CN106149361A - 一种高耐磨防污座椅面料的制备方法 - Google Patents

一种高耐磨防污座椅面料的制备方法 Download PDF

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CN106149361A
CN106149361A CN201610634459.6A CN201610634459A CN106149361A CN 106149361 A CN106149361 A CN 106149361A CN 201610634459 A CN201610634459 A CN 201610634459A CN 106149361 A CN106149361 A CN 106149361A
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seat
cover fabric
high abrasion
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蔡再生
周乾飞
陈丽
李智星
原家辉
冯奇
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SAIC Motor Corp Ltd
Donghua University
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Shanghai Automobile Group Ltd By Share Ltd Prospective Technology Research Department
Donghua University
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Abstract

本发明涉及一种高耐磨防污座椅面料的制备方法，包括：将防污整理剂、摩擦牢度提升组分和水混合后，搅拌，得到整理液；其中，防污整理剂由改性纳米二氧化硅水溶胶无氟超拒水成分和含丙烯酸的亲水性组分构成；将座椅面料浸于整理液中，二浸二轧，烘干，焙烘，得到高耐磨防污座椅面料。本发明的方法简单，成本低廉，生态环保；得到的座椅面料具有很好的耐磨性，以满足车用内饰经常受磨的需要，有广泛的推广和应用价值。

