基于混合多糖增稠剂的天然纤维织物活性干法转移印花
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摘要
活性干法转移印花，即通过热压将转印纸与未上浆的干态织物紧密贴合后，再经由汽蒸完成活性染料的溶解渗透及固色该原理不同于分散染料的升华转移，因而无需改性天然纤维以增加其对分散染料的可染性；也不同于湿法溶解转移染料的原理，因而可避免对织物的上浆湿处理用含有热熔粘合剂高取代羟丙基纤维素νH-HPCξ的糊料对纸张进行涂层改性以制备具有粘合力的干法转移印花纸考虑H-HPC的热凝胶性会引起涂层干燥时糊料粘度的降低，因此将另一种不具明显热凝胶性的多糖增稠剂，即海藻酸钠νSAξ羧甲基纤维素钠νCMCξ羟乙基纤维素νHECξ瓜尔胶νSG-9ξ和羧甲基淀粉νSG-24ξ与H-HPC共混为实现染料的溶解渗透及固色还需在糊料中加入适量的吸湿剂和固色碱剂
在第二章的研究中，首先对H-HPC的热熔性六种多糖增稠剂的热稳定性和溶胀性进行了测试，并着重探讨了五种混合多糖增稠剂，即H-HPC/SA H-HPC/CMC H-HPC/HEC H-HPC/SG-9和H-HPC/SG-24对糊料流变性，转印纸涂层量和印花织物色深的影响研究表明：H-HPC的热熔点约为120℃五种基于H-HPC的糊料均体现出适合纸张涂层的假塑性流体特征，另一种多糖增稠剂决定了糊料的粘弹性具有较高弹性比例的糊料会导致涂层量的降低当糊料的粘性高于弹性时，其表观粘度越高，涂层量越大印花织物的正面色深取决于H-HPC的涂层量及另一种多糖增稠剂的化学性质H-HPC/SA的印花织物得色最深但轮廓清晰度欠佳综合评价表观色深花型清晰度色牢度手感以及织物可剥离度这五个关键的印花性能指标，可得H-HPC/CMC的干法转移印花效果与可应用性能最佳
第三章针对综合印花性能最佳的H-HPC/CMC展开流变学和形貌学研究稳态剪切实验表明，随着固含量的增加，H-HPC和CMC的假塑性特征越明显CMC的结构粘度更高，并在较低的剪切速率下即体现出变稀的行为用power-law模型可对H-HPC和CMC的稳态剪切曲线进行较好的拟合触变性测试表明H-HPC的触变性较CMC小动态频率扫描结果表明，随着角频率或固含量的增加，两种增稠剂均表现出弹性增强且粘性减弱的特征CMC的粘弹性较H-HPC的稳定对比不同条件下H-HPC/CMC流变性的变化，可知其在弱酸性中性弱碱性及不同尿素含量的环境中均具有较好的相容性采用光学和原子力显微镜观测了不同温度和不同成膜方法下制备的H-HPC CMC及糊料膜的微观形貌，可知H-HPC在80℃以上干燥的糊料膜中分布得更为均匀
第四五两章分别对基于H-HPC/CMC的真丝及棉织物活性转移印花进行研究先从制备转印纸和优化工艺的角度探究影响织物表观色深染料渗透率和固色率的关键因素，并分析了两种织物的印花性能的差异，最后从印花废液和织物颜色及服用性能两方面对干法转移印花与传统筛网印花进行对比真丝印花性能的研究表明：H-HPC提供的贴合力固色碱剂的种类糊料与织物间的吸湿度对真丝的表观色深具有关键影响将三氯乙酸作为固色碱剂及尿素的加入均可显著提高色深值染料渗透率与转印纸上涂层量及尿素和双氰胺的含量有关用含有3%H-HPC0.7%CMC3%三氯乙酸5%尿素3%双氰胺0.5%SiO2的糊料制备转印纸时，获得的印花真丝具有较高的色深3级以上的色牢度轮廓清晰的花型和良好的手感棉与真丝印花性能的最大区别在于：棉织物在碱性较强的碳酸钠/三氯乙酸缓冲固色体系中可获得较高的固色率和色深值两种织物优化的转移印花工艺为：贴合压力1-3Mpa，贴合温度115-125℃，汽蒸温度102-112℃，汽蒸时间10-20min两种印花方法的对比表明：两种织物转移印花废液的COD均较筛网印花废液的COD低，但其中的染料量较高印花废液的COD主要由增稠剂所引起对两种织物而言，筛网印花织物的匀染性染料渗透率和色牢度较高，但是转移印花织物的手感更为柔软两种印花方法均会降低两种织物的白度和强力，但对它们透湿性的影响不大
The transfer mechanism of the reactive dry-transfer printing can be stated that reactivedyes are dissolved, permeated and fixed via a steaming after giving a tight adhesionbetween transfer printing paper and unsized dry fabrics via a hot-pressing. This mechanismis different with the sublimation transfer of disperse dyes, thus there is no need to modifynatural fibers to improve their dyeability towards to disperse dyes; which is also differentwith the dissolution and transfer of dyes by the wetting method, thus the wet sizingpretreatment can be avoided. To prepare the adhesive dry-transfer printing paper, the pastecontaining high-substituted hydroxypropyl cellulose (H-HPC) acted as the hot-meltadhesive was used to modify the paper by coating. As the thermal gelation of H-HPCbrings about a decline of the paste viscosity during the process of drying coating, anotherpolysaccharide thickener without obvious thermal gelation, i.e. sodium alginate (SA),carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), guar gum (SG-9) andcarboxymethyl starch (SG-24) was mixed with H-HPC individually. To achieve thedissolution, permeation and fixation of reactive dyes, appropriate humectants and fixationalkaline agents were required in the paste.
