改性多糖类活性染料印花糊料的制备与应用研究
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摘要
活性染料问世以来，一直采用海藻酸钠作为其主要的印花糊料。随着印花技术的发展，海藻酸钠糊在圆、平网印花中暴露出了种种缺陷，且海藻酸钠的价格日趋攀升，因此人们竞相开始了对其替代品的研究。目前，改性多糖类糊料是主流的研究方向，包括羧甲基淀粉(CMS)、羧甲基纤维素(CMC)以及羧甲基瓜尔胶(CMG)，但三种改性糊料性能之间的差异却不为人知。
为了比较CMS、CMC及CMG这三种改性糊料的实际应用性能，分别先对这三种高取代度的改性糊料进行了制备，采用正交实验对反应条件进行了优化，探讨了各因素对产物取代度的影响，得到了最佳的制备工艺，并采用红外光谱(FTIR)和X射线衍射光谱(XRD)对反应前后的产物结构进行了分析。
对制备高取代度CMC的方法进行了改进，采用了浓碱预处理法，结果得到了取代度更高的产物。为究其原因，采用扫描电镜(SEM)及X射线衍射光谱(XRD)对浓碱处理前后纤维素表观形貌和微结构的变化进行了深入的分析，分析结果表明：纤维素经浓碱处理后发生溶胀，晶型发生了改变，部分纤维素Ⅰ转变成了纤维素Ⅱ，同时结晶度降低，大分子间的氢键被拆散，致使过多的反应基团暴露，提高了反应活性，从而得到了较高的取代度；随着碱液浓度的提高，处理后纤维素的结晶度越来越低，当浓度达到500～600g/L时，结晶度下降不是很明显，处理后纤维素的反应活性达到最大值，因而取代度不再上升。
对制备的CMC、CMG以及CMS系列糊料的应用性能进行了测试，包括原糊的基本性能以及印制性能，并与海藻酸钠糊进行了对比。结果表明：CMC、CMG以及CMS系列的原糊都属于假塑性流体，印花粘度指数(PVI值)较低，比海藻酸钠更适于圆、平网印花；CMC与CMG的成糊率相近，粘度较高，印制轮廓清晰度较好，相比之下CMS系列糊料的成糊率较低，属高含固量的印花糊料，但其在抱水性，脱糊率，印制表观得色量以及渗透性方面有不错的表现；以马铃薯淀粉、红薯淀粉、小麦淀粉及玉米淀粉为原料制备的四种CMS糊料中，CMS-马铃薯的各项性能最好。
对比三种糊料的应用性能发现，CMC、CMG两种糊料性能相近，CMS系列糊料与两者存在差异，为了将各糊料单一的优良特性复合在一起，选取了性能较好的CMC与CMS-马铃薯两种糊料进行拼混，对其应用性能进行了测试。结果表明：混合糊料中CMC所占的比例越大时，混合糊的粘度越大，印制的花纹精细度也越高，适合印制较为精细的花纹图案；CMS-马铃薯的比例越大时，混合糊的抱水性越好，对水具有较强的亲和能力，印制渗透性也越好，色浆易均匀的渗透到织物组织内部，获得较为均匀的印制效果，因而适合印制大块、满地的花纹图案。
Sodium alginate has been used as the main printing paste since reactive dyes appeared.With the development of the printing tecnology, a variety of weakness comes out when sodiumalginate use as the round and flat nets printing paste, and the price of sodium alginate never stopincreasing. So people scrambling to start the research of its alternatives. At present, themainstream of research direction is modified polysaccharides paste, including CMC, CMG andCMS, but the difference between the performance of them are unknown.
In order to compare the application performance of CMC, CMG and CMS, the three highsubstitution degree of modified paste were prepared, the reaction conditions were optimizedthrough the orthogonal experiment, the factor’s influence to the product were discussed, and thebest preparation process were obtained. In addition, the structure of the product was analyzed byFTIR and XRD.
According to the character that cellulose goes swelling when contract strong alkali, cottonfiber will be treated after a strong alkali treatment before the experiment start, so that the productwith higher degree was obtained. In order to find the reason, the cotton cellulose which treatedwith and without strong alkali were analyzed by SEM and XRD, the results showed that:cellulose goes swelling after the strong alkali treatment, the cryatal changed, part of celluloseⅠturned into cellulose Ⅱ, meanwhile its crystallinity turned lower, the hydrogen bondingbetween molecules were separated, too much reactive groups exposed, the reaction activity wereinproved, so that the higher substitution degree were obtained. At the same time, the higherconcentration of the alkali, the lower crystallinity of the cellulose. When the concentrationreached500～600g/L, the dropment of crystallinity turned unconspicuous, the reaction activityof the cellulose reached its maximum, thus the substitution degree rise no longer.
