分散染料转移印花用棉织物改性剂的合成及应用技术研究
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摘要
分散染料转移印花技术具有工艺简单、设备投资少、艺术感高、图案精细和无需水洗及再行干燥等优点,属无水印花工艺。但该技术只适合于合成纤维织物,因此将该印花工艺应用于棉织物而实现清洁生产具有现实意义。现有棉织物分散染料转移印花技术存在游离甲醛含量超标、印花织物得色量低、色牢度差、手感硬和亲水性差等诸多问题,严重阻碍了该技术的普及和推广。基于此,本文通过聚合单体和交联体系的优化,考察乳化剂配比及用量、聚合工艺对乳液性能的影响,合成了一种环保型分散染料转移印花用棉织物改性剂。采用FT-IR、DSC、TG、TEM、粒径分析等多种现代仪器分析手段对改性剂结构、性能进行表征,并对其应用工艺进行研究。论文的主要研究内容分为三部分:
     (1)改性剂聚合单体和交联体系的优化。具体开发以丙烯酸丁酯为聚合主体单体,以苯乙烯、丙烯腈等为改性单体的共聚物,探讨了共聚物配比与印花品得色量之间的关系。通过分析不同交联单体对胶膜力学性能、K/S值以及印花品色牢度的影响,筛选出对印花品色牢度影响最为显著的交联单体,并系统性分析了该交联单体用量对印花品色牢度、胶膜力学性能和耐水性的影响。结果表明:苯乙烯(St)和丙烯腈(AN)对印花K/S值影响较为显著,其用量分别为30%和5%(%—相对单体总重量)时,印花品可获得较为满意的色深度和鲜艳度。交联单体聚乙二醇(200)二甲基丙烯酸酯(PEG(200)DMA)可作为转移印花改性剂的理想无甲醛交联剂,且其用量越多,水溶失率越低。当其用量为3%时,改性剂胶膜吸水率较低、断裂强度和断裂延伸率较好,印花色牢度较佳。
     (2)改性剂的合成及表征。以无APEO阴离子乳化剂A-6820、非离子乳化剂A-980及可聚合乳化剂V-10S复配组成乳液聚合用乳化剂,并应用于预乳化半连续乳液聚合法制备棉织物转移印花改性剂。系统研究了阴/非离子乳化剂配比和用量对预乳液稳定性、聚合稳定性、聚合后胶乳稳定性、乳胶粒粒径大小及分布的影响,探讨了聚合温度、保温时间、引发剂用量等因素对胶乳性能的影响。并采用FT-IR、DSC、TG、TEM、粒径分析等多种手段对改性剂结构、性能进行表征。结果表明:阴/非离子乳化剂配比在2:1、用量6%,可聚合乳化剂V-10S用量1%时,乳液聚合具有良好的预乳液稳定性、聚合稳定性和聚合后胶乳稳定性,以及较好的印花色牢度。改性剂最佳制备工艺:聚合温度80℃、保温时间50min、引发剂用量6%。在该工艺下聚合稳定性较好、单体转化率较高、凝聚率较低。透射电子显微镜显示:采用该工艺制备的改性剂乳胶粒呈规则的圆球状、粒子大小均匀;动态光散射纳米粒度仪显示:乳胶粒粒径在60~70nm,分布较窄;红外光谱图证实:各聚合单体均较好地参与了反应;差示扫描量热分析表明:改性剂的玻璃化温度为19.01℃;热重分析显示:改性剂胶膜的初始分解温度为439℃。
     (3)改性剂的应用工艺研究。通过分析不同发泡剂的发泡力和泡沫稳定性,优选出适合自制棉织物改性剂的发泡剂。分析了发泡剂用量、稳泡剂用量和搅拌转速对泡沫性能的影响,考察了改性剂用量、预烘温度及时间、焙烘温度及时间、转印温度及时间对印花品性能的影响。结果表明:最佳发泡工艺:发泡剂十二烷基硫酸钠用量5g/L、稳泡剂十二醇用量2g/L、搅拌转速2000r/min。最佳泡沫施加工艺:改性剂用量60%、预烘温度80℃、预烘时间100s、焙烘温度150℃、焙烘时间80s。最佳转移印花工艺:转印温度220℃、转印时间20s。
     采用最佳合成工艺制备的改性剂对棉织物改性,再经分散红转移印花,其印花品耐水、耐汗渍、耐干、湿摩擦色牢度和甲醛含量等各项指标均符合GB18401-2010《纺织品基本安全技术规范》A类标准。因此,该改性剂属于环保型分散染料转移印花改性剂,能较好地实现棉织物无水或少水印染的目的。
Transfer printing technology with disperse dye, a water-free printing process,owns a lot ofadvantages including simple process, low investment in equipment, high artistic quality, finepatterns, without washing and further drying, etc. However, this technique is only suitable forsynthetic fiber, so it has a realistic significance when applied to cotton fabric and implementclean production. There are some problems in currently transfer printing process, such as lowcolor yield, poor color fastness, hard handle, bad hydrophilic and existing free formaldehyde,which seriously hindered the popularization and promotion of the process. Therefore, the paperexplored an environment-friendly modifier for transfer printing with disperse dye on cottonfabric through optimizing polymer monomer and cross-linking system, as well as analyzing theeffects of emulsifier composition and dosage and polymerization process on the latex properties.The structure and properties of modifier was characterized by a variety of means of moderninstrument analysis, such as FT-IR, DSC, TG, TEM and particle size analysis. Meanwhile itsapplication process was also studied. The research content of paper was divided into three partsas follows.
