CN115434144B - 一种低烘焙温度的多元羧酸抗皱整理方法 - Google Patents
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Abstract
本发明涉及一种低烘焙温度的多元羧酸抗皱整理方法。该整理方法包括：(1)将织物浸轧整理液A，预烘，得到预处理织物，其中整理液A包括：多元羧酸抗皱整理剂、催化剂和水；(2)将整理液B喷射在步骤(1)中预处理织物表面，烘焙，其中整理液B为高沸点溶剂。该方法相比于传统多元羧酸整理工艺，在整理织物取得相同折皱回复角的同时，显著降低了烘焙的温度，提高了整理后织物的强力保留率，并有利于工业化发展。
Description
技术领域
本发明属于织物抗皱整理领域，特别涉及一种低烘焙温度的多元羧酸抗皱整理方法。
背景技术
天然棉纤维织物具有柔软、透气、吸湿性好等优点，因而广受人们的喜爱。但其却有着回弹性差、缩水率大、易于起皱等缺点，在服用过程中给人类带来了极大的不便。因此，棉织物的易护理整理也成为了棉纺织品重要的后整理工序。棉织物起皱的主要原因在于其无定型区中大分子链上的羟基互相之间形成氢键，在受到外力的作用下氢键被打断，分子链发生滑移，并在新的位置上重新形成了氢键，由此便产生了折皱。目前工业上使用最多的抗皱整理剂为2D树脂，主要成分为二羟甲基二羟基乙烯脲。该交联剂整理效果好，处理过后的织物折皱回复角高，但存在着释放游离甲醛的危险，在长期的服用过程中会引发皮肤细胞的癌变。随着人们对甲醛危害认识的不断深入和健康意识的提高，无甲醛抗皱整理受到了研究人员的关注，多元羧酸类抗皱整理剂应运而生。
多元羧酸在磷酸盐催化剂的作用下，通过与棉纤维上的羟基发生酯化反应，从而赋予棉织物防皱效果。在众多多元羧酸整理剂中，丁烷四羧酸的防皱整理效果最好，但存在着整理温度过高等缺点，通常需要在180℃下烘焙2～3分钟。2001年，Yang等人采用傅利叶红外光谱较为系统的研究了催化剂次亚磷酸钠的催化机理，发现多元羧酸可以在120℃下形成酸酐中间体，高活性的酸酐中间体继而与棉纤维上的羟基发生酯化交联反应。该研究结果表明，多元羧酸在低温下也可和棉纤维发生交联反应，而目前多元羧酸在低温下整理效果不佳的主要原因在于其发生交联反应的速率过慢。为此，提高多元羧酸与棉纤维在低温下的反应速率可以有效的提升其整理效果，使织物获得令人满意的折皱回复性能。同时，较低的整理温度也可有效改善棉织物的强力保留率。提高多元羧酸与棉织物的交联速率主要有两个途径。第一个是提高游离多元羧酸的扩散能力，增大多元羧酸与棉织物上羟基的碰撞概率，增加反应速率。第二个是提高纤维素大分子链的热运动，增大接枝多元羧酸与相邻大分子链上羟基碰撞的概率，加大反应速率。
目前在工业中采用多元羧酸对棉织物进行抗皱整理，烘焙温度至少需要170℃。在该温度下，不仅大大提高了生产过程中的能耗，更加重了设备的损耗，还释放出大量的温室气体，对生态环境的保护和资源的可持续利用带来了不小的挑战。因此，研究低温多元羧酸抗皱整理工艺具有重要的意义。
发明内容
本发明所要解决的技术问题是提供一种低烘焙温度的多元羧酸抗皱整理方法，以克服现有技术中织物抗皱整理需要过高烘焙温度的缺陷。
本发明提供一种低烘焙温度低强力损伤的多元羧酸复配抗皱整理液，包括整理液A和整理液B；所述整理液A包括：多元羧酸抗皱整理剂、催化剂和水；所述整理液B为高沸点溶剂，所述高沸点溶剂的沸点高于150℃。
