浸轧温度为50-60℃，轧余率为80-130％；所述烘干处理的过程包括：60-70℃下烘干3-5min。
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