【作者】 柯贵珍；

【导师】 于伟东；

【作者基本信息】 东华大学 ， 纺织材料与纺织品设计， 2011， 博士

【摘要】 黄连上染蚕丝和羊毛的染色标准亲和力用分配系数进行了近似估计,所得亲和力随温度升高而降低,相应的染色热和染色熵均为负值。黄连上染羊毛纤维的标准亲和力,染色热和染色熵的绝对值均小于蚕丝纤维。黄连上染腈纶纤维和棉纤维的吸附等温线分别属于朗缪尔(Langmuir)吸附等温线和佛莱因德利胥(Freundlich)吸附等温线。随染色温度增加,黄连对腈纶的平衡吸附量均升高,对棉纤维的平衡吸附量降低。在较低温度染色时,黄连对蛋白质纤维的亲和性要高于腈纶,而接近沸染时,黄连对腈纶的上染量远高于其他纤维。黄连对棉纤维的上染性能较差。从上染率曲线,扩散系数,半染时间和染色速率常数等方面研究了黄连上染各纤维的动力学原理。实验结果表明,除棉纤维外,黄连上染各纤维的扩散系数均随染色温度的升高而提高,较高的染色温度可增加初始阶段的染色速率,半染时间则随染色温度的升高而降低。研究了黄连上染蚕丝织物,毛织物和腈纶纤维的染色工艺,分析了染液浓度,染色温度,上染时间,染液pH值,媒染剂等染色条件对染色织物颜色特征值的影响,通过正交实验确定了较优工艺参数。在黄连染蚕丝织物的直接染色和同浴媒染中,染液的pH值对色差的影响最大；在预媒处理和后媒处理中,温度和媒染剂用量都是相对较重要的因素,预媒染的增深作用较明显。在各媒染剂中,硫酸铜的增深效果相对较好。黄连染毛织物的直接染色实验中,pH值对染色结果影响最大,pH值越高,染色织物的颜色越深浓；预媒染实验中,温度是影响染色结果的的最显著因素,媒染剂,尤其是铁盐有明显的增深效果。在黄连染腈纶纤维的直接染色和同浴媒染中,染色温度具有显著的影响,染色纤维的色差均随染色温度的升高而增加；在铁盐的预媒处理和后媒处理中,媒染剂用量是最为重要的影响因素；而在铜盐的预媒处理和后媒处理中,温度则是最为重要的因素；媒染剂铁盐和铜盐对黄连染腈纶有明显的增深作用。黄连染色丝绸和毛织物的摩擦牢度尚可,而皂洗牢度普遍较差。媒染剂对皂洗牢度的改善程度不高。黄连染色腈纶的耐洗牢度和摩擦牢度均在4级以上。黄连无损伤地上染到织物上后,其抗菌保健作用的获得或保持要受环境因素的制约。通过观察黄连染色织物在自然光照射下色差的变化情况,得知黄连的耐太阳光牢度较差,但某些助剂的加入可提高其耐光牢度。媒染剂硫酸铜明显可以降低光褪色速度,抗氧化剂尤其是没食子酸能显著提高黄连的日晒牢度。另外,染液浓度的增加也可减缓黄连的光褪色速率。棉、毛、丝等织物经黄连染色后对其抗紫外线性能有明显提高。织物染色前用没食子酸进行预处理可以明显提高其抗紫外性能。通过黄连染色织物的静态,动态释放实验和洗衣机洗涤实验,研究了黄连的释放规律。结果表明染色纤维中黄连的释放量和速度均受温度和释放介质的影响。高温作用和酸性释放介质会明显增加黄连的释放速度和释放量,NaCl的加入也会促进黄连的释放；电解质Na2HPO4则对黄连的释放有一定的延缓作用。Higuchi方程均能较好地表征在动态释放过程中各种释放条件下蛋白质纤维中黄连的释放过程和释放动力学特征。黄连染色腈纶的释放率远低于黄连染色蛋白质纤维。丝绸和羊毛织物的机洗褪色曲线均符合递减的指数规律。ATR红外光谱分析表明染色纤维表面黄连色素的存在。通过黄连水提取液和黄连染色织物释放液冷冻粉的ATR红外光谱分析,明确了小檗碱作为最主要的色素来源,其在提取,上染和水浴释放过程中的一致性和无损伤性。抗菌测试结果表明黄连染色丝绸有明显的抗菌效果,且抗菌效果较稳定。研究了黄连对等离子体改性毛织物的染色性能。采用电晕法对毛织物表面进行改性,可使纤维表面活性基团增多,表面浸润性得到改善,从而改善了对黄连的上染性能。在空气气氛中,采用介质阻挡放电对毛织物表面进行改性处理,用黄连对改性毛织物进行染色,结果表明介质放电等离子体处理方式可提高毛纤维对黄连的平衡吸附量及染色织物的K/S值,提高放电电压,或延长处理时间,或增大处理电流都能使改善效果更加明显。研究了黄连对改性棉织物的染色性能。用柠檬酸作为交联剂使丝胶顺利附着在棉织物表面,用黄连对丝胶改性棉织物进行染色,结果表明上染率比未经过处理的棉织物有明显提高,染色织物颜色更鲜艳,且水洗牢度和耐摩擦牢度有所提高。通过高碘酸钠对棉纤维进行选择性氧化,可固着丝肽,从而改善了棉纤维对黄连的上染性能。更多还原

【Abstract】 Multifunctional fabrics, especially the fabrics with physiological function, physical therapy function, health protection function and security function have been paid more and more attention to in modern consciousness and opinions on wearing characteristics. A large number of plant medicines used in Traditional Chinese Medicine possess evident antibacterium, physical therapy and health care functions. Among them, many plant medicines can be boiled for a long time and used as bright-coloured pigment. If the medicine is extracted with proper process and the extract is used to dye fabrics, at the same time, the medical function is kept and the dyeing process is cleanly, the fabrics with medical functions will be obtained and dyeing problem will be solved simultaneously.In this paper, plant medicine rhizoma coptidis was selected as research objective. Extract processs of rhizoma coptidis and the stability of the extract were studied; the dyeing performance and technics of rhizoma with different fibers were investigated; the light fastness and release properties of the fabrics dyed with rhizoma coptidis under different conditions and the undamage of rhizoma coptidis were discussed; and the methods to improve the dyeing properties of wool fibers and cotton fibers with rhizoma coptidis were explored.Main coloring matter of rhizoma coptidis extract was confirmed as berberine by UV-visble spectrometry and thin layer chromatography analysis. Rhizoma coptidis was extracted using conventional water extract processs and optimal extract process was selected by orthogonal scheme. The orthogonal analysis results showed extract times was the most important factor, extract time, soak time and material-liquid ratio followed. The optimum extract conditions are that soak time is 60min, rhizoma coptidis and water ratio is 1:100, rhizoma coptidis is decocted twice and for 50min each time. Extraction ratio was 50.2%, R.S.D was 1.086%.The stability of rhizoma coptidis extract under different conditions was invesitgated by spectrometry analysis and color change observation. The results showed rhizoma coptidis extract was stable to general temperature, indoor natural light, weak acid and alkalid environment