优选地，所述多元羧酸抗皱整理剂包括丁烷四羧酸、柠檬酸、丙三酸、马来酸、衣康酸、硫代二丁二酸、乙二硫醇二琥珀酸、丙二硫醇二琥珀酸中的一种或几种。
优选地，所述催化剂包括次亚磷酸钠、次亚磷酸钾或酒石酸钠。
优选地，所述整理液A中多元羧酸抗皱整理剂浓度为30-100g/L，催化剂浓度为20-70g/L。
优选地，所述高沸点溶剂包括二甲基亚砜、二甲基乙酰胺、二甲基甲酰胺、环丁砜或二甲基砜。
优选地，所述整理液A包括：50-85g/L的丁烷四羧酸、30-40g/L的次亚磷酸钾，整理液B为二甲基亚砜。
更优选地，所述整理液A包括80g/L的丁烷四羧酸，34g/L的次亚磷酸钾，整理液B为二甲基亚砜。
本发明还提供一种多元羧酸复配抗皱整理液在抗皱整理中的应用。
本发明还提供一种多元羧酸复配抗皱整理液的抗皱整理方法，包括：
(1)将织物浸轧整理液A，预烘，得到预处理织物；
(2)将整理液B喷射在步骤(1)中预处理织物表面，烘焙。
优选地，所述步骤(1)中浸轧为二浸二轧，二浸二轧带液率为60-100％。
优选地，所述步骤(1)中预烘为：在90-115℃下预烘1-3min。更优选地，预烘为：110℃烘干1.5min。
优选地，所述步骤(1)中织物为纯棉织物。
优选地，所述步骤(2)中喷射采用气泵。
优选地，所述步骤(2)中喷射的量为织物重的10～40％。更优选地，喷射的量为织物重的20％。
优选地，所述步骤(2)中烘焙为：110～155℃烘焙2-6min。更优选地，烘焙为：150℃烘焙4min。
本发明可以在低于160℃的烘焙温度下对织物进行防皱整理，整理后织物的折皱回复角高于245°，并且织物强力损伤较小。整理后织物中残留的添加剂可以通过水洗方式除去，操作方式简单。该工艺不仅可以取得较好的织物抗皱整理效果，还可以降低生产过程中的能耗和设备损伤，有利于环保和工业化发展。
本发明降低烘焙温度机理：一方面，高沸点溶剂使得原来的多元羧酸扩散相从“固固”相转化为“固液固”相，纤维孔道中的高沸点溶剂成为了多元羧酸的扩散介质，让其扩散更为容易，使得更多的羧酸分子扩散至纤维的内部，增大了与纤维素大分子链上的羟基发生碰撞的概率，提高反应速率。另一方面，高沸点溶剂可以渗透至纤维的内部，打破纤维素大分子链之间的氢键，引起纤维的适当溶胀，促进分子链的热运动，使得接枝的多元羧酸有更大的概率与另一纤维素大分子链上的羟基发生酯化反应，形成交联。
有益效果
本发明所采用的两步法工艺，相比于传统多元羧酸整理工艺所需的170～180℃的烘焙温度，在整理织物取得相同折皱回复角的同时，显著降低了烘焙的温度，提高了整理后织物的强力保留率，并有利于工业化发展。
本发明所采用的两步法工艺，在烘焙温度低于160℃的条件下，根据AATCC 66-2008的测试方法，整理后织物的折皱回复角高于245°，相比于传统工艺提高了20～30°。
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。
折皱回复角测试标准：AATCC 66-2008。
强力保留率测试标准：GB3923.1-1997。
实施例1
将棉织物浸轧整理液A，整理液A成分为80g/L丁烷四羧酸、34g/L次亚磷酸钾，二浸二轧，带液率为100％，110℃下烘干1.5min；采用气泵将整理液B喷射至织物表面，整理液B成分为二甲基亚砜，喷射量为织物质量的20％，150℃下烘焙4min。最后在常温水洗机中洗涤30min。整理织物的折皱回复角为254°，纬向强力保留率为68.74％，原布折皱回复角125°。
