WO2019237466A1 - 一种天然染料可染的再生纤维素纤维的制备方法 - Google Patents

一种天然染料可染的再生纤维素纤维的制备方法 Download PDF

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WO2019237466A1
WO2019237466A1 PCT/CN2018/097866 CN2018097866W WO2019237466A1 WO 2019237466 A1 WO2019237466 A1 WO 2019237466A1 CN 2018097866 W CN2018097866 W CN 2018097866W WO 2019237466 A1 WO2019237466 A1 WO 2019237466A1
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solution
chitosan
regenerated cellulose
viscose spinning
tannic acid
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PCT/CN2018/097866
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English (en)
French (fr)
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毛军
陈红霞
陆鹏
袁洪兵
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江苏金太阳纺织科技股份有限公司
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Priority to AU2018428229A priority Critical patent/AU2018428229A1/en
Publication of WO2019237466A1 publication Critical patent/WO2019237466A1/zh

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/34—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using natural dyestuffs

Definitions

  • the invention belongs to the technical field of textile raw materials, and particularly relates to a method for preparing regenerated cellulose fibers dyeable by natural dyes.
  • Regenerated cellulose fiber is a renewable fiber made from natural cellulose through a series of complex chemical and physical changes.
  • the main component is cellulose, which has excellent dyeing properties and gloss, and also has excellent wearability and a wide range of properties. Applicable performance.
  • its drape is far superior to textiles made of cotton and linen. Its use covers almost all aspects of industry, agriculture, daily life, etc. It is one of the important raw materials for the textile industry.
  • regenerated cellulose Because of the so many advantages of regenerated cellulose, it has become more and more popular with consumers in recent years. Regardless of the commonly used reactive dyeing or printing products, they have unique characteristics in terms of color fastness, gloss and vividness Advantage. At the same time, regenerated cellulose fibers have better crystallinity than natural cellulose fibers, so when dyeing and printing, there will be a higher dyeing rate, which reduces the difficulty of sewage treatment and can improve the current to a certain extent. The problem of pollution caused by fabric dyeing, but due to the characteristics of synthetic dyes, the problem of pollution during reactive dyeing cannot be avoided.
  • natural dye is an environmentally friendly, healthy and environmentally friendly dye, good biodegradability, good compatibility with the ecological environment, non-toxic and harmless, non-irritating and carcinogenic to the skin, and its source is renewable, and natural dyes Dyeing wastewater does not cause water pollution problems caused by chemical dye wastewater, and the treatment of wastewater decolorization is relatively difficult, which has good research and development prospects.
  • This method is also to first regenerate cellulose fibers. After modification, when dyeing it with natural dyes to obtain a better dyeing rate and various color fastness, there are still problems of complicated processes and high costs. Therefore, it has not yet been possible to completely solve the regeneration of natural dyes.
  • Cellulose fibers have the problems of low dyeing rate, poor color fastness, high cost, and long processing time. Technical breakthroughs are urgently needed.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art, and to provide a method for preparing regenerated cellulose fibers dyeable with natural dyes. After spinning the regenerated cellulose fibers dyed with natural dyes, the yarn made of the fibers Thread or fabric has good color fastness, which can meet production and consumption.
  • the invention is achieved by:
  • a method for preparing regenerated cellulose fiber dyeable by natural dyes including the following steps:
  • Step 2 Preparation of a viscose spinning solution-chitosan mixed solution: firstly dispose a chitosan solution in a reaction kettle, and then add the viscose spinning solution to the reaction kettle and mix thoroughly to obtain
  • Step 3 Cross-linking reaction of tannic acid and viscose spinning solution-chitosan mixed solution: configure a tannic acid solution in the reaction kettle, and then add the viscose spinning solution-chitosan mixed solution to the reaction kettle , Adjust the temperature in the reaction kettle to allow the solution to fully react in the reaction kettle, that is,
  • step 4 the tannin viscose spinning solution obtained in step 3 is wet-spun to obtain a regenerated cellulose fiber dyeable with natural dyes.
  • the solvent used in the chitosan solution in step 2 is water, and the mass fraction of chitosan is 10% -20%.
  • the mass of chitosan in step 2 accounts for 10% to 20% of the content of nail fiber in the viscose spinning solution.
