CN109680522B - 一种纺织品用有机硅改性涂料印花浆及制备方法 - Google Patents

一种纺织品用有机硅改性涂料印花浆及制备方法 Download PDF

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CN109680522B
CN109680522B CN201910026986.2A CN201910026986A CN109680522B CN 109680522 B CN109680522 B CN 109680522B CN 201910026986 A CN201910026986 A CN 201910026986A CN 109680522 B CN109680522 B CN 109680522B
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董明东
张艺赢
孟庆尧
冷璐
李萃
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Eastern Liaoning University
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Abstract

本发明一种纺织品用有机硅改性涂料印花浆及制备方法,由离子水60~90份、阴离子乳化剂2~4份、非离子反应型乳化剂1~2份、八甲基环四硅氧烷25~35份、N‑(β‑氨乙基‑γ‑氨丙基)甲基二甲氧基硅烷2~5份,制得有机硅预乳液;加入去离子水90~110份、丙烯酸丁酯60~80份、苯乙烯5~10份、甲基丙烯酸5~10份、乙基丙烯酸10~20份、衣康酸1~3份、丙烯酸0.5~1份、甲基丙烯酸乙酰乙酸乙二醇双酯2~5份,制得丙烯酸酯预乳液;再经种子乳液制备、乳液聚合、增稠制得。