and common metal ion such as Na+, K+, Ca2+. The absorbance of rhizoma coptidis extract would decrease when under long-time high temperature.The addition of Fe2+ and Cu2+ increased absobency value and color value of the extract. Strong acid environment reduced absorbance value of the extract, while alkalid environment resulted in the dissimilation of the absorbance peak and the change of absorbance value.The thermodynamic principles of rhizoma coptidis dyeing with silk, wool, acrylic and cotton fibers have been studied in terms of adsorption isotherm, standard affinity, enthalpy change and entropy change. The results showed the adsorption isotherm of rhizoma coptidis on silk and wool fibers belonged to Nernst type and accorded with assignment law when dyed with low concentration, while the whole trend can be assigned as a Langmuir type, and equilibrium absorbance decreased with the increase of dyeing temperature. The standard affinity of rhizoma coptidis to silk and wool fibers was estimated with partition coefficient. The gained affinity decreased with the increase of dyeing temperature, and the calculated enthalpy change value and entropy change value both were negative, which indicated the adsorption of rhizoma coptidis on silk and wool fibers was an exothermic process. Silk fibers showd higher affinity to rhizoma coptidis dye than wool fibers. The adsorption isotherm of rhizoma coptidis on acrylic and cotton fibers belonged to Langmuir type and Freundlich type respectively. The dye uptake saturation of acrylic fibers increased with the increase of dyeing temperature, while cotton fibers’decreased. When dyed at lower temperature, the affinty of rhizoma coptidis to protein fibers was higher than to acylic fibers, however, when dyeing temperature reached 95℃, the equilibrium dye uptake in acylic fibers was much higher than that in the other fibers. Rhizoma coptidis showed poor affinity to cotton fiber.The kinetic mechanism of rhizoma coptidis dyeing with silk, wool, acrylic and cotton fibers have been investigated in terms of dye uptake rate curves, diffusion coefficient, time of half dyeing and dyeing rate constant. The results showed that for silk, wool and acrylic fiber, dyeing rate at the early stage and the diffusion coefficient increased and time of half dyeing decreased with the increae of dyeing temperature.Dyeing process of rhizoma coptidis wth different fibers has been studied. Color evaluation was characterized with color difference(ΔE)、lightness(L*)、redness-greenness (a*)、yellowness-blueness (b*)、saturation of color (c*)、hue value (H°)、K/S. The effects of dyeing conditions such as dye concentration, dyeing temperature, dyeing time, pH value of dyebath and mordant dyeing on color characters of the dyed fabrics and fibers were discussed, and optimal dyeing process was selected by orthogonal experimental. For silk fabric dyeing with rhizoma coptidis, pH value was the most important influencing factor andΔE value increased with pH value increase during direct dyeing and mordant dyeing; dyeing temperature and mordant content play much important role onΔE during pre-mordant-dyeing and after-mordant-dyeing; pre-mordant-dyeing deepened the colour particularly; and copper mordant deepened the colour much effectively. For wool fabric dyeing with rhizoma coptidis, pH value was the most important influencing factor onΔE during direct dyeing and higher pH value deepened the colour clearly; the most important influencing factor was dyeing temperature during pre-mordant-dyeing; mordant, especially iron deepened the colour evidently. For acrylic fibers dyeing with rhizoma coptidis, dyeing temperature was the most important influencing factor during direct dyeing, mordant dyeing and copper salt after-mordant-dyeing and pre-mordant-dyeing, andΔE value increased clearly with the increase of dyeing temperature; the most important influencing factor was mordant content during iron salt after-mordant-dyeing and pre-mordant-dyeing; and mordant deepened the colour clearly. The color fastness test showed that