Description

一种高耐磨防污座椅面料的制备方法
技术领域
本发明属于座椅面料的制备领域，特别涉及一种高耐磨防污座椅面料的制备方法。
背景技术
座椅(交通工具如汽车、火车、飞机、沙发等)内饰用材料除了具备传统纺织品要求的舒适美观、经济耐用性能外，在防污、阻燃、抗静电、易去污和耐日晒等安全环保性方面有更高的要求。涤纶纤维因其机械性能和抗折皱性优异，且耐霉变、价格较便宜等原因，在交通工具内饰纺织品市场占有90％以上的份额，广泛应用于汽车座椅、地毯、车顶内饰、安全气囊等
座椅装饰织物固定在座椅上，往往伴随着整个座椅的寿命。座椅套不能像服装一样经常洗涤，所以座椅织物的抗污、自清洁性能倍受关注。一般服用织物已有性能不错的商用防污整理剂，显示较好的防水防油剂的性能，但由于交通工具内饰(座椅、地毯等)与服装面料所承受的污物情况不一样：座椅用内饰往往是正面垂直方向受污，并有较大冲击力或压力，而服装面料常常是侧面受污，冲击力或压力较小；服装去污较方便、可以水洗，而座椅内饰纺织品基本不能换洗。所以服用纺织品防污、自清洁整理技术不能简单的平移到座椅内饰功能材料上。
近年来，我国汽车、动车、高铁、飞机等工业发展迅速，因而对交通工具内饰纺织品提出了更多更高的功能性要求。为此，需要根据实际生产情况，综合考虑各方面因素，优化组合，在赋予座椅内饰材料相应功能性的同时，达到经济、社会、环境效益的最大化。随着我国高档交通工具国产化的加速发展，座椅用功能纺织品的市场将十分广阔，但同时也对我国交通工具用内饰材料的研究和开发提出了更高的要求和更大的挑战。
由此可见，开展自清洁座椅内饰功能材料的研究开发，不仅可以获得具有自主知识产权的防污、自清洁内饰功能材料，为开发贴近市场、满足消费者的需求，并且可以为后续多功能性内饰材料的开发积累经验，为提高我国交通工具的国际竞争力做出贡献，具有深远的意义。
早期的拒水整理剂较多的是有机硅化合物，有机硅化合物没有拒油性能，拒水效果也不是十分理想，经过有机硅涂层整理的织物，织物失去了原先的透气性能，使整理材料一些使用性能大大下降即舒适感大打折扣。近年来含氟整理剂已经替代了有机硅整理剂。
含氟整理剂整理在材料表面上，在材料表面排满具有疏水疏油的基团，生成一层很薄拒水拒油薄膜，使织物临界表面张力降低，达到拒水拒油效果，并且这层膜只是在材料表面，在材料间歇的地方不形成膜，所以整理后的材料仍能保持良好的透气和透湿性能，因而得到迅速发展。
上世纪50年代，美国Du Pont公司率先以聚四氟乙烯(PTFE)乳液作为织物整理剂，并发表了专利。1953年，美国3M公司研制成功以全氟羧酸铬络合物为主体的织物整理剂，由于耐洗涤性很差，很快被性能更好的含氟丙烯酸酯的聚合物所取代，1956年，3M公司研制成功了以“Scotchgard FC-208”为代表的FC系列织物整理剂，其有效成份组成为含氟丙烯酸酯的聚合物。而后，杜邦、大金工业、旭硝子等相继研制成功此类产品，并实现商品化。这些含氟整理剂不仅具有拒水拒油功能，而且还具有防污和异去污功能。
虽然有机氟整理剂具有优良的拒水拒油性、透气性以及耐洗、防污和易去污性能，它的主要成分是全氟烷基(Rf)长链化合物，它形成的薄膜具有Rf基所赋予的低临界表面张力。因此经过它处理的材料不仅有拒水性，还有拒油性，而且仍能保持原有的色泽、手感、透气性和穿着舒适性。目前，含氟整理剂的应用重点是防雨外衣织物、服装、窗帘、工作服及地毯等，在此基础上可以开发生产防水剂、防污剂、造纸防油施胶剂等系列产品。但是含氟整理剂的开发大部分是以全氟辛基磺酰氟为原料，而全氟辛基磺酰基化合物(PFOS)容易在人体中累积，对健康不利，并且对环境也有危害。研究人员应致力于研发环保型面料、皮革整理剂。
发明内容
本发明所要解决的技术问题是提供一种高耐磨防污座椅面料的制备方法，该方法不需使用昂贵的仪器设备，方法简单，成本低廉，得到的座椅面料具有很好的耐磨性，以满足车用内饰经常受磨的需要，有广泛的推广和应用价值。
本发明的一种高耐磨防污座椅面料的制备方法：
(1)将防污整理剂、摩擦牢度提升组分和水混合后，剧烈搅拌，得到整理液；其中，防污整理剂由改性纳米二氧化硅水溶胶无氟超拒水成分和含丙烯酸的亲水性组分构成，超拒水组分和亲水性组分的质量比为3～5：1～3；
(2)将座椅面料浸于步骤(1)中的整理液中，二浸二轧，烘干，焙烘，得到高耐磨防污座椅面料；其中，轧余率为70％～80％。
所述步骤(1)中含丙烯酸的亲水性组分为丙烯酸、甲基丙烯酸、羟基丙烯酸等中一种与丙三醇、丙二醇、三乙醇胺、二乙醇胺中的一种组成。
所述丙烯酸、甲基丙烯酸或羟基丙烯酸与丙三醇、丙二醇、三乙醇胺或二乙醇胺的摩尔比为4：1～3：2。
所述步骤(1)中改性纳米二氧化硅水溶胶无氟超拒水成分采用溶胶-凝胶法，以水为溶剂以氨水为催化剂，通过前驱体及改性剂在阴离子表面活性剂作用下的水解缩合反应制备而成(201010515767.X)。
所述步骤(1)中摩擦牢度提升组分为聚乙烯、聚乙烯醇、聚苯乙烯、油酸酰胺中的一种或二种；其质量占整理液质量的1～6％。
所述步骤(1)中超拒水成分、亲水性组分和水的质量比为3～5：1～3：92～96。
所述步骤(2)中烘干的条件为：80℃烘干2～5min。
所述步骤(2)中烘焙的条件为：150～170℃焙烘1～3min。
所述防污整理剂由改性纳米二氧化硅水溶胶无氟超拒水成分和含丙烯酸的亲水性组分构成，具有良好的低温成膜性能，改变共聚物的组成可调节膜的软硬度，对纤维有良好的粘附性；在座椅面料上施加防污整理剂中添加易成膜、耐磨组分，采用浸轧整理工艺，方法简单，适应面广，可操作性强。该整理剂具有较好的稳定性、优异的拒水性，便于满足开发高档座椅面料的需要。
本发明公开防污座椅内饰材料主要靠含高化学活性组分的化合物的水解与缩合，陈化，形成凝胶，并通过浸轧法使凝胶在材料表面成膜，最后经过固化烧结获得具有微米及纳米结构的薄膜。
本发明的高耐磨防污座椅面料的性能测试：
(1)接触角的测定：
将织物平整地粘附在玻璃片上，用德国克吕士DSA 30接触角测量仪测量织物表面与水/油的静态接触角，纯水体积一律为5μL，油(正十六烷)体积一律为3μL，每个试样在同一样品不同位置测试5次，取平均值。
