CN106894224A - 一种纺织品用无卤阻燃自修复超疏水涂层胶及阻燃自修复超疏水织物 - Google Patents

一种纺织品用无卤阻燃自修复超疏水涂层胶及阻燃自修复超疏水织物 Download PDF

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CN106894224A
CN106894224A CN201710144280.7A CN201710144280A CN106894224A CN 106894224 A CN106894224 A CN 106894224A CN 201710144280 A CN201710144280 A CN 201710144280A CN 106894224 A CN106894224 A CN 106894224A
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retardant
fabric
flame
halogen
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李洋
许富昌
孙俊奇
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Jilin University
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Abstract

一种纺织品用无卤阻燃自修复超疏水涂层胶及阻燃自修复超疏水织物，属于纺织品整理剂技术领域。该涂层胶是由100mL溶剂、0～10.0g无卤阻燃剂、0.01～10.0g阻燃增效剂、0.01～10.0g增稠剂、0.01～10.0g无卤疏水剂混合后充分搅拌至均匀，配制成混合分散液后得到。本发明可以方便的赋予织物阻燃和自修复超疏水功能。超疏水性能赋予织物良好的防水性和自清洁作用，同时可以有效地提高织物阻燃功能的稳定性。此外，超疏水性可以在受损后通过自修复得以恢复。本发明制备的阻燃自修复超疏水涂层胶制备工艺过程简单，符合环保，低成本的工艺要求并可广泛应用于床上用品，家居装饰等，符合发展新材料的要求，具有广阔的市场应用前景。

