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CN108797153B - 一种基于低共熔溶剂的功能染色方法 - Google Patents

一种基于低共熔溶剂的功能染色方法 Download PDF

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CN108797153B
CN108797153B CN201810647141.0A CN201810647141A CN108797153B CN 108797153 B CN108797153 B CN 108797153B CN 201810647141 A CN201810647141 A CN 201810647141A CN 108797153 B CN108797153 B CN 108797153B
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邢彦军
王新
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Abstract

本发明公开了一种基于低共熔溶剂的功能染色方法，其特征在于，将氢键受体化合物与可光引发聚合的氢键给体化合物混合均匀后制备低共熔溶剂，加入分散染料并搅拌溶解，制得预染液；在预染液中加入光引发聚合剂并搅拌溶解，制得染液；使用染液对待染织物进行染色，紫外光照射预染织物，得到染色织物。本发明采用绿色、新型的低共熔溶剂作为分散染料的功能型印染介质，利用现有织物染色设备直接进行处理，将分散染料固定在织物上。本发明作为一种功能性染色技术，具有绿色无污染、废水排放低、价格低廉、操作方便、适合工业化生产等优点。

Description

一种基于低共熔溶剂的功能染色方法
技术领域
本发明涉及一种基于低共熔溶剂的功能染色方法，属于纺织品的染色和后整理领域。
背景技术
分散染料早在20世纪初便已问世，当时主要是为了对醋酯纤维进行染色。后来随着合成纤维的快速发展，分散染料逐渐成为发展最快的染料之一。分散染料染色的主要方法为载体染色法、高温高压染色法、热熔染色法三种方法，由于分散染料在水中的溶解性比较差，需要加入分散剂等难以生物降解的助剂进行协助染色，对环境造成的污染十分明显。此外随着生态环境问题的日趋严峻，分散染料所造成的废水问题愈加突出，染色残液中含有的大量分散剂以及还原清洗液中无法回收的染料都增加了废水处理的难度。
有机溶剂染色被认为是可以降低印染废水排放的绿色环保染色技术。但此前研究较多的三氯乙烯或四氯乙烯溶剂染色，由于分散染料在三氯乙烯或四氯乙烯中的溶解度过高导致染料上染率较低，以及染色后织物上可能残留对健康有害的卤代烃类溶剂等原因，该技术未能得到进一步发展。
经分散染料染色后的化纤纺织产品，色泽艳丽，耐洗牢度优良，但由于分散染料本身结构和染色工艺等方面的影响，目前分散染料仅主要用于聚酯纤维等合成纤维的染色和印花，这极大限制了分散染料的应用。为了扩展分散染料的应用，目前运用最多的是涂料印花方式，这是由于涂料印花对于染料和织物的选择性没有要求，适用于任何纤维制成的纺织品，是通过涂料对织物的粘附效果达成固着染色效果，但这种印花方式对所用粘着剂和增稠剂的要求较高，而且目前主要所用的粘着剂和交联剂主要是增强成膜后的机械性能，附加值不高。
可见，以上方法在应用中都存在一定的局限性，分散染料在涤纶纤维染色中用量非常大，因而产生印染废水也非常高。因此，开发一套工艺简单、染色效果好、废水排放少、可适用于更多类型纤维的染色技术显得非常重要。
发明内容
本发明所要解决的技术问题是：提供一种基于低共熔溶剂的功能染色方法，该方法利能在现有织物染色设备的基础上直接染色，不增添设备，不增大成本；所用原料成本低，具有良好的化学物理稳定性，绿色无污染，适用于工业化生产。
为了解决上述问题，本发明提供了一种基于低共熔溶剂的功能染色方法，其特征在于，包括以下步骤：
步骤1)：将氢键受体化合物与可光引发聚合的氢键给体化合物混合均匀后在80～100℃下加热2～4小时制备低共熔溶剂，然后向低共熔溶剂中加入分散染料并搅拌溶解，制得预染液；
步骤2)：在预染液中加入光引发聚合剂并搅拌溶解，制得染液；