Description

一种纺织品用有机硅改性涂料印花浆及制备方法
技术领域
本发明涉及的是纺织品用涂料印花浆,是一种环保的有机硅改性涂料印花浆及制备方法,可以替代染料印花使用。
技术背景
涂料印花是借助于印花浆将不具亲合性和反应性的颜料粘着在纤维表面而形成图案。其工艺简单、无废水排放,色谱齐全、色彩鲜艳,花纹轮廓清晰、日晒牢度好,其工艺适用于各种纤维及混纺织物。
近年来,涂料印花不仅用于直接印花,还被用于特种印花工艺,如罩印,金银粉印花,起绒印花等,深受国内外客户的青睐。
涂料印花产品的质量跟印花浆的性能有直接的关系,印花织物的手感,色彩鲜艳度,色牢度主要决定于印花浆的质量,因此,制备高性能印花浆是提高涂料印花质量的关键所在。
国内市场上普遍使用的同类产品仍然是停留在以N-羟甲基丙烯酰胺(NMA)和改性蜜胺树脂为交联剂的印花浆,虽然其有粘结性、耐候性、保色性和力学性能均佳及成本低等优点。但是在成膜和使用过程中能够持续释放甲醛,环保问题还没有得到圆满解决, 在涤纶、锦纶及其混纺织物上印花的色牢度低,尤其是水洗和溶剂浸后颜色由于印花浆的成膜性能低而很容易脱落,说明皮膜的耐水性和耐溶剂性差,而且硬度大,低温变脆,高温发粘,说明此类丙烯酸酯类印花浆存在着柔韧性、耐磨性差及“热粘冷脆”及色牢度差等缺点。
CN1851112A公开了一种制备涂料印花粘合剂的方法,所述的粘合剂由N-环氧丙基丙稀酰胺交联单体、丙烯酸丁酯、丙烯酸异辛酯、丙烯酸乙酯、甲基丙烯酸甲酯、苯乙烯、醋酸乙烯、丙烯酸、甲基丙烯酸、反应性表面活性剂、不饱和强亲水性单体、含乙烯基的有机硅单体等组成。粘合剂的粒径可达纳米级,并且不含甲醛。但是其干湿磨牢度只能达到2-3,达不到深色印花对干湿磨牢度3-4级的要求。
CN101748617A公开了一种防粘柔软涂料印花粘合剂以及制备方法,通过调整单体的使用种类及合成方法,引进合适的交联单体调整丙烯酸酯热粘手和手感差的问题。虽然也安全环保,干湿磨牢度也能达到3-4级,但是却只适用于色浆用量在2.5-3%的浅色染料印花中。
CN1544566 A 公开了一种无甲醛涂料印花用粘合剂的制备方法,通过使用无醛单体,无醛交联剂,使用更合理的合成方法,使产品无甲醛释放,产品的干湿磨牢度也得到了提升,但使用了0.8-1.2%的含有APEO的乳化剂,不能做到安全环保。
发明内容
本发明的目的是提供一种环保的有机硅改性涂料印花浆及制备方法,其印花的织物手感和色牢度,鲜艳度,渗透性,颜色饱和度等性能指标可以直接同各种染料印花媲美,尤其是在涤纶、锦纶及其混纺织物印花色牢度能达到各种染料印花的要求,无甲醛和其他有害物质,符合OkO-STANDARD100和Reanch 等欧盟标准。
本发明纺织品用有机硅改性涂料印花浆制备方法
(1)有机硅预乳液配制:在反应釜A内加入去离子水60~90份、阴离子乳化剂 2~4份、非离子反应型乳化剂1~2份、在35~45℃快速搅拌至乳化剂分散均匀,然后加入八甲基环四硅氧烷25~35份和N-(β-氨乙基-γ-氨丙基)甲基二甲氧基硅烷2~5份,升温至70~80℃,预聚2.5-3h,得有机硅预乳液;
(2)丙烯酸酯预乳液配制:将步骤(1)得到的有机硅预乳液降温至30-~40℃,加入去离子水90~110份、丙烯酸丁酯60~80份、苯乙烯5~10份、甲基丙烯酸5~10份、乙基丙烯酸10~20份、衣康酸1~3份、丙烯酸0.5~1份、甲基丙烯酸乙酰乙酸乙二醇双酯2~5份,高速搅拌得丙烯酸酯预乳液;
(3)种子乳液制备:在反应釜B中加入去离子水50~70份、步骤(2)得到的丙烯酸酯预乳液30~50份、过硫酸铵0.01~0.02份,升温至75~80℃,保温反应至体系呈现蓝光;
(4)乳液聚合:反应釜B升温至80~85℃,同时向反应釜B内滴加步骤(2)剩余的丙烯酸酯预乳液和过硫酸铵0.2~0.5份与去离子水60~80份配制而成的硫酸铵水溶液,2-4小时滴加完毕,升温至85~90℃,保温2~3小时,降温至室温,加入聚丙烯酸酯型增稠剂5~10份,增稠至粘度15000~20000cps,得产品。
本发明采用了反应型乳化剂,对于其他预乳液合成使用传统乳化剂附着于聚合物表面的方式,反应性乳化剂直接参与反应,不会在聚合物中残留,当乳液受到高离心力、剪切力影响时也不会破乳,从而增强了乳液的稳定性。提高了成膜率,成膜过程中,键接有反应性乳化剂的乳胶颗粒更容易靠近。有更好的光学性能和防渗化性能。
在合成中采用甲基丙烯酸乙酰乙酸乙二醇双酯(AAEM)作交联剂,解决了使用过程中的甲醛持续释放难题。AAEM含有一个端基双键和一个端基乙酰乙酰基团,位于端基的双键,使得AAEM 极容易发生自由基聚合反应。另一端的乙酰乙酰基团由于双羰基的共轭效应,导致中间的亚甲基上的 -H 极为活泼,易于发生多种基团反应。 反应过程中释放的甲醛在1ppm以下,很好的解决了NMA作为交联单体甲醛持续释放的问题,安全环保,另外本发明选用的非离子反应型乳化剂含有双官能度基团,可以和AAEM形成网状结构,增加胶浆本身成膜后的柔韧性能。
本发明采用八甲基环四硅氧烷(D4)与N-(β-氨乙基-γ-氨丙基)甲基二甲氧基硅烷(A-2120)开环聚合,形成有活性自由基的氨基硅乳化物,再与丙烯酸类单体聚合,形成目标聚合物,产品有合成稳定,凝胶率低,无毒无污染,且成本较低等优点,通过此方法在聚合物中引进了一定数量Si-O-Si键,Si-O-Si键键长较长,健角较大,易旋转,有良好柔顺性。且Si-O-Si键有良好耐水性能,所以Si-O-Si键的引入,可以显著提高印花浆成膜后的耐水性,耐候性,耐沾污性,柔软性,色牢度和弹性等应用性能。同时AAEM的端基双键也能在硅烷开环聚合的过程中,参与聚合,增加大份子链长,也可以增加分子接枝过程中枝杈上的自由活性基团,促进硅烷分子与丙烯酸分子之间的聚合,提高聚合率,降低凝胶率,从而提高生产效率。
具体实施方式
实施例1
(1)有机硅预乳液配制:在反应釜A内加入去离子水75份、阴离子乳化剂4份、非离子反应型乳化剂2份、在40℃快速搅拌30min;待乳化剂分散均匀后投入25份八甲基环四硅氧烷和5份N-(β-氨乙基-γ-氨丙基)甲基二甲氧基硅烷,升温至75℃预聚2.5h,得有机硅预乳液;
(2) 丙烯酸酯预乳液配制:反应釜A内降温至40℃,加入去离子水90份、丙烯酸丁酯70份、苯乙烯5份、甲基丙烯酸5份、乙基丙烯酸15份、衣康酸2份、丙烯酸0.5份、甲基丙烯酸乙酰乙酸乙二醇双酯2份,高速搅拌0.5小时,得丙烯酸酯预乳液;