Description

一种纺织品用无卤阻燃自修复超疏水涂层胶及阻燃自修复超 疏水织物
技术领域
本发明属于纺织品整理剂技术领域，具体涉及一种纺织品用无卤阻燃自修复超疏水涂层胶及阻燃自修复超疏水织物。
背景技术
织物在人们的生活中随处可见。但由于其易燃的特性，近些年来由于织物燃烧造成的人身伤亡和财产损失也愈来愈多。因此，对织物进行阻燃处理势在必行。相比于我国，欧美较早就开始了对阻燃织物的研究。我国阻燃织物的研发生产始于20世纪60年代。时至今日，我国阻燃织物的研发及生产虽然取得了长足的进展，但仍然无法满足日益增长的需求。如今，使用阻燃涂层胶对织物进行阻燃处理是最为常用的一种制备阻燃织物的方法。但是，现有的阻燃涂层胶存在一些缺点，其中之一就是涂层胶的稳定性欠佳。由于阻燃涂层胶易溶或易分解的特点，对阻燃织物进行水洗清洁后，织物的阻燃性会急剧的降低甚至丧失。因此，如何以低成本的方式制备具有良好稳定性的阻燃涂层胶仍然是一个挑战。
近些年，随着仿生学和纳米科学的发展，人们对超疏水材料的研究愈发透彻。类似于荷叶、水禽类的羽毛等，人造超疏水材料具有极强的疏水能力。水滴在超疏水材料上接触角大于150°，滚动角小于10°。因此，超疏水材料在防腐蚀、自清洁领域有广泛的应用前景。将超疏水功能引入到阻燃涂层胶中，可以得到具有超强防水能力和自清洁性能的新型阻燃织物。由于超疏水功能带来的自清洁性，阻燃超疏水织物不需要长时间的浸泡洗涤，只需要用少量水冲洗即可除去织物表面的灰尘和污渍，大大的减少了涂层胶与水接触的时间和面积，因此可以有效地提高阻燃织物的使用寿命。此外，近期自修复超疏水材料的研发受到了广泛关注。在受到紫外线照射、化学腐蚀或划伤后，自修复超疏水材料能够自发的对受损的功能进行修复，从而有效地提高材料的使用寿命。因此，阻燃自修复超疏水涂层胶的制备具有重要的科研和经济意义。然而这方面的研究却少之又少。通过文献检索，仅有一篇期刊文献报道了制备阻燃自修复超疏水织物的方法(参见ACS Nano 2015,9,4070–4076)。但该方法具有一定的缺陷：(1)该方法过于复杂。为了实现阻燃超疏水织物的制备，需要对织物进行多次修饰处理，耗费大量的时间与能源，且很难与现有的生产设备相兼容。(2)该方法使用的材料具有含氟的物质，价格昂贵且对环境和使用者的健康具有潜在的危害。
发明内容
本发明的目的是为了克服现有技术存在的缺陷，制备一种低成本的纺织品用无卤阻燃自修复超疏水涂层胶及由该涂层胶涂敷后得到的阻燃自修复超疏水织物。该涂层胶可以通过一次浸泡的方法涂敷到织物表面，提供良好的阻燃性能和自修复超疏水性能。
本发明所述的一种低成本的纺织品用无卤阻燃自修复超疏水涂层胶，其组份为：每100mL溶剂中包含0～10.0g无卤阻燃剂，0.01～10.0g阻燃增效剂，0.01～10.0g增稠剂，0.01～10.0g无卤疏水剂。
上述组份混合后充分搅拌至均匀，配制成混合分散液，即得到无卤阻燃自修复超疏水涂层胶。
作为优选，所述的无卤阻燃剂可以选择聚磷酸铵(APP)、三聚氰胺甲醛树脂乳液、磷酸三苯酯中的一种或多种组合。
作为优选，所述的无卤疏水剂可以选择石蜡、蜂蜡、棕榈蜡、十八烷基胺、十八烷酸中的一种或多种组合。
作为优选，所述的阻燃增效剂可以选择三氧化二锑、纳米氧化锌、纳米二氧化硅中的一种或多种组合。
作为优选，所述的增稠剂可以选择聚丙烯酸酯乳液、聚二甲基硅氧烷(PDMS)、聚氨酯乳液中的一种或多种组合。
作为优选，所述的溶剂可以选择四氢呋喃、丙酮中的一种或多种组合。
一种阻燃自修复超疏水织物，是将织物(纯棉、涤纶等)浸入到前面所述的纺织品用无卤阻燃自修复超疏水涂层胶溶液中5～30分钟后，取出晾干后得到，该阻燃自修复超疏水织物具有良好阻燃性能和自修复超疏水性能。
使用本发明制备的织物具有良好的阻燃效果，火源撤离后织物自行熄灭，为织物的大规模使用提供了安全、可靠的保证。超疏水性能赋予织物良好的防水性，水滴在其表面的接触角大于150°，滚动角小于10°，可以有效的保护阻燃剂。超疏水性在受到紫外线、化学腐蚀后，在30～90℃下保持0.5～8个小时，疏水剂会扩散到受损的区域，使织物的疏水性恢复到受损前的状态。这样的修复破坏可以重复10次以上，从而有效地延长阻燃自修复超疏水织物的使用寿命。此外，本发明不限于为易燃织物提供阻燃自修复超疏水功能，也可以通过调节配方组成，去掉无卤阻燃剂，涂敷在已经具有阻燃功能的织物上为其提供持久的自修复超疏水功能。本发明制备的阻燃自修复超疏水涂层胶制备工艺过程简单，所使用的阻燃剂、疏水剂均不含卤素，环保无毒可广泛应用于床上用品，家居装饰等，符合发展新材料的要求，具有广阔的市场应用前景。
附图说明
图1：a)新制备的阻燃自修复超疏水织物表面接触角照片；b)阻燃自修复超疏水织物受氧等离子体刻蚀后表面的接触角照片；c)被氧等离子体刻蚀后的织物进行自修复后表面的接触角照片；对应实施例1。
图2：阻燃自修复超疏水织物燃烧测试照片。a)织物与火源接触照片；b)火源撤离后织物自熄灭后的照片，对应实施例1。
图3：a)新制备的阻燃自修复超疏水织物表面接触角照片；b)阻燃自修复超疏水织物受氧等离子体刻蚀后表面的接触角照片；c)被氧等离子体刻蚀后的织物进行自修复后表面的接触角照片；对应实施例3。