实施例2
将棉织物浸轧整理液A，整理液A成分为80g/L丁烷四羧酸、34g/L次亚磷酸钠，二浸二轧，带液率为90％，100℃下烘干3min；采用气泵将整理液B喷射至织物表面，整理液B成分为二甲基乙酰胺，喷射量为织物质量的15％，145℃下烘焙6min。最后在常温水洗机中洗涤30min。整理织物的折皱回复角为252°，纬向强力保留率为63.64％，原布折皱回复角125°。
实施例3
将棉织物浸轧整理液A，整理液A成分为80g/L丁烷四羧酸、33.56g/L次亚磷酸钾，二浸二轧，带液率为90％，105℃下烘干2.5min；采用气泵将整理液B喷射至织物表面，整理液B成分为环丁砜，喷射量为织物质量的30％，150℃下烘焙3min。最后在常温水洗机中洗涤30min。整理织物的折皱回复角为248°，纬向强力保留率为69.32％，原布折皱回复角125°。
实施例4
将棉织物浸轧整理液A，整理液A成分为80g/L丁烷四羧酸、32.72g/L次亚磷酸钾，二浸二轧，带液率为90％，90℃下烘干3min；采用气泵将整理液B喷射至织物表面，整理液B成分为二甲基砜，喷射量为织物质量的10％，140℃下烘焙4min。最后在常温水洗机中洗涤30min。整理织物的折皱回复角为253°，纬向强力保留率为64.58％，原布折皱回复角125°。
实施例5
将棉织物浸轧整理液A，整理液A成分为80g/L丁烷四羧酸、33g/L次亚磷酸钠，二浸二轧，带液率为90％，100℃下烘干3min；采用气泵将整理液B喷射至织物表面，整理液B成分为二甲基砜，喷射量为织物质量的40％，130℃下烘焙4min。最后在常温水洗机中洗涤30min。整理织物的折皱回复角为247°，纬向强力保留率为70.12％，原布折皱回复角125°。
对比例1
将棉织物浸轧整理液A，整理液A成分为80g/L丁烷四羧酸、34g/L次亚磷酸钾，二浸二轧，带液率为100％，110℃下烘干1.5min，150℃下烘焙4min。最后在常温水洗机中洗涤30min。整理织物的折皱回复角为226°，纬向强力保留率为75.64％，原布折皱回复角125°。
对比例2
将棉织物浸轧整理液A，整理液A成分为80g/L丁烷四羧酸、34g/L次亚磷酸钠，二浸二轧，带液率为90％，100℃下烘干3min，145℃下烘焙6min。最后在常温水洗机中洗涤30min。整理织物的折皱回复角为232°，纬向强力保留率为67.84％，原布折皱回复角125°。
对比例3
将棉织物浸轧整理液A，整理液A成分为80g/L丁烷四羧酸、34g/L次亚磷酸钾，二浸二轧，带液率为100％，110℃下烘干1.5min，165℃下烘焙4min。最后在常温水洗机中洗涤30min。整理织物的折皱回复角为253°，纬向强力保留率为63.79％，原布折皱回复角125°。
对比例4
将棉织物浸轧整理液A，整理液A成分为80g/L丁烷四羧酸、34g/L次亚磷酸钠，二浸二轧，带液率为90％，100℃下烘干3min，160℃下烘焙6min。最后在常温水洗机中洗涤30min。整理织物的折皱回复角为254°，纬向强力保留率为53.87％，原布折皱回复角125°。
对比例5
