CN108252110B - 一种在织物表面沉积高分子材料的方法及用该方法制备得到的织物 - Google Patents
一种在织物表面沉积高分子材料的方法及用该方法制备得到的织物 Download PDFInfo
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Abstract
本发明公开了一种在织物表面沉积高分子材料的方法，具体按照以下步骤：(1)织物上浸渍或喷涂固化剂；(2)将能够与该固化剂反应的高分子材料通过静电纺丝的方法沉积在织物表面。本发明所制备得到的织物表面形成微纳米纤维膜，能够在不影响织物原有性能如色彩、透气性、手感的情况下，实现织物表面功能化；并且在织物上预处理固化剂的方法，能够改善功能层和织物之间的界面结合力，提高改性后织物的耐水洗性能。
Description
技术领域
本发明涉及一种对织物进行整理的方法，尤其涉及一种在织物表面沉积高分子材料的方法。
背景技术
纺织品功能化是人们普遍追求的，其能赋予传统纺织品高价值，提高纺织品的利润。现有技术中人们使用不同的试剂和方法对织物进行整理，赋予织物各种不同的功能，如使用抗菌剂、抗皱剂、柔软剂、阻燃剂等功能，现有技术中通常使用的整理方法包括浸渍法、喷涂法、涂层法等，用上述的方法将功能试剂整理到织物上，赋予织物相应的功能。然而使用浸渍、喷涂和涂层法都会存在整理剂附着不均匀、处理过程中对织物物理形态影响较大、织物力学性能受损等缺陷，另外上述处理方法往往需要将织物进过高温干燥或固着处理，将整理剂附着到织物上，而高温处理会使织物的物化性能发生较大的变化，宏观表现为织物的手感及柔软性等力学性能进一步劣化。
现有专利申请文件中，如CN107354738A公开了一种使用NMMO制备壳聚糖/棉抗菌复合织物的方法，该方法包括如下步骤：(1)溶解液的制备：将NMMO加入蒸馏水中，形成含水13％(w/w)的N-甲基吗啉-N-氧化物水合物体系；(2)将微晶壳聚糖加入到步骤(1)所得的溶解液中，90-110℃下机械搅拌至完全溶解；(3)将棉织物在步骤(2)所得的壳聚糖溶解液中多次浸轧；(4)浸轧后的棉织物在红外线下辐照；(5)将辐照后的棉织物浸渍于饱和氯化钠水溶液中凝固，然后水洗、烘干。该备技术简单易行，成本低廉，有效改变棉织物表面性能，壳聚糖在棉织物上具有较好的牢度，但是通过浸轧后的织物存在手感差的缺陷。
本发明为了克服现有技术的缺陷，提出了通过静电纺丝技术在织物基材表面附着几十纳米到几微米之间的高分子纤维膜，将高分子材料的功能性赋予织物，并且不损害织物原有的性能，能够拓宽该织物的应用领域。
发明内容
针对现有技术中的不足，本发明的目的在于提供一种通过静电纺丝的方法将高分子物质整理到织物的方法。解决现有技术中通过浸渍法、涂层法和喷涂法处理织物时对基材织物造成不良影响的问题。
具体按照以下步骤进行。
(1)织物上浸渍或喷涂固化剂。
由于固化剂一般为小分子试剂，其溶液的粘度较小，并且不与织物之间发生化学反应，织物在浸渍或喷涂固化剂的过程中，其对织物的影响较小，因此，处理后织物整体性能基本不变。
(2)将能够与该固化剂反应的高分子材料通过静电纺丝的方法沉积在织物表面，高分子材料与织物上预处理的固化剂反应，形成耐水洗的功能层。
现有技术中获得的静电纺丝膜，通常是先通过静电纺丝法得到高分子纤维膜，然后将收集装置上的纤维薄膜取下，浸渍在固化液中固化。然而，在静电纺丝进行时，由于高分子溶液在未固化前具有一定的流动性，造成接收装置上的高分子溶液出现黏连，或因重力等作用力而产生形变，所获得的高分子膜难以保持完整的纤维形态，继而影响后续固化定型所得纤维膜的形态和性能。