In the research of chapter two, the hot-melt property of H-HPC as well as the thermalstability and swelling ability of the six polysaccharide thickeners were mearsured first.Effects of five kinds of mixed polysaccharide thickeners, i.e. H-HPC/SA, H-HPC/CMC,H-HPC/HEC, H-HPC/SG-9and H-HPC/SG-24on the rheology of the pastes, coatingamount on the transfer printing paper and color depth of the printed fabric wereinvestigated emphatically. The results of the research showed: the hot-melt temperature ofH-HPC was about120℃. All the pastes based on H-HPC possessed a shear-thinningbehavior suitable for the paper coating, and their viscoelasticity depended on the nature ofanother thickener used, i.e. SA, CMC, HEC, SG-9and SG-24. The coating amount on the transfer printing paper might be reduced by a higher elasticity of the paste, andproportionally related to the dynamic viscosity of the paste whose viscous was higher thanelasticity. The face color depth of the prints was governed by the coating amount and thechemical nature of another thickener. The deepest color was obtained upon usingH-HPC/SA, while the sharpness was poor. The printing effects and applicability based onH-HPC/CMC were the best when comprehensively evaluating the color depth, sharpness,color fastness, handle and fabric peelable degree.
The research of chapter three was focused on the rheology and morphology ofH-HPC/CMC which possessed the best transfer printing performance. Steady-shearexperiments showed: an increasing solid content contributed to a more obviouspseudo-plastic characteristic of H-HPC and CMC. CMC had a higher structural viscosityand exhibited the thinning behavior at a lower shear rate. Power-law model can be used todescribe the steady-shear curves of H-HPC and CMC. Thixotropic tests showed: thethixotropy of H-HPC was smaller than that of CMC. Dynamic frequency sweep showed:the two thickeners both displayed an increasing elasticity and a decreasing viscous with thepromotion of angular frequency or solid content, and the viscoelasticity of CMC was morestable than that of H-HPC. The compatibility of H-HPC/CMC was good under theconditions of weakly acidic, neutral, weakly alkali and different urea content viacomparing the variations in its rheology. Observing the micro-morphology of H-HPC,CMC and paste films obtained at the different dry temperatures or by the different filmforming methods using optical and atomic force microscopes found that the distribution ofH-HPC in the paste film was more uniform when drying at over80℃.
In the researches of chapters four and five, the reactive dry-transfer printingperformances of silk and cotton fabrics based on H-HPC/CMC were researchedsystematically. The key impact factors on the color depth of the prints, dye penetration andfixation rate were tried to seek from the two aspects of transfer paper preparation andprinting process optimization, and the differences of the printing performance of the twofabrics were analyzed. Meanwhile, the printing effluents as well as the color characteristic and wearability of the prints respectively obtained by the dry-transfer printing andtraditional screen printing were compared. The study about the silk printing performanceshowed: color depth of the silk prints was crucially influenced by the adhesion extentimparted by H-HPC, the type of fixing alkaline agent, the hygroscopic extent of the pasteand fabric. Trichloroacetic acid (TCAA) as the fixing alkaline agent and adding ureaenhanced the color yield markedly. Dye penetration depended on the coating amount onthe transfer printing paper, the content of urea and dicyandiamide. The printed silkpossessed a deeper color, color fastness of grade3or above, clear pattern and good handlewhen the paste containing3%H-HPC,0.7%CMC,3%TCAA,5%urea,3%dicyandiamide,and0.5%SiO2was used to prepare the transfer printing paper. The biggest differencebetween cotton and silk printing performance was that cotton achieved a deeper color inthe Na2CO3/TCAA buffer fixation system with stronger alkality. The transfer printingprocess was optimized as follows: the adhesion pressure and temperature were1-3Mpa and115-125℃respectively, and the steaming temperature and duration were102-112℃and10-20min respectively. The comparisons between dry-transfer printing and screen printingshowed: COD value of the transfer printing effluent was lower than that of the screenprinting effluent, but dyes content in which was higher. COD value of the printing effluentwas mainly caused by the thickeners used. Regardless of the substrates, levelness, dyepenetration and color fastness of the prints obtained by the screen printing were higher thanthose obtained by the transfer printing, while the substrates obtained by the transferprinting had a softer handle. Both the printing methods decreased the whiteness andstrength of the silk and cotton but had practically no effect on their water-vapourpermeability.