步骤3)：使用染液对待染织物进行染色，紫外光照射预染织物10s～3min，100-120℃下烘30～60min，常温水洗，晾干，得到染色织物。
优选地，所述步骤1)中的氢键受体化合物为胆碱、甜菜碱和氨基酸中的至少一种；可光引发聚合的氢键给体化合物为马来酸、富马酸、丙烯酸、甲基丙烯酸、丙烯酰胺、甲基丙烯酰胺、N-甲基丙烯酰胺、N-甲基-甲基丙烯酰胺、N-乙基丙烯酰胺、N-羟甲基丙烯酰胺、N-羟甲基-甲基丙烯酰胺和N-羟乙基丙烯酰胺中的至少一种。
优选地，所述步骤1)中氢键受体化合物与可光引发聚合的氢键给体化合物的摩尔比为(1～3)∶(1～6)。
更优选地，所述氢键受体化合物与可光引发聚合的氢键给体化合物的摩尔比为1∶2。
更优选地，所述胆碱为氯化胆碱和溴化胆碱中的至少一种；所述甜菜碱为甜菜碱和甜菜碱盐酸盐中的至少一种；所述氨基酸为甘氨酸、丙氨酸和谷氨酸中的至少一种；所述分散染料为C.I.分散红54、60、73、74、153、167、177，C.I.分散黄64、54、104、211，以及C.I.分散蓝56、60、79中的至少一种。
优选地，所述步骤1)中分散染料为未添加分散剂的常规纯分散染料；分散染料的加入量为1～20g/L(低共熔溶剂)。
优选地，所述步骤2)中光引发聚合剂为偶氮二异丁脒盐酸盐V-50、偶氮二异丙基咪唑啉盐酸盐VA-044、安息香二甲醚、2，2-二甲氧基-2-苯基苯乙酮、2，4-二烷基硫杂蒽酮、Norrish II型光引发剂或Norrish I型光引发剂。
优选地，所述步骤2)中光引发聚合剂的加入量为可光引发聚合的氢键给体化合物质量的0.05～1％。
优选地，所述步骤3)中待染织物为天然纤维织物、合成纤维织物或两者的混纺。
优选地，所述步骤3)中的紫外光是由100～800W的紫外灯产生，其光强范围为0.01～3mW/cm2，主波长为254nm或365nm。
本发明中低共熔溶剂溶解分散染料后制备的预染液性能稳定，避光可长时间储备放置。本发明还可以应用于其他可溶于低共熔溶剂并且不与氢键受体化合物或者氢键给体化合物发生反应的染料，制得的染色织物还同时具有抗菌、抗静电、导电或抗皱等性能。
本发明采用低共熔溶剂作为分散染料对于天然纤维织物染色或者印花的介质，不同于一般意义上的粘着剂、交联剂和固色剂。低共熔溶剂不仅本身为低粘度的液体，在溶解分散染料后在引发聚合条件之前仍为低粘度的液体，因此可以利用常规的印染设备对织物进行整理加工，并且整理加工后在织物的表面均匀分布；低共熔溶剂中的可光引发聚合的氢键给体化合物在引发聚合后可以快速聚合成膜，能够达到防止染料颗粒物聚集、印染无瑕疵等效果，而且织物手感更好。由于低共熔溶剂中的氢键受体化合物本身具有导电、抗菌等效果，可光引发聚合的氢键给体化合物聚合后还可以使棉织物产生防皱效果，因此本方法能够在对织物进行染色的同时，赋予织物抗菌、导电(防静电)、防皱等特性，在印染过程中可以达到织物功能整理的效果，大大增加了织物的附加值。
与现有技术相比，本发明的有益效果在于：
(1)本发明方法利用现有织物染色设备直接染色，不增添设备，不增大成本，应用于纺织工业的绿色环保生产，可大量生产；
(2)不同于一般染色方法，分散染料可以溶解于低共熔溶剂中，不会发生染料颗粒聚集等状况，所以印染效果更均匀，减少了印染瑕疵，手感更好；
(3)由于低共熔溶剂中的可光引发聚合的氢键给体化合物可通过交联反应成膜，染料可以被聚合膜长久固着在织物上，耐洗牢度高；
(4)本发明中低共熔溶剂溶解分散染料后制备的预染液性能稳定，避光可长时间储备放置；
(5)本发明所使用的低共熔溶剂在紫外光引发聚合之前为低粘度的液体，可以通过浸染、轧染或印花等方式对织物进行处理，操作便利；经紫外光引发聚合后，聚合速度快，所以可以按照产品设计灵活运用聚合引发时间和方式；
(6)本发明在对织物进行染色的同时，也对织物进行了功能整理，通过利用低共熔溶剂中具有抗菌性的氢键受体化合物赋予织物抗菌、导电(防静电)等性能，氢键给体化合物聚合成膜可以赋予织物防皱性能；
(7)所制备的低共熔溶剂无毒且具有可生物降解性，降低了废液处理的难度和资源投入，减少了水资源的浪费和印染废水的排放，适于工业化生产；
(8)本发明可以应用于各种类型的织物。
具体实施方式
为使本发明更明显易懂，兹以优选实施例，作详细说明如下。
实施例1