本发明将固化剂预先处理到织物上，由于固化剂粘度低以及织物的毛细作用，固化剂首先在织物上形成均匀扩散，当静电纺丝高分子纤维附着在织物上时，高分子溶液与固化剂之间在织物上形成双向扩散，使得高分子能够在接触织物时短时间内完成固化，因此，织物上的高分子膜能够形成较好的纤维形态。本发明通过静电纺丝法，采用一步法纤维原位固化成型工艺，增强了纤维形态及性能的稳定性，提高了纤维膜与织物基体的界面粘结力，同时简化了后续处理工艺，减少了三废的排放。
本发明提供的一步法纤维原位固化成型工艺方法与常规的先通过静电纺丝形成纤维膜，再浸渍于固化液中进行固化成型的两步法不同。两步法中，将成型的高分子纤维膜浸渍在固化液中时，小分子固化剂由纤维外层向内层方向渗透，纤维外层的固化速度快，固化程度高，将迅速形成致密的固化层，阻止固化液的进一步渗入，使得纤维芯层固化不充分；同时，由于纤维膜与织物之间没有物理或者化学结合力，浸渍在固化剂中时，纤维膜会与织物发生明显的分离，纤维膜在外力作用下容易脱落，因此织物不耐水洗。而本发明将固化剂溶液首先浸渍或喷涂在织物上，固化剂通过织物上纤维的毛细作用渗透到纤维内部，当高分子溶液通过静电纺丝的方法沉积到到织物上后，高分子与固化剂在溶液体系中形成双向扩散，使得高分子材料向织物内部渗透并在纤维中与固化剂反应，由于高分子材料能够在织物纤维的组织结构中固化，因此高分子材料与织物之间的结合力大，在宏观上的表现是整理后织物具有优越的耐水洗性能。
固化剂的质量百分浓度为1-20％，优选的1-15％，优选的5-15％，优选的5-10％；固化剂溶液为织物重量的50-200％。
固化剂的浓度以及织物上固化剂溶液的重量直接影响固化剂与高分子之间的反应程度及高分子与织物之间的结合力。固化剂浓度太低则固化不充分；太高则会使反应不均匀，也会造成浪费。织物上固化剂溶液太少则无法充分润湿织物，高分子在织物上的反应不均匀；固化剂溶液过多，高分子在接触到织物表面的固化剂时即会发生固化，纤维膜成型后与织物之间结合力差，耐水洗性差，并且织物的吸湿性有限，溶液过多就会流失，造成不必要的浪费。因此需要控制固化剂溶液的浓度及其占织物重量。
不同的高分子材料采用相应的固化剂进行固化，高分子材料优选亲水性良好且无毒或低毒的材料，固化剂优选无毒或低毒的原料。比如，高分子材料为海藻酸钠，固化剂为氯化钙溶液；或者高分子材料为明胶，固化剂为京尼平；或者高分子材料为壳聚糖，固化剂为京尼平，或者高分子材料为聚丙烯酸，固化剂为乙二醇。
静电纺丝的条件为电压10-25kV，纤维接收距离5-20cm。
电压小于10kV时，纤维接收距离小于5cm时，无法得到纤维形态良好，且直径分布均匀的静电纺丝纤维膜。电压大于25kV时，纤维形态变化不明显，因此无需过大的电压。纤维接收距离大于20cm，静电纺丝时高分子材料纤维无法完全收集到织物上，造成纤维膜沉积不均匀。因此，需要控制电压和纤维接收距离。
本发明还提供了一种通过该方法制备得到的织物，该织物表面具有一层静电纺丝纤维膜，所述纤维膜的直径不大于5μm，优选不大于1μm，优选不大于500nm，更优选不大于100nm。
本发明的技术方案中，由于固化的过程与静电纺丝过程同时发生，因此所得纤维膜成型良好，其纤维直径较小且均匀分布。
本发明制备得到的织物具有较好的透气性，因为本发明得到的织物表面是一层网状纤维膜，网状结构使织物具有较好的透气性。而通过常规的浸渍等方法处理所得到的织物，高分子整理液在织物表面通常呈片状分布，会降低织物透气性和柔软性。