在第二章的研究中，首先对H-HPC的热熔性六种多糖增稠剂的热稳定性和溶胀性进行了测试，并着重探讨了五种混合多糖增稠剂，即H-HPC/SA H-HPC/CMC H-HPC/HEC H-HPC/SG-9和H-HPC/SG-24对糊料流变性，转印纸涂层量和印花织物色深的影响研究表明：H-HPC的热熔点约为120℃五种基于H-HPC的糊料均体现出适合纸张涂层的假塑性流体特征，另一种多糖增稠剂决定了糊料的粘弹性具有较高弹性比例的糊料会导致涂层量的降低当糊料的粘性高于弹性时，其表观粘度越高，涂层量越大印花织物的正面色深取决于H-HPC的涂层量及另一种多糖增稠剂的化学性质H-HPC/SA的印花织物得色最深但轮廓清晰度欠佳综合评价表观色深花型清晰度色牢度手感以及织物可剥离度这五个关键的印花性能指标，可得H-HPC/CMC的干法转移印花效果与可应用性能最佳
第三章针对综合印花性能最佳的H-HPC/CMC展开流变学和形貌学研究稳态剪切实验表明，随着固含量的增加，H-HPC和CMC的假塑性特征越明显CMC的结构粘度更高，并在较低的剪切速率下即体现出变稀的行为用power-law模型可对H-HPC和CMC的稳态剪切曲线进行较好的拟合触变性测试表明H-HPC的触变性较CMC小动态频率扫描结果表明，随着角频率或固含量的增加，两种增稠剂均表现出弹性增强且粘性减弱的特征CMC的粘弹性较H-HPC的稳定对比不同条件下H-HPC/CMC流变性的变化，可知其在弱酸性中性弱碱性及不同尿素含量的环境中均具有较好的相容性采用光学和原子力显微镜观测了不同温度和不同成膜方法下制备的H-HPC CMC及糊料膜的微观形貌，可知H-HPC在80℃以上干燥的糊料膜中分布得更为均匀
第四五两章分别对基于H-HPC/CMC的真丝及棉织物活性转移印花进行研究先从制备转印纸和优化工艺的角度探究影响织物表观色深染料渗透率和固色率的关键因素，并分析了两种织物的印花性能的差异，最后从印花废液和织物颜色及服用性能两方面对干法转移印花与传统筛网印花进行对比真丝印花性能的研究表明：H-HPC提供的贴合力固色碱剂的种类糊料与织物间的吸湿度对真丝的表观色深具有关键影响将三氯乙酸作为固色碱剂及尿素的加入均可显著提高色深值染料渗透率与转印纸上涂层量及尿素和双氰胺的含量有关用含有3%H-HPC0.7%CMC3%三氯乙酸5%尿素3%双氰胺0.5%SiO2的糊料制备转印纸时，获得的印花真丝具有较高的色深3级以上的色牢度轮廓清晰的花型和良好的手感棉与真丝印花性能的最大区别在于：棉织物在碱性较强的碳酸钠/三氯乙酸缓冲固色体系中可获得较高的固色率和色深值两种织物优化的转移印花工艺为：贴合压力1-3Mpa，贴合温度115-125℃，汽蒸温度102-112℃，汽蒸时间10-20min两种印花方法的对比表明：两种织物转移印花废液的COD均较筛网印花废液的COD低，但其中的染料量较高印花废液的COD主要由增稠剂所引起对两种织物而言，筛网印花织物的匀染性染料渗透率和色牢度较高，但是转移印花织物的手感更为柔软两种印花方法均会降低两种织物的白度和强力，但对它们透湿性的影响不大
The transfer mechanism of the reactive dry-transfer printing can be stated that reactivedyes are dissolved, permeated and fixed via a steaming after giving a tight adhesionbetween transfer printing paper and unsized dry fabrics via a hot-pressing. This mechanismis different with the sublimation transfer of disperse dyes, thus there is no need to modifynatural fibers to improve their dyeability towards to disperse dyes; which is also differentwith the dissolution and transfer of dyes by the wetting method, thus the wet sizingpretreatment can be avoided. To prepare the adhesive dry-transfer printing paper, the pastecontaining high-substituted hydroxypropyl cellulose (H-HPC) acted as the hot-meltadhesive was used to modify the paper by coating. As the thermal gelation of H-HPCbrings about a decline of the paste viscosity during the process of drying coating, anotherpolysaccharide thickener without obvious thermal gelation, i.e. sodium alginate (SA),carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), guar gum (SG-9) andcarboxymethyl starch (SG-24) was mixed with H-HPC individually. To achieve thedissolution, permeation and fixation of reactive dyes, appropriate humectants and fixationalkaline agents were required in the paste.
