CN1311123C - Method for treating cellulosic moulded bodies - Google Patents

Method for treating cellulosic moulded bodies Download PDF

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Publication number
CN1311123C
CN1311123C CNB028253175A CN02825317A CN1311123C CN 1311123 C CN1311123 C CN 1311123C CN B028253175 A CNB028253175 A CN B028253175A CN 02825317 A CN02825317 A CN 02825317A CN 1311123 C CN1311123 C CN 1311123C
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cellulose
textile auxiliary
moulded bodies
fibers
solution
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Expired - Fee Related
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CN1604979A (en
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C·罗雷尔
W·里查德特
E·肖贝斯伯格
G·赖特
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Lenzing AG
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Lenzing AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358—Triazines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention relates to a process for the treatment of cellulosic moulded bodies produced from a solution of cellulose in an aqueous tertiary amine oxide, in particular fibres, wherein the moulded bodies are contacted with a textile auxiliary agent. The process according to the invention is characterized in that the textile auxiliary agent comprises a cyclodextrin and/or a cyclodextrin derivative.

Description

纤维素模制体的处理方法Treatment method of cellulose molded body

本发明涉及纤维素模制体，特别是纤维和含有纤维的织物的处理方法，所述模制体由纤维素在含水的叔胺氧化物中的溶液制备，在该方法中将模制体和一种纺织助剂接触，赋予模制体改善的性能。The invention relates to a process for the treatment of cellulosic molded bodies, in particular fibers and fabrics containing fibers, prepared from a solution of cellulose in an aqueous tertiary amine oxide, in which process the molded body and A textile auxiliary contact that imparts improved properties to molded objects.

对于本发明的目的，术语“模制体”还特别包括海绵。For the purposes of the present invention, the term "molded body" also includes in particular sponges.

近年来描述了一系列方法来代替粘胶法，其中在不生成衍生物的情况下将纤维素溶解在有机溶剂、有机溶剂与无机盐的组合物或者盐的水溶液中。将由此溶液制得的纤维素纤维称为“溶液纺丝的”纤维，并在BISFA(人造纤维标准化国际局)得到属名Lyocell，BISFA将通过纺织方法从有机溶剂中得到的纤维素纤维定义为Lyocell。BISFA将“有机溶剂”解释为由有机的化学品和水组成的混合物。“溶液纺丝”是指未发生衍生化的溶解和纺织。In recent years, instead of the viscose method, a series of methods have been described in which cellulose is dissolved in an organic solvent, a combination of an organic solvent and an inorganic salt, or an aqueous salt solution without forming a derivative. The cellulose fibers obtained from this solution are called "solution spun" fibers and get the generic name Lyocell at BISFA (International Bureau for the Standardization of Man-Made Fibres), which defines cellulose fibers obtained from organic solvents by spinning methods as Lyocell. BISFA defines "organic solvent" as a mixture of organic chemicals and water. "Solution spinning" means dissolving and spinning without derivatization.

然而至今只有唯一的一种制备溶液纺丝的纤维素纤维的方法实现了工业化。该方法中使用叔胺氧化物，特别是N-甲基吗啉-N-氧化物(NMMO)作为溶剂。例如在US-A4246221中描述了这样的方法，其提供的纤维以高强度、高湿度模量以及高勾接强度为特征。To date, however, only one single process for the production of solution-spun cellulose fibers has been achieved industrially. Tertiary amine oxides, especially N-methylmorpholine-N-oxide (NMMO), are used as solvents in this method. Such a method is described, for example, in US-A4246221, which provides fibers characterized by high tenacity, high wet modulus and high interlocking strength.

WO99/19555描述了一种处理溶液纺丝的纤维的方法，该方法中纤维与2，4-二氯-6-羟基-1，3，5-三嗪或其盐接触。与原纤维相比，这样得到的纤维表现出改善的强度。WO 99/19555 describes a method of treating solution spun fibers in which the fibers are contacted with 2,4-dichloro-6-hydroxy-1,3,5-triazine or a salt thereof. The fibers thus obtained exhibit improved strength compared to fibrils.

