WO2004009881A1 - Fibre de viscose modifiee et son procede de preparation - Google Patents

Fibre de viscose modifiee et son procede de preparation Download PDF

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Publication number
WO2004009881A1
WO2004009881A1 PCT/CN2003/000582 CN0300582W WO2004009881A1 WO 2004009881 A1 WO2004009881 A1 WO 2004009881A1 CN 0300582 W CN0300582 W CN 0300582W WO 2004009881 A1 WO2004009881 A1 WO 2004009881A1
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Prior art keywords
chitosan
viscose
denatured
solution
fiber
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PCT/CN2003/000582
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English (en)
French (fr)
Inventor
Yufeng Huang
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Xiangtan Zenith Fine Chemicals, Co.,Ltd
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Priority to AU2003281538A priority Critical patent/AU2003281538A1/en
Publication of WO2004009881A1 publication Critical patent/WO2004009881A1/zh

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Classifications

    • 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
    • D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
    • 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
    • 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

Definitions

  • the present invention relates to a denatured viscose fiber, which can be spun into long fibers and used directly in various aspects, or it can be spun into short fibers and sent to ordinary cotton spinning equipment.
  • the denatured viscose fibers are mixed with other fibers through appropriate cotton blending
  • the antibacterial mixed fiber yarn that can be used for the production of various fabrics is obtained through the processes of clearing cotton and carded rovings.
  • chitosan is dissolved in a mixed solvent of lithium chloride and dimethylformamide and then spun through special equipment. Chitosan fiber, the process is complicated, the production cost is high, and a large number of applications are limited.
  • chitosan alone is spun after alkalization, yellowing, dissolving, or mixed with viscose. When used as antibacterial textiles, it is either used in large amounts, high cost, or mixed with other fibers when weaving. Will significantly reduce its antibacterial properties.
  • An object of the present invention is to provide a denatured viscose fiber and a manufacturing method thereof, which can significantly improve the antibacterial and antifungal properties of a fabric.
  • the object of the present invention is achieved by the following methods:
  • chitosan because natural quality chitosan is added to the fiber by a specific process, it can give the fabric good biocompatibility, breathability and moisture retention, meanwhile, it has no toxic side effects and has certain antibacterial properties.
  • Hull polymer The sugar quaternary ammonium salt compound, in addition to having a good promotion effect on various properties of the fabric, is more important in that it can significantly improve the antibacterial and mildew resistance of the fabric; the quaternary chitosan salt used in the present invention is Chitosan comes from quaternization.
  • the quaternization modification ratio of chitosan is controlled so that the quaternary chitosan salt in the modified viscose fiber is only hydrophilic but insoluble in water.
  • the fiber has excellent antibacterial properties and is resistant to washing.
  • the ordinary viscose fiber production equipment can be used to easily produce denatured viscose fibers.
  • the denatured viscose fibers can be spun into direct fibers and applied to various aspects, or they can be spun into short fibers and sent to ordinary cotton spinning equipment.
  • Cotton blends denatured viscose with other fibers, and the antibacterial mixed fiber yarns that can be used for various fabrics are obtained through the process of clearing cotton and carded roving and spun yarns. Therefore, the implementation of this patent enables the use of cotton spinning technology to prepare antibacterial properties. Good mixed fibers become possible, which reduces the amount of functional ingredients, simplifies the processing process, and greatly saves costs.
  • the specific method of the modified chitosan mentioned in the present invention is: firstly dissolve the chitosan in a dilute acid, and then add the screened quaternary glycidyl amine salt, and then obtain it by reacting at a temperature of 5-60 ° C for a period of time.
  • dilute acid is used as both a solvent and a reaction catalyst in the reaction process.
  • the partially modified chitosan paddle liquid was added with a co-dispersant, sent to a homogenizer, and pulverized to a particle size of 4 ⁇ m.
  • Example 2 A partially modified chitosan slurry containing 20% of the chitosan quaternary amine salt was prepared according to the method described in Example 1, and the slurry was centrifuged to obtain a paste of modified chitosan 22.
  • Example 3 Similar to Example 2, except that 9.5 kg of a xanthate solution containing chitosan and its quaternary amine salt was mixed with 25 kg of cellulose xanthate, and after proper ripening, Filtered, defoamed, and spun to obtain 0.8% denatured viscose long fibers containing chitosan and 0.2% quaternary amine salt of chitosan.
  • the manual feeding method is used to feed the open and clean cotton combined machine to make mixed cotton rolls, and then into the carding machine to make mixed sliver, and then draw into the roving frame and then to the spinning frame to make mixed fibers.
  • the finished fiber yarn contained 0.8% chitosan, 0.2% chitosan amine salt, 9% viscose, and 90% cotton.
  • the following table is a statistical table of the antibacterial rate of each fiber obtained above.
  • Example 4 The method of Example 4 is only used for Example 1 Example 2 Example 3 Example 4
  • denatured viscose can be made into long fibers and used in many aspects of people's lives, and denatured viscose can also be made into short fibers, which can then be blended with other fibers to form various fibers.
  • Mixed fibers therefore, the manufacture of antibacterial mixed fibers does not require specific new equipment.
  • Staple fibers are produced using existing viscose production equipment, and then denatured viscose staple fibers are blended with other fibers in an ordinary cotton textile mill.
  • the composition of the antibacterial mixed fiber and the mixed fiber can be adjusted by different manufacturers according to different application objects. Therefore, the method has great flexibility and versatility.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)