  • the solvent used in the tannic acid solution in step 3 is water, and the mass fraction of the tannic acid is 10% to 20%.
  • the mass ratio of tannic acid to chitosan in the reaction kettle of step 3 is 1: 1.
  • reaction temperature in the reaction kettle of step 3 is 20 to 40 ° C, and the reaction time is 4 to 8 hours.
  • the nail fiber used in the description of the present invention refers to: a kind of cellulose is also called ⁇ -cellulose.
  • the cellulose raw material was immersed in a 17.5% to 18% sodium hydroxide solution at 20 ° C for 45 minutes, and the portion was not dissolved.
  • the tannic acid used in the present invention is preferably an extract of natural origin, preferably an extract of a plant gallic raw material. Tannin is a water-soluble dendritic polyphenol with natural antioxidant, antibacterial and antiviral activities.
  • the tannic acid molecule contains a large number of phenolic hydroxyl groups, which can not only be used as a natural crosslinking agent. Tannic acid can react with alkaloids, proteins, polysaccharides and other substances. The principle is that polyphenols first approach the surface of large molecules such as proteins through hydrophobic bonds and enter their hydrophobic pockets. Two-point hydrogen bonding occurs. Simultaneous action makes it react on the polysaccharide macromolecular structure in a multi-point binding manner.
  • Chitosan is the only basic amino polysaccharide that exists in nature. Compared with synthetic polymer materials, chitosan not only has a wide range of sources, low price, stable properties, no irritation, no sensitization, and no mutagenicity. Biocompatible, biodegradable, film-forming and antibacterial.
  • the advantage of the invention is that firstly, the similarity between the molecular structure of chitosan and cellulose is used to dissolve the chitosan in the viscose spinning solution, and then the naturally extracted tannic acid is used to crosslink with the chitosan polysaccharide structure. In the reaction, tannic acid is grafted onto the chitosan macromolecular structure, and then the viscose spinning solution after cross-linking is subjected to solid spinning to obtain chitosan regenerated cellulose fibers containing the tannic acid macromolecule.
  • tannic acid is used as a mordant, and natural fibers are used to dye the prepared fibers, which can greatly improve the dyeing fastness of regenerated cellulose fibers.
  • naturally extracted tannic acid is preferred to heavy metal ions and rare earth elements. Said that tannic acid is non-toxic and harmless to the human body, safe and environmentally friendly without pollution.
  • the invention uses chitosan as the reaction main body to graft tannic acid to the regenerated cellulose fiber, which can greatly improve the fixation rate of tannic acid in the fiber, and can also further improve the various characteristics of the fiber dyed by natural dyes. Color fastness index.
  • after adding chitosan to the fiber it can also give the fiber better antibacterial properties and increase the added value of the fiber product.
  • the raw material is wood pulp with a degree of polymerization of 500-600, the content of nail fiber is greater than 90%, and the gum is made according to the following process routes: impregnation, pressing, crushing, aging, yellowing, continuous dissolution, filtration, and defoaming.
  • the viscose spinning solution has a fiber content of 9.0%, a NaOH mass fraction of 5.8%, a viscosity (drop ball method) of 60 s, and a maturity of (10% NH 4 Cl) 8.9 mL.
  • a 10% mass fraction of chitosan solution was prepared with distilled water, and then the viscose spinning stock solution was added according to the proportion of the mass of chitosan to 10% of the content of nail fiber, and the viscose spinning solution was thoroughly stirred to prepare a viscose spinning Silk liquid-chitosan mixed solution.
  • Step 3 Cross-linking reaction of tannic acid and viscose spinning solution-chitosan mixed solution
  • the tannin viscose spinning solution is sent to the wet spinning process for spinning.
  • the spinneret specifications are 21000 holes ⁇ 0.06mm, the spinning speed is 55m / min, the coagulation bath temperature is 52 ° C, and the plasticizing bath temperature is 95 ° C.
  • the composition of the coagulation bath was: 115 g / L of sulfuric acid, 325 g / L of sodium sulfate, and 11.5 g / L of zinc sulfate.