此外，US5728823公开了环糊精衍生物，特别是2-氯-4-羟基-1，3，5-三嗪基环糊精的钠盐。US5728823进一步描述了环糊精衍生物所结合的膜、箔、纺织品或皮革。用环糊精衍生物处理的纺织品适合于例如吸收令人不快的气味。Furthermore, US5728823 discloses cyclodextrin derivatives, especially the sodium salt of 2-chloro-4-hydroxy-1,3,5-triazinylcyclodextrin. US5728823 further describes films, foils, textiles or leathers to which cyclodextrin derivatives are incorporated. Textiles treated with cyclodextrin derivatives are suitable, for example, for absorbing unpleasant odors.

WO01/48025描述的环糊精借助交联剂与聚糖共价结合。The cyclodextrins described in WO 01/48025 are covalently bound to glycans by means of crosslinkers.

现在发现，可以使用包含环糊精和/或环糊精衍生物的纺织助剂处理由纤维素在含水的叔胺氧化物中的溶液制得的纤维素模制体，由此形成性能改善的产品。It has now been found that cellulose moldings produced from solutions of cellulose in aqueous tertiary amine oxides can be treated with textile auxiliaries comprising cyclodextrins and/or cyclodextrin derivatives, thereby forming cellulose moldings with improved properties. product.

优选模制体涉及从不以干燥状态存在的纤维。可以在连续加工产品装置的后处理步骤中处理未从不以干燥状态存在的纤维。Preferably the molded body involves fibers which are never present in a dry state. Fibers that have never existed in a dry state can be processed in a post-processing step of a continuous processing product plant.

已知环糊精可以包含活性物质，所述活性物质然后例如经过长时间释放出。根据本发明的方法，可以在用环糊精或环糊精衍生物处理的纤维的连续生产方法过程中同时和/或先后负载这种活性物质。It is known that cyclodextrins can contain active substances which are then released, eg over a long period of time. According to the method according to the invention, this active substance can be loaded simultaneously and/or sequentially during the continuous production process of fibers treated with cyclodextrin or cyclodextrin derivatives.

用纺织助剂进行的处理优选在碱性环境中进行。The treatment with textile auxiliaries is preferably carried out in an alkaline environment.

此外优选纺织助剂还包括一种交联剂。特别优选使用2，4-二氯-6-羟基-1，3，5-三嗪或其盐作为交联剂。Furthermore, it is preferred that the textile auxiliary also comprises a crosslinking agent. Particular preference is given to using 2,4-dichloro-6-hydroxy-1,3,5-triazine or a salt thereof as crosslinking agent.

根据US5728823的现有技术，必须首先制备昂贵的环糊精衍生物，例如2-氯-4-羟基-1，3，5-三嗪基环糊精的钠盐，随后在待处理的材料上涂布该衍生物。According to the prior art of US5728823, expensive cyclodextrin derivatives, such as the sodium salt of 2-chloro-4-hydroxy-1,3,5-triazinylcyclodextrin, must first be prepared, and then on the material to be treated Apply the derivative.

现在表明，可以向待处理的纤维中加入环糊精和交联剂，特别是2，4-二氯-6-羟基-1，3，5-三嗪，并得到良好的结果，而不必首先由该两种物质制备一种化合物。It has now been shown that cyclodextrins and crosslinkers, especially 2,4-dichloro-6-hydroxy-1,3,5-triazine, can be added to fibers to be treated with good results without having to first One compound is prepared from the two substances.

在根据本发明方法的另一实施方案中包括纺织助剂2-氯-4-羟基-1，3，5-三嗪基环糊精(MCT-CD)或其盐。Another embodiment of the method according to the invention comprises the textile auxiliary 2-chloro-4-hydroxy-1,3,5-triazinylcyclodextrin (MCT-CD) or a salt thereof.

本发明还涉及按照本发明方法得到的溶液纺丝的纤维素纤维，以及含有该纤维的纤维织物。The invention also relates to solution-spun cellulosic fibers obtained according to the process of the invention, and to fibrous webs containing such fibers.

实施例1：Example 1:

根据WO93/19230中描述的方法制备的溶液纺丝的纤维，其具有1.3dtex纤度，在从不以干燥状态存在的情况下进行按如下处理：Solution spun fibers prepared according to the method described in WO93/19230, having a titer of 1.3 dtex, were processed as follows, never in the dry state:

室温下，将纤维在溶液中浸渍5分钟，浴比为1∶10，该溶液含有20g/l的2，4-二氯-6-羟基-1，3，5-三嗪的钠盐、16g/l的NaOH和100g/l的环糊精(CAVAMAX W7，Wacker化学公司生产)。随后借助一种挤压机挤出湿度为100-110％的纤维，用饱和蒸汽(100％)在100℃热处理5分钟、洗涤并干燥。At room temperature, the fiber was immersed in the solution for 5 minutes, the bath ratio was 1:10, and the solution contained 20 g/l of 2,4-dichloro-6-hydroxyl-1,3,5-triazine sodium salt, 16 g /l of NaOH and 100 g/l of cyclodextrin (CAVAMAX W7, produced by Wacker Chemical Company). The fibers are then extruded by means of an extruder with a moisture content of 100-110%, heat-treated with saturated steam (100%) at 100°C for 5 minutes, washed and dried.