Description

变性粘胶纤维及其制造方法 技术领域
本发明涉及一种变性粘胶纤维， 它可以纺成长纤而直接应用于 各个方面，也可以紡成短纤维，再送到普通棉纺设备，经过适当的配 棉将变性粘胶纤维与其它纤维混合， 经开清棉和梳棉并条粗纱细纱 工艺而得能够用于各种面料生产的抗菌混合纤维纱。
背景技术
随着科学技术的高速发展和人们生活水平的提高， 在世界范围 内对纺织品的要求越来越高， 不仅要求纺织品无毒、 无刺激， 对人 体无害， 与生物相容性好， 而且要求纺织品要有良好的透气性， 穿 着舒适性， 同时还要求具有一定的抗菌防霉特性。
目前已经有很多利用壳聚糖为有效成份生产抗菌纤维的技术， 例如： 在中国专利 CN1109530A 中是将壳聚糖溶解在氯化锂和二甲 基甲酰胺的混合溶剂中再经专用设备纺成壳聚糖纤维，该工艺复杂, 生产品成本很高， 大量应用受到限制。 在 USP 5756111中是将单独 的壳聚糖经碱化、 黄化、 溶解之后纺丝或与粘胶混合纺丝， 用作抗 菌紡织品时要么用量大， 成本高， 要么与其它纤维混合织造时会显 著降低其抗菌性。
发明内容
本发明的目的在于提供一种变性粘胶纤维及其制造方法， 它能 显著提高织物的抗菌防霉特性。
本发明的目的.是通过如下途径实现的：
本发明中， 由于在纤维中用特定工艺加入了天然品质的壳聚 糖， 它能赋予织物良好的生物相容性、 透气性和保湿性， 同时无毒 副作用并具有一定的抗菌性； 纤维中还加入了特定工艺制备的壳聚 糖季胺盐化合物， 它除了对织物的各项性能有良好的促进作用外， 更重要的特点是它能显著提高织物的抗菌防霉特性； 本发明所使用 的壳聚糖季胺盐是由壳聚糖季胺化而来， 在本发明中控制了壳聚糖 的季胺化改性比例， 使得制成的变性粘胶纤维中壳聚糖季胺盐仅有 亲水性但不溶于水， 从而使纤维的抗菌性能优良， 而且耐洗涤。 利 用普通的粘胶纤维生产设备可以很方便地制造出变性粘胶纤维， 该 变性粘胶纤维可以纺成长纤而直接应用于各个方面， 也可以纺成短 纤维送到普通棉纺设备， 经过适当的配棉将变性粘胶与其它纤维混 合， 经开清棉和梳棉并条粗纱细纱工艺而得能够用于各种面料生产 的抗菌混合纤维纱， 因此本专利的实施使得用棉纺工艺制备抗菌性 能良好的混合纤维成为可能， 它降低了功能成份的用量， 简化了处 理工艺， 大大地节省了成本。
具体实施方式
本发明中提到的改性壳聚糖其具体做法是： 先将壳聚糖溶解在 稀酸中， 再加入经筛选的缩水甘油季胺盐， 在 5- 60°C反应一段时间 即可得到部分改性的壳聚糖， 反应过程中稀酸既作溶剂又是反应催 化剂， 控制季胺盐的加入比例， 可以得到不同季胺化程度的改性壳 聚糖。