The application performance of CMC, CMG and CMS were tested, including basicproperties and printing properties, and compared with sodium alginate. The results showed that:CMC, CMG and CMS all belong to fake plastic fluid which has low PVI value, so that they aremore suitble for the round、flat nets printing than sodium alginate. The viscosity of CMC and CMG are close, with fine outline of pattern. The viscosity of CMS is lower, but its morehydrophilic, easy removing, high color quantity and good penetrability. The CMS which made ofpotato starch has the best performance in CMS series.
The contrast of three paste showed that: CMC and CMG have the similar performance,CMS series paste are different to the two. For purpose of composite the single excellent featuresof each paste, CMC and CMS-potato which both have fine performance but different to eachother were chosen to mixed, and the application performance were tested. The results showedthat: if mixed paste contains more CMC, the viscosity will be large, the outline of pattern will bemore clear, so it is suitble for the fine pattern printing. If the proportion of CMS-patato is larger,the mixed paste will be more hydrophilic, with good penetrability, so that it is more suitble forthe large pattern printing.
为了比较CMS、CMC及CMG这三种改性糊料的实际应用性能，分别先对这三种高取代度的改性糊料进行了制备，采用正交实验对反应条件进行了优化，探讨了各因素对产物取代度的影响，得到了最佳的制备工艺，并采用红外光谱(FTIR)和X射线衍射光谱(XRD)对反应前后的产物结构进行了分析。
对制备高取代度CMC的方法进行了改进，采用了浓碱预处理法，结果得到了取代度更高的产物。为究其原因，采用扫描电镜(SEM)及X射线衍射光谱(XRD)对浓碱处理前后纤维素表观形貌和微结构的变化进行了深入的分析，分析结果表明：纤维素经浓碱处理后发生溶胀，晶型发生了改变，部分纤维素Ⅰ转变成了纤维素Ⅱ，同时结晶度降低，大分子间的氢键被拆散，致使过多的反应基团暴露，提高了反应活性，从而得到了较高的取代度；随着碱液浓度的提高，处理后纤维素的结晶度越来越低，当浓度达到500～600g/L时，结晶度下降不是很明显，处理后纤维素的反应活性达到最大值，因而取代度不再上升。
对制备的CMC、CMG以及CMS系列糊料的应用性能进行了测试，包括原糊的基本性能以及印制性能，并与海藻酸钠糊进行了对比。结果表明：CMC、CMG以及CMS系列的原糊都属于假塑性流体，印花粘度指数(PVI值)较低，比海藻酸钠更适于圆、平网印花；CMC与CMG的成糊率相近，粘度较高，印制轮廓清晰度较好，相比之下CMS系列糊料的成糊率较低，属高含固量的印花糊料，但其在抱水性，脱糊率，印制表观得色量以及渗透性方面有不错的表现；以马铃薯淀粉、红薯淀粉、小麦淀粉及玉米淀粉为原料制备的四种CMS糊料中，CMS-马铃薯的各项性能最好。
对比三种糊料的应用性能发现，CMC、CMG两种糊料性能相近，CMS系列糊料与两者存在差异，为了将各糊料单一的优良特性复合在一起，选取了性能较好的CMC与CMS-马铃薯两种糊料进行拼混，对其应用性能进行了测试。结果表明：混合糊料中CMC所占的比例越大时，混合糊的粘度越大，印制的花纹精细度也越高，适合印制较为精细的花纹图案；CMS-马铃薯的比例越大时，混合糊的抱水性越好，对水具有较强的亲和能力，印制渗透性也越好，色浆易均匀的渗透到织物组织内部，获得较为均匀的印制效果，因而适合印制大块、满地的花纹图案。
Sodium alginate has been used as the main printing paste since reactive dyes appeared.With the development of the printing tecnology, a variety of weakness comes out when sodiumalginate use as the round and flat nets printing paste, and the price of sodium alginate never stopincreasing. So people scrambling to start the research of its alternatives. At present, themainstream of research direction is modified polysaccharides paste, including CMC, CMG andCMS, but the difference between the performance of them are unknown.