In the research of chapter two, the hot-melt property of H-HPC as well as the thermalstability and swelling ability of the six polysaccharide thickeners were mearsured first.Effects of five kinds of mixed polysaccharide thickeners, i.e. H-HPC/SA, H-HPC/CMC,H-HPC/HEC, H-HPC/SG-9and H-HPC/SG-24on the rheology of the pastes, coatingamount on the transfer printing paper and color depth of the printed fabric wereinvestigated emphatically. The results of the research showed: the hot-melt temperature ofH-HPC was about120℃. All the pastes based on H-HPC possessed a shear-thinningbehavior suitable for the paper coating, and their viscoelasticity depended on the nature ofanother thickener used, i.e. SA, CMC, HEC, SG-9and SG-24. The coating amount on the transfer printing paper might be reduced by a higher elasticity of the paste, andproportionally related to the dynamic viscosity of the paste whose viscous was higher thanelasticity. The face color depth of the prints was governed by the coating amount and thechemical nature of another thickener. The deepest color was obtained upon usingH-HPC/SA, while the sharpness was poor. The printing effects and applicability based onH-HPC/CMC were the best when comprehensively evaluating the color depth, sharpness,color fastness, handle and fabric peelable degree.
The research of chapter three was focused on the rheology and morphology ofH-HPC/CMC which possessed the best transfer printing performance. Steady-shearexperiments showed: an increasing solid content contributed to a more obviouspseudo-plastic characteristic of H-HPC and CMC. CMC had a higher structural viscosityand exhibited the thinning behavior at a lower shear rate. Power-law model can be used todescribe the steady-shear curves of H-HPC and CMC. Thixotropic tests showed: thethixotropy of H-HPC was smaller than that of CMC. Dynamic frequency sweep showed:the two thickeners both displayed an increasing elasticity and a decreasing viscous with thepromotion of angular frequency or solid content, and the viscoelasticity of CMC was morestable than that of H-HPC. The compatibility of H-HPC/CMC was good under theconditions of weakly acidic, neutral, weakly alkali and different urea content viacomparing the variations in its rheology. Observing the micro-morphology of H-HPC,CMC and paste films obtained at the different dry temperatures or by the different filmforming methods using optical and atomic force microscopes found that the distribution ofH-HPC in the paste film was more uniform when drying at over80℃.
In the researches of chapters four and five, the reactive dry-transfer printingperformances of silk and cotton fabrics based on H-HPC/CMC were researchedsystematically. The key impact factors on the color depth of the prints, dye penetration andfixation rate were tried to seek from the two aspects of transfer paper preparation andprinting process optimization, and the differences of the printing performance of the twofabrics were analyzed. Meanwhile, the printing effluents as well as the color characteristic and wearability of the prints respectively obtained by the dry-transfer printing andtraditional screen printing were compared. The study about the silk printing performanceshowed: color depth of the silk prints was crucially influenced by the adhesion extentimparted by H-HPC, the type of fixing alkaline agent, the hygroscopic extent of the pasteand fabric. Trichloroacetic acid (TCAA) as the fixing alkaline agent and adding ureaenhanced the color yield markedly. Dye penetration depended on the coating amount onthe transfer printing paper, the content of urea and dicyandiamide. The printed silkpossessed a deeper color, color fastness of grade3or above, clear pattern and good handlewhen the paste containing3%H-HPC,0.7%CMC,3%TCAA,5%urea,3%dicyandiamide,and0.5%SiO2was used to prepare the transfer printing paper. The biggest differencebetween cotton and silk printing performance was that cotton achieved a deeper color inthe Na2CO3/TCAA buffer fixation system with stronger alkality. The transfer printingprocess was optimized as follows: the adhesion pressure and temperature were1-3Mpa and115-125℃respectively, and the steaming temperature and duration were102-112℃and10-20min respectively. The comparisons between dry-transfer printing and screen printingshowed: COD value of the transfer printing effluent was lower than that of the screenprinting effluent, but dyes content in which was higher. COD value of the printing effluentwas mainly caused by the thickeners used. Regardless of the substrates, levelness, dyepenetration and color fastness of the prints obtained by the screen printing were higher thanthose obtained by the transfer printing, while the substrates obtained by the transferprinting had a softer handle. Both the printing methods decreased the whiteness andstrength of the silk and cotton but had practically no effect on their water-vapourpermeability.
引文
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