(2)拒水拒油等级的测定：
座椅面料拒水性能评定。参照3M方法评定整理后织物的拒水性能。标准溶液是由水与异丙醇按不同体积比配制而成，用1-10级来表示，拒水等级分别由不能润湿织物表面的测试液的最高等级确定。异丙醇的体积比越大，该溶液的表面张力越低，拒水级数越高，织物拒水性能越好。如果试样不能阻止某一配比溶液的润湿或渗透，则表明此试样的拒水性低于该配比溶液对应的拒水等级。标准液的配制及对应评定等级详见表1。
表1 3M拒水效果测试标准及试剂组成
具体操作方法：用取液枪取1级标准试液50μL，在织物表面间隔一定距离同时滴5滴，每滴直径大约5mm，以45°观察液滴在30s内的反光程度、边缘稳定性。如果反光程度、边缘稳定性好，再滴加高一级的标准试液，观察30s(混合试液法为3min)，继续此步操作，直到某级标准试液滴在织物表面上30s后铺展为止，使其表面不铺展的最后一个等级为该织物的拒水等级。
拒油性评定，参照3M标准评定整理后织物的拒油性能。采用一系列不同表面张力的烃类作为标准液，滴于织物表面上，观察溶液在织物表面的润湿情况。拒油级别以织物表面不润湿的测试液体的最高等级确定。拒油标准液、对应等级与表面张力详见表2。
表2 3M拒油效果测试标准及试剂组分
拒油等级 试剂组成 表面张力(25℃)/(10-5N/cm)
1 矿物油 31.45
2 65％矿物油/35％正十六烷 29.60
3 正十六烷 27.30
4 正十四烷 26.35
5 正十二烷 24.70
6 葵烷 23.50
7 辛烷 21.40
8 庚烷 19.75
具体操作方法：用取液枪取1级标准试液50μL，在织物表面间隔一定距离同时滴5滴，每滴直径大约5mm，以45°角观察液滴在30s内的反光程度、边缘稳定性。如果反光程度、边缘稳定性好，再滴加高一级的标准试液，观察30s，继续此步操作，直到某级标准试液滴在织物表面上30s后铺展为止，使其表面不铺展的最后一个等级为该织物的拒油等级。
(3)耐磨性能的测定：
马丁代尔耐磨实验按SMTC 5 241-2011(V1)(即GB/T 21196.1-2007)执行，使试样在12kP的重压下做李莎茹图形运动。
有益效果
本发明采用非C8有机氟防污剂，不含PFOA、PFOS等物质，生态环保；在整理工作液中加入摩擦牢度提升组分(一些易挥发或易煅烧的而易成膜的高分子有机物如聚乙二醇、聚乙烯醇、聚苯乙烯、油酸酰胺等)，增加了成膜的粗糙度，提供了座椅面料的耐磨牢度；本发明的方法不需使用昂贵的仪器设备，方法简单，成本低廉，具得到的座椅面料有很好的耐磨性，以满足车用内饰经常受磨的需要，有广泛的推广和应用价值。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
座椅面料→二浸二轧整理液(轧余率70％)→80℃烘干2.5min→160℃焙烘1min。其中，整理液：取按专利号201010515767.X制备的改性SiO2水溶胶4g(将2g甲基三甲氧基硅烷、0.19g(0.8CMC)十二烷基硫酸钠与100g水混合，在25℃下剧烈搅拌1h后，缓慢滴加催化剂氨水3mL，搅拌3h，再添加2g十二烷基三甲氧基硅烷，继续搅拌3h，制得改性SiO2水溶胶)，含丙烯酸的亲水性组分(丙烯酸与丙三醇摩尔比3:1混合)2g，摩擦牢度提升组分(聚乙烯)2％(占整理液质量)，水92g剧烈搅拌配制成。
座椅面料的防污耐磨性能测试结果见表3。
表3
注：*CA指水或油滴与座椅面料的接触角；
**3M指3M公司方法测试的拒水或拒油等级。
实施例2
座椅面料→二浸二轧(轧余率80％)→80℃烘干3min→150℃焙烘1.5min。其中，整理液：取按专利号201010515767.X制备的改性SiO2水溶胶3.5g(将2g甲基三甲氧基硅烷、0.19g(0.8CMC)十二烷基硫酸钠与100g水混合，在25℃下剧烈搅拌1h后，缓慢滴加催化剂氨水3mL，搅拌3h，再添加2g十二烷基三甲氧基硅烷，继续搅拌3h，制得改性SiO2水溶胶)，含丙烯酸的亲水性组分(甲基丙烯酸与丙二醇摩尔比2:1混合)3g，摩擦牢度提升组分(聚乙烯与聚乙烯醇摩尔比4：1)2％(占整理液质量)，水90g剧烈搅拌配制成整理液。
座椅面料的防污耐磨性能测试结果见表4。
表4
注：*CA指水或油滴与座椅面料的接触角；
**3M指3M公司方法测试的拒水或拒油等级。
实施例3
座椅织物→二浸二轧(轧余率75％)→80℃烘干2min→170℃焙烘1min。其中，整理液：取按专利号201010515767.X制备的改性SiO2水溶胶4g(将2g甲基三甲氧基硅烷、0.19g(0.8CMC)十二烷基硫酸钠与100g水混合，在25℃下剧烈搅拌1h后，缓慢滴加催化剂氨水3mL，搅拌3h，再添加2g十二烷基三甲氧基硅烷，继续搅拌3h，制得改性SiO2水溶胶)，含丙烯酸的亲水性组分(羟基丙烯酸与三乙醇胺摩尔比3:2混合)2g，摩擦牢度提升组分(油酸乙酰)3％(占整理液质量)，水91g剧烈搅拌配制成整理液。
座椅面料的防污耐磨性能测试结果见表5。
表5
注：*CA指水或油滴与座椅面料的接触角；
**3M指3M公司方法测试的拒水或拒油等级。
实施例4
座椅织物→二浸二轧(轧余率80％)→80℃烘干2min→160℃焙烘1.5min。其中，整理液：取按专利号201010515767.X制备的改性SiO2水溶胶4g(将2g甲基三甲氧基硅烷、0.19g(0.8CMC)十二烷基硫酸钠与100g水混合，在25℃下剧烈搅拌1h后，缓慢滴加催化剂氨水3mL，搅拌3h，再添加2g十二烷基三甲氧基硅烷，继续搅拌3h，制得改性SiO2水溶胶)，含丙烯酸的亲水性组分(丙烯酸与二乙醇胺摩尔比4:1混合)1.5g，摩擦牢度提升组分(油酸乙酰与聚乙烯醇摩尔比3：1)2％(占整理液质量)，水92g剧烈搅拌配制成整理液。
座椅面料的防污性能测试结果见表6。
表6
注：*CA指水或油滴与座椅面料的接触角；
**3M指3M公司方法测试的拒水或拒油等级。