本发明制备得到的织物表面形成微纳米纤维膜，能够在不影响织物原有性能，如色彩、透气性、手感的情况下，实现织物表面功能化；并且采用在织物上预处理固化剂的方法，能够改善功能层和织物之间的界面结合力，提高改性后织物的耐水洗性能。
附图说明
图1实施例1所得到织物的SEM图，(a)放大倍数为200倍，(b)放大倍数为5000倍
图2对比例1所得织物的SEM图
表1实施例1与对比例1所得改性织物的性能对比
具体实施例
实施例1
一种织物表面沉积海藻酸钙改性织物的制备方法，包括以下步骤：
(1)涤纶织物上浸渍固化剂：将织物浸渍在10wt％的CaCl2溶液中，充分润湿，取出，浸轧，轧液率为80％。
(2)配制浓度5wt％海藻酸钠水溶液，作为静电纺丝溶液，将步骤(1)中的织物作为收集静电纺丝纤维的基材，静电纺丝，干燥，水洗，干燥，得到织物表面沉积海藻酸钙的改性涤纶织物。静电纺丝电压为20kV，针头与收丝基材距离15cm。
实施例2
一种织物表面沉积明胶纤维膜改性织物的制备方法，包括以下步骤：
(1)涤纶织物上浸渍固化剂：将织物浸渍在浓度为0.33wt％的京尼平溶液中，取出，浸轧，轧液率为80％。
(2)配制浓度为20wt％明胶水溶液，作为静电纺丝溶液，将步骤(1)中的织物作为收集静电纺丝纤维的基材，静电纺丝，干燥，水洗，干燥，得到织物表面沉积明胶的改性涤纶织物。静电纺丝电压为20kV，针头与收丝基材距离10cm。
实施例3
一种织物表面沉积壳聚糖改性织物的制备方法，包括以下步骤：
(1)腈纶织物上浸渍固化剂：将织物浸渍在0.6wt％的京尼平溶液中，取出，浸轧，轧液率为80％。
(2)将壳聚糖溶解于浓度为0.3wt％的乙酸/水溶液，配制成2.5wt％的溶液，作为静电纺丝溶液，将步骤(1)中的织物作为收集静电纺丝纤维的基材，静电纺丝，干燥，水洗，干燥，得到织物表面沉积壳聚糖的改性腈纶织物。静电纺丝电压为25kV，针头与收丝基材距离10cm。
实施例4
一种织物表面沉积聚丙烯酸改性织物的制备方法，包括以下步骤：
(1)腈纶织物上浸渍固化剂：将织物浸渍在乙二醇中，取出，浸轧，轧液率为80％。
(2)配制浓度为6wt％的聚丙烯酸/乙醇溶液，作为静电纺丝溶液，将步骤(1)中的织物作为收集静电纺丝纤维的基材，静电纺丝，干燥，水洗，干燥，得到织物表面沉积聚丙烯酸的改性腈纶织物。静电纺丝电压为15kV，针头与收丝基材距离10cm。
实施例5
一种织物表面沉积海藻酸改性织物的制备方法，包括以下步骤：
(1)涤纶织物上喷洒固化剂：将10wt％的CaCl2溶液喷洒在织物上，充分润湿织物。
(2)配制浓度为5wt％海藻酸钠水溶液，作为静电纺丝溶液，将步骤(1)中的织物作为收集静电纺丝纤维的基材，静电纺丝，干燥，水洗，干燥，得到织物表面沉积海藻酸钙的改性涤纶织物。静电纺丝电压为20kV，针头与收丝基材距离15cm。
对比例1
一种织物表面沉积海藻酸改性织物的制备方法，包括以下步骤：
(1)配制2wt％的海藻酸钠水溶液。
(2)将涤纶织物浸渍在步骤(1)制备得到的海藻酸钠溶液中，取出，浸轧，轧液率50％。
(3)将步骤(2)得到的织物浸渍在10wt％的CaCl2溶液中固化，取出，干燥，水洗，干燥。
对比例2
一种织物表面沉积海藻酸改性织物的制备方法，包括以下步骤：
(1)制备2wt％的海藻酸钠溶液。
(2)将涤纶织物浸渍在步骤(1)制备得到的海藻酸钠溶液中，浸轧，轧液率50％。
(3)将10wt％的CaCl2溶液喷洒到步骤(2)得到的织上固化，取出，干燥，水洗，干燥。
对比例3
一种织物表面沉积壳聚糖改性织物的制备方法，包括以下步骤：
(1)将壳聚糖溶解于浓度为0.3wt％的乙酸/水溶液中，配制浓度为2.5wt％的壳聚糖溶液。
(2)将腈纶织物浸渍在步骤(1)制备得到的壳聚糖溶液中，浸轧，轧液率50％。