  • Embodiment 2 Preparation method of regenerated cellulose fiber dyeable by natural dye
  • the raw material is wood pulp with a degree of polymerization of 500-600, the content of nail fiber is greater than 90%, and the gum is made according to the following process routes: impregnation, pressing, crushing, aging, yellowing, continuous dissolution, filtration, and defoaming.
  • the viscose spinning solution has a fiber content of 9.0%, a NaOH mass fraction of 5.8%, a viscosity (drop ball method) of 60 s, and a maturity of (10% NH 4 Cl) 8.9 mL.
  • Step 3 Cross-linking reaction of tannic acid and viscose spinning solution-chitosan mixed solution
  • the tannin viscose spinning solution is sent to the wet spinning process for spinning.
  • the spinneret specifications are 21000 holes ⁇ 0.06mm, the spinning speed is 55m / min, the coagulation bath temperature is 52 ° C, and the plasticizing bath temperature is 95 ° C.
  • the composition of the coagulation bath was: 115 g / L of sulfuric acid, 325 g / L of sodium sulfate, and 11.5 g / L of zinc sulfate.
  • Embodiment 3 Preparation method of regenerated cellulose fiber dyeable by natural dye
  • the raw material is wood pulp with a degree of polymerization of 500-600, the content of nail fiber is greater than 90%, and the gum is made according to the following process routes: impregnation, pressing, crushing, aging, yellowing, continuous dissolution, filtration, and defoaming.
  • the viscose spinning solution has a fiber content of 9.0%, a NaOH mass fraction of 5.8%, a viscosity (drop ball method) of 60 s, and a maturity of (10% NH 4 Cl) 8.9 mL.
  • Step 3 Cross-linking reaction of tannic acid and viscose spinning solution-chitosan mixed solution
  • the tannin viscose spinning solution is sent to the wet spinning process for spinning.
  • the spinneret specifications are 21000 holes ⁇ 0.06mm, the spinning speed is 55m / min, the coagulation bath temperature is 52 ° C, and the plasticizing bath temperature is 95 ° C.
  • the composition of the coagulation bath was: 115 g / L of sulfuric acid, 325 g / L of sodium sulfate, and 11.5 g / L of zinc sulfate.
  • Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the viscose spinning dope was directly used for spinning, no chitosan was added, and no tannic acid was added to cause a crosslinking reaction.
  • the raw material is wood pulp with a degree of polymerization of 500-600, the content of nail fiber is greater than 90%, and the gum is made according to the following process routes: impregnation, pressing, crushing, aging, yellowing, continuous dissolution, filtration, and defoaming.
  • the viscose spinning solution has a fiber content of 9.0%, a NaOH mass fraction of 5.8%, a viscosity (drop ball method) of 60 s, and a maturity of (10% NH 4 Cl) 8.9 mL.
  • the viscose spinning solution is sent to a wet spinning process for spinning.
  • the spinneret specifications are 21000 holes ⁇ 0.06mm, the spinning speed is 55m / min, the coagulation bath temperature is 52 ° C, and the plasticizing bath temperature is 95 ° C.
  • the composition of the coagulation bath was: 115 g / L of sulfuric acid, 325 g / L of sodium sulfate, and 11.5 g / L of zinc sulfate.
  • Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the viscose spinning dope was directly used for spinning, and no chitosan solution was added, and only tannic acid was added for crosslinking reaction.
  • the raw material is wood pulp with a degree of polymerization of 500-600, the content of nail fiber is greater than 90%, and the gum is made according to the following process routes: impregnation, pressing, crushing, aging, yellowing, continuous dissolution, filtration, and defoaming.
  • the viscose spinning solution has a fiber content of 9.0%, a NaOH mass fraction of 5.8%, a viscosity (drop ball method) of 60 s, and a maturity of (10% NH 4 Cl) 8.9 mL.
  • Step 2 Cross-linking reaction of tannic acid and viscose spinning solution-chitosan mixed solution
  • reaction kettle prepare a tannic acid solution with a mass fraction of 10% with distilled water, and then add the viscose spinning stock solution according to the proportion of the mass of chitosan to 10% of the content of the nail fiber, and adjust the temperature in the reaction kettle to 30 ° C. The reaction was continued for 4 to 6 hours under constant stirring conditions to obtain a uniform tannic acid viscose spinning solution.