借助酚酞溶液变色的光度法(552nm)测量这样得到的纤维的活性环糊精含量，为2.33重量％。The active cyclodextrin content of the fibers thus obtained was measured photometrically (552 nm) by means of the color change of a phenolphthalein solution and was 2.33% by weight.

借助单纤维的湿耐磨性(根据WO99/19555的测试方法)测定纤维的帚化度。按照该测试方法得到根据本发明处理的样品的平均值为210转。与之相比，未处理的纤维的湿耐磨值只有40-60转。The degree of scouring of the fibers is determined by means of the wet abrasion resistance of the individual fibers (test method according to WO99/19555). An average value of 210 revolutions was obtained for the samples treated according to the invention according to this test method. In comparison, the wet abrasion value of untreated fibers was only 40-60 revolutions.

实施例2：Example 2:

如上述实施例1进行，其中处理溶液含有20g/l的2，4-二氯-6-羟基-1，3，5-三嗪的钠盐、16g/l的NaOH、30g/l的苏打和50g/l的环糊精(CAVAMAX W7，Wacker化学公司生产)。Carried out as in Example 1 above, wherein the treatment solution contained 20 g/l of the sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine, 16 g/l of NaOH, 30 g/l of soda and 50 g/l of cyclodextrin (CAVAMAX W7, manufactured by Wacker Chemical Company).

这样得到的纤维的活性环糊精的含量为1.65重量％，湿耐磨值为470转。The fibers thus obtained had an active cyclodextrin content of 1.65% by weight and a wet abrasion value of 470 revolutions.

实施例3：Example 3:

如上述实施例1进行，其中处理溶液含有30g/l的苏打和100g/l的2-氯-4-羟基-1，3，5-三嗪基环糊精(MCT-CD；CAVASOL W7MCT，Wacker化学公司生产)。Carried out as in Example 1 above, wherein the treatment solution contained 30 g/l of soda and 100 g/l of 2-chloro-4-hydroxyl-1,3,5-triazinylcyclodextrin (MCT-CD; CAVASOL W7MCT, Wacker chemical company).

这样得到的纤维中的活性MCT-CD的含量为1.89重量％。The active MCT-CD content in the fiber thus obtained was 1.89% by weight.

Claims (10)

1. never handle the method for the cellulose fibre that exists with drying regime, the solution of this cellulose fibre in moisture tertiary amino oxides makes, and fiber is contacted with textile auxiliary, it is characterized in that textile auxiliary comprises cyclodextrin and/or cyclodextrine derivatives.
2. according to the method for claim 1, it is characterized in that described textile auxiliary also comprises crosslinking agent.
3. handle the method for cellulose moulded bodies, this molding is made by the solution of cellulose in moisture tertiary amino oxides, and molding is contacted with textile auxiliary, it is characterized in that, textile auxiliary comprises cyclodextrin and/or cyclodextrine derivatives, and textile auxiliary also comprises crosslinking agent.
4. according to the method for claim 3, it is characterized in that described cellulose moulded bodies is a fiber.
5. according to the method for claim 4, it is characterized in that described molding is the fiber that never exists with drying regime.
6. according to the method for one of claim 3 to 5, it is characterized in that use 2,4-two chloro-6-hydroxyl-1,3,5-triazines or its salt are as crosslinking agent.
7. according to the method for claim 1, it is characterized in that described textile auxiliary comprises 2-chloro-4-hydroxyl-1,3,5-triazines basic ring dextrin or its salt.
8. the cellulose moulded bodies that obtains according to the method for one of claim 1 to 7.
9. cellulose moulded bodies according to Claim 8, wherein this cellulose moulded bodies is a fiber.
10. the fabric that contains claim 8 or 9 described solution spun fiber cellulose fibers.
CNB028253175A 2001-12-20 2002-12-19 Method for treating cellulosic moulded bodies Expired - Fee Related CN1311123C (en)