(3)将步骤(2)得到的织物浸渍在浓度为0.33wt％的京尼平溶液中固化，取出，干燥，水洗，干燥。
性能测试：
采用YG(B)216型织物测试仪测试处理后织物的透气性能；
采用LFY-207自动织物硬挺度试验仪测试织物的弯曲长度；
毛效值测试：取经向30cm、纬向5cm的布条，在离布条一端1cm处沿纬向用铅笔作一平行线，并在此末端沿纬向穿一根约重2g的短玻璃棒作重荷。调节液面与标尺读数零点对齐，然后升高横架，把试样布条上端夹在夹子上固定，使其下端的铅笔线正好与标尺读数的零点对齐。将横架连同标尺及试样一起下降，直到标尺读数零点与水平面接触为止，测量30min后液体上升高度，即为毛效值，该值可用来表征织物亲水性能。
测试结果见表1
表1
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员，在不脱离本发明构思的前提下，还可以做出若干改变、改进和润饰，这些改变、改进和润饰也应视为本发明的保护范围。
Claims (5)
1.一种在织物表面沉积高分子材料的方法，其特征在于，该方法包括以下步骤：(1)织物上浸渍或喷涂固化剂溶液；(2)将能够与该固化剂反应的高分子材料通过静电纺丝的方法沉积在织物表面；
固化剂的浓度质量百分数为1-20％，固化剂溶液为织物重量的50-200％；
高分子材料为海藻酸钠，固化剂为氯化钙溶液；或高分子材料为明胶，固化剂为京尼平；或高分子材料为壳聚糖，固化剂为京尼平；或高分子材料为聚丙烯酸，固化剂为乙二醇；
静电纺丝的条件为电压10-25kV，纤维接收距离5-20cm。
2.一种如权利要求1所述的在织物表面沉积高分子材料的方法制备得到的织物，其特征在于：织物表面的高分子材料纤维直径为微纳米，高分子材料纤维的直径不大于5μm。
3.一种如权利要求2所述的在织物表面沉积高分子材料的方法制备得到的织物，其特征在于：高分子材料纤维的直径不大于1μm。
4.一种如权利要求3所述的在织物表面沉积高分子材料的方法制备得到的织物，其特征在于：高分子材料纤维的直径不大于500nm。
5.一种如权利要求4所述的在织物表面沉积高分子材料的方法制备得到的织物，其特征在于：高分子材料纤维的直径不大于100nm。
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Effective date of registration: 20221206 Address after: 430200 The second floor of Building J, Phase II Workshop, Tuochuang Technology Industrial Park, Wuhan Tuochuang Technology Co., Ltd., Liangshantou Village, Canglong Island, Jiangxia District Economic Development Zone, Wuhan City, Hubei Province Patentee after: Hubei testele New Material Technology Co.,Ltd. Address before: 430073 Wuhan Textile University, No. 1, Yangguang Avenue, Jiangxia District, Wuhan City, Hubei Province Patentee before: Wuhan Textile University |