  • the tannin viscose spinning solution is sent to the wet spinning process for spinning.
  • the spinneret specifications are 21000 holes ⁇ 0.06mm, the spinning speed is 55m / min, the coagulation bath temperature is 52 ° C, and the plasticizing bath temperature is 95 ° C.
  • the composition of the coagulation bath was: 115 g / L of sulfuric acid, 325 g / L of sodium sulfate, and 11.5 g / L of zinc sulfate.
  • Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that only the chitosan solution was added to the viscose spinning solution, and the regenerated cellulose fibers were directly spun to produce a crosslinked reaction without adding tannic acid.
  • the raw material is wood pulp with a degree of polymerization of 500-600, the content of nail fiber is greater than 90%, and the gum is made according to the following process routes: impregnation, pressing, crushing, aging, yellowing, continuous dissolution, filtration, and defoaming.
  • the viscose spinning solution has a fiber content of 9.0%, a NaOH mass fraction of 5.8%, a viscosity (drop ball method) of 60 s, and a maturity of (10% NH 4 Cl) 8.9 mL.
  • a 10% mass fraction of chitosan solution was prepared with distilled water, and then the viscose spinning stock solution was added according to the proportion of the mass of chitosan to 10% of the content of nail fiber, and the viscose spinning solution was thoroughly stirred to prepare a viscose spinning Silk liquid-chitosan mixed solution.
  • the viscose spinning solution-chitosan mixed solution is sent to a wet spinning process for spinning.
  • the spinneret specifications are 21000 holes ⁇ 0.06mm, the spinning speed is 55m / min, the coagulation bath temperature is 52 ° C, and the plasticizing bath temperature is 95 ° C.