Claims (8)

1.一种高耐磨防污座椅面料的制备方法，包括：
(1)将防污整理剂、摩擦牢度提升组分和水混合后，搅拌，得到整理液；其中，防污整理剂由改性纳米二氧化硅水溶胶无氟超拒水成分和含丙烯酸的亲水性组分构成，超拒水组分和亲水性组分的质量比为3～5：1～3；
(2)将座椅面料浸于步骤(1)中的整理液中，二浸二轧，烘干，焙烘，得到高耐磨防污座椅面料；其中，轧余率为70％～80％。
2.根据权利要求1所述的一种高耐磨防污座椅面料的制备方法，其特征在于，所述步骤(1)中含丙烯酸的亲水性组分为丙烯酸、甲基丙烯酸或羟基丙烯酸与丙三醇、丙二醇、三乙醇胺或二乙醇胺的混合。
3.根据权利要求2所述的一种高耐磨防污座椅面料的制备方法，其特征在于，所述丙烯酸、甲基丙烯酸或羟基丙烯酸与丙三醇、丙二醇、三乙醇胺或二乙醇胺的摩尔比为4：1～3：2。
4.根据权利要求1所述的一种高耐磨防污座椅面料的制备方法，其特征在于，所述步骤(1)中改性纳米二氧化硅水溶胶无氟超拒水成分采用溶胶-凝胶法，以水为溶剂，以氨水为催化剂，通过前驱体及改性剂在阴离子表面活性剂作用下的水解缩合反应制备而成。
5.根据权利要求1所述的一种高耐磨防污座椅面料的制备方法，其特征在于，所述步骤(1)中摩擦牢度提升组分为聚乙烯、聚乙烯醇、聚苯乙烯、油酸酰胺中的一种或二种；其质量占整理液质量的1～6％。
6.根据权利要求1所述的一种高耐磨防污座椅面料的制备方法，其特征在于，所述步骤(1)中超拒水成分、亲水性组分和水的质量比为3～5：1～3：92～96。
7.根据权利要求1所述的一种高耐磨防污座椅面料的制备方法，其特征在于，所述步骤(2)中烘干的条件为：80℃烘干2～5min。
8.根据权利要求1所述的一种高耐磨防污座椅面料的制备方法，其特征在于，所述步骤(2)中烘焙的条件为：150～170℃焙烘1～3min。
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