     Part one: The optimization of polymer monomers and cross linking systems of modifier.
     The relationship between copolymer composition and color yield of printing products wereexplored by specific development for copolymer with butyl acrylate as the main polymermonomer and styrene and acrylonitrile as modified monomer. The best crosslinking monomerwith significant influence on color fastness can be obtained by analyzing the effects of thedifferent crosslinking monomers on film mechanical properties,K/S value and the color fastnessof printing products. Then the effect of amount of crosslinking monomer on color fastness, filmmechanical properties and water resistances were studied. The results showed that the styrene(St) and acrylonitrile (AN) had significant impact on the K/S value of printing products. Thesatisfactory color depth and brilliance of printing products can be obtained when the amount ofstyrene and acrylonitrile were30%and5%, respectively. The crosslinking monomer of polyethylene glycol (200) dimethyl acrylate (PEG (200) DMA) can be used as an idealnon-formaldehyde crosslinker at the emulsion polymerization of transfer printing modifier. Andthe more dosage of crosslinking monomer is, the lower dissolve-loss rate of film will be. Whenthe crosslinking monomer was3%, the latex film presented lower water absorption, superiorbreaking tenacity and elongation, and the printing products had excellent color fastness.
     Part two: Synthesis and characterization of modifier.
     In this part, the polymerization of compound emulsifier was confected by non-APEOanionic emulsifier A-6820, nonionic emulsifier A-980and polymerizable emulsifier V-10S,which were used to synthesis modifier for transfer printing with disperse dye on cotton fabricby semi-continuous pre-emulsifying emulsion polymerization. The influences of compoundemulsifier ratio and its dosage on pre-emulsion stability,polymerization stability, latex stability,latex particle size and distribution were studied. The effects of polymerization temperature,holding-temperature time, initiator dosage on the properties of emulsion were discussed.Moreover, the FT-IR, DSC, TG, TEM and particle size analysis were used to characterize thestructure and properties of modifier, which showed that the emulsion polymerization gainedgood pre-emulsion, polymerization and latex stability, as well as good color fastness when thecompound emulsifier was confected by anionic and nonionic emulsifier at the ratio of2:1, atamount of6%, and the amount of polymerizable emulsifier V-10S was1%. The optimalpolymerization process for modifier is that polymerization temperature was80℃,with50minholding-temperature time and0.6%initiator dosage. In this process, the emulsionpolymerization exhibited better polymerization stability, higher monomer conversion and lowerpolymerization coagulation rate. TEM photos demonstrated that latex particles had regularspherical shape and uniform particle size. The Dynamic Light Scattering Particle Size Analyzermeasured that its diameter was65to70nm and the distribution was narrow. FT-IRcharacterization of modifier groups showed that individual monomer well carried outpolymerization. DSC analysis showed that the glass transition temperature of modifier was19.01℃. TGA curves indicated that thermal decomposition temperature of modifier was439℃.
     Part three: Study on the application process of modifier.
     The optimal foaming agents for self-made modifier on cotton fabrics were optimized by analyzing the foaming capacity and stability of different foaming agents. Primary factorsinfluencing foaming performance including the concentration of foaming agents and stabilizer,and the agitation speed, were analyzed. The effects of the modifier dosage, pre-dryingtemperature and time, baking temperature and time,transfer printing temperature and time onthe performance of printing products were investigated. The experimental results showed thatthe best foaming process was gained when the sodium dodecyl sulfate as a foaming agent was5g/L, the dodecanol as a stabilizer, was2g/L and the stirring speed was2000r/min. The bestapplied process of foam was that the modifier was60%, the pre-drying temperature and timewere80℃and100s, respectively, the baking temperature and time was150℃and80s,respectively. The best transfer printing process was that the transfer temperature and time were220℃and20s, respectively.
     Modifier was prepared using the best synthesis process and cotton fabric was modified bythe modifier. Then the modified fabric was transfer printed with disperse red dye. The testingresults indicated that the water, perspiration, dry and wet rubbing fastness and formaldehydecontent of printing products conform to the A grade of GB18401-2003《National general safetytechnical code for textile products》. Therefore, the modifier can be taken as anenvironment-friendly agent on transfer printing with disperse dye and achieve the purpose ofprinting and dyeing on cotton fabric with less or no water well.
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