CN107955129B - 一种仿活性涂料印花用交联剂及其制备方法 - Google Patents
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Abstract
本发明一种仿活性涂料印花用交联剂及其制备方法，由六亚甲基二异氰酸酯三聚体70‑90份、聚乙二醇10‑20份、亲水扩链剂2‑4份、三羟甲基丙烷1‑1.5份、有机溶剂30‑40份、聚乙二醇单甲醚1‑3份得到的预聚物，经甲乙酮肟25‑35份封端、三乙胺1.5‑3份中和、去离子水160‑230份分散制得交联剂乳液。具有良好的干湿摩擦牢度及皂洗牢度，且印花后不影响织物手感。
Description
技术领域
本发明涉及的是纺织品印染助剂，具体涉及的是一种仿活性涂料印花交联剂及其制备方法。
背景技术
涂料印花是利用粘合剂将不溶性颜料颗粒结合成膜粘附固着在纤维表面以获得所需图案的印花工艺，它对各种纤维的织物均适用，具有色谱齐全、操作简单、易于调制等特点，涂料印花工艺无需水洗，相比于染料印花具有节能、节水的优点，但它的手感不如染料印花（如活性染料印花）自然柔软，特别在大面积的花型上更为突出。涂料印花产品的手感和牢度取决于粘合剂的品质，所以为了改善涂料印花的效果，需要选用成膜较柔软的粘合剂来达到涂料仿活性染料印花的目的。
目前质量较好的仿活性涂料印花粘合剂已经可以达到较柔软的手感，但由于其自身内聚力普遍不如常规的涂料印花粘合剂品种，及在成膜后进一步的交联固化程度有限，造成了仿活性印花涂料在织物上的附着牢度差、耐皂洗牢度差、耐磨性差等缺陷，尤其对于一些深色品种其干湿摩擦牢度指标却难以达到4级的要求，需要向涂料印花浆中加入交联剂以提高印花的牢度。常用的涂料印花交联剂有氮丙啶类、聚氨酯类、有机硅类及三聚氰胺树脂类等等，这些交联剂加入后，均可以不同程度的起到提高摩擦色牢度及皂洗牢度，但除聚氨酯类之外其他类型的交联剂均存在毒性高、不环保、释放游离甲醛、成膜易黄变、制备的印花浆不能存放等问题。
目前现有的水性封闭型聚氨酯交联剂可以在受热时解开封闭，释放出活泼的异氰酸酯基团，同粘合剂乳液中的羟基、羧基、酰胺基发生反应，将线型共聚物交联成三维网状结构的高分子，从而使粘合剂乳液的交联程度及成膜效果得到提升，特别是耐湿摩擦牢度及皂洗牢度得到显著提高；同时活泼的异氰酸酯基团与纤维中游离的羟基、羧基、氨基发生交联反应，使乳液成膜对纤维的附着力进一步增强，使印花牢度得到提高。但是，向涂料印花浆中加入交联剂后会使粘合剂乳液成膜变硬，摩擦系数增大，往往干摩擦牢度会有所降低，而且印花后织物的手感变差，尤其是应用于仿活性涂料印花时，印花后的面料手感变硬尤其明显，这样就失去了涂料仿活性的意义。
CN102816294A专利公开了“一种水性封闭异氰酸酯交联剂的制备方法”，其是一种用于织物涂层的水性交联剂，采用异氰酸酯与亲水扩链剂预聚后直接进行封闭，但其结构上来看交联剂分子较小，且支化程度低，交联点较少，应用于涂料印花中会使粘合剂使成膜变硬脆，从而影响干摩擦牢度及印花手感。
CN103865032A专利公开了“高度支化结构的水性封闭型聚异氰酸酯交联剂及其制备方法”，其是通过异氰酸酯与三乙醇胺相互封端形成树枝型的羟基封端骨架，再用异氰酸酯封端，聚乙二醇扩链，最后用咪唑类衍生物对异氰酸酯进行封闭。其支化成都较高，有很好的交联性能，但其作为柔段所用的聚乙二醇分子量较小，成膜后手感仍会变硬，且咪唑类的封端剂在解封后均为固体状态，会残留在布面也会明显影响手感。
发明内容
本发明的目的是提供一种仿活性涂料印花用水性封闭型聚氨酯交联剂及其制备方法，以使仿活性涂料印花具有良好的干湿摩擦牢度及皂洗牢度，且印花后不影响织物手感，可以更好的达到涂料仿活性的印花效果。
本发明仿活性涂料印花用交联剂制备方法：
原料按重量配比：
(1)在氮气保护下，将六亚甲基二异氰酸酯三聚体70-90份、聚乙二醇10-20份、亲水扩链剂2-4份、三羟甲基丙烷1-1.5份、有机溶剂30-40份加入到反应器中，搅拌升温至75-85℃保温反应1.5-2小时；
(2)加入聚乙二醇单甲醚1-3份，于80-85℃保温反应1-1.5h，得到预聚产物；
