CN107338640A - 一种涤/棉织物稀土多功能复合整理剂及其制备方法 - Google Patents

一种涤/棉织物稀土多功能复合整理剂及其制备方法 Download PDF

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CN107338640A
CN107338640A CN201710469433.5A CN201710469433A CN107338640A CN 107338640 A CN107338640 A CN 107338640A CN 201710469433 A CN201710469433 A CN 201710469433A CN 107338640 A CN107338640 A CN 107338640A
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rare earth
finishing agent
cotton fabric
polyester cotton
multifunctional composite
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夏德慧
蒋灿雄
薛雄坚
张婉婷
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Jiangmen Polytechnic
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Abstract

本发明公开了一种涤/棉织物稀土多功能复合整理剂，包括以下重量份的组分：0.4‑6份纳米CeO2、0.1‑4份分散剂、0.1‑1份表面活性剂、8‑15份粘合剂、4‑8份增稠剂和80‑150份水。本发明的涤/棉织物稀土多功能复合整理剂具有优异的性能，采用本发明的涤/棉织物稀土多功能复合整理剂对含涤棉混纺织物进行后整理，处理后的织物具有优异耐久的紫外线吸收性能；采用纳米CeO2作为主要成分，使织物具有优异的抗菌性能；在使用理剂对含涤棉混纺织物进行后整理时，采用超声波分散，能提供分散效果，从而提高整理剂的使用效果。

Description

一种涤/棉织物稀土多功能复合整理剂及其制备方法
技术领域
本发明涉及一种纺织品整理剂，具体涉及一种涤/棉织物稀土多功能复合整理剂及其制备方法。
背景技术
随着经济的持续快速发展和工业化进程的加快，人类活动在创造出前所未有的物质财富且人们生活水平得到很大提高的同时，也给我们的地球带来了巨大的压力，随之而来的就是许多环境问题，如臭氧层空洞逐渐加大，紫外线辐射逐渐增强，诱发皮肤病甚至皮肤癌等等诸多问题。同时随着科学技术的发展和人民生活水平的提高，人们对日常使用的纺织产品的各种性能提出了更多更高的要求，比如安全性、舒适性，以及其它功能性要求。
我国素有“稀土王国”之美誉，目前，全世界己探明的稀土储量的90％分布在我国，世界稀土总销量的70％是由我国供应的，己形成南、北两大体系。近十多年来，我国稀土工业发展很快，无论是科技开发，还是产业化方面，都进入高速发展时期。随着稀土产业化水平的不断提高，我国的稀土产品已成功地应用于冶金、机械、石油、化工、玻璃陶瓷等行业。各种稀土永磁、荧光材料也有明显提高，己接近世界水平，尤其是我国独立开发的稀土农用领域是世界上独一无二的。随着稀土应用范围的扩大，稀土在纺织工业领域也逐渐被重视并得以运用，目前已应用于羊毛、亚麻、纯棉、真丝、粘胶、人造棉、腈纶纶等各种天然纤维及化纤等制品的加工。然而，利用稀土的特性用于涤棉织物抗紫外线后整理加工的应用研究国内鲜见。