(3)种子乳液制备:在反应釜B中加入去离子水60份、步骤(2)得到的丙烯酸酯预乳液45份、过硫酸铵0.01份,升温至75℃,保温反应至体系呈现蓝光;
(4)乳液聚合:反应釜B升温至85℃,同时向反应釜B内滴加步骤(2)剩余的丙烯酸酯预乳液和过硫酸铵0.5份与去离子水60份配制而成的硫酸铵水溶液,3小时滴加完毕,滴加完毕升温至85℃保温3小时,降温至室温,加入8份增稠剂增稠,得产品。
实施例2
(1)有机硅预乳液配制:在反应釜A内加入去离子水80份、阴离子乳化剂3份、非离子反应型乳化剂1.5份、在40℃快速搅拌30min;待乳化剂分散均匀后投入30份八甲基环四硅氧烷和4份N-(β-氨乙基-γ-氨丙基)甲基二甲氧基硅烷,升温至75℃预聚2.5h,得有机硅预乳液;
(2) 丙烯酸酯预乳液配制:反应釜A内降温至40℃,加入去离子水85份、丙烯酸丁酯65份、苯乙烯8份、甲基丙烯酸4份、乙基丙烯酸20份、衣康酸3份、丙烯酸0.5份、甲基丙烯酸乙酰乙酸乙二醇双酯2份,高速搅拌0.5小时,得丙烯酸酯预乳液;
(3)种子乳液制备:在反应釜B中加入去离子水60份、步骤(2)得到的丙烯酸酯预乳液50份、过硫酸铵0.01份,升温至75℃,保温反应至体系呈现蓝光;
(4)乳液聚合:反应釜B升温至87℃,同时向反应釜B内滴加步骤(2)剩余的丙烯酸酯预乳液和过硫酸铵0.4份与去离子水50份配制而成的硫酸铵水溶液,2.5小时滴加完毕,滴加完毕升温至85℃保温3小时,降温至室温,加入10份增稠剂增稠,得产品。
实施例3
(1)有机硅预乳液配制:在反应釜A内加入去离子水85份、阴离子乳化剂4份、非离子反应型乳化剂2份、在40℃快速搅拌30min;待乳化剂分散均匀后投入25份八甲基环四硅氧烷和5份N-(β-氨乙基-γ-氨丙基)甲基二甲氧基硅烷,升温至75℃预聚2.5h,得有机硅预乳液;
(2) 丙烯酸酯预乳液配制:反应釜A内降温至40℃,加入去离子水90份、丙烯酸丁酯75份、苯乙烯10份、甲基丙烯酸5份、乙基丙烯酸15份、衣康酸5份、丙烯酸0.8份、甲基丙烯酸乙酰乙酸乙二醇双酯2份,高速搅拌0.5小时,得丙烯酸酯预乳液;
(3)种子乳液制备:在反应釜B中加入去离子水70份、步骤(2)得到的丙烯酸酯预乳液50份、过硫酸铵0.01份,升温至75℃,保温反应至体系呈现蓝光;
(4)乳液聚合:反应釜B升温至85℃,同时向反应釜B内滴加步骤(2)剩余的丙烯酸酯预乳液和过硫酸铵0.4份与去离子水70份配制而成的硫酸铵水溶液,3小时滴加完毕,滴加完毕升温至85℃保温3小时,降温至室温,加入8份增稠剂增稠,得产品。
实施例4
(1)有机硅预乳液配制:在反应釜A内加入去离子水75份、阴离子乳化剂4份、非离子反应型乳化剂2份、在45℃快速搅拌30min;待乳化剂分散均匀后投入35份八甲基环四硅氧烷和5份N-(β-氨乙基-γ-氨丙基)甲基二甲氧基硅烷,升温至75℃预聚2.5h,得有机硅预乳液;
(2) 丙烯酸酯预乳液配制:反应釜A内降温至40℃,加入去离子水80份、丙烯酸丁酯60份、苯乙烯5份、甲基丙烯酸5份、乙基丙烯酸10份、衣康酸2份、丙烯酸0.5份、甲基丙烯酸乙酰乙酸乙二醇双酯2份,高速搅拌0.5小时,得丙烯酸酯预乳液;
(3)种子乳液制备:在反应釜B中加入去离子水60份、步骤(2)得到的预乳液50份、过硫酸铵0.01份,升温至75℃,保温反应至体系呈现蓝光;
(4)乳液聚合:反应釜B升温至85℃,同时向反应釜B内滴加步骤(2)剩余的丙烯酸酯预乳液和过硫酸铵0.3份与去离子水60份配制而成的硫酸铵水溶液,3小时滴加完毕,滴加完毕升温至85℃保温3小时,降温至室温,加入8份增稠剂增稠,得产品。
上述实施例:
原料按重量配比;
阴离子乳化剂:上海忠诚精细化工有限公司产品M-30S;
非离子反应型乳化剂:上海忠诚精细化工有限公司产品 EFS-1080T;
八甲基环四硅氧烷:日本信越化学工业株式会社产品D4;
N-(β-氨乙基-γ-氨丙基)甲基二甲氧基硅烷:美国联碳公司产品A-2120;
增稠剂:辽宁恒星精细化工有限公司生产品FS-2000。
实验检测
面料:涤纶锦纶混纺针织布,200g/㎡;
印花浆配制:分别用实施例1~4涂料印花浆100g与色浆(GA111大红)3g充分搅拌均匀;
印花过程:
手工台板印花(一次一刀),烘干(100℃,2min)、培烘(150℃,3min)。
Figure 686230DEST_PATH_IMAGE001
对比例
面料:涤纶锦纶混纺针织布,200g/㎡;
涂料印花浆:
1、国内印花浆GZ-101;
2、日本产品印花浆NR-101HN;
3、土耳其的印花浆COBPRINT BPE;
印花浆配制:用上述涂料印花浆100g与色浆(GA111大红)3g充分搅拌均匀。充分搅拌均匀;
印制过程:
手工台板印花(一次一刀),烘干(100℃,2min),培烘(150℃,3min)。
Figure 541053DEST_PATH_IMAGE002
耐干、湿摩擦牢度:按GB/T 3920-1997检测。
柔软度:按GB/T 18318-2001《纺织品弯曲性能测定 第一部分:斜面法》检测。
皮膜耐水性:按GB/T 1733-1993《漆膜耐水性测定法》检测;
耐沾污性:将涤棉织物浸轧合成树脂,(一浸一轧),100℃烘干,150℃培烘,3min,与未浸轧树脂的涤棉织物同时浸入0.02g/L 分散染料染浴中,于80℃处理5min,水洗、100℃烘干,测试K/S值,并计算表观沾色比值,比值越小,耐沾污性越好。表观沾色比值=(K/S)A/(K/S)B.其中(K/S)A是浸轧树脂织物的K/S 值;(K/S)B是未浸轧树脂织物的K/S值。
抗高温泛黄性:在净洗的纯面漂布上印制500Gg/L的树脂,100℃烘干后,180℃培烘2min,冷却后测试其泛黄指数Y=[100(1.30X -1.15Z)]/Y,式中X,Y,Z 为样品在D65/10光源条件下的三刺激值。Y1值越大,说明样品越黄。
涂膜吸水率:从膜片上剪取30mm*30mm的试样。称其质量为M1.室温下浸泡在去离子水中,24h后取出胶膜,用试纸迅速摖干表面水分,称其质量为M2.按下式计算膜的吸水率:吸水率=【(M2-M1)/M1】*100%。
力学性能测试:按GB/T1040-1992,测量成膜物的断裂伸长率,拉伸速率为100mm/min。
从实验结果看,本发明产品在各个性能上都要好于国内外正在使用的产品,是一种安全环保有相当市场前景的涂料印花糊料。