图4：阻燃自修复超疏水织物燃烧测试照片。a)织物与火源接触照片；b)火源撤离后织物自熄灭后的照片，对应实施例3。
具体实施方式
实施例1
纯棉织物用无卤阻燃自修复超疏水涂层胶配方如下：
溶剂：100mL四氢呋喃；无卤阻燃剂：2.0g聚磷酸胺(APP)；阻燃增效剂：1.0g氧化锌纳米粒子；增稠剂：1.0g聚丙烯酸酯乳液；无卤疏水剂：0.2g石蜡。
按照以上配方，依次向250mL的烧杯中加入100mL四氢呋喃，2.0g聚磷酸胺(APP)，1.0g氧化锌纳米粒子，1.0g聚丙烯酸酯乳液，0.2g石蜡，充分搅拌至均匀，配制成混合分散液，即得到本发明所述的无卤阻燃自修复超疏水涂层胶。将纯棉织物浸泡于上述混合分散液5min，取出，悬挂自然晾干，即可得阻燃自修复超疏水织物。
通过以上方法所制备的阻燃自修复超疏水织物，水滴在其上接触角达到158°，滚动角小于5°，具有良好的超疏水性质(图1a)。在受到200瓦的氧等离子体刻蚀5分钟后，织物的超疏水性受到破坏，接触角变为0°(图1b)。将受损的织物加热到80℃保持30min，即可使接触角恢复到158°(图1c)，实现超疏水性的自修复。这一受损/修复过程可以重复10次以上。同时该织物具有良好的阻燃效果。当火源移开后(图2a)，织物立即熄灭，过火长度小于4cm(图2b)。作为对比，未经修饰的织物在火源移开后继续燃烧直至全部烧尽。
实施例2
纯棉织物用无卤阻燃自修复超疏水涂层胶配方如下：
溶剂：100mL丙酮；无卤阻燃剂：10.0g磷酸三苯酯；阻燃增效剂：10.0g氧化锌纳米粒子；增稠剂：10.0g聚二甲基硅氧烷(PDMS)；无卤疏水剂：10.0g棕榈蜡。
按照以上配方，依次向250mL的烧杯中加入100mL丙酮，10.0g磷酸三苯酯，10.0g氧化锌纳米粒子，10.0g聚二甲基硅氧烷(PDMS)，10.0g棕榈蜡，充分搅拌至均匀，配制成混合分散液，即得到本发明所述的无卤阻燃自修复超疏水涂层胶。将纯棉织物浸泡于上述混合分散液5min，取出，悬挂自然晾干，即可得阻燃自修复超疏水织物。
通过以上方法所制备的阻燃自修复超疏水织物，水滴在其上接触角达到159°，滚动角小于3°，具有良好的超疏水性质。同时该织物具有良好的阻燃效果。当火源移开后，织物立即熄灭，过火长度小于4cm。在受到200瓦的氧等离子体刻蚀5分钟后，织物的超疏水性受到破坏，接触角变为0°。将受损的织物加热到30℃保持8小时，即可使接触角恢复到159°，实现超疏水性的自修复。与实施例1相比，本实例中所制备的无卤阻燃自修复超疏水涂层胶具有更大的浓度，因此使用此涂层胶制备的阻燃自修复超疏水织物比实施例1中的阻燃自修复超疏水织物具有更强的修复性。该阻燃自修复超疏水织物可以经过20次受损/修复过程依然保持良好的超疏水性。
实施例3
阻燃涤纶织物用无卤阻燃自修复超疏水涂层胶配方如下：
溶剂：100mL丙酮溶剂；阻燃增效剂：1.5g二氧化硅纳米粒子；增稠剂：1.0g聚二甲基硅氧烷(PDMS)；无卤疏水剂：0.25g蜂蜡。
按照以上配方，依次向250mL的烧杯中加入100mL丙酮，1.5g二氧化硅纳米粒子，1.0g聚二甲基硅氧烷(PDMS)，0.25g蜂蜡，充分搅拌至均匀，配制成混合分散液。将阻燃涤纶织物浸泡于上述混合分散液10min，取出，悬挂自然晾干，得阻燃自修复超疏水织物。
通过以上方法所制备阻燃超疏水织物，水滴在其表面接触角达到160°，滚动角小于3°，具有良好的超疏水性质(图3a)。在受到200瓦的氧等离子体刻蚀5分钟后，超疏水性受到破坏，接触角变为0°(图3b)。将受损的织物加热到80℃保持30min，即可使接触角恢复到160°(图3c)，实现超疏水性的自修复。同时该织物具有良好的阻燃效果。当火源移开后(图4a)，织物立即熄灭(图4b)。
实施例4
阻燃涤纶织物用无卤阻燃自修复超疏水涂层胶配方如下：
溶剂：100mL四氢呋喃；阻燃增效剂：0.01g三氧化二锑；增稠剂：0.01g聚二甲基硅氧烷(PDMS)；无卤疏水剂：0.01g十八烷基胺。
按照以上配方，依次向250mL的烧杯中加入100mL四氢呋喃，0.01g三氧化二锑，0.01g聚二甲基硅氧烷(PDMS)，0.01g十八烷基胺，充分搅拌至均匀，配制成混合分散液。将阻燃涤纶织物浸泡于上述混合分散液30min，取出，悬挂自然晾干，得阻燃自修复超疏水织物。
通过以上方法所制备阻燃超疏水织物，水滴在其表面接触角达到160°，滚动角小于3°，具有良好的超疏水性质。同时该织物具有良好的阻燃效果。当火源移开后，织物立即熄灭。在受到200瓦的氧等离子体刻蚀5分钟后，超疏水性受到破坏，接触角变为0°。将受损的织物加热到90℃保持30min，即可使接触角恢复到160°(图3c)，实现超疏水性的自修复。与实施例3相比，本实例中所制备的无卤阻燃自修复超疏水涂层胶浓度低，使用此涂层胶制备的阻燃自修复超疏水织物比实施例3中的阻燃自修复超疏水织物修复性稍差。该阻燃自修复超疏水织物可以经过5次受损/修复过程依然保持良好的超疏水性。本实例中所制备的无卤阻燃自修复超疏水涂层胶适用于制备对修复性要求不高的阻燃自修复超疏水织物。