  • the composition of the coagulation bath was: 115 g / L of sulfuric acid, 325 g / L of sodium sulfate, and 11.5 g / L of zinc sulfate.
  • the fiber obtained by spinning in the above embodiment is subjected to spinning, weaving, dyeing and finishing of the fiber fabric, and the color fastness test is performed on the fabric.
  • the results obtained are as follows:
  • Fibers prepared by adding tannic acid to the viscose spinning solution alone can also improve the color fastness of fiber products to some extent, but because the binding force between the fiber and tannic acid is relatively poor, Various color fastness cannot meet the requirements of superior products.
  • the addition of chitosan can also give the fiber better antibacterial and antibacterial properties.

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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

本发明公开了一种天然染料可染的再生纤维素纤维的制备方法，先将壳聚糖溶液加至粘胶纺丝液中制成粘胶纺丝液-壳聚糖混合溶液，然后加入单宁酸溶液，混合后充分反应，最后将得到的单宁酸粘胶纺丝液液进行湿法纺丝，即可制得天然染料可染的再生纤维素纤维。制得的再生纤维素纤维通过天然染料染色后，该纤维制成的纱线或面料具有较好的各项色牢度，能够满足生产和服用。

Description

一种天然染料可染的再生纤维素纤维的制备方法 技术领域
本发明属于纺织原料技术领域，具体涉及一种天然染料可染的再生纤维素纤维的制备方法。
背景技术
再生纤维素纤维是天然纤维素经过一系列复杂的化学变化和物理变化制成的可再生纤维，主要组成物质为纤维素，具有优良的染色性能和光泽，同时还拥有极佳服用性能和广泛的适用性能，此外，其悬垂性远胜于棉、麻所制成的纺织品。其用途几乎遍及所有的工业、农业、生活衣着等各方面，是纺织工业的重要原料之一。
由于再生纤维素具有如此多的优点，近年来也越来越多地受到消费者的喜爱，无论普遍采用的活性染料染色还是印花的产品，在色牢度、光泽和鲜艳度方面都有着独特的优势。同时由于再生纤维素纤维的比天然的纤维素纤维具有较好结晶度，所以因此在染色印花时，会有一个更高的上染率，减轻了污水处理的难度，在一定程度上能够改善目前面料染色带来的污染问题，但是由于合成染料的特性，仍然无法避免活性染料染色时污染的问题。
众所周知，天然染料是一种环保、健康环保染料，生物降解性良好，与生态环境相容性好，而且无毒无害，对皮肤无刺激性和致癌性，且其来源可再生，同时天然染料染色废水不会产生化学染料废水所引发的水污染问题，废水脱色等处理难度较小，具有良好的研究发展前景。
但是，采用天然染料对再生纤维素纤维进行染色，拥有诸多优点，安全环保，生态无毒等，目前在采用天然染料对再生纤维素纤维染色印花时，仍然存在着各项色牢度不达标的问题，虽然在这方面研究也非常多。其中申请号为：CN201610050735.4的专利，利用提取的然薰衣草染料对改性后的再生纤维素纤维进行染色，得到较好的上染率和色牢度，但是该方法过程繁琐，成本较高，主要问题是要对再生纤维素纤维进行改性后方可染色；申请号为CN201610050277.4的专利公开了一种板蓝根染料上染再生纤维素纤维的方法，该方法同样是先对再生纤维素纤维进行改性，在用天然染料对其染色从而获得较好的上染率和各项色牢度，仍然存在着过程繁杂成本较高的问题，因此，目前尚未出现能够彻底解决天然染料上染再生纤维素纤维存在的上染率低、色牢度差以及成本高、加工过程长的问题，急需技术突破。