rhizoma coptidis in silk and wool fabric had poor washing fastness and better rub fastness. Mordant gave no evident improvement in the washfastness and rubfastness. Washfastness and rubfastness of the dyed acrylic are both above 4 grade.After rhizoma coptidis dye was absorbed into fabrics, the realization of its antibacterium relied on environmental factors to some extent. Photodegradation characteristics of rhizoma coptidis were studied on the basis of solar radiant treatment. The effect of mordant and dyeing concentration and antioxidants on the light fastness of the dyed fabrics were evaluated. Rhizoma coptidis was observed to have poor light fastness. However, mordant CUSO4 decreased light fading rate obviously and antioxidants especially gallic acid improved light fastness of rhizoma coptidis effectively. In addition, the increase of dyeing concentration slowed down lightness fading rate. Anti-UV properties of the dyed fabrics were evaluated and the results showed the dyed fabrics exhibited good anti-UV abilities. Pre-treatment of fabrics with vitamin acid and gallic acid can increase UV absorbance obviously.Releasing behavior of rhizoma coptidis on the dyed fabrics was studied through satic and dynamic release experiment and machine washing test. The results showed the release amount and rate were both affected by bath temperature and release medium. The addition of NaCl, and especially acidic medium and higher bath temperature increased release amount and rate obviously; conversely the addition of Na2HPO4 delayed the release of rhizoma coptidis. Higuchi equation could effectively characterize the release process and kinetics of rhizoma coptidis in protein fibers under different temperature and medium. The accumulated release amount of the dyed acrylic fibers was much lower than that of the dyed protein fibersColour fading curves of the dyed silk and wool fabrics were accorded with degression exponent rule.ATR infra-red spectrum analysis indicated rhizoma coptidis dye existence in fiber surface. The rhizoma coptidis extract and release solution was freezed into powder under vacuum and the freezed powder was analyzed by ATR infra-red spectrum. And the results showed that berberine, as main source of pigment, was confirmed the consistency and undamage during extracting, dyeing and releasing process.Anti-bacterium testing results showed the silk dyed with rhizoma coptidis had evident anti-bacterium effect to Staphylococcus aureus and it was stable.The dyeing properties of the wool fabrics treated by plasma with rhizoma coptidis were investigated. After the wool fabric was treated by corona discharge, some epicuticle scales on the wool surface became loose and some oxygen groups such as -OH and -COOH was incorporated into the wool surface and therefore the wetting properties and hydrophilicity of the wool fabric were improved. As a result the dyeing rate and dye exhaustion increased after corona treatment. Wool fabrics were treated in air by using dielectric barrier discharge plasma. The treated fabrics were dyed with rhizoma coptidis extract and corresponding dyeing rate and K/S value were measeured. The results indicated that dielectric barrier discharge plasma treatment was a effective way in improving final dye exhaustion and color depth of the wool fabric. The increase of the discharge voltage and treating time and electrical current all can make evident improvement.The dyeing properties of the modified cotton fabrics with rhizoma coptidis were studied. Sericin protein was adhered to the cotton fabric through cross-linking agent citric acid. The modified cotton fabrics were dyed with rhizoma coptidis extract and corresponding measurement showed that final dye exhaustion and the color difference and saturation increased obviously after modification, in addition, washing fastness and rub-fastness were improved. Cotton fibre was selectively oxidized with NaIO4 and treated by silk peptide solution that covered cotton fibre, which improved dyeing performance of the cotton fiber with rhizoma coptidis.更多还原