将氯化胆碱与丙烯酸以摩尔比1∶2混合，配制低共熔溶剂；将分散红73染料超声溶解于低共熔溶剂中，配制浓度为4g/L的预染液，避光储备；染色时，在预染液中加入2，2-二甲氧基-2-苯基苯乙酮作为聚合引发剂，用量为丙烯酸质量的0.5％；将预染液对涤纶织物进行二浸二轧，紫外(300W紫外灯，光强范围是1mW/cm2，产生的紫外光主波长为254nm)照射20s，100℃烘45分钟，水洗晾干，得到染色织物。
上述染色织物的K/S值15，染色后的涤纶织物表面比电阻4×105Ohms，抗静电效果好，对大肠杆菌和金黄色葡萄球菌的抑菌率大于99％。染色织物耐洗牢度4-5级，耐干磨擦牢度4-0级，耐湿摩擦牢度4-0级。
实施例2
将氯化胆碱与丙烯酰胺以摩尔比1∶2混合，配制低共熔溶剂；将分散蓝56染料超声溶解于低共熔溶剂中，配制浓度为18g/L的预染液，避光保存；染色时，在预染液中加入偶氮二异丁脒盐酸盐V-50作为聚合引发剂，用量为丙烯酰胺质量的0.5％；将预染液对棉织物进行三浸三轧，浸泡时间为5分钟；紫外(300W紫外灯，光强范围是1.5mW/cm2，产生的紫外光主波长为254nm)照射20s使低共熔溶剂发生聚合和交联反应，100℃烘60分钟，水洗晾干，得到染色织物。
上述染色织物的K/S值为20，染色后棉织物折皱回复角200°，对大肠杆菌和金黄色葡萄球菌的抑菌率大于99％。得到的染色织物耐洗牢度4-5级，耐干磨擦牢度4-0级，耐湿摩擦牢度4-0级。
实施例3
将甜菜碱与丙烯酰胺以摩尔比1∶2混合，配制低共熔溶剂；将分散黄64染料超声溶解于低共熔溶剂中，配制浓度为8g/L的预染液，避光保存；染色时，在预染液中加入偶氮二异丙基咪唑啉盐酸盐VA-044作为聚合引发剂，用量为丙烯酰胺质量的0.6％；将预染液对锦纶织物进行三浸三轧；紫外(100W紫外灯，光强范围是0.5mW/cm2，产生的紫外光主波长为365nm)照射40s，120℃烘30分钟，水洗晾干，得到染色织物。
上述染色织物的K/S值为15，染色后的锦纶织物表面比电阻9×107Ohms，对大肠杆菌和金黄色葡萄球菌的抑菌率大于99％。染色织物的耐洗牢度4-5级，耐干磨擦牢度4-0级，耐湿摩擦牢度4-0级。
实施例4
将甜菜碱与甲基丙烯酰胺以摩尔比1∶2混合，配制低共熔溶剂；将分散红74染料超声溶解于低共熔溶剂中，配制浓度为10g/L的预染液，避光保存；染色时，在预染液中加入Norrish II型光引发剂作为聚合引发剂，用量为甲基丙烯酰胺质量的0.6％；将预染液对棉织物进行三浸三轧；紫外(500W紫外灯，光强范围是2mW/cm2，产生的紫外光主波长为365nm)照射15s，110℃烘45分钟，水洗晾干，得到染色织物。
上述染色织物的K/S值为15，染色后棉织物折皱回复角200°，对大肠杆菌和金黄色葡萄球菌的抑菌率大于99％。染色织物的耐洗牢度4-5级，耐干磨擦牢度4-0级，耐湿摩擦牢度4-0级。
实施例5
通过甘氨酸与N-羟甲基丙烯酰胺以摩尔比1∶3混合，配制低共熔溶剂；将分散红177染料超声溶解于低共熔溶剂中，配制浓度为12g/L的预染液，避光保存；染色时，在预染液中加入2，2-二甲氧基-2-苯基苯乙酮作为聚合引发剂，用量为N-羟甲基丙烯酰胺质量的1％；将预染液对棉织物进行二浸二轧；紫外(800W紫外灯，光强范围是3mW/cm2，产生的紫外光主波长为254nm)照射10s，120℃烘30分钟，水洗晾干，得到染色织物。
上述染色织物的K/S值为16，染色后棉织物折皱回复角200°，对大肠杆菌和金黄色葡萄球菌的抑菌率大于99％。染色织物的耐洗牢度4-5级，耐干磨擦牢度4-0级，耐湿摩擦牢度4-0级。
实施例6
通过氯化胆碱与N-羟甲基-甲基丙烯酰胺以摩尔比1∶2混合，配制低共熔溶剂；将分散蓝79染料超声溶解于低共熔溶剂中，配制浓度为10g/L的预染液，避光保存；染色时，在预染液中加入偶氮二异丁脒盐酸盐V-50作为聚合引发剂，用量为N-羟甲基-甲基丙烯酰胺质量的0.6％；将预染液对棉织物进行三浸三轧；紫外(300W紫外灯，光强范围是1.5mW/cm2，产生的紫外光主波长为365nm)照射30s，100℃烘60分钟，水洗晾干，得到染色织物。
上述染色织物的K/S值为15，染色后棉织物折皱回复角200°，对大肠杆菌和金黄色葡萄球菌的抑菌率大于99％。染色织物的耐洗牢度4-5级，耐干磨擦牢度4-0级，耐湿摩擦牢度4-0级。