发明内容
本发明的目的是克服上述现有技术的不足，提供一种天然染料可染的再生纤维素纤维的制备方法，纺丝制得的再生纤维素纤维通过天然染料染色后，该纤维制成的纱线或面料具有较好的各项色牢度，能够满足生产和服用。
本发明是通过如下方式实现的：
一种天然染料可染的再生纤维素纤维的制备方法，包括以下步骤：
步骤1，粘胶纺丝液的制备；
步骤2，粘胶纺丝液-壳聚糖混合溶液的制备：先在反应釜内配置壳聚糖溶液，然后向反应釜加入粘胶纺丝液，充分混合，即得；
步骤3，单宁酸与粘胶纺丝液-壳聚糖混合溶液的交联反应：在反应釜中配置单宁酸溶液，然后向反应釜中加入粘胶纺丝液-壳聚糖混合溶液，调节反应釜中的温度，让溶液在反应釜中充分反应，即得；
步骤4，将步骤3得到的单宁酸粘胶纺丝液液进行湿法纺丝，即可制得天然染料可染的再生纤维素纤维。
进一步地，步骤2中的壳聚糖溶液所用的溶剂为水，壳聚糖的质量分数为10％～20％。
进一步地，步骤2中壳聚糖的质量占粘胶纺丝液中甲纤含量的10％～20％。
进一步地，步骤3中单宁酸溶液所用的溶剂为水，单宁酸的质量分数为10％～20％。
进一步地，步骤3反应釜中单宁酸与壳聚糖的质量比为1:1。
进一步地，步骤3反应釜中的反应温度为20～40℃，反应时为4～8h。
作为说明本发明中所述的甲纤是指：甲种纤维素又称α-纤维素。纤维素原料在20℃浸于17.5％～18％的氢氧化钠溶液中经过45分钟后不溶解的部分。
本发明所用的单宁酸优选天然来源的提取物，优选植物五倍子原料的提取物。单宁酸是一种水溶性树枝状多酚，具有天然的抗氧化，抗菌和抗病毒活性。此外，单宁酸分子中含有大量的酚羟基基团，不但可以作为一种天然的交联剂。单宁酸可以生物碱、蛋白质、多糖等物质发生反应，其原理是多酚先通过疏水键向蛋白质等大分子表面靠近，进入其疏水袋，发生两点氢键结合，疏水键和氢键的同时作用使其以多点结合的方式在多糖大分子结构上反应。
壳聚糖是自然界中唯一存在的碱性氨基多糖，与合成高分子材料相比，其不但具有来源广泛、价格低廉、性质稳定、无刺激、无致敏以及无致突变等特性，而且具有良好的生物相容性、生物可降解性、成膜性和抗菌性。
本发明的优点在于首先利用壳聚糖和纤维素分子结构的相似性，将壳聚糖溶解在粘胶纺丝液中，后再利用天然提取的单宁酸与壳聚糖多糖结构发生交联反应，将单宁酸接枝到壳聚糖大分子结构上，后将交联后的粘胶纺丝液进行实发纺丝后得到含有单宁酸大分子的壳聚糖再生纤维素纤维。同时利用单宁酸作为媒染剂，采用天然染料对制备好的纤维进行染色，可大大提升再生纤维素纤维各项染色牢度，同时优选天然提取的单宁酸，相对于重金属离子及稀土元素来说，单宁酸具有对人体无毒无害，安全环保无污染的特点。此外，本发明利用壳聚糖作为反应主体将单宁酸接枝到再生纤维素纤维上，可大大提高单宁酸在纤维中的固着率，也可进一步提升天然染料染色后的纤维的各项色牢度指标。同时将壳聚糖添加到纤维中后， 还可赋予纤维较好的抗菌性能，提升纤维制品的附加值。
具体实施方式
实施例1天然染料可染的再生纤维素纤维的制备方法
步骤1，粘胶纺丝液的制备
原料为聚合度为500～600的木浆粕，其甲纤含量大于90％，且按照以下工艺路线制胶：浸渍、压榨、粉碎、老成、黄化、连续溶解、过滤、脱泡。
按照上述工艺制造而成粘胶纺丝液甲纤含量为9.0％，NaOH质量分数为5.8％，粘度为(落球法)60s，熟程度为(10％NH 4Cl)8.9mL。
步骤2，粘胶纺丝液-壳聚糖混合溶液
在反应釜内，用蒸馏水配制质量分数为10％的壳聚糖溶液，后按壳聚糖的质量占甲纤含量的10％的比例加入粘胶纺丝原液，充分搅拌，制得粘胶纺丝液-壳聚糖混合溶液。
步骤3，单宁酸与粘胶纺丝液-壳聚糖混合溶液的交联反应
在反应釜内，用蒸馏水配制质量分数为10％的单宁酸溶液，后按单宁酸与壳聚糖质量比为1:1的比例加入粘胶纺丝原液-壳聚糖混合溶液，调节反应釜内温度值30℃，在不断搅拌的条件下反应4～6h，得到均匀的单宁酸粘胶纺丝液液。