纳米材料作为一种性能特殊的新型材料，有许多普通材料所不具备的特性，越来越多的产品使用纳米技术，纳米产业给产品增添了许多特殊的功能，开展纳米材料在纺织品上的应用研究是一项抓住新材料革命的机遇而进行高科技开发的研究项目。充分利用纳米技术改造传统的染整工艺，提高我国的纺织品科技含量，开发集舒适、休闲、保健为一体的多功能纺织品，提高其市场竞争力是当代纺织染整工作者的历史使命。
纳米材料是近年发展的新型材料，尽管对其研究的理论和手段还不很成熟，但是作为功能材料，它与传统材料相比具有许多特殊性质。无机类防紫外线整理剂，也称为无机类紫外线反射剂(或屏蔽剂)，如纳米TiO2和纳米ZnO为无机成分，有很高的化学稳定性、热稳定性、非迁移性、无味、无毒、无刺激性，使用安全，还兼具杀菌除臭作用。更为可贵的是它们还是广谱屏蔽剂，对UVA、UVB都有屏蔽作用，不像有机类防紫外线整理剂一般只单一地对UVA或UVB有吸收。应用纳米材料作防紫外线试剂，仅需极少的量就可达到防护效果，且对织物无任何损害，对人体安全性很高，故纳米材料防紫外线试剂自问世以来就倍受人们的青睐。
紫外线(ultraviolet rays)是阳光中波长最短的一种光波，它具有很高的能量，作用于皮肤的紫外线分为～短波紫外线(UVC:200nm-280nm)、中波紫外线(UVB:280nm-315nm)和长波紫外线(UVA:315nm-400nm)。短波紫外线UVC穿透力极强对人类影响大，UVC虽然能被臭氧层吸收，但近年来由于臭氧层的破坏，少量短波紫外线也能到达地面；中波紫外线UVB的能量极高，大部分能被皮肤真皮吸收，引起真皮血管扩张，呈红肿、水疙等症状；长波紫外线UVA能阶为同剂量UVB的1/1000，但对衣服和人体皮肤的穿透性远比UVB深。UVA对皮肤虽然不会引起急性炎症，但长期积累仍可导致皮肤的老化和严重损害。防止紫外线对皮肤造成的伤害，从纺织品方面来说，必须减小紫外线透过织物的量。织物对光的作用表现为对光的吸收、漫反射、和透射三种形式。因此，减少紫外线透过量具有以下两种方法：(1)提高织物对紫外线的反射能力。可以选用适当的纤维如高比表面纤维，或使用反光性强的物质如纳米陶瓷粉(MgO、ZnO、TiO2等)进行织物的后整理加工；(2)提高织物对紫外线的吸收能力，即选用适当的紫外线吸收剂对织物进行处理，或在化学纤维纺丝时加入纺丝浴中。利用其本身吸收紫外线能量，并使之向低能级转化，变为低能的热能或波长较短的电磁波，从而消除紫外线对人体和织物的危害。
因此，有必要提供一种涤/棉织物的复合整理剂，对衣服或织物进行整理，以提高衣物对紫外线的吸收能力，从而降低紫外线对人体的危害。
发明内容
稀土多功能复合整理剂的开发是利用稀土的特殊性质而将两种或多种功能复合于一种纺织品的技术，以提高产品的档次和附加值。本发明使用含有稀土元素的化合物对含涤棉混纺织物进行后整理使其具有防紫外线、增加亮度、抗菌等多重功能。
本发明提供了一种涤/棉织物稀土多功能复合整理剂，利用该整理剂对衣服进行整理，整理后的衣服具有优异耐久的紫外线吸收性能。
本发明所采取的技术方案为：一种涤/棉织物稀土多功能复合整理剂，包括以下重量份的组分：
优选的，所述分散剂是无机分散剂或有机分散剂。
优选的，所述无机分散剂是海藻酸钠、六偏磷酸钠或硅酸钠。
优选的，所述有机分散剂是聚丙烯酰胺、羧甲基纤维、聚丙烯酞胺、聚丙烯酸钠、木质碳酸钠、石油磺酸钠、水解丙烯酸胺、磷酸脂或乙氧基化合物。
本发明中，可以选用无机分散剂或有机分散剂，当使用无机分散剂时，无机分散剂的用量为0.1-0.5份，优选是0.2份；当使用有机分散剂时，无机分散剂的用量为1.5-4份，优选是2份。