(3)将预聚产物降温至50-55℃，滴加封端剂甲乙酮肟25-35份，于50-60℃保温反应2-3h；
(4)加入中和剂三乙胺1.5-3份，搅拌20-30分钟后，加去离子水160-230份快速搅拌分散，得交联剂乳液；
外观：微蓝白色乳液
离子性：阴
PH值：7-8
固含量：35±1%。
所述的聚乙二醇：分子量为1000-3000；
所述的亲水扩链剂：为二羟甲基丙酸或二羟甲基丁酸其一；
所述的有机溶剂：为N-甲基吡咯烷酮或N-乙基吡咯烷酮其一；
所述的聚乙二醇单甲醚：分子量为500-1000。
本发明交联剂采用三官能的异氰酸酯三聚体进行水溶性接枝改性，同时引入三官能的三羟甲基丙烷使预聚体形成交联度较高的大分子支化结构的异氰酸酯封端预聚体骨架，以封闭剂对活性异氰酸酯基团进行封闭。由于采用了大分子支化的结构，可大幅提高交联剂的活性基团的含量及交联点。当把交联剂添加至涂料印花胶浆中，与粘合剂树脂在加热解封固化时得到良好的交联性能，使粘合剂成膜效果更好，印花后织物的干湿摩擦牢度及皂洗牢度均得到有效提高。
本发明在合成预聚体时，后加入聚乙二醇单甲醚使其接枝于预聚体大分子的链端上，使预聚体得到端基亲水基团，使其易于自乳化水分散，在减少亲水扩链剂用量的同时，使交联剂乳液的离子性减弱，大大提高了交联剂分子的水溶性及贮存稳定性，而且易于与粘合剂进行复配，复配后浆料可在密封及室温状态下较长时间保存不失效。
本发明在预聚体中引入柔性的长链段的聚乙二醇、聚乙二醇单甲醚，其含有的醚键可以自由旋转，使化合物的柔软性得到提升，即可有效改善交联剂固化时使材料变硬脆的缺点；同时封端剂采用沸点较低的甲乙酮肟，在受热解封时可以完全挥发，不会残存于织物表面影响手感。
本发明交联剂为水性脂肪族聚氨酯，其成膜柔软不黄变，具有良好的耐日晒色牢度及耐候性，受热解封交联时无甲醛释放，推荐与无醛型的粘合剂复配使用，以满足环保的要求。
具体实施方式
实施例1
(1)在氮气保护下，将六亚甲基二异氰酸酯三聚体70份、分子量1000的聚乙二醇10份、二羟甲基丙酸2份、三羟甲基丙烷1份、N-甲基吡咯烷酮30份加入到反应器中，搅拌升温至80℃保温反应2小时；
(2)加入分子量500的聚乙二醇单甲醚1份，于80℃保温反应1.5h，得到预聚产物；
(3)将预聚产物降温至50℃，滴加封端剂甲乙酮肟25份，于50℃保温反应3h；
(4)加入中和剂三乙胺1.5份，反应20分钟后，加去离子水160份快速搅拌分散，得交联剂乳液。
实施例2
(1)在氮气保护下，将六亚甲基二异氰酸酯三聚体70份、分子量2000的聚乙二醇15份、二羟甲基丙酸2份、三羟甲基丙烷1份、N-甲基吡咯烷酮30份加入到反应器中，搅拌升温至80℃保温反应2小时；
(2)加入分子量500的聚乙二醇单甲醚1.5份，于85℃保温反应1h，得到预聚产物；
(3)将预聚产物降温至50℃，滴加封端剂甲乙酮肟28份，于50℃保温反应3h；
(4)加入中和剂三乙胺1.5份，搅拌20分钟后，加去离子水170份快速搅拌分散，得交联剂乳液。
实施例3
(1)在氮气保护下，将六亚甲基二异氰酸酯三聚体80份、分子量2000的聚乙二醇10份、二羟甲基丙酸3份、三羟甲基丙烷1份、N-乙基吡咯烷酮40份加入到反应器中，搅拌升温至80℃保温反应2小时；
(2)加入分子量750的聚乙二醇单甲醚2份，于85℃保温反应1h，得到预聚产物；
(3)将预聚产物降温至50℃，滴加封端剂甲乙酮肟30份，于50℃保温反应3h；
(4)加入中和剂三乙胺2.3份，搅拌20分钟后，加去离子水190份快速搅拌分散，得交联剂乳液。
实施例4
(1)在氮气保护下，将六亚甲基二异氰酸酯三聚体80份、分子量2000的聚乙二醇15份、二羟甲基丙酸3份、三羟甲基丙烷1.5份、N-乙基吡咯烷酮40份加入到反应器中，搅拌升温至85℃保温反应1.5小时；
(2)加入分子量750的聚乙二醇单甲醚2份，于85℃保温反应1.5h，得到预聚产物；
(3)将预聚产物降温至50℃，滴加封端剂甲乙酮肟31份，于50℃保温反应3h；
(4)加入中和剂三乙胺2.3份，搅拌20分钟后，加去离子水200份快速搅拌分散，得交联剂乳液。
实施例5