Claims (4)

1.一种纺织品用无卤阻燃自修复超疏水涂层胶，其特征在于：由100mL溶剂、0～10.0g无卤阻燃剂、0.01～10.0g阻燃增效剂、0.01～10.0g增稠剂、0.01～10.0g无卤疏水剂混合后充分搅拌至均匀，配制成混合分散液后得到；其中，无卤阻燃剂为聚磷酸铵、三聚氰胺甲醛树脂乳液、磷酸三苯酯中的一种或多种；无卤疏水剂为石蜡、蜂蜡、棕榈蜡、十八烷基胺、十八烷酸中的一种或多种；阻燃增效剂为三氧化二锑、纳米氧化锌、纳米二氧化硅中的一种或多种；增稠剂为聚丙烯酸酯乳液、聚二甲基硅氧烷、聚氨酯乳液中的一种或多种。
2.如权利要求1所述的一种纺织品用无卤阻燃自修复超疏水涂层胶，其特征在于：溶剂为四氢呋喃、丙酮中的一种或多种。
3.一种阻燃自修复超疏水织物，其特征在于：是将织物浸入到权利要求1或2所述的纺织品用无卤阻燃自修复超疏水涂层胶溶液中5～30分钟后，取出晾干后得到。
4.如权利要求3所述的一种阻燃自修复超疏水织物，其特征在于：织物为纯棉或涤纶。
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