上述有机分散剂属于静电位阻分散的分散剂，静电位阻稳定，是固体颗粒表面吸附了一层带电较强的聚合物分子层，带电的聚合物分子层既通过本身所带的电荷排斥周围的粒子，又利用位阻效应防止作布朗运动的粒子靠近，产生复合稳定作用。其中静电电荷来源主要为颗粒表面静电荷、外加电解质和锚固基团高聚电解质。颗粒在距离较远时，双电层产生斥力。颗粒在距离较近时，空间位阻阻止颗粒靠近。
在实际应用中，纳米颗粒在介质中的分散与许多因素有关，如pH值、分散剂种类、分子量、分散剂用量、球磨方式等。调节体系pH值，可以改变粉体颗粒表面载荷量，进而影响颗粒间的双电层排斥力。分散剂吸附在粉体表面通过静电或位阻作用，或二者共同作用，使颗粒排斥能增强，克服范德华引力，从而使颗粒稳定地悬浮在介质中。同时应该考虑分散剂的分子量、分散剂的用量对颗粒分散效果的影响，使颗粒在介质中的分散尽量达到最佳化。
优选的，所述表面活性剂是Sp60。
优选的，所述粘合剂是聚氨酯、聚苯乙烯、聚丙烯酸或环氧树脂。
优选的，所述增稠剂是聚丙烯酰胺或聚乙烯醇。
本发明还提供了制备涤/棉织物稀土多功能复合整理剂的方法，包括以下步骤：将纳米CeO2投入分散缸中，再依次分散剂、表面活性剂、粘合剂、增稠剂和水，搅拌均匀，即可得到涤/棉织物稀土多功能复合整理剂。
本发明还提供了涤/棉织物稀土多功能复合整理剂的应用方法，包括以下步骤：高速剪切混合→超声分散→搅拌→浸轧整理液二浸二轧，带液率65-70％→预烘→焙烘→测试。
优选的，超声分散的功率为350-500W，时间为5-15min,优选的，超声分散的功率为450W，时间为15min。
其中，高速剪切速率为3000-6000r/min,时间为5-20min；优选的，高速剪切速率为4000r/min，时间为15min。
纳米粒子分散就是将纳米粒子的团聚体分离成单个纳米粒子或者是为数不多的纳米粒子的小团聚体均匀分布在分散介质中的过程。这是纳米材料应用到织物上的关键一步。
纳米粒子因特殊的表面结构很容易团聚，形成团聚体，粒子间存在着有别于常规粒子(或颗粒)间的作用能，暂且称为纳米作用能(Fn)。定性地讲，这种纳米作用能就是纳米粒子的表面因缺少邻近配位的原子，具有很高的活性而使纳米粒子彼此团聚的内在属性，其物理意义应是单位比表面积纳米粒子具有的吸附力，它是纳米粒子几个方面吸附的总和：纳米粒子间氢键、静电作用产生的吸附、纳米粒子间的量子隧道效应、电荷转移和界面原子的局部藕合产生的吸附，纳米粒子巨大的比表面产生的吸附纳米作用能是纳米粒子易团聚的内在因素。要得到分散性好、粒径小、粒径分布窄的纳米粒子，必须削弱或减小纳米作用能。
要使纳米粒子分散，就必须增强纳米粒子间的排斥作用能：(1)强化纳米粒子表面对分散介质的浸湿性，改变其界面结构，提高溶剂化膜的强度和厚度，增强溶剂化排斥作用；(2)增大纳米粒子表面双电层的电位绝对值，增强纳米粒子问的静电排斥作用；(3)通过高分子分散剂在纳米粒子表面吸附，产生并强化立体保护作用。
剪切速率的增加和超声波分散时间的增加都会提高工作液的分散效果。但随着超声波分散时间的延长，工作液的发热情况严重，这一缺点将严重影响到实际的生产加工，并且有可能导致工作液内部化学药品之间因为高温而发生化学反应。因此在采用超声波分散时，选择的时间应避免大于15min，剪切速率4000r/min为最优。
优选的，预烘的温度为60-100℃，时间为2-5min。
优选的，焙烘的温度为100-200℃，时间为1-5min。
本发明的有益效果是：采用本发明的涤/棉织物稀土多功能复合整理剂对含涤棉混纺织物进行后整理，处理后的织物具有优异耐久的紫外线吸收性能；采用纳米CeO2作为主要成分，使织物具有优异的抗菌性能；在使用理剂对含涤棉混纺织物进行后整理时，采用超声波分散，能提供分散效果，从而提高整理剂的使用效果。
具体实施方式
抗紫外线防护系数UPF的测试