(1)在氮气保护下，将六亚甲基二异氰酸酯三聚体90份、分子量3000的聚乙二醇20份、二羟甲基丙酸4份、三羟甲基丙烷1.5份、N-乙基吡咯烷酮40份加入到反应器中，搅拌升温至85℃保温反应1.5小时；
(2)加入分子量750的聚乙二醇单甲醚2份，于80℃保温反应1h，得到预聚产物；
(3)将预聚产物降温至55℃，滴加封端剂甲乙酮肟35份，于60℃保温反应2h；
(4)加入中和剂三乙胺3份，搅拌20分钟后，加去离子水230份快速搅拌分散，得交联剂乳液。
实施例6
(1)在氮气保护下，将六亚甲基二异氰酸酯三聚体80份、分子量2000的聚乙二醇15份、二羟甲基丁酸4份、三羟甲基丙烷1份、N-乙基吡咯烷酮40份加入到反应器中，搅拌升温至80℃保温反应2小时；
(2)加入分子量1000的聚乙二醇单甲醚3份，于80℃保温反应1.5h，得到预聚产物；
(3)将预聚产物降温至50℃，滴加封端剂甲乙酮肟30份，于50℃保温反应3h；
(4)加入中和剂三乙胺2.7份，搅拌20分钟后，加去离子水200份快速搅拌分散，得交联剂乳液。
试验检测
分别取本实施例1－6交联剂产品3g，与去离子水68g、增稠剂4g、仿活性涂料粘合剂20g、蓝色浆5g，充分混合均匀制得印花浆。
采用平网刮刀印花，印花布用纯棉斜纹（规格为40x40/133x72）,印花后再经过烘箱150-160℃烘干2分钟，然后进行测试。
对比例：采用市售应用较广的涂料印花用交联剂：FH-10（苏州联盛化学）、CL-FF2（上海雅韵），配浆及印花工艺同上。
测试结构如下表：
耐摩擦色牢度检测：依照GB/T 3920-2008《纺织品 色牢度试验 耐摩擦色牢度》对印花后布样进行测试。
耐皂洗色牢度检测：依照GB/T 3921-2008《纺织品 色牢度试验 耐皂洗色牢度》对印花后布样进行测试。
柔软性效果评定：以6人对手感的综合评价结果为准，++++为最好，+为最差。
由上表数测试数据可以看出，本发明交联剂产品干、湿摩擦色牢度效果好，在印花浆里添加3%即可提高干、湿摩擦牢度半级至一级，好于市售产品；耐皂洗牢度好，普遍能够提高皂洗牢度一级左右，明显优于市售交联剂产品FH-10、CL-FF2；柔软性好，印花后布样与未加入交联剂的空白对照印花布样手感基本一致，明显好于市售交联剂FH-10、CL-FF2。
Claims (2)
1.仿活性涂料印花用交联剂制备方法，其特征是：
原料按重量配比：
(1)在氮气保护下，将六亚甲基二异氰酸酯三聚体70-90份、聚乙二醇10-20份、亲水扩链剂2-4份、三羟甲基丙烷1-1.5份、有机溶剂30-40份加入到反应器中，搅拌升温至75-85℃保温反应1.5-2小时；
(2)加入聚乙二醇单甲醚1-3份，于80-85℃保温反应1-1.5h，得到预聚产物；
(3)将预聚产物降温至50-55℃，滴加封端剂甲乙酮肟25-35份，于50-60℃保温反应2-3h；
(4)加入中和剂三乙胺1.5-3份，搅拌20-30分钟后，加去离子水160-230份快速搅拌分散，得交联剂乳液；
外观：微蓝白色乳液
离子性：阴
PH值：7-8
固含量：35±1%；
所述的聚乙二醇：分子量为1000-3000；
所述的亲水扩链剂：为二羟甲基丙酸或二羟甲基丁酸其一；
所述的有机溶剂：为N-甲基吡咯烷酮或N-乙基吡咯烷酮其一；
所述的聚乙二醇单甲醚：分子量为500-1000。
2.如权利要求1制备方法得到的仿活性涂料印花用交联剂。
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| CN105968304A (zh) * | 2016-05-11 | 2016-09-28 | 华南理工大学 | 一种高性能水性聚氨酯固化剂及其制备方法与应用 |
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| CN105968304A (zh) * | 2016-05-11 | 2016-09-28 | 华南理工大学 | 一种高性能水性聚氨酯固化剂及其制备方法与应用 |
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