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AT0201201A AT413988B (en) 2001-12-20 2001-12-20 METHOD FOR THE TREATMENT OF CELLULOSIC FORM BODIES
ATA2012/2001 2001-12-20

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CN1311123C true CN1311123C (en) 2007-04-18

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JP (1) JP2005535790A (en)
KR (1) KR100910989B1 (en)
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AU (1) AU2002361375A1 (en)
DE (1) DE50214703D1 (en)
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WO (1) WO2003054283A2 (en)

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CN100398741C (en) * 2006-09-21 2008-07-02 浙江理工大学 A kind of preparation method of cyclodextrin-phthalocyanine dual mimetic enzyme function fiber
CN100415980C (en) * 2006-09-21 2008-09-03 浙江理工大学 A preparation method of cyclodextrin-phthalocyanine double mimetic enzyme functional fiber
CN100392173C (en) * 2006-09-21 2008-06-04 浙江理工大学 Preparation method of cyclodextrin mimetic enzyme functional fiber
CN100392172C (en) * 2006-09-21 2008-06-04 浙江理工大学 Preparation method of cyclodextrin polymer mimic enzyme functional fiber
CN101220557B (en) * 2007-12-06 2010-06-02 浙江理工大学 A kind of preparation method of simulated enzyme catalytic fiber
AT506334B1 (en) * 2008-01-22 2010-12-15 Chemiefaser Lenzing Ag METHOD FOR THE TREATMENT OF CELLULOSIC FORM BODIES
AT509289B1 (en) * 2009-12-28 2014-06-15 Chemiefaser Lenzing Ag FUNCTIONALIZED CELLULOSIC FORM BODY AND METHOD FOR THE PRODUCTION THEREOF
JP4832573B2 (en) * 2010-02-27 2011-12-07 慶一郎 金久 Antiviral and antibacterial processing methods for textile structures

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1157574A (en) * 1994-08-12 1997-08-20 普罗克特和甘保尔公司 Compositions containing beta-cyclodextrin for treating fabrics
US5728823A (en) * 1994-08-18 1998-03-17 Consortium Fur Elektrochemische Industrie Gmbh Cyclodextrin derivatives having at least one nitrogen-containing heterocycle, their preparation and use
WO1999019555A1 (en) * 1997-10-15 1999-04-22 Lenzing Aktiengesellschaft Method for treating cellulosic shaped bodies
CN1045117C (en) * 1989-04-12 1999-09-15 普罗格特-甘布尔公司 Treating Fabrics with Fragrance/Cyclodextrin Complexes

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19520967A1 (en) * 1995-06-08 1996-12-12 Consortium Elektrochem Ind Treatment of leather, synthetic or natural textiles
JP2000505692A (en) * 1996-12-17 2000-05-16 ザ、プロクター、エンド、ギャンブル、カンパニー Absorbent products with odor control system

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1045117C (en) * 1989-04-12 1999-09-15 普罗格特-甘布尔公司 Treating Fabrics with Fragrance/Cyclodextrin Complexes
CN1157574A (en) * 1994-08-12 1997-08-20 普罗克特和甘保尔公司 Compositions containing beta-cyclodextrin for treating fabrics
US5728823A (en) * 1994-08-18 1998-03-17 Consortium Fur Elektrochemische Industrie Gmbh Cyclodextrin derivatives having at least one nitrogen-containing heterocycle, their preparation and use
WO1999019555A1 (en) * 1997-10-15 1999-04-22 Lenzing Aktiengesellschaft Method for treating cellulosic shaped bodies
CN1241230A (en) * 1997-10-15 2000-01-12 连津格股份公司 Method for treating cellulosic shaped bodies

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AU2002361375A1 (en) 2003-07-09
AT413988B (en) 2006-08-15
KR100910989B1 (en) 2009-08-05
AU2002361375A8 (en) 2003-07-09
JP2005535790A (en) 2005-11-24
ATA20122001A (en) 2005-11-15
EP1463858B1 (en) 2010-10-06
DE50214703D1 (en) 2010-11-18
WO2003054283A3 (en) 2004-08-05
ATE483848T1 (en) 2010-10-15
EP1463858A2 (en) 2004-10-06
CN1604979A (en) 2005-04-06
TW200301325A (en) 2003-07-01
WO2003054283A2 (en) 2003-07-03
KR20040070238A (en) 2004-08-06

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