紫外防护因子UPF(UV Protection Factor)也称为紫外线遮挡因子或抗紫外指数，它是衡量织物抗紫外性能的一个重要参数。UPF值是指是皮肤在使用纺织品前后可接受紫外线辐射量之比。即在一定的辐射强度下，皮肤在使用纺织品后可延长辐射时间的倍数。UPF的定义与测试，是建立在织物紫外光透过率的测试基础上的。
测算UPF值的方法，可采用下式：
Eλ—相对红斑的紫外光谱效能
Sλ—太阳光谱辐射度，W/(m·nm)
Tλ—波长为λ时的紫外线透过率(％)
△λ—紫外光波长间距(nm)
根据GB/T 18830-2002《纺织品防紫外线性能的评定》采用HB902防紫外线透过及防晒保护测试仪测定织物的紫外线透过率及UPF防护系数。根据国家标准中的定义，UPF指的是“皮肤无防护时计算出的紫外线辐射平均效应与皮肤有织物防护时计算出的紫外线辐射平均效应的比值”。国家质检总局颁布的《纺织品防紫外线性能的评定》标准中规定：只有当样品的UPF值大于30，并且UVA的透过率小于5％时，才能称之为“防紫外线产品”。
白度的测试
根据GB/T 18834-2009进行织物的白度测试，数值越高，说明织物的白度越好。
实施例1
此例为考察分散剪切速率与超声波分散时间对涤/棉织物稀土多功能复合整理剂分散效果的影响。
一种涤/棉织物稀土多功能复合整理剂，包括以下重量份的组分：
采用以下工艺处理复合整理剂:高速剪切混合→超声分散→搅拌→观察分散情况，经过处理后，所得分散结果如表1所示。
表1分散剪切速率与超声波分散时间对整理剂分散效果的影响
从表1可以看出，剪切速率的增加和超声波分散时间的增加都会提高纳米氧化铈的分散效果。但随着超声波分散时间的延长，工作液的发热情况严重，这一缺点将严重影响到实际的生产加工，并且有可能导致工作液内部化学药品之间因为高温而发生化学反应。因此采用超声波分散时，超声分散的时间应避免大于15min，优选的是10-15min，剪切速率4000r/min为最优。
实施例2
此例为考察氧化铈的用量对织物的抗紫外线能力的影响
采用实施例1中较佳的分散工艺(剪切速率4000r/min、剪切时间10min、超声波分散功率450w和超声波分散时间15min)，选取不同量的氧化铈，考察氧化铈的用量对织物的抗紫外线能力的影响。
工艺流程与条件控制如下：剪切(4000r/min,10min)→超声波(450W，15min)→二浸二轧(65％-70％，浸渍时间20s)→预烘(80℃，3min)→焙烘(150℃，90s，焙烘后剪一块进行水洗处理)→水洗(50-60℃，3min)→烘干(80℃)
其中，涤/棉织物稀土多功能复合整理剂的配方如下表2所示：
表2涤/棉织物稀土多功能复合整理剂的配方(重量份)
测试涤/棉织物稀土多功能复合整理剂对织物的抗紫外线的效果，所得结果如下表3所示。
表3纳米氧化铈用量对织物的抗紫外线能力的影响
1# 2# 3# 4# 5#
UPF 2.0 10.3 10 13.6 8.8
T(UVA) 33.31％ 19.44％ 17.74％ 14.13％ 20.38％
T(UVB) 65.30％ 6.22％ 6.13％ 4.91％ 7.91％
T(UVC) 42.28％ 15.58％ 14.34％ 11.44％ 16.73％
从表3可以看出，纳米氧化铈用量会影响织物的抗紫外线效果，用量为2份(4#组)时抗紫外线效果最好。
实施例3
此例为考察无机分散剂硅酸钠对涤棉织物抗紫外线效果的影响和对涤棉织物白度的影响。
工艺流程与条件：高速剪切混合(4000r/min，10min)→超声波(功率450W，15min)→二浸二轧(65％-70％，浸渍时间20s)→预烘(80℃，3min)→焙烘(160℃，90s)→测试抗紫外线效果
其中，涤/棉织物稀土多功能复合整理剂的配方如下表5所示：