In order to compare the application performance of CMC, CMG and CMS, the three highsubstitution degree of modified paste were prepared, the reaction conditions were optimizedthrough the orthogonal experiment, the factor’s influence to the product were discussed, and thebest preparation process were obtained. In addition, the structure of the product was analyzed byFTIR and XRD.
According to the character that cellulose goes swelling when contract strong alkali, cottonfiber will be treated after a strong alkali treatment before the experiment start, so that the productwith higher degree was obtained. In order to find the reason, the cotton cellulose which treatedwith and without strong alkali were analyzed by SEM and XRD, the results showed that:cellulose goes swelling after the strong alkali treatment, the cryatal changed, part of celluloseⅠturned into cellulose Ⅱ, meanwhile its crystallinity turned lower, the hydrogen bondingbetween molecules were separated, too much reactive groups exposed, the reaction activity wereinproved, so that the higher substitution degree were obtained. At the same time, the higherconcentration of the alkali, the lower crystallinity of the cellulose. When the concentrationreached500～600g/L, the dropment of crystallinity turned unconspicuous, the reaction activityof the cellulose reached its maximum, thus the substitution degree rise no longer.
The application performance of CMC, CMG and CMS were tested, including basicproperties and printing properties, and compared with sodium alginate. The results showed that:CMC, CMG and CMS all belong to fake plastic fluid which has low PVI value, so that they aremore suitble for the round、flat nets printing than sodium alginate. The viscosity of CMC and CMG are close, with fine outline of pattern. The viscosity of CMS is lower, but its morehydrophilic, easy removing, high color quantity and good penetrability. The CMS which made ofpotato starch has the best performance in CMS series.
The contrast of three paste showed that: CMC and CMG have the similar performance,CMS series paste are different to the two. For purpose of composite the single excellent featuresof each paste, CMC and CMS-potato which both have fine performance but different to eachother were chosen to mixed, and the application performance were tested. The results showedthat: if mixed paste contains more CMC, the viscosity will be large, the outline of pattern will bemore clear, so it is suitble for the fine pattern printing. If the proportion of CMS-patato is larger,the mixed paste will be more hydrophilic, with good penetrability, so that it is more suitble forthe large pattern printing.
引文
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[2]胡平藩.印花糊料[M].北京:纺织工业出版社,1988:5-13.
[3]唐增荣.活性染料印花糊料概述[J].印染助剂,2000,17(2):1-6.
[4]赵军子,翁志学.活性染料印花糊料研究进展[J].精细石油化工,2002,(1):53-56.
[5]王春兰,柳启煌,施美琴,等.海藻酸酯的合成和性能研究[J].印染,1993,19(11):5-9.
[6]叶建中.海藻酸酯FZ-MA在圆网拉元印花中的应用[J].染整技术,1994,16(1):50-52.
[7]唐增荣.新型活性染料印花用原糊的探讨[J].印染,1998,24(9):8-13.
[8]胡平藩.印花糊料[M].北京:纺织工业出版社,1988:106-115.
[9]黄正伟,丁长银.高取代度高均匀性羧甲基纤维素钠的合成及表征[J].纤维素醚工业.2002,10(2):18-23.
[10]邵自强.纤维素醚[M].北京:化学工业出版社,2007:157-158
[11]黄艳,朱平等.活性染料用印花糊料现状[J].印染助剂,2008,25（5）:5-8.
[12] Ragheb A A, EI-Sayiad H S, Hebeish A. Preparation and characterization of carboxymexyl starch (CMS)products and their utilization in textile Printing[J]. Starch/Ataerke,1997,49(6):238-245.
[13]康跃惠,郝军,侯彦平等.活性染料印花用增稠剂RPT的研制、性能和应用[J].印染助剂,2000,17(6):4-9.
[14]贾开成,乔剑锋.高取代高粘度羧甲基纤维素钠的制备[J].纤维素醚工业,2003,11(4):24-26.
[15]胡兵,龙化云,黄光斗等.用漂白纸浆制备高取代度羧甲基纤维素[J].湖北造纸,2003,3:20-22.
[16]谭义秋,黄祖强,农克良.高取代度木薯羧甲基淀粉的合成及表征[J].过程工程学报,2010,10(1):173-178.
[17]张晓东,刘馨.高取代度羧甲基淀粉的合成与性能研究[J].纺织学报,2003,24(6):552-554.
[18] Rekaby M M, EI-Thalouth I A, Rahman A A H. Technological evaluation of carboxymethyl sesbaniagalactomannan gum derivatives as thickeners in reactive[J]. Bioresources,2010,5(3):1517-1529.
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