实施例 1 : 取片状壳聚糖 2. 8kg， 加入到 150kg水中， 充分润 湿后， 再加入冰醋酸 2. 3kg， 搅拌到全部溶解， 之后加入自制的缩 水甘油季胺盐溶夜 2. 5kg,保持 30°C反应 16h，之后将 10%的氢氧化 钠溶液慢慢加入到上述溶液中， 调整 ra=7， 得含 20%壳聚糖季胺盐 的部分改性壳聚糖浆状液。 将该部分改性壳聚糖桨状液加入助分散 剂， 送入均质机中研磨粉碎到 4 μ πι粒径， 悬浮液静置 12小时， 分 去上层清水，下层凝沉物送到粘胶生产过程中，与含 25kg纤维黄化 后的纤维素黄酸盐混和，再加入液碱，调整到碱含量 5%，进行碱溶， 之后经过适当的熟成、 过滤、 脱泡、 纺丝、 拉伸、 塑化、 分切、 精 练、 开松、干燥得到含壳聚糖 8%、壳聚糖季胺盐 2%的变性粘胶短纤 维 26kg0
实施例 2 :按照例 1所述方法制得含壳聚糖季胺盐 20%的部分改 性壳聚糖浆状液， 将浆状液离心过滤， 得改性壳聚糖的糊状物 22. 8kg, 加入 50%的液碱 11. 4kg， 升温到 80°C， 保温 1小时， 冷却 到 20°C， 加入 2. 2kgCS2， 密封黄化 6小时， 之后再加入 60kg的碎 冰，搅拌溶解 16小时，得到含壳聚糖及其季胺盐的黄酸盐溶液 95kg， 将此溶液送到粘胶生产过程， 与含 25kg纤维的纤维素黄酸盐混合， 再经例 2类似的后续工艺，得到含壳聚糖 8%，壳聚糖季胺盐 2%的变 性粘胶短纤维 26kg。
实施例 3 : 与例 2类似， 不同之处是将含壳聚糖及其季胺盐的 黄酸盐溶液 9. 5kg与含 25kg纤维素的纤维素黄酸盐混合，再经适当 的熟成、过滤、脱泡、纺丝得到含壳聚糖 0. 8%,含壳聚糖季胺盐 0. 2% 的变性粘胶长纤维。
实施例 4: 将例 2或例 3得到的变性粘胶短纤 26kg， 送入到棉 纺工艺过程， 按照变性粘胶短纤与纯棉的比例 =1. 1 : 8. 9进行配棉， 之后用手工喂棉的方法送入开清棉联合机制成混合棉卷，之后送入梳 棉机制成混合棉条， 再经并条机到粗纱机再到细纱机制成混合纤维。 成品纤维纱中含壳聚糖 0. 8%，壳聚糖季胺盐 0. 2%， 粘胶 9%， 棉 90%。
下表是上述所得的各纤维抗菌率统计表
采用例 4的方法仅不 例 1 例 2 例 3 例 4 对壳聚糖作季胺化处 理， 所得纤维 金黄色葡
99. 9% 99. 9% 99% 72% 45% 萄球菌
大肠埃希 99. 9% 99. 9% 99% 58% 无作用
氏菌 在本发明中， 根据应用对象的不同， 可以将变性粘胶制成长纤 维而应用在人们生活中的许多方面，也可以将变性粘胶制成短纤维， 用之再与其它纤维混纺成各种混合纤维， 因此， 抗菌性混合纤维的 制造它不需要特定的新设备，利用现有的粘胶生产设备生产出短纤， 再在普通的棉纺织厂将变性粘胶短纤与其它纤维混纺成抗菌性混合 纤维， 混纺纤维的成份可以在不同厂家根据不同的应用对象调整， 因此， 本方法具有很大的灵活性与通用性。