Claims (2)

1.纺织品用有机硅改性涂料印花浆制备方法,其特征是:
原料按重量配比:
(1)有机硅预乳液配制:在反应釜A内加入去离子水60~90份、阴离子乳化剂 2~4份、非离子反应型乳化剂1~2份、在35~45℃快速搅拌至乳化剂分散均匀,然后加入八甲基环四硅氧烷25~35份和N-(β-氨乙基-γ-氨丙基)甲基二甲氧基硅烷2~5份,升温至70~80℃,预聚2.5-3h,得有机硅预乳液;
(2)丙烯酸酯预乳液配制:将步骤(1)得到的有机硅预乳液降温至30~40℃,加入去离子水90~110份、丙烯酸丁酯60~80份、苯乙烯5~10份、甲基丙烯酸5~10份、乙基丙烯酸10~20份、衣康酸1~3份、丙烯酸0.5~1份、甲基丙烯酸乙酰乙酸乙二醇双酯2~5份,高速搅拌得丙烯酸酯预乳液;
(3)种子乳液制备:在反应釜B中加入去离子水50~70份、步骤(2)得到的丙烯酸酯预乳液30~50份、过硫酸铵0.01~0.02份,升温至75~80℃,保温反应至体系呈现蓝光;
(4)乳液聚合:反应釜B升温至80~85℃,同时向反应釜B内滴加步骤(2)剩余的丙烯酸酯预乳液和过硫酸铵0.2~0.5份与去离子水60~80份配制而成的硫酸铵水溶液,2-4小时滴加完毕,升温至85~90℃,保温2~3小时,降温至室温,加入聚丙烯酸酯型增稠剂5~10份,增稠至粘度15000~20000cps,得产品。
2.如权利要求1所述制备方法得到的纺织品用有机硅改性涂料印花浆。
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