湿法纺丝：将单宁酸粘胶纺丝溶液送入湿法纺丝工序进行纺丝。喷丝头规格为21000孔×0.06mm，纺丝速度为55m/min，凝固浴温度为52℃，塑化浴温度为95℃。凝固浴组成为：硫酸115g/L，硫酸钠325g/L，硫酸锌11.5g/L。
实施例2：天然染料可染的再生纤维素纤维的制备方法
步骤1，粘胶纺丝液的制备
原料为聚合度为500～600的木浆粕，其甲纤含量大于90％，且按照以下工艺路线制胶：浸渍、压榨、粉碎、老成、黄化、连续溶解、过滤、脱泡。
按照上述工艺制造而成粘胶纺丝液甲纤含量为9.0％，NaOH质量分数为5.8％，粘度为(落球法)60s，熟程度为(10％NH 4Cl)8.9mL。
步骤2，粘胶纺丝液-壳聚糖混合溶液
在反应釜内，用蒸馏水配制质量分数为15％的壳聚糖溶液，后按壳聚糖的质量占甲纤含量的15％的比例加入粘胶纺丝原液，充分搅拌，制得粘胶纺丝液-壳聚糖混合溶液。
步骤3，单宁酸与粘胶纺丝液-壳聚糖混合溶液的交联反应
在反应釜内，用蒸馏水配制质量分数为15％的单宁酸溶液，后按单宁酸与壳聚糖质量比为1:1的比例加入粘胶纺丝原液-壳聚糖混合溶液，调节反应釜内温度值30℃，在不断搅拌的条件下反应4～6h，得到均匀的单宁酸粘胶纺丝液液。
湿法纺丝：将单宁酸粘胶纺丝溶液送入湿法纺丝工序进行纺丝。喷丝头规格为21000孔×0.06mm，纺丝速度为55m/min，凝固浴温度为52℃，塑化浴温度为95℃。凝固浴组成为：硫酸115g/L，硫酸钠325g/L，硫酸锌11.5g/L。
实施例3：天然染料可染的再生纤维素纤维的制备方法
步骤1，粘胶纺丝液的制备
原料为聚合度为500～600的木浆粕，其甲纤含量大于90％，且按照以下工艺路线制胶：浸渍、压榨、粉碎、老成、黄化、连续溶解、过滤、脱泡。
按照上述工艺制造而成粘胶纺丝液甲纤含量为9.0％，NaOH质量分数为5.8％，粘度为(落球法)60s，熟程度为(10％NH 4Cl)8.9mL。
步骤2，粘胶纺丝液-壳聚糖混合溶液
在反应釜内，用蒸馏水配制质量分数为20％的壳聚糖溶液，后按壳聚糖的质量占甲纤含量的20％的比例加入粘胶纺丝原液，充分搅拌，制得粘胶纺丝液-壳聚糖混合溶液。
步骤3，单宁酸与粘胶纺丝液-壳聚糖混合溶液的交联反应
在反应釜内，用蒸馏水配制质量分数为20％的单宁酸溶液，后按单宁酸与壳聚糖质量比为1:1的比例加入粘胶纺丝原液-壳聚糖混合溶液，调节反应釜内温度值30℃，在不断搅拌的条件下反应4～6h，得到均匀的单宁酸粘胶纺丝液液。
湿法纺丝：将单宁酸粘胶纺丝溶液送入湿法纺丝工序进行纺丝。喷丝头规格为21000孔×0.06mm，纺丝速度为55m/min，凝固浴温度为52℃，塑化浴温度为95℃。凝固浴组成为：硫酸115g/L，硫酸钠325g/L，硫酸锌11.5g/L。
对照例1
对照例1与实施例1的区别在于直接用粘胶纺丝原液纺丝，不加入壳聚糖，也不加入单宁酸发生交联反应。
粘胶纺丝液的制备
原料为聚合度为500～600的木浆粕，其甲纤含量大于90％，且按照以下工艺路线制胶：浸渍、压榨、粉碎、老成、黄化、连续溶解、过滤、脱泡。
按照上述工艺制造而成粘胶纺丝液甲纤含量为9.0％，NaOH质量分数为5.8％，粘度为(落球法)60s，熟程度为(10％NH 4Cl)8.9mL。
湿法纺丝：将粘胶纺丝溶液送入湿法纺丝工序进行纺丝。喷丝头规格为21000孔×0.06mm，纺丝速度为55m/min，凝固浴温度为52℃，塑化浴温度为95℃。凝固浴组成为：硫酸115g/L，硫酸钠325g/L，硫酸锌11.5g/L。
对照例2
对照例2与实施例1的区别在于直接用粘胶纺丝原液纺丝，不加入壳聚糖溶液，仅加入单宁酸发生交联反应。
步骤1，粘胶纺丝液的制备
原料为聚合度为500～600的木浆粕，其甲纤含量大于90％，且按照以下工艺路线制胶：浸渍、压榨、粉碎、老成、黄化、连续溶解、过滤、脱泡。
按照上述工艺制造而成粘胶纺丝液甲纤含量为9.0％，NaOH质量分数为5.8％，粘度为(落球法)60s，熟程度为(10％NH 4Cl)8.9mL。
步骤2，单宁酸与粘胶纺丝液-壳聚糖混合溶液的交联反应
在反应釜内，用蒸馏水配制质量分数为10％的单宁酸溶液，后按壳聚糖的质量占甲纤含量的10％的比例加入粘胶纺丝原液，调节反应釜内温度值30℃，在不断搅拌的条件下反应4～6h，得到均匀的单宁酸粘胶纺丝液液。