Claims

1.一种变性粘胶纤维，其特征在于该纤维中含有 0. 5%-30%的壳 聚糖， 0. 25%- 20%的壳聚糖季胺盐， 50%- 99. 25%的纤维素粘胶。
2. 一种变性粘胶纤维的制造方法， 其特征在于：
先将壳聚糖溶解在无机酸或稀醋酸或 CI- C8有机酸中， 再按照 权
摩尔比为 1 : 0. 2-0. 6的量加入缩水甘油季胺盐， 在 5-60°C的温度 下反应 6- 16小时后加入助分散剂， 利用 5%-10%的氢氧化钠（NaOH) 溶液将 PH值调至 7-8， 即得到包括壳聚糖和壳聚糖季胺盐的部分改 性壳聚糖；
上述产物部分改性壳聚糖可通过物理求或化学两种途径进行再加 工， 其中的物理方法为： 将部分改性壳聚糖经超细粉碎过滤而得到 颗粒小于 4 μ πι的分散液，再把此分散液加入到纤维素黄酸盐中，经 溶解熟成得到变性粘胶纺丝液； 所提到的化学方法为： 将部分改性 壳聚糖经过滤， 滤饼中加入适当比例的液碱， 经碱化、 CS2黄化之后 再溶解得到部分改性壳聚糖黄酸盐溶液， 将此溶液混合到纤维素粘 液丝原液中也可得到变性粘胶纺丝液；
最后将变性粘胶纺丝液经过湿法纺丝工艺成型而得到变性粘胶 纤维。
3.如权利要求 2中所述的变性粘胶纤维的制造方法， 其特征在 于： 缩水甘油季胺盐的结构式为
Figure imgf000007_0001
I II 它是指通式为 I或 II的化合物， 其中 R1、 R2、 R3可以相同， 也可以 不同， 分别可以是 C1-C24的垸基、 芳基、 苄基、 烯基等取代基， X 是卤素原子。
4.如权利要求 1或 2所述的变性粘胶纤维的制造方法， 其特征 在于： 所述的壳聚糖其分子量为 1-5 X 105, 脱乙酰率为 60-85%， 灰
PCT/CN2003/000582 2002-07-23 2003-07-21 Fibre de viscose modifiee et son procede de preparation WO2004009881A1 (fr)

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AU2003281538A AU2003281538A1 (en) 2002-07-23 2003-07-21 Modified viscose fibre and its preparing process

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CN02114294.7 2002-07-23
CNB021142947A CN1173082C (zh) 2002-07-23 2002-07-23 变性粘胶纤维及其制造方法

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CN101361987B (zh) * 2008-09-12 2011-11-16 西南交通大学 一种具有抗菌功能的人工心脏瓣膜缝合环涤纶材料
CN103668520B (zh) * 2013-12-04 2016-05-25 阜宁澳洋科技有限责任公司 一种抗菌再生纤维素纤维及其制备方法
CN103835022B (zh) * 2014-03-07 2014-10-29 宏远纺织科技（泉州）有限公司 一种纤维素共混纤维及其制备方法
CN104532408A (zh) * 2014-09-24 2015-04-22 江苏金太阳纺织科技有限公司 阳离子接枝改性无盐染色再生纤维素纤维的制备方法
CN106757459B (zh) * 2016-11-17 2019-06-14 汕头市珂玲服饰有限公司 一种含苦豆子提取物的抗菌防螨粘胶纤维及制备方法
CN108532053A (zh) * 2018-03-02 2018-09-14 宁波三邦超细纤维有限公司 有色涤锦云母复合冰感纤维及其制备方法
CN108707991B (zh) * 2018-06-12 2020-02-21 江苏金太阳纺织科技股份有限公司 一种天然染料可染的再生纤维素纤维的制备方法
CN111235687A (zh) * 2020-03-25 2020-06-05 泉州嘉宸科技有限公司 一种抗菌多层复合中空纤维膜材料及其制备方法

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CN1266922A (zh) * 2000-01-25 2000-09-20 天津大学 抗菌粘胶纤维及其制造方法
CN1300886A (zh) * 1999-12-13 2001-06-27 富士纺织株式会社 改良再生纤维素纤维的制法
KR20020036398A (ko) * 2000-11-09 2002-05-16 김영호 항미생물성 재생 셀룰로오스 섬유의 제조 방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000073280A (ja) * 1998-08-26 2000-03-07 Japan Exlan Co Ltd 抗菌性アクリル繊維及びその製造方法
CN1300886A (zh) * 1999-12-13 2001-06-27 富士纺织株式会社 改良再生纤维素纤维的制法
CN1266922A (zh) * 2000-01-25 2000-09-20 天津大学 抗菌粘胶纤维及其制造方法
KR20020036398A (ko) * 2000-11-09 2002-05-16 김영호 항미생물성 재생 셀룰로오스 섬유의 제조 방법

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