表5涤/棉织物稀土多功能复合整理剂的配方(重量份)
测试涤/棉织物稀土多功能复合整理剂对织物的抗紫外线的效果，其中每组测两次，所得结果如下表6所示。
表6无机分散剂硅酸钠对涤棉织物抗紫外线效果的影响
由表6可以看出，硅酸钠用量对织物的抗紫外线效果影响很大，在用量为0.2份时，织物的UPF最高。大于0.2份时，用量越高，UPF值反而减小，这种现象的出现有可能是硅酸钠的适量加入会使氧化铈分散的均匀，但添加量过大，氧化铈小颗粒会再次聚集及沉淀。因此，使用硅酸钠分散剂时，较优的用量是0.2份。
测试涤/棉织物稀土多功能复合整理剂对织物白度的影响，其中每组测两次，所得结果如下表7所示。
表7无机分散剂硅酸钠对涤棉织物白度的影响
由表7可以看出，无机分散剂硅酸钠对涤棉织物白度具有一定的影响，硅酸钠的加入使得织物的白度有所下降，3#和4#下降的最为严重。说明硅酸钠的添加会影响织物的白度，这会对有色织物的颜色有一定影响，因此，当织物为有色织物时，可考虑选用有机分散剂。
实施例4
此例为考察有机分散剂的种类对涤棉织物抗紫外线效果的影响
由于硅酸钠分散剂对织物的白度有影响，因此我们有选择了其它的有机高分子分散剂或表面活性剂对织物进行处理，考察它们的抗紫外线能力。
工艺流程与条件：剪切(4000r/min,10min)→超声波(450W，15min)→二浸二轧(65％-70％，浸渍时间20s)→预烘(80℃，3min)→焙烘(150℃，90s，焙烘后剪一块进行水洗处理)→水洗(50-60℃，3min)→烘干(80℃)。
其中，涤/棉织物稀土多功能复合整理剂的配方如下表8所示：
表8涤/棉织物稀土多功能复合整理剂的配方(重量份)
表9有机分散剂对涤棉织物抗紫线效果的影响
由表9可知，有机分散剂的种类对涤棉织物抗紫线效果有一定的影响，用量为2份的羧甲基纤维对织物的抗紫外线效果是最佳的，接着依次为2份聚丙烯酸钠、2份聚丙烯酰胺和2份聚丙烯酰胺。

Claims (10)

1.一种涤/棉织物稀土多功能复合整理剂，其特征在于，包括以下重量份的组分：
2.根据权利要求1所述的涤/棉织物稀土多功能复合整理剂，其特征在于，所述分散剂是无机分散剂或有机分散剂。
3.根据权利要求2所述的涤/棉织物稀土多功能复合整理剂，其特征在于，所述无机分散剂是海藻酸钠、六偏磷酸钠或硅酸钠。
4.根据权利要求2所述的涤/棉织物稀土多功能复合整理剂，其特征在于，所述有机分散剂是聚丙烯酰胺、羧甲基纤维、聚丙烯酞胺、聚丙烯酸钠、木质碳酸钠、石油磺酸钠、水解丙烯酸胺、磷酸脂或乙氧基化合物。
5.根据权利要求1所述的涤/棉织物稀土多功能复合整理剂，其特征在于，所述表面活性剂是Sp60。
6.根据权利要求1所述的涤/棉织物稀土多功能复合整理剂，其特征在于，所述粘合剂是聚氨酯、聚苯乙烯、聚丙烯酸或环氧树脂。
7.根据权利要求1所述的涤/棉织物稀土多功能复合整理剂，其特征在于，所述增稠剂是聚丙烯酰胺或聚乙烯醇。
8.制备权利要求1-7中任一项所述的涤/棉织物稀土多功能复合整理剂的方法，其特征在于，包括以下步骤：将纳米CeO2投入分散缸中，再依次分散剂、表面活性剂、粘合剂、增稠剂和水，搅拌均匀，即可得到涤/棉织物稀土多功能复合整理剂。
9.权利要求1-7中任一项所述的涤/棉织物稀土多功能复合整理剂的应用方法，其特征在于，包括以下步骤：高速剪切混合→超声分散→搅拌→浸轧整理液二浸二轧，带液率65-70％→预烘→焙烘→测试。
10.根据权利要求9所述的应用方法，其特征在于，超声分散的功率为350-500W，时间为5-15min。
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Application publication date: 20171110