将棉织物浸轧整理液A，整理液A成分为80g/L丁烷四羧酸、33g/L次亚磷酸钠，二浸二轧，带液率为90％，100℃下烘干3min，130℃下烘焙4min。最后在常温水洗机中洗涤30min。整理织物的折皱回复角为213°，纬向强力保留率为79.87％，原布折皱回复角125°。
对比例6
将棉织物浸轧整理液A，整理液A成分为80g/L丁烷四羧酸、34g/L次亚磷酸钾，二浸二轧，带液率为100％，110℃下烘干1.5min；采用气泵将整理液B喷射至织物表面，整理液B成分为水，喷射量为织物质量的20％，150℃下烘焙4min。最后在常温水洗机中洗涤30min。整理织物的折皱回复角为198°，纬向强力保留率为73.74％，原布折皱回复角125°。
对比例7
将棉织物浸轧整理液A，整理液A成分为80g/L丁烷四羧酸、34g/L次亚磷酸钾，二浸二轧，带液率为100％，110℃下烘干1.5min；采用气泵将整理液B喷射至织物表面，整理液B成分为乙醇，喷射量为织物质量的20％，150℃下烘焙4min。最后在常温水洗机中洗涤30min。整理织物的折皱回复角为208°，纬向强力保留率为71.28％，原布折皱回复角125°。
本发明实施例1-2与对比例3-4的比较如表1所示，可知，在整理后织物折皱回复角大致相等的情况下，含有高沸点溶剂的实施例1和实施例2的烘焙温度明显低于对比例3和对比例4。
表1：折皱回复角相当的情况下烘焙温度对比
注：在折皱回复角相当的情况下，含高沸点溶剂的实施例1和实施例2的烘焙温度低于比例1和对比例2，同时低烘焙温度使织物的强力保留率更高。
本发明实施例1-2、实施例5和对比例1-2、对比例5的比较如表2所示，可知，对比例1和对比例2中的整理液不加入任何添加剂，使用该整理液对棉织物进行整理，折皱回复效果明显小于含有添加剂的实施例1和实施例2。
表2：整理液中包含与不包含添加剂的整理效果对比
本发明实施例1与对比例6-7的比较如表3所示，可知，当采用非高沸点溶剂时，对比例6-7中织物的折皱回复性明显小于高沸点溶剂。
表3：添加高沸点溶剂与非高沸点溶剂的整理效果对比
Claims (5)
1.一种多元羧酸复配抗皱整理液的抗皱整理方法，包括：
（1）将织物浸轧整理液A，预烘，得到预处理织物；其中，所述整理液A包括：多元羧酸抗皱整理剂、催化剂和水；所述多元羧酸抗皱整理剂包括丁烷四羧酸、柠檬酸、丙三酸、马来酸、衣康酸、硫代二丁二酸、乙二硫醇二琥珀酸、丙二硫醇二琥珀酸中的一种或几种；所述催化剂包括次亚磷酸钠、次亚磷酸钾或酒石酸钠；
（2）将整理液B喷射在步骤（1）中预处理织物表面，烘焙；其中，所述烘焙为：110~155℃烘焙2-6min；所述整理液B为高沸点溶剂，所述高沸点溶剂的沸点高于150℃；所述高沸点溶剂包括二甲基亚砜、二甲基乙酰胺、二甲基甲酰胺、环丁砜或二甲基砜。
2. 根据权利要求1所述的抗皱整理方法，其特征在于，所述步骤（1）中浸轧为二浸二轧，二浸二轧带液率为60-100%；预烘为：在90-115℃下预烘1-3 min。
3.根据权利要求1所述的抗皱整理方法，其特征在于，所述步骤（1）中的整理液A中多元羧酸抗皱整理剂浓度为30-100g/L，催化剂浓度为20-70g/L。
4.根据权利要求1所述的抗皱整理方法，其特征在于，所述步骤（1）中织物为纯棉织物。
5.根据权利要求1所述的抗皱整理方法，其特征在于，所述步骤（2）中喷射的量为织物重的10~40%。
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