Claims (9)

1.一种基于低共熔溶剂的功能染色方法，其特征在于，包括以下步骤：
步骤1）：将氢键受体化合物与可光引发聚合的氢键给体化合物混合均匀后在80~100℃下加热2~4小时制备低共熔溶剂，然后向低共熔溶剂中加入分散染料并搅拌溶解，制得预染液；
步骤2）：在预染液中加入光引发聚合剂并搅拌溶解，制得染液；
步骤3）：使用染液对待染织物进行染色，紫外光照射预染织物10s~3min，100-120℃下烘30~60min，常温水洗，晾干，得到染色织物；
所述步骤1）中的氢键受体化合物为胆碱、甜菜碱和氨基酸中的至少一种；可光引发聚合的氢键给体化合物为马来酸、富马酸、丙烯酸、甲基丙烯酸、丙烯酰胺、甲基丙烯酰胺、N-甲基丙烯酰胺、N-甲基-甲基丙烯酰胺、N-乙基丙烯酰胺、N-羟甲基丙烯酰胺、N-羟甲基-甲基丙烯酰胺和N-羟乙基丙烯酰胺中的至少一种；所述分散染料为C.I.分散红54、60、73、74、153、167、177，C.I.分散黄64、54、104、211，以及C.I.分散蓝56、60、79中的至少一种。
2.如权利要求1所述的基于低共熔溶剂的功能染色方法，其特征在于，所述步骤1）中氢键受体化合物与可光引发聚合的氢键给体化合物的摩尔比为（1~3）：（1~6）。
3.如权利要求2所述的基于低共熔溶剂的功能染色方法，其特征在于，所述氢键受体化合物与可光引发聚合的氢键给体化合物的摩尔比为1：2。
4.如权利要求1所述的基于低共熔溶剂的功能染色方法，其特征在于，所述胆碱为氯化胆碱和溴化胆碱中的至少一种；所述氨基酸为甘氨酸、丙氨酸和谷氨酸中的至少一种。
5.如权利要求1所述的基于低共熔溶剂的功能染色方法，其特征在于，所述步骤1）中分散染料为未添加分散剂的常规纯分散染料；分散染料的加入量为1~20g/L，是相对于每升低共熔溶剂确定分散染料的加入克重。
6.如权利要求1所述的基于低共熔溶剂的功能染色方法，其特征在于，所述步骤2）中光引发聚合剂为偶氮二异丁脒盐酸盐V-50、偶氮二异丙基咪唑啉盐酸盐VA-044、安息香二甲醚、2,2-二甲氧基-2-苯基苯乙酮、2,4-二烷基硫杂蒽酮、Norrish Ⅱ型光引发剂或NorrishⅠ型光引发剂。
7.如权利要求1所述的基于低共熔溶剂的功能染色方法，其特征在于，所述步骤2）中光引发聚合剂的加入量为可光引发聚合的氢键给体化合物质量的0.05~1%。
8.如权利要求1所述的基于低共熔溶剂的功能染色方法，其特征在于，所述步骤3）中待染织物为天然纤维织物、合成纤维织物或两者的混纺。
9.如权利要求1所述的基于低共熔溶剂的功能染色方法，其特征在于，所述步骤3）中的紫外光是由100~800W的紫外灯产生，其光强范围为0.01~3mW/cm2，主波长为254nm或365nm。
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