湿法纺丝：将单宁酸粘胶纺丝溶液送入湿法纺丝工序进行纺丝。喷丝头规格为21000孔×0.06mm，纺丝速度为55m/min，凝固浴温度为52℃，塑化浴温度为95℃。凝固浴组成为：硫酸115g/L，硫酸钠325g/L，硫酸锌11.5g/L。
对照例3
对照例3与实施例1的区别在于仅向粘胶纺丝液中添加壳聚糖溶液后直接纺丝制得再生纤维素纤维，不加入单宁酸发生交联反应。
步骤1，粘胶纺丝液的制备
原料为聚合度为500～600的木浆粕，其甲纤含量大于90％，且按照以下工艺路线制胶：浸渍、压榨、粉碎、老成、黄化、连续溶解、过滤、脱泡。
按照上述工艺制造而成粘胶纺丝液甲纤含量为9.0％，NaOH质量分数为5.8％，粘度为(落球法)60s，熟程度为(10％NH 4Cl)8.9mL。
步骤2，粘胶纺丝液-壳聚糖混合溶液
在反应釜内，用蒸馏水配制质量分数为10％的壳聚糖溶液，后按壳聚糖的质量占甲纤含量的10％的比例加入粘胶纺丝原液，充分搅拌，制得粘胶纺丝液-壳聚糖混合溶液。
湿法纺丝：将粘胶纺丝液-壳聚糖混合溶液送入湿法纺丝工序进行纺丝。喷丝头规格为21000孔×0.06mm，纺丝速度为55m/min，凝固浴温度为52℃，塑化浴温度为95℃。凝固浴组成为：硫酸115g/L，硫酸钠325g/L，硫酸锌11.5g/L。
将上述实施例中纺丝得到的纤维经过纺纱，织造，染整等该纤维的面料，对面料进行各项色牢度测试，得到的结果如下：
面料 耐酸 耐碱 耐水 干摩擦牢度 湿摩擦牢度 日晒牢度 抑菌率
实施例1 4 4 4-5 4 3 3-4 90.5％
实施例2 4 4 4-5 4 3 3-4 93.1％
实施例3 4 4-5 4-5 4 3-4 4 96.8％
对照例1 2 1-2 2 2 1-2 1-2 63.9％
对照例2 3-4 3 3 3-4 3 3 72.4％
对照例3 2 2 2-3 2 2 1-2 91.1％
从上表的测试结果可以看出，将经过单宁酸与粘胶纺丝液-壳聚糖混合溶液的交联反应纺丝后制得的再生纤维素纤维制成的面料经过天然染料染色后面料具有着较好的各项色牢度性能，能够达到国标规定的色牢度指标要求。进一步研究发现，壳聚糖的加入能够与单宁酸发生协同作用，提升单宁酸在纤维中的固着率，进一步提升纤维经过天然染料染色后各项色牢度。单独向粘胶纺丝液中加入单宁酸后纺丝制得的纤维也能够在一定程度上提升纤维制品的各项色牢度，但是由于纤维与单宁酸之间的结合力比较差，各项色牢度无法达到优等品的要求。同时壳聚糖的加入还能赋予纤维较好的抗菌抑菌性能。

Claims (6)

  1. 一种天然染料可染的再生纤维素纤维的制备方法，其特征在于：包括以下步骤：
    步骤1，粘胶纺丝液的制备；
    步骤2，粘胶纺丝液-壳聚糖混合溶液的制备：先在反应釜内配置壳聚糖溶液，然后向反应釜加入粘胶纺丝液，充分混合，即得；
    步骤3，单宁酸与粘胶纺丝液-壳聚糖混合溶液的交联反应：在反应釜中配置单宁酸溶液，然后向反应釜中加入粘胶纺丝液-壳聚糖混合溶液，调节反应釜中的温度，让溶液在反应釜中充分反应，即得；
    步骤4，将步骤3得到的单宁酸粘胶纺丝液液进行湿法纺丝，即可制得天然染料可染的再生纤维素纤维。
  2. 根据权利要求1所述的天然染料可染的再生纤维素纤维的制备方法，其特征在于：步骤2中的壳聚糖溶液所用的溶剂为水，壳聚糖的质量分数为10％～20％。
  3. 根据权利要求1所述的天然染料可染的再生纤维素纤维的制备方法，其特征在于：步骤2中壳聚糖的质量占粘胶纺丝液中甲纤含量的10％～20％。
  4. 根据权利要求1所述的天然染料可染的再生纤维素纤维的制备方法，其特征在于：步骤3中单宁酸溶液所用的溶剂为水，单宁酸的质量分数为10％～20％。
  5. 根据权利要求1所述的天然染料可染的再生纤维素纤维的制备方法，其特征在于：步骤3反应釜中单宁酸与壳聚糖的质量比为1:1。
  6. 根据权利要求1所述的天然染料可染的再生纤维素纤维的制备方法，其特征在于：步骤3反应釜中的反应温度为20～